CA2058631A1 - Process for producing manganese-containing phosphate coatings on metal surfaces - Google Patents
Process for producing manganese-containing phosphate coatings on metal surfacesInfo
- Publication number
- CA2058631A1 CA2058631A1 CA002058631A CA2058631A CA2058631A1 CA 2058631 A1 CA2058631 A1 CA 2058631A1 CA 002058631 A CA002058631 A CA 002058631A CA 2058631 A CA2058631 A CA 2058631A CA 2058631 A1 CA2058631 A1 CA 2058631A1
- Authority
- CA
- Canada
- Prior art keywords
- aluminum
- steel
- phosphate coatings
- phosphate
- manganese
- 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.)
- Abandoned
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
- C23C22/34—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
- C23C22/36—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 containing also phosphates
- C23C22/364—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 containing also phosphates containing also manganese cations
- C23C22/365—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 containing also phosphates containing also manganese cations containing also zinc and nickel 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
- C23C22/34—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
- C23C22/36—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 containing also phosphates
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)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
PROCESS FOR PRODUCING PHOSPHATE COATINGS
CONTAINING MANGANESE ON METAL SURFACES
Abstract of the Disclosure The invention relate to a process for producing phosphate coatings containing manganese on surfaces of steel, galvanized steel, aluminum and/or the alloys thereof or of aluminum-steel composite materials by spraying or spray-immersion with an aqueous solution containing 0.8 to 1.4 g/l of Zn2+, 0.6 to 2.0 g/l of Mn2+, 0.3 to 1.4 g/l of Ni2+, to 25 g/l of PO43-, 2 to 10 g/l of NO3-, 0.2 to 1.0 g/l of F3- and, as an accelerator of the phosphate deposition, 0.04 to 0.12 g/l of NO2-, 0.6 to 2.0 g/l of ClO3- and/or 0.2 to 1.0 g/l of sodium-3-nitrobenzene-sulfonate, the content of free acid having been adjusted to from 1. 4 to 1. 8 points and the solution having a total acid content of from 18 to 30.
CONTAINING MANGANESE ON METAL SURFACES
Abstract of the Disclosure The invention relate to a process for producing phosphate coatings containing manganese on surfaces of steel, galvanized steel, aluminum and/or the alloys thereof or of aluminum-steel composite materials by spraying or spray-immersion with an aqueous solution containing 0.8 to 1.4 g/l of Zn2+, 0.6 to 2.0 g/l of Mn2+, 0.3 to 1.4 g/l of Ni2+, to 25 g/l of PO43-, 2 to 10 g/l of NO3-, 0.2 to 1.0 g/l of F3- and, as an accelerator of the phosphate deposition, 0.04 to 0.12 g/l of NO2-, 0.6 to 2.0 g/l of ClO3- and/or 0.2 to 1.0 g/l of sodium-3-nitrobenzene-sulfonate, the content of free acid having been adjusted to from 1. 4 to 1. 8 points and the solution having a total acid content of from 18 to 30.
Description
20~86~1 .
D 8 4 ~:~
PROCESS FOR PRODUCING PHOSPHATE COATINGS
CONTAINING MANGANESE ON_METAL SURFACES
: The present invention relates to a~process for producing phosphate coatings containing manganese on surfaces of steel, galvanized steel, aluminum and/or the alloys thereof by spraying or immersion.
~: .
In order to improve the protection from corrosion, ~ -: ;~ commodities such as automotive bodies, automobile accessories and spare parts, agricultural implements, re~rigerators and any kind of small parts are phosphated in accordance with so-called low-zinc processes and then mostly cataphoretically dip-coated.~ Such manganese-modified zinc phosphate coatingæ as primers or modern coating equipment have been Xnown, for example, from .A. Roland and K.-H. Gottwald, Metalloberflache, 1988/6. Herein it is determined that the use of mangan-ese ions in addition to zinc and nickel ion~ in low-zinc phosphating processes demonstrably improves the anti-corrosive properties, particularly upon US2 Or sur~ace-modified metal :sheets. The incorporation of manganese in the zinc phosphate coatings results in smaller and more compact crystals having an increased alXali resist-ance. ~t the same time the working range o~ phosphating baths is extended; aluminum also can be phosphated in a composite with steel and galvanized steel to form a layer, with the quality standard reached in general :
'~
.
