JP5891609B2 - Passivation method - Google Patents

Passivation method Download PDF

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JP5891609B2
JP5891609B2 JP2011120399A JP2011120399A JP5891609B2 JP 5891609 B2 JP5891609 B2 JP 5891609B2 JP 2011120399 A JP2011120399 A JP 2011120399A JP 2011120399 A JP2011120399 A JP 2011120399A JP 5891609 B2 JP5891609 B2 JP 5891609B2
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pipe
gas
gas supply
ozone
supply pipe
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JP2012246543A (en
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敏徳 三浦
敏徳 三浦
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Meidensha Corp
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Description

本発明は鋼材表面を不動態化処理する技術に関する。   The present invention relates to a technique for passivating a steel surface.

半導体部品の高集積化、高性能化のために半導体製造装置の原料ガス供給系に係る鋼材（例えばステンレス鋼）はその表面が不動態処理されることで当該鋼材の成分に由来する不純物質の原料ガスへの混入の抑制が図られている。   Steel materials (for example, stainless steel) related to the raw material gas supply system of semiconductor manufacturing equipment for high integration and high performance of semiconductor parts are subjected to passive treatment on the surface, so that impurities derived from the components of the steel materials Suppression of mixing into the raw material gas is attempted.

不動態化処理には濃硝酸等の強酸化剤が適用されているが、当該酸化剤の取り扱いに注意が必要であること及び不動態膜への強酸化剤の成分混入を懸念し、近年ではオゾンガスを利用した処理法が適用され始めている（例えば特許文献１，２）。   A strong oxidizing agent such as concentrated nitric acid is applied to the passivation treatment. However, due to concerns about the handling of the oxidizing agent and the inclusion of strong oxidizing agent components in the passive film, Treatment methods using ozone gas are beginning to be applied (for example, Patent Documents 1 and 2).

特許文献１の処理法はオゾン含有量が０．５〜１０ｖｏｌ％の乾燥酸素雰囲気中で１５０〜３００℃のもとで１〜５０時間の処理時間をかけて鋼材の表面に酸化不動態膜を形成する。   In the treatment method of Patent Document 1, an oxidation passivation film is formed on the surface of a steel material over a treatment time of 1 to 50 hours at 150 to 300 ° C. in a dry oxygen atmosphere having an ozone content of 0.5 to 10 vol%. Form.

特許文献２の処理法はオゾンガス濃度５０ｖｏｌ％以上の高濃度オゾンガスを鋼材の表面に供して当該表面に不動態膜を形成しているが、オゾンの特性上高温で処理することができないので２０〜６０℃のもと処理時間に２０〜４０時間をかけている。   In the treatment method of Patent Document 2, a high-concentration ozone gas having an ozone gas concentration of 50 vol% or more is applied to the surface of the steel material to form a passive film on the surface. The treatment time is 20 to 40 hours at 60 ° C.

特開平５−２８７４９６号公報Japanese Patent Laid-Open No. 5-287696 特開平９−１９５０３１号公報Japanese Patent Laid-Open No. 9-195031 特公平５−１７１６４号公報Japanese Patent Publication No. 5-17164

鈴木亮輔、太田勝也、小野勝敏，「オゾンガス酸化による液体ＣｒＯ3を用いた鉄の耐酸化皮膜生成」，第１０回日本オゾン協会年次研究講演会，２０００年１０月２５，２６日，滋賀県立県民交流センター，講演番号２０，講演集ｐｐ．８３−８６Ryosuke Suzuki, Katsuya Ota, Katsutoshi Ono, "Oxidation film formation of iron using liquid CrO3 by ozone gas oxidation", 10th Annual Meeting of the Japan Ozone Society, October 25 and 26, 2000, Shiga Prefectural Exchange Center, Lecture Number 20, Lecture Collection pp. 83-86 Fu Su, Jack G. Calvert, John H. Shaw,"A FT IR Spectroscopic Study of the Ozone-Ethene Reaction Mechanism in O2-Rich Mixtures", The Journal of Physical Chemistry, Vol. 84, No.3, 1980, pages 239-246Fu Su, Jack G. Calvert, John H. Shaw, "A FT IR Spectroscopic Study of the Ozone-Ethene Reaction Mechanism in O2-Rich Mixtures", The Journal of Physical Chemistry, Vol. 84, No. 3, 1980, pages 239-246 株式会社スリーボンド・テクニカルニュース編集委員会編，「紫外線―オゾンによる表面処理」，スリーボンド・テクニカルニュース，昭和６２年３月２０日発行，ｐｐ．１〜１０3Bond Technical News Editorial Board, “Ultraviolet-Ozone Surface Treatment”, ThreeBond Technical News, published on March 20, 1987, pp. 1-10

上述のようにオゾンを用いた鋼材の不動態処理は室温または室温よりも高温の条件にも関わらず数十時間に及ぶ長い処理時間を要する。また、鋼材であるステンレス鋼の成分の一つであるクロムは約１００〜２００℃程度でオゾンと反応して融点の低い過酸化物を形成させてしまう（非特許文献１）。さらに、高温の加熱ではオゾンが高温の雰囲気に曝された時点でほとんど酸素に分解されるので、鋼材の表面での酸化効果は期待できない。したがって、加熱された雰囲気のもとでのオゾンによる鋼材表面の不動態化は半導体製造装置の製造コストの観点からも有効ではない。   As described above, the passive treatment of steel using ozone requires a long treatment time of several tens of hours regardless of the room temperature or a temperature higher than the room temperature. Further, chromium, which is one of the components of stainless steel, which is a steel material, reacts with ozone at about 100 to 200 ° C. to form a peroxide having a low melting point (Non-patent Document 1). Furthermore, since the ozone is almost decomposed into oxygen when exposed to a high temperature atmosphere in high temperature heating, the oxidation effect on the surface of the steel material cannot be expected. Therefore, the passivation of the steel material surface by ozone under a heated atmosphere is not effective from the viewpoint of the manufacturing cost of the semiconductor manufacturing apparatus.

