EP0596121A1 - Procede de formation d'un film passif sur l'acier inoxydable, et element entrant en contact avec les gaz, les liquides et l'acier inoxydable - Google Patents

Procede de formation d'un film passif sur l'acier inoxydable, et element entrant en contact avec les gaz, les liquides et l'acier inoxydable Download PDF

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Publication number
EP0596121A1
EP0596121A1 EP92917389A EP92917389A EP0596121A1 EP 0596121 A1 EP0596121 A1 EP 0596121A1 EP 92917389 A EP92917389 A EP 92917389A EP 92917389 A EP92917389 A EP 92917389A EP 0596121 A1 EP0596121 A1 EP 0596121A1
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EP
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Prior art keywords
gas
stainless steel
contacting part
treatment
passivated
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EP92917389A
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German (de)
English (en)
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EP0596121A4 (fr
Inventor
Tadahiro 1-17-301 Komegabukuro 2-Chome Ohmi
Masakazu Dept. Of Electronics Faculty Nakamura
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Osaka Oxygen Industries Ltd
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Osaka Oxygen Industries Ltd
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Publication of EP0596121A1 publication Critical patent/EP0596121A1/fr
Publication of EP0596121A4 publication Critical patent/EP0596121A4/fr
Withdrawn legal-status Critical Current

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    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/80—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/002—Heat treatment of ferrous alloys containing Cr
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/02—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material

