EP0089455B1 - Procédé pour la phosphatation des surfaces métalliques dans des bains de phosphatation non-aqueux - Google Patents

Procédé pour la phosphatation des surfaces métalliques dans des bains de phosphatation non-aqueux Download PDF

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Publication number
EP0089455B1
EP0089455B1 EP83100386A EP83100386A EP0089455B1 EP 0089455 B1 EP0089455 B1 EP 0089455B1 EP 83100386 A EP83100386 A EP 83100386A EP 83100386 A EP83100386 A EP 83100386A EP 0089455 B1 EP0089455 B1 EP 0089455B1
Authority
EP
European Patent Office
Prior art keywords
phosphating
seconds
boiling
gas phase
aqueous
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
Application number
EP83100386A
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German (de)
English (en)
Other versions
EP0089455A1 (fr
Inventor
Dieter Jürgen Dr. Müller
Heinrich Spielbrink
Hermann Dr. Fricke
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.)
Huels AG
Original Assignee
Huels AG
Chemische Werke Huels AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Huels AG, Chemische Werke Huels AG filed Critical Huels AG
Priority to AT83100386T priority Critical patent/ATE15234T1/de
Publication of EP0089455A1 publication Critical patent/EP0089455A1/fr
Application granted granted Critical
Publication of EP0089455B1 publication Critical patent/EP0089455B1/fr
Expired legal-status Critical Current

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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
    • C23C22/02—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 non-aqueous solutions
    • C23C22/03—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 non-aqueous solutions containing phosphorus compounds

