EP1230423B1 - Procede pour appliquer des couches de phosphate de manganese - Google Patents

Procede pour appliquer des couches de phosphate de manganese Download PDF

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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
Application number
EP00972661A
Other languages
German (de)
English (en)
Other versions
EP1230423A1 (fr
Inventor
Klaus-Dieter Nittel
Detlev Seifert
Ralf Stickler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemetall GmbH
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Chemetall GmbH
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Publication date
Application filed by Chemetall GmbH filed Critical Chemetall GmbH
Publication of EP1230423A1 publication Critical patent/EP1230423A1/fr
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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)

Claims (7)

  1. Procédé pour l'application de couches de phosphate de manganèse sur des surfaces en fer ou en acier au moyen de solutions de phosphatation contenant des ions manganèse, des ions phosphates, des ions fer (II) et de la nitroguanidine, caractérisé en ce que, pour la formation d'une couche de phosphate de manganèse ayant une épaisseur minimale de 2 µm et présentant une profondeur maximale moyenne des rugosités (Rz) de 2, 5 µm, cette profondeur étant mesurée après séchage, on met les pièces à traiter en contact, à une température d'au moins 75 °C, avec une solution de phosphatation qui contient
    0 ,2 à 4 g/l d'ions fer (II),
    10 à 25 g/l d'ions manganèse,
    25 à 50 g/l d'ions phosphates (calculés en P2O5),
    3 à 35 g/l d'ions nitrates, et
    0, 5 à 5 g/l de nitroguanidine,
    et qui présente 7 à 24 points d'acide libre, 50 à 140 points d'acide total et une valeur S de 0, 2 à 1.
  2. Procédé selon la revendication 1, caractérisé en ce que l'on met en contact les pièces à traiter avec une solution de phosphatation qui contient 0,5 à 2 g/l de nitroguanidine.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'on met les pièces à traiter en contact avec une solution de phosphatation qui contient au maximum 2, 5 g/l d'ions fer (II).
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que l'on met les pièces à traiter en contact avec une solution de phosphatation qui, dans le cas du traitement de l'acier, contient un complexant pour les constituants d'alliage de l'acier, de préférence de l'acide citrique.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que l'on met les pièces à traiter en contact avec une solution de phosphatation qui contient en plus 0, 2 à 4 g/l d'ions nickel ou 0, 2 à 4 g/l d'ions magnésium.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que l'on met les pièces à traiter en contact avec une solution de phosphatation dans laquelle au moins une partie des ions manganèse est complétée par du carbonate de manganèse afin de neutraliser l'acide libre.
  7. Utilisation du procédé selon l'une quelconque des revendications 1 à 6, sur des pièces à traiter qui sont soumises à un frottement de glissement, telles que des axes, des parties d'engrenage, des pistons de moteur.
EP00972661A 1999-09-30 2000-09-20 Procede pour appliquer des couches de phosphate de manganese Expired - Lifetime EP1230423B1 (fr)

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 (fr) 1999-09-30 2000-09-20 Procede pour appliquer des couches de phosphate de manganese

Publications (2)

Publication Number Publication Date
EP1230423A1 EP1230423A1 (fr) 2002-08-14
EP1230423B1 true EP1230423B1 (fr) 2004-08-11

Family

ID=7924098

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00972661A Expired - Lifetime EP1230423B1 (fr) 1999-09-30 2000-09-20 Procede pour appliquer des couches de phosphate de manganese

Country Status (6)

Country Link
EP (1) EP1230423B1 (fr)
AT (1) ATE273404T1 (fr)
DE (2) DE19947232A1 (fr)
ES (1) ES2223598T3 (fr)
PL (1) PL196365B1 (fr)
WO (1) WO2001023638A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018202859A1 (fr) 2017-05-05 2018-11-08 Federal-Mogul Nürnberg GmbH Isolation thermique d'un piston en acier au moyen d'une couche de phosphate de manganèse et d'une couche de scellement à base de polysilazane, de verre soluble ou de polysiloxane

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20230031905A (ko) * 2020-07-01 2023-03-07 케메탈 게엠베하 망가니즈 포스페이트처리 방법을 위한 개선된 활성화제

Family Cites Families (5)

* Cited by examiner, † Cited by third party
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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018202859A1 (fr) 2017-05-05 2018-11-08 Federal-Mogul Nürnberg GmbH Isolation thermique d'un piston en acier au moyen d'une couche de phosphate de manganèse et d'une couche de scellement à base de polysilazane, de verre soluble ou de polysiloxane

Also Published As

Publication number Publication date
WO2001023638A1 (fr) 2001-04-05
PL196365B1 (pl) 2007-12-31
EP1230423A1 (fr) 2002-08-14
DE50007405D1 (de) 2004-09-16
DE19947232A1 (de) 2001-04-05
PL354447A1 (en) 2004-01-12
ATE273404T1 (de) 2004-08-15
ES2223598T3 (es) 2005-03-01

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