Definitions

  • the present invention relates to a method for forming stainless steel passivated films, stainless steel, and gas-contacting and liquid-contacting parts, and in particular relates to a method for forming passivated films of oxidized passivated stainless steel, as well as stainless steel, and gas-contacting and liquid-contacting parts which can be preferably applied to ultra-high vacuum apparatuses, ultra-high clean apparatuses, ultra-pure water apparatuses and the like.
  • the size of a unit element becomes small year by year in accordance with high integration of LSI, and research and development for semiconductor devices having a size of 1 ⁇ m to sub micron, and further 0.5 ⁇ m or below is being actively performed directing realization of practical use.
  • a step of forming a thin film, a step of etching the formed thin film into a predetermined circuit pattern and the like are repeatedly performed. And it is common that these processes are performed in a ultra-high vacuum state, or in a pressure-reduced atmosphere in which predetermined gas is introduced. If these steps are contaminated by impurities, problems are caused such that, for example, the film quality of thin films to be formed is deteriorated, the accuracy of fine processing is not obtained and the like. This is the reason why the ultra-high vacuum and the ultra-high clean pressure-reduced atmosphere are required.
  • Fig. 16 is a graph showing the relation between the gas pollution and the total leak amount of a system including a gas pipe arrangement line and a reaction chamber (the sum of the external leak and the release gas amount from the inner surface of the pipe arrangement line and the reaction chamber) in a conventional apparatus.
  • a plurality of lines in the figure show the relation between the impurity concentration in the atmosphere and the total leak amount of the system with respect to cases in which the flow rate of gas is changed to various values.
  • the semiconductor process is in a tendency that the flow rate of gas is more and more decreased in order to realize a process having higher accuracy, and for example, it becomes common to use a flow rate of 10 cc/min or less.
  • a flow rate of 10/min is used (symbol V)
  • the impurity concentration in the gas becomes 10 ppm to 1 %, which is far from a high clean process.
  • the present inventors have invented a ultra-high clean gas supply system, and succeeded to suppress the leak amount from the outside of the system to be not more than 1 x 10- 11 Torr ⁇ l/sec which is the detection limit of a detector in the present circumstance.
  • the inside of the system that is the above-mentioned gas release from the surface of stainless steel, so that consequently it was impossible to lower the impurity concentration in the pressure-reduced atmosphere.
  • the minimum value of the surface release gas amount obtained by the surface treatment in the present ultra-high vacuum technique is 1 x 10- 11 Torr ⁇ l/sec ⁇ cm 2 in the case of stainless steel.
  • a leak amount of 1 x 10- 7 Torr ⁇ l/sec is given as a total, and consequently in the case of a gas flow rate of 10 cc/min, gas having a purity of an impurity concentration of about 1 ppm is only obtained. It is needless to say that when the gas flow rate is made further small, the purity further drops.
  • various gases ranging from relatively stable general gases (0 2 , N 2 , Ar, H 2 , He) to special gases having strong reactivity, corrosion property and toxicity are used.
  • special gases there are gases which generate hydrochloric acid or hydrofluoric acid exhibiting a strong corrosion property when moisture exists in the atmosphere such as for example hydrogen chloride (HCI), chlorine (C1 2 ), trichloroboron (BC1 3 ), trifluoroboron (BF 3 ) and the like.
  • HCI hydrogen chloride
  • chlorine C1 2
  • BC1 3 trichloroboron
  • BF 3 trifluoroboron
  • stainless steel is often used for pipe arrangements and chamber materials for handling these gases because of corrosion resistance, high strength, easiness of secondary processing, easiness of welding, and easiness of polishing treatment for the inner surface.
  • the stainless steel is excellent in corrosion resistance in a ultra-high purity atmosphere of an extremely minute amount of moisture, however, it is easily corroded in a chlorine type or a fluorine type gas atmosphere in which moisture exists. Thus, a treatment for corrosion resistance becomes indispensable after the surface polishing of stainless steel.
  • Ni-W-P coating cleaning coating method
  • passivated film formation method in which a thin oxide film is made on the metallic surface in a nitric acid solution and the like.
  • an oxidized passivated film formed in a high purity atmosphere having a moisture content of, for example, about 100 ppb is improved in the degassing characteristic as compared with a passivated film formed by the wet method ((b) in Fig. 1).
  • the degassing characteristic was not sufficient yet, which could not result in the use as a material for ultra-high vacuum or ultra-high clean pressure-reduced apparatuses.
  • the surface roughness which can be achieved by the electrolytic polishing at present has a limit of R max :0.05-0.1 /1.m, and usually a surface roughness of 0.5 /1.m is used.
  • R max 0.05-0.1 /1.m
  • the surface roughness during the electrolytic polishing is not maintained, and the surface becomes rough.
  • the surface of a base material (bulk portion) is finished to have R max : 0.05-0.1 ⁇ m before the formation of the passivated film, the surface roughness of the passivated film becomes rougher than R max : 0.1 after the passivated film is formed.
  • the present invention has been made on the basis of the finding of the above-mentioned problems with respect to the oxidized passivated film.
  • the first gist of the present invention lies in a method for forming stainless steel passivated films characterized in that the surface of stainless steel is subjected to an electrolytic polishing treatment, thereafter an oxidation treatment is performed in oxidizable atmospheric gas, and subsequently iron oxide on the surface is reduced and removed using hydrogen gas.