本発明はかかる事情に鑑みなされたものでその目的はより一層短時間に鋼材表面を不動態化できる不動態化処理方法の提供にある。   The present invention has been made in view of such circumstances, and an object thereof is to provide a passivation treatment method capable of passivating a steel material surface in a shorter time.

そこで、本発明の不動態化処理方法はオゾンガスとオゾン分解因子とを鋼材に供してこの鋼材の表面を不動態化処理する。前記オゾン分解因子としては不飽和炭化水素、紫外光が例示される。   Therefore, the passivation treatment method of the present invention applies ozone gas and an ozonolysis factor to a steel material to passivate the surface of the steel material. Examples of the ozonolysis factor include unsaturated hydrocarbons and ultraviolet light.

本発明の態様としては、鋼材から成る配管の内面を不動態化処理する不動態化処理方法であって、鋼材から成る配管内にオゾンガス供給管を当該配管と同軸に挿通して当該供給管の先端付近の外周面からオゾンガスを供給すると共に当該外周面と当該配管の内面との間隙にオゾン分解因子として不飽和炭化水素ガスを供給しながら前記外周面を当該配管の軸方向に動作させることにより当該配管の内面を不動態化する。
以上の方法によれば、配管系の施工過程で逐次に各配管の内面を不動態化処理できる。 As an aspect of the present invention, there is provided a passivation processing method for passivating an inner surface of a pipe made of steel, and an ozone gas supply pipe is inserted coaxially with the pipe into the pipe made of steel. By supplying ozone gas from the outer peripheral surface near the tip and operating the outer peripheral surface in the axial direction of the piping while supplying unsaturated hydrocarbon gas as an ozone decomposition factor to the gap between the outer peripheral surface and the inner surface of the piping Passivate the inner surface of the pipe.
According to the above method, the inner surface of each pipe can be passivated sequentially in the construction process of the pipe system.

以上の発明によればより一層短時間に鋼材表面を不動態化できる。   According to the above invention, the steel surface can be passivated in a shorter time.

発明の実施形態１に係る不動態化処理方法を説明した概略断面図。The schematic sectional drawing explaining the passivation processing method which concerns on Embodiment 1 of invention. 発明の実施形態２に係る不動態化処理方法を説明した概略断面図。The schematic sectional drawing explaining the passivation processing method which concerns on Embodiment 2 of invention. 発明の実施形態３に係る不動態化処理方法を説明した概略断面図。The schematic sectional drawing explaining the passivation processing method which concerns on Embodiment 3 of invention. 発明の実施形態４に係る不動態化処理方法を説明した概略断面図。The schematic sectional drawing explaining the passivation processing method which concerns on Embodiment 4 of invention. 発明の実施形態５に係る不動態化処理方法を説明した概略断面図。The schematic sectional drawing explaining the passivation processing method which concerns on Embodiment 5 of invention. 発明の実施形態に係る方法で処理したステンレス鋼の表面のＸＰＳ測定結果。The XPS measurement result of the surface of the stainless steel processed with the method which concerns on embodiment of invention.

以下、図面を参照しながら本発明の実施の形態について説明する。   Hereinafter, embodiments of the present invention will be described with reference to the drawings.

［実施形態１］
図１に示した実施形態１に係る不動態化処理では鋼材からなる配管１ｂの内面に対してオゾンガスと共にオゾン分解因子として不飽和炭化水素ガスを供して当該内面を不動態化する。本実施形態では不動態化済みの既存の配管１ａに新たな配管１ｂが接続される毎にこの配管１ｂの内面が不動態化処理される。 [Embodiment 1]
In the passivation treatment according to the first embodiment shown in FIG. 1, the inner surface of the pipe 1b made of steel is provided with an unsaturated hydrocarbon gas as an ozonolysis factor together with ozone gas to passivate the inner surface. In this embodiment, every time a new pipe 1b is connected to the existing pipe 1a that has been passivated, the inner surface of the pipe 1b is passivated.

既存の配管１ａの一端側には配管１ａ，１ｂ内にてガス流を生じさせるための真空ポンプ２が予め気密に接続される。オゾンガスはオゾン発生装置３から供給されるようになっている。オゾン発生装置３は周知のオゾン発生装置（例えば特許文献３に開示のオゾン発生装置）を適用すればよい。特許文献３のオゾン発生装置はオゾン濃度１００ｖｏｌ％のオゾンガスを供給できるが、オゾン濃度１０ｖｏｌ％以上好ましくは２０ｖｏｌ％以上のオゾンガスを供給できるオゾンガス発生装置であれば特に限定しない。不飽和炭化水素ガスは当該ガスを充填したボンベ４から供給される。不飽和炭化水素ガスとしてはエチレンガスが例示される。   A vacuum pump 2 for generating a gas flow in the pipes 1a and 1b is airtightly connected in advance to one end side of the existing pipe 1a. The ozone gas is supplied from the ozone generator 3. The ozone generator 3 may be a known ozone generator (for example, an ozone generator disclosed in Patent Document 3). The ozone generator of Patent Document 3 can supply ozone gas with an ozone concentration of 100 vol%, but is not particularly limited as long as it is an ozone gas generator that can supply ozone gas with an ozone concentration of 10 vol% or more, preferably 20 vol% or more. The unsaturated hydrocarbon gas is supplied from a cylinder 4 filled with the gas. An example of the unsaturated hydrocarbon gas is ethylene gas.

オゾン発生装置３には伸縮自在のガス供給管５が接続されている。ガス供給管５としてはオゾン耐性の材料（石英、不動態化処理されたステンレス等）から成る伸縮配管構造のものやフレキシブル配管構造のものが挙げられる。伸縮配管構造のものは二重配管の外側の配管部が駆動装置によって動作可能なものが挙げられる。   A stretchable gas supply pipe 5 is connected to the ozone generator 3. Examples of the gas supply pipe 5 include an expansion pipe structure made of ozone-resistant material (quartz, passivated stainless steel, etc.) and a flexible pipe structure. The thing of the expansion pipe structure can be one in which the pipe section outside the double pipe can be operated by a driving device.