Definitions

  • the invention relates to the technique of phosphating metal surfaces in non-aqueous phosphating baths.
  • the immersion time is generally 0.5 to 3 min, layer thicknesses of 0.1 ⁇ m to approximately 1 ⁇ m being generally achieved, depending on the immersion time and the composition of the organic phosphating bath. In individual cases, larger layer thicknesses can also be achieved.
  • empirical test methods are generally used after a defined coating, such as. B. the salt spray test on scratched test panels according to DIN 50 021 and DIN53167, the cross cut test according to DIN 53 151, the determination of the degree of rust according to DIN 53 210, the determination of the degree of bubbles according to DIN 53 209 and other application-related test methods.
  • solvent phosphating offers considerable advantages over conventional aqueous phosphating processes. So there are no environmental problems from wastewater, the number of treatment steps is reduced due to the elimination of various washing and rinsing processes, and the energy-intensive oven drying is not necessary.
  • This object was achieved by a process for phosphating metal surfaces in non-aqueous phosphating baths based on low-boiling halogenated hydrocarbons with the addition of aqueous phosphoric acid as a phosphating agent, an alcohol as a solubilizer and, if appropriate, other stabilizers, inhibitors or accelerators of known components, as described in the Claims was presented.
  • This phosphating technique therefore requires phosphating with a boiling phosphating bath that has a sufficiently large vapor space above the liquid phase.
  • the process according to the invention therefore preferably relates to phosphating baths with a low boiling point of, for example, approximately 40 ° C., as is the case with phosphating baths based on dichloromethane as the main solvent.
  • low-boiling halogenated hydrocarbons suitable as main solvents are: chloroform, trichlorotrifluoromethane, dichloroethane, trichlorethylene, 1,1,1-trichiorethane, 1,1,3-trichiortrifluoroethane and mixtures thereof.
  • low-boiling alcohols which can be used as solubilizers: methanol, ethanol, propanol, isopropanol, butanol, sec-butanoi, tert-butanol and mixtures thereof.
  • Higher homologs such as n-pentanol, sec.-pentanoi, n-hexanol, sec.-hexanol, isohexanol, heptanol, n-octanol, 2-ethylhexanol, nonanol, decanol, undecanol, dodecanol or mixtures thereof can also be used.
  • the following may optionally be used as stabilizers: quinones, phenols, nitrophenols, nitromethane and other customary stabilizers for chlorinated hydrocarbons.
  • urea dimethylurea, diethylurea, nitrourea, thiourea, methylthiourea, ethylthiourea, dimethylthiourea, diethylthiourea and other alkylated urea and thioureas.
  • nitrobenzene dinitrobenzene, nitrotoluene, dinitrotoluene, nitroethylbenzene, pyridine, prikric acid and mixtures thereof.
  • the main solvent will generally be present at 60 to 85 percent by weight, preferably 70 to 80 percent by weight, based on the total phosphating bath, while the aqueous phosphoric acid should be used in such an amount that an H 3 PO 4 concentration of 0.1 to 2 , 0 percent by weight, preferably 0.3 to 1.0 percent by weight, based on the total phosphating bath, is present.
  • the concentration of the water in the phosphating bath should be 0.5 to 7 percent by weight, preferably 3.0 to 6.0 percent by weight.
  • Methanol or a mixture of alcohols with a predominant proportion of methanol is used as a solubilizer.
  • concentration of methanol or the alcohol mixture with a predominant methanol content should be 10 to 30 percent by weight, preferably 15 to 25 percent by weight, based on the total phosphating bath.
  • the accelerators, stabilizers and inhibitors can each be present in a concentration of 0.01 to 1.0 percent by weight, preferably 0.05 to 0.3 percent by weight, based on the total phosphating bath.
  • the formic acid ester can be present in a concentration of 0.01 to 2.0 percent by weight, preferably 0.1 to 1.0 percent by weight, based on the total phosphating bath.
  • the preferred formic acid ester is methyl formate, but it is also possible to use formic acid ethyl ester, propyl ester, isopropyl ester, butyl ester, sec-butyl ester, tert-butyl ester and mixtures thereof. It can also use higher homologous formic acid esters, such as. B. formic acid pentyl ester, sec.
  • the formic acid esters can therefore contain 1 to 12 carbon atoms in the alcohol part.
  • Low-carbon, cold-rolled deep drawing sheets St 1405 with the dimensions 10 x 20 cm are used as test workpieces, which are degreased with steam or immersion using commercially available metal degreasing baths.
  • Two series of steel sheets have been used, which have been designated A and B and which differ only in their surface roughness. Series B has the greater roughness.
  • these test panels are weighed in a dry state and then subjected to phosphating.
  • Phosphating baths with dichloromethane as the base solvent have been chosen, although phosphating baths with other low-boiling halogenated hydrocarbons or mixtures thereof are also suitable in principle.
  • a heated jacket is used as the phosphating vessel, half of which is filled with phosphating solution and which is provided with cooling coils at the top of the vessel to prevent evaporation losses and is somewhat narrowed.
  • the cooling medium is kept at - 10 ° C.
  • the vessel can also be provided with a cover with a passage for a hanging device for the sheets.
  • the phosphating bath indicated in Table 1 is kept in a boiling state in a half-filled jacket vessel of the type described above in such a way that the space up to the cooling coils consists of a gas phase which is in equilibrium with the liquid phase.
  • the prepared test sheets are then hung in the gas phase for preheating until no more condensate runs off.
  • the test panels are then immersed in the liquid phase and left for a certain time (see Table 1) in the boiling liquid phase for phosphating. Then the test sheets are hung in the gas phase again for a certain time (see Table 1). During this hanging interval, the excess phosphating solution drips off, and the remaining phosphating bath film, which is in equilibrium with the gas phase, acts on the metal surface. This process is repeated once or twice (see Table 1).
  • the sheet is then lifted into the atmosphere through the cooling zone, where it dries immediately.
  • the sheets are subjected to a test coating in the manner customary in production.
  • a test coating in the manner customary in production.
  • all commercially available coating systems can be used for the test coating.
  • a baked enamel based on an alkyd resin has been used, which is baked for 6 min at 100 ° C after coating.
  • the dry paint layers have a uniform thickness of approx. 30 ⁇ m.
  • the painted metal sheets are subjected to a 240-hour salt spray test in accordance with DIN 50 021 and 53167, and the width of the rusting is determined and the cross-cut test in accordance with DIN 53 151 is carried out.
  • test plates with different immersion times in the liquid phase and hanging times in the gas phase were phosphated using the phosphating bath specified in Table 2.
  • a test coating with a stoving lacquer based on an alkyd resin was used, which is stoved for 6 min at 100 ° C after coating.
  • the dry layers of paint have a uniform thickness of approx. 30 ⁇ m
  • Example 1 The results show that despite the same total diving time, the layer thickness of the phosphate layer increases significantly with the number of dives and the corrosion protection properties are significantly improved in the case of multiple dives.
  • the greater increase compared to Example 1 can be attributed to the presence of the formic acid ester.
  • the presence of the formic acid ester has a positive effect on the anti-corrosion properties in the case of multiple dips.
  • test plates with different immersion times in the liquid phase and hanging times in the gas phase were phosphated with the phosphating baths given in Table 3.
  • a test coating with a stoving varnish based on saturated polyester resins was used, which is baked at 150 ° C for 20 min after coating.
  • the dry layers of paint have a uniform thickness of approx. 30 ⁇ m.

