JP2001271184A - Corrosion protection treating agent and method for stainless steel - Google Patents
Corrosion protection treating agent and method for stainless steelInfo
- Publication number
- JP2001271184A JP2001271184A JP2000083529A JP2000083529A JP2001271184A JP 2001271184 A JP2001271184 A JP 2001271184A JP 2000083529 A JP2000083529 A JP 2000083529A JP 2000083529 A JP2000083529 A JP 2000083529A JP 2001271184 A JP2001271184 A JP 2001271184A
- Authority
- JP
- Japan
- Prior art keywords
- stainless steel
- treatment
- hydroxylamine
- anticorrosion
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 38
- 239000010935 stainless steel Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000005260 corrosion Methods 0.000 title abstract description 29
- 230000007797 corrosion Effects 0.000 title abstract description 29
- 150000002443 hydroxylamines Chemical class 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims description 16
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical group C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 claims description 8
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- HYYHQASRTSDPOD-UHFFFAOYSA-N hydroxylamine;phosphoric acid Chemical compound ON.OP(O)(O)=O HYYHQASRTSDPOD-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 238000011109 contamination Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- -1 sodium hydroxylamine Chemical compound 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 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
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/50—Treatment of iron or alloys based thereon
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
-
- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ステンレス鋼表面
の防食処理剤、およびそれを用いた防食処理方法に関
し、特に苛酷な環境下でのステンレス鋼表面の耐食性を
高めるのに有利に用いることができる、防食処理剤およ
び防食処理方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anticorrosion treating agent for a stainless steel surface and a method of using the same for anticorrosion treatment. More particularly, the present invention relates to an anticorrosion treating agent which is advantageously used to enhance the corrosion resistance of a stainless steel surface in a harsh environment. The present invention relates to an anticorrosion treatment agent and an anticorrosion treatment method.
【０００２】[0002]
【従来の技術】従来より、金属表面の腐食を抑制または
防止するために、無機系や有機系など各種の腐食抑制剤
や防食処理剤を用いて金属表面を防食被覆あるいは防食
処理することが知られている。2. Description of the Related Art Conventionally, in order to suppress or prevent corrosion of a metal surface, it has been known that a metal surface is subjected to anticorrosion coating or anticorrosion treatment using various types of corrosion inhibitors such as inorganic or organic ones or anticorrosion treatment agents. Have been.
【０００３】金属のうちでもクロムを多く含むステンレ
ス鋼が耐食性に優れていることはよく知られているが、
そのようなステンレス鋼であっても、強酸や強アルカリ
の環境条件下では、あるいは弱酸や弱アルカリであって
も、長時間さらされるような条件下では、その表面が徐
々に腐食される。このようなステンレス鋼材料の腐食
は、材料の損傷を引き起こす原因となるとともに、ステ
ンレス鋼材料が化学反応を行なうための反応容器または
保存容器などである場合には腐食により生じた生成物が
不純物として容器中の物質を汚染することがある。It is well known that stainless steel containing a large amount of chromium is excellent in corrosion resistance among metals.
The surface of such stainless steel is gradually corroded under environmental conditions of strong acids and strong alkalis, or under conditions of long-term exposure to weak acids and weak alkalis. Such corrosion of the stainless steel material causes damage to the material, and when the stainless steel material is a reaction vessel or a storage vessel for performing a chemical reaction, a product generated by the corrosion is an impurity. May contaminate material in containers.
【０００４】ヒドロキシルアミン塩（ＮＨ2ＯＨ・Ａ、
Ａは、Ｈ2ＳＯ4、Ｈ3ＰＯ4、ＨＣｌなどの酸）は、例え
ば重亜硫酸ナトリウムと亜硝酸ナトリウムとを水溶液中
で反応させてヒドロキシルアミンジスルホン酸ナトリウ
ム水溶液を得たのち、これを加水分解することにより製
造することができ、固体でも水溶液中でも安定な化合物
である。これまで、ヒドロキシルアミン塩は一般にそれ
自体として化学反応の原料として用いられるが、それ以
外にも、化学薬品や電子材料の加工、洗浄に有用である
ものの化学的に非常に不安定なヒドロキシルアミンを必
要に応じて遊離調製するためにも利用されてきた。Hydroxylamine salts (NH 2 OH.A,
A is an acid such as H 2 SO 4 , H 3 PO 4 , or HCl), for example, by reacting sodium bisulfite and sodium nitrite in an aqueous solution to obtain an aqueous solution of sodium hydroxylamine disulfonate, which is then hydrolyzed. It can be produced by decomposition and is a compound that is stable in both solid and aqueous solutions. Until now, hydroxylamine salts have generally been used as a raw material in chemical reactions themselves, but other than that, hydroxylamine, which is useful for processing and cleaning chemicals and electronic materials, but is very chemically unstable, is also used. It has also been used for free preparation as needed.
