[Technical Field]
[0001] The present disclosure relates to a hot-rolled steel sheet having high composite
corrosion resistance to sulfuric acid and hydrochloric acid and applicable as a material
for thermal power plant equipment such as desulfurization equipment, denitrification
equipment, preheaters, or parts thereof, and a method for manufacturing the hot-rolled
steel sheet.
[Background Art]
[0002] Steels having resistance to sulfuric acid corrosion or sulfuric acid-hydrochloric
acid composite corrosion are used as materials for desulfurization equipment and denitrification
equipment in thermal power plants in which sulfuric acid corrosion or sulfuric acid-hydrochloric
acid composite corrosion is serious, due to sulfuric acid and hydrochloric acid produced
by a reaction between moisture and exhaust gas containing sulfurous acid gas and chlorine
gas generated when fossil fuels such as coal or petroleum are combusted, pipes of
combined cycle power plants, and gas-gas heater (GGH) heat elements required to be
made of relatively thick steel sheets, etc.
[0003] In general, it has been commonly known that a large amount of copper (Cu) may be
added to steel having resistance to sulfuric acid-hydrochloric acid composite corrosion
so as to decrease the rate of corrosion in a composite atmosphere of sulfuric acid
and hydrochloric acid, as compared to the rate of corrosion of normal steels.
[0004] Although copper (Cu) is more effective than other alloying elements in decreasing
the rate of sulfuric acid corrosion, copper (Cu) added in large amounts causes problems
such as the formation of cracks in steel sheets during a hot rolling process, and
thus, steels to which an appropriate amount of copper (Cu) and other elements are
added have been developed (Japanese Patent Application Laid-open Publication No.
1997-025536, Japanese Patent Application Laid-open Publication No.
1998-110237, Korean Patent Application Laid-open Publication No.
2009-0070249, etc). For example elements such as phosphorus in a range of 0.03 to 0.15 wt%, nickel
in a range of 0.1 to 0.4 wt% and cobalt in a range of 0.03 to 0.1 wt% has been added
to a steel sheet for resistance to composite corrosion from sulfuric acid and hydrochloric
acid as described in patent document
KR 2015 0029468 A.
[0005] As described above, although the corrosion resistance of steels resistant to sulfuric
acid-hydrochloric acid composite corrosion is improved as the content of copper (Cu)
is increased, copper (Cu) is a relatively expensive alloying element, and thus production
costs may be increased in proportion to the amount of copper (Cu). In addition, copper
(Cu), having a low melting point, may be segregated or easily cause cracks, even if
only a small amount of deformation occurs in copper-rich regions. Therefore, cracks
may be easily formed in portions such as slab corners undergoing a large amount of
processing during a continuous casting process, and thus, surface defects undergoing
corrosion earlier that other portions may remain after a hot rolling process.
[0006] Therefore, there is a need for a method of imparting high composite corrosion resistance
to steel resistant to sulfuric acid-hydrochloric acid composite corrosion while minimizing
the content of copper (Cu) in the steel.
[Disclosure]
[Technical Problem]
[0007] Aspects of the present disclosure may provide a hot-rolled steel sheet having high
corrosion resistance in a composite corrosive environment containing sulfuric acid
and hydrochloric acid, and a method for manufacturing the hot-rolled steel sheet.
[Technical Solution]
[0008] According to claim 1 a hot-rolled steel sheet having high composite corrosion resistance
to sulfuric acid and hydrochloric acid comprises, by wt%, carbon (C) : 0.05% to 0.1%,
manganese (Mn) : 0.5% to 1.5%, phosphorus (P): 0.02% or less, sulfur (S): 0.02% to
less, aluminum (Al): 0.01% to 0.1%, copper (Cu): 0.2% to 0.6%, antimony (Sb): 0.05%
to 0.1%, and a balance of iron (Fe) and inevitable impurities, wherein copper (Cu)
and antimony (Sb) may be concentrated in a region from a surface to a 500-nm position
in a thickness direction of the hot-rolled steel sheet, and the hot-rolled steel sheet
may have a corrosion loss of 2.0 mg/cm
2/hr in 6 hours or less in a solution of 16.9 volume% sulfuric acid and 0.35 volume%
hydrochloric acid having a temperature of 60°C.
