U.S. patent application number 17/633018 was filed with the patent office on 2022-09-01 for method and system for electrolytically coating a steel strip by means of pulse technology.
This patent application is currently assigned to SMS group GmbH. The applicant listed for this patent is SMS group GmbH. Invention is credited to Thomas DAUBE, Henry GORTZ, Frank PLATE, Walter TIMMERBEUL.
Application Number | 20220275530 17/633018 |
Document ID | / |
Family ID | 1000006392902 |
Filed Date | 2022-09-01 |
United States Patent
Application |
20220275530 |
Kind Code |
A1 |
GORTZ; Henry ; et
al. |
September 1, 2022 |
Method and system for electrolytically coating a steel strip by
means of pulse technology
Abstract
An electroplating method and a system for electrolytically
coating a steel strip, in particular for the automotive sector,
with a coating based on zinc and/or a zinc alloy utilizes pulse
technology.
Inventors: |
GORTZ; Henry; (Bergisch
Gladbach, DE) ; DAUBE; Thomas; (Duisburg, DE)
; PLATE; Frank; (Dusseldorf, DE) ; TIMMERBEUL;
Walter; (Wuppertal, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SMS group GmbH |
Dusseldorf |
|
DE |
|
|
Assignee: |
SMS group GmbH
Dusseldorf
DE
|
Family ID: |
1000006392902 |
Appl. No.: |
17/633018 |
Filed: |
August 5, 2020 |
PCT Filed: |
August 5, 2020 |
PCT NO: |
PCT/EP2020/072020 |
371 Date: |
February 4, 2022 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C25D 17/10 20130101;
C25D 3/22 20130101; C25D 17/007 20130101 |
International
Class: |
C25D 3/22 20060101
C25D003/22; C25D 17/10 20060101 C25D017/10; C25D 17/00 20060101
C25D017/00 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 5, 2019 |
DE |
10 2019 211 719.8 |
Dec 12, 2019 |
DE |
10 2019 219 455.9 |
Dec 12, 2019 |
DE |
10 2019 219 490.7 |
Dec 12, 2019 |
DE |
10 2019 219 491.5 |
Dec 12, 2019 |
DE |
10 2019 219 496.6 |
Claims
1.-21. (canceled)
22. A method for electrolytically coating a steel strip (2) with a
coating based on zinc and/or a zinc alloy, comprising: feeding the
steel strip (2) to a coating section (1) comprising at last one
electrolytic cell (3) and successively electrolytically coating the
steel strip (2) therein, wherein the steel strip (2) is initially
cathodically connected via at least one current roller (6) and is
guided within the at least one electrolytic cell (3) at a defined
distance parallel to at least one anode (5) arranged in the
electrolytic cell (3), wherein the at least one anode (5) is
supplied with a modulated current and the coating takes place
within the coating section (1) using a defined pulse pattern
sequence (10), which is formed from at least one pulse pattern
(11), wherein, in accordance with the pulse pattern sequence (10),
the coating based on zinc and/or a zinc alloy is deposited and
formed from an electrolyte (4) on the steel strip (2).
23. The method according to claim 22, wherein the modulated current
is provided by at least one pulse rectifier (9), a negative pole of
which is electrically connected to the at least one current roller
(7) and a positive pole to the at least one anode (5).
24. The method according to claim 23, wherein the at least one
pulse rectifier (9) is electrically connected to a central control
unit (12) via which the coating is regulated.
25. The method according to claim 24, wherein the at least one
pulse pattern (11) of the pulse pattern sequence (10) is
transmitted from the central control unit (12) to the at least one
pulse rectifier (9).
26. The method according to claim 22, wherein the at least one
pulse pattern (11) of the pulse pattern sequence (10) comprises at
least one cathodic pulse, at least one anodic pulse, and/or at
least one pulse time-out, and wherein the cathodic pulse and the
anodic pulse are defined by a pulse duration.
27. The method according to claim 22, wherein the at least one
anode (5) is formed as a plate anode, which is formed in one piece
or from two or more partial anodes (16) formed in rod shape.
28. The method according to claim 22, wherein the steel strip (2)
is guided within the at least one electrolytic cell (3) through at
least two anode arrangements (13), each comprising two anodes (5)
arranged parallel to one another.
29. The method according to claim 28, wherein each of the anodes
(5) of each anode arrangement (13) is supplied with current via a
separate pulse rectifier (9), such that each of the anodes (5) is
electrically connected to a respective positive pole of each pulse
rectifier (9) and a negative pole of each pulse rectifier (9) is
electrically connected to the at least one current roller (6,
7).
30. The method according to claim 28, wherein the steel strip (2)
is deflected between the at least two anode arrangements (13) via a
deflection roller (8) arranged within the electrolytic cell (3,
5).
