DE584411C - Process for the production of corrosion-resistant coatings on iron and steel - Google Patents
Process for the production of corrosion-resistant coatings on iron and steelInfo
- Publication number
- DE584411C DE584411C DEP63956D DEP0063956D DE584411C DE 584411 C DE584411 C DE 584411C DE P63956 D DEP63956 D DE P63956D DE P0063956 D DEP0063956 D DE P0063956D DE 584411 C DE584411 C DE 584411C
- Authority
- DE
- Germany
- Prior art keywords
- iron
- steel
- production
- corrosion
- solution
- 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.)
- Expired
Links
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
- C23C22/46—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 oxalates
- C23C22/47—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 oxalates containing also phosphates
-
- 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
- C23C22/40—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 molybdates, tungstates or vanadates
- C23C22/42—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 molybdates, tungstates or vanadates containing also phosphates
-
- 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
- C23C22/40—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 molybdates, tungstates or vanadates
- C23C22/44—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 molybdates, tungstates or vanadates containing also fluorides or complex fluorides
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)
- Chemical Treatment Of Metals (AREA)
Description
Es ist bisher üblich gewesen, Gegenstände aus Eisen oder Stahl in einer verdünnten, meist heißen Phosphorsäurelösung bzw. in einer Lösung·, die Phosphate enthält, zu behandeln und dabei auf diesen Gegenständen einen verhältnismäßig dünnen, aber korrosionsfesten Überzug von Phosphaten zu bilden. Hierbei wurde entweder so vorgegangen, daß man ein Bad aus verdünnter Phos-It has hitherto been customary to place objects of iron or steel in a thinned, usually hot phosphoric acid solution or in a solution containing phosphates to be treated and a relatively thin, but corrosion-resistant, on these objects Form coating of phosphates. The procedure here was either that a bath of dilute phos-
ΐσ phorsäure allein oder mit einem Gehalt an primären Phosphaten der Schwermetalle bildete und die Gegenstände in dieses Bad eintauchte, wobei die Temperatur nahe dem Siedepunkt gehalten wurde. Ein derartiger Überzug, der meistens aus tertiärem Eisenphosphat oder einem Gemisch von Eisenphosphat und Phosphaten anderer Schwermetalle bestand, weist nun eine verhältnismäßig rauhe Oberfläche auf, ist jedoch in sich relativ locker. Er eignet sich aus diesem Grunde ganz vorzüglich als Unterlage für etwaige weitere Farbanstriche, ist jedoch für sich allein noch nicht allen Ansprüchen der Korrosionsbeständigkeit gewachsen. Außer-' dem ist die Zeit, die man braucht, um diesen Phosphatüberzug auf dem Eisen zu erzeugen, ziemlich lang, da man, um einen einigermaßen ausreichend dichten Überzug zu erzeugen, etwa ι Stunde oder mehr die Gegenstände in den heißen Phosphatbädern belassen mußte.ΐσ phosphoric acid alone or with a content of formed primary phosphates of heavy metals and immersed the objects in this bath, keeping the temperature near the boiling point. Such a coating, which is mostly made of tertiary iron phosphate or a mixture of iron phosphate and phosphates of other heavy metals, now shows a proportionate rough surface, but is relatively loose in itself. He lends itself to this Basically excellent as a base for any further coats of paint, but is for not yet able to cope with all the demands of corrosion resistance on its own. Except-' this is the time it takes to create this phosphate coating on the iron, quite long, since in order to produce a reasonably dense coating, the objects in the hot phosphate baths for about 1 hour or more had to leave.
