U.S. patent application number 11/961095 was filed with the patent office on 2008-09-04 for electrodeposition material, process for providing a corrosion-protective layer of tio2 on an electrically conductive substrate and metal substrate coated with a layer of tio2.
Invention is credited to Hans Dolhaine, Seishiro Ito, Subbian Karuppuchamy, Schweinsberg Matthias, Christine Schroeder, Naoki Suzuki, Frank Wiechmann.
Application Number | 20080210567 11/961095 |
Document ID | / |
Family ID | 37487387 |
Filed Date | 2008-09-04 |
United States Patent
Application |
20080210567 |
Kind Code |
A1 |
Karuppuchamy; Subbian ; et
al. |
September 4, 2008 |
Electrodeposition Material, Process for Providing a
Corrosion-Protective Layer of TiO2 on an Electrically Conductive
Substrate and Metal Substrate Coated with a Layer of TiO2
Abstract
The present invention relates to electrodeposition material for
the electrochemical deposition of a corrosion-protective layer of
TiO.sub.2 on an electrically conductive substrate comprising a
titanium compound, a complexing agent, an accelerator, water and
optionally organic solvents, buffering agents and one or more
additives, characterized in that the titanium compound is titanyl
sulfate and/or titanyl oxalate, the complexing agent is selected
from the group consisting of citric acid, citrates, tartaric acid,
tartrates, lactic acid, lactates, gluconic acid, gluconates,
polyhydroxy-polycarbonic acids, ethylenediaminetetraacetate,
methylglycinediacetate, iminodisuccinate, nitrilotriacetic acid and
nitrilotriacetate, triethanolamine, phosphonic acid and
phosphonates, polyaspartic acid and polyaspartates, polyacrylic
acid and polyacrylates and the accelerator is selected from the
group consisting of H.sub.2O.sub.2 and organic peroxides. The
invention further relates to a process for providing a
corrosion-protective layer of TiO.sub.2 on an electrically
conductive substrate and to a metal substrate coated with a layer
of TiO.sub.2.
Inventors: |
Karuppuchamy; Subbian;
(Tamilnadu, IN) ; Suzuki; Naoki; (Osaka, JP)
; Ito; Seishiro; (Nara, JP) ; Matthias;
Schweinsberg; (Langenfeld, DE) ; Dolhaine; Hans;
(Korschenbroich, DE) ; Wiechmann; Frank;
(Duesseldorf, DE) ; Schroeder; Christine;
(Duesseldorf, DE) |
Correspondence
Address: |
HENKEL CORPORATION
1001 TROUT BROOK CROSSING
ROCKY HILL
CT
06067
US
|
Family ID: |
37487387 |
Appl. No.: |
11/961095 |
Filed: |
December 20, 2007 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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PCT/EP2006/005790 |
Jun 16, 2006 |
|
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11961095 |
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Current U.S.
Class: |
205/261 |
Current CPC
Class: |
C25D 9/08 20130101 |
Class at
Publication: |
205/261 |
International
Class: |
C25D 3/54 20060101
C25D003/54 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 22, 2005 |
EP |
05013424.6 |
Claims
1. An electrodeposition material for the electrochemical deposition
of a corrosion-protective layer of TiO.sub.2 on an electrically
conductive substrate comprising: a.) at least one titanium compound
comprising titanyl sulfate and/or titanyl oxalate; b.) a complexing
agent selected from the group consisting of one or more of citric
acid, citrates, tartaric acid, tartrates, lactic acid, lactates,
gluconic acid, gluconates, polyhydroxy-polycarbonic acids,
ethylenediaminetetraacetate, methylglycinediacetate,
iminodisuccinate, nitrilotriacetic acid, nitrilotriacetate,
triethanolamine, phosphonic acid, phosphonates, polyaspartic acid,
polyaspartates, polyacrylic acid and polyacrylates; c.) an
accelerator selected from the group consisting of H.sub.2O.sub.2
and organic peroxides; d.) water; and e.) optionally organic
solvents, buffering agents and one or more additives.
