JP2018204107A - Pickling and passive state film treating agent for removing scales and rusts on welding parts of stainless steel pipes and structures - Google Patents
Pickling and passive state film treating agent for removing scales and rusts on welding parts of stainless steel pipes and structures Download PDFInfo
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- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 29
- 239000010935 stainless steel Substances 0.000 title claims abstract description 28
- 238000005554 pickling Methods 0.000 title claims abstract description 22
- 238000003466 welding Methods 0.000 title description 5
- 241000221535 Pucciniales Species 0.000 title 1
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 101
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 44
- 239000001569 carbon dioxide Substances 0.000 claims description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 22
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 22
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 15
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 14
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 14
- 239000000176 sodium gluconate Substances 0.000 claims description 14
- 235000012207 sodium gluconate Nutrition 0.000 claims description 14
- 229940005574 sodium gluconate Drugs 0.000 claims description 14
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 13
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 12
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 12
- 238000005273 aeration Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 abstract description 79
- 238000005406 washing Methods 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 12
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 8
- 238000009434 installation Methods 0.000 abstract description 2
- 230000003472 neutralizing effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 238000006386 neutralization reaction Methods 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 description 37
- 230000007797 corrosion Effects 0.000 description 37
- 238000004458 analytical method Methods 0.000 description 20
- 230000000704 physical effect Effects 0.000 description 17
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 16
- 239000011651 chromium Substances 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 239000004593 Epoxy Substances 0.000 description 12
- 238000002845 discoloration Methods 0.000 description 12
- 150000003839 salts Chemical class 0.000 description 12
- 239000007921 spray Substances 0.000 description 12
- 238000010586 diagram Methods 0.000 description 9
- 239000000383 hazardous chemical Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005530 etching Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229940050410 gluconate Drugs 0.000 description 3
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- -1 dampness Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Description
本発明は、一般鋼鉄（Ｓｔｅｅｌ）に比べて大気中で酸素雰囲気、湿り気、水溶液のような環境的な条件下で錆、腐食が易しく発生しないステンレススチールに関するものであり、より詳細には、ステンレススチールで作られた配管、構造物、プラントなどの設置による溶接部位及び錆が発生する部分を酸洗い（ｐｉｃｋｉｎｇ）と不動態被膜を形成する組成物に関するものである。 The present invention relates to stainless steel that does not easily rust and corrode under atmospheric conditions such as oxygen atmosphere, dampness, and aqueous solution compared to general steel (Steel), and more specifically, stainless steel. The present invention relates to a composition for pickling and forming a passive film on a welded part and a part where rust is generated by installation of pipes, structures, plants, etc. made of steel.
現在造船所と海洋プラントに一番多く使われるステンレススチールはＳＴＳ ３０４とＳＴＳ ３１６Ｌであり、このようなものなどは外部露出による傷、溶接によって酸化された表面層が汚染されるか、または変形されて錆、腐食が発生する。 Currently, the most commonly used stainless steels in shipyards and offshore plants are STS 304 and STS 316L, such as scratches due to external exposure, surface layers oxidized by welding are contaminated or deformed. Rust and corrosion.
正常なステンレススチールはＦｅが基礎成分であり、ＣｒとＮｉを主成分にして少量のＭｏ、Ｔｉ、Ｍｎ、Ｚｒ、Ｎｂ、Ｎなどで組成されている。 Normal stainless steel has Fe as a basic component, and is composed of a small amount of Mo, Ti, Mn, Zr, Nb, N, etc. with Cr and Ni as main components.
現在ステンレススチールは、冷間圧延、溶接、熱処理、酸洗いと不動態被膜処理方法などによって板材、コイル、鋼管、その他の製品で出荷される。 Currently, stainless steel is shipped in plate materials, coils, steel pipes and other products by cold rolling, welding, heat treatment, pickling and passive film processing methods.
また、酸化された表面は、主にＦｅＯ、Ｆｅ３Ｏ４、Ｆｅ２Ｏ３、ＮｉｉＯ、Ｎｉ３Ｏ４、Ｎｉ２Ｏ３、ＣｒＯ３及びＣｒ２Ｏ３などで表面に形成される。 The oxidized surface is mainly formed of FeO, Fe 3 O 4 , Fe 2 O 3 , NiiO, Ni 3 O 4 , Ni 2 O 3 , CrO 3 and Cr 2 O 3 .
このように酸化された表面にＣｒ２Ｏ３とＮＩ２Ｏ３が多くの場合には耐酸性、耐腐食性、耐酸化性が強くなって易しく錆が発生しなくなる。 Acid resistance when the thus oxidized surface Cr 2 O 3 and NI 2 O 3 many, corrosion resistance, is easy rust oxidation resistance is strong not occur.
また、酸化鉄の場合もＦｅ２O３＞Ｆｅ３Ｏ４＞ＦｅＯで耐酸性、耐腐食性、耐酸化性が強い。 Further, in the case of iron oxide, it is Fe 2 O 3 > Fe 3 O 4 > FeO and has strong acid resistance, corrosion resistance, and oxidation resistance.
また、既存の酸洗いおよび不動態化処理剤の場合大部分が酸性雰囲気または酸性溶液で作業をして、危害化学物質が含まれていて、一部中性溶液の場合も原料で使われる酸と塩基性化学物質が危害化学物質で分類されることで、このような物質で製造された製品の場合物質情報に危害化学物質を表記しなければならない。 In addition, most of the existing pickling and passivating agents work in an acidic atmosphere or acidic solution and contain hazardous chemicals. And basic chemical substances are classified as hazardous chemical substances, and in the case of products manufactured with such substances, hazardous chemical substances must be indicated in the substance information.
現在危害化学物質を使用する場合化学物質管理法と産業安全保健法によって化学安全保護装具を着して作業をしなければならないし、防護施設も取り揃えなければならない。 If you currently use hazardous chemicals, you must wear chemical safety protection equipment and have protective facilities in place according to the Chemical Management Law and the Industrial Safety and Health Law.
特に、造船とプラント産業では酸洗いおよび不動態化作業時に区域を統制して他の作業と併行作業をしない。 In particular, the shipbuilding and plant industries control the area during pickling and passivating operations and do not co-operate with other operations.
また、船舶建造と海洋プラントを建設する時にステンレススチール配管と構造物らは船舶や現場で設置し、設置された配管と構造物は汚染されるか、または溶接によって腐食が発生することで酸洗いおよび不動態被膜処理をしなければならない。 Stainless steel pipes and structures are installed on ships and in the field when building ships and offshore plants, and installed pipes and structures are contaminated or pickled due to corrosion caused by welding. And a passive film treatment must be applied.
一般に、酸洗いおよび不動態化剤で硝酸、硫酸、塩酸とフッ酸が混合された強い酸性溶液を使って処理し、この時酸性溶液剤は底表面に垂れ下がるか、または洗浄作業時に洗浄液が底に垂れ下がれば、一般に塗装されたエポキシ樹脂と反応して変色されるか、または変形が発生して再び塗装をする場合がたびたび発生する。 In general, it is treated with a pickling and passivating agent using a strong acidic solution in which nitric acid, sulfuric acid, hydrochloric acid and hydrofluoric acid are mixed. If it hangs down, it generally changes its color by reacting with a painted epoxy resin, or it is often deformed and painted again.