ガス供給管５は配管１ｂよりも小径であり且つ先端部が密閉されている。また、ガス供給管５の先端付近の外周面にはオゾンガスを散気するための散気孔５１が複数形成されている。ガス供給管５は配管１ｂの不動態化処理時に配管１ｂ内に挿通され、配管１ｂの軸方向に伸縮動作可能となるようにマニホールド継ぎ手６にて支持される。ガス供給管５を気密に動作できるようにガス供給管５とマニホールド継ぎ手６との間に気密部材としてＯリング６１を介在させている。マニホールド継ぎ手６は配管１ｂの施工時すなわち配管１ｂを配管１ａに接続する際に配管１ａと対向しない配管１ｂの端部に装着される。また、マニホールド継ぎ手６にはボンベ４から不飽和炭化水素ガスが供されるガス供給管７が接続される。   The gas supply pipe 5 has a smaller diameter than the pipe 1b and is sealed at the tip. A plurality of air diffusion holes 51 are provided on the outer peripheral surface in the vicinity of the tip of the gas supply pipe 5 to diffuse ozone gas. The gas supply pipe 5 is inserted into the pipe 1b during the passivating process of the pipe 1b, and is supported by the manifold joint 6 so as to be able to extend and contract in the axial direction of the pipe 1b. An O-ring 61 is interposed as an airtight member between the gas supply pipe 5 and the manifold joint 6 so that the gas supply pipe 5 can be operated in an airtight manner. The manifold joint 6 is attached to the end of the pipe 1b that does not face the pipe 1a when the pipe 1b is constructed, that is, when the pipe 1b is connected to the pipe 1a. Further, a gas supply pipe 7 to which unsaturated hydrocarbon gas is supplied from the cylinder 4 is connected to the manifold joint 6.

図１を参照しながら本実施形態の不動態化処理について説明する。   The passivating process of this embodiment will be described with reference to FIG.

不動態化済みの配管１ａの一端側に配管１ａと同径の新たな配管１ｂが溶接固定される。配管１ａのもう一端側には真空ポンプ２が気密に接続される。次いで、ガス供給管５，７を備えたマニホールド継ぎ手６が配管１ｂの一端側に装着される。ガス供給管５は配管１ｂ内に導入された先端部が配管１ａと配管１ｂとの接続部分と略同位置となるように設定される。   A new pipe 1b having the same diameter as the pipe 1a is welded and fixed to one end of the passivated pipe 1a. A vacuum pump 2 is hermetically connected to the other end of the pipe 1a. Next, a manifold joint 6 having gas supply pipes 5 and 7 is attached to one end side of the pipe 1b. The gas supply pipe 5 is set so that the tip portion introduced into the pipe 1b is substantially at the same position as the connecting portion between the pipe 1a and the pipe 1b.

次いで、室温のもとで真空ポンプ２によって配管１ａ，１ｂ内を負圧状態（数百Ｐａ以下例えば２００Ｐａ）にした状態で配管１ｂとガス供給管５との間隙にガス供給管７から不飽和炭化水素ガスを供給する。一方、ガス供給管５の散気孔５１からはオゾンガスを供給して配管１ａ，１ｂ内にてオゾンと不飽和炭化水素とを反応させる。この反応により生じた原子状酸素やＯＨラジカル等の酸化性化学種（非特許文献２）によって配管１ｂの内面が酸化されクロム酸化物（Ｃｒ2Ｏ3）から成る不動態膜が形成される。その後、一定時間毎（例えば１０分間毎）に散気孔５１の位置がオゾンガスのガス流の上流方向に移行するようにガス供給管５を縮小させる。ガス供給管５の先端部がマニホールド継ぎ手６側の配管１ｂの一端に達した時点で配管１ｂの内面の不動態化が完了する。 Next, in the state where the inside of the pipes 1a and 1b is brought into a negative pressure state (several hundred Pa or less, for example, 200 Pa) by the vacuum pump 2 at room temperature, the gap between the pipe 1b and the gas supply pipe 5 is unsaturated from the gas supply pipe 7 Supply hydrocarbon gas. On the other hand, ozone gas is supplied from the diffuser hole 51 of the gas supply pipe 5 to react ozone and unsaturated hydrocarbons in the pipes 1a and 1b. The inner surface of the pipe 1b is oxidized by oxidizing chemical species (Non-patent Document 2) such as atomic oxygen and OH radical generated by this reaction, and a passive film made of chromium oxide (Cr 2 O 3 ) is formed. Thereafter, the gas supply pipe 5 is reduced so that the position of the diffuser holes 51 moves in the upstream direction of the ozone gas flow at regular intervals (for example, every 10 minutes). Passivation of the inner surface of the pipe 1b is completed when the tip of the gas supply pipe 5 reaches one end of the pipe 1b on the manifold joint 6 side.

また、この不動態化処理した配管１ｂの内面に対してオゾンガスのみを供すると、当該表面に残留した不飽和炭化水素の構成成分が分解される。これにより、不飽和炭化水素由来の不純物を除去できる。この過程は炭素成分の混入を避けなければならないプロセス・用途で使用される配管の不動態化に好適である。   Moreover, when only ozone gas is provided to the inner surface of the passivated pipe 1b, the constituent components of the unsaturated hydrocarbon remaining on the surface are decomposed. Thereby, impurities derived from unsaturated hydrocarbons can be removed. This process is suitable for passivating piping used in processes and applications in which mixing of carbon components must be avoided.

配管１ｂの不動態化が完了すると、ガス供給管５，７と共にマニホールド継ぎ手６が配管１ｂから外される。そして、この配管１ｂの一端に新たな配管が溶接されると、上述と同じ方法で当該配管の内面が不動態化処理される。新たに配管が増設される毎にこの不動態化処理が実行される。   When the passivation of the pipe 1b is completed, the manifold joint 6 together with the gas supply pipes 5 and 7 is removed from the pipe 1b. When a new pipe is welded to one end of the pipe 1b, the inner surface of the pipe is passivated by the same method as described above. This passivating process is executed every time a new pipe is added.

