EP0291891B1 - Procédé pour appliquer des couches de conversion sur le titane - Google Patents

Procédé pour appliquer des couches de conversion sur le titane Download PDF

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Publication number
EP0291891B1
EP0291891B1 EP88107776A EP88107776A EP0291891B1 EP 0291891 B1 EP0291891 B1 EP 0291891B1 EP 88107776 A EP88107776 A EP 88107776A EP 88107776 A EP88107776 A EP 88107776A EP 0291891 B1 EP0291891 B1 EP 0291891B1
Authority
EP
European Patent Office
Prior art keywords
titanium
solution
concentration
conversion
ratio
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
EP88107776A
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German (de)
English (en)
Other versions
EP0291891A1 (fr
Inventor
Hiroyoshi C/O Nihon Parkerizing Co. Ltd. Nakagawa
Eiichi C/O Nihon Parkerizing Co. Ltd. Nishi
Masanori C/O Nihon Parkerizing Co. Ltd. Kanda
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.)
Nihon Parkerizing Co Ltd
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Nihon Parkerizing Co Ltd
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Filing date
Publication date
Application filed by Nihon Parkerizing Co Ltd filed Critical Nihon Parkerizing Co Ltd
Publication of EP0291891A1 publication Critical patent/EP0291891A1/fr
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Publication of EP0291891B1 publication Critical patent/EP0291891B1/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
    • C23C22/34—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 fluorides or complex fluorides