また、強い酸性剤であるので、塩基性剤で中和処理をした後清い水で最終水洗い処理をしなければならないし、危害化学物質を使用することで作業場を統制しなければならないし、他の作業と併行ができなくて、化学物質安全保護装備と防護物質も取り揃えなければならない。 In addition, since it is a strong acid agent, it must be neutralized with a basic agent and then washed with clean water, and the workplace must be controlled by using hazardous chemicals. Chemical safety protection equipment and protective substances must also be prepared.
本発明は、酸洗いおよび不動態化剤でｐＨ６．９〜７．１である中性剤を使用することで、工程上塩基性剤で中和処理する必要がないし、すぐ水洗い処理ができて工程が短縮されるようにするためのものである。 In the present invention, a neutral agent having a pH of 6.9 to 7.1 is used as a pickling and passivating agent, so that it is not necessary to neutralize with a basic agent in the process and can be immediately washed with water. This is to shorten the process.
また、中性剤であるため樹脂と反応しなくて、塗装部分が変色と変形される現象が発生しなくて使用が便利にさせるためのものである。 Further, since it is a neutral agent, it does not react with the resin, and the phenomenon that the painted part is discolored and deformed does not occur, so that it can be used conveniently.
また、製品規格は原料で使われる物質情報に危害化学物質が含まれておらず、化学物質管理法、危険物安全管理法、産業安全保健法に規制を受けることなく便利に作業するためのものである。 In addition, product standards do not include hazardous chemical substances in the information on substances used in raw materials, and are intended for convenient work without being regulated by the Chemical Substance Management Law, Dangerous Goods Safety Management Law, and Industrial Safety and Health Law. It is.
このために本発明は、ステンレススチール配管と構造物の溶接部位のスケールおよび錆をとり除くための酸洗いおよび不動態被膜処理剤であって、リン酸水素二ナトリウム２〜１０重量部、グルコン酸ナトリウム１〜５重量部、トリポリリン酸ナトリウム０．５〜３重量部などの塩基性水溶液にリン酸二水素ナトリウム１．１〜４．５重量部を反応させてｐＨ６．９〜７．１に中性化し、二酸化炭素が除去された空気を曝気して溶存酸素量を増加させて酸化還元電位を１７０〜３１０ｍＶにする中性剤である。 For this purpose, the present invention is a pickling and passivating film treatment agent for removing scale and rust at weld sites of stainless steel pipes and structures, 2-10 parts by weight of disodium hydrogen phosphate, sodium gluconate 1 to 5 parts by weight, sodium tripolyphosphate 0.5 to 3 parts by weight and the like are reacted with sodium dihydrogen phosphate 1.1 to 4.5 parts by weight to neutralize to pH 6.9 to 7.1 It is a neutral agent that aerated the air from which carbon dioxide has been removed to increase the amount of dissolved oxygen to bring the redox potential to 170-310 mV.
したがって本発明は、ステンレススチール配管と構造物の溶接部位のスケールおよび錆を除去するための酸洗いおよび不動態化処理時に中性剤の組成物で使用することで危害和合物質の使用に他の問題点を解消することはもちろん、他の作業と併行して作業をすることができ、また、中性剤であるためエポキシ樹脂で塗装されて底に落ちても変色と変形が発生しない長所があるものである。 Therefore, the present invention is useful in the use of hazardous compounds by using a neutral agent composition during pickling and passivation treatment to remove the scale and rust of the weld sites of stainless steel piping and structures. Not only can the problem be solved, it can also be performed in parallel with other work, and since it is a neutral agent, it has the advantage that it will not discolor and deform even if it falls to the bottom because it is painted with epoxy resin. There is something.
そして、既存の工程では酸液塗布、水洗い、塩基性液塗布、水洗いなどで多くの段階で作業をしなければならない不便さを中性剤塗布後水洗いだけであり工程が簡単で作業時間も短縮されることができる長所があるものである。 And in the existing process, the inconvenience that must be worked in many stages such as acid solution application, water wash, basic solution application, water wash, etc. is only water wash after applying neutral agent, the process is simple and the work time is also shortened There are advantages that can be done.
本発明を実施するための最良の形態は、水にリン酸水素二ナトリウム２〜１０重量部とグルコン酸ナトリウム１〜５重量部と、トリポリリン酸ナトリウム０．５〜３重量部を含むようにして塩基性水溶液を得て、前記塩基性水溶液にリン酸二水素ナトリウム１．１〜４．５重量部を反応させてｐｈ６．９〜７．１に中性化した後、二酸化炭素が除去された空気を曝気して溶存酸素量を増加させ、酸化還元電位を１７０ｍＶ〜３１０ｍＶにしてステンレススチール配管と構造物の溶接部位のスケールおよび錆をとり除くための酸洗いおよび不動態被膜処理剤である。 The best mode for carrying out the present invention is such that water contains 2 to 10 parts by weight of disodium hydrogen phosphate, 1 to 5 parts by weight of sodium gluconate, and 0.5 to 3 parts by weight of sodium tripolyphosphate. After obtaining an aqueous solution, the basic aqueous solution was reacted with 1.1 to 4.5 parts by weight of sodium dihydrogen phosphate to neutralize to ph 6.9 to 7.1, and then the air from which carbon dioxide was removed was removed. It is a pickling and passivating film treatment agent for removing the scale and rust of stainless steel pipes and structures by increasing the amount of dissolved oxygen by aeration and setting the redox potential to 170 mV to 310 mV.
本発明は、中性剤であり、既存の酸性剤に比べて作業工程が簡単で危害化学物質を使わない親環境的なものであることを特徴とする。 The present invention is a neutral agent, characterized in that it has a simpler work process than existing acid agents and is environmentally friendly without using hazardous chemicals.
特に、中性剤を腐食が発生した部位に塗布すれば、リン酸塩、グルコン酸塩などが腐食で発生した酸化鉄、水酸化鉄などが反応して表面に錆が除去されてクロム、ニッケル、鉄などが溶存酸素と反応して表面に酸化物層が形成されて不動態被膜を形成する。 In particular, if a neutral agent is applied to a site where corrosion has occurred, phosphate, gluconate, etc. react with iron oxide, iron hydroxide, etc. generated by the corrosion to remove rust on the surface, and chromium, nickel Iron or the like reacts with dissolved oxygen to form an oxide layer on the surface to form a passive film.
リン酸二ナトリウム（Disodium Hydrogen Phosphate、Ｎａ２ＨＰＯ４）１０重量部、グルコン酸ナトリウム（Sodium Gluconate、Ｃ６Ｈ１１ＮａＯ７）３重量部、トリポリリン酸ナトリウム（Sodium Tripolyphosphate、Ｎａ５Ｐ３Ｏ１０）１重量部、水８１．９重量部である塩基性水溶液にリン酸二水素ナトリウム（Monobasic sodium phosphate、ＮａＨ２ＰＯ４）４．１重量部を反応させて中性剤を製造する。 Disodium phosphate (Disodium Hydrogen Phosphate, Na 2 HPO 4 ) 10 parts by weight, sodium gluconate (Sodium Gluconate, C 6 H 11 NaO 7 ) 3 parts by weight, sodium tripolyphosphate (Sodium Tripolyphosphate, Na 5 P 3 O 10 ) A neutral agent is produced by allowing 4.1 parts by weight of sodium dihydrogen phosphate (NaH 2 PO 4 ) to react with a basic aqueous solution of 1 part by weight and 81.9 parts by weight of water.
