DE1286873B - Aqueous, acidic solution for removing rust and other iron oxides, especially scale, on metal surfaces with simultaneous formation of protective phosphate layers - Google Patents
Aqueous, acidic solution for removing rust and other iron oxides, especially scale, on metal surfaces with simultaneous formation of protective phosphate layersInfo
- Publication number
- DE1286873B DE1286873B DE1960G0031103 DEG0031103A DE1286873B DE 1286873 B DE1286873 B DE 1286873B DE 1960G0031103 DE1960G0031103 DE 1960G0031103 DE G0031103 A DEG0031103 A DE G0031103A DE 1286873 B DE1286873 B DE 1286873B
- Authority
- DE
- Germany
- Prior art keywords
- aqueous
- acidic solution
- iron oxides
- metal surfaces
- sodium
- 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.)
- Pending
Links
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims description 5
- 235000013980 iron oxide Nutrition 0.000 title claims description 5
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 title claims description 5
- 229910052751 metal Inorganic materials 0.000 title claims description 5
- 239000002184 metal Substances 0.000 title claims description 5
- 229910019142 PO4 Inorganic materials 0.000 title claims description 4
- 239000003929 acidic solution Substances 0.000 title claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims description 4
- 239000010452 phosphate Substances 0.000 title claims description 4
- 230000015572 biosynthetic process Effects 0.000 title claims description 3
- 230000001681 protective effect Effects 0.000 title description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- -1 ammonium ions Chemical class 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 235000011007 phosphoric acid Nutrition 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000000080 wetting agent Substances 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 4
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000011241 protective layer Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910001437 manganese ion Inorganic materials 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000002253 acid Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 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 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- 241000221535 Pucciniales Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C22/07—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 containing phosphates
- C23C22/08—Orthophosphates
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Description
In der französischen Patentschrift 1078182 ist eine wäßrige Lösung zur Entfernung von Rost und anderen Eisenoxyden, wie Zunder, beschrieben, die mindestens eine schwache Säure sowie mindestens ein sauerstoffhaltiges Metallsalz und mindestens ein Netzmittel enthält. Es wurde jedoch gefunden, daß die Geschwindigkeit und die Vollständigkeit der Entfernung der Eisenoxyde noch zu wünschen übriglassen.In French patent 1078182 there is an aqueous solution for the removal of rust and other iron oxides, such as scale, described at least a weak acid and at least one oxygen-containing metal salt and at least contains a wetting agent. However, it has been found that the speed and the The completeness of the removal of the iron oxides still leaves something to be desired.
Weiterhin ist aus der deutschen Patentschrift 659125 eine wäßrige Lösung von saurem Zinkphosphat zur Reinigung von eisernen Oberflächen von Rost bekannt. Die Konzentration dieser Lösung an Zink beträgt 15 bis 50 g pro Liter, der Gewichtsanteil an freier Phosphorsäure (als P205 berechnet) beträgt die zwei- bis vierfache Menge des Zinks. Die Lösung kann weiterhin Netzmittel enthalten.Furthermore, from the German patent specification 659125 an aqueous one Solution of acid zinc phosphate known for cleaning iron surfaces from rust. The concentration of zinc in this solution is 15 to 50 g per liter, the proportion by weight of free phosphoric acid (calculated as P205) is two to four times the amount of zinc. The solution can also contain wetting agents.
Nach der deutschen Patentschrift 660 436 kann an Stelle oder in Ergänzung des zur Reinigung verwendeten Zinkphosphats eine wäßrige Lösung von saurem Manganphosphat mit einer Konzentration von 12 bis 45 g Mangan pro Liter und mit einem gewichtsmäßig der 11/z- bis 31/2fachen Menge Mangan entsprechenden Anteil an freier Phosphorsäure (als P205 berechnet) verwendet werden.According to German Patent 660 436, instead of or in addition to of the zinc phosphate used for cleaning is an aqueous solution of acidic manganese phosphate with a concentration of 12 to 45 g of manganese per liter and with a weight the proportion of free phosphoric acid corresponding to 11/2 to 31/2 times the amount of manganese (calculated as P205) can be used.
