JP3221302B2 - Titanium or titanium alloy strip with beautiful surface and method of manufacturing the same - Google Patents
Titanium or titanium alloy strip with beautiful surface and method of manufacturing the sameInfo
- Publication number
- JP3221302B2 JP3221302B2 JP31836995A JP31836995A JP3221302B2 JP 3221302 B2 JP3221302 B2 JP 3221302B2 JP 31836995 A JP31836995 A JP 31836995A JP 31836995 A JP31836995 A JP 31836995A JP 3221302 B2 JP3221302 B2 JP 3221302B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- strip
- pickling
- acid
- washing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000010936 titanium Substances 0.000 title claims description 40
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 37
- 229910001069 Ti alloy Inorganic materials 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title description 6
- 238000005554 pickling Methods 0.000 claims description 47
- 229910052719 titanium Inorganic materials 0.000 claims description 39
- 239000002253 acid Substances 0.000 claims description 33
- 238000005406 washing Methods 0.000 claims description 23
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 6
- 238000010924 continuous production Methods 0.000 claims description 4
- 239000000110 cooling liquid Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims 1
- 230000007423 decrease Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- -1 titanium ions Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 102200110702 rs60261494 Human genes 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/106—Other heavy metals refractory metals
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、チタンまたはチタ
ン合金ストリップを酸洗・水洗する連続製造処理ライン
において、ストリップ表面に発生する赤茶色の着色斑
（以下、「酸焼け」と称することがある）の発生を防止
して、表面の美麗なチタンまたはチタン合金ストリップ
を製造するための有用な方法、およびこの様にして得ら
れる該ストリップに関するものである。BACKGROUND OF THE INVENTION The present invention relates to a continuous production line for pickling and washing titanium or titanium alloy strips, wherein red-brown colored spots (hereinafter referred to as "acid burns") are generated on the surface of the strip. The present invention relates to a useful method for producing a titanium or titanium alloy strip having a beautiful surface by preventing the occurrence of (a), and a strip obtained in this way.
【０００２】[0002]
【従来の技術】チタンまたはチタン合金（以下、チタン
で代表することがある）ストリップは、熱間圧延または
熱間圧延と冷間圧延を経て製造されるのが一般的である
が、これらストリップはこのまま出荷されることはほと
んどない。多くの場合には、圧延を行なった後に、歪み
取りの為の大気中での焼鈍を行ない、その後圧延または
焼鈍の際にに発生したスケールや酸素富化層をショット
ブラストやソルトバス等の処理によってある程度除去
し、更に弗酸を含んだ酸洗液、例えば硝弗酸によって残
存するスケールを完全に除去し、ストリップ表面に金属
光沢をもたせる。2. Description of the Related Art Generally, titanium or titanium alloy (hereinafter sometimes referred to as titanium) strips are manufactured through hot rolling or hot rolling and cold rolling. It is rarely shipped as is. In most cases, after rolling, annealing is performed in the air to remove strain, and then the scale or oxygen-enriched layer generated during rolling or annealing is treated by shot blasting or salt bath. The strips are completely removed by a pickling solution containing hydrofluoric acid, for example, nitric hydrofluoric acid, and the strip surface is given a metallic luster.
【０００３】しかしながらこの酸洗工程においては、時
としてストリップ表面のほぼ全面または局所的に赤茶色
の酸焼けが発生するという欠点がある。こうした酸焼け
は、チタンストリップを熱交換器等の様に人目に触れな
い構造材に用いる場合には、実用上問題はないのである
が、屋根材やカーテンウオール等の様に人目に触れる部
材に用いる際には美観が損なわれることになる。[0003] However, in this pickling process, there is a disadvantage that red-brown acid burns sometimes occur almost entirely or locally on the strip surface. In the case of such acid burning, there is no problem in practical use when titanium strip is used for invisible structural materials such as heat exchangers, etc., but it is used for visible materials such as roofing materials and curtain walls. When used, aesthetics will be impaired.