【０００５】鉄などの防食処理の一方法として、金属表
面を酸性のリン酸塩水溶液で処理することからなるリン
酸塩処理が知られている。例えば、米国特許第４１４９
９０９号、第４８６５６５３号および第５５９７４６５
号明細書；ヨーロッパ特許第０６９５８１７Ａ１号およ
び第０３１５０５９Ａ１号公報；並びに国際特許出願第
ＷＯ９３／０３１９８号および第ＷＯ９３／２０２５９
号公報には、鉄や亜鉛などの金属をリン酸亜鉛やリン酸
鉄の水溶液に浸漬することによって、その表面にリン酸
塩被膜を形成して腐食を防止する方法が開示されてい
る。その際に、リン酸塩被膜の形成を促進する目的で、
リン酸塩水溶液に硫酸ヒドロキシルアミンなどのヒドロ
キシルアミン塩を多くても数重量％加えることが記載さ
れている。[0005] As one method of anticorrosion treatment of iron or the like, a phosphate treatment comprising treating a metal surface with an acidic aqueous phosphate solution is known. For example, US Pat.
Nos. 909, 4865653 and 5597465.
Nos .; EP 0 699 817 A1 and EP 0315059 A1; and International Patent Applications WO 93/03198 and WO 93/20259.
Japanese Patent Application Laid-Open Publication No. H11-163873 discloses a method in which a metal such as iron or zinc is immersed in an aqueous solution of zinc phosphate or iron phosphate to form a phosphate film on the surface thereof, thereby preventing corrosion. At that time, in order to promote the formation of a phosphate film,
It is described that at most several weight% of a hydroxylamine salt such as hydroxylamine sulfate is added to an aqueous phosphate solution.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、苛酷な環境
下でのステンレス鋼の耐食性を高めるのに有用な防食処
理剤およびそれを用いた防食処理方法を提供するもので
ある。SUMMARY OF THE INVENTION An object of the present invention is to provide an anticorrosion treating agent useful for enhancing the corrosion resistance of stainless steel in a severe environment and a method for using the same.
【０００７】[0007]
【課題を解決するための手段】本発明者は、酸やアルカ
リなどの苛酷な環境下に長時間さらされてもステンレス
鋼に腐食を生じさせない防食処理剤および防食処理方法
について研究を重ねた結果、防食処理剤としてヒドロキ
シルアミン塩の水溶液を用いてステンレス鋼表面を一定
時間加熱すると、極めて耐食性の優れたステンレス鋼が
得られることを見い出し、本発明に到達したものであ
る。Means for Solving the Problems The present inventor has conducted research on an anticorrosion treatment agent and an anticorrosion treatment method which do not cause corrosion of stainless steel even when exposed to severe environments such as acids and alkalis for a long time. The present inventors have found that when the surface of a stainless steel is heated for a certain period of time using an aqueous solution of a hydroxylamine salt as an anticorrosion treatment agent, a stainless steel having extremely excellent corrosion resistance can be obtained, and the present invention has been achieved.
【０００８】本発明は、ヒドロキシルアミン塩からなる
スレンレス鋼表面の防食処理剤にある。また本発明は、
ステンレス鋼表面を、上記ヒドロキシルアミン塩防食処
理剤で５０℃以上の温度で加熱することからなる防食処
理方法にもある。[0008] The present invention relates to an anticorrosion treating agent for a stainless steel surface comprising a hydroxylamine salt. The present invention also provides
There is also an anticorrosion treatment method comprising heating a stainless steel surface at a temperature of 50 ° C. or higher with the above hydroxylamine salt anticorrosion treatment agent.
【０００９】本発明のステンレス鋼表面用のヒドロキシ
ルアミン塩防食処理剤は以下の態様であることが好まし
い。 （１）ヒドロキシルアミン塩が、硫酸ヒドロキシルアミ
ンもしくはリン酸ヒドロキシルアミンであるヒドロキシ
ルアミン塩防食処理剤。 （２）ヒドロキシルアミン塩を０．２〜５０重量％の範
囲で含有する水溶液からなるヒドロキシルアミン塩防食
処理剤。The hydroxylamine salt anticorrosion treating agent for a stainless steel surface of the present invention preferably has the following aspects. (1) A hydroxylamine salt anticorrosion agent wherein the hydroxylamine salt is hydroxylamine sulfate or hydroxylamine phosphate. (2) A hydroxylamine salt anticorrosion treating agent comprising an aqueous solution containing a hydroxylamine salt in the range of 0.2 to 50% by weight.