2. The electrodeposition material according to claim 1, comprising
0.05 to 0.3 mol/l titanium compound, 0.01 to 0.2 mol/l complexing
agent and 0.02 to 0.2 mol/l accelerator.
3. The electrodeposition material according to claim 2, wherein the
electrodeposition material has a pH of 5 to 10.
4. The electrodeposition material according to claim 1, comprising:
a.) 0.05 to 0.3 mol/l titanyl oxalate; b.) 0.01 to 0.2 mol/l
complexing agent selected from one or more of citric acid,
citrates, tartaric acid, tartrates, lactic acid, lactates, gluconic
acid, and gluconates; and c.) 0.02 to 0.2 mol/l accelerator.
5. The electrodeposition material according to claim 4, wherein the
electrodeposition material further comprises urea.
6. The electrodeposition material according to claim 1, wherein the
electrodeposition material has a pH of 6 to 9 and further comprises
a polymeric cationic binder.
7. The electrodeposition material according to claim 6, comprising
the polymeric cationic binder in an amount of 5 to 60% by weight
based on the total weight of the electrodeposition material.
8. The electrodeposition material according to claim 7, wherein the
polymeric cationic binder comprises at least one electrodepositable
resin.
9. The electrodeposition material according to claim 8, wherein the
at least one electrodepositable resin is selected from amine salt
group-containing resins, and quaternary ammonium salt
group-containing resins.
10. A process for providing a corrosion-protective layer of
TiO.sub.2 on an electrically conductive substrate comprising
electrodepositing on an electrically conductive substrate a
corrosion-protective layer of TiO.sub.2 by contacting the
electrically conductive substrate with the electrodeposition
material according to claim 1 at a current density of 0.01 to 100
mA/cm.sup.2 and a temperature of 0 to 100.degree. C., for 0.15 to
20 minutes.
11. The process of claim 10 wherein the electrodeposition material
has a pH of 6 to 9 and further comprises a polymeric cationic
binder.
12. The process of claim 10 wherein the electrodeposition material
comprises: 0.05 to 0.3 mol/l titanium compound; 0.01 to 0.2 mol/l
complexing agent; and 0.02 to 0.2 mol/l accelerator.
13. The process of claim 10, wherein the electroconductive
substrate is selected from the group consisting of steel and
aluminium.
14. The process of claim 13, comprising the polymeric cationic
binder in an amount of 5 to 60% by weight based on the total weight
of the electrodeposition material.
15. The process of claim 12, wherein the electrodepositing step is
carried out by contacting the electrically conductive substrate
with the electrodeposition material at a current density of 0.1 to
20 mA/cm.sup.2 and a temperature of 20 to 60.degree. C., for 0.5 to
10 minutes.
16. The process according to claim 15, wherein the
electroconductive substrate is selected from the group consisting
of steel and aluminium.
17. The process of claim 10, wherein the electrodeposition material
comprises: a.) 0.05 to 0.3 mol/l titanyl oxalate; b.) 0.01 to 0.2
mol/l complexing agent selected from one or more of citric acid,
citrates, tartaric acid, tartrates, lactic acid, lactates, gluconic
acid, and gluconates; and c.) 0.02 to 0.2 mol/l accelerator.
18. The process of claim 10, wherein the electrodeposition material
further comprises urea.
19. The process of claim 10, wherein the corrosion-protective layer
of TiO.sub.2 is deposited on the electrically conductive substrate
such that said layer has a uniform layer thickness in the range of
from 0.01 to 3.5 g/m.sup.2.
20. A metal substrate coated with a layer of TiO.sub.2 produced by
the process of claim 10.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation under 35 U.S.C. .sctn.
365(c) and 35 U.S.C. .sctn. 120 of international application
PCT/EP2006/005790, filed 16 Jun. 2006, and published 28 Dec. 2006
in English as WO 2006/136333, which is incorporated herein by
reference in its entirety. This application also claims priority
under 35 U.S.C. .sctn. 119 of EP 05013424.6 filed 22 Jun. 2005,
which is incorporated herein by reference in its entirety.