31. The method according to claim 22, wherein the steel strip (2)
is guided within the coating section (1) through a plurality of at
least two electrolytic cells (3) arranged one behind the other in a
direction of strip travel (R).
32. The method according to claim 31, wherein the steel strip (2)
is deflected between the at least two electrolytic cells (3) via at
least one deflection roller formed as an intermediate current
roller (14).
33. The method according to claim 22, wherein a hydrogen
concentration is determined in the at least one electrolytic cell
(3).
34. The method according to claim 22, wherein the steel strip (2)
has a tensile strength R.sub.e.gtoreq.1000 MPa.
35. The method according to claim 22, wherein the at least one
pulse pattern (11) of the pulse pattern sequence (10) in the at
least one electrolytic cell (3) is selected with respect to its
pulse type, its pulse shape, its pulse off-time, its pulse length
along with its pulse number in such a way that the steel strip (2)
is isolated from hydrogen adsorption.
36. The method according to claim 35, wherein the pulse length of
at least one cathodic pulse and/or at least one anodic pulse
amounts to 3 to 5 ms.
37. The method according to claim 35, wherein the pulse off-time
between each two of a plurality of pulses amounts to 1.0 to 5.0
ms.
38. The method according to claim 35, wherein the pulse number
between each of two types of pulses, a cathodic pulse and an anodic
pulse, amounts to 1 to 50.
39. The method according to claim 35, wherein a ratio of pulse
length to pulse time-out of the cathodic pulse amounts to 0.1 or
0.02.
40. The method according to claim 22, wherein the steel strip (2),
after coating in the coating section (1), is fed to a
post-treatment unit, in which the coated steel strip (2) is
annealed.
41. The method according to claim 39, wherein the annealing is
performed at a temperature of .ltoreq.300.degree. C. (PMT).
42. A system for electrolytically coating a steel strip (2) with a
coating based on zinc and/or a zinc alloy, comprising: optionally,
a cleaning and/or an activation unit in which the steel strip (2)
can be cleaned and/or activated; a coating section (1) with at
least one electrolytic cell (3), in which the steel strip (2) can
be successively electrolytically coated, and at least one current
roller (6), via which the steel strip (2) can be cathodically
switched, wherein the at least one electrolytic cell (3) comprises
at least one anode (5), which is arranged in such a way that the
steel strip (2) that can be passed through the at least one
electrolytic cell (3) can be passed through at a defined and
parallel distance from the at least one anode (5), wherein the
system comprises at least one pulse rectifier (9), a negative pole
of which is electrically connected to the at least one current
roller (6) and a positive pole of which is electrically connected
to the at least one anode (5), in such a way that the at least one
anode (5) can be supplied with a modulated current, wherein a
coating process can be carried out within the coating section (1)
using a defined pulse pattern sequence (10), wherein the pulse
pattern sequence (10) is formed from individual pulse patterns
(11), wherein in accordance with a pulse pattern sequence (10) a
coating based on zinc and/or a zinc alloy can be deposited from an
electrolyte (4) on the steel strip (2).
Description
TECHNICAL FIELD
[0001] The present disclosure relates to an electroplating method
and a system for electrolytically coating a steel strip, in
particular for the automotive sector, with a coating based on zinc
and/or a zinc alloy.
BACKGROUND
[0002] Nowadays, electrolytically refined steel strip is used as a
semi-finished product in many branches of industry, such as the
automotive industry, aerospace technology, mechanical engineering,
the packaging industry, and in the manufacture of household
appliances and electrical devices. Traditionally, the production of
such strips is carried out in continuously operating strip
processing lines with a constant-speed passage of the steel strip
through one or more electrolytic cells connected in series.
[0003] The coatings electrolytically deposited on one or both sides
of the steel strip can perform various tasks and impart new product
properties on the steel strip in question. These are, for example,
protection against corrosion or oxidation, wear protection, the
production of decorative product properties, and/or the production
of magnetic and/or electrical surface properties.
[0004] For example, electrolytically galvanized steel strip is
given active corrosion protection by the zinc coating and provides
a good adhesion base for painting and/or laminating with plastic
films. A chrome coating also imparts on a steel strip or a plastic
strip increased corrosion and wear protection, along with
decorative properties. Nickel and nickel alloys, on the other hand,
can increase the surface hardness of the substrate in question.
[0005] The production of the respective coatings with the desired
properties is, in particular under economic and business aspects,
strongly dependent on various parameters, such as the type and
composition of the electrolyte, its metal salt concentration and
temperature, the geometrical arrangement of the electrolytic cells
and their electrodes, the electrochemical current conduction along
with its amount, time and polarity.
[0006] In the prior art, the electrolytic coating of steel strips
is carried out by means of direct current, wherein thyristor
technology is used thereby. Such so-called "DC electrolysis" can be
designed to be unipolar and partially pole-reversible, but does not
allow specific current sequences in magnitude, time and polarity.