【０００４】上記の様な酸焼けの除去は、再度酸洗する
ことによって行なわれるのが一般的であるが、こうした
方法によれば再酸洗前に発生した酸焼けについては除去
できるのであるが、再度酸洗を行なった際に新たな酸焼
けが発生することもあり、根本的な解決策にはならな
い。また上記の様な酸焼けを、酸洗液の組成を工夫する
ことによって解消する技術も提案されている。例えば、
特開昭６４−４４９１号や特開平１−１２３０９７号に
は、弗酸に過酸化水素、蓚酸、酒石酸等のキレート剤を
添加して酸焼け発生を防止する技術が提案されている。
但し、これらの公報に記載された技術は、着色チタン材
を対象とするものである。[0004] The removal of acid burns as described above is generally performed by pickling again. According to such a method, acid burns generated before re-picking can be removed. However, when pickling is performed again, a new acid burn may occur, which is not a fundamental solution. Further, there has been proposed a technique for eliminating the acid burning as described above by devising the composition of the pickling solution. For example,
JP-A-64-4491 and JP-A-1-12397 propose a technique of adding a chelating agent such as hydrogen peroxide, oxalic acid or tartaric acid to hydrofluoric acid to prevent acid burning.
However, the techniques described in these publications are directed to colored titanium materials.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら実際問題
として、通常のチタンストリップの酸洗には、上記各公
報に記載されている着色チタン材の着色前処理に比べて
比較にならない程の多量の酸洗液を必要とするので、弗
酸に上記各種キレート剤を添加することは、廃液処理の
問題やコストの大幅な上昇を招くという欠点がある。ま
た酸洗浴の管理上の問題や酸洗装置の耐食性の問題、更
には大量のキレート剤の使用許可の問題等、様々な問題
を抱えているので、キレート剤を安易に使用することは
できない。However, as a practical problem, the pickling of ordinary titanium strips requires a large amount of acid which is incomparable with the pretreatment for coloring titanium materials described in the above publications. Since a washing solution is required, the addition of the above-mentioned various chelating agents to hydrofluoric acid has a drawback of causing a problem of waste liquid treatment and a significant increase in cost. Further, there are various problems such as a problem in the management of the pickling bath, a problem in the corrosion resistance of the pickling apparatus, and a problem in permitting the use of a large amount of the chelating agent. Therefore, the chelating agent cannot be easily used.
【０００６】本発明はこうした状況のもとになされたも
のであって、その目的は、従来からチタンまたはチタン
合金ストリップの酸洗に用いられている弗酸系の酸洗液
を用いることを前提とし、製造現場でも比較的容易に対
応でき、酸焼けを有効に防止することのできる様なチタ
ンまたはチタン合金ストリップの製造方法、およびこう
した製造方法によって得られた表面の美麗なチタンまた
はチタン合金ストリップを提供することにある。The present invention has been made under such circumstances, and its object is to use a hydrofluoric acid-based pickling solution conventionally used for pickling titanium or titanium alloy strips. A method for producing a titanium or titanium alloy strip which can be relatively easily handled even at a production site and which can effectively prevent acid burning, and a titanium or titanium alloy strip with a beautiful surface obtained by such a production method Is to provide.
【０００７】[0007]
【課題を解決するための手段】上記目的を達成すること
のできた本発明方法とは、チタンまたはチタン合金スト
リップを弗酸含有酸洗液で酸洗した後、水洗する連続製
造処理ラインにおいて、酸洗から水洗に至るまでの間に
ストリップ表面を冷却する点に要旨を有するチタンまた
はチタン合金ストリップの製造方法である。SUMMARY OF THE INVENTION The method of the present invention, which has achieved the above objects, comprises a step of pickling a titanium or titanium alloy strip with a pickling solution containing hydrofluoric acid, followed by washing with water. This is a method for producing a titanium or titanium alloy strip which has a gist in cooling the strip surface from washing to washing.