--`` 2~8~31 being ensured. Such composite material parts, consist-ing of a variety of metals, for example aluminum and steel, more recently ha-~e been used to an increased degree in the manufacture of automobiles.
From the EP-A-O 261 70~ there has been known a process for producing phosphate coatings on such sur--faces, wherein, in order to form uniform phosphate layers having a high degree of covering, spraying or spray-immersion is employed with a phosphating solution which must comprise, in addition to zinc and phosphate, at least one accelerator and an amount of fluoride ions to be accurakely maintained. Furthermore, according to the EP-A-O 261 704 the content of free acid (FS) is to be adjusted in accordance with a Pormula mentioned therein.
In contrast thereto, it is the object of ~he pxesent invention to provide an improved process for producing phosphate coatings on surfaces of steel, galvanized steel, aluminum and/or the alloys thereof which leads to still more uni.form phosphate coatings, while, moreover, any change of the phosphating technology should not be required.
Th~ object mentioned above was attained by means of a process for producing phosphate coating~ cont~ining manganes~ on surfaces of steel, galvanized steel, aluminum and/or the alloys thereo~ or of aluminum-steel composite materials by spraying or spray-immersion with an a~ueous solution containing 008 to 1.4 g/l of Zn2~, 0.6 to 2.0 g/l of Mn2 , 0.3 to 1.4 g/l of Ni2 , 3 ~
lO to 25 g/l of P043 , 2 to 10 g/l o~ N~3 , 0.2 ko 1.0 g/l of F and, as an accelerator o the phosphate deposition, 0.04 to 0.12 g/l of N0~ , 0.6 to 2.0 g/l of Cl03 and/or 0.2 to l.0 g/l oP sodium-3-nitrobenzene-sulfonate, the content of free acid having been adjusted to from 1.4 to 1.8 points and the solution having a total acid content of from 18 to 30.
In conventional low-zinc processes the content of free acid is known to be about 0.6 to 0.9 points. At higher values, on the surfaces thus treated there are being formed no~-uniform non-continuous phosphate layers; on steel the formation of rust film is also observed. In the fluoride-containing phosphating baths ~hQ addition o~ manganese basically allows an increase in th~ free acid cont~t without the drawbacks mention-ed.
The use of manganese in the phosphate layer ha~
various advantages in the above-mentioned substrate lay~rs.
By means of the present invention it was found that, especially upon application of the process accord-ing to the present invention to aluminum sur~aces, a relative low amount of fluoride can be employed in order to obtain op~ically uniform phosphate layer.s.
In the surface treatment of steel th~ proven low-zinc technology may b2 maintained for the formation of , 3 ~
D 8 4 ~:~
PROCESS FOR PRODUCING PHOSPHATE COATINGS
CONTAINING MANGANESE ON_METAL SURFACES
: The present invention relates to a~process for producing phosphate coatings containing manganese on surfaces of steel, galvanized steel, aluminum and/or the alloys thereof by spraying or immersion.
~: .
In order to improve the protection from corrosion, ~ -: ;~ commodities such as automotive bodies, automobile accessories and spare parts, agricultural implements, re~rigerators and any kind of small parts are phosphated in accordance with so-called low-zinc processes and then mostly cataphoretically dip-coated.~ Such manganese-modified zinc phosphate coatingæ as primers or modern coating equipment have been Xnown, for example, from .A. Roland and K.-H. Gottwald, Metalloberflache, 1988/6. Herein it is determined that the use of mangan-ese ions in addition to zinc and nickel ion~ in low-zinc phosphating processes demonstrably improves the anti-corrosive properties, particularly upon US2 Or sur~ace-modified metal :sheets. The incorporation of manganese in the zinc phosphate coatings results in smaller and more compact crystals having an increased alXali resist-ance. ~t the same time the working range o~ phosphating baths is extended; aluminum also can be phosphated in a composite with steel and galvanized steel to form a layer, with the quality standard reached in general :
'~
.