The high degree of hydrogen development is particularly problematic
here, since the hydrogen diffusing into the steel strip has a
massive negative impact on the product properties of the steel
strip in the subsequent production steps. Thus, the diffusing
hydrogen is primarily responsible for so-called "spontaneous
brittle fracture" and the reduction of the material yield strength
or the required strength of a steel strip. Furthermore, the
hydrogen trapped in a galvanized steel strip during the curing
process of a painted component, preferably a component painted by
means of a cathodic electrodeposition (CED) process, leads to the
effusion of the trapped hydrogen, with the result that hydrogen
bubbles form underneath the paint layer, resulting in so-called
"paint bursts."
[0007] The hydrogen-induced reduction in material strength
represents an additional significant process disadvantage in the
prior art, because if the material is no longer strong enough, it
is generally unusable for an application in the field of
safety-relevant components, for example in the automotive
sector.
SUMMARY
[0008] The present disclosure provides an improved process and an
improved system for the electrolytic coating of steel strips with a
coating based on zinc and/or a zinc alloy.
[0009] The method provides that the steel strip, after optionally
prior cleaning and/or activation, is fed to a coating section
comprising at least one, preferably at least two or more,
electrolytic cell(s) and is successively electrolytically coated
therein, wherein the steel strip is initially cathodically
connected via at least one current roller and is guided within the
at least one electrolytic cell at a defined distance parallel to at
least one anode arranged in the electrolytic cell.
[0010] The at least one anode is supplied with a modulated current,
wherein the coating process takes place within the coating section
using a defined pulse pattern sequence, which is formed from at
least one pulse pattern, wherein, in accordance with the pulse
pattern sequence, zinc and/or a zinc alloy is deposited from an
electrolyte on the steel strip and the coating is formed on the
basis of zinc and/or a zinc alloy.
[0011] The present disclosure also provides for a system for the
electrolytic coating of a steel strip. The system can comprise a
cleaning and/or an activation unit, in which the steel strip can be
cleaned and/or activated; a coating section with at least one,
preferably at least two or more electrolytic cell(s), in which the
steel strip can be successively electrolytically coated, and at
least one current roller, via which the steel strip can be
cathodically switched, wherein the at least one electrolytic cell
comprises at least one anode, which is arranged in such a way that
the steel strip that can be passed through the at least one
electrolytic cell can be passed through at a defined and parallel
distance from the at least one anode. The system comprises at least
one pulse rectifier, which is designed in switching power supply
technology, the negative pole of which is electrically connected to
the at least one current roller and the positive pole of which is
electrically connected to the at least one anode in such a way that
the at least one anode can be supplied with a modulated current, in
that the coating process can be carried out within the coating
section using a defined pulse pattern sequence, wherein the pulse
pattern sequence is formed from individual pulse patterns, wherein
in accordance with a pulse pattern sequence a coating based on zinc
and/or a zinc alloy can be deposited from an electrolyte on the
steel strip.
[0012] Surprisingly, it has been shown that, using a defined pulse
pattern sequence that is formed from individual pulse patterns,
cathodic hydrogen evolution and its diffusion into the steel strip
can be reduced to such an extent that hydrogen-induced brittle
fracture, the decrease in tensile strength and the formation of
surface defects in subsequent process steps can be effectively
avoided. As such, a steel strip coated with a zinc and/or zinc
alloy coating by the method in accordance with the disclosure can
be produced directly in a strength-maintaining manner, such that a
possibly necessary heat process step downstream of the coating
process can be spared.
[0013] The coating process takes place within the coating section
using a defined pulse pattern sequence, which is formed from
individual pulse patterns. Thereby, the pulse pattern sequence can
be formed from a single pulse pattern and/or from a combination of
at least two or a plurality of identical and/or different pulse
patterns of a pulse pattern collection.
[0014] The features listed individually in the dependent claims can
be combined with one another in a technologically useful manner and
can define further embodiments. In addition, the features indicated
in the claims are further specified and explained in the
description, wherein further preferred embodiments are illustrated.
In this connection, it is pointed out that all the present device
features, which are explained in the course of the individual
method steps or vice versa, can be combined in the same way with
the system and/or the method in accordance with the disclosure,
without explicitly referring to them.
[0015] Preferably, the steel strip is one that has a tensile
strength of at least R.sub.e.gtoreq.500 MPa, more preferably of at
least R.sub.e.gtoreq.600 MPa and most preferably of at least
R.sub.e.gtoreq.800 MPa. In terms of maximum tensile strength, the
steel strip is limited to a tensile strength of R.sub.e.ltoreq.2000
MPa, more preferably to a tensile strength of R.sub.e.ltoreq.1500
MPa, even more preferably to a tensile strength of
R.sub.e.ltoreq.1200 MPa.
[0016] A preferred zinc alloy coating includes zinc-magnesium.