ステンレス製（ＳＵＳ３０４）の配管の内面を処理温度５０℃、圧力２００Ｐａ、オゾンガス（オゾン濃度１００ｖｏｌ％）：不飽和炭化水素（エチレン）＝２：１の雰囲気のもとで本実施形態の処理方法により１０分間処理した後のＸＰＳ測定結果を図６に示した。配管の内面にてＣｒ2Ｏ3の形成が確認された。従来ではステンレス製の鋼材の不動態化処理に数時間以上要していたのに対して本実施例によれば６０分未満の短時間で鋼材表面を不動態化できることが示された。 The inner surface of the pipe made of stainless steel (SUS304) is treated at a processing temperature of 50 ° C., a pressure of 200 Pa, ozone gas (ozone concentration: 100 vol%): unsaturated hydrocarbon (ethylene) = 2: 1 under the atmosphere of this embodiment. FIG. 6 shows the XPS measurement results after 10 minutes of treatment. Formation of Cr 2 O 3 was confirmed on the inner surface of the pipe. Conventionally, it took several hours or more to passivate the stainless steel material, but according to this example, it was shown that the steel surface can be passivated in a short time of less than 60 minutes.

［実施形態２］
図２に示された実施形態２の不動態化処理はガス供給管５から不飽和炭化水素ガスを供給する一方でガス供給管５と配管１ａ，１ｂとの間隙にオゾンガスを供給すること以外は実施形態１と同じ処理態様を成している。すなわち、ガス供給管５には不飽和炭化水素ガスを供給するボンベ４が接続される一方でガス供給管７にはオゾン発生装置３が接続されている。 [Embodiment 2]
The passivating process of the second embodiment shown in FIG. 2 is that except that the unsaturated hydrocarbon gas is supplied from the gas supply pipe 5 while ozone gas is supplied to the gap between the gas supply pipe 5 and the pipes 1a and 1b. This is the same processing mode as that of the first embodiment. That is, the gas supply pipe 5 is connected to the cylinder 4 for supplying unsaturated hydrocarbon gas, while the gas supply pipe 7 is connected to the ozone generator 3.

図２を参照しながら本実施形態の不動態化処理について説明する。   The passivation process of this embodiment will be described with reference to FIG.

配管１ａの一端側に配管１ａと同径の新たな配管１ｂが溶接固定される。配管１ａのもう一端側には真空ポンプ２が気密に接続される。次いで、ガス供給管５，７を備えたマニホールド継ぎ手６が配管１ｂの一端側に装着される。ガス供給管５は配管１ｂ内に導入された先端部が配管１ａと配管１ｂとの接続部分と略同位置となるように設定される。   A new pipe 1b having the same diameter as the pipe 1a is welded and fixed to one end of the pipe 1a. A vacuum pump 2 is hermetically connected to the other end of the pipe 1a. Next, a manifold joint 6 having gas supply pipes 5 and 7 is attached to one end side of the pipe 1b. The gas supply pipe 5 is set so that the tip portion introduced into the pipe 1b is substantially at the same position as the connecting portion between the pipe 1a and the pipe 1b.

次いで、室温のもとで真空ポンプ２によって配管１ａ，１ｂ内を負圧状態（数百Ｐａ以下例えば２００Ｐａ）にした状態で配管１ｂとガス供給管５との間隙にガス供給管７からオゾンガスを供給する。一方、ガス供給管５の散気孔５１からは不飽和炭化水素ガスを供給して配管１ａ，１ｂ内にてオゾンと不飽和炭化水素とを反応させる。この反応により生じた原子状酸素やＯＨラジカル等の酸化性化学種によって配管１ｂの内面が酸化されクロム酸化物（Ｃｒ2Ｏ3）から成る不動態膜が形成される。 Subsequently, ozone gas is supplied from the gas supply pipe 7 to the gap between the pipe 1b and the gas supply pipe 5 in a state where the inside of the pipes 1a and 1b is brought into a negative pressure state (several hundred Pa or less, for example, 200 Pa) by the vacuum pump 2 at room temperature. Supply. On the other hand, unsaturated hydrocarbon gas is supplied from the air diffuser hole 51 of the gas supply pipe 5 to react ozone and unsaturated hydrocarbon in the pipes 1a and 1b. The inner surface of the pipe 1b is oxidized by oxidizing chemical species such as atomic oxygen and OH radicals generated by this reaction, and a passive film made of chromium oxide (Cr 2 O 3 ) is formed.

その後、一定時間毎（例えば１０分間毎）に散気孔５１の位置がオゾンガスのガス流の上流方向に移行するようにガス供給管５を縮小させる。ガス供給管５の先端部がマニホールド継ぎ手６側の配管１ｂの一端に達した時点で配管１ｂの内面の不動態化が完了する。また、この不動態化処理した配管１ｂの内面に対してオゾンガスのみが供されることで、当該表面に残留した不飽和炭化水素の構成成分が分解除去される。   Thereafter, the gas supply pipe 5 is reduced so that the position of the diffuser holes 51 moves in the upstream direction of the ozone gas flow at regular intervals (for example, every 10 minutes). Passivation of the inner surface of the pipe 1b is completed when the tip of the gas supply pipe 5 reaches one end of the pipe 1b on the manifold joint 6 side. Moreover, only ozone gas is provided to the inner surface of the passivated pipe 1b, whereby the constituent components of the unsaturated hydrocarbon remaining on the surface are decomposed and removed.

配管１ｂの不動態化が完了すると、ガス供給管５，７と共にマニホールド継ぎ手６が配管１ｂから外される。そして、この配管１ｂの一端に新たな配管が溶接されると、上述と同じ方法で当該配管の内面が不動態化処理される。新たに配管が増設される毎にこの不動態化処理が実行される。   When the passivation of the pipe 1b is completed, the manifold joint 6 together with the gas supply pipes 5 and 7 is removed from the pipe 1b. When a new pipe is welded to one end of the pipe 1b, the inner surface of the pipe is passivated by the same method as described above. This passivating process is executed every time a new pipe is added.