Mit Hilfe dieser Lösungen werden Rost- und Zunderschichten auf Eisenoberflächen zwar verhältnismäßig rasch entfernt, doch wird auch die Eisenoberfläche angegriffen, wobei sich Streifen bilden. Außerdem beginnt die Eisenoberfläche nach einiger Zeit wieder zu rosten, wenn sich der entrostete Gegenstand in einer feuchten Atmosphäre befindet, was darauf hindeutet, daß sich keine zusammenhängende Phosphat-Schutzschicht gebildet hat. Schließlich müssen Eisengegenstände, die mit diesen bekannten Entrostungslösungen behandelt wurden, gründlich gespült werden.With the help of these solutions, rust and scale layers are created on iron surfaces removed relatively quickly, but the iron surface is also attacked, whereby stripes are formed. In addition, the iron surface begins to surface after a while to rust again if the rusted object is in a humid atmosphere which suggests that there is no cohesive protective phosphate layer has formed. Finally, iron items need to be made with these well known rust removal solutions must be rinsed thoroughly.
Es wurde nun überraschenderweise gefunden, daß diese Nachteile ausgeschaltet werden können, wenn man Lösungen verwendet, die neben den bekannten Bestandteilen noch Natrium-, Kalium- oder Ammonium-Ionen enthalten. Diese Ionen üben wahrscheinlich eine Pufferwirkung aus und verhindern einen Angriff der Metalloberfläche durch die Phosphorsäure. Daneben wird eine zusammenhängende Schutzschicht aus Eisen- und Zink- oder Manganphosphat gebildet, die ein Weiterrosten in einer feuchten Atmosphäre verhindert. Schließlich braucht die Lösung nach der Behandlung nicht abgespült zu werden.It has now been found, surprisingly, that these disadvantages are eliminated can be used if one uses solutions that are in addition to the known ingredients still contain sodium, potassium or ammonium ions. These ions are likely to exercise have a buffer effect and prevent the metal surface from being attacked by the Phosphoric acid. In addition, a cohesive protective layer made of iron and zinc or manganese phosphate, which rusts further in a humid atmosphere prevented. After all, the solution doesn't need to be rinsed off after treatment will.
Die Erfindung betrifft somit eine wäßrige, saure Lösung zur Entfernung von Rost und anderen Eisenoxyden, insbesondere Zunder, auf Metalloberflächen unter gleichzeitiger Bildung von Phosphatschutzschichten, die Orthophosphorsäure, Zink- oder Mangan-Ionen und mindestens ein Netzmittel enthält; sie ist gekennzeichnet durch einen zusätzlichen Gehalt an Natrium-, Kalium- oder Ammonium-Ionen neben Polyoxyäthylen oder Alkylsulfonat als Netzmittel.The invention thus relates to an aqueous, acidic solution for removal rust and other iron oxides, especially scale, on metal surfaces simultaneous formation of phosphate protective layers, the orthophosphoric acid, zinc or contains manganese ions and at least one wetting agent; it is marked due to an additional content of sodium, potassium or ammonium ions in addition to polyoxyethylene or alkyl sulfonate as a wetting agent.
Vorzugsweise ist die Lösung durch Mischen von 250 bis 500 g Orthophosphorsäure, 5 bis 20 g Natrium- oder Kaliumcarbonat, 3 bis 10 g Zink- oder Manganoxyd, 0,5 bis 2 g Polyoxyäthylen oder Alkylsulfonat und 500 bis 750 g Wasser zubereitet.Preferably the solution is made by mixing 250 to 500 g of orthophosphoric acid, 5 to 20 g sodium or potassium carbonate, 3 to 10 g zinc or manganese oxide, 0.5 to Prepared 2 g of polyoxyethylene or alkyl sulfonate and 500 to 750 g of water.
Wenn die Bestandteile rein sind, ist das Endprodukt eine vollständig flüssige und farblose Lösung. Sie verändert sich nicht und behält ihre Eigenschaften bis zum Verbrauch. Die damit behandelten Eisengegenstände werden einfach getrocknet, und infolge ihrer Passivität können sie gelagert werden, ohne daß erneut eine Oxydation ihrer Oberfläche stattfindet.When the ingredients are pure, the end product is complete liquid and colorless solution. It does not change and it retains its properties until consumption. The iron objects treated with it are simply dried, and because of their passivity they can be stored without renewed oxidation their surface takes place.