[0017] In principle, the coating section of the system can comprise
an electrolytic cell with an anode, for example in the form of a
plate anode. In a further development, the only one electrolytic
cell can comprise two anodes, which are arranged one behind the
other, for example in the direction of strip travel, in such a way
that the steel strip can be coated on one side. In a preferred
embodiment, the two anodes may be formed in an anode arrangement,
in which the two anodes are then arranged parallel to each other
within the one electrolytic cell.
[0018] In a preferred embodiment, the coating section comprises at
least two electrolytic cells, more preferably at least three
electrolytic cells, even more preferably at least four electrolytic
cells, further preferably at least five electrolytic cells, and,
for reasons of process economy, is limited to a maximum of twenty
electrolytic cells, preferably to a maximum of 16, more preferably
to a maximum of fifteen electrolytic cells. The plurality of
electrolytic cells is preferably arranged one behind the other in
the direction of strip travel, through which the steel strip is
then fed within the coating section.
[0019] The individual electrolytic cells can be in the form of
horizontal or preferably vertical electrolytic cells, through which
the steel strip is guided by deflection rollers.
[0020] The deposition process within the individual electrolytic
cells takes place in an electrolyte through which the steel strip
is passed. The electrolyte medium is usually aqueous and usually
has a pH value of less than 5.0. Alternatively, the electrolyte
medium can be formed from a non-aqueous medium, such as an ionic
liquid. A preferred ionic liquid comprises a mixture of choline
chloride and urea.
[0021] The modulated current is provided by a pulse rectifier,
which uses switching power supply technology. The use of such a
pulse rectifier enables the defining of the magnitude, the time
course along with the polarity of the respective desired pulse
pattern and thus of the entire pulse pattern sequence, in such a
way that the electrolytic process can be optimally adapted
according to the given parameters.
[0022] A pulse rectifier formed in such a way is defined by the
fact that the AC voltage on the line side is initially rectified
and smoothed. The DC voltage then generated, which has much higher
frequencies, as a rule in the range of 5 kHz to 300 kHz, is then
divided, transformed at this high frequency and then rectified and
screened. The superimposed voltage and current control usually
works via pulse width modulation or pulse phase modulation.
[0023] Due to the high frequency at the power transformer, the
transformer is much smaller, such that the energy losses are much
lower. This results in a much higher power effectiveness of the DC
power supply and thus of the overall production plant, due to the
system.
[0024] Due to its design, the pulse rectifier can be provided in
modular form. This leads to a much higher availability, since the
power to be provided by a defective module can be taken over by
another module, and upon the repair of a defective module, it can
be replaced quickly.
[0025] An additional advantage is that the quality of the DC
current, in particular its lower residual ripple, is much better
with lower losses than with conventional thyristor-based DC
electrolysis, the repair of defective devices is much faster and
easier to realize, and existing DC current/DC voltage supply
systems can be expanded by additional modules at a later date by
using appropriate control technology, by means of which the power
of the DC current/DC voltage supply system can be increased.
[0026] The at least one pulse rectifier, which provides the
modulated current, is advantageously electrically connected via its
negative pole to the at least one current roller and the positive
pole to the at least one anode. In this connection, it is
preferably provided that the at least one pulse rectifier is
electrically connected to a central control unit, via which the
entire coating process is regulated. Via the control unit, the at
least one pulse pattern of the pulse pattern sequence is
transmitted to the at least one, preferably each, pulse rectifier,
which then transmits it to the respective assigned electrolytic
cell by means of signal technology.
[0027] Usually, a pulse pattern of the pulse pattern sequence
comprises at least one cathodic pulse, at least one anodic pulse,
and/or at least one pulse time-out, wherein the cathodic and anodic
pulses are defined by a pulse duration and its respective shape,
for example rectangular. The cathodic pulse is used to deposit the
zinc and/or zinc alloy on the steel strip. In particular, an anodic
pulse can be used to oxidize the nascent state hydrogen adsorbed on
the steel strip surface back to the proton and thus remove it from
the steel strip surface in a targeted manner.
[0028] The at least one anode is preferably formed as a plate
anode. In principle, such plate anodes can be designed in the form
of a soluble or an insoluble anode. In the case of soluble anodes,
also known as active anode systems, the anode goes into solution
during electrolysis. Insoluble anodes, also known as inert anode
systems, on the other hand, do not pass into solution during
electrolysis. Insoluble anodes consist of a carrier material, on
the one hand, and a coating applied to it, which can be referred to
as the active layer, on the other hand. Thereby, titanium, niobium
or other reaction carrier metals are usually used as the carrier
material, but in any case materials that passivate under the
electrolysis conditions. Electron-conducting materials such as
platinum, iridium or other precious metals, their mixed oxides or
compounds of such elements are typically used as the material for
the active layer. Thereby, the active layer can either be applied
directly to the surface of the carrier material or be located on a
substrate at a distance from the carrier material. Among other
things, materials that can be considered as carrier materials, such
as titanium, niobium or the like, can also serve as the
substrate.
