EP1230423B1 - Verfahren zum aufbringen von manganphosphatschichten - Google Patents
Verfahren zum aufbringen von manganphosphatschichten Download PDFInfo
- Publication number
- EP1230423B1 EP1230423B1 EP00972661A EP00972661A EP1230423B1 EP 1230423 B1 EP1230423 B1 EP 1230423B1 EP 00972661 A EP00972661 A EP 00972661A EP 00972661 A EP00972661 A EP 00972661A EP 1230423 B1 EP1230423 B1 EP 1230423B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ions
- workpieces
- manganese
- phosphate
- iron
- 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 - Lifetime
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
- C23C22/07—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
- C23C22/18—Orthophosphates containing manganese cations
-
- 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
- C23C22/18—Orthophosphates containing manganese cations
- C23C22/188—Orthophosphates containing manganese cations containing also magnesium cations
Definitions
- the invention relates to a method for applying manganese phosphate layers on iron or steel surfaces with manganese, phosphate, ferrous ions, as well as Nitroguanidine containing phosphating solutions and its application Workpieces subject to sliding friction.
- manganese phosphate layers have become because of their high mechanical Resistance well proven.
- manganese phosphate solutions were obtained relatively thick, coarsely crystalline Layers that are particularly disadvantageous when fine mechanical parts should be treated.
- With the aim of thin fine crystalline Manganese phosphate layers are therefore numerous proposals been submitted. For example, it is known by the addition of condensed phosphates to obtain a refinement of the phosphate layer.
- manganese phosphate phosphating solutions generally become used at high temperatures, so that as a result of high temperatures considerable hydrolysis, the effectiveness of the condensed phosphates quickly decreases or continuously condensed phosphate must be replenished.
- the known method has in common that manganese phosphate layers with considerable roughness depths arise. The reason is that the Beizangriff with manganese phosphate systems from the beginning is strong and after extremely short exposure time leads to a punctiform metal removal. In contrast, the layer formation continues - compared with zinc phosphate systems - comparatively delayed. Strong pickling attack and delayed stratification are visually characterized by a strong gas evolution of longer duration, the so-called Gas time, recognizable.
- the object of the invention is to provide a method that Manganese phosphate layers with the lowest possible roughness leads, whose layer thickness nevertheless lies in the middle to high range.
- the object is achieved by the method of the aforementioned type according to the invention is designed such that the workpieces for the purpose of forming a manganese phosphate layer with a minimum thickness of 2.5 microns and an average maximum surface roughness (R z ) of 2.5 microns - measured after drying - contacted with a phosphating solution at a temperature of at least 75 ° C, the 0.2 to 4 g / l iron (II) ions 10 to 25 g / l manganese ions 25 to 50 g / l phosphate ions (calc. as P 2 O 5 ) 3 to 35 g / l nitrate ions 0.5 to 5 g / l nitroguanidine contains 7 to 24 points of free acid, 50 to 140 points total acid and has an S value of 0.2 to 1.
- the claimed maximum value of 2.5 ⁇ m refers only to the roughness of the Manganese phosphate layer and leaves the depth of the untreated metal surface unconsidered.
- the above-mentioned total score is in a conventional manner determined by adding 10 ml of the phosphating solution after dilution with water About 50 ml using phenolphthalein as indicator until Color change from colorless to red are filtered. The number of this 0.1 ml of sodium hydroxide solution used gives the total number of points.
- Others for the Titration suitable indicators are thymolphthalein and ortho-cresolphthalein.
- the free acid points are determined using dimethyl yellow as an indicator and titrating to pink to yellow to pink.
- interfering metal ions are removed by addition of hexacyanoferrate (II) or hexacyanocobaltate (III) ions.
- the S value is defined as the ratio of free P 2 O 5 to total P 2 O 5 .
- Oxidizing agents may also contain nitroguanidine.
- the Phosphating solutions significantly lower concentrations containing phosphating components and - according to the The aim of the known processes was to increase the corrosion resistance of metals improve - create layers with a very low coating weight. a contains some kind of reference to the surface roughness of the phosphate layer Patent specification not.
- iron (II) oxidizing substances preferably potassium permanganate added become.
- iron (II) - concentration of 0.2 g / l under no circumstances. Otherwise, the desired coating weight will not achieved.
- a preferred embodiment of the invention provides, the workpieces with a Phosphating solution containing 0.5 to 2 g / l nitroguanidine. In particular cost reasons are decisive for this.
- the phosphating solution Complexing agent for complexing the alloy components of the steel add.
- Such an alloying ingredient is especially chromium.