Befriedigende Ergebnisse können auch erhalten werden, wenn die Lösung an Stelle von Kalium- oder Natriumcarbonat mit 8 bis 15 g Ammoniak zubereitet ist. Das Wasservolumen wird im gleichen Verhältnis verringert. Die Anwesenheit von Ammoniak beschleunigt die Reaktion und ergibt eine gegen Oxydation sehr beständige Oberfläche.Satisfactory results can also be obtained if the solution Instead of potassium or sodium carbonate, it is prepared with 8 to 15 g of ammonia. The volume of water is reduced in the same proportion. The presence of ammonia accelerates the reaction and results in a surface that is very resistant to oxidation.
Um Zunder zu entfernen, kann man der Lösung Schwefelsäure und Trinatriumphosphat zusetzen; vorzugsweise setzt man 101/o Schwefelsäure von 55 bis 65° B6 hinzu, wodurch die Einwirkungsdauer der Lösung verkürzt werden kann. Das Trinatriumphosphat wird in Mengen von etwa 1% zugesetzt; auf diese Weise wird eine beständigere phosphatierte Oberfläche erzielt.To remove scale, sulfuric acid and trisodium phosphate can be added to the solution add to; 101 / o sulfuric acid at 55 to 65 ° B6 is preferably added, whereby the exposure time of the solution can be shortened. The trisodium phosphate will added in amounts of about 1%; this way it becomes a more permanent phosphated Surface achieved.
Nachstehend ist als Beispiel eine Lösung angegeben, die gute Ergebnisse bei der Entfernung von Zunderresten liefert: Orthophosphorsäure . . . . . . . . . . 150 bis 300 g Zinkoxyd oder Manganoxyd .... 2 bis 5 g Natrium- oder Kaliumcarbonat .. 3 bis 6 g Trinatriumphosphat . . . . . . . . . . . 7 bis 14 g Polyoxyäthylen oder Alkylsulfonat . . . . . . . . . . 0,5 bis 2 g Schwefelsäure . . . . . . . . . . . . . . . . 100 g Wasser . . . . . . . . . . . . . . . . . . . . . . 600 bis 750 g Um den Beginn der Reaktion zu erleichtern und zu beschleunigen, kann man dieser Lösung, und zwar in einer Menge von 0,5 bis 1 Promille, das Tetranatriumsalz der Äthylendiaminotetraessigsäure zusetzen.The following is an example of a solution that gives good results in removing scale residues: orthophosphoric acid. . . . . . . . . . 150 to 300 g zinc oxide or manganese oxide .... 2 to 5 g sodium or potassium carbonate .. 3 to 6 g trisodium phosphate. . . . . . . . . . . 7 to 14 g of polyoxyethylene or alkyl sulfonate. . . . . . . . . . 0.5 to 2 g of sulfuric acid. . . . . . . . . . . . . . . . 100 g of water. . . . . . . . . . . . . . . . . . . . . . 600 to 750 g In order to facilitate and accelerate the start of the reaction, the tetrasodium salt of ethylenediaminotetraacetic acid can be added to this solution, specifically in an amount of 0.5 to 1 per thousand.
Claims (4)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR39964A FR1242159A (en) | 1959-12-08 | 1959-12-08 | Product to remove rust, scale and more |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1286873B true DE1286873B (en) | 1969-01-09 |
Family
ID=8593562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1960G0031103 Pending DE1286873B (en) | 1959-12-08 | 1960-12-07 | Aqueous, acidic solution for removing rust and other iron oxides, especially scale, on metal surfaces with simultaneous formation of protective phosphate layers |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE1286873B (en) |
| FR (1) | FR1242159A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5851443A (en) * | 1996-12-06 | 1998-12-22 | Rajendren; Richard B. | Aerator with dual path discharge |
| US7028992B2 (en) | 2004-05-28 | 2006-04-18 | American Aerators, Inc. | Aerator with intermediate bearing |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE659124C (en) * | 1933-04-01 | 1938-04-26 | Metallgesellschaft Akt Ges | Process for cleaning iron surfaces |
| DE660436C (en) * | 1933-05-27 | 1938-05-25 | Metallgesellschaft Akt Ges | Process for cleaning iron surfaces |
-
1959
- 1959-12-08 FR FR39964A patent/FR1242159A/en not_active Expired
-
1960
- 1960-12-07 DE DE1960G0031103 patent/DE1286873B/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE659124C (en) * | 1933-04-01 | 1938-04-26 | Metallgesellschaft Akt Ges | Process for cleaning iron surfaces |
| DE660436C (en) * | 1933-05-27 | 1938-05-25 | Metallgesellschaft Akt Ges | Process for cleaning iron surfaces |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1242159A (en) | 1960-09-23 |
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