--`` 2~8~31 being ensured. Such composite material parts, consist-ing of a variety of metals, for example aluminum and steel, more recently ha-~e been used to an increased degree in the manufacture of automobiles.
From the EP-A-O 261 70~ there has been known a process for producing phosphate coatings on such sur--faces, wherein, in order to form uniform phosphate layers having a high degree of covering, spraying or spray-immersion is employed with a phosphating solution which must comprise, in addition to zinc and phosphate, at least one accelerator and an amount of fluoride ions to be accurakely maintained. Furthermore, according to the EP-A-O 261 704 the content of free acid (FS) is to be adjusted in accordance with a Pormula mentioned therein.
In contrast thereto, it is the object of ~he pxesent invention to provide an improved process for producing phosphate coatings on surfaces of steel, galvanized steel, aluminum and/or the alloys thereof which leads to still more uni.form phosphate coatings, while, moreover, any change of the phosphating technology should not be required.
Th~ object mentioned above was attained by means of a process for producing phosphate coating~ cont~ining manganes~ on surfaces of steel, galvanized steel, aluminum and/or the alloys thereo~ or of aluminum-steel composite materials by spraying or spray-immersion with an a~ueous solution containing 008 to 1.4 g/l of Zn2~, 0.6 to 2.0 g/l of Mn2 , 0.3 to 1.4 g/l of Ni2 , 3 ~
lO to 25 g/l of P043 , 2 to 10 g/l o~ N~3 , 0.2 ko 1.0 g/l of F and, as an accelerator o the phosphate deposition, 0.04 to 0.12 g/l of N0~ , 0.6 to 2.0 g/l of Cl03 and/or 0.2 to l.0 g/l oP sodium-3-nitrobenzene-sulfonate, the content of free acid having been adjusted to from 1.4 to 1.8 points and the solution having a total acid content of from 18 to 30.
In conventional low-zinc processes the content of free acid is known to be about 0.6 to 0.9 points. At higher values, on the surfaces thus treated there are being formed no~-uniform non-continuous phosphate layers; on steel the formation of rust film is also observed. In the fluoride-containing phosphating baths ~hQ addition o~ manganese basically allows an increase in th~ free acid cont~t without the drawbacks mention-ed.
The use of manganese in the phosphate layer ha~
various advantages in the above-mentioned substrate lay~rs.
By means of the present invention it was found that, especially upon application of the process accord-ing to the present invention to aluminum sur~aces, a relative low amount of fluoride can be employed in order to obtain op~ically uniform phosphate layer.s.
In the surface treatment of steel th~ proven low-zinc technology may b2 maintained for the formation of , 3 ~
- 4 ~
phosphophyllite or manganese containing phosphophylli~e, and at the same time the zinc content may be increased without any deterioration in quality.
On galvanized steel sheets, alloy-galvanized steel sheets and on aluminum, the use of manganese gives improved results, at a simultaneously increased Zirl~
content due to the incorpora~ion o~ manganese in the layer, in the subsequent coating by means of a cata-phoretic electro-dipcoating. This simultaneous inter-action between the contents of zinc and manganese in the phosphating solution has been surprisingly found by means of the present invention.