前記のように製造された中性剤は、ｐＨ７．１でありＯＲＰ（Oxidation Reduction Potential meter）測定機を使って酸化還元電位を測定した結果−２１０ｍＶであり、前記のように製造された中性剤をエポキシで塗装された部位に塗布して１週間後に確認した結果、変色と変形がない。 The neutral agent produced as described above has a pH of 7.1, and the result of measuring the oxidation-reduction potential using an ORP (Oxidation Reduction Potential meter) measuring machine is -210 mV, and the neutral agent produced as described above. As a result of applying the agent to the part painted with epoxy and confirming it one week later, there is no discoloration and deformation.
このような物性は表１で確認される。 Such physical properties are confirmed in Table 1.
前記のように製造された中性剤の酸洗いおよび不動態被膜の程度を調べるための試片で船舶配管（ＳＴＳ３０４、オーステナイト系ステンレススチール）に溶接によって腐食が発生した部分の一部分を採取してＳＡＭ（Scanning Auger Microscope、走査型オージェ電子顕微鏡）分析をした結果が図２に現われている。 Using a test piece for examining the degree of pickling and passivating film of the neutral agent produced as described above, a part of the portion where corrosion was generated by welding on ship piping (STS304, austenitic stainless steel) was collected. FIG. 2 shows the result of SAM (Scanning Auger Microscope) analysis.
前記図２で確認することができるように表面にはＣ（６０％）、Ｆｅ（１０％）、Ｃａ（４％）、酸素（２６％）だけが存在して表面で２８nm、内側でＣｒ、Ｎｉが現われる。 As can be seen in FIG. 2, only C (60%), Fe (10%), Ca (4%), and oxygen (26%) are present on the surface, 28 nm on the surface, Cr on the inside, Ni appears.
すなわち、２８nmの腐食層が形成された配管である。 That is, it is a pipe in which a 28 nm corrosion layer is formed.
前記配管に前記のように製造された中性剤を塗布して表面に異物（水酸化物、酸化物、油など）が反応して水洗い後配管表面がきれいな状態を反応終了時間で見て測定した結果、略１４０分が所要される。 Apply the neutral agent produced as described above to the pipe and measure the condition that the surface of the pipe is clean after washing with water and foreign matter (hydroxide, oxide, oil, etc.) reacts on the surface. As a result, approximately 140 minutes are required.
洗浄された配管の一部分を試片で採取してＳＡＭ（走査型オージェ電子顕微鏡）分析をした結果が図３である。 FIG. 3 shows the result of SAM (scanning Auger electron microscope) analysis by collecting a part of the cleaned pipe with a test piece.
前記図３で確認することができるように表面でＣの含有量が５３％、Ｃｒの含有量が６％、Ｎｉの含有量が３％、Ｆｅの含有量が７％、Ｃａの含有量は６．５％、酸素の含有量が２４．５％である。 As can be seen in FIG. 3, the content of C on the surface is 53%, the content of Cr is 6%, the content of Ni is 3%, the content of Fe is 7%, and the content of Ca is It is 6.5% and the oxygen content is 24.5%.
すなわち、Ｃの含有量が少ないほど酸洗いによる蝕刻が良いことを見られるか、Ｃの含有量が５３％であることを見て酸洗いによる蝕刻が少なくて、酸化層が略８０nmの厚さで存在することを確認することができる。 That is, it can be seen that the smaller the C content, the better the etching by pickling, or the less the etching by pickling because the C content is 53%, and the oxide layer has a thickness of about 80 nm. Can be confirmed.
また、金属の総含有量が２２．５％で酸素の含有量２４．５％と比べると略１:１の割合で存在することで表面の酸化物はＦｅＯ、ＣｒＯ、ＮｉＯで存在する不動態被膜が形成される。 Further, since the total metal content is 22.5% and the oxygen content is 24.5%, the surface oxides are FeO, CrO, and NiO. A film is formed.
前記試片（ステンレススチール）の不動態被膜に対する耐腐食性を調べるためにＪＩＳ Ｈ８５０２規格の塩水噴霧テスト結果を図４で確認することができるように８０時間後錆が発生されたことを確認することができるし、不動態被膜が不良水準である。 In order to investigate the corrosion resistance of the specimen (stainless steel) to the passive film, it is confirmed that rust was generated after 80 hours so that the salt spray test result of JIS H8502 standard can be confirmed in FIG. And the passive film is at a poor level.
（比較例１）
リン酸２０重量部、クエン酸５重量部、グルコン酸ナトリウム５重量部、水７０重量部を混合して製造した酸性剤を製造して物性を確認した結果ｐＨ１．２であり酸化還元電位は１２０ｍＶであり、この酸性剤をエポキシで塗装された部位に塗布した結果、１時間後に変色が発生し、１週後には変形が発生される。
(Comparative Example 1)
As a result of producing an acidic agent prepared by mixing 20 parts by weight of phosphoric acid, 5 parts by weight of citric acid, 5 parts by weight of sodium gluconate, and 70 parts by weight of water, the pH was 1.2 and the oxidation-reduction potential was 120 mV. As a result of applying this acidic agent to the part painted with epoxy, discoloration occurs after 1 hour and deformation occurs after 1 week.
したがって、現場で酸性剤を使って配管の酸洗いおよび不動態被膜作業をする時、底に垂れ下がることを防止するさまざまな措置を取らなければならない不便さがあって、作業衣効率が相当に落ちる。このような物性を表１に示した。 Therefore, when pickling pipes and using a passive film with acid agents on site, there are inconveniences that must be taken to prevent drooping to the bottom, and work clothes efficiency is considerably reduced. . Such physical properties are shown in Table 1.
比較例１によって製造された酸性剤を使って腐食が発生した配管に酸性剤を塗布して５０分後に水で洗浄して、水酸化ナトリウム２重量部、水９８重量部の塩基性剤を使って配管に再び塗布した後３０分後に水で洗浄した配管の一部を採取してＳＡＭを分析した結果が図５である。 An acidic agent was applied to a pipe where corrosion occurred using the acidic agent produced in Comparative Example 1, and washed with water after 50 minutes, and a basic agent containing 2 parts by weight of sodium hydroxide and 98 parts by weight of water was used. FIG. 5 shows the result of analyzing a SAM by collecting a part of the pipe washed with water 30 minutes after being applied again to the pipe.
図５で確認することができるように表面でＣの含有量が４５％、Ｃｒの含有量が５．５％、Ｎｉの含有量が３％、Ｆｅの含有量が１０％、酸素（Ｏ）の含有量が２９．５％、Ｃａの含有量が７％である。 As can be seen in FIG. 5, the C content on the surface is 45%, the Cr content is 5.5%, the Ni content is 3%, the Fe content is 10%, oxygen (O) The content of is 29.5%, and the content of Ca is 7%.
Ｃの含有量４５％で腐食された試片（６０％）に比べて蝕刻がたくさんなされたことを確認することができるし、金属の総含有量が２５．５％で酸素の含有量２９．５％と比べると酸素／金属の割合は１．１４で存在することで、表面の酸化物は少量のＣｒ２Ｏ３、Ｎｉ２Ｏ３とＦｅ２Ｏ３存在して大部分はＦｅＯ、ＣｒＯ、ＮｉＯで存在する不動態被膜が形成される。 It can be confirmed that a lot of etching was performed as compared with the specimen (60%) corroded at a C content of 45%, and the total metal content was 25.5% and the oxygen content was 29. Compared to 5%, the oxygen / metal ratio is present at 1.14, the surface oxide is present in small amounts of Cr 2 O 3 , Ni 2 O 3 and Fe 2 O 3, most of which are FeO, CrO. A passive film present with NiO is formed.