【００１０】[0010]
【発明の実施の形態】以下に、本発明のヒドロキシルア
ミン塩防食処理剤およびそれを用いた防食処理方法につ
いて詳細に説明する。本発明のヒドロキシルアミン塩防
食処理剤は一般に、ヒドロキシルアミン塩の水溶液から
なり、その濃度は０．２〜５０重量％の範囲にある。好
ましくは、濃度は５〜２０重量％の範囲にある。ヒドロ
キシルアミン塩としては、例えば硫酸ヒドロキシルアミ
ン、リン酸ヒドロキシルアミン、および塩酸ヒドロキシ
ルアミンを挙げることができる。特に好ましいのは、硫
酸ヒドロキシルアミンおよびリン酸ヒドロキシルアミン
である。これらのヒドロキシルアミン塩は、前述したよ
うな公知の方法により製造することができる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the hydroxylamine salt anticorrosion treatment agent of the present invention and the anticorrosion treatment method using the same will be described in detail. The hydroxylamine salt anticorrosion agent of the present invention generally comprises an aqueous solution of a hydroxylamine salt, the concentration of which is in the range of 0.2 to 50% by weight. Preferably, the concentration is in the range of 5-20% by weight. Hydroxylamine salts include, for example, hydroxylamine sulfate, hydroxylamine phosphate, and hydroxylamine hydrochloride. Particularly preferred are hydroxylamine sulfate and hydroxylamine phosphate. These hydroxylamine salts can be produced by a known method as described above.
【００１１】上記のヒドロキシルアミン塩水溶液を用い
たステンレス鋼の防食処理は、一般には、ステンレス鋼
をヒドロキシルアミン塩水溶液に浸漬したのち、常圧
下、５０℃以上の温度で加熱することにより行われる。
処理時間は、ヒドロキシルアミン塩水溶液の濃度や処理
温度などによっても異なるが、一般には少なくとも３分
以上であり、好ましくは１〜２０時間である。また、オ
ートクレーブなどを使用することにより、沸点である約
１００℃より高い温度で加熱してもよく、処理温度は一
般には６０℃〜１６０℃の範囲にある。The corrosion prevention treatment of stainless steel using the above-mentioned aqueous solution of hydroxylamine salt is generally carried out by immersing the stainless steel in the aqueous solution of hydroxylamine salt and then heating it at a temperature of 50 ° C. or more under normal pressure.
The treatment time varies depending on the concentration of the aqueous hydroxylamine salt solution, the treatment temperature, and the like, but is generally at least 3 minutes or more, preferably 1 to 20 hours. Further, by using an autoclave or the like, heating may be performed at a temperature higher than the boiling point of about 100 ° C, and the treatment temperature is generally in the range of 60 ° C to 160 ° C.
【００１２】上記本発明の防食処理方法を適用すること
ができるステンレス鋼は、一般にどのような組成のもの
であってもよいが、好ましくはニッケルやクロムを多く
含むステンレス鋼である。本発明に従う防食処理によ
り、苛酷な環境下でのステンレス鋼の腐食を抑制して、
腐食生成物の発生による不純物の混入や汚染を有効に防
ぐことができる。例えば、医薬品や電子材料の洗浄剤と
して有用なフリーのヒドロキシルアミン水溶液を蒸留し
て純度の高いものを得ようとする場合に、ステンレス鋼
からなる蒸留装置に予め上述したような防食処理を施し
ておくことによって、腐食性の強いヒドロキシルアミン
による腐食を有効に防いで、装置からの不純物の混入や
汚染を防止することができる。The stainless steel to which the anticorrosion treatment method of the present invention can be applied generally has any composition, but is preferably a stainless steel containing a large amount of nickel or chromium. By the anticorrosion treatment according to the present invention, the corrosion of stainless steel in a harsh environment is suppressed,
It is possible to effectively prevent contamination and contamination of impurities due to generation of corrosion products. For example, when a free hydroxylamine aqueous solution useful as a detergent for pharmaceuticals and electronic materials is distilled to obtain a high-purity product, the anticorrosion treatment described above is performed in advance on a distillation apparatus made of stainless steel. By doing so, it is possible to effectively prevent corrosion due to highly corrosive hydroxylamine, and to prevent contamination or contamination of impurities from the apparatus.