The aluminum materials to be treated by the process according to the invention comprise the pure metal and the alloys thereof. Thus, as the examples, th~re may be mentioned high-grade alumlnum, AlMg and AlMgSi wrought materials. An extensive presentation of these aluminum materials is found, for exampl~, in the "Aluminium Taschenbuchl', 14th Edition, Aluminium-Verlag, Dussel-dor~, 1983. The steels to be tr ated by the proce~s according to the invention especially comprise commodi-ties such as automotive bodies, automobile accessories and spar~ parts, aqricultural implements, r~rrigera~ors and any other kind of small parts usually used in the form of sheets. The term "galvanized steel" includes galvanization by electrolytic deposition and melt immersion application and, thus9 r~feres to zinc and known zinc alloys.
If the process according to he invention is carried out in the spray-immersion mode, the period of spraying must be such as to ensure the fo~mation o~ a largely continuous phosphate layer.
' 3 ~
Modern fulL~immersion plants are distinguished by a great number of steps in sequence. The term "full immersion plant" is derived from phosphating by means of an immersion application. In other process steps, spraying operations are also carried out, the body being after-sprayed once it has emerged from the immersion bath. Important for an optimum phosphating is a separate activating step. The layer to be phosphated, for pre-cleaning and activating same, is usually clean-ed, rinsed and subsequently activated prior to the phosphating operation. Here, for example, aqueous suspensions containing titanium phosphate may be employed.
Maintaining the concentration ranges according to the main claim is an essential condition for the production of high-quality, i . e. unifo:rm, phosphate coating~. If the values fall below the concentration limits indicated, the layers become non-uniform. More particularly, they become less suited for the subsequent electro-dipcoat paintin~.
The fluoride concentrations mentioned according to the invention are measured with a special ion-sensltive electrode in a bufPered solution at p~l 5. 3 . Thus, these values are by no means oomparable to the v~lues mention-ed in prior art wherein the concentrations of fluoride were dixectly measured in the phosphating solution.
In a preferred embodiment of the present invention, the process is charac:terized by the us~ of an aqueous solution containing 0 . 8 to 1. 0 g/l of Zn2+, 0.8 to 1.2 g/l of Mn2, o. 3 to o. R g/l o~ Ni2~, -`` 2~8~3~
14 to 20 g/l of P043 , 3 to 6 g/l of N03 , 0.3 ~o 0.6 g~l of F
The surfaces coated by means of the process described above can be subsequently employed in known processes for paint electro-dipcoating. Accordingly, one further embodiment of th~ present invention consists of the use of the process for the preparation o~ the sur~aces for paint electro-dipcoating.
The invention is ~urther illustrated by the follow-ing Examples.
EXAMPLE l.
Within the course o~ the conventional process sequence comprising the steps of cleaning, rinsing, (activating) phosphating, rinsing, after-passivation, rinsing wit'h fully-desalted water the conversion-coating step was carried out under ~he following bath conditions corresponding to the three compositions A, B and C: -2~63~
, T y p e o ~ A p p 1 i c a t i o n Bath parameters Sprayin~ Spraying(B) Spray-Immer-(A) (Comparison) sion(C~
"Free Acid" (points) 1.5 1.5 1.5 "~otal Acid" 26.5 26.3 22.2 Zn ~g/l~ 0O9 0.9 1.0 Mn (~/1) 0.9 - 0.6 Ni (g/l) 0.7 0.7 0.7 po43 ~g/l) 20.5 20.2 17.1 ~103 (g/l) 0.95 o.g5 F (ppm~* 380 380 400 Accelerator~* 1.0 1.1 1.7 (ml of gas) points Temperature (-C) 5Q 58 58 Time (s) 120 120 180 * measured with an ion-sensitive electrode in a buffered solution at pH 5.3 ** = sodium nitrite - For steel, to ~orm phosphophyllite and/or phospho-phyllite containing manganes~, the "low-zinc" tech~
nology can be retained, and the zinc content ~an be increased without any loss in quality.
- On galvanized, alloy~galvanized steel shets and on aluminum, due to the incorporation o~ manganese in the layer there ensues a distinct improvement in the anticorrosive property results upon subsequent coating with a KET primer (se~ Example 2).