［実施形態３］
図３に示された実施形態３の不動態化処理はオゾンガスを供給するガス供給管８と不飽和炭化水素ガスを供給するガス供給管９とを配管１ｂ内に同軸挿通しこのガス供給管８，９を配管１ｂの軸方向に移動させることにより配管１ｂの内面を不動態化処理する。実施形態１，２と同様に既存の配管１ａの一端側には配管１ａ,１ｂ内にてガス流を生じさせるための真空ポンプ２が予め気密に接続される。 [Embodiment 3]
In the passivating process of the third embodiment shown in FIG. 3, a gas supply pipe 8 for supplying ozone gas and a gas supply pipe 9 for supplying unsaturated hydrocarbon gas are coaxially inserted into the pipe 1b. , 9 are moved in the axial direction of the pipe 1b to passivate the inner surface of the pipe 1b. As in the first and second embodiments, a vacuum pump 2 for generating a gas flow in the pipes 1a and 1b is airtightly connected in advance to one end of the existing pipe 1a.

ガス供給管８はガス供給管９よりも小径に形成されていると共に先端部が密閉されている一方で先端付近の外周面にはオゾンガスを散気するための散気孔８１が複数形成されている。ガス供給管８は散気孔８１が形成された外周面がガス供給管９から露出した状態でガス供給管９と同軸にガス供給管９内に具備される。ガス供給管８はオゾン発生装置３に接続されている。   The gas supply pipe 8 is formed to have a smaller diameter than the gas supply pipe 9 and the tip is sealed. On the outer peripheral surface near the tip, a plurality of air holes 81 are provided to diffuse ozone gas. . The gas supply pipe 8 is provided in the gas supply pipe 9 coaxially with the gas supply pipe 9 in a state where the outer peripheral surface in which the air diffusion holes 81 are formed is exposed from the gas supply pipe 9. The gas supply pipe 8 is connected to the ozone generator 3.

ガス供給管９は配管１ｂの軸方向に動作可能となるように配管１ｂの一端にて継ぎ手１０によって気密に支持される。ガス供給管９と継ぎ手１０との間には気密部材としてＯリング１０１を介在させることでガス供給管９を気密に動作できるようになっている。継ぎ手１０は配管１ｂの施工時すなわち配管１ｂを配管１ａに接続する際に配管１ａと対向しない配管１ｂの端部に装着される。ガス供給管９は不飽和炭化水素ガスが充填されたボンベ４に接続されている。   The gas supply pipe 9 is airtightly supported by the joint 10 at one end of the pipe 1b so as to be operable in the axial direction of the pipe 1b. The gas supply pipe 9 can be operated in an airtight manner by interposing an O-ring 101 as an airtight member between the gas supply pipe 9 and the joint 10. The joint 10 is attached to the end of the pipe 1b not facing the pipe 1a when the pipe 1b is constructed, that is, when the pipe 1b is connected to the pipe 1a. The gas supply pipe 9 is connected to a cylinder 4 filled with unsaturated hydrocarbon gas.

また、実施形態２と同様にガス供給管８から不飽和炭化水素ガスを供給する一方でガス供給管９からオゾンガスを供給するようにしてもよい。   Further, as in the second embodiment, the ozone gas may be supplied from the gas supply pipe 9 while the unsaturated hydrocarbon gas is supplied from the gas supply pipe 8.

図３を参照しながら本実施形態の不動態化処理について説明する。   The passivating process of the present embodiment will be described with reference to FIG.

配管１ａの一端側に配管１ａと同径の新たな配管１ｂが溶接固定される。配管１ａのもう一端側には真空ポンプ２が気密に接続される。次いで、ガス供給管９を備えた継ぎ手１０が配管１ｂの一端側に装着される。ガス供給管８は配管１ｂ内に導入された先端部が配管１ａと配管１ｂとの接続部分と略同位置となるように設定される。   A new pipe 1b having the same diameter as the pipe 1a is welded and fixed to one end of the pipe 1a. A vacuum pump 2 is hermetically connected to the other end of the pipe 1a. Next, a joint 10 provided with a gas supply pipe 9 is attached to one end side of the pipe 1b. The gas supply pipe 8 is set so that the tip portion introduced into the pipe 1b is substantially at the same position as the connecting portion between the pipe 1a and the pipe 1b.

次いで、室温のもとで真空ポンプ２によって配管１ａ，１ｂ内を負圧状態（数百Ｐａ以下例えば２００Ｐａ）にした状態でボンベ４から不飽和炭化水素ガスをガス供給管９内に供給する。一方、オゾン発生装置３で生成されたオゾンガスをガス供給管８の散気孔８１から供給して配管１ａ，１ｂ内にてオゾンと不飽和炭化水素とを反応させる。この反応により生じた原子状酸素やＯＨラジカル等の酸化性化学種によって配管１ｂの内面が酸化されクロム酸化物（Ｃｒ2Ｏ3）から成る不動態膜が形成される。 Next, an unsaturated hydrocarbon gas is supplied from the cylinder 4 into the gas supply pipe 9 in a state where the inside of the pipes 1 a and 1 b is brought into a negative pressure state (several hundred Pa or less, for example, 200 Pa) by the vacuum pump 2 at room temperature. On the other hand, ozone gas generated by the ozone generator 3 is supplied from the diffuser hole 81 of the gas supply pipe 8 to react ozone and unsaturated hydrocarbons in the pipes 1a and 1b. The inner surface of the pipe 1b is oxidized by oxidizing chemical species such as atomic oxygen and OH radicals generated by this reaction, and a passive film made of chromium oxide (Cr 2 O 3 ) is formed.