[0009] According to claim 5, a method for manufacturing a hot-rolled steel sheet having
high composite corrosion resistance to sulfuric acid and hydrochloric acid may include:
reheating a steel slab to 1100°C to 1300°C, the steel slab including, by wt%, carbon
(C): 0.05% to 0.1%, manganese (Mn): 0.5% to 1.5%, phosphorus (P): 0.02% or less, sulfur
(S): 0.02% or less, aluminum (Al): 0.01% to 0.1%, copper (Cu): 0.2% to 0.6%, antimony
(Sb):
0.05% to 0.1%, and a balance of iron (Fe) and inevitable impurities; obtaining a hot-rolled
steel sheet by hot rolling the reheated steel slab and finish hot rolling the steel
slab at a temperature of 850°C to 950°C; rapidly cooling the hot-rolled steel sheet
at a rate of 120°C/s to 150°C/s; coiling the cooled hot-rolled steel sheet at a temperature
of 650°C to 750°C; and slowly cooling the coiled hot-rolled steel sheet at a rate
of 30°C/hr to 40°C/hr to a cooling finish temperature of 350°C to 400°C.
[0010] The above-described aspects of the present disclosure do not include all aspects
or features of the present disclosure. Other aspects or features, and effects of the
present disclosure will be clearly understood from the following descriptions of exemplary
embodiments.
[Advantageous Effects]
[0011] The present disclosure may provide a hot-rolled steel sheet having high composite
corrosion resistance even though the hot-rolled steel sheet has lower amounts of alloying
elements than steel sheets of the related art having composite corrosion resistance
to sulfuric acid and hydrochloric acid. In addition, the hot-rolled steel sheet of
the present disclosure may be used as a material, required to have a relatively thick
thickness, for denitrification equipment and desulfurization equipment of power plants,
exhaust gas pipes of boilers, and preheaters, and may markedly increase the lifespans
of such facilities and apparatuses.
[Best Mode]
[0012] The inventors have repeatedly conducted research into compositions of steel sheets
and methods of manufacturing steel sheets in order to provide a method of imparting
high composite corrosion resistance to steel resistant to sulfuric acid-hydrochloric
acid composite corrosion while minimizing the content of copper (Cu) in the steel.
As a result, the inventors have found that if antimony (Sb) is added to a steel sheet
as an alloying element, and cooling conditions after a hot rolling process and a coiling
process are properly controlled, a Cu-Sb rich layer, guaranteeing high composite corrosion
resistance, is formed on the steel sheet to an appropriate thickness in a corrosive
environment containing sulfuric acid and hydrochloric acid. Based on this knowledge,
the inventors have invented the present invention.
[0013] Hereinafter, a hot-rolled steel sheet having high composite corrosion resistance
to sulfuric acid and hydrochloric acid will be described in detail according to an
aspect of the present disclosure.
[0014] First, the alloying composition of the hot-rolled steel sheet of the present disclosure
will be described in detail.
Carbon (C): 0.05 wt% to 0.1 wt%
[0015] Carbon (C) is effective in increasing the strength of a steel sheet. If the
content of carbon (C) is less than 0.05 wt%, it is difficult to obtain a desired degree
of strength, and wear resistance reduces. Conversely, if the content of carbon (C)
is greater than 0.1 wt%, the weldability of the steel sheet markedly reduces, thereby
markedly increasing the possibility of defects during welding and
decreasing the corrosion resistance of the steel sheet.
Manganese (Mn): 0.5 wt% to 1.5 wt%
[0016] Manganese (Mn) dissolves in steel and precipitates sulfur (S) in the form of manganese
sulfide, thereby preventing hot shortness caused by dissolved sulfur (S) and having
a solid-solution strengthening effect. If the content of manganese (Mn) is less than
0.5 wt%, manganese sulfide is not sufficiently precipitated. Thus, hot shortness may
be caused by dissolved sulfur (S), and it may be difficult to obtain a desired degree
of strength. Conversely, if the content of manganese (Mn) is greater than 1.5 wt%,
the above-described effects are saturated, and product cost markedly increases.