The determination of the area-related mass, after the application of th~ proce~s variant A on the indivi~
dual substrates, according to DI~ 50942 gave the following measured values (average values):
Steel St 1405 2.0 g/m 2 Steel, electrogalvanized 2.4 g/m 2 Aluminum (AlMg 0.4 Si 1.2) 2.8 g/m 2 Aluminum (AlMg 4.5 Mn) 2.7 g/m 2.
The manganese content of the pho~phate layer was quantit~tively determined by atomic absorption spectro-metry (AAS) (average values):
5teel St 1405 6.4 %
Steel, electrogalvanized 4.7 %
Aluminum (AlMg 0.4 Si 1.2) 6.2 %
By means of X-ray diffra~tion, no new spe ific band was found on the phosphate layers containing manganese.
By way of the VDA Changing Climate ~est (VDA Test Procedure 621 415, the corrosion resistance of the phosphate coatings set ~orth hereinbelow was tested on different suhstrates. After the application of the coating, a standard electrophoretic dipcoat composition (K~T-Primer FT 85 7042 of the E3ASF Farben und Lacke) was used.
The testing period of the VDA Changing Climate Test is 5 to 10 cycles. Within this period, the treated substrate is exposed to condensation water changing climate according to DIN 50017. Furthermore, the substrate is stored within the test period for a de~inite time at room temperature (18 ~C to 28 ~C) according to DIN 50014. In addition, within said ' .
. ; ' ,.
:
~8~3~
_ ~3 Changing Climate Test, a salt spray tes according to DIN 50021 is carried out.
Upon completion of the test cycles the following data were determined.
A. Phos~hatinq solution, containina manqanese Substrate Permeation under the coating at the cut after 10 cycles 20 cycles Steel St 1405 0.6 - 0.8 -Steel, electrogalvanized 2 . O - 2 . 5 Aluminum (AlMg 0.4 Si 1.2) - 0.2 Aluminu~ " without fluoride - up to lO
B. Phosphatinq solution,~manqanese-free (comparison) SubstratePermeation under the coating at the cut a~ter lO cycles 20 cyclss mm mm :
~ ;.
Steel St 1405 0.9 - 1.2 Steel, ~lectrogalvanized 3.4 - 4.0 Aluminum (Al~g 0.4 Si 1.2) 0.8 - 1.0 Aluminum " without fluoride - up to 10 -. ' .
phosphophyllite or manganese containing phosphophylli~e, and at the same time the zinc content may be increased without any deterioration in quality.
On galvanized steel sheets, alloy-galvanized steel sheets and on aluminum, the use of manganese gives improved results, at a simultaneously increased Zirl~
content due to the incorpora~ion o~ manganese in the layer, in the subsequent coating by means of a cata-phoretic electro-dipcoating. This simultaneous inter-action between the contents of zinc and manganese in the phosphating solution has been surprisingly found by means of the present invention.
The aluminum materials to be treated by the process according to the invention comprise the pure metal and the alloys thereof. Thus, as the examples, th~re may be mentioned high-grade alumlnum, AlMg and AlMgSi wrought materials. An extensive presentation of these aluminum materials is found, for exampl~, in the "Aluminium Taschenbuchl', 14th Edition, Aluminium-Verlag, Dussel-dor~, 1983. The steels to be tr ated by the proce~s according to the invention especially comprise commodi-ties such as automotive bodies, automobile accessories and spar~ parts, aqricultural implements, r~rrigera~ors and any other kind of small parts usually used in the form of sheets. The term "galvanized steel" includes galvanization by electrolytic deposition and melt immersion application and, thus9 r~feres to zinc and known zinc alloys.
If the process according to he invention is carried out in the spray-immersion mode, the period of spraying must be such as to ensure the fo~mation o~ a largely continuous phosphate layer.