【００１３】[0013]
【実施例】以下に本発明の実施例および比較例を記載す
る。 ［実施例１］ガラス製フラスコに、濃度２０重量％のリ
ン酸ヒドロキシルアミン水溶液を入れ、これに下記のス
テンレス鋼からなる試験片（サイズ：約４０ｍｍ×２０
ｍｍ×３ｍｍ）を加えた後、還流コンデンサーを装着し
てオイルバス中で加熱し、常圧下、約１００℃の温度で
加熱して、試験片に防食処理を施した。処理時間は８時
間または２４時間であった。 （１）ＳＵＳ３０４Ｌステンレス鋼（組成：Ｆｅ約７３
％，Ｎｉ約９％，約Ｃｒ１８％） （２）ＳＵＳ３１６Ｌステンレス鋼（組成：Ｆｅ約７０
％，Ｎｉ約１２％，約Ｃｒ１６％，Ｍｏ約２％） （３）ＳＵＳ３１０Ｓステンレス鋼（組成：Ｆｅ約５７
％，Ｎｉ約１９％，約Ｃｒ２４％）EXAMPLES Examples and comparative examples of the present invention will be described below. Example 1 A 20% by weight aqueous solution of hydroxylamine phosphate was placed in a glass flask, and a test piece (size: about 40 mm × 20) made of the following stainless steel was placed in the flask.
After the addition of a reflux condenser, the test piece was heated in an oil bath at a temperature of about 100 ° C. under normal pressure, and the test piece was subjected to anticorrosion treatment. Processing time was 8 hours or 24 hours. (1) SUS304L stainless steel (composition: about 73 Fe
%, About 9% Ni, about 18% Cr) (2) SUS316L stainless steel (composition: about 70% Fe)
%, About 12% Ni, about 16% Cr, about 2% Mo) (3) SUS310S stainless steel (composition: about 57% Fe)
%, Ni about 19%, Cr about 24%)
【００１４】耐熱ガラスねじ瓶に１０重量％硫酸を入
れ、これに防食処理した試験片を加えた後、耐熱ガラス
ねじ瓶を温度８０℃の恒温層中で一定時間放置した。次
いで、試験片を取り出して洗浄、乾燥した後、その重量
を測定することにより、耐食試験を行った。比較のため
に、防食処理していない試験片についても同様に耐食試
験を行った。得られた結果をまとめて表１〜３に示す。After adding 10% by weight sulfuric acid to a heat-resistant glass screw bottle and adding a test piece subjected to anticorrosion treatment, the heat-resistant glass screw bottle was allowed to stand in a constant temperature layer at a temperature of 80 ° C. for a certain period of time. Next, the test piece was taken out, washed and dried, and then its weight was measured to perform a corrosion resistance test. For comparison, a test piece that had not been subjected to anticorrosion treatment was similarly subjected to a corrosion resistance test. The obtained results are summarized in Tables 1 to 3.
【００１５】[0015]
【表１】 表１ （１）ＳＵＳ３０４Ｌ ──────────────────────────────────── 試験時間 ８時間処理 ２４時間処理 無処理 （ｈｒ） 重量（ｇ） 重量（ｇ） 重量（ｇ） ──────────────────────────────────── ０ １６．４５２６ １７．９５５８ １８．５５４３ １ − − １８．２３７８ ２４ １６．４５２３ １７．９５５７ − ４４ １６．４５２１ １７．９５５６ − ６８ １６．４５１８ １７．９５５４ − １１６ １６．４５１７ １７．９５５３ − １６４ １６．４５１３ １７．９５４８ − １８８ １６．４５１３ １７．９５４８ − ２３６ １６．４５１４ １７．９５５４ − ２８４ １６．４５１６ １７．９５５４ − ３８０ − １７．９５４６ − ５２９ − １７．９５４４ − ────────────────────────────────────[Table 1] Table 1 (1) SUS304L ──────────────────────────────────── Test time 8 hours Treatment 24 hours treatment No treatment (hr) Weight (g) Weight (g) Weight (g) ───────────────────────────── ０ 0 16.4526 17.9558 18.5543 1--18.2378 24 16.4523 17.9557-44 16.4521 17.9556-68 16.4518 17.9554-116 16. 4517 17.9553-164 16.4513 17.9548-188 16.4513 17.9548-236 16.4514 17.9554-284 16.4516 17.9554-380-17.9546-529- 17.9544-────────────────────────────────────
【００１６】[0016]