FIELD OF THE INVENTION
[0002] The present invention relates to an electrodeposition
material for the electrochemical deposition of a
corrosion-protective layer of TiO.sub.2 on an electrically
conductive substrate comprising a titanium compound, a complexing
agent, an accelerator, water and optionally organic solvents,
buffering agents and one or more additives. Such TiO.sub.2 layer
deposited electrochemically may serve as an appropriate primer
layer for subsequent coating treatment (e.g. coating with organic
materials, such as for instance lacquers, varnishes, paints,
organic polymers, adhesives, etc.).
BACKGROUND OF THE INVENTION
[0003] A very common industrial task involves providing metallic or
non-metallic substrates with a first coating, which has a
corrosion-inhibiting effect and/or which constitutes a primer for
the application thereon of a subsequent coating containing e.g.
organic polymers. An example of such a task is the pre-treatment of
metals prior to lacquer coating, for which various processes are
available in the art. Examples of such processes are layer-forming
or non-layer-forming phosphating, chromating or a chromium-free
conversion treatment, for example using complex fluorides of
titanium, zirconium, boron or silicon. Technically simpler to
perform, but less effective, is the simple application of a primer
coat to a metal prior to lacquer-coating thereof. An example of
this is the application of red lead. An alternative to so-called
"wet" processes are so-called "dry" processes, in which a
corrosion-protection or coupling layer is applied by gas phase
deposition. Such processes are known, for example, as PVD or CVD
processes. They may be assisted electrically, for example by plasma
discharge.
[0004] A layer produced or applied in this way may serve as a
corrosion-protective primer for subsequent lacquer coating.
However, the layer may also constitute a primer for subsequent
bonding. Metallic substrates in particular, but also substrates of
plastics or glass, are frequently pre-treated chemically or
mechanically prior to bonding in order to improve adhesion of the
adhesive to the substrate. For example, in vehicle or equipment
construction, metal or plastic components may be bonded metal to
metal, plastic to plastic or metal to plastic. At present, front
and rear windshields of vehicles are as a rule bonded directly into
the bodywork. Other examples of the use of coupling layers are to
be found in the production of rubber/metal composites, in which
once again the metal substrate is as a rule pre-treated
mechanically or chemically before a coupling layer is applied for
the purpose of bonding with rubber.
[0005] The conventional wet or dry coating processes in each case
exhibit particular disadvantages. For example, chromating processes
are disadvantageous from both an environmental and an economic
point of view owing to the toxic properties of the chromium and the
occurrence of highly toxic sludge. However, chromium-free wet
processes, such as phosphating, as a rule, also result in the
production of sludge containing heavy metals, which has to be
disposed of at some expense. Another disadvantage of conventional
wet coating processes is that the actual coating stage frequently
has to be preceded or followed by further stages, thereby
increasing the amount of space required for the treatment line and
the consumption of chemicals. For example, phosphating, which is
used virtually exclusively in automobile construction, entails
several cleaning stages, an activation stage and generally a
post-passivation stage. In all these stages, chemicals are consumed
and waste is produced which requires disposal.
[0006] Although dry coating processes entail fewer waste problems,
they have the disadvantage of being technically complex to perform
(for example requiring a vacuum) or of having high energy
requirements. The high operating costs of these processes are
therefore a consequence principally of plant costs and energy
consumption.
[0007] Further, it is known from the prior art that thin layers of
metals compounds, for example oxide layers, may be produced
electrochemically on an electrically conductive substrate. For
example, the article by Y. Zhou and J. A. Switzer entitled
"Electrochemical Deposition and Microstructure of Copper (I) Oxide
Films", Scripta Materialia, Vol. 38, No. 11, pages 1731 to 1738
(1998), describes the electrochemical deposition and microstructure
of copper (I) oxide films on stainless steel. The article
investigates above all the influence of deposition conditions on
the morphology of the oxide layers; it does not disclose any
practical application of the layers.
[0008] According to Blandeu et al. in Thin Solid Film, 42, 147
(1997) (Abstract), TiO.sub.2-layers are obtained on a Ti-sheet from
H.sub.2SO.sub.4 aqueous solution by anodic oxidation methods. This
is obtained at potentials below 50 V. However, this process can
produce TiO.sub.2 only on Ti-substrates by anodic oxidation.