  • the second gist of the present invention lies in a method for forming stainless steel passivated films characterized in that the surface of stainless steel is subjected to an electrolytic polishing treatment, thereafter welding is performed, an oxidation treatment is performed in oxidizable atmospheric gas after the welding while heating a welded portion, and then iron oxide on the surface is reduced and removed using hydrogen gas.
  • the third gist of the present invention lies in stainless steel characterized in that it has a passivated film in which R max is 0.1 /1.m or below for the surface roughness.
  • the fourth gist of the present invention lies in a gas-contacting part and a liquid-contacting part characterized in that they have on the surface a stainless steel passivated film formed such that the surface of stainless steel is subjected to an electrolytic polishing treatment, thereafter an oxidation treatment is performed in oxidizable atmospheric gas, and subsequently iron oxide on the surface is reduced and removed using hydrogen gas.
  • the electrolytic polishing is performed before the formation of the passivated film.
  • a combined electrolytic polishing method may be used.
  • the combined electrolytic polishing method is a method in which anodic metal subjected to polishing is electrolyzed and eluted by electrolysis, and a passivated film generated on the surface of the metal subjected to polishing is processed to have a specular face by means of an abrasive action using polishing abrasive grains (for example, official gazette of Japanese Patent Publication No. SHO-57-47759-1982).
  • the electrolytic polishing of stainless steel By means of the electrolytic polishing of stainless steel, a processed denatured layer on the surface is removed. In addition, it is possible to allow the surface roughness to have R max : 1 /1.m or below. It is preferable that the surface roughness after the electrolytic polishing is as fine as possible, and hence it is possible to make it to be 0.05-0.1 tim.
  • Fig. 2 (a) shows a surface state after the polishing
  • Fig. 2 (b) shows a surface state before the polishing.
  • large irregularity of crystal grains exists before the polishing, and no continuous film is obtained even when an oxidized passivated film is formed in this state, resulting in a film inferior in corrosion resistance. Further, moisture and the like is occluded and adsorbed between crystal grains, so that no film having a good degassing characteristic is obtained.
  • the irregularity on the surface disappears, and a smooth face is provided. As a result, the surface area decreases, and the adsorption and occlusion amount of moisture greatly decreases.
  • the passivated film formation treatment may be performed immediately after the electrolytic polishing, however, it is preferable that high temperature baking is performed before the passivated film formation treatment.
  • high temperature baking treatment is performed before the passivated film formation treatment, the chromium concentration at the stainless surface side increases, and a passivated film which is close and excellent in corrosion resistance is formed.
  • the high temperature baking pretreatment is performed, for example, in an inert gas atmosphere such as Ar, He, N 2 gas and the like.
  • the time is preferably 1-10 hours.
  • the treatment temperature is preferably 300-600 ° C, and more preferably 400-520 ° C. When it is performed in a temperature range of 400-520 ° C, the roughness on the surface is further suppressed, an oxidized passivated film formed becomes a closer film as compared with cases of execution in other temperature ranges, and the degassing characteristic is more improved.
  • the oxidized passivated film is also formed in this high temperature baking treatment.
  • the baking is performed in an inert gas atmosphere.
  • the reason why the oxidized passivated film is formed on the surface irrelevant to the fact that the baking is performed in the inert gas atmosphere (that is to say, an atmosphere containing no oxygen) is not necessarily clear, however, it is considered that a porous oxide layer is formed on the stainless steel surface by the electrolytic polishing, and oxygen in the layer serves as a supply source of oxygen for the passivated film formation.
  • the surface roughness of the passivated film formed by the high temperature baking maintains a surface roughness after the electrolytic baking.
  • the thickness of this passivated film changes also depending on the baking temperature and time, which becomes, for example, a thickness of about 30A in the case of 500 ° C x 10 hours, so that an exact state after the high temperature baking can be also put to practical use.
  • the high temperature baking treatment which is heated to, for example, 350-450 ° C to form an oxidized passivated film on the stainless surface.
  • a layer containing much chromium oxide on the stainless surface is formed, and a layer containing much iron oxide is formed thereon.
  • the layer containing much iron oxide is a porous film having cracks and pin holes as described above, The degree of these cracks, pin holes and the like changes depending on the moisture amount in the oxidizable atmosphere, and the more minute the moisture content is, the more preferable it is.
  • the oxidizable gas is exhausted after the passivated film formation treatment, and successively hydrogen gas is introduced to reduce and remove the layer of the passivated outermost surface.
  • the outermost surface of the passivated film becomes a clean and flat face. This is considered to result from the fact that the layer containing much iron oxide in which the pin holes and crack exist is reduced and removed by hydrogen, and the close layer containing much chromium oxide appears.
  • the hydrogen concentration in the hydrogen treatment gas is preferably 0.1 ppm to 10 %, and more preferably 0.5-100 ppm. In the range of 0.5-100 ppm, the close passivated film having a more excellent degassing characteristic is formed.
  • the temperature for the hydrogen treatment is preferably 200-500 °C, and more preferably 300-400 °C. The hydrogen brittleness of stainless is suppressed in this range, and the passivated film which contains close chromium oxide having an excellent degassing characteristic as a main component is obtained.