【０００８】上記方法において、ストリップ表面を冷却
する為の具体的手段としては、下記〜の手段が挙げ
られる。 ストリップ表面に水，液体空気，液体窒素等の冷却用
液体、または氷やドライアイス等の冷却用固体を散布
（液体の場合は「噴霧」することを含む）する。 ストリップ表面に、例えば液体空気や液体窒素等の低
温液体、または氷やドライアイス等の低温固体からの気
化ガスを吹き付ける。 酸洗から水洗に至るまでの間を前記した様な低温液体
または低温固体からの気化ガス雰囲気とすることによっ
てストリップ表面を冷却する。 酸洗から水洗に至るまでの間の雰囲気を冷却器によっ
て冷却してストリップ表面を冷却する。[0008] In the above method, specific means for cooling the strip surface include the following means. A cooling liquid such as water, liquid air, or liquid nitrogen, or a cooling solid such as ice or dry ice is sprayed on the strip surface (in the case of a liquid, this includes "spraying"). A vaporized gas from a low-temperature liquid such as liquid air or liquid nitrogen, or a low-temperature solid such as ice or dry ice is sprayed on the strip surface. The strip surface is cooled by setting the low temperature liquid or low temperature solid vaporized gas atmosphere as described above during the period from pickling to water cleaning. The atmosphere from pickling to water washing is cooled by a cooler to cool the strip surface.
【０００９】尚前記の手段において、酸洗から水洗に
至るまでの雰囲気を冷却によって積極的に冷却する場合
は勿論のこと、外気を導入して雰囲気を冷却する場合を
含む趣旨である。In the above-mentioned means, the purpose is to include not only the case where the atmosphere from pickling to washing is actively cooled by cooling but also the case where the atmosphere is cooled by introducing outside air.
【００１０】また上記の方法によって製造されたチタン
またはチタン合金ストリップは、酸焼けの無い美麗な表
面性状のを有するものとなるが、具体的には、酸焼けの
発生領域が板表面の１０％以下のものとなる。[0010] The titanium or titanium alloy strip produced by the above-mentioned method has a beautiful surface property without acid scorch. Specifically, the acid scorch generation area is 10% of the plate surface. It is as follows.
【００１１】[0011]
【発明の実施の形態】酸焼けの発生原因については、
「酸洗時にチタン弗化物が生成し、これが原因となる」
（特開平１−１２３０９７号）や、「酸洗により酸化皮
膜が除去された後の活性化したチタン表面が硝酸の酸化
作用を受けて再酸化される」（特開昭６４−４４９１
号）等、様々な見解が主張されているが、明確に解明さ
れているとは言えない。BEST MODE FOR CARRYING OUT THE INVENTION
"Titanium fluoride is generated during pickling, which is the cause."
(Japanese Patent Application Laid-Open No. 1-123097) and "The activated titanium surface after the oxide film is removed by pickling is re-oxidized by the oxidizing action of nitric acid" (Japanese Patent Application Laid-Open No. 64-4491).
), But various opinions have not been clarified.
【００１２】そこで本発明者らは、酸焼けの実態および
発生原因について鋭意研究を重ねた。その結果、酸焼け
の実態は厚さ百数十〜数百Åのチタンの酸化皮膜であ
り、これは次の機構で生成することがわかった。即ち、
酸洗によってチタンイオンおよび弗化チタンイオンが生
成されるが、これらが酸洗中または酸洗終了直後（酸洗
液から取り出した状態でも表面に酸洗液が付着してい
る）に、酸洗液中の水分や溶存酸素と反応してチタン酸
化物を形成し、これがチタン表面に吸着して酸化皮膜を
形成する。そしてこの酸化皮膜が光の干渉作用で赤茶色
に見えるのである。従って、チタンイオンや弗化チタン
イオンを過剰に生成させない様にすれば、酸焼けが防止
または軽減できると考えられた。The present inventors have conducted intensive studies on the actual conditions and causes of acid burning. As a result, it was found that the actual state of the acid burn was an oxide film of titanium having a thickness of several hundred to several hundreds of millimeters, which was formed by the following mechanism. That is,
The pickling produces titanium ions and titanium fluoride ions, which are pickled during or immediately after the pickling (the pickling solution adheres to the surface even after being removed from the pickling solution). It reacts with water and dissolved oxygen in the liquid to form titanium oxide, which is adsorbed on the titanium surface to form an oxide film. The oxide film looks reddish brown due to the interference of light. Therefore, it was considered that acid burning can be prevented or reduced by preventing excessive generation of titanium ions and titanium fluoride ions.