Phosphorus (P): 0.02 wt% or less
[0017] Phosphorus (P) is an element inevitably added to steel, and if the content of phosphorus
(P) is greater than 0.02 wt%, composite corrosion resistance
may markedly decrease from a desired value.
Sulfur (S): 0.02 wt% or less
[0018] Sulfur (S) is an element dissolved in steel causing hot shortness, and thus, the
content of sulfur (S) is adjusted to be as low as possible. If the content of sulfur
(S) is greater than 0.02 wt%, there is a high possibility that defects will be formed
due to hot shortness.
Aluminum (Al): 0.01 wt% to 0.1 wt%
[0019] Aluminum (Al) is an element inevitably added to Alkilled steel, and it may be preferable
that the content of aluminum (Al) be within the range of 0.01 wt% or greater for the
effect of deoxidation. However, if the content of aluminum (Al) is greater than 0.1
wt%, surface defects may very likely be formed on the steel sheet, and the weldability
of the steel sheet may be decreased.
Copper (Cu): 0.2 wt% to 0.6 wt%
[0020] Copper (Cu) is an element added for composite corrosion resistance to sulfuric acid
and hydrochloric acid. If the content of copper (Cu) is excessively low, it may be
difficult to obtain desired composite corrosion resistance. Thus, preferably, copper
(Cu) may be added in an amount of 0.3% or greater. Although composite corrosion resistance
increases in proportion to the content of copper (Cu), if the content of copper (Cu)
is excessively high, the increase of corrosion resistance is markedly lowered, and
production costs may be markedly increased. In addition, surface defects known as
star cracks may be formed. Therefore, according to the present disclosure, preferably,
the upper limit of the content of copper (Cu) may be set to be 0.5 wt%.
Antimony (Sb): 0.05 wt% to 0.1 wt%
[0021] Together with copper (Cu), antimony (Sb) is a key element for improving composite
corrosion resistance. In particular, antimony (Sb) forms a Cu-Sb composite oxide in
a corrosive environment, thereby effectively improving composite corrosion resistance.
If the content of antimony (Sb) is less than 0.05 wt%, it is difficult to obtain the
above-described effects. Conversely, if the content of antimony (Sb) is greater than
0.1 wt%, the above-described
effects are saturated, and production costs markedly increase.
[0022] The steel sheet includes iron (Fe) and inevitable impurities in addition to the above-described
alloying elements. Although the addition of elements other than the above-described
elements is not excluded, it may be preferable that the total content of tungsten
(W), molybdenum (Mo), cobalt (Co), and nickel (Ni) be adjusted to be less than 10
ppm. The reason for this is that these elements may deteriorate the properties of
the hot-rolled steel sheet, for example, ductility.
[0023] Furthermore, in the hot-rolled steel sheet of the present disclosure, copper (Cu)
and antimony (Sb) may be concentrated in a region from the surface to a 500-nm position
in the thickness direction of the hot-rolled steel sheet. These elements are concentrated
in the surface of the hot-rolled steel sheet during manufacturing processes, and if
the hot-rolled steel sheet is exposed to a corrosive environment containing sulfuric
acid and hydrochloric acid, the elements change into a Cu-Sb composite oxide, thereby
markedly improving the corrosion resistance of the hot-rolled steel sheet.
[0024] In this case, the contents of concentrated copper (Cu) and antimony (Sb) are not
particularly limited. As described below, the contents of concentrated copper (Cu)
and antimony (Sb) may be adjusted such that an oxide layer having a thickness of 400
nm or greater from the surface of the hot-rolled steel sheet may be formed in a corrosive
environment containing sulfuric acid and hydrochloric acid. If the thickness of the
oxide layer is less than 400 nm, it may be difficult to obtain a degree of corrosion
resistance intended in the present disclosure. Since corrosion resistance increases
as the thickness of the oxide layer increases, the upper limit of the thickness of
the oxide layer is not particularly set in the present disclosure. However, if the
thickness of the oxide layer is greater than 500 nm, the effect of improving corrosion
resistance is relatively low when the addition of large amounts of alloying elements
is considered, and production costs may be excessively increased. Thus, it may be
more preferable that the thickness of the oxide layer be within the range of 400 nm
to 500 nm.