[0029] The at least one anode can preferably be formed in one piece
and/or, in accordance with an advantageous embodiment, from at
least two or more partial anodes formed in rod shape, wherein each
of the partial anodes is then electrically connected to the current
source. The at least two or more rod-shaped partial anodes are
advantageously arranged in such a way that the distance of each
partial anode from the strip can be adjusted over its width.
Thereby, along the strip width of the steel strip, via the
adjustment of the distance of each of the partial anodes to the
strip and/or the current density, locally different layer
thicknesses can be applied and/or corrected by means of desorption.
For example, the partial anodes arranged at the strip edges, in
comparison to those arranged in the middle segment, can be supplied
with current with a lower current density and/or positioned a
greater distance from the strip, in order to control the deposition
of the zinc and/or zinc alloy at the strip edges.
[0030] In a particularly advantageous embodiment, the at least one
electrolytic cell comprises at least one anode arrangement
consisting of two anodes arranged parallel to one another, through
which the steel strip is passed. In such a configuration, it is
preferably provided that each of the anodes of the at least one
anode arrangement is supplied with current via a separate pulse
rectifier, such that each of the anodes is electrically connected
to a respective positive pole of each pulse rectifier and the
negative pole of each pulse rectifier is electrically connected to
the at least one current roller. In other words, the electrolytic
cell in this configuration includes two anodes, two pulse
rectifiers along with a current roller through which the strip
substrate is cathodically switched.
[0031] In a further preferred embodiment, the at least one
electrolytic cell comprises at least two anode arrangements, each
with two anodes arranged parallel to one another, through which the
steel strip is passed. If such an electrolytic cell is formed as an
immersion tank, it is particularly preferred that the steel strip
is deflected between the at least two anode arrangements by means
of a deflection roller, which may be arranged inside the
electrolytic cell. In a configuration formed in this way, each of
the anodes of the at least two anode arrangement is also supplied
with current via a separate pulse rectifier, such that a total of
four pulse rectifiers are provided in this configuration. Thereby,
each of the four anodes is electrically connected to one positive
pole of each pulse rectifier and the negative pole of each two
pulse rectifiers is electrically connected to one of the two
current rollers. In other words, the electrolytic cell in this
configuration comprises four anodes, four pulse rectifiers, two
current rollers along with a deflection roller, which may be
arranged inside the electrolytic cell.
[0032] In an additional preferred embodiment, the electrolytic cell
can be formed substantially from the anode arrangement by closing
the two open flanks thereof. Thereby, the steel strip passes
through the partially enclosed chamber bounded by the anode
arrangement and is washed around by the electrolyte in such
chamber. The electrolyte can, for example, be fed to and flow
through the entire cross-section of the chamber via corresponding
pumps. Compared to an immersion tank, such a structure has a
smaller installation space and thus requires smaller volumes of
electrolyte.
[0033] In a particularly preferred embodiment, the coating section
comprises a plurality of electrolytic cells arranged one behind the
other in the direction of strip travel, through which the steel
strip is passed. In this connection, it is advantageously provided
that the steel strip is deflected between at least two, more
preferably between each of the plurality of electrolytic cells, via
at least one deflection roller formed as an intermediate current
roller, and if necessary additionally cathodically switched. In an
exemplary embodiment with two electrolytic cells each comprising
two anode arrangements, each of the anodes of the four anode
arrangements is also supplied with current via a separate pulse
rectifier, such that a total of eight pulse rectifiers are provided
in this configuration. Thereby, each of the eight anodes is
electrically connected to one positive pole of each pulse
rectifier. With regard to the cathodic circuit, it is provided that
this is distributed over the total of three current rollers in such
a way that the negative pole of two pulse rectifiers in each case
is electrically connected to one of the two outer current rollers
(strip inlet current roller and strip outlet current roller) and
the negative pole of the remaining four pulse rectifiers is
electrically connected to the deflection roller formed as an
intermediate current roller.
[0034] In a preferred embodiment, a hydrogen concentration is
determined in the at least one electrolytic cell, more preferably
in each of the electrolytic cells. The hydrogen concentration is
preferably detected by hydrogen probes that directly measure the
concentration in the exhaust air of the electrolytic cell(s). By
detecting the hydrogen, it is possible to indirectly conclude the
amount of hydrogen adsorbed on the steel strip and/or diffused into
the steel strip, such that a correction can still be made in the
coating process, by adjusting the pulse patterns within the pulse
pattern sequence.