[0009] According to Nogami et al. in J. Electrochem. Soc., 135,
3008 (1988) (Abstract), TiO.sub.2 is obtained on a Ti-sheet from an
aqueous solution containing 0.5 mol/L H.sub.2SO.sub.4 and 0.03
mol/L HNO.sub.3 by an anodic oxidation method (titanium
anodization). Constant current is 1 mAcm.sup.2. The oxidation is
performed in a cooled bath of 278.degree. K. to 283.degree. K.
However, this process can produce TiO.sub.2 only on a Ti-substrate
by anodic oxidation.
[0010] EP 1 285 105 B1 discloses a process for producing a coating
comprising at least two layers on an electrically conductive
surface wherein in a first stage a chromium-free layer of at least
one X-ray crystalline inorganic compound of at least one metal is
electrochemically deposited on an electrically conductive surface
from a solution containing the metal in dissolved form. Besides
many other metals, titanium is disclosed.
[0011] According to the applicant's not yet published application
PCT/EP2004/014140 corrosion-protective layers of TiO.sub.2 are
electrochemically deposited on a metal substrate from an
electrodeposition material comprising titanyl sulfate or titanyl
oxalate as a titanium component, citrate or citric acid, tartaric
acid and tartrates, lactic acid and lactates as chelating agents
and hydroxylamines and their derivates or nitrates as
accelerators.
SUMMARY OF THE INVENTION
[0012] It is an object of the present invention to provide further
electrodeposition materials for the electrochemical deposition of a
corrosion-protective layer of TiO.sub.2 on an electrically
conductive substrate which result in TiO.sub.2 layers providing
excellent corrosion protection and which may serve as an excellent
primer layer for subsequent coating treatment. Surprisingly this
object can be achieved by the use of titanyl sulfate and/or titanyl
oxalate as the titanium component combined with a special
combination of complexing agents and accelerators.
[0013] Subject-matter of the present invention is an
electrodeposition material as specified above characterized in that
the titanium compound is titanyl sulfate and/or titanyl oxalate,
the complexing agent is selected from the group consisting of
citric acid, citrates, tartaric acid, tartrates, lactic acid,
lactates, gluconic acid, gluconates, polyhydroxy-polycarbonic
acids, ethylenediaminetetraacetate, methylglycinediacetate,
iminodisuccinate, nitrilotriacetic acid and nitrilotriacetate,
triethanolamine, phosphonic acid and phosphonates, poly-aspartic
acid and polyaspartates, polyacrylic acid and polyacrylates and the
accelerator is selected from the group consisting of H.sub.2O.sub.2
and organic peroxides.
[0014] Further, according to a second aspect of the invention, the
present invention relates to a process for providing a
corrosion-protective layer of TiO.sub.2 on an electrically
conductive substrate by electrodeposition of an electrodeposition
material comprising a titanium compound, a complexing agent, an
accelerator, water and optionally organic solvents, buffering
agents and one or more additives.
[0015] Finally, according to a third aspect of the invention, the
present invention relates to a metal substrate coated with a layer
of TiO.sub.2 produced by the process of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0016] In one embodiment, the invention provides an
electrodeposition material for the electrochemical deposition of a
corrosion-protective layer of TiO.sub.2 on an electrically
conductive substrate comprising a titanium compound, a complexing
agent, an accelerator, water and optionally organic solvents,
buffering agents and one or more additives, characterized in that
the titanium compound is titanyl sulfate and/or titanyl oxalate,
the complexing agent is selected from the group consisting of
citric acid, citrates, tartaric acid, tartrates, lactic acid,
lactates, gluconic acid, gluconates, polyhydroxy-polycarbonic
acids, ethylenediaminetetraacetate, methylglycinediacetate,
iminodisuccinate, nitrilotriacetic acid and nitrilotriacetate,
triethanolamine, phosphonic acid and phosphonates, poly-aspartic
acid and polyaspartates, polyacrylic acid and polyacrylates and the
accelerator is selected from the group consisting of H.sub.2O.sub.2
and organic peroxides. Desirably, an electrodeposition material
having a pH of 5 to 10, preferably 6 to 9, more preferably 7.5 to
8.0 is provided.