Definitions

  • the invention relates to a process for producing conversion coatings on surfaces of titanium or titanium alloys by means of aqueous solutions which contain fluoride ions and one or more metal ions from the group consisting of magnesium, calcium, manganese, iron, cobalt, nickel, zinc and molybdenum and a pH value have above 1.5 and its application for the preparation of workpieces made of titanium or titanium alloys for cold forming.
  • the object of the invention is to provide a method for applying conversion coatings on titanium or titanium alloys, which does not have the known, in particular the aforementioned disadvantages, and which permits the production of firmly adhering conversion coatings which are particularly suitable as a lubricant carrier layer.
  • the fluoride is usually introduced in the form of hydrogen fluoride, bifluoride or fluoride.
  • Particularly suitable bifluorides or fluorides are those of sodium, potassium or ammonium. In this respect, the choice of the type of contribution is arbitrary.
  • the fluoride concentration is below 5 g / l, the caustic effect of the solution on titanium or titanium alloy is insufficient and the coating formation is low. In the event that the concentration exceeds 40 g / l, the etching effect becomes too strong and the coating formation is also low.
  • the nitrate is introduced via nitric acid or its salts, for example as sodium, potassium or ammonium nitrate.
  • the importance of the nitrate is primarily to oxidize the hydrogen formed when the solution is attacked on the titanium surface and thereby prevent embrittlement of the titanium or the titanium alloy by absorption of hydrogen. If the nitrate concentration is measured in such a way that the ratio of NO3: F falls below 0.005, the effect of the nitrate with regard to the oxidation of hydrogen is inadequate and embrittlement of the titanium surface cannot be ruled out with certainty. in the As a result, the liability of the conversion coating would be reduced. On the other hand, the coating adhesion is reduced even if the NO3 / F ratio of 0.2 is exceeded. Only if the NO3 / F ratio of 0.005 to 0.2 is observed, that is if the nitrate concentration is adjusted to the fluoride concentration actually present, is it ensured that conversion coatings of the desired quality are obtained.
  • Sulfate is usually introduced into the solution via sulfuric acid or sulfate or bisulfate of sodium or ammonium.
  • the sulfate is used in particular to support the action of the metal ions in the treatment solution. If the sulfate content is below the SO4 / F ratio of 0.02, the solubility of the metal ions in the solution is reduced and there is some tendency for the metal ions to precipitate. This in turn results in disadvantageous layer formation. In contrast, when the SO Mattersch / F ratio exceeds 0.5, the etching effect on the titanium is increased and the deposition of titanium compound becomes weaker. As a result, coatings with poor adhesion and coarseness would be formed.
  • the metal ions in the solution are presumably used for nucleation for the deposition of the conversion coating. To achieve such an effect, a certain minimum content of metal ions is required. On the other hand, if the metal ion content becomes too high, the deposition of a titanium compound, which is the main component of the conversion coating, with special needs. Since the amount of titanium compound to be deposited depends on the amount of fluoride, which in turn determines the extent of the etching, the amount of metal ions must be adjusted in relation to the amount of fluoride ions. That is, the metal ion / F ratio must be in the range of 0.02 to 0.5. If the ratio is less than 0.02, the amount of metal ions in the solution is too small and does not cause high quality coating. On the other hand, if it exceeds 0.5, the metal ions tend to precipitate. It is then impossible to obtain fine and sufficient amounts of deposited crystal nuclei.
  • Suitable organic chelating agents are, in particular, organic acids such as gluconic acid, citric acid, tartaric acid, succinic acid, tannic acid, nitrilotriacetic acid, malic acid, but also ethylenediaminetetraacetic acid.
  • the effect of the organic chelating agent is presumably based on increasing the effectiveness of the metal ions and thereby improving the formation of the conversion coating.
  • the concentration of the chelating agent is in the range from 0.1 to 2 g / l. Within this area, he makes a significant contribution to improving coating training. If its concentration is below 0.1 g / l, an improving effect is practically undetectable, while quantities greater than 2 g / l have no additional effect.
  • a variety of compounds are useful with respect to the water-soluble organic polymer.
  • polyvinyl alcohol, gelatin, polyvinyl pyrrolidone are particularly suitable. In any case, a considerable effect is achieved with these substances.
  • concentration of the chelating agent there is practically no dependence on the fluoride ion content in the concentration of the organic polymer.