酸化層が存在する不動態被膜の厚さは略８〜１８ｎｍである。 The thickness of the passive film in which the oxide layer is present is approximately 8 to 18 nm.
試片をステンレススチールの不動態被膜に対する耐腐食性を調べるためにＪＩＳ Ｈ８５０２規格の塩水噴霧テスト結果を図６で確認することができるように２００時間後に少量の錆が発生されたことを確認することができるし、不動態被膜が普通水準である。 In order to check the corrosion resistance of the specimen against the stainless steel passive film, the salt spray test result of JIS H8502 standard can be confirmed in FIG. And the passive film is at a normal level.
（比較例２）
酒石酸５重量部、チオ乳酸５重量部、クエン酸１０重量部、水６０重量部である酸性溶液に水酸化カリウム２０重量部を反応させて中性剤を製造する。
(Comparative Example 2)
A neutral agent is produced by reacting 5 parts by weight of tartaric acid, 5 parts by weight of thiolactic acid, 10 parts by weight of citric acid and 60 parts by weight of water with 20 parts by weight of potassium hydroxide.
前記のように本実施例によって製造された中性剤の物性を確認した結果ｐＨ７．３であり酸化還元電位は−１９０ｍＶであり、塗装部位に塗布した結果１週後にも変形が発生しない。 As described above, as a result of confirming the physical properties of the neutral agent produced according to this example, the pH was 7.3, the oxidation-reduction potential was -190 mV, and no deformation occurred even after one week as a result of application to the painted site.
このような物性を表１に示したし、原料に危害化学物質である水酸化カリウムを使ったことが短所である。 Such physical properties are shown in Table 1, and the disadvantage is that potassium hydroxide, which is a hazardous chemical, is used as a raw material.
このような本実施例によって製造された中性剤で腐食が発生した配管に中性剤を塗布して１１０分後に水で洗浄して、配管の一部を採取してＳＡＭ分析をした結果が図７である。 The result of having applied the neutral agent to the pipe produced by this embodiment and corroded with the neutral agent, washing with water 110 minutes later, collecting a part of the pipe, and performing the SAM analysis. FIG.
図７で確認することができるように表面でＣの含有量が６０％、Ｃｒは存在しないで、Ｎｉの含有量が１％、Ｆｅの含有量が８％、Ｃａの含有量が７％、酸素（Ｏ）の含有量が２４％である。 As can be seen in FIG. 7, the C content is 60% on the surface, Cr is not present, the Ni content is 1%, the Fe content is 8%, the Ca content is 7%, The content of oxygen (O) is 24%.
すなわち、表面にＣの含有量が６０％で酸洗いによる蝕刻が発生しないし、不動態被膜の耐腐食性を左右するＣｒがなくて、Ｎｉも少量存在して表面に易しく錆が発生する。 That is, when the C content is 60% on the surface, etching by pickling does not occur, there is no Cr that affects the corrosion resistance of the passive film, and there is a small amount of Ni, and rust is easily generated on the surface.
試片の不動態被膜に対する耐腐食性を調べるためにＪＩＳ Ｈ８５０２規格の塩水噴霧テスト結果を図８で確認することができるように５０時間後に錆が発生されたことを確認することができるし、不動態被膜が不良である。 In order to check the corrosion resistance of the specimen to the passive film, the salt spray test result of JIS H8502 standard can be confirmed in FIG. Passive film is poor.
実施例１と同一な方法で中性剤を製造した後中性剤１００ｇに二酸化炭素が除去された空気を１００ｍｌ／ｍｉｎの流速で略３０分を曝気して酸化還元電位が６ｍＶで上昇された中性剤が製造される。 After producing the neutral agent by the same method as in Example 1, the redox potential was increased at 6 mV by aeration of approximately 30 minutes at a flow rate of 100 ml / min with air from which carbon dioxide had been removed to 100 g of the neutral agent. A neutral agent is produced.
空気中の二酸化炭素は０．０３〜０．０５％存在し、二酸化炭素は酸素より中性剤に溶解性が良くて酸素溶解を干渉する現象が発生することで、空気中に二酸化炭素をとり除いて中性剤に曝気をする。 Carbon dioxide in the air is present in an amount of 0.03 to 0.05%. Carbon dioxide is more soluble in neutral agents than oxygen and causes a phenomenon that interferes with oxygen dissolution. Except for neutralizing agent.
二酸化炭素のとり除く方法は、液状消石灰がいっぱいになった連続式反応器を通過させてとり除く。 Carbon dioxide is removed by passing it through a continuous reactor filled with liquid slaked lime.
本実施例によって製造された中性剤に空気を曝気する前に自動吸入式二酸化炭素測定機を使って二酸化炭素がないことを確認した後空気を曝気する。 Before aeration of air to the neutral agent produced in this example, air is aerated after confirming the absence of carbon dioxide using an automatic inhalation type carbon dioxide measuring machine.
このように本実施例によって製造された中性剤をエポキシで塗装された部位に塗布して１週間後に確認した結果変色と変形がない。 Thus, the neutral agent manufactured by the present Example was apply | coated to the site | part coated with the epoxy, and as a result confirmed after one week, there is no discoloration and a deformation | transformation.
このような物性を表１に示した。 Such physical properties are shown in Table 1.
腐食が発生した配管に本実施例によって製造された中性剤を塗布して表面に異物が反応されて水洗い後配管表面がきれいな状態を反応終了時間で見て測定した結果略１００分が所要されて実施例１より４０分ぐらい短縮される。 As a result of applying the neutral agent produced in this example to the pipe where corrosion has occurred and measuring the reaction completion time after the water is washed with water and the surface of the pipe is clean after washing, approximately 100 minutes are required. Thus, it is shortened by about 40 minutes from the first embodiment.
洗浄された配管の一部分を試片で採取してＳＡＭ分析をした結果が図９である。 FIG. 9 shows the result of SAM analysis by collecting a part of the cleaned pipe with a test piece.
図９で確認することができるように表面においてＣの含有量が５０％、Ｃｒの含有量が５．５％、Ｎｉの含有量が３％、Ｆｅの含有量が１０％、Ｃａの含有量が５％、Ｏの含有量が２６．５％である。 As can be seen in FIG. 9, the C content is 50%, the Cr content is 5.5%, the Ni content is 3%, the Fe content is 10%, and the Ca content on the surface. Is 5% and the O content is 26.5%.
すなわち、表面にＣの含有量が５０％で酸洗いによる蝕刻が少なく発生したことを確認することができるし、金属の総含有量が２３．５％で酸素の含有量２６．５％と比べると酸素／金属の割合は１．１３で存在することで表面に酸化物は略２０％以上はＭ２Ｏ３形態であるＣｒ２Ｏ３、Ｎｉ２Ｏ３とＦｅ２Ｏ３存在して大部分はＦｅＯ、ＣｒＯ、ＮｉＯで存在する不動態被膜が形成される。 That is, it can be confirmed that the surface has a C content of 50% and little etching by pickling, and the total metal content is 23.5%, which is compared with the oxygen content of 26.5%. And the ratio of oxygen / metal is 1.13, and on the surface, approximately 20% or more of the oxide is present in the form of M 2 O 3 Cr 2 O 3 , Ni 2 O 3 and Fe 2 O 3. A passive film is formed in which portions are made of FeO, CrO, and NiO.