[0017] In one embodiment, the electrodeposition material
characterized in that it comprises 0.05 to 0.3 mol/l titanium
compound, 0.01 to 0.2 mol/l complexing agent and 0.02 to 0.2 mol/l
accelerator.
[0018] In some embodiments, the electrodeposition material further
comprises a polymeric cationic binder. It is a further object of
the invention to provide an electrodeposition material that
comprises polymeric cationic binder in an amount of 5 to 60% by
weight based on the total weight of the electrodeposition
material.
[0019] Another aspect of the invention is a process for providing a
corrosion-protective layer of TiO.sub.2 on an electrically
conductive substrate by electrodeposition of a electrodeposition
material comprising a titanium compound, a complexing agent, an
accelerator, water and optionally organic solvents, buffering
agents and one or more additives, characterized in that the
titanium compound is titanyl sulfate and/or titanyl oxalate; the
complexing agent is selected from the group consisting of citric
acid, citrates, tartaric acid, tartrates, lactic acid, lactates,
gluconic acid, gluconates, polyhydroxy-polycarbonic acids,
ethylenediaminetetraacetate, methylglycinediacetate,
iminodisuccinate, nitrilotriacetic acid and nitrilotriacetate,
triethanolamine, phosphonic acid and phosphonates, poly-aspartic
acid and polyaspartates, polyacrylic acid and polyacrylates and the
accelerator is selected from the group consisting of H.sub.2O.sub.2
and organic peroxides. It is a further object of the invention to
provide such a process using the electrodeposition material as
described above. Desirably, the electrodeposition is carried out
under the following conditions: current density: 0.01 to 100,
preferably 0.1 to 20, more preferably 0.5 to 10 mA/cm.sup.2;
coating time: 0.15 to 20, preferably 0.5 to 10, more preferably 1
to 4 minutes; temperature: 0 to 100, preferably 20 to 60.degree.
C.; and pH: 5 to 10, preferably 6 to 9, more preferably 7.5 to
8.0.
[0020] It is also an object of the invention to provide a process
as described above wherein the electroconductive substrate is
selected from the group consisting of steel, especially cold rolled
steel and galvanized steel, and aluminium.
[0021] It is a further object of the invention to provide a process
as described above, characterized in that the TiO.sub.2-layer is
deposited on the electrically conductive substrate with an
essentially uniform layer thickness, calculated as weight per unit
area, in the range of from 0.01 to 3.5 g/m.sup.2, preferably in the
range of from 0.5 to 1.4 g/m.sup.2.
[0022] Another aspect of the invention is a metal substrate coated
with a layer of TiO.sub.2 produced by the process described herein.
Desirably, the metal substrate is selected from the group
consisting of steel, especially cold rolled steel and galvanized
steel, and aluminium.
[0023] The electrodeposition material preferably comprises 0.05 to
0.3 mol/l titanium compound, 0.01 to 0.2 mol/l complexing agent and
0.02 to 0.2 mol/l accelerator.
[0024] The pH of the electrodeposition material preferably is 5 to
10, more preferably 6 to 9, most preferably 7.5 to 8.0.
[0025] The electrodeposition material preferably comprises a
polymeric cationic binder in addition to the components specified
above. As the cationic binder all electrodepositable resins known
in the art may be used. Examples of such cationic film-forming
resins include amine salt group-containing resins such as the
acid-solubilized reaction products of polyepoxides and primary or
secondary amines. Usually, these amine salt group-containing resins
are used in combination with a blocked isocyanate curing agent.
Besides amine salt group-containing resins, quaternary ammonium
salt group-containing resins can also be employed. Examples of
these resins are those which are formed from reacting an organic
polyepoxide with a tertiary amine salt. Also, film-forming resins
which cure via transesterification can be used. Further, cationic
compositions prepared from Mannich bases can be used. From an
electrodeposition material comprising the components of the present
invention combined with a polymeric cationic binder, a layer of
TiO.sub.2 and a resinous layer can be deposited simultaneously.