その後、一定時間毎（例えば１０分間毎）に散気孔８１の位置がオゾンガスのガス流の上流方向に移行するようにガス供給管８，９を配管１ｂの軸方向に移動させる。ガス供給管８の先端部が継ぎ手１０側の配管１ｂの一端に達した時点で配管１ｂの内面の不動態化が完了する。また、この不動態化処理した配管１ｂの内面に対してオゾンガスのみが供されることで、当該表面に残留した不飽和炭化水素の構成成分が分解除去される。   Thereafter, the gas supply pipes 8 and 9 are moved in the axial direction of the pipe 1b so that the position of the air diffuser 81 is shifted in the upstream direction of the ozone gas flow at regular time intervals (for example, every 10 minutes). Passivation of the inner surface of the pipe 1b is completed when the tip of the gas supply pipe 8 reaches one end of the pipe 1b on the joint 10 side. Moreover, only ozone gas is provided to the inner surface of the passivated pipe 1b, whereby the constituent components of the unsaturated hydrocarbon remaining on the surface are decomposed and removed.

配管１ｂの不動態化が完了すると、ガス供給管９と共に継ぎ手１０が配管１ｂから外される。そして、この配管１ｂの一端に新たな配管が溶接されると、上述と同じ方法で当該配管の内面が不動態化処理される。新たに配管が増設される毎にこの不動態化処理が実行される。   When the passivation of the pipe 1b is completed, the joint 10 is removed from the pipe 1b together with the gas supply pipe 9. When a new pipe is welded to one end of the pipe 1b, the inner surface of the pipe is passivated by the same method as described above. This passivating process is executed every time a new pipe is added.

［実施形態４］
図４に示された実施形態４の処理態様は配管１ｂ内にオゾンガスと不飽和炭化水素ガスとの混合ガスを供給するガス供給管１１を配管１ｂと同軸に挿通させている。そして、ガス供給管１１の先端付近の外周面から前記オゾンガスと前記不飽和炭化水素ガスとの混合ガスを供給しながらガス供給管１１を配管１ｂの軸方向に動作させることにより配管１ｂの内面を不動態化する。 [Embodiment 4]
In the processing mode of Embodiment 4 shown in FIG. 4, a gas supply pipe 11 for supplying a mixed gas of ozone gas and unsaturated hydrocarbon gas is inserted into the pipe 1b coaxially with the pipe 1b. The inner surface of the pipe 1b is moved by operating the gas supply pipe 11 in the axial direction of the pipe 1b while supplying a mixed gas of the ozone gas and the unsaturated hydrocarbon gas from the outer peripheral surface near the tip of the gas supply pipe 11. Passivate.

ガス供給管１１はその一端がオゾン発生装置３に接続されている。配管１ｂ内に導入される先端部は密閉されている一方で先端付近の外周面にはオゾンガスを散気するための散気孔１１１が複数形成されている。   One end of the gas supply pipe 11 is connected to the ozone generator 3. The front end portion introduced into the pipe 1b is sealed, while a plurality of air diffusion holes 111 are formed on the outer peripheral surface near the front end to diffuse ozone gas.

ガス供給管１１の内部には不飽和炭化水素ガスを供給するためのガス供給管１２がガス供給管１１と同軸に具備されている。ガス供給管１２もガス供給管１１と同様に先端部が密閉されている一方で先端付近の外周面には不飽和炭化水素ガスを散気するための散気孔１２１が複数形成されている。   Inside the gas supply pipe 11, a gas supply pipe 12 for supplying unsaturated hydrocarbon gas is provided coaxially with the gas supply pipe 11. Similarly to the gas supply pipe 11, the gas supply pipe 12 is sealed at the tip, while a plurality of gas diffusion holes 121 are formed on the outer peripheral surface near the tip to diffuse unsaturated hydrocarbon gas.

ガス供給管１１，１２は実施形態１に係るガス供給管５と同様にオゾン耐性の材料（石英、不動態化処理されたステンレス等）から構成される。尚、実施形態２と同様にガス供給管１１から不飽和炭化水素ガスを供給する一方でガス供給管１２からオゾンガスを供給するようにしてもよい。   The gas supply pipes 11 and 12 are made of an ozone-resistant material (quartz, passivated stainless steel, etc.) in the same manner as the gas supply pipe 5 according to the first embodiment. Note that, similarly to the second embodiment, the unsaturated hydrocarbon gas may be supplied from the gas supply pipe 11 while the ozone gas may be supplied from the gas supply pipe 12.

図４を参照しながら本実施形態の不動態化処理について説明する。   The passivation process of this embodiment will be described with reference to FIG.

配管１ａの一端側に配管１ａと同径の新たな配管１ｂが溶接固定される。配管１ａのもう一端側には真空ポンプ２が気密に接続される。次いで、ガス供給管１１を備えた継ぎ手１０が配管１ｂの一端側に装着される。ガス供給管１１は配管１ｂ内に導入された先端部が配管１ａと配管１ｂとの接続部分と略同位置となるように設定される。   A new pipe 1b having the same diameter as the pipe 1a is welded and fixed to one end of the pipe 1a. A vacuum pump 2 is hermetically connected to the other end of the pipe 1a. Next, the joint 10 including the gas supply pipe 11 is attached to one end side of the pipe 1b. The gas supply pipe 11 is set so that the tip portion introduced into the pipe 1b is substantially at the same position as the connecting portion between the pipe 1a and the pipe 1b.

次いで、室温のもとで真空ポンプ２によって配管１ａ，１ｂ内を負圧状態（数百Ｐａ以下例えば２００Ｐａ）にした状態でボンベ４から供給された不飽和炭化水素ガスがガス供給管１２の散気孔１２１からガス供給管１１内に供される。また、オゾン発生装置３からはオゾンガスがガス供給管１１内に供される。そして、ガス供給管１１の散気孔１１１からは前記オゾンガスと前記不飽和炭化水素の混合ガスが配管１ｂの内面に供される。前記混合ガスはオゾンガスと不飽和炭化水素ガスとの反応により生じた酸化性化学種（原子状酸素やＯＨラジカル）等）を含んでいる。配管１ｂの内面は前記酸化性化学種によって酸化されてクロム酸化物（Ｃｒ2Ｏ3）から成る不動態膜が形成される。 Next, the unsaturated hydrocarbon gas supplied from the cylinder 4 in a state where the pipes 1 a and 1 b are brought into a negative pressure state (several hundred Pa or less, for example, 200 Pa) by the vacuum pump 2 at room temperature is dispersed in the gas supply pipe 12. The gas is supplied from the pores 121 into the gas supply pipe 11. Further, ozone gas is supplied from the ozone generator 3 into the gas supply pipe 11. And the mixed gas of the said ozone gas and the said unsaturated hydrocarbon is provided to the inner surface of the piping 1b from the diffuser hole 111 of the gas supply pipe | tube 11. FIG. The mixed gas contains oxidizing chemical species (atomic oxygen, OH radicals, etc.) generated by the reaction between ozone gas and unsaturated hydrocarbon gas. The inner surface of the pipe 1b is oxidized by the oxidizing chemical species to form a passive film made of chromium oxide (Cr 2 O 3 ).