試片の不動態被膜に対する耐腐食性を調べるためにＪＩＳ Ｈ８５０２規格の塩水噴霧テスト結果を図１０で確認することができるように１５０時間後に少量の錆が発生されたことを確認することができるし、不動態被膜が普通水準である。 In order to examine the corrosion resistance of the specimen to the passive film, it can be confirmed that a small amount of rust was generated after 150 hours so that the salt spray test result of JIS H8502 standard can be confirmed in FIG. However, the passive film is at a normal level.
実施例１と同一な方法で中性剤を製造した後、この中性剤１００ｇに二酸化炭素が除去された空気を１００ｍｌ／ｍｉｎの流速で略２時間を曝気すると酸化還元電位が９０ｍＶに上昇された中性剤が製造される。 After producing a neutral agent by the same method as in Example 1, when 100 g of this neutral agent was aerated with carbon dioxide removed at a flow rate of 100 ml / min for about 2 hours, the oxidation-reduction potential was raised to 90 mV. A neutral agent is produced.
本実施例によって製造された中性剤をエポキシで塗装された部位に塗布して１週間後に確認した結果変色と変形がない。 As a result of applying the neutral agent produced in this example to the part painted with epoxy and confirming it one week later, there is no discoloration or deformation.
このような物性を表１に示した。 Such physical properties are shown in Table 1.
腐食が発生した配管に本実施例によって製造された中性剤を塗布して表面に異物が反応されて水洗い後配管表面がきれいな状態になるには略９０分が所要され、実施例１より５０分が短縮される。 It takes about 90 minutes for the surface of the pipe to be clean after washing with water by applying the neutral agent produced in this example to the pipe where corrosion has occurred and washing the surface with water. Shortened.
洗浄された配管の一部分を試片で採取してＳＡＭ分析をした結果が図１１である。 FIG. 11 shows the result of SAM analysis by collecting a part of the cleaned pipe with a test piece.
図１１で確認することができるように表面でＣの含有量が３４％、Ｃｒの含有量が７．５％、Ｎｉの含有量が３．５％、Ｆｅの含有量が１２％、Ｃａの含有量が７％、Ｏの含有量が３６％である。 As can be seen in FIG. 11, the C content on the surface is 34%, the Cr content is 7.5%, the Ni content is 3.5%, the Fe content is 12%, the Ca content The content is 7% and the O content is 36%.
すなわち、表面にＣの含有量が３４％で酸洗いによる蝕刻がたくさん発生したことを確認することができるし、金属の総含有量が３０％で酸素の含有量３６％と比べると酸素／金属の割合は、１．２で存在することで表面に酸化物は略４０％以上がＣｒ２Ｏ３、Ｎｉ２Ｏ３とＦｅ２Ｏ３存在して一部分はＦｅＯ、ＣｒＯ、ＮｉＯで存在する不動態被膜が形成される。 In other words, it can be confirmed that a large amount of etching due to pickling occurred when the C content was 34% on the surface, and the oxygen / metal content was 30% compared with the oxygen content of 36%. The ratio is about 1.2%, so that approximately 40% or more of the oxide on the surface is present in Cr 2 O 3 , Ni 2 O 3 and Fe 2 O 3 , and part of the oxide is present in FeO, CrO, NiO. A dynamic film is formed.
試片の不動態被膜に対する耐腐食性を調べるためにＪＩＳ Ｈ８５０２規格の塩水噴霧テスト結果を図１２で確認することができるように３００時間後に錆が発生されて、不動態被膜が普通水準である。 In order to check the corrosion resistance of the specimen to the passive film, rust is generated after 300 hours so that the salt spray test result of JIS H8502 standard can be confirmed in FIG. 12, and the passive film is at a normal level. .
実施例１と同一な方法で中性剤を製造した後、この中性剤１００ｇに二酸化炭素が除去された空気を１００ｍｌ／ｍｉｎの流速で略４時間を曝気すると酸化還元電位が１７０ｍＶに上昇された中性剤が製造される。 After producing a neutral agent by the same method as in Example 1, when 100 g of this neutral agent was aerated with carbon dioxide removed at a flow rate of 100 ml / min for about 4 hours, the oxidation-reduction potential was increased to 170 mV. A neutral agent is produced.
本実施例によって製造された中性剤をエポキシで塗装された部位に塗布して１週間後に確認した結果、変色と変形がない。 As a result of applying the neutral agent produced by this example to the part painted with epoxy and confirming it after one week, there is no discoloration and deformation.
このような物性を表１に示した。 Such physical properties are shown in Table 1.
腐食が発生した配管に本実施例によって製造された中性剤を塗布して表面に異物が反応されて水洗い後配管表面がきれいな状態は略７０分が所要され、実施例１より７０分が短縮される。 Applying the neutral agent produced in this example to the pipe where corrosion has occurred and reacting foreign matter on the surface and washing the water with a clean pipe surface requires approximately 70 minutes, which is 70 minutes shorter than in Example 1. Is done.
洗浄された配管の一部分を試片で採取してＳＡＭ分析をした結果が図１３である。 FIG. 13 shows the result of SAM analysis by collecting a part of the cleaned pipe with a test piece.
図１３で確認することができるように表面でＣの含有量が２７％、Ｃｒの含有量が８％、Ｎｉの含有量が４％、Ｆｅの含有量が１３．５％、Ｃａの含有量が３．５％、Ｏの含有量が４４％である。 As can be seen in FIG. 13, the C content is 27%, the Cr content is 8%, the Ni content is 4%, the Fe content is 13.5%, and the Ca content on the surface. Is 3.5% and the O content is 44%.
すなわち、表面にＣの含有量が２７％で酸洗いによる蝕刻がたくさん発生したことが確認され、金属の総含有量が２９％で酸素の含有量４４％と比べると酸素／金属の割合は１．５で存在することで、表面に酸化物は大部分がＣｒ２Ｏ３、Ｎｉ２Ｏ３とＦｅ２Ｏ３存在する不動態被膜が形成される。 That is, it was confirmed that a large amount of etching due to pickling was generated when the C content was 27% on the surface, and the oxygen / metal ratio was 1 as compared with the total metal content of 29% and the oxygen content of 44%. .5, a passive film in which most of the oxide is Cr 2 O 3 , Ni 2 O 3 and Fe 2 O 3 is formed on the surface.
試片の不動態被膜に対する耐腐食性を調べるためにＪＩＳ Ｈ８５０２規格の塩水噴霧テスト結果を図１４で確認することができるように３００時間後に錆が発生されないし、不動態被膜が良好である。 In order to check the corrosion resistance of the specimen to the passive film, rust is not generated after 300 hours so that the salt spray test result of JIS H8502 standard can be confirmed in FIG. 14, and the passive film is good.
実施例１と同一な方法で中性剤を製造した後、この中性剤１００ｇに二酸化炭素が除去された空気を１００ｍｌ／ｍｉｎの流速で略１０時間を曝気すると、酸化還元電位が２７８ｍＶに上昇された中性剤が製造される。 After producing a neutral agent by the same method as in Example 1, when 100 g of this neutral agent was aerated with carbon dioxide removed at a flow rate of 100 ml / min for about 10 hours, the oxidation-reduction potential increased to 278 mV. A neutral agent is produced.