[0026] Preferably the electrodeposition material of the present
invention comprises the polymeric cationic binder in an amount of 5
to 60% by weight based on the total weight of the electrodeposition
material.
[0027] The present invention further relates to a process for
providing a corrosion-protective layer of TiO.sub.2 on an
electrically conductive substrate by electrodeposition of a
electrodeposition material comprising a titanium compound, a
complexing agent, an accelerator, water and optionally organic
solvents, buffering agents and one or more additives, characterized
in that the titanium compound is titanyl sulfate and/or titanyl
oxalate, the complexing agent is selected from the group consisting
of citric acid, citrates, tartaric acid, tartrates, lactic acid,
lactates, gluconic acid, gluconates, polyhydroxy-polycarbonic
acids, ethylenediaminetetraacetate, methylglycinediacetate,
iminodisuccinate, nitrilotriacetic acid and nitrilotriacetate,
triethanolamine, phosphonic acid and phosphonates, poly-aspartic
acid and polyaspartates, polyacrylic acid and polyacrylates and the
accelerator is selected from the group consisting of H.sub.2O.sub.2
and organic peroxides. Desirably the electro-deposition materials
described herein may be used in the process.
[0028] The electrodeposition preferably is carried out under the
following conditions current density: 0.01 to 100, preferably 0.1
to 20, more preferably 0.5 to 10 mA/cm.sup.2, coating time: 0.15 to
20, preferably 0.5 to 10, more preferably 1 to 4 minutes,
temperature: 0 to 100.degree. C., preferably 20 to 60.degree. C.,
pH: 5 to 10, preferably 6 to 9, more preferably 7.5 to 8.0.
[0029] The electroconductive substrate preferably is selected from
the group consisting of steel, especially cold rolled steel and
galvanized steel, and aluminium.
[0030] The TiO.sub.2-layer is deposited on the electrically
conductive substrate preferably with an essentially uniform layer
thickness, calculated as weight per unit area, in the range of from
0.01 to 3.5 g/m.sup.2, more preferably in the range of from 0.5 to
1.4 g/m.sup.2.
[0031] Illustrating the invention are the following examples which,
however, are not to be considered as limiting the invention to
their details. All parts and percentages in the following examples
as well as throughout the specification are by weight unless
otherwise indicated.
EXAMPLES
Example 1
TABLE-US-00001 [0032] Ti Compound 0.14 mol/l Titanium potassium
oxalate dihydrate (50 g/L) Complexing Agent 0.02 mol/L Citric acid
monohydrate(5 g/L) Accelerator 0.04 mol/L H.sub.2O.sub.2 (5 g/L 30%
by weight) Process Parameters pH = 7.5; Current density 0.5-1.8
mA/cm.sup.2; t = 5 min; T = 60.degree. C.; Substrate: galvanized
steel
Example 2
TABLE-US-00002 [0033] Ti Compound 0.14 mol/l Titanium potassium
oxalate dihydrate (50 g/L) Complexing Agent 0.03 mol/L
L(+)-Tartaric acid (5 g/L) Accelerator 0.04 mol/L H.sub.2O.sub.2 (5
g/L 30% by weight) Process Parameters pH = 7.5; Current density
0.5-1.8 mA/cm.sup.2; t = 5 min; T = 60.degree. C.; Substrate:
galvanized steel
Example 3
TABLE-US-00003 [0034] Ti Compound 0.14 mol/l Titanium potassium