Gegenstand vorliegender Erfindung ist nun die Erzeugung eines phosphathaltigen Überzuges auf Gegenständen, die aus Eisen oder. Stahl bestehen, der wesentlich dichter und daher korrosionsbeständiger ist als die bisher üblichen Überzüge und dessen Herstellung außerdem in wesentlich kürzerer Zeit möglich ist. Zu diesem Zweck setzt man dem aus Phosphorsäure bestehenden oder Phosphate der Schwermetalle enthaltenden Bade noch eine Molybdänsäureverbindung zu. An derartigen Molybdänverbindungen kommen in erster Linie Alkalimolybdate oder insbesondere Ammoniummolybdat in Frage. Vorteilhafterweise wird -die Molybdänverbindung in Mengen von etwa 2 bis S g Molybdat pro ■ Liter Lösung zugesetzt. Außerdem hat es sich als vorteilhaft erwiesen, neben dem Molybdat noch einen weiteren Zusatz an Salzen zuzusetzen, die aus dem Molybdat Molybdänoxyd frei machen, welches sich dann auf der Eisenoberfläche zusammen mit den Phosphaten niederschlägt. Derartige Zusätze sind z. B. Salze der Oxalsäure, weiterhin Fluoride, und zwar vorzugsweise saure Fluoride, wie ζ. B. NatriumsiliciumfiuOrid, NatriumbifLuorid. Zum Festhalten des Überzuges wird man schließlich gemäß Erfindung noch ein neutrales Fluorid hinzufügen bzw. im Bade bilden. Hierzu gehören z. B. ein Natriumfluorid, Kaliumfluorid oder Ammoniumfluorid oder der Zusatz einer geringen' Menge Alkalicarbonat, welches zusammen mit den sauren Fluoriden ein heutrales Fluorid bildet.The present invention is now the production of a phosphate-containing coating on objects made of iron or. Steel exist, which is much denser and therefore more resistant to corrosion than before customary coatings and their production also possible in a much shorter time is. For this purpose, the bath consisting of phosphoric acid or containing phosphates of heavy metals is added a molybdic acid compound to it. Such molybdenum compounds are primarily or particularly alkali molybdates Ammonium molybdate in question. The molybdenum compound is advantageously used added in amounts of about 2 to 5 g molybdate per liter of solution. Besides, it has proved to be advantageous, in addition to the molybdate, another additive To add salts, which make molybdenum oxide free from the molybdate, which then precipitates on the iron surface together with the phosphates. Such additives are z. B. salts of oxalic acid, also fluorides, preferably acidic fluorides, such as ζ. B. sodium silicon fluoride, Sodium bifluoride. In order to hold the coating in place, one finally becomes according to the invention add a neutral fluoride or form it in the bath. These include z. B. a sodium fluoride, potassium fluoride or ammonium fluoride or the addition of a small ' Amount of alkali carbonate, which together with the acidic fluorides forms a modern fluoride.
Folgendes Beispiel mag die Erfindung näher erläutern:The following example may explain the invention in more detail:
iog einer Mischung von gleichen Teilen Ammoniummolybdat, Natriumcarbonat und Natriumsilicofluorid wird in ι 1 Wasser aufgelöst und erhitzt. Zu der heißen Lösung werden dann noch 20 g einer Mischung von Eisen- und Manganoorthophosphat mit etwa 5 °/0 freier Phosphorsäure zugegeben und gleichfalls darin gelöst. In diese vorbereitete Lösung werden nun die zu schützenden eisernen Gegenstände eingetaucht und bei einer Temperatur von etwa 970 15 Minuten belassen. Durch diese Behandlung wird ein sehr dichter und hochkorrosionsbeständiger Überzug von dunkler Farbe auf den Gegenständen erzeugt, der aus einem Gemisch von Phosphaten des Eisens und Mangans sowie von Molybdänoxyden besteht. Die Wirkung einer derartigen Behandlung für die Erhöhung der Korrosionsbeständigkeit besteht vermutlich darin, daß sich in die vorhandenen feinen Zwischenräume des einfachen krystallinischen Phosphatüberzuges Molybdänoxyd «5 in sehr fein verteilter Form niederschlägt und so den Angriff korrodierender Agenzien noch stärker unterbindet.A mixture of equal parts of ammonium molybdate, sodium carbonate and sodium silicofluoride is dissolved in 1 of water and heated. To the hot solution, then 20 g of a mixture of iron and Manganoorthophosphat with about 5 ° / 0 free phosphoric acid added and also dissolved therein. The iron objects to be protected are then immersed in this prepared solution and left at a temperature of about 97 ° for 15 minutes. This treatment produces a very dense and highly corrosion-resistant coating of dark color on the objects, which consists of a mixture of phosphates of iron and manganese and of molybdenum oxides. The effect of such a treatment for increasing the corrosion resistance is presumably that in the existing fine interstices of the simple crystalline phosphate coating molybdenum oxide precipitates in very finely divided form and thus prevents the attack of corrosive agents even more.
Es ist zwar bereits der Vorschlag gemacht, Mischungen von SuIf omolyb daten zusam-3a men mit Phosphorchromaten zur Bildung von Überzügen auf Aluminium, Magnesium und Zink zu machen. Gegenüber diesen Vorschlägen besteht das Wesen der Erfindung darin, daß man die Überzüge nunmehr auf Eisen oder Stahl anbringt, und vor allem darin, daß jeder Chromgehalt im Bade vermieden wird, da nur so die beschleunigte Herstellung des Überzuges möglich ist. Darüber hinaus muß auch betont werden, daß 4<* gerade dem Molybdän eine Sonderrolle gegenüber allen sonstigen Metalloxyden zukommt, da weder das Vanadin noch das Wolfram usw. die gleiche Wirkung hervorzubringen geeignet sind.The proposal has already been made to combine mixtures of sulfomolybeta men with phosphorus chromates to form coatings on aluminum, magnesium and To make zinc. Compared to these proposals, the essence of the invention is that the coatings are now on Iron or steel attaches, and above all in that any chromium content in the bath is avoided as this is the only way to accelerate the production of the coating. About that It must also be emphasized that 4 <* has a special role in relation to molybdenum all other metal oxides, since neither the vanadium nor the tungsten etc. produce the same effect are suitable.