[0035] In a particularly preferred embodiment, the at least one
pulse pattern of the pulse pattern sequence in the at least one,
more preferably first, electrolytic cell of the plurality of
electrolytic cells is selected with respect to its pulse type, i.e.
cathodic and anodic pulse, its pulse shape, its pulse time-out, its
pulse length along with its pulse number, in such a way that the
steel strip is isolated from hydrogen adsorption.
[0036] For this purpose, a pulse pattern that enables the rapid
formation of a fine-grained, closed zinc and/or zinc alloy coating
is advantageously selected. A high number of uniformly distributed
crystal nuclei can be formed on the steel strip surface via a
sequence of short cathodic pulses, which nuclei can then be formed
into a flat, closed zinc and/or zinc alloy layer with few defects
as the crystals continue to grow on each nucleus. The reduction of
imperfections, at which hydrogen preferentially deposits, reduces
hydrogen adsorption and isolates the steel strip surface from
protons present in the electrolyte. The increasing amount of
adsorbed zinc and/or zinc alloy on the steel strip surface then
reduces the hydrogen evolution in favor of the zinc and/or zinc
alloy.
[0037] The pulse length of the at least one cathodic pulse and/or
the at least one anodic pulse amount to advantageously 3.0 to 100
ms, more preferably 3.0 to 50 ms, even more preferably 3.0 to 20
ms, further preferably 3.0 to 10 ms and most preferably 3.0 to 5
ms.
[0038] Advantageous pulse times between any two of the plurality of
pulses amount to 1.0 to 200 ms, preferably 1.0 to 100 ms, more
preferably 1.0 to 50 ms, even more preferably 1.0 to 25 ms and most
preferably 1.0 to 5.0 ms.
[0039] With regard to the pulse number between the two types of
pulses, it is advantageously provided that these amount to 1 to
5000, preferably 1 to 2500, more preferably 1 to 2000, even more
preferably 1 to 1000, further preferably 1 to 200, more preferably
1 to 100 and most preferably 1 to 50.
[0040] In a particularly preferred embodiment, the ratio of pulse
length to pulse time-out of the cathodic pulse amounts to 0.1
and/or 0.02, which advantageously leads to the reduction of the
diffusion coefficient of hydrogen by up to 40% compared to DC
electrolysis.
[0041] After the steel strip has been coated in the coating section
of the system, it can be fed to a post-treatment unit, in which the
coated steel strip is annealed. Preferably, the system for this
purpose comprises an induction strip heating furnace and/or a
gas-heated circulating air continuous furnace, in particular a
floating strip continuous furnace, which enables contactless
annealing and thus protects the zinc and/or zinc alloy coating.
[0042] Annealing of the coated steel strip is advantageously
carried out at a maximum temperature of .ltoreq.300.degree. C.
(PMT), more preferably in a range of 150 to 250.degree. C.
(PMT).
[0043] The invention and the technical environment are explained in
more detail below with reference to figures and examples. It should
be noted that the invention is not intended to be limited by the
embodiments shown. In particular, unless explicitly shown
otherwise, it is also possible to extract partial aspects of the
facts explained in the figures and combine them with other
components and findings from the present description and/or
figures. In particular, it should be noted that the figures and in
particular the size relationships shown are only schematically.
Identical reference signs designate identical objects, such that
explanations from other figures can be used as a supplement if
necessary.
BRIEF DESCRIPTION OF THE DRAWINGS
[0044] FIG. 1 shows a first embodiment of a part of a coating
section of a system for the electrolytic coating of a steel strip
with a coating in a schematic representation,
[0045] FIG. 2 shows a second embodiment of a part of the coating
section of the system for the electrolytic coating of a steel strip
with a coating in a schematic representation,
[0046] FIG. 3 shows an embodiment of a part of a coating section
with n-cells,
[0047] FIG. 4 shows an embodiment of a partial anode
arrangement,
[0048] FIG. 5 shows a third embodiment of a part of the coating
section of the system for the electrolytic coating of a steel strip
with a coating in a schematic representation,
[0049] FIG. 6 shows a first embodiment of a pulse pattern that can
form part of the pulse pattern sequence,
[0050] FIG. 7 shows a second embodiment of a pulse pattern that can
form part of the pulse pattern sequence,
[0051] FIG. 8 shows a third embodiment of a pulse pattern that can
form part of the pulse pattern sequence, and
[0052] FIG. 9 shows a fourth embodiment of a pulse pattern that can
form part of the pulse pattern sequence.
DETAILED DESCRIPTION
[0053] FIG. 1 shows a part of a coating section 1 of a system for
the electrolytic coating (electroplating) of a steel strip with a
coating based on zinc and/or a zinc alloy in a schematic
representation. Such a system can comprise one or more coiling
devices for uncoiling and recoiling the steel strip to be coated,
an inlet accumulator, a stretcher leveler, a cleaning and
activation unit, the coating section 1, a post-treatment unit, an
outlet accumulator, an inspection section along an oiling device
arranged upstream of the coiling station (coiling device).