【００１３】ストリップの連続酸洗では、酸洗終了後直
ちに水洗することは不可能である。つまり、水洗領域に
ストリップが到達するまでの間、酸洗液が表面に付着し
た状態が存在することにより、この間に上記の様な反応
が生じてしまい、酸焼けが生じてしまうものと考えられ
た。そこで、酸洗から水洗に至るまでの間のストリップ
表面を何らかの手段で冷却する様にすれば、上記の様な
反応が抑制されるという考えのもとに本発明を完成し
た。[0013] In continuous pickling of the strip, it is impossible to wash with water immediately after the completion of pickling. In other words, it is considered that the above-described reaction occurs during the period in which the pickling liquid adheres to the surface until the strip reaches the water-washing region, and acid scorching occurs. Was. Therefore, the present invention has been completed based on the idea that the above-described reaction is suppressed if the strip surface is cooled by any means during the period from pickling to water washing.
【００１４】本発明は上記の如く構成されるが、要する
に、酸洗から水洗に至るまでの間にストリップ表面を冷
却する点に最大の特徴を有するものである。また本発明
において、ストリップ表面を冷却する為の具体的手段と
しては、前記〜の手段が挙げられるが、これら手段
を組み合わせて実施することはより効果的である。The present invention is constructed as described above, but in short, has the greatest feature in that the surface of the strip is cooled during the period from pickling to washing with water. In the present invention, specific means for cooling the surface of the strip include the above-mentioned means, but it is more effective to combine and implement these means.
【００１５】ところで本発明においては、ストリップ表
面が冷却される程度については特に規定していない。こ
れは酸洗反応等の化学反応速度は温度が低くなればなる
ほど低下するので、たとえ冷却によって極わずかしか表
面の酸洗液の温度が低下しなかったとしても、酸洗反応
の速度は小さくなり、酸焼けの発生も軽度になるからで
ある。但し、酸焼けの発生度合いの減少程度から判断す
ると、ストリップ表面の温度が少なくとも３℃以上低下
するように表面を冷却することが好ましい。こうした方
法を採用することによって、得られるチタン（またはチ
タン合金）ストリップは、酸焼けが全くないか、または
許容できる程度にまで抑制されるので、建材等の美観が
要求される部材に好適に利用できる。In the present invention, the degree to which the strip surface is cooled is not specified. This is because the rate of chemical reaction such as pickling reaction decreases as the temperature decreases, so even if the temperature of the pickling liquid on the surface decreases only slightly by cooling, the rate of pickling reaction decreases. This is because the occurrence of acid burning becomes mild. However, judging from the degree of decrease in the degree of occurrence of acid burning, it is preferable to cool the surface of the strip so that the temperature of the surface of the strip decreases by at least 3 ° C. or more. By adopting such a method, the resulting titanium (or titanium alloy) strip is completely free of acid burns or suppressed to an acceptable level, so that it can be suitably used for members requiring aesthetics such as building materials. it can.
【００１６】以下本発明を実施例によって更に詳細に説
明するが、下記実施例は本発明を限定する性質のもので
なく、前・後記の趣旨に徴して設計変更することはいず
れも本発明の技術的範囲に含まれるものである。Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following Examples are not intended to limit the present invention, and any change in design based on the above and following points is not limited to the present invention. It is included in the technical scope.
【００１７】[0017]
実施例１ 図１は、本発明方法を実施するために構成されるチタン
ストリップの連続製造処理ラインの概略説明図であり、
図中１は酸洗槽、２はチタンストリップ、３は水洗槽、
４は冷却領域を夫々示す。即ち、本発明においては、酸
洗（酸洗槽１）から水洗（水洗槽３）に至るまで間の冷
却領域４において、チタンストリップ表面を冷却するも
のである。Example 1 FIG. 1 is a schematic explanatory diagram of a continuous production line for titanium strip configured to carry out the method of the present invention,
In the figure, 1 is a pickling tank, 2 is a titanium strip, 3 is a washing tank,
Numeral 4 indicates a cooling area. That is, in the present invention, the surface of the titanium strip is cooled in the cooling area 4 from the pickling (the pickling tank 1) to the washing (the washing tank 3).