♦5 Es ist auch weiterhin der \rorschlag gemacht, Gegenstände aus Eisen oder Stahl lediglich mit Molybdänoxydüberzügen zu versehen. Auch dieses Verfahren ist jedoch dem Verfahren gemäß vorliegender Erfindung unterlegen, da gerade die Kombination von Molybdänoxyden und Phosphaten einen ganz besonders guten, dichten und korrosionsfesten Überzug ergibt. In Kombination mit Phosphaten können natürlich sonstige Verfahrenseinzelheiten, wie sie durch das 'er-, wähnte Verfahren bereits bekannt sind, gleichfalls zur Ausführung vorliegender Erfindung angewendet werden.♦ 5 It is also still made of the \ r PROPOSAL to provide articles made of iron or steel with only Molybdänoxydüberzügen. However, this method is also inferior to the method according to the present invention, since it is precisely the combination of molybdenum oxides and phosphates that results in a particularly good, dense and corrosion-resistant coating. In combination with phosphates, other process details, as they are already known from the process mentioned, can of course also be used to carry out the present invention.
Es ist schließlich der Vorschlag gemacht, Lösungen von Molybdänmetaphosphaten zur Erzeugung von Rostschutzschichten auf Eisen zu benutzen. Versuche haben jedoch gezeigt, daß eine 11^ °/oige Lösung von Molybdänmetaphosphat in Wasser nach 10 Minuten bei etwa 70 ° noch überhaupt keine Überzugsbildung zeigt, während eine gemäß Erfindung hergestellte Lösung, z. B. aus 3 g Natriumfluorid, 3 g Natriummolybdat und 10 g Mänganphosphat plus Eisenphosphat je Liter, bei gleicher Temperatur und Behandlungsdauer schon sehr wertvolle Rostschutzschichten auf dem Eisen bildete. Das Verfahren gemäß Erfindung ermöglicht also ein Arbeiten bei niedrigerer Temperatur bzw. ein schnelleres Aufbringen der Schutzschichten und ist daher erheblich wirtschaftlicher als die bisher vorgeschlagenen Verfahren. Finally, the proposal is made to use solutions of molybdenum metaphosphates for the production of rust protection layers on iron. However, experiments have shown that a 1 ^ 1 ° / o solution of Molybdänmetaphosphat in water after 10 minutes is still no coating formation at about 70 °, while a solution prepared according to the invention such. B. from 3 g of sodium fluoride, 3 g of sodium molybdate and 10 g of manganese phosphate plus iron phosphate per liter, at the same temperature and duration of treatment, very valuable rust protection layers formed on the iron. The method according to the invention thus enables working at a lower temperature or faster application of the protective layers and is therefore considerably more economical than the previously proposed methods.
Zur weiteren Verbesserung des Überzuges kann man die Gegenstände nach der oben beschriebenen Behandlung dann noch einer weiteren Behandlung unterziehen, die darin besteht, sie während kurzer Zeit in ein Chromsäure oder Salze der Chromsäure enthaltendes Bad zu tauchen.To further improve the coating, the objects can be used as described above Then undergo one more treatment, which consists of turning them into one for a short period of time Dip the bath containing chromic acid or salts of chromic acid.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP63956D DE584411C (en) | 1931-09-22 | 1931-09-23 | Process for the production of corrosion-resistant coatings on iron and steel |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE728364X | 1931-09-22 | ||
| DEP63956D DE584411C (en) | 1931-09-22 | 1931-09-23 | Process for the production of corrosion-resistant coatings on iron and steel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE584411C true DE584411C (en) | 1933-09-20 |
Family
ID=25947100
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEP63956D Expired DE584411C (en) | 1931-09-22 | 1931-09-23 | Process for the production of corrosion-resistant coatings on iron and steel |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE584411C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2502441A (en) * | 1946-11-22 | 1950-04-04 | Oakite Prod Inc | Phosphate coating of metals |
| US2514941A (en) * | 1946-05-13 | 1950-07-11 | Walterisation Company Ltd | Process for increasing the corrosion-resistance of metals |
| US3169160A (en) * | 1960-10-28 | 1965-02-09 | Stora Kopparbergs Bergslags Ab | Means for protecting the nose of rotary furnaces |
-
1931
- 1931-09-23 DE DEP63956D patent/DE584411C/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2514941A (en) * | 1946-05-13 | 1950-07-11 | Walterisation Company Ltd | Process for increasing the corrosion-resistance of metals |
| US2502441A (en) * | 1946-11-22 | 1950-04-04 | Oakite Prod Inc | Phosphate coating of metals |
| US3169160A (en) * | 1960-10-28 | 1965-02-09 | Stora Kopparbergs Bergslags Ab | Means for protecting the nose of rotary furnaces |
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