' 3 ~
Modern fulL~immersion plants are distinguished by a great number of steps in sequence. The term "full immersion plant" is derived from phosphating by means of an immersion application. In other process steps, spraying operations are also carried out, the body being after-sprayed once it has emerged from the immersion bath. Important for an optimum phosphating is a separate activating step. The layer to be phosphated, for pre-cleaning and activating same, is usually clean-ed, rinsed and subsequently activated prior to the phosphating operation. Here, for example, aqueous suspensions containing titanium phosphate may be employed.
Maintaining the concentration ranges according to the main claim is an essential condition for the production of high-quality, i . e. unifo:rm, phosphate coating~. If the values fall below the concentration limits indicated, the layers become non-uniform. More particularly, they become less suited for the subsequent electro-dipcoat paintin~.
The fluoride concentrations mentioned according to the invention are measured with a special ion-sensltive electrode in a bufPered solution at p~l 5. 3 . Thus, these values are by no means oomparable to the v~lues mention-ed in prior art wherein the concentrations of fluoride were dixectly measured in the phosphating solution.
In a preferred embodiment of the present invention, the process is charac:terized by the us~ of an aqueous solution containing 0 . 8 to 1. 0 g/l of Zn2+, 0.8 to 1.2 g/l of Mn2, o. 3 to o. R g/l o~ Ni2~, -`` 2~8~3~
14 to 20 g/l of P043 , 3 to 6 g/l of N03 , 0.3 ~o 0.6 g~l of F
The surfaces coated by means of the process described above can be subsequently employed in known processes for paint electro-dipcoating. Accordingly, one further embodiment of th~ present invention consists of the use of the process for the preparation o~ the sur~aces for paint electro-dipcoating.
The invention is ~urther illustrated by the follow-ing Examples.
EXAMPLE l.
Within the course o~ the conventional process sequence comprising the steps of cleaning, rinsing, (activating) phosphating, rinsing, after-passivation, rinsing wit'h fully-desalted water the conversion-coating step was carried out under ~he following bath conditions corresponding to the three compositions A, B and C: -2~63~
, T y p e o ~ A p p 1 i c a t i o n Bath parameters Sprayin~ Spraying(B) Spray-Immer-(A) (Comparison) sion(C~
"Free Acid" (points) 1.5 1.5 1.5 "~otal Acid" 26.5 26.3 22.2 Zn ~g/l~ 0O9 0.9 1.0 Mn (~/1) 0.9 - 0.6 Ni (g/l) 0.7 0.7 0.7 po43 ~g/l) 20.5 20.2 17.1 ~103 (g/l) 0.95 o.g5 F (ppm~* 380 380 400 Accelerator~* 1.0 1.1 1.7 (ml of gas) points Temperature (-C) 5Q 58 58 Time (s) 120 120 180 * measured with an ion-sensitive electrode in a buffered solution at pH 5.3 ** = sodium nitrite - For steel, to ~orm phosphophyllite and/or phospho-phyllite containing manganes~, the "low-zinc" tech~
nology can be retained, and the zinc content ~an be increased without any loss in quality.
- On galvanized, alloy~galvanized steel shets and on aluminum, due to the incorporation o~ manganese in the layer there ensues a distinct improvement in the anticorrosive property results upon subsequent coating with a KET primer (se~ Example 2).
The determination of the area-related mass, after the application of th~ proce~s variant A on the indivi~
dual substrates, according to DI~ 50942 gave the following measured values (average values):
Steel St 1405 2.0 g/m 2 Steel, electrogalvanized 2.4 g/m 2 Aluminum (AlMg 0.4 Si 1.2) 2.8 g/m 2 Aluminum (AlMg 4.5 Mn) 2.7 g/m 2.
The manganese content of the pho~phate layer was quantit~tively determined by atomic absorption spectro-metry (AAS) (average values):
5teel St 1405 6.4 %
Steel, electrogalvanized 4.7 %
Aluminum (AlMg 0.4 Si 1.2) 6.2 %
By means of X-ray diffra~tion, no new spe ific band was found on the phosphate layers containing manganese.