  • the surface roughness of the passivated film manufactured as described above is extremely smooth, and for example, when the above-mentioned passivated film formation treatment is performed after finishing into 0.05-0.1 ⁇ m by the electrolytic polishing, and further the hydrogen gas treatment is performed, then the passivated film having a surface roughness of not more than 0.01 ⁇ m is obtained.
  • Annealing treatment is further performed in inert gas after the hydrogen gas treatment, thereby the chromium oxide concentration in the outermost surface of the thermally oxidized passivated film is much increased, and stainless steel having the passivated film with much more excellent corrosion resistance is obtained.
  • the annealing is preferably performed at 200-500 °C for 1-10 hours, and by performing the annealing under a condition within this range, the surface state of the thermally oxidized passivated film becomes smoother, the chromium oxide concentration in the outermost surface is much increased, and the corrosion resistance is much improved.
  • the inert gas to be used for the annealing treatment for example, Ar, He, N 2 and the like are used.
  • a passivated film containing much Cr oxide can be formed at the welded portions by heating the welded portions after the welding and again performing the high temperature baking (300-600 ° C x 1-10 hours) in the inert gas atmosphere, or by performing the passivated film formation treatment in the oxidizable atmospheric gas and successively reducing and removing iron oxide on the surface using hydrogen gas.
  • the surface roughness of the passivated film at the welded portions formed by the method of 2 becomes to have R max : 0.1 ⁇ m or below.
  • the fact that the passivated film is also formed by the high temperature baking is as described above, and the fact that the surface roughness during the electrolytic polishing is maintained also by the high temperature baking is also as described above. Therefore, when the high temperature baking is performed after the electrolytic polishing with respect to the surface roughness of 0.05-0.1 ⁇ m, the passivated film having the surface roughness of 0.05-0.1 ⁇ m is obtained.
  • this passivated film is an extremely close passivated film in which the surface is extremely rich in chromium, Cr/Fe is of course 1 and more, and one having Cr/Fe of about 7 is also achieved (see Fig. 5).
  • this stainless steel is extremely excellent in the degassing characteristic because R max is 0.1 ⁇ m and more for the surface roughness, and it has the close passivated film.
  • Another method for obtaining the stainless steel having the passivated film with the surface roughness of R max : not more than 0.1 ⁇ m is the method in which the surface of stainless steel is finished to have the surface roughness of R max : 0.05-0.1 ⁇ m by means of the electrolytic polishing, and the above-mentioned hydrogen gas treatment is performed (the high temperature baking may be performed before the hydrogen gas treatment).
  • the high temperature baking may be performed before the hydrogen gas treatment.
  • Cr/Fe at the surface of the passivated one after the hydrogen gas treatment becomes larger than Cr/Fe in the base material (see Fig. 6, for example, Cr/Fe is 0.35 in Fig. 6 (a)), so that the stainless steel which is also excellent in the gas disengage characteristic and the corrosion resistance is obtained.
  • the stainless steel of the present invention is, for example, those of the Fe-Cr type and the Fe-Cr-Ni type.
  • any stainless steel of the ferrite type, the martensite type or the austenite type is available.
  • SUS 316 is preferable.
  • the passivated stainless steel manufactured according to the passivated film formation method of the present invention as described above exhibits extremely good degassing characteristics and corrosion resistance, which makes it possible to use as constituting materials for ultra-high vacuum apparatuses, ultra-high clean pressure-reducing apparatuses and the like.
  • the passivated stainless steel manufactured according to the passivated film formation method of the present invention as described above exhibits extremely good degassing characteristics and corrosion resistance, which is preferably used also for gas-contacting parts.
  • the stainless steel according to the present invention can be preferably used also for liquid-contacting parts such as liquid supply tubes, liquid storing tanks and the like.
  • a system of a gas supply line for supplying gas from a gas bomb to a use point of the gas such as a film formation apparatus or the like generally has constitution as shown in Fig. 7.
  • 100 is the gas cylinder
  • 101 is a gas cylinder valve
  • 102 is a regulator
  • 103 is a valve
  • 104 is an integrated branched valve
  • 105 is a mass flow controller
  • 106 is the film formation apparatus
  • 107 is a pipe arrangement
  • 108 is a filter.
  • gas-contacting parts for example, there are exemplified parts such as the gas cylinder valve, a pressure gauge, the regulator, the valve, the mass flow controller, the filter, the regulator and the like, or for example, a valve seat, a valve chamber, a valve main body, a diaphragm, a seal ring, a stem and the like constituting these parts.
  • cylinder valve for example, one having a structure shown in Fig. 8 is exemplified (official gazette of Japanese Utility Model Application Laid- open No. HEI-1-178281-1989).
  • Fig. 9 for the pressure gauge in Fig. 10 for the regulator
  • Fig. 11 for the valve in Fig. 11 for the valve
  • Fig. 12 for the mass flow controller are exemplified as each of examples, respectively.
  • the diaphragm has its small surface roughness from a viewpoint of the sealing property.
  • resiliency is required.
  • an excellent fatigue resistance characteristic is required.
  • R max is not more than 0.1 /1.m for its surface roughness, so that the sealing property is extremely good.