本実施例によって製造された中性剤をエポキシで塗装された部位に塗布し、１週間後に確認した結果変色と変形がない。 As a result of applying the neutral agent produced by this example to the part painted with epoxy and confirming it after one week, there is no discoloration and deformation.
このような物性を表１に示した。 Such physical properties are shown in Table 1.
腐食が発生した配管に本実施例によって製造された中性剤を塗布して表面に異物が反応されて水洗い後配管表面がきれいな状態は略７０分が所要される。 It takes about 70 minutes for the surface of the pipe to be clean after washing with water by applying the neutral agent produced in this embodiment to the pipe where corrosion has occurred and reacting foreign matters on the surface.
洗浄された配管の一部分を試片で採取してＳＡＭ分析をした結果が実施例４と類似な形態と成分を見せて、不動態被膜に対する耐腐食性を調べるためにＪＩＳ Ｈ８５０２規格の塩水噴霧テスト結果も実施例４と等しく３００時間後に錆が発生されないし、不動態被膜が良好である。 A sample of a part of the cleaned pipe was collected with a specimen and the result of SAM analysis showed a form and components similar to those in Example 4 to examine the corrosion resistance against the passive film. As a result, rust is not generated after 300 hours as in Example 4, and the passive film is good.
リン酸水素二ナトリウム１重量部、グルコン酸ナトリウム３重量部、トリポリリン酸ナトリウム１重量部、水９４．３重量部である塩基性水溶液にリン酸二水素ナトリウム０．７重量部を反応させてｐＨ６．９の中性剤を製造する。 A basic aqueous solution of 1 part by weight of disodium hydrogen phosphate, 3 parts by weight of sodium gluconate, 1 part by weight of sodium tripolyphosphate and 94.3 parts by weight of water was reacted with 0.7 part by weight of sodium dihydrogen phosphate to pH 6 Produce 9 neutral agents.
本実施例によって製造された中性剤１００ｇに二酸化炭素が除去された空気を１００ｍｌ／ｍｉｎの流速で略１０時間を曝気すると酸化還元電位が２９３ｍＶに上昇された中性剤が製造される。 When neutralized 100 g produced in this example is aerated with air from which carbon dioxide has been removed at a flow rate of 100 ml / min for about 10 hours, a neutralized agent having a redox potential increased to 293 mV is produced.
このような物性を表１に示した。 Such physical properties are shown in Table 1.
腐食が発生した配管に本実施例によって製造された中性剤を塗布して表面に異物が反応される程度を確認した結果１０時間が経っても異物が除去されない。 As a result of applying the neutral agent manufactured by the present example to the pipe where corrosion occurred and confirming the extent of the foreign substance reacting on the surface, the foreign substance is not removed even after 10 hours.
このような現象はリン酸塩成分が少なくて反応が起きない。 Such a phenomenon causes no reaction due to a small amount of phosphate component.
リン酸水素二ナトリウム２重量部、グルコン酸ナトリウム３重量部、トリポリリン酸ナトリウム１重量部、水９２．９重量部である塩基性水溶液にリン酸二水素ナトリウム１．１重量部を反応させてｐＨ７．０の中性剤を製造する。 A basic aqueous solution of 2 parts by weight of disodium hydrogen phosphate, 3 parts by weight of sodium gluconate, 1 part by weight of sodium tripolyphosphate and 92.9 parts by weight of water was reacted with 1.1 parts by weight of sodium dihydrogen phosphate to pH 7 0. Neutral agent is produced.
本実施例によって製造された中性剤１００ｇに二酸化炭素が除去された空気を１００ｍｌ／ｍｉｎの流速で略１０時間を曝気すると、酸化還元電位が２８３ｍＶに上昇された中性剤が製造される。 When air from which carbon dioxide has been removed is aerated at a flow rate of 100 ml / min for about 10 hours with 100 g of the neutral agent produced according to this example, a neutral agent having a redox potential increased to 283 mV is produced.
このような物性を表１に示した。 Such physical properties are shown in Table 1.
本実施例によって製造された中性剤をエポキシで塗装された部位に塗布して１週間後に確認した結果変色と変形がない。 As a result of applying the neutral agent produced in this example to the part painted with epoxy and confirming it one week later, there is no discoloration or deformation.
腐食が発生した配管に本実施例によって製造された中性剤を塗布して表面に異物が反応されて水洗い後配管表面のきれいな状態は略９０分が所要される。 About 90 minutes are required for a clean state of the pipe surface after washing with water by applying the neutral agent produced in this embodiment to the pipe where corrosion has occurred and reacting foreign matter on the surface.
洗浄された配管の一部分を試片で採取してＳＡＭ分析をした結果が実施例４と類似な形態と成分を見せて、不動態被膜に対する耐腐食性を調べるためにＪＩＳ Ｈ８５０２規格の塩水噴霧テスト結果も実施例４と等しく３００時間後にも錆が発生せず、不動態被膜が良好である。 A sample of a part of the cleaned pipe was collected with a specimen and the result of SAM analysis showed a form and components similar to those in Example 4 to examine the corrosion resistance against the passive film. The result is the same as in Example 4, and no rust is generated after 300 hours, and the passive film is good.
リン酸水素二ナトリウム５重量部、グルコン酸ナトリウム３重量部、トリポリリン酸ナトリウム１重量部、水８８．８重量部である塩基性水溶液にリン酸二水素ナトリウム２．２重量部を反応させてｐＨ７．０の中性剤を製造する。 A basic aqueous solution of 5 parts by weight of disodium hydrogen phosphate, 3 parts by weight of sodium gluconate, 1 part by weight of sodium tripolyphosphate and 88.8 parts by weight of water was reacted with 2.2 parts by weight of sodium dihydrogen phosphate to pH 7 0. Neutral agent is produced.
本実施例によって製造された中性剤１００ｇに二酸化炭素が除去された空気を１００ｍｌ／ｍｉｎの流速で略１０時間を曝気すると、酸化還元電位が２８０ｍＶに上昇された中性剤が製造される。 When air from which carbon dioxide has been removed is aerated at a flow rate of 100 ml / min for approximately 10 hours with 100 g of the neutral agent produced according to this example, a neutral agent having a redox potential increased to 280 mV is produced.
このような物性を表１に示した。 Such physical properties are shown in Table 1.
本実施例によって製造された中性剤をエポキシで塗装された部位に塗布して１週間後に確認した結果、変色と変形がない。 As a result of applying the neutral agent produced by this example to the part painted with epoxy and confirming it after one week, there is no discoloration and deformation.
腐食が発生した配管に本実施例によって製造された中性剤を塗布して表面に異物が反応されて水洗い後配管表面のきれいな状態は略７０分が所要される。 The neutral agent produced by this embodiment is applied to the pipe where corrosion has occurred, and foreign matters are reacted on the surface. After washing with water, a clean state of the pipe surface requires approximately 70 minutes.
洗浄された配管の一部分を試片で採取してＳＡＭ分析をした結果が実施例４と類似な形態と成分を見せて、不動態被膜に対する耐腐食性を調べるためにＪＩＳ Ｈ８５０２規格の塩水噴霧テスト結果も実施例４と等しく３００時間後にも錆が発生せず、不動態被膜が良好である。 A sample of a part of the cleaned pipe was collected with a specimen and the result of SAM analysis showed a form and components similar to those in Example 4 to examine the corrosion resistance against the passive film. The result is the same as in Example 4, and no rust is generated after 300 hours, and the passive film is good.