【００１８】図１に示した連続処理ラインを用いて、厚
さ：２ｍｍ，幅：１２００ｍｍの純チタンストリップを
連続的に通過させながら、酸洗槽１から水洗槽３に至る
まで間でチタンストリップ表面を種々の手段で冷却し、
水洗槽３から出てきたチタンストリップ表面を観察し
た。Using the continuous processing line shown in FIG. 1, while continuously passing a pure titanium strip having a thickness of 2 mm and a width of 1200 mm, the titanium strip is moved from the pickling tank 1 to the washing tank 3. Cooling the surface by various means,
The surface of the titanium strip coming out of the washing tank 3 was observed.
【００１９】このとき、酸洗槽１中の酸洗液としては硝
弗酸を用い、夫々の濃度が酸洗中において硝酸：５〜１
０重量％、弗酸：１〜３重量％となる様に適宜補給しな
がら酸洗を行なった。また、酸洗液の温度は、３５〜４
５℃の範囲に調節した。At this time, nitric hydrofluoric acid is used as the pickling solution in the pickling tank 1, and the concentration of nitric acid is 5 to 1 during pickling.
Pickling was carried out while appropriately replenishing the solution so as to be 0% by weight and hydrofluoric acid: 1 to 3% by weight. The temperature of the pickling solution is 35 to 4
The temperature was adjusted to 5 ° C.
【００２０】その結果を、冷却手段と共に下記表１およ
び２に示す。尚表１，２中、酸焼け発生度相対評価は、
目視観察によって下記に示す５段階の基準によるもので
あり、評価が１、２のものが不合格レベルである。また
冷却手段が同じであってもストリップ表面の温度低下が
異なるのは、例えば噴霧量や噴霧方法等の条件の違いに
よるものである。 （酸焼け発生度相対評価基準） ５…酸焼けが全く無い ４…板表面の１〜５％の範囲に酸焼けが発生 ３…板表面の５〜１０％の範囲に酸焼けが発生 ２…板表面の１０〜９０％の範囲に酸焼けが発生 １…酸焼けが板のほぼ全面に発生The results are shown in Tables 1 and 2 below together with the cooling means. In Tables 1 and 2, the acid burn occurrence relative evaluation was
It is based on the following five grades by visual observation, and those with an evaluation of 1 or 2 are reject levels. Further, the difference in temperature drop on the strip surface even when the cooling means is the same is due to a difference in conditions such as a spray amount and a spray method. (Relative evaluation criteria of acid burn occurrence degree) 5 ... No acid burn at all 4 ... Acid burn occurs in the range of 1-5% of the plate surface 3 ... Acid burn occurs in the range of 5-10% of the plate surface 2 ... Acid scorch occurs in the range of 10 to 90% of the plate surface 1 ... Acid scorch occurs on almost the entire surface of the plate
【００２１】[0021]
【表１】 [Table 1]
【００２２】[0022]
【表２】 [Table 2]
【００２３】表１，２から明らかな様に、本発明の実施
例のものは（試験Ｎｏ．１〜２１）、酸焼けの発生が非
常に少ないか、または全く発生していないことがわか
る。特に、ストリップ表面を３℃以上冷却したものは
（試験Ｎｏ．３，４，６〜２１）、酸焼け発生抑制効果
が顕著に現れていることがわかる。これに対し、チタン
ストリップ表面を冷却しなかったり（試験Ｎｏ．２
２）、または反対にチタンストリップ表面を加熱したも
のでは（試験Ｎｏ．２３）、酸焼けが著しく発生してい
ることがわかる。As is clear from Tables 1 and 2, it can be seen that the examples of the present invention (Test Nos. 1 to 21) produced very little or no acid burns. In particular, when the strip surface was cooled by 3 ° C. or more (Test Nos. 3, 4, 6 to 21), it can be seen that the effect of suppressing the occurrence of acid burning was remarkably exhibited. On the other hand, the titanium strip surface was not cooled (Test No. 2).