【表２】 表２ （２）ＳＵＳ３１６Ｌ ─────────────────────────── 試験時間 ８時間処理 無処理 （ｈｒ） 重量（ｇ） 重量（ｇ） ─────────────────────────── ０ １８．２６４１ １８．２１０３ ２４ １８．１２４４ １７．６７３３ ４４ １８．０１３２ − ───────────────────────────Table 2 (2) SUS316L ─────────────────────────── Test time 8 hours treatment No treatment (hr) Weight (g) ) Weight (g) ─────────────────────────── 0 18.2641 18.2103 24 18.1244 17.6733 44 18.0132 − ───────────────────────────
【００１７】[0017]
【表３】 表３ （３）ＳＵＳ３１０Ｓ ─────────────────────────── 試験時間 ８時間処理 無処理 （ｈｒ） 重量（ｇ） 重量（ｇ） ─────────────────────────── ０ １７．３６９０ １７．５４８９ １ − １７．４１９１ ８ １７．３６９０ − ２３ １７．３６８６ − ４７ １７．３６８７ − ７１ １７．３６８５ − ９５ １７．３６８８ − １１９ １７．３６８６ − １６１ １７．３６８４ − ２０９ １７．３６８３ − ２８１ １７．３６８５ − ３２９ １７．３６８１ − ４５５ １７．３６７９ − ───────────────────────────Table 3 (3) SUS310S ─────────────────────────── Test time 8 hours treatment No treatment (hr) Weight (g) ) Weight (g) ０ 0 17.3690 17.5489 1-17.4191 8 17.3690-23 17.3686-47 17.3687-71 17.3885-95 17.3688-119 17.3686-161 17.3684-209 17.7.383-281 17.3685-329 17.3681-455 17.3679-─ ──────────────────────────
【００１８】［実施例２］実施例１において、リン酸ヒ
ドロキシルアミン水溶液の代わりに濃度２０重量％の硫
酸ヒドロキシルアミン水溶液を用いたこと以外は実施例
１と同様にして、試験片に防食処理を施した。処理時間
は８時間、２４時間または７２時間であった。防食処理
した試験片について、実施例１と同様にして耐食試験を
行った。得られた結果をまとめて表４〜６に示す。Example 2 A test piece was subjected to anticorrosion treatment in the same manner as in Example 1 except that an aqueous solution of hydroxylamine sulfate having a concentration of 20% by weight was used instead of the aqueous solution of hydroxylamine phosphate. gave. Processing time was 8, 24, or 72 hours. The test piece subjected to the anticorrosion treatment was subjected to a corrosion resistance test in the same manner as in Example 1. The obtained results are collectively shown in Tables 4 to 6.
【００１９】[0019]
【表４】 表４ （１）ＳＵＳ３０４Ｌ ─────────────────────────── 試験時間 ８時間処理 無処理 （ｈｒ） 重量（ｇ） 重量（ｇ） ─────────────────────────── ０ １５．５９４３ １８．５５４３ １ − １８．２３７８ ２４ １５．５９４４ − ４４ １５．５９４０ − ６８ １５．５９３７ − １１６ １５．５９３５ − １６４ １５．５９３１ − １８８ １５．５９３１ − ２３６ １５．５９３５ − ２８４ １５．５９３７ − ３８０ １５．５９３０ − ５２９ １５．５９２９ − ───────────────────────────Table 4 (1) SUS304L ─────────────────────────── Test time 8 hours treatment No treatment (hr) Weight (g) ) Weight (g) ─────────────────────────── 0 15.5943 18.5543 1-18.2378 24 15.5944-44 15.5940-68 15.5937-116 15.5935-164 15.5931-188 15.5931-236 15.5935-284 15.5937-380 15.5930-529 15.5929-────── ─────────────────────
【００２０】[0020]
【表５】 表５ （２）ＳＵＳ３１６Ｌ ─────────────────────────── 試験時間 ８時間処理 無処理 （ｈｒ） 重量（ｇ） 重量（ｇ） ─────────────────────────── ０ １８．２０４５ １８．２１０３ ２４ １８．０６７２ １７．６７３３ ４４ １７．９５２７ − ───────────────────────────Table 5 (2) SUS316L ─────────────────────────── Test time 8 hours treatment No treatment (hr) Weight (g) ) Weight (g) ０ 0 18.2045 18.2103 24 18.0672 17.6733 44 17.9527 − ───────────────────────────
【００２１】[0021]
【表６】 表６−１ （３）ＳＵＳ３１０Ｓ ─────────────────────────── 試験時間 ８時間処理 無処理 （ｈｒ） 重量（ｇ） 重量（ｇ） ─────────────────────────── ０ １７．７９００ １７．５４８９ １ − １７．４１９１ ８ １７．７９０１ − ２４ １７．７８９７ − ４７ １７．７８９７ − ７１ １７．７８９５ − ９５ １７．７８９８ − １１９ １７．７８９６ − １６７ １７．７８９２ − ２１５ １７．７８９４ − ２８７ １７．７８９５ − ３３５ １７．７８８８ − ４５５ １７．７８８９ − ６２８ １７．７８８７ − ───────────────────────────Table 6-1 (3) SUS310S ─────────────────────────── Test time 8 hours treatment No treatment (hr) Weight (G) Weight (g) ０ 0 17.7900 17.5489 1-17.4191 8 17.7901 -24 17.77897 -47 17.7.797 -71 17.7895 -95 17.7798 -119 11.7789 -167 177.7892 -215 17.7894 -287 177.78995 -335 17.7888 -455 17.7889 −628 17.77887 −───────────────────────────