リン酸水素二ナトリウム１０重量部、トリポリリン酸ナトリウム１重量部、水８５重量部である塩基性水溶液にリン酸二水素ナトリウム４重量部を反応させてｐＨ７．１の中性剤を製造する。 A neutral agent having a pH of 7.1 is prepared by reacting 4 parts by weight of sodium dihydrogen phosphate with a basic aqueous solution of 10 parts by weight of disodium hydrogen phosphate, 1 part by weight of sodium tripolyphosphate, and 85 parts by weight of water.
本実施例によって製造された中性剤１００ｇに二酸化炭素が除去された空気を１００ｍｌ／ｍｉｎの流速で略１０時間を曝気すると、酸化還元電位が２７５ｍＶに上昇された中性剤が製造される。 When air from which carbon dioxide has been removed is aerated at a flow rate of 100 ml / min for approximately 10 hours with 100 g of the neutral agent produced according to this example, a neutral agent having a redox potential increased to 275 mV is produced.
このような物性を表１に示した。 Such physical properties are shown in Table 1.
腐食が発生した配管に本実施例によって製造された中性剤を塗布して表面に異物が反応される位を確認した結果、１０時間が経ってもオイル成分の異物が除去されない。 As a result of applying the neutral agent manufactured by the present example to the pipe where corrosion occurred and confirming the position where the foreign substance reacts on the surface, the foreign substance of the oil component is not removed even after 10 hours.
このような現象はグルコン酸塩成分がなくて反応が起きない。 Such a phenomenon does not occur because there is no gluconate component.
リン酸水素二ナトリウム１０重量部、グルコン酸ナトリウム１重量部、トリポリリン酸ナトリウム１重量部、水８３．９重量部である塩基性水溶液にリン酸二水素ナトリウム４．１重量部を反応させてｐＨ６．９の中性剤を製造する。 A basic aqueous solution of 10 parts by weight of disodium hydrogen phosphate, 1 part by weight of sodium gluconate, 1 part by weight of sodium tripolyphosphate and 83.9 parts by weight of water was reacted with 4.1 parts by weight of sodium dihydrogen phosphate to pH 6 Produce 9 neutral agents.
本実施例によって製造された中性剤１００ｇに二酸化炭素が除去された空気を１００ｍｌ／ｍｉｎの流速で略１０時間を曝気すると酸化還元電位が２７０ｍＶに上昇された中性剤が製造される。 When neutralized 100 g produced in this example is aerated with air from which carbon dioxide has been removed at a flow rate of 100 ml / min for approximately 10 hours, a neutralized agent having an oxidation-reduction potential increased to 270 mV is produced.
このような物性を表１に示した。 Such physical properties are shown in Table 1.
本実施例によって製造された中性剤をエポキシで塗装された部位に塗布して１週間後に確認した結果、変色と変形がない。 As a result of applying the neutral agent produced by this example to the part painted with epoxy and confirming it after one week, there is no discoloration and deformation.
腐食が発生した配管に本実施例によって製造された中性剤を塗布して表面に異物が反応されて水洗い後配管表面のきれいな状態は略７０分が所要された。 The neutral agent produced in this example was applied to the pipe in which corrosion occurred, and foreign matters reacted on the surface. After washing with water, a clean state of the pipe surface required approximately 70 minutes.
実施例９に比べてグルコン酸塩が１重量部で存在すると、オイル成分の異物が除去される。 When gluconate is present at 1 part by weight as compared with Example 9, foreign matters of the oil component are removed.
洗浄された配管の一部分を試片で採取してＳＡＭ分析をした結果が実施例４と類似な形態と成分を見せて、不動態被膜に対する耐腐食性を調べるためにＪＩＳ Ｈ８５０２規格の塩水噴霧テスト結果も実施例４と等しく３００時間後にも錆が発生せず、不動態被膜が良好である。 A sample of a part of the cleaned pipe was collected with a specimen and the result of SAM analysis showed a form and components similar to those in Example 4 to examine the corrosion resistance against the passive film. The result is the same as in Example 4, and no rust is generated after 300 hours, and the passive film is good.
リン酸水素二ナトリウム１０重量部、グルコン酸ナトリウム５重量部、トリポリリン酸ナトリウム１重量部、水７９．８重量部である塩基性水溶液にリン酸二水素ナトリウム４．２重量部を反応させてｐＨ７．１の中性剤を製造する。 PH 7 by reacting 4.2 parts by weight of sodium dihydrogen phosphate with a basic aqueous solution of 10 parts by weight of disodium hydrogen phosphate, 5 parts by weight of sodium gluconate, 1 part by weight of sodium tripolyphosphate and 79.8 parts by weight of water. .1 Neutral agent is produced.
本実施例によって製造された中性剤１００ｇに二酸化炭素が除去された空気を１００ｍｌ／ｍｉｎの流速で略１０時間を曝気すると、酸化還元電位が２６３ｍＶに上昇された中性剤が製造される。 When air from which carbon dioxide has been removed is aerated at a flow rate of 100 ml / min for about 10 hours with 100 g of the neutral agent produced according to this example, a neutral agent having a redox potential increased to 263 mV is produced.
このような物性を表１に示した。 Such physical properties are shown in Table 1.
本実施例によって製造された中性剤をエポキシで塗装された部位に塗布して１週間後に確認した結果変色と変形がない。 As a result of applying the neutral agent produced in this example to the part painted with epoxy and confirming it one week later, there is no discoloration or deformation.
腐食が発生した配管に本実施例によって製造された中性剤を塗布して表面に異物が反応されて水洗い後配管表面のきれいな状態は略７０分が所要される。 The neutral agent produced by this embodiment is applied to the pipe where corrosion has occurred, and foreign matters are reacted on the surface. After washing with water, a clean state of the pipe surface requires approximately 70 minutes.
洗浄された配管の一部分を試片で採取してＳＡＭ分析をした結果が実施例４と類似な形態と成分を見せて、不動態被膜に対する耐腐食性を調べるためにＪＩＳ Ｈ８５０２規格の塩水噴霧テスト結果も実施例４と等しく３００時間後にも錆が発生せず、不動態被膜が良好である。 A sample of a part of the cleaned pipe was collected with a specimen and the result of SAM analysis showed a form and components similar to those in Example 4 to examine the corrosion resistance against the passive film. The result is the same as in Example 4, and no rust is generated after 300 hours, and the passive film is good.
リン酸水素二ナトリウム１０重量部、グルコン酸ナトリウム３重量部、水８３．１重量部である塩基性水溶液にリン酸二水素ナトリウム３．９重量部を反応させてｐＨ６．９の中性剤を製造する。 A neutral aqueous solution of pH 6.9 is prepared by reacting 3.9 parts by weight of sodium dihydrogen phosphate with a basic aqueous solution of 10 parts by weight of disodium hydrogen phosphate, 3 parts by weight of sodium gluconate, and 83.1 parts by weight of water. To manufacture.
本実施例によって製造された中性剤１００ｇに二酸化炭素が除去された空気を１００ｍｌ／ｍｉｎの流速で略１０時間を曝気すると、酸化還元電位が-４５ｍＶに上昇された中性剤が製造される。 When air from which carbon dioxide has been removed is aerated at a flow rate of 100 ml / min for approximately 10 hours with 100 g of the neutral agent produced according to this example, a neutral agent having a redox potential increased to −45 mV is produced. .
このような物性を表１に示した。 Such physical properties are shown in Table 1.