By way of the VDA Changing Climate ~est (VDA Test Procedure 621 415, the corrosion resistance of the phosphate coatings set ~orth hereinbelow was tested on different suhstrates. After the application of the coating, a standard electrophoretic dipcoat composition (K~T-Primer FT 85 7042 of the E3ASF Farben und Lacke) was used.
The testing period of the VDA Changing Climate Test is 5 to 10 cycles. Within this period, the treated substrate is exposed to condensation water changing climate according to DIN 50017. Furthermore, the substrate is stored within the test period for a de~inite time at room temperature (18 ~C to 28 ~C) according to DIN 50014. In addition, within said ' .
. ; ' ,.
:
~8~3~
_ ~3 Changing Climate Test, a salt spray tes according to DIN 50021 is carried out.
Upon completion of the test cycles the following data were determined.
A. Phos~hatinq solution, containina manqanese Substrate Permeation under the coating at the cut after 10 cycles 20 cycles Steel St 1405 0.6 - 0.8 -Steel, electrogalvanized 2 . O - 2 . 5 Aluminum (AlMg 0.4 Si 1.2) - 0.2 Aluminu~ " without fluoride - up to lO
B. Phosphatinq solution,~manqanese-free (comparison) SubstratePermeation under the coating at the cut a~ter lO cycles 20 cyclss mm mm :
~ ;.
Steel St 1405 0.9 - 1.2 Steel, ~lectrogalvanized 3.4 - 4.0 Aluminum (Al~g 0.4 Si 1.2) 0.8 - 1.0 Aluminum " without fluoride - up to 10 -. ' .
Claims (4)
1. A process for producing phosphate coatings containing manga-nese on surfaces of steel, galvanized steel, aluminum and/or the alloys thereof or of aluminum-steel composite materials by spray-ing or spray-immersion with an aqueous solution containing Zn2+, Mn2+, Ni2+, PO43-, NO3-, F-, NO2-, and ClO3- ions characterized in that the metal surfaces are treated with solutions containing the following components:
0.8 to 1.4 g/l of Zn2+, 0.6 to 2.0 g/l of Mn2+, 0.3 to 1.4 g/l of Ni2+, to 25 g/l of PO4-, 2 to 10 g/l of NO3-, 0.2 to 1 g/l of F- and as accelerator of the phosphate deposition 0.04 to 0.12 g/l of NO2- and 0.6 to 2.0 g/l of ClO3-, wherein the content of free acid is adjusted to from 1.4 to 1.8 points and the solution has a total acid content from 18 to 30.
Substitute Sheet
0.8 to 1.4 g/l of Zn2+, 0.6 to 2.0 g/l of Mn2+, 0.3 to 1.4 g/l of Ni2+, to 25 g/l of PO4-, 2 to 10 g/l of NO3-, 0.2 to 1 g/l of F- and as accelerator of the phosphate deposition 0.04 to 0.12 g/l of NO2- and 0.6 to 2.0 g/l of ClO3-, wherein the content of free acid is adjusted to from 1.4 to 1.8 points and the solution has a total acid content from 18 to 30.
Substitute Sheet
2. A process according to claim 1, characterized in that an aqueous solution is employed which contains 0.8 to 1.0 g/l of Zn2+, 0.8 to 1.2 g/l of Mn2+, 0.3 to 0.8 g/l of Ni2+, 14 to 20 g/l of PO4-, 3 to 6 g/l of NO3-, 0.3 to 0.6 g/l of F-.
3. A process according to claims 1 - 2, characterized in that the phosphate coatings are produced on aluminum-steel composite materials.