[0054] In accordance with the coating section 1 shown herein, a
steel strip 2 can be electrolytically coated with a coating based
on zinc and/or a zinc alloy. For this purpose, the coating section
1 in the embodiment shown in FIG. 1 comprises an electrolytic cell
3, which is formed in the present case as an immersion tank and has
a correspondingly electrochemically adjusted electrolyte 4
containing zinc and/or a zinc alloy in cationic form.
[0055] In the embodiment shown in the present case, the
electrolytic cell 3 comprises two anodes 5, which are positioned in
the electrolytic cell 3 in such a way that the steel strip 2 to be
coated can be passed through the electrolytic cell 3 at a defined
and parallel distance from them. Both anodes 5 are formed as
one-piece plate anodes and are arranged one behind the other in
direction of strip travel R in such a way that the steel strip 2
can be coated on one side with the coating based on zinc and/or
zinc alloy.
[0056] In the present case, two current rollers 6, 7 are assigned
to the electrolytic cell 3, wherein the first current roller 6 is
arranged within the coating section 1 on the inlet side (strip
inlet current roller) of the electrolytic cell 3 and the second
current roller 7 is arranged on the outlet side (strip outlet
current roller) of the electrolytic cell 3. Via the strip inlet
current roller 6, the steel strip 2, which may have been subjected
to a previous cleaning and/or activation step, is deflected from a
horizontal movement to a vertical movement, such that it enters the
electrolytic cell 3, and is thereby simultaneously cathodically
switched. After the coating process, the steel strip 2 is then
deflected from the vertical back into the horizontal direction by
the strip outlet current roller 7, wherein it can also be
cathodically switched via the strip outlet current roller 7 if
necessary. A deflection roller 8 is also arranged inside the
electrolytic cell 3, via which the steel strip 2 is deflected.
[0057] To carry out the coating process, both anodes 5 are supplied
with current by means of a modulated current, which is provided in
each case by a separate pulse rectifier 9, which is designed in
switching power supply technology. Thereby, each of the pulse
rectifiers 9 is electrically connected via its negative pole to one
of the two current rollers 6, 7 and the positive pole to one of the
two anodes 5. The two anodes 5 can be supplied with current via the
modulated current in such a way that the coating process can be
carried out using a defined pulse pattern sequence 10 that is
formed from individual pulse patterns 11.
[0058] Advantageously, both pulse rectifiers 9 are electrically
connected to a central control unit 12, via which the respective
desired pulse pattern 11 of the pulse pattern sequence 10 is
transmitted to each of the pulse rectifiers 9. This allows the
entire coating process to be controlled in an automated manner.
[0059] FIG. 2 shows a second embodiment of a part of the coating
section 1. In contrast to the embodiment shown in FIG. 1, the
electrolytic cell 3 comprises two anode arrangements 13, each with
two anodes 5 arranged parallel to one another, through which the
steel strip 2 is passed. As can be seen from FIG. 2, each of the
anodes 5 of the two anode arrangements 13 is also supplied with
current via a separate pulse rectifier 9. Thereby, each of the four
anodes 5 is electrically connected to a positive pole of each pulse
rectifier 9, and the negative pole of each two pulse rectifiers 9
is electrically connected to one of the two current rollers 6 or 7,
as the case may be.
[0060] FIG. 3 shows an embodiment of a part of a coating section 1
with n-electrolytic cells 3, of which four are shown as an example.
All electrolytic cells 3 are arranged one behind the other in the
direction of strip travel R. Thereby, a deflection roller in the
form of an intermediate current roller 14 is arranged between each
of the plurality of electrolytic cells 3, via which deflection
roller the steel strip 2 is deflected from one preceding
electrolytic cell 3 to the next and is also cathodically switched.
As can be seen from FIG. 3, each of the anodes 5 of the plurality
of anode arrangements 13 is supplied with current via a separate
pulse rectifier 9. Thereby, each of the anodes 5 is electrically
connected to a positive pole of each pulse rectifier 9. With regard
to the cathodic circuit, it is provided that this is distributed
over the different current rollers 6, 7, 14 in such a way that the
negative pole of in each case two pulse rectifiers 9 is
electrically connected to in each case one of the two outer current
rollers 6, 7, i.e. the strip inlet current roller 6 and the strip
outlet current roller 7, and the negative pole of the remaining
pulse rectifiers 9 is electrically connected to the deflection
roller formed as an intermediate current roller 14.
[0061] FIG. 4 shows an embodiment of a partial anode arrangement
15, which comprises a plurality of rod-shaped partial anodes 16,
wherein each of the partial anodes 16 is electrically connected to
the current source or to a negative pole of a pulse rectifier
9.