  • the content of the organic polymer in the coating solution is in the range of 0.1 to 10 g / l. It also favors the formation of the conversion coating. If the content is below 0.1 g / l, practically no improvement is achieved, whereas no further improving effect can be found if the limit of 10 g is exceeded. On the contrary, the coating training may be impaired.
  • surfactant those of anionic, cationic, amphoteric and nonionic character are suitable.
  • Amphoteric and nonionic surfactants are preferred.
  • condensates come from as nonionic surfactants higher alcohols of the type RO- [CH2-CH2-O-] n -H, of higher aliphatic acids of the type R-CO-O - [- CH2-CH2-O-] n -H, of higher aliphatic acid amides of the type R-CO-NH - [- CH2-CH2-O-] n -H, of higher alkyl amines of the type and of alkylphenols of the type into consideration.
  • amphoteric surfactants those of the betaine type, the glycine type, the alanine type, etc. are suitable. These can all be used within the method according to the invention.
  • the concentration of surfactants in the treatment liquid ranges from 0.01 to 3 g / l.
  • the surfactant also favors the formation of the conversion coating. No effect can be seen at concentrations below 0.01 g / l, whereas no additional effect can be achieved at concentrations above 3 g / l. Instead, the higher content of the surfactant in the treatment liquid only has an adverse effect on the wastewater treatment.
  • One or more types of the aforementioned additives from the groups of the organic chelating agents, the water-soluble organic polymers and the surfactants can be provided, the respective permissible concentrations then having to be observed.
  • the pH of the treatment solution to be used in the process according to the invention is in the range from 1.5 to 5.
  • the surfaces are brought into contact with a solution which has a pH of 2 to 3.5.
  • the pH is usually adjusted with alkalis, such as with ammonia or sodium hydroxide solution or with sulfuric acid or hydrofluoric acid.
  • alkalis such as with ammonia or sodium hydroxide solution or with sulfuric acid or hydrofluoric acid.
  • a pH value below 1.5 increases the caustic effect of the solution on titanium or titanium alloys considerably and also leads to coarse and less adhesive coatings. At pH above 5 there is practically no coating formation.
  • a further advantageous embodiment of the invention provides for the metal surfaces to be brought into contact with the solution at a temperature of 40 to 80 ° C., preferably 45 to 55 ° C., and the treatment time to be 3 to 15 minutes. adjust. If the treatment temperature is below 40 ° C, the reactivity of the solution drops, while at temperatures higher than 80 ° C the reactivity increases and becomes too intense. Both cases are inherently undesirable in attempting to obtain well adherent coatings.
  • the method according to the invention serves to generate conversion layers for purposes for which such coatings are usually applied.
  • a lubricant is applied after the conversion treatment.
  • Particularly suitable lubricants are molybdenum disulfide, metal soaps, press oils, waxes, resins and the like.
  • the advantage of the invention is that uniform and outstandingly adhering coatings are obtained which allow a high reduction in cross-section even under the highest demands, namely during cold forming. A peeling of the conversion coating is prevented and the lubricant film on the surface of the fixed workpiece to be formed.
  • the fact that the conversion coating has a large number of very fine pores makes it particularly suitable as a lubricant carrier layer.
  • Wire rod of the type mentioned in Example 1 was brightly annealed and then subjected to the process mentioned in Example 1 without any conversion treatment.
  • Wire rod of the type mentioned in Example 1 was annealed in a conventional manner.
  • the wire rod provided with scale was then treated with lubricant according to Example 1.
  • the wire drawing was repeated under the tabulated conditions and was stopped as soon as signs of seizure appeared.
  • the lubricant treatment was done as shown in Table 5.
  • Wire rod of the aforementioned nature was polished and subjected to the conversion treatment according to Table 1.
  • a lubricant treatment was then carried out as shown in Table 5.
  • the individual workpieces were formed by cold upsetting under the same conditions.
  • the type of lubricant treatment and the results observed during the forming are shown in Table 5.
  • Ti-3AL-2.5V quality cylinders with a diameter of 2.5 mm and a height of 7 mm were cleaned by blasting and then subjected to the conversion treatment as in the case of Example 1.
  • Lubricant treatment and lubrication behavior are given in Table 6.
  • the aforesaid blasted material was converted according to Table 1 and subjected to the lubricant treatment of Example 2.
  • the cold forming was then carried out by cold extrusion under the same conditions. The details are given in Table 6.