その後、一定時間毎（例えば１０分間毎）に散気孔１１１の位置がオゾンガスのガス流の上流方向に移行するようにガス供給管１１を配管１ｂの軸方向に移動させる。ガス供給管１１の先端部が継ぎ手１０側の配管１ｂの一端に達した時点で配管１ｂの内面の不動態化が完了する。また、この不動態化処理した管１ｂの内面に対してオゾンガスのみが供されることで、当該表面に残留した不飽和炭化水素の構成成分が分解除去される。   Thereafter, the gas supply pipe 11 is moved in the axial direction of the pipe 1b so that the position of the diffuser hole 111 moves in the upstream direction of the ozone gas flow at regular intervals (for example, every 10 minutes). Passivation of the inner surface of the pipe 1b is completed when the tip of the gas supply pipe 11 reaches one end of the pipe 1b on the joint 10 side. Further, only ozone gas is supplied to the inner surface of the passivated tube 1b, whereby the constituent components of the unsaturated hydrocarbon remaining on the surface are decomposed and removed.

配管１ｂの不動態化が完了すると、ガス供給管１１と共に継ぎ手１０が配管１ｂから外される。そして、この配管１ｂの一端に新たな配管が溶接されると、上述と同じ方法で当該配管の内面が不動態化処理される。新たに配管が増設される毎にこの不動態化処理が実行される。   When the passivation of the pipe 1b is completed, the joint 10 is removed from the pipe 1b together with the gas supply pipe 11. When a new pipe is welded to one end of the pipe 1b, the inner surface of the pipe is passivated by the same method as described above. This passivating process is executed every time a new pipe is added.

［実施形態５］
図５に示された実施形態５の不動態化処理では配管１ｂ内に光供給管１３を挿通して光供給管１３の端面からオゾン分解因子として紫外光を照射させると共に光供給管１３と配管１ｂとの間隙にオゾンガスを供給する。そして、この状態で光供給管１３の端面を配管１ｂの軸方向に動作させることにより配管１ｂの内面を不動態化する。実施形態１〜４と同様に既存の配管１ａの一端側には配管１ａ,１ｂ内にてガス流を生じさせるための真空ポンプ２が予め気密に接続される。 [Embodiment 5]
In the passivating process of the fifth embodiment shown in FIG. 5, the light supply pipe 13 is inserted into the pipe 1b to irradiate ultraviolet light from the end face of the light supply pipe 13 as an ozone decomposition factor, and the light supply pipe 13 and the pipe. Ozone gas is supplied to the gap with 1b. In this state, the inner surface of the pipe 1b is passivated by operating the end face of the light supply pipe 13 in the axial direction of the pipe 1b. As in the first to fourth embodiments, a vacuum pump 2 for generating a gas flow in the pipes 1a and 1b is airtightly connected in advance to one end side of the existing pipe 1a.

光供給管１３は配管１ｂよりも小径に形成された光ファイバーからなり、マニホールド継ぎ手１４によって配管１ｂ内に当該配管１ｂと略同軸に気密に挿通されている。光ファイバーは紫外光を透過させると共にオゾンに耐性のある石英から成るものが適用される。また、配管１ｂ内に導入された光供給管１３の先端部の位置を調節できるように光供給管１３とマニホールド継ぎ手１４との間に気密部材としてＯリング１４１を介在させている。光供給管１３の動作手段には例えば光ファイバー用の巻き取り装置が適用される。   The light supply pipe 13 is made of an optical fiber having a diameter smaller than that of the pipe 1b, and is inserted into the pipe 1b by a manifold joint 14 in an airtight manner substantially coaxially with the pipe 1b. An optical fiber made of quartz that transmits ultraviolet light and is resistant to ozone is applied. Further, an O-ring 141 is interposed as an airtight member between the light supply pipe 13 and the manifold joint 14 so that the position of the tip of the light supply pipe 13 introduced into the pipe 1b can be adjusted. For example, an optical fiber winding device is applied to the operation means of the light supply tube 13.

配管１ｂ内に導入されない方の光供給管１３の一端には紫外光領域を含む光（２５０ｎｍ程度の波長領域を含む光）を発する光源１５が具備されている。光源１５には周知の紫外光の光源を適用すればよい。マニホールド継ぎ手１４は配管１ｂの施工時すなわち配管１ｂを配管１ａに接続する際に配管１ａと対向しない配管１ｂの端部に装着される。また、マニホールド継ぎ手１４にはオゾン発生装置３からオゾンガスが供されるガス供給管１６が接続される。   A light source 15 that emits light including an ultraviolet region (light including a wavelength region of about 250 nm) is provided at one end of the light supply tube 13 that is not introduced into the pipe 1b. A known ultraviolet light source may be applied as the light source 15. The manifold joint 14 is attached to the end of the pipe 1b that does not face the pipe 1a when the pipe 1b is constructed, that is, when the pipe 1b is connected to the pipe 1a. A gas supply pipe 16 to which ozone gas is supplied from the ozone generator 3 is connected to the manifold joint 14.

図５を参照しながら本実施形態の不動態化処理について説明する。   The passivation process of this embodiment will be described with reference to FIG.