[0062] FIG. 5 shows a third embodiment of a part of a coating
section 1. Thereby, the electrolytic cell 3 is substantially formed
from the anode arrangement 13 by closing the two open flanks
thereof. In this embodiment, the steel strip 2 is passed through
the partially enclosed chamber bounded by the anode arrangement 13
and in this chamber the electrolyte 4 flows around it. The
electrolyte 4 is conveyed from a reservoir 17 arranged below the
anode arrangement 13 via a pump 18 into the chamber, where it flows
through it over the entire cross-section.
[0063] FIGS. 6 to 9 show different embodiments of pulse patterns 11
that form part of the pulse pattern sequence 10.
[0064] FIG. 6 shows an initial current pulse of time length t,
which is subsequently reduced to a constant current intensity. The
initial current pulse can be used to increase the number of crystal
nuclei on the cathode, resulting in the deposition of fine and
small crystal forms. In contrast to this, the dashed line in FIGS.
6 to 8 shows a constant-time cathodic current as used in direct
current (DC) electrolysis.
[0065] FIG. 7 shows an embodiment variant, which shows a repetitive
pulse pattern 11 that is similar in current amount and time. The
switching pauses in the current flow result in a relaxation of the
Nernst double layer, which is associated with a reduction of the
diffusion layer that impedes mass transfer and thus supports the
formation of a homogeneous coating thickness over the surface of
the strip.
[0066] FIG. 8 shows a pulse pattern 11 with a periodic current
pulse formed in a rectangular shape, which can be used in
combination with one of the preceding patterns to form a multilayer
cathodic coating. Thereby, in the cathodic phase, the coating is
deposited on the steel strip by electroplating, and the reverse
pulse then applies it anodically, with currents that are lower in
magnitude, and the deposition is prevented. The anodic switching
time preferentially reduces crystal peaks and, again by cathodic
switching, deposits another zinc and/or zinc alloy layer on top of
the existing layer. By means of the pulse pattern shown in FIG. 8,
the metallic coatings can be built up periodically and in layers,
which is associated with an improvement in corrosion resistance.
This so-called reverse pulse current process is also called the
bipolar pulse current process, since, thereby, the cathodic and
anodic current conduction is alternated; i.e., the current flow is
changed when the zero crossing is crossed. In other words, the
cathode is temporarily switched to the anode, such that the
electroplating deposition process can be temporarily reversed. The
current amount, duration and polarity change can be designed
according to the user's specification and can be optimized for the
process.
EXAMPLES
[0067] To study hydrogen evolution and diffusion, a steel strip
with a tensile strength of R.sub.e=1200 MPa was coated with a zinc
coating in a system with ten electrolytic cells. For this purpose,
each of the cells had a sulfuric acid aqueous electrolyte
containing zinc sulfate at a concentration in the range of 280 and
320 g/l. The bath temperature was 50 and 70.degree. C.
Example 1
[0068] To isolate the steel strip from hydrogen adsorption, a pulse
pattern sequence was selected with the following pulse pattern
(FIG. 9), which allows the rapid deposition of a fine crystalline,
dense, zinc coating.
[0069] Pulse pattern: [0070] Pulse: cathodic [0071] Pulse shape:
rectangular [0072] Pulse time-out: 5 ms [0073] Pulse length: 5 ms
[0074] Pulse number: 10 [0075] Pulse: anodic [0076] Pulse shape:
rectangular [0077] Pulse length: 5 ms [0078] Pulse number: 2 [0079]
Pulse time-out: 2 ms
[0080] The pulse current density was 100 A/dm.sup.2.
[0081] No significant reduction in yield strength (R.sub.e) was
observed for the coated steel strip.
Example 2
[0082] To study the diffusion of hydrogen into the steel strip, a
pulse pattern sequence with the following pulse pattern was
selected.
[0083] Pulse pattern: [0084] Pulse: cathodic [0085] Pulse shape:
rectangular [0086] Pulse time-out: 135 ms [0087] Pulse length: 3
ms
[0088] The pulse current density was 50 A/dm.sup.2.
[0089] Analysis of the steel strip coated in this way showed a
significant reduction in the hydrogen measured compared to a pulse
pattern with a pulse length to pulse time-out ratio of 3/1.
LIST OF REFERENCE SIGNS
[0090] 1 Coating section [0091] 2 Strip/fabric/cathode [0092] 3
Electrolytic cell [0093] 4 Electrolyte [0094] 5 Anode [0095] 6
First current roller/strip inlet current roller [0096] 7 Second
current roller/strip outlet current roller [0097] 8 Deflection
roller [0098] 9 Pulse rectifier [0099] 10 Pulse pattern sequence
[0100] 11 Pulse pattern [0101] 12 Control unit [0102] 13 Anode
arrangement [0103] 14 Intermediate current roller [0104] 15 Partial
anode arrangement [0105] 16 Partial anodes [0106] 17 Reservoir
[0107] 18 Pumps [0108] R Direction of strip travel
* * * * *