2) Or, on the contrary, when the surface of the titanium strip was heated (Test No. 23), it was found that acid burning was remarkably generated.
【００２４】上記実施例では、純チタンストリップのみ
を採用したが、これは本発明の要旨が酸洗（酸洗槽１）
から水洗（水洗槽３）に至るまで間の冷却領域４におい
て、ストリップ表面を冷却するものであるので、こうし
た効果はチタン合金ストリップでも同様に達成されると
の認識に基づくものである。従って、上記実施例は本発
明が純チタンのみに適用できることを示したものでな
い。In the above embodiment, only the pure titanium strip was used, but this is because the gist of the present invention is pickling (pickling tank 1).
Since the surface of the strip is cooled in the cooling area 4 from the washing to the washing (washing tank 3), such an effect is based on the recognition that the titanium alloy strip can be similarly achieved. Therefore, the above examples do not show that the present invention is applicable only to pure titanium.
【００２５】実施例２ 実施例１における試験Ｎｏ．１〜２１で得られたチタン
ストリップを、外壁パネルに加工し、ビルの外壁に装着
したところ、表面の光沢および色調がパネル間で均一で
あり、非常に美麗な外観を呈しており、パネル材として
最適の清浄さが得られていた。一方、実施例１における
試験Ｎｏ．２２，２３で得られたチタンストリップを、
上記と同様にして外壁パネルに加工し、ビルの外壁に装
着したところ、酸焼けのためにパネル間の光沢および色
調が大きく異なり使用できなかった。Example 2 Test No. 1 in Example 1 When the titanium strip obtained in 1-21 was processed into an outer wall panel and mounted on the outer wall of a building, the gloss and color tone of the surface were uniform between the panels, giving a very beautiful appearance. As a result, optimal cleanliness was obtained. On the other hand, Test No. The titanium strip obtained in 22, 23 is
When processed into an outer wall panel in the same manner as above and mounted on the outer wall of the building, the gloss and color tone between the panels were greatly different due to acid burning, and the panel could not be used.
【００２６】[0026]
【発明の効果】本発明は以上の様に構成されており、過
剰なチタンイオンおよび弗化チタンイオンの発生を防止
でき、その結果酸焼けの発生を完全に防止もしくは大幅
に低減することができた。また本発明方法によって得ら
れたチタンストリップは、酸焼けによる光沢や色調の局
所的なむらがないので、美観が要求される建材等の人目
に付く部材に使用できる。The present invention is configured as described above, and can prevent the generation of excessive titanium ions and titanium fluoride ions. As a result, the generation of acid burn can be completely prevented or greatly reduced. Was. In addition, the titanium strip obtained by the method of the present invention has no local unevenness in gloss or color tone due to acid burning, so that it can be used as a noticeable member such as a building material requiring aesthetic appearance.
【図１】本発明方法を実施する為に構成されるチタンス
トリップの連続製造処理ラインの概略説明図である。FIG. 1 is a schematic explanatory diagram of a continuous production line for titanium strip configured to carry out the method of the present invention.
１ 酸洗槽 ２ チタンストリップ ３ 水洗槽 ４ 冷却領域 Reference Signs List 1 pickling tank 2 titanium strip 3 washing tank 4 cooling area
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C23G 1/12 C23G 3/02 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. 7 , DB name) C23G 1/12 C23G 3/02
Claims (6)
酸含有酸洗液で酸洗した後、水洗する連続製造処理ライ
ンにおいて、酸洗から水洗に至るまでの間にストリップ
表面を冷却することを特徴とする表面の美麗なチタンま
たはチタン合金ストリップの製造方法。1. A continuous production line for pickling a titanium or titanium alloy strip with a pickling solution containing hydrofluoric acid, followed by washing with water, wherein the strip surface is cooled from pickling to washing with water. Of producing titanium or titanium alloy strip with beautiful surface.
用固体を散布することによって冷却を行なう請求項１に
記載の製造方法。2. The method according to claim 1, wherein the cooling is performed by spraying a cooling liquid or a cooling solid on the strip surface.