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)

Claims (5)

1. Procédé de formation de revêtements de conversion sur des surfaces de titane ou d'alliages de titane, au moyen de solutions aqueuses qui contiennent des ions fluorure et un ou plusieurs ions métalliques du groupe magnésium, calcium, manganèse, fer, cobalt, nickel, zinc et molybdène, qui présentent également une valeur de pH supérieure à 1,5, caractérisé en ce qu'on amène les surfaces en contact avec une solution qui contient
a)   5 à 40 g/l de fluorure
b)   du nitrate dans un rapport pondéral de NO₃: F tel que 0,005 à 0,2
c)   du sulfate dans un rapport pondéral de SO₄: F tel que 0,02 à 0,5
d)   au moins un des ions métalliques magnésium, calcium, manganèse, fer, cobalt, nickel, zinc ou molybdène dans un rapport pondéral de Me: F tel que 0,02 à 0,5 ainsi que
e)   au moins une substance des groupes des formateurs de chélate à une concentration de 0,1 à 2 g/l, des polymères organiques solubles dans l'eau à une concentration de 0,1 à 10 g/l et des composés tensioactifs à une concentration de 0,01 à 3 g/l


et qui présente une valeur de pH de 1,5 à 5,0.
2. Procédé selon la revendication 1, caractérisé en ce qu'on amène les surfaces en contact avec une solution qui présente une valeur de pH de 2 à 3,5.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'on amène les surfaces en contact avec une solution à une température de 40 à 80°C, de préférence de 45 à 55°C, pendant une durée de 3 à 15 mn.
4. Procédé selon la revendication 1, 2 ou 3, caractérisé en ce qu'on lave les pièces à travailler avec de l'eau, après la formation du revêtement de conversion et on les sèche, le cas échéant en plusieurs étapes.
5. Utilisation du procédé selon l'une ou plusieurs des revendications 1 à 4 pour la préparation de pièces à travailler en titane ou alliages de titane pour le formage à froid.
EP88107776A 1987-05-16 1988-05-14 Procédé pour appliquer des couches de conversion sur le titane Expired - Lifetime EP0291891B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP62118099A JPS63286585A (ja) 1987-05-16 1987-05-16 チタンまたはその合金の化成処理液ならびに該化成処理液でのチタンまたはその合金の表面処理方法
JP118099/87 1987-05-16

Publications (2)

Publication Number Publication Date
EP0291891A1 EP0291891A1 (fr) 1988-11-23
EP0291891B1 true EP0291891B1 (fr) 1991-08-07

Family

ID=14727979

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88107776A Expired - Lifetime EP0291891B1 (fr) 1987-05-16 1988-05-14 Procédé pour appliquer des couches de conversion sur le titane

Country Status (6)

Country Link
US (1) US4846897A (fr)
EP (1) EP0291891B1 (fr)
JP (1) JPS63286585A (fr)
CA (1) CA1308004C (fr)
DE (2) DE3816557A1 (fr)
ES (1) ES2023975B3 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6867324B2 (en) 2000-05-26 2005-03-15 Basf Aktiengesellschaft Method and device for the continuous production of organic mono or polyisocyanates

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA903494B (en) * 1989-05-18 1991-02-27 Henkel Corp Compositions and processes for improved preparation of metals for cold forming
US5158623A (en) * 1990-03-30 1992-10-27 Rem Chemicals, Inc. Method for surface refinement of titanium and nickel
US5051141A (en) * 1990-03-30 1991-09-24 Rem Chemicals, Inc. Composition and method for surface refinement of titanium nickel
NO924697D0 (no) * 1992-12-04 1992-12-04 Jan Erik Ellingsen Kirurgisk implantat og en fremgangsmaate for behandling avkirurgisk implantat
US6026695A (en) * 1998-06-16 2000-02-22 Ingersoll-Rand Company Engine starter housing and an annular housing extension therefor
EP1853394A4 (fr) * 2005-02-24 2009-09-30 Biomet 3I Llc Procede de traitement de surface pour implants fabriques en titane ou en alliage de titane
US7923425B2 (en) * 2006-08-21 2011-04-12 Henkel Ag & Co. Kgaa Low-foaming, acidic low-temperature cleaner and process for cleaning surfaces

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3041215A (en) * 1955-02-07 1962-06-26 Parker Rust Proof Co Solutions and methods for forming protective coatings on titanium
FR1146748A (fr) * 1955-02-07 1957-11-14 Parker Ste Continentale Procédé de revêtement du titane et de ses alliages et compositions pour sa mise en oeuvre
US4004064A (en) * 1974-01-02 1977-01-18 Joseph W. Aidlin Protective coating for articles
US4298404A (en) * 1979-09-06 1981-11-03 Richardson Chemical Company Chromium-free or low-chromium metal surface passivation
JPS6267181A (ja) * 1985-09-19 1987-03-26 Nippon Parkerizing Co Ltd チタン又はその合金材料の化成処理方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6867324B2 (en) 2000-05-26 2005-03-15 Basf Aktiengesellschaft Method and device for the continuous production of organic mono or polyisocyanates

Also Published As

Publication number Publication date
ES2023975B3 (es) 1992-02-16
US4846897A (en) 1989-07-11
DE3864074D1 (de) 1991-09-12
JPS63286585A (ja) 1988-11-24
CA1308004C (fr) 1992-09-29
DE3816557A1 (de) 1988-11-24
EP0291891A1 (fr) 1988-11-23
JPH044397B2 (fr) 1992-01-28

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