  • metal having a passivated film is inferior in resiliency to metal having no passivated film, however, in the present invention, resiliency which is not different from that of stainless having no passivated film at all has been exhibited. Further, as a result of a fatigue test, a critical fatigue strength which is more excellent than that of stainless steel formed with a conventional passivated film has been exhibited. In addition, in the case of the stainless formed with the conventional passivated film, generation of small cracks was found on its surface, however, in the case of the stainless according to the present invention, generation of such cracks was not found.
  • the good sealing property is also required in the case of the valves such as the cylinder valve for gas cylinders and the like, however, the valve of the present invention has a better sealing property than a valve having a conventional passivated film on the gas-contacting surface, in which the leak amount is remarkably reduced, and it has become possible to supply gas of ultra-high purity.
  • a SUS 316L stainless tube having a length of 2 m and a diameter of 3/8" was subjected to electrolytic polishing, and the surface was made into a specular face in which the maximum value of difference in irregularity (R max ) was 0.05 ⁇ m in within a circumference having a radius of 5 ⁇ m. As shown in Fig. 3, this surface state is a smooth face in which the crystal grain boundary is observed.
  • hot water washing 90 ° C
  • ultra-pure water which was dried with isopropyl alcohol.
  • This stainless tube was installed in an oxidation furnace, Ar gas was allowed to flow at 1 I/min, purging was performed at an ordinary temperature for 1 hour, thereafter the temperature was raised to 450-550 °C, and a baking treatment was performed for 10 hours.
  • Inner surface states of the stainless after the thermal treatment at various temperatures are shown in Fig. 13. As clarified from Fig. 13, even after the thermal treatment for a long time at a high temperature, the specular face after the electrolytic polishing was maintained for the stainless surface. That is to say, R max : 0.05 ⁇ m was maintained.
  • a result of measurement by XPS of the inner surface of the stainless tube after the baking at 500 °C is shown in Fig. 5. Owing to the above-mentioned baking treatment, chromium atoms increased at the surface side, while iron atoms inversely decreased, and the chromium/iron composition ratio was inverted with respect to the inside of the bulk.
  • chromium oxide is more than iron oxide in one of about 22 A from the surface (left end of the graph in Fig. 5).
  • Fig. 14 (a) indicates the case in which the hydrogen gas treatment time was 10 minutes
  • Fig. 14 (b) indicates the case in which the hydrogen gas treatment time was 30 minutes.
  • Fig. 14 (a) indicates the case in which the hydrogen gas treatment time was 10 minutes
  • Fig. 14 (b) indicates the case in which the hydrogen gas treatment time was 30 minutes.
  • the cracks and pin holes having existed after the oxidation treatment were not observed on the surface of the passivated film subjected to the hydrogen reduction treatment (hydrogen gas treatment), and the smooth surface state was provided.
  • a high concentration of chromium oxide existed in the passivated film, and the chromium atomic ratio with respect to iron became by far larger than that in the base material.
  • the thickness of the passivated films shown in Fig. 6 (a) and Fig. 6 (b) was about 60 ⁇ .
  • the degassing characteristic was greatly improved, and it has been shown that the oxidized passivated film stainless steel manufactured according to the present embodiment can be applied to ultra-high vacuum apparatuses and ultra-high clean pressure-reduced apparatuses.
  • the moisture amount became 3 ppb about 40 minutes after the gas application, in which the degassing characteristic was inferior to that of the oxidized passivated film of embodiment 1, however, it was greatly improved as compared with the conventional oxidized passivated film.
  • An oxidized passivated film was formed on the inner surface of a stainless tube, in which the temperature of the hydrogen reduction treatment was 600 °C, and other treatment conditions were the same as those in embodiment 1, and the same evaluation was performed.
  • An oxidized passivated film was formed on the inner surface of a stainless tube, in which the hydrogen reduction treatment gas was Ar gas containing 20 % hydrogen, and other conditions were the same as those in embodiment 1, and the same evaluation was performed.
  • An oxidized passivated stainless tube was manufactured, in which the oxidizable atmosphere was a ultra-high purity atmosphere of a moisture concentration of 5 ppb, and other treatment conditions were the same as those in embodiment 1, and its degassing characteristics was evaluated.
  • the results is as in (h) in Fig. 1.
  • the moisture amount in the Ar gas became not more than 3 ppb as the background level 10 minutes after the gas application, and it was found that even in the case of the film at the highest level at the present circumstance, the degassing characteristic was improved by the treatment according to the present embodiment.
  • the hydrogen reduction treatment was performed in the same manner as embodiment 1, and then the annealing treatment was further performed at various temperatures for 10 hours in Ar gas. Concentration profiles in the depth direction by XPS at the surface of the thermally oxidized passivated films are shown in Fig. 15 (a) to Fig. 15 (f).
  • the concentration of chromium having high corrosion resistance increased at the outermost surface layer. Moreover, it was found that the chromium concentration increased more and more in accordance with the increase in the treatment temperature, and the concentrations of chromium and iron became inverted at not less than 475 ° C. Incidentally, the thickness of the passivated films shown in Fig. 8 (a) to Fig. 8 (f) was about 70 ⁇ .
  • the corrosion resistance was improved owing to the increase in the chromium concentration at the outermost surface, and extremely good corrosion resistance was exhibited against a strongly corrosive solution of 36 % HCI.
  • the present invention it becomes possible to form the passivated film which is extremely excellent in the degassing characteristic and the corrosion resistance, and it becomes possible to supply the oxidized passivated stainless steel which is applicable to ultra-high vacuum, ultra-high clean pressure-reduced apparatuses and the like.