【００２２】[0022]
【表７】 表６−２ （３）ＳＵＳ３１０Ｓ ─────────────────────────── 試験時間 ２４時間処理 無処理 （ｈｒ） 重量（ｇ） 重量（ｇ） ─────────────────────────── ０ １７．９７８６ １７．５４８９ １ − １７．４１９１ ２４ １７．９７８７ − ４４ １７．９７８８ − ６８ １７．９７８５ − １１６ １７．９７８２ − １６４ １７．９７８４ − ２３６ １７．９７８４ − ２８４ １７．９７７９ − ３３５ １７．９７７７ − ───────────────────────────Table 7-2 (3) SUS310S ─────────────────────────── Test time 24 hours treatment No treatment (hr) Weight (G) Weight (g) 0 0 17.9786 17.5489 1-17.4191 24 17.9787 -44 17.9788 -68 17.9785 -116 17.9798 -164 17.9784 -236 17.9784 -284 17.9779 -335 17.9777- ─────────────
【００２３】[0023]
【表８】 表６−３ （３）ＳＵＳ３１０Ｓ ─────────────────────────── 試験時間 ７２時間処理 無処理 （ｈｒ） 重量（ｇ） 重量（ｇ） ─────────────────────────── ０ １７．５７１２ １７．５４８９ １ − １７．４１９１ １９ １７．５７１３ − ６７ １７．５７１０ − １１５ １７．５７１１ − １８７ １７．５７１１ − ２３５ １７．５７０７ − ３５５ １７．５７０７ − ５２８ １７．５７０６ − ───────────────────────────Table 6-3 (3) SUS310S ─────────────────────────── Test time 72 hours treatment No treatment (hr) Weight (G) Weight (g) ０ 0 17.5712 17.5489 1-17.4191 19 17.5713 -67 17.5710 -115 17.5711 -187 17.5711 -235 17.5707 -355 17.5707 -528 17.5706-─────────────────── ────────
【００２４】［実施例３］オートクレーブに濃度２０重
量％の硫酸ヒドロキシルアミン水溶液を入れ、これに実
施例１と同様の試験片（３）を加えた後、オイルバス中
で加熱し、１６０℃の温度で３時間加熱して、試験片に
防食処理を施した。防食処理した試験片について、実施
例１と同様にして耐食試験を行った。得られた結果を表
７に示す。Example 3 A 20% by weight aqueous solution of hydroxylamine sulfate was placed in an autoclave, and the same test piece (3) as in Example 1 was added thereto. The mixture was heated in an oil bath at 160 ° C. The test piece was heated at a temperature for 3 hours to perform an anticorrosion treatment. The test piece subjected to the anticorrosion treatment was subjected to a corrosion resistance test in the same manner as in Example 1. Table 7 shows the obtained results.
【００２５】[0025]
【表９】 表７ （３）ＳＵＳ３１０Ｓ ─────────────────────────── 試験時間 ３時間処理 無処理 （ｈｒ） 重量（ｇ） 重量（ｇ） ─────────────────────────── ０ １７．１０４５ １７．５４８９ １ − １７．４１９１ １２４ １７．１０４１ − ───────────────────────────Table 7 (3) SUS310S ─────────────────────────── Test time 3 hours treatment No treatment (hr) Weight (g) ) Weight (g) {0 17.1045 17.5489 1-17.4191 124 17.1041-} ──────────────────────────
【００２６】［実施例４］オートクレーブに濃度５重量
％の硫酸ヒドロキシルアミン水溶液を入れ、これに実施
例１と同様の試験片（１）または（３）を加えた後、オ
イルバス中で加熱し、１６０℃の温度で８時間加熱し
て、試験片に防食処理を施した。防食処理した試験片に
ついて、実施例１と同様にして耐食試験を行った。得ら
れた結果を表８および９に示す。Example 4 A 5% by weight aqueous solution of hydroxylamine sulfate was placed in an autoclave, and the same test piece (1) or (3) as in Example 1 was added thereto, followed by heating in an oil bath. The test piece was heated at a temperature of 160 ° C. for 8 hours to perform an anticorrosion treatment. The test piece subjected to the anticorrosion treatment was subjected to a corrosion resistance test in the same manner as in Example 1. The results obtained are shown in Tables 8 and 9.