腐食が発生した配管に本実施例によって製造された中性剤を塗布して表面に異物が反応される程度を確認した結果、１０時間が経っても異物が除去されない。 As a result of applying the neutral agent manufactured according to the present example to the pipe where corrosion occurred and confirming the extent to which the foreign matter reacts on the surface, the foreign matter is not removed even after 10 hours.
このような現象は溶存酸素量を増加させて、浸透反応性を増加させるトリポリリン酸ナトリウム成分がなくて反応が起きない。 Such a phenomenon increases the amount of dissolved oxygen and causes no reaction because there is no sodium tripolyphosphate component that increases osmotic reactivity.
リン酸水素二ナトリウム１０重量部、グルコン酸ナトリウム３重量部、トリポリリン酸ナトリウム０．５重量部、水８２．５重量部である塩基性水溶液にリン酸二水素ナトリウム４重量部を反応させてｐＨ７．０の中性剤を製造する。 PH 7 by reacting 4 parts by weight of sodium dihydrogen phosphate with a basic aqueous solution of 10 parts by weight of disodium hydrogen phosphate, 3 parts by weight of sodium gluconate, 0.5 parts by weight of sodium tripolyphosphate, and 82.5 parts by weight of water. 0. Neutral agent is produced.
本実施例によって製造された中性剤１００ｇに二酸化炭素が除去された空気を１００ｍｌ／ｍｉｎの流速で略１０時間を曝気すると、酸化還元電位が２２０ｍＶに上昇された中性剤が製造される。 When air from which carbon dioxide has been removed is aerated at a flow rate of 100 ml / min for approximately 10 hours with 100 g of the neutral agent produced according to the present example, a neutral agent having a redox potential increased to 220 mV is produced.
このような物性を表１に示した。 Such physical properties are shown in Table 1.
本実施例によって製造された中性剤をエポキシで塗装された部位に塗布して１週間後に確認した結果、変色と変形がない。 As a result of applying the neutral agent produced by this example to the part painted with epoxy and confirming it after one week, there is no discoloration and deformation.
腐食が発生した配管に本実施例によって製造された中性剤を塗布して表面に異物が反応されて水洗い後配管表面のきれいな状態は略８０分が所要される。 The neutral agent produced in this embodiment is applied to the pipe where corrosion has occurred, and foreign matter reacts on the surface. After washing with water, the clean state of the pipe surface requires approximately 80 minutes.
このような現象はトリポリリン酸ナトリウムが０．５重量部で存在すると、実施例１２に比べて中性剤の浸透成果反応性が増加し、溶存酸素量が増加して酸化還元電位が増加される。 In such a phenomenon, when sodium tripolyphosphate is present at 0.5 part by weight, the permeation result reactivity of the neutral agent is increased as compared with Example 12, the amount of dissolved oxygen is increased, and the redox potential is increased. .
洗浄された配管の一部分を試片で採取してＳＡＭ分析をした結果が実施例４と類似な形態と成分を見せて、不動態被膜に対する耐腐食性を調べるためにＪＩＳ Ｈ８５０２規格の塩水噴霧テスト結果も実施例４と等しく３００時間後にも錆が発生せず、不動態被膜が良好である。 A sample of a part of the cleaned pipe was collected with a specimen and the result of SAM analysis showed a form and components similar to those in Example 4 to examine the corrosion resistance against the passive film. The result is the same as in Example 4, and no rust is generated after 300 hours, and the passive film is good.
リン酸水素二ナトリウム１０重量部、グルコン酸ナトリウム３重量部、トリポリリン酸ナトリウム３重量部、水７９．５重量部である塩基性水溶液にリン酸二水素ナトリウム４．５重量部を反応させてｐＨ７．０の中性剤を製造する。 PH 7 by reacting 4.5 parts by weight of sodium dihydrogen phosphate with a basic aqueous solution of 10 parts by weight of disodium hydrogen phosphate, 3 parts by weight of sodium gluconate, 3 parts by weight of sodium tripolyphosphate, and 79.5 parts by weight of water. 0. Neutral agent is produced.
本実施例によって製造された中性剤１００ｇに二酸化炭素が除去された空気を１００ｍｌ／ｍｉｎの流速で略１０時間を曝気すると、酸化還元電位が３１０ｍＶに上昇された中性剤が製造される。 When air from which carbon dioxide has been removed is aerated at a flow rate of 100 ml / min for approximately 10 hours with 100 g of the neutral agent produced according to this example, a neutral agent having a redox potential increased to 310 mV is produced.
このような物性を表１に示した。 Such physical properties are shown in Table 1.
本実施例によって製造された中性剤をエポキシで塗装された部位に塗布して１週間後に確認した結果、変色と変形がない。 As a result of applying the neutral agent produced by this example to the part painted with epoxy and confirming it after one week, there is no discoloration and deformation.
腐食が発生した配管に本実施例によって製造された中性剤を塗布して表面に異物が反応されて水洗い後配管表面のきれいな状態は略６０分が所要される。 The neutral agent produced in this embodiment is applied to the pipe where corrosion has occurred, and foreign matter reacts on the surface. After washing with water, a clean state of the pipe surface requires approximately 60 minutes.
洗浄された配管の一部分を試片で採取してＳＡＭ分析をした結果が実施例４と類似な形態と成分を見せて、不動態被膜に対する耐腐食性を調べるためにＪＩＳ Ｈ８５０２規格の塩水噴霧テスト結果も実施例４と等しく３００時間後にも錆が発生せず、不動態被膜が良好である。 A sample of a part of the cleaned pipe was collected with a specimen and the result of SAM analysis showed a form and components similar to those in Example 4 to examine the corrosion resistance against the passive film. The result is the same as in Example 4, and no rust is generated after 300 hours, and the passive film is good.
Claims (2)
前記の塩基性水溶液にリン酸二水素ナトリウム１．１〜４．５重量部を反応させてｐＨ６．９〜７．１で中性化した後、
二酸化炭素が除去された空気を曝気して溶存酸素量を増加させて酸化還元電位を１７０ｍＶ〜３１０ｍＶにしてステンレススチール配管と構造物の溶接部位のスケールおよび錆をとり除くための酸洗いおよび不動態被膜処理剤。 A basic aqueous solution was obtained by containing 2 to 10 parts by weight of disodium hydrogen phosphate, 1 to 5 parts by weight of sodium gluconate and 0.5 to 3 parts by weight of sodium tripolyphosphate in water,
After reacting 1.1 to 4.5 parts by weight of sodium dihydrogen phosphate with the basic aqueous solution to neutralize at pH 6.9 to 7.1,
Pickling and passivating coating to remove the scale and rust of stainless steel pipes and welded parts of the structure by aeration of air from which carbon dioxide has been removed to increase the amount of dissolved oxygen to a redox potential of 170 mV to 310 mV Processing agent.
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| PCT/KR2017/005708 WO2017209524A1 (en) | 2016-06-01 | 2017-05-31 | Treatment agent for pickling to remove scales and rust at welding regions of stainless steel pipes and structures and for forming passivation film |
| WOPCT/KR2017/005708 | 2017-05-31 | ||
| WOPCT/KR2017/012787 | 2017-11-13 | ||
| PCT/KR2017/012787 WO2018221797A1 (en) | 2016-06-01 | 2017-11-13 | Pickling and passivation layer treating agent for removing scales and rust from welding zones of stainless steel pipe and structure |
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