Abstract

Procédé de formation d'un film passif présentant une aptitude au dégazage et une résistance à la corrosion excellentes puisqu'il est extrêmement plat et dense. Le procédé consiste à soumettre la surface de l'acier inoxydable au polissage électrolytique, à réaliser l'oxydation dans une atmosphère oxydante, et à éliminer l'oxyde de fer ainsi formé à la surface par une réduction à l'aide d'hydrogène.
EP19920917389 1991-05-28 1992-05-28 Procede de formation d'un film passif sur l'acier inoxydable, et element entrant en contact avec les gaz, les liquides et l'acier inoxydable. Withdrawn EP0596121A4 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP152466/91 1991-05-28
JP15246691 1991-05-28
JP198718/91 1991-07-12
JP19871891 1991-07-12
JP3212592A JP3045576B2 (ja) 1991-05-28 1991-07-30 ステンレス鋼の不動態膜形成方法及びステンレス鋼
JP212592/91 1991-07-30
PCT/JP1992/000699 WO1992021786A1 (fr) 1991-05-28 1992-05-28 Procede de formation d'un film passif sur l'acier inoxydable, et element entrant en contact avec les gaz, les liquides et l'acier inoxydable

Publications (2)

Publication Number Publication Date
EP0596121A1 true EP0596121A1 (fr) 1994-05-11
EP0596121A4 EP0596121A4 (fr) 1994-11-23

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EP19920917389 Withdrawn EP0596121A4 (fr) 1991-05-28 1992-05-28 Procede de formation d'un film passif sur l'acier inoxydable, et element entrant en contact avec les gaz, les liquides et l'acier inoxydable.