【００２７】[0027]
【表１０】 表８ （１）ＳＵＳ３０４Ｌ ─────────────────────────── 試験時間 ８時間処理 無処理 （ｈｒ） 重量（ｇ） 重量（ｇ） ─────────────────────────── ０ １７．９５８８ １８．５５４３ １ − １８．２３７８ １２４ １７．９５８３ − ───────────────────────────Table 8 (1) SUS304L ─────────────────────────── Test time 8 hours treatment No treatment (hr) Weight (g) ) Weight (g) {0 17.9588 18.5543 1-18.2378 124 17.9583-} ──────────────────────────
【００２８】[0028]
【表１１】 表９ （３）ＳＵＳ３１０Ｓ ─────────────────────────── 試験時間 ８時間処理 無処理 （ｈｒ） 重量（ｇ） 重量（ｇ） ─────────────────────────── ０ ３５．５０７４ １７．５４８９ １ − １７．４１９１ １２４ ３５．５０６６ − ───────────────────────────Table 9 (3) SUS310S ─────────────────────────── Test time 8 hours treatment No treatment (hr) Weight (g) ) Weight (g) {0 35.5507 17.5489 1-17.4191 124 35.5066-} ──────────────────────────
【００２９】表１〜９に示した結果から明らかなよう
に、本発明の方法に従って防食処理したステンレス鋼は
数十時間乃至数百時間、高温の希硫酸中に浸漬しておい
てもその重量が殆ど変化せず、腐食の発生は殆どなかっ
た。一方、防食処理しなかったステンレス鋼について
は。いずれも浸漬後１乃至２４時間のうちにその表面が
黒色化したり、発泡したりして激しく腐食した。これに
より、本発明の防食処理剤および防食処理方法がステン
レス鋼の腐食防止に有効であることがわかる。As is clear from the results shown in Tables 1 to 9, the stainless steel subjected to the anticorrosion treatment according to the method of the present invention weighs several ten hours to several hundred hours even if it is immersed in high-temperature dilute sulfuric acid. Hardly changed, and almost no corrosion occurred. On the other hand, for stainless steel not subjected to anticorrosion treatment. In all cases, the surface blackened or foamed within 1 to 24 hours after immersion, and corroded violently. This shows that the anticorrosion treatment agent and the anticorrosion treatment method of the present invention are effective in preventing corrosion of stainless steel.
【００３０】[0030]
【発明の効果】本発明のヒドロキシルアミン塩からなる
防食処理剤は、ステンレス鋼、特にクロム含有ステンレ
ス鋼の耐食性を顕著に高めるのに有用である。また、本
発明の防食処理方法によれば、ステンレス鋼が酸やアル
カリなどの苛酷な環境下に長時間さらされても腐食を生
じることがなく、よって、ステンレス鋼材料表面の腐食
による不純物の混入や汚染を有効に防止することができ
る。The anticorrosion agent comprising the hydroxylamine salt of the present invention is useful for significantly improving the corrosion resistance of stainless steel, especially chromium-containing stainless steel. Further, according to the anticorrosion treatment method of the present invention, even if stainless steel is exposed to a severe environment such as acid or alkali for a long time, corrosion does not occur, and thus contamination of impurities by corrosion of the stainless steel material surface is prevented. And contamination can be effectively prevented.
Claims (5)
ス鋼表面の防食処理剤。An anticorrosion treating agent for a stainless steel surface, comprising a hydroxylamine salt.
シルアミンもしくはリン酸ヒドロキシルアミンであるこ
とを特徴とする請求項１に記載のヒドロキシルアミン塩
防食処理剤。2. The hydroxylamine salt anticorrosion treatment according to claim 1, wherein the hydroxylamine salt is hydroxylamine sulfate or hydroxylamine phosphate.
量％の範囲で含有する水溶液からなるステンレス鋼表面
の防食処理剤。3. An anticorrosion treating agent for a stainless steel surface, comprising an aqueous solution containing a hydroxylamine salt in the range of 0.2 to 50% by weight.