4. Use of the process according to claims 1 - 3 for the prepa-ration of the surfaces for electro-dip paint coating.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3918136A DE3918136A1 (en) | 1989-06-03 | 1989-06-03 | METHOD FOR PRODUCING MANAGE-CONTAINING PHOSPHATE COATINGS ON METAL SURFACES |
| DEP3918136.7 | 1989-06-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2058631A1 true CA2058631A1 (en) | 1990-12-04 |
Family
ID=6381999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002058631A Abandoned CA2058631A1 (en) | 1989-06-03 | 1990-05-25 | Process for producing manganese-containing phosphate coatings on metal surfaces |
Country Status (9)
| Country | Link |
|---|---|
| EP (2) | EP0401616A1 (en) |
| JP (1) | JPH04505479A (en) |
| KR (1) | KR920701517A (en) |
| CA (1) | CA2058631A1 (en) |
| DE (1) | DE3918136A1 (en) |
| FI (1) | FI915683A0 (en) |
| PT (1) | PT94242A (en) |
| WO (1) | WO1990015167A1 (en) |
| ZA (1) | ZA904222B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5795407A (en) * | 1994-05-11 | 1998-08-18 | Henkel Corporation | Method for pre-treating aluminum materials prior to painting |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07173643A (en) * | 1993-12-21 | 1995-07-11 | Mazda Motor Corp | Method for phosphating metal surface and phosphating solution |
| US5900073A (en) * | 1996-12-04 | 1999-05-04 | Henkel Corporation | Sludge reducing zinc phosphating process and composition |
| JPH11264076A (en) * | 1998-01-14 | 1999-09-28 | Nippon Paint Co Ltd | Chemical conversion treatment for low lead ed |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0135622B1 (en) * | 1983-08-22 | 1988-12-07 | Nippon Paint Co., Ltd. | Phosphating metal surfaces |
| GB8329250D0 (en) * | 1983-11-02 | 1983-12-07 | Pyrene Chemical Services Ltd | Phosphating processes |
| DE3650659T2 (en) * | 1985-08-27 | 1998-07-02 | Henkel Corp | Process for phosphating metal surfaces |
| DE3631759A1 (en) * | 1986-09-18 | 1988-03-31 | Metallgesellschaft Ag | METHOD FOR PRODUCING PHOSPHATE COATINGS ON METAL SURFACES |
| JPS62174385A (en) * | 1987-01-23 | 1987-07-31 | Nippon Parkerizing Co Ltd | Pretreatment for painting by cationic electrodeposition |
| ES2036023T3 (en) * | 1988-11-25 | 1993-05-01 | Metallgesellschaft Aktiengesellschaft | PROCEDURE FOR THE APPLICATION OF PHOSPHATE COATING. |
-
1989
- 1989-06-03 DE DE3918136A patent/DE3918136A1/en not_active Withdrawn
-
1990
- 1990-05-25 EP EP90109944A patent/EP0401616A1/en not_active Withdrawn
- 1990-05-25 CA CA002058631A patent/CA2058631A1/en not_active Abandoned
- 1990-05-25 WO PCT/EP1990/000842 patent/WO1990015167A1/en not_active Application Discontinuation
- 1990-05-25 JP JP2507939A patent/JPH04505479A/en active Pending
- 1990-05-25 EP EP90908214A patent/EP0477204A1/en active Pending
- 1990-05-25 KR KR1019910701245A patent/KR920701517A/en not_active Application Discontinuation
- 1990-06-01 ZA ZA904222A patent/ZA904222B/en unknown
- 1990-06-01 PT PT94242A patent/PT94242A/en not_active Application Discontinuation
-
1991
- 1991-12-02 FI FI915683A patent/FI915683A0/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5795407A (en) * | 1994-05-11 | 1998-08-18 | Henkel Corporation | Method for pre-treating aluminum materials prior to painting |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1990015167A1 (en) | 1990-12-13 |
| EP0477204A1 (en) | 1992-04-01 |
| ZA904222B (en) | 1991-02-27 |
| PT94242A (en) | 1991-02-08 |
| JPH04505479A (en) | 1992-09-24 |
| DE3918136A1 (en) | 1990-12-06 |
| FI915683A0 (en) | 1991-12-02 |
| KR920701517A (en) | 1992-08-11 |
| EP0401616A1 (en) | 1990-12-12 |
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