- Complexing agents are, for example, tartaric acid, but especially citric acid suitable. Due to the addition of complexing agents, the components of the Steel, which may affect the quality of the coating, intercepted.
- a further advantageous embodiment of the invention is to bring the workpieces with a phosphating in contact, in addition 0.2 to 4 g / l nickel ions or 0.2 to 4 g / l magnesium ions.
- the contact of the workpieces with the phosphating solution is preferably carried out at a temperature in the range of 75 to 95 ° C.
- the workpieces can be mixed with the phosphating solution in any way Contact is preferred, the immersion treatment is preferred. As treatment duration are generally 1 to 15 minutes appropriate.
- phosphate layers having a coating weight of generally from 5 to 30 g / m 2 are achieved.
- the phosphate layers produced by the invention can be known per se Painted or provided with plastic coatings. Combined with Corrosion protection oils serve to increase the rust resistance.
- the main application of the method according to the invention lies in the Treatment of workpieces subjected to sliding friction. These are, for example, axles, transmission parts and pistons of Internal combustion engines and compressors.
- the phosphating solution contained 11.8 g / l manganese, 0.5 g / l nickel, 1 g / l iron (II), 36 g / l phosphate (calculated as P 2 O 5 ), 4.6 g / l nitrate and 0.36 g / l citrate (calculated as citric acid).
- the total number of dots of the phosphating solution was 80, the number of points of Free acid 11 (measured with 60 g of concentrate per 1 l of water). To determine the Total Acid Score and Free Acid Score is based on the above References.
- the 6.45 wt .-% manganese, 0.28 wt .-% nickel, 0.05 wt .-% iron (II), 19.8 wt .-% P 2 O 5 was used , 2.5% by weight of nitrate and 0.2% by weight of citric acid, in an amount of 183 g, which was made up to one liter with demineralized water.
- Fine-crystalline phosphate layers having a coating weight of 7 g / m 2 , corresponding to a layer thickness of 3 to 4 ⁇ m, and an average roughness R z of 1.3 to 2.4 ⁇ m were obtained.
- the gas time was 2 to 3 minutes.
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)
- Materials For Medical Uses (AREA)
- Diaphragms For Electromechanical Transducers (AREA)
Description
0,2 bis 4 | g/l Eisen (II)-Ionen |
10 bis 25 | g/l Manganionen |
25 bis 50 | g/l Phosphationen (ber. als P2O5) |
3 bis 35 | g/l Nitrationen |
0,5 bis 5 | g/l Nitroguanidin |
0,2 bis 4 g/l Nickelionen
oder
0,2 bis 4 g/l Magnesiumionen enthalten.
11,8 | g/l Mangan, |
0,5 | g/l Nickel, |
1 | g/l Eisen (II), |
36 | g/l Phosphat (berechnet als P2O5), |
4,6 | g/l Nitrat und |
0,36 | g/l Citrat (berechnet als Citronensäure). |
Claims (7)
- Verfahren zum Aufbringen von Manganphosphatschichten auf Eisen- oder Stahloberflächen mit Mangan-, Phosphat-, Eisen (II) - Ionen sowie Nitroguanidin enthaltenden Phosphatierungslösungen, dadurch gekennzeichnet, dass man die Werkstücke zwecks Ausbildung einer Manganphosphatschicht mit einer Mindestdicke von 2 µm und einer gemittelten. maximalen Rauhtiefe (Rz) von 2,5 µm gemessen nach dem Trocknen - mit einer Phosphatierungslösung bei einer Temperatur von mindestens 75 °C in Kontakt bringt, die
0,2 bis 4 g/l Eisen (II) - Ionen 10 bis 25 g/l Manganionen 25 bis 50 g/l Phosphationen (ber. als P2O5) 3 bis 35 g/l Nitrationen 0,5 bis 5 g/l Nitroguanidin - Verfahren nach Anspruch 1 dadurch gekennzeichnet, dass man die Werkstücke mit einer Phosphatierungslösung in Kontakt bringt, die 0,5 bis 2 g/l Nitroguanidin enthält.
- Verfahren nach Anspruch 1 oder 2 dadurch gekennzeichnet, dass man die Werkstücke mit einer Phosphatierungslösung in Kontakt bringt, die maximal 2,5 g/l Eisen (II) - Ionen enthält.
- Verfahren nach Anspruch 1, 2 oder 3, dadurch gekennzeichnet, dass man die Werkstücke mit einer Phosphatierungslösung in Kontakt bringt, die im Falle der Behandlung von Stahl einen Komplexbildner für die Legierungsbestandteile des Stahls, vorzugsweise Zitronensäure, enthält.