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)

Claims (4)

1. Procédé pour la phosphatation de surfaces métalliques dans des bains de phosphatation non aqueux à base d'hydrocarbures halogénés à bas point d'ébullition, avec addition d'acide phosphorique aqueux comme agent de phosphatation, d'un alcool comme unisseur et éventuellement d'autres constituants connus comme stabilisants, inhibiteurs ou accélérateurs, caractérisé par le fait qu'après le préchauffage dans la phase gazeuse, on plonge les pièces à phosphater au moins à deux reprises pendant au moins 10 secondes dans le bain de phosphatation bouillant et que, dans l'intervalle, on les laisse au moins 20 secondes dans la phase gazeuse.
2. Procédé selon la revendication 1, caractérisé par le fait que le temps total d'immersion est d'au moins 30 secondes.
3. Procédé selon les revendications 1 à 2, caractérisé par le fait que les temps de suspension dans la phase gazeuse, entre les processus d'immersion, sont d'au moins 30 secondes.
4. Procédé selon les revendications 1 à 3, caractérisé par le fait que le bain de phosphatation contient comme constituant activant un ester d'acide formique et, comme unisseur du méthanol ou un mélange d'alcools formé principalement de méthanol.
EP83100386A 1982-03-18 1983-01-18 Procédé pour la phosphatation des surfaces métalliques dans des bains de phosphatation non-aqueux Expired EP0089455B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83100386T ATE15234T1 (de) 1982-03-18 1983-01-18 Verfahren zum phosphatieren von metalloberflaechen in nicht-waessrigen phosphatierbaedern.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3209828 1982-03-18
DE19823209828 DE3209828A1 (de) 1982-03-18 1982-03-18 Verfahren zum phosphatieren von metalloberflaechen in nichtwaessrigen phosphatierbaedern

Publications (2)

Publication Number Publication Date
EP0089455A1 EP0089455A1 (fr) 1983-09-28
EP0089455B1 true EP0089455B1 (fr) 1985-08-28

Family

ID=6158566

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83100386A Expired EP0089455B1 (fr) 1982-03-18 1983-01-18 Procédé pour la phosphatation des surfaces métalliques dans des bains de phosphatation non-aqueux

Country Status (8)

Country Link
US (1) US4447273A (fr)
EP (1) EP0089455B1 (fr)
JP (1) JPS58167780A (fr)
AT (1) ATE15234T1 (fr)
DE (2) DE3209828A1 (fr)
DK (1) DK119583A (fr)
ES (1) ES8401147A1 (fr)
GR (1) GR77946B (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61132782A (ja) * 1984-11-29 1986-06-20 Toshiba Corp 圧縮機のバルブカバ−の製造方法
US4698269A (en) * 1986-05-08 1987-10-06 Narusch Jr Michael J Sintered, corrosion-resistant powdered metal product and its manufacture
US5118333A (en) * 1986-11-07 1992-06-02 At&T Bell Laboratories Apparatus for contacting a preform rod to cause the preform rod to have a substantially straight longitudinal axis and a transverse cross section which is substantially circular and disposed concentrically about its longitudinal axis
US6162508A (en) * 1998-11-02 2000-12-19 Nortel Networks Limited Molybdenum phosphate based corrosion resistant conversion coatings

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA690340A (en) * 1964-07-07 Hooker Chemical Corporation Process and composition for phosphatizing metals
CA607061A (en) * 1960-10-18 B. Copelin Harry Composition and process for phosphatizing metal
US2854370A (en) * 1957-10-04 1958-09-30 Oakite Prod Inc Composition and method for phosphate coating of metal
US2992146A (en) * 1959-02-26 1961-07-11 Du Pont Process of phosphating in a trichlorethylene vapor zone
US4008101A (en) * 1975-03-20 1977-02-15 Diamond Shamrock Corporation Methylene chloride phosphatizing
US4029523A (en) * 1975-03-20 1977-06-14 Diamond Shamrock Corporation Solvent phosphatizing compositions yielding non water soluble coatings

Also Published As

Publication number Publication date
DK119583A (da) 1983-09-19
ES520735A0 (es) 1983-12-16
US4447273A (en) 1984-05-08
DE3209828A1 (de) 1983-09-22
DK119583D0 (da) 1983-03-15
JPS58167780A (ja) 1983-10-04
EP0089455A1 (fr) 1983-09-28
GR77946B (fr) 1984-09-25
ES8401147A1 (es) 1983-12-16
DE3360628D1 (en) 1985-10-03
ATE15234T1 (de) 1985-09-15

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