oxalate dihydrate (50 g/L) Complexing Agent 0.03 mol/L Gluconic
acid (12 g/L 50% by weight) Accelerator 0.04 mol/L H.sub.2O.sub.2
(5 g/L 30% by weight) Process Parameters pH = 7.5; Current density
0.5-1 mA/cm.sup.2; t = 5 min; T = 60.degree. C.; Substrate:
galvanized steel
Example 4
TABLE-US-00004 [0035] Ti Compound 0.14 mol/l Titanium potassium
oxalate dihydrate (50 g/L) Additive: Urea 0.08 mol/L (5 g/l)
Complexing Agent 0.1 mol/L Citric acid monohydrate Accelerator 0.04
mol/L H.sub.2O.sub.2 (5 g/L 30% by weight) Process Parameters pH =
7-7.5; Current density 0.5-1.8 mA/cm.sup.2; t = 1-5 min; T =
60.degree. C.; Substrate: galvanized steel
Example 5
TABLE-US-00005 [0036] Ti Compound 0.14 mol/l Titanium potassium
oxalate dihydrate (50 g/L) Additive: Urea 0.08 mol/L (5 g/l)
Additive: Phosphoric acid 5 g/L Complexing Agent 0.1 mol/L Citric
acid monohydrate Accelerator 0.04 mol/L H.sub.2O.sub.2 (5 g/L 30%
by weight) Process Parameters pH = 7-7.5; Current density 0.5-1.8
mA/cm.sup.2; t = 1-5 min; T = 60.degree. C.; Substrate: galvanized
steel
Example 6
TABLE-US-00006 [0037] Ti Compound 0.14 mol/l Titanium potassium
oxalate dihydrate (50 g/L) Additive: Urea 0.08 mol/L (5 g/l)
Additive: Phosphoric acid 5 g/L Complexing Agent 0.1 mol/L Citric
acid monohydrate Accelerator 0.04 mol/L H.sub.2O.sub.2 (5 g/L 30%
by weight) Process Parameters pH = 7-7.5; Current density 0.5-1.8
mA/cm.sup.2; t = 1-5 min; T = 60.degree. C.; Substrate: galvanized
steel
Example 7
TABLE-US-00007 [0038] Ti Compound 0.14 mol/l Titanium potassium
oxalate dihydrate (50 g/L) Additive: Urea 0.08 mol/L (5 g/l)
Additive: Hydroxybenzoic ca. 0.03 mol/L (5 g/L) acid: 3-; 3,5 Di-
and 2,5 Di- Hydroxybenzoic acid Complexing Agent 0.1 mol/L Citric
acid monohydrate Accelerator 0.04 mol/L H.sub.2O.sub.2 (5 g/L 30%
by weight) Process Parameters pH = 7-7.5; Current density 0.5-1.8
mA/cm.sup.2; t = 1-5 min; T = 60.degree. C.; Substrate: galvanized
steel
Example 8
TABLE-US-00008 [0039] Ti Compound 0.14 mol/l Titanium potassium
oxalate dihydrate (50 g/L) Additive: Urea 0.08 mol/L (5 g/l)
Additive: 5 g/L Gum arabic Complexing Agent 0.1 mol/L Citric acid
monohydrate Accelerator 0.04 mol/L H.sub.2O.sub.2 (5 g/L 30% by
weight) Process Parameters pH = 7-7.5; Current density 0.5-1.8
mA/cm.sup.2; t = 1-5 min; T = 60.degree. C.; Substrate: galvanized
steel
Example 9
TABLE-US-00009 [0040] Ti Compound 0.14 mol/l Titanium potassium
oxalate dihydrate (50 g/L) Additive: Urea 0.08 mol/L (5 g/l)
Adhesion promoter: 0.1 g/L Formaldehyde resin modified with
phenylsalicylic acid Complexing Agent 0.1 mol/L Citric acid
monohydrate Accelerator 0.04 mol/L H.sub.2O.sub.2 (5 g/L 30% by
weight) Process Parameters pH = 7-7.5; Current density 0.5-1.8
mA/cm.sup.2; t = 1-5 min; T = 60.degree. C.; Substrate: galvanized
steel
Preparing of the Electrodeposition Material:
[0041] The titanium compound was dissolved in deionized water
(accelerated by heating to 30 to 50.degree. C.) [0042] The
complexing agent was added. [0043] Thereafter, the accelerator and
optionally the additives were added. [0044] The pH was adjusted by
the addition of KOH (0.5 to 1.5 mol/l) at a temperature of 45 to
60.degree. C.
* * * * *