- Verfahren nach einem oder mehreren der Ansprüche 1 bis 4 dadurch gekennzeichnet, dass man die Werkstücke mit einer Phosphatierungslösung in Kontakt bringt, die zusätzlich
0,2 bis 4 g/l Nickelionen
oder
0,2 bis 4 g/l Magnesiumionen enthält. - Verfahren nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass man die Werkstücke mit einer Phosphatierungslösung in Kontakt bringt, in die zwecks Abstumpfung der Freien Säure mindestens ein Teil der Manganionen durch Mangankarbonat ergänzt wird.
- Anwendung des Verfahrens nach einem oder mehreren der Ansprüche 1 bis 6 auf Werkstücke, die einer gleitenden Reibung, wie Achsen, Getriebeteile, Motorkolben, ausgesetzt sind.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19947232A DE19947232A1 (de) | 1999-09-30 | 1999-09-30 | Verfahren zum Aufbringen von Manganphosphatschichten |
DE19947232 | 1999-09-30 | ||
PCT/EP2000/009193 WO2001023638A1 (de) | 1999-09-30 | 2000-09-20 | Verfahren zum aufbringen von manganphosphatschichten |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1230423A1 EP1230423A1 (de) | 2002-08-14 |
EP1230423B1 true EP1230423B1 (de) | 2004-08-11 |
Family
ID=7924098
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00972661A Expired - Lifetime EP1230423B1 (de) | 1999-09-30 | 2000-09-20 | Verfahren zum aufbringen von manganphosphatschichten |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP1230423B1 (de) |
AT (1) | ATE273404T1 (de) |
DE (2) | DE19947232A1 (de) |
ES (1) | ES2223598T3 (de) |
PL (1) | PL196365B1 (de) |
WO (1) | WO2001023638A1 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018202859A1 (de) | 2017-05-05 | 2018-11-08 | Federal-Mogul Nürnberg GmbH | Thermische isolierung eines stahlkolbens mittels einer mangan-phosphat- und einer versiegelungsschicht auf polysilazan-, wasserglas- oder polysiloxan-basis |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022002792A1 (en) * | 2020-07-01 | 2022-01-06 | Chemetall Gmbh | Improved activation agent for manganese phosphating processes |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2375468A (en) * | 1938-02-04 | 1945-05-08 | Parker Rust Proof Co | Phosphate coating of metals |
DE1246356B (de) * | 1963-07-30 | 1967-08-03 | Metallgesellschaft Ag | Verfahren zur Erzeugung von Manganphosphatueberzuegen auf Eisen und Stahl |
US3860455A (en) * | 1973-03-16 | 1975-01-14 | Oxy Metal Finishing Corp | Method for phosphatizing ferrous surfaces |
DE3023479A1 (de) * | 1980-06-24 | 1982-01-14 | Metallgesellschaft Ag, 6000 Frankfurt | Phosphatierverfahren |
DE4440300A1 (de) * | 1994-11-11 | 1996-05-15 | Metallgesellschaft Ag | Verfahren zum Aufbringen von Phosphatüberzügen |
-
1999
- 1999-09-30 DE DE19947232A patent/DE19947232A1/de not_active Withdrawn
-
2000
- 2000-09-20 PL PL354447A patent/PL196365B1/pl unknown
- 2000-09-20 AT AT00972661T patent/ATE273404T1/de active
- 2000-09-20 DE DE50007405T patent/DE50007405D1/de not_active Expired - Lifetime
- 2000-09-20 WO PCT/EP2000/009193 patent/WO2001023638A1/de active IP Right Grant
- 2000-09-20 EP EP00972661A patent/EP1230423B1/de not_active Expired - Lifetime
- 2000-09-20 ES ES00972661T patent/ES2223598T3/es not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018202859A1 (de) | 2017-05-05 | 2018-11-08 | Federal-Mogul Nürnberg GmbH | Thermische isolierung eines stahlkolbens mittels einer mangan-phosphat- und einer versiegelungsschicht auf polysilazan-, wasserglas- oder polysiloxan-basis |
Also Published As
Publication number | Publication date |
---|---|
ATE273404T1 (de) | 2004-08-15 |
EP1230423A1 (de) | 2002-08-14 |
PL354447A1 (en) | 2004-01-12 |
WO2001023638A1 (de) | 2001-04-05 |
DE19947232A1 (de) | 2001-04-05 |
DE50007405D1 (de) | 2004-09-16 |
ES2223598T3 (es) | 2005-03-01 |
PL196365B1 (pl) | 2007-12-31 |
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