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EP (1) EP0596121A4 (fr)
JP (2) JP3045576B2 (fr)
WO (1) WO1992021786A1 (fr)

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US8037928B2 (en) 2005-12-21 2011-10-18 Exxonmobil Research & Engineering Company Chromium-enriched oxide containing material and preoxidation method of making the same to mitigate corrosion and fouling associated with heat transfer components
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CN104160057A (zh) * 2012-03-08 2014-11-19 杰富意钢铁株式会社 不锈钢复合钢
CN112449658A (zh) * 2018-07-06 2021-03-05 富士胶片株式会社 部件、容器、药液收容体、反应槽、蒸馏塔、过滤器单元、存储罐、管路、药液的制造方法

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JPH07197206A (ja) * 1993-12-30 1995-08-01 Tadahiro Omi ステンレス鋼及び配管システム
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1278804B (de) * 1964-04-02 1968-09-26 Owens Jllinois Inc Verfahren zum Voroxydieren von Werkstuecken aus Chromeisen und Chromnickeleisenlegierungen zur Erleichterung des Anschmelzens derselben an Glas
US4078949A (en) * 1976-09-02 1978-03-14 United States Steel Corporation Method for improving the surface quality of stainless steels and other chromium-bearing iron alloys
EP0294558A1 (fr) * 1984-08-29 1988-12-14 Shinko Pantec Co., Ltd. Procédé de traitement de surfaces d'acier inoxydable par oxydation à haute température
JPH0192389A (ja) * 1987-09-30 1989-04-11 Aichi Steel Works Ltd ステンレス鋼線材の酸洗肌荒れ防止方法
EP0327831A2 (fr) * 1988-02-12 1989-08-16 Thyssen Edelstahlwerke AG Procédé et dispositif pour augmenter la résistance à la fatigue thermique de matériaux conducteurs de la chaleur
JPH02141566A (ja) * 1988-11-21 1990-05-30 Shinko Pantec Co Ltd 超純水製造供給装置用機器配管材料
EP0388710A1 (fr) * 1989-03-23 1990-09-26 Mitsubishi Jidosha Kogyo Kabushiki Kaisha Traitement de surface de titane ou d'un alliage de titane

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2517727B2 (ja) * 1987-07-25 1996-07-24 忠弘 大見 半導体製造装置用ステンレス鋼部材の製造方法
JP2768952B2 (ja) * 1988-08-04 1998-06-25 忠弘 大見 金属酸化処理装置及び金属酸化処理方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1278804B (de) * 1964-04-02 1968-09-26 Owens Jllinois Inc Verfahren zum Voroxydieren von Werkstuecken aus Chromeisen und Chromnickeleisenlegierungen zur Erleichterung des Anschmelzens derselben an Glas
US4078949A (en) * 1976-09-02 1978-03-14 United States Steel Corporation Method for improving the surface quality of stainless steels and other chromium-bearing iron alloys
EP0294558A1 (fr) * 1984-08-29 1988-12-14 Shinko Pantec Co., Ltd. Procédé de traitement de surfaces d'acier inoxydable par oxydation à haute température
EP0173564B1 (fr) * 1984-08-29 1989-02-22 Shinko-Pfaudler Company, Ltd. Procédé pour le traitement d'une surface d'acier inoxydable par oxydation à haute température
JPH0192389A (ja) * 1987-09-30 1989-04-11 Aichi Steel Works Ltd ステンレス鋼線材の酸洗肌荒れ防止方法
EP0327831A2 (fr) * 1988-02-12 1989-08-16 Thyssen Edelstahlwerke AG Procédé et dispositif pour augmenter la résistance à la fatigue thermique de matériaux conducteurs de la chaleur
JPH02141566A (ja) * 1988-11-21 1990-05-30 Shinko Pantec Co Ltd 超純水製造供給装置用機器配管材料
EP0388710A1 (fr) * 1989-03-23 1990-09-26 Mitsubishi Jidosha Kogyo Kabushiki Kaisha Traitement de surface de titane ou d'un alliage de titane