固体からの気化ガスを吹き付けることによって冷却を行
なう請求項１に記載の製造方法。3. The method according to claim 1, wherein cooling is performed by blowing a vaporized gas from a low-temperature liquid or a low-temperature solid onto the strip surface.
または低温固体からの気化ガスの雰囲気とすることによ
ってストリップ表面を冷却する請求項１に記載の製造方
法。4. The method according to claim 1, wherein the surface of the strip is cooled by setting an atmosphere of a vaporized gas from a low-temperature liquid or a low-temperature solid during a period from pickling to washing with water.
冷却器によって冷却してストリップ表面を冷却する請求
項１に記載の製造方法。5. The method according to claim 1, wherein the atmosphere from pickling to washing is cooled by a cooler to cool the surface of the strip.
よって製造されたものであり、酸焼けの発生領域が板表
面の１０％以下である表面の美麗なチタンまたはチタン
合金ストリップ。6. A beautiful titanium or titanium alloy strip produced by the method according to any one of claims 1 to 5, wherein a region where acid scorching occurs is 10% or less of the plate surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31836995A JP3221302B2 (en) | 1995-12-06 | 1995-12-06 | Titanium or titanium alloy strip with beautiful surface and method of manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31836995A JP3221302B2 (en) | 1995-12-06 | 1995-12-06 | Titanium or titanium alloy strip with beautiful surface and method of manufacturing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09157871A JPH09157871A (en) | 1997-06-17 |
| JP3221302B2 true JP3221302B2 (en) | 2001-10-22 |
Family
ID=18098388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31836995A Expired - Fee Related JP3221302B2 (en) | 1995-12-06 | 1995-12-06 | Titanium or titanium alloy strip with beautiful surface and method of manufacturing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3221302B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6267831B1 (en) | 1998-05-06 | 2001-07-31 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Method of making a titanium or titanium alloy strip having a decorative surface appearance |
-
1995
- 1995-12-06 JP JP31836995A patent/JP3221302B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09157871A (en) | 1997-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2876144A (en) | Metal pickling solutions and methods | |
| US2032256A (en) | Metal articles for coating | |
| US2127388A (en) | Metal article for coating | |
| JP3221302B2 (en) | Titanium or titanium alloy strip with beautiful surface and method of manufacturing the same | |
| JPH06220662A (en) | Pickling and passivation methods for titanium products | |
| JP4543519B2 (en) | Manufacturing method of titanium cold rolled sheet | |
| JP3829731B2 (en) | Manufacturing method and lubricant for titanium material | |
| JP3221303B2 (en) | Titanium or titanium alloy member with beautiful surface and method of manufacturing the same | |
| US1989884A (en) | Method of annealing and cleaning ferrous articles | |
| ATE124092T1 (en) | METHOD FOR HOT METALLIZING STEEL STRIP. | |
| US3467549A (en) | Descaling of alloys by high temperature surface vaporization | |
| US2175620A (en) | Treatment of sheets, thin bars, and the like | |
| JP3397927B2 (en) | Method for producing titanium material with excellent anti-glare properties | |
| US2142869A (en) | Treatment of nickel-chromium alloys | |
| JP3204598B2 (en) | Pickling method for titanium plate | |
| JPS6138270B2 (en) | ||
| JPS62146300A (en) | Method for degreasing cold rolled stainless steel strip | |
| JPS6261672B2 (en) | ||
| JPS58199880A (en) | Molten salt bath for pickling | |
| US3118330A (en) | Rolling method | |
| US1980331A (en) | Cold rolled iron chromium alloy article | |
| US1974571A (en) | Descaling process | |
| US114956A (en) | Caleb mabshall | |
| JPS62284056A (en) | Pretreatment of titanium and titanium alloy before heating | |
| KR850000348B1 (en) | Continuous annealing of cold rolled low carbon steel strip |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20010717 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20070817 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080817 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080817 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090817 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090817 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100817 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110817 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110817 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120817 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120817 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130817 Year of fee payment: 12 |
|
| LAPS | Cancellation because of no payment of annual fees |