うちのいずれかの項に記載の防食処理剤に接触させ、５
０℃以上の温度で加熱することを特徴とするステンレス
鋼表面の防食処理方法。4. A stainless steel surface is brought into contact with the anticorrosion treatment agent according to any one of claims 1 to 3,
A method for anticorrosion treatment of stainless steel surface, characterized by heating at a temperature of 0 ° C. or higher.
を特徴とする請求項４に記載のステンレス鋼表面の防食
処理方法。5. The method of claim 4, wherein the heating is performed at a temperature of 50 ° C. to 200 ° C.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000083529A JP2001271184A (en) | 2000-03-24 | 2000-03-24 | Corrosion protection treating agent and method for stainless steel |
| EP01915719A EP1266981A4 (en) | 2000-03-24 | 2001-03-23 | Anticorrosive agent for stainless steel and method of anticorrosive treatment of stainless steel |
| AU42764/01A AU4276401A (en) | 2000-03-24 | 2001-03-23 | Anticorrosive agent for stainless steel and method of anticorrosive treatment ofstainless steel |
| KR1020027012610A KR20030007476A (en) | 2000-03-24 | 2001-03-23 | Anticorrosive agent for stainless steel and method of anticorrosive treatment of stainless steel |
| PCT/JP2001/002319 WO2001071061A1 (en) | 2000-03-24 | 2001-03-23 | Anticorrosive agent for stainless steel and method of anticorrosive treatment of stainless steel |
| CN01809442A CN1429281A (en) | 2000-03-24 | 2001-03-23 | Anticorrosive agent for stainless steel and method of anticorrosive treatment of stainless steel |
| US09/816,386 US20010032658A1 (en) | 2000-03-24 | 2001-03-26 | Corrosion prevention of stainless steel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000083529A JP2001271184A (en) | 2000-03-24 | 2000-03-24 | Corrosion protection treating agent and method for stainless steel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001271184A true JP2001271184A (en) | 2001-10-02 |
Family
ID=18600147
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000083529A Withdrawn JP2001271184A (en) | 2000-03-24 | 2000-03-24 | Corrosion protection treating agent and method for stainless steel |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20010032658A1 (en) |
| EP (1) | EP1266981A4 (en) |
| JP (1) | JP2001271184A (en) |
| KR (1) | KR20030007476A (en) |
| CN (1) | CN1429281A (en) |
| AU (1) | AU4276401A (en) |
| WO (1) | WO2001071061A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103966591B (en) * | 2013-01-30 | 2017-03-29 | 中国科学院金属研究所 | A kind of chemical treatment method for improving austenitic stainless steel corrosion resistance |
| CN105694538A (en) * | 2016-01-05 | 2016-06-22 | 萧县金鹭纺织品有限公司 | Preparation method of low-oil-absorption-amount anticorrosion iron oxide red pigment |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5355427A (en) * | 1976-10-30 | 1978-05-19 | Furukawa Electric Co Ltd | Antioxidation method for metals |
| US4350606A (en) * | 1980-10-03 | 1982-09-21 | Dearborn Chemical Company | Composition and method for inhibiting corrosion |
| US4865653A (en) * | 1987-10-30 | 1989-09-12 | Henkel Corporation | Zinc phosphate coating process |
| CH689307A5 (en) * | 1995-04-13 | 1999-02-15 | Cement Intellectual Property L | Process for both corrosion inhibition and strengthening the bonding properties of reinforcing metals. |
-
2000
- 2000-03-24 JP JP2000083529A patent/JP2001271184A/en not_active Withdrawn
-
2001
- 2001-03-23 AU AU42764/01A patent/AU4276401A/en not_active Abandoned
- 2001-03-23 WO PCT/JP2001/002319 patent/WO2001071061A1/en not_active Ceased
- 2001-03-23 EP EP01915719A patent/EP1266981A4/en not_active Withdrawn
- 2001-03-23 CN CN01809442A patent/CN1429281A/en active Pending
- 2001-03-23 KR KR1020027012610A patent/KR20030007476A/en not_active Ceased
- 2001-03-26 US US09/816,386 patent/US20010032658A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| AU4276401A (en) | 2001-10-03 |
| EP1266981A1 (en) | 2002-12-18 |
| WO2001071061A1 (en) | 2001-09-27 |
| US20010032658A1 (en) | 2001-10-25 |
| KR20030007476A (en) | 2003-01-23 |
| CN1429281A (en) | 2003-07-09 |
| EP1266981A4 (en) | 2006-12-27 |
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