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 13, no. 302 (C-616) (3650) 12 July 1989 & JP-A-01 092 389 (AICHI STEEL WORKS) 11 April 1989 *
PATENT ABSTRACTS OF JAPAN vol. 14, no. 382 (C-749) (4325) 17 August 1990 & JP-A-02 141 566 (SHINKO PANTEC) 30 May 1990 *
See also references of WO9221786A1 *

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EP1043421A2 (fr) * 1999-04-06 2000-10-11 Crucible Materials Corporation Objet en acier inoxydable austénitique ayant une couche superficielle passivée
EP1043421A3 (fr) * 1999-04-06 2002-08-21 Crucible Materials Corporation Objet en acier inoxydable austénitique ayant une couche superficielle passivée
US8465599B2 (en) 2005-12-21 2013-06-18 Exxonmobil Research And Engineering Company Chromiun-enriched oxide containing material and preoxidation method of making the same to mitigate corrosion and fouling associated with heat transfer components
CN101379362B (zh) * 2005-12-21 2012-03-28 埃克森美孚研究工程公司 用于减少结焦的防腐蚀材料、具有改进的防腐蚀性和抗结焦性的传热组件以及减少结焦的方法
US8211548B2 (en) 2005-12-21 2012-07-03 Exxonmobil Research & Engineering Co. Silicon-containing steel composition with improved heat exchanger corrosion and fouling resistance
US8286695B2 (en) 2005-12-21 2012-10-16 Exxonmobil Research & Engineering Company Insert and method for reducing fouling in a process stream
US8037928B2 (en) 2005-12-21 2011-10-18 Exxonmobil Research & Engineering Company Chromium-enriched oxide containing material and preoxidation method of making the same to mitigate corrosion and fouling associated with heat transfer components
US8470097B2 (en) 2005-12-21 2013-06-25 Exxonmobil Research And Engineering Company Silicon-containing steel compostition with improved heat exchanger corrosion and fouling resistance
CN104160057A (zh) * 2012-03-08 2014-11-19 杰富意钢铁株式会社 不锈钢复合钢
CN104160056A (zh) * 2012-03-08 2014-11-19 杰富意钢铁株式会社 耐海水不锈钢复合钢
EP2824206A4 (fr) * 2012-03-08 2015-07-29 Jfe Steel Corp Acier inoxydable revêtu
CN104160057B (zh) * 2012-03-08 2016-08-24 杰富意钢铁株式会社 不锈钢复合钢
CN104160056B (zh) * 2012-03-08 2017-03-08 杰富意钢铁株式会社 耐海水不锈钢复合钢
US20180298477A1 (en) * 2012-03-08 2018-10-18 Jfe Steel Corporation Seawater-resistant stainless clad steel
US10774396B2 (en) 2012-03-08 2020-09-15 Jfe Steel Corporation Seawater-resistant stainless clad steel
CN112449658A (zh) * 2018-07-06 2021-03-05 富士胶片株式会社 部件、容器、药液收容体、反应槽、蒸馏塔、过滤器单元、存储罐、管路、药液的制造方法
CN112449658B (zh) * 2018-07-06 2023-11-07 富士胶片株式会社 部件、容器、药液收容体、反应槽、蒸馏塔、过滤器单元、存储罐、管路、药液的制造方法

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WO1992021786A1 (fr) 1992-12-10
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JPH10204526A (ja) 1998-08-04
JP3045576B2 (ja) 2000-05-29

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