不動態化済みの配管１ａの一端側に配管１ａと同径の新たな配管１ｂが溶接固定される。配管１ａのもう一端側には真空ポンプ２が気密に接続される。次いで、マニホールド継ぎ手１４が配管１ｂの一端側に装着される。光供給管１３は配管１ｂ内に導入された先端部が配管１ａと配管１ｂとの接続部分と略同位置となるように設定される。   A new pipe 1b having the same diameter as the pipe 1a is welded and fixed to one end of the passivated pipe 1a. A vacuum pump 2 is hermetically connected to the other end of the pipe 1a. Next, the manifold joint 14 is attached to one end side of the pipe 1b. The light supply pipe 13 is set so that the tip portion introduced into the pipe 1b is substantially at the same position as the connecting portion between the pipe 1a and the pipe 1b.

次いで、室温のもとで真空ポンプ２によって配管１ａ，１ｂ内を負圧状態（数百Ｐａ以下例えば２００Ｐａ）にした状態で配管１ｂと光供給管１３との間隙にガス供給管１６からオゾンガスを供給する。一方、光供給管１３の端面からは光源１５の光が配管１ｂ内のオゾンガスのガス流に照射される。この照射によって生じた酸化性化学種である原子状酸素（非特許文献３）によって配管１ｂの内面が酸化されクロム酸化物（Ｃｒ2Ｏ3）から成る不動態膜が形成される。 Next, ozone gas is supplied from the gas supply pipe 16 into the gap between the pipe 1b and the light supply pipe 13 in a state where the inside of the pipes 1a and 1b is brought into a negative pressure state (several hundred Pa or less, for example, 200 Pa) by the vacuum pump 2 at room temperature. Supply. On the other hand, the light from the light source 15 is irradiated from the end face of the light supply pipe 13 onto the ozone gas flow in the pipe 1b. The inner surface of the pipe 1b is oxidized by atomic oxygen (Non-patent Document 3), which is an oxidizing chemical species generated by this irradiation, to form a passive film made of chromium oxide (Cr 2 O 3 ).

その後、一定時間毎（例えば１０分間毎）に光供給管１３の端面の位置がオゾンガスのガス流の上流方向に移行するように光供給管１３を配管１ｂの軸方向に動作させる。光供給管１３の先端部がマニホールド継ぎ手１４側の配管１ｂの一端に達した時点で配管１ｂの内面の不動態化が完了する。   Thereafter, the light supply pipe 13 is operated in the axial direction of the pipe 1b so that the position of the end face of the light supply pipe 13 shifts in the upstream direction of the ozone gas flow at regular intervals (for example, every 10 minutes). Passivation of the inner surface of the pipe 1b is completed when the tip of the light supply pipe 13 reaches one end of the pipe 1b on the manifold joint 14 side.

配管１ｂの不動態化が完了すると、光供給管１３と共にマニホールド継ぎ手１４が配管１ｂから外される。そして、この配管１ｂの一端に新たな配管が溶接されると、上述と同じ方法で当該配管の内面が不動態化処理される。新たに配管が増設される毎にこの不動態化処理が実行される。尚、本実施形態ではオゾン分解因子に不飽和炭化水素ガスを用いていないので不飽和炭化水素由来成分の除去過程が不要となる。   When the passivation of the pipe 1b is completed, the manifold joint 14 together with the light supply pipe 13 is removed from the pipe 1b. When a new pipe is welded to one end of the pipe 1b, the inner surface of the pipe is passivated by the same method as described above. This passivating process is executed every time a new pipe is added. In the present embodiment, since the unsaturated hydrocarbon gas is not used for the ozonolysis factor, the process of removing the unsaturated hydrocarbon-derived component is unnecessary.

ステンレス製（ＳＵＳ３０４）の配管の内面を処理温度３０℃、圧力６０Ｐａ、波長２５０ｎｍを含む紫外光の照射のもとオゾン濃度１００ｖｏｌ％のガス雰囲気で本実施形態の処理方法により１０分間処理した。本実施例においても、図６に示された特性図と略同等のＸＰＳ結果が得られ、室温に近い温度条件のもとでも６０分未満の短時間で鋼材表面を不動態化できるが示された。   The inner surface of a stainless steel (SUS304) pipe was treated by a treatment method of this embodiment for 10 minutes in a gas atmosphere having an ozone concentration of 100 vol% under irradiation with ultraviolet light including a treatment temperature of 30 ° C., a pressure of 60 Pa, and a wavelength of 250 nm. Also in this example, an XPS result substantially equivalent to the characteristic diagram shown in FIG. 6 is obtained, and it is shown that the steel surface can be passivated in a short time of less than 60 minutes even under a temperature condition close to room temperature. It was.

１ａ，１ｂ…配管
５，８，９，１０，１１，１２…ガス供給管
１３…光供給管
５１，８１，１１１，１２１…散気孔 1a, 1b ... piping 5, 8, 9, 10, 11, 12 ... gas supply tube 13 ... light supply tube 51, 81, 111, 121 ... air diffuser

Claims (2)

鋼材から成る配管の内面を不動態化処理する不動態化処理方法であって、
鋼材から成る配管内にオゾンガス供給管を当該配管と同軸に挿通して当該供給管の先端付近の外周面からオゾンガスを供給すると共に当該外周面と当該配管の内面との間隙にオゾン分解因子として不飽和炭化水素ガスを供給しながら前記外周面を当該配管の軸方向に動作させることにより当該配管の内面を不動態化すること
を特徴とする不導態化処理方法。 A passivation treatment method for passivating the inner surface of a pipe made of steel,
An ozone gas supply pipe is inserted coaxially with the pipe into the pipe made of steel to supply ozone gas from the outer peripheral surface in the vicinity of the tip of the supply pipe, and the gap between the outer peripheral surface and the inner surface of the pipe is not an ozone decomposition factor. A passivation treatment method, wherein the inner surface of the pipe is passivated by operating the outer peripheral surface in the axial direction of the pipe while supplying a saturated hydrocarbon gas. 前記不動態化処理した配管の内面に対してオゾンガスのみを供することを特徴とする請求項１に記載の不動態化処理方法。 The passivation treatment method according to claim 1 , wherein only ozone gas is provided to the inner surface of the passivated pipe.
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