[0025] The hot-rolled steel sheet of the present disclosure has a corrosion loss of 2.0
mg/cm
2/hr or less in a solution of 16.9 volume% sulfuric acid and 0.35 volume% hydrochloric
acid.
[0026] Hereinafter, a method for manufacturing a hot-rolled steel sheet having high composite
corrosion resistance to sulfuric acid and hydrochloric acid will be described in detail,
according to another aspect of the present disclosure.
[0027] First, a steel slab having the above-described composition is prepared and reheated
to a temperature of 1100°C to 1300°C. If the reheating temperature is lower than 1100°C,
it is difficult to secure a temperature for a subsequent hot rolling process. Conversely,
if the reheating temperature is higher than 1300°C, copper (Cu) having a relatively
low melting point may melt out, and thus cracks may very likely be formed in the surface
of the steel slab.
[0028] Thereafter, the reheated steel slab is subjected to hot rolling, and is then subjected
to finish hot rolling at a temperature of 850°C to 950°C, to obtain a hot-rolled steel
sheet. If the finish hot rolling temperature is lower than 850°C, the elongation of
the hot-rolled steel sheet is markedly decreased due to elongated grains, and properties
of the hot-rolled steel sheet have directional deviations. Conversely, if the finish
hot rolling temperature is higher than 950°C, austenite grains become coarse, and
thus hardenability markedly increases.
[0029] Thereafter, the hot-rolled steel sheet is rapidly cooled at a rate of 120°C/s to
150°C/s, based on the surface temperature of the hot-rolled steel sheet. The rapid
cooling may provide driving force such that alloying elements improving corrosion
resistance may move to the surface of the hot-rolled steel sheet after a coiling process.
If the cooling rate is less than 120°C/s, the surface temperature of the hot-rolled
steel sheet may be too high to sufficiently drive oxide-forming elements from the
interior to the surface of the hot-rolled steel sheet, and thus when the hot-rolled
steel sheet is exposed to a composite corrosive environment, oxides may not be sufficiently
formed. Conversely, if the cooling rate is greater than 150°C/s, the interior temperature
of the hot-rolled steel sheet becomes excessively low, and thus heat recuperation
may not occur to a desired temperature after a coiling process. In this case, alloying
elements effective in forming an oxide layer may not move smoothly. Therefore, preferably,
the cooling rate may be set to be within the range of 120°C/s to 150°C/s.
[0030] Thereafter, the cooled hot-rolled steel sheet is coiled at a temperature of 650°C
to 750°C. If the coiling temperature is lower than 650°C, atoms may not easily move
during the coiling process. As a result, a rich layer may not be easily formed, and
thus an oxide layer may not be formed in a corrosive environment. That is, corrosion
resistance may not be sufficiently guaranteed. If the coiling temperature is higher
than 750°C, heat recuperation occurs to an excessively high temperature, and thus,
defects such as dents may be formed on the coiled hot-rolled steel sheet. Therefore,
the coiling temperature may preferably be set to be within the range of 650°C to 750°C.
[0031] In addition, during the coiling process, it may be preferable that the surface of
the hot-rolled steel sheet have a temperature of 720°C to 750°C owing to a heat recuperation
phenomenon. Although the interior temperature of the hot-rolled steel sheet is adjusted
to be within the range of 650°C to 750°C through the cooling process, the surface
temperature of the hot-rolled steel sheet is lower than the range because of rapid
cooling. Therefore, the hot-rolled steel sheet may be allowed to undergo heat recuperation
so as to activate the movement of alloying elements effective in forming an oxide
layer and thus to form a rich layer having a sufficient thickness. To sufficiently
obtain these effects, the surface temperature of the hot-rolled steel sheet may preferably
be 720°C or higher after heat recuperation. However, the surface temperature of the
hot-rolled steel sheet will not exceed 750°C even if the heat recuperation is sufficient.
[0032] The coiled hot-rolled steel sheet is slowly cooled to a cooling finish temperature
of 350°C to 400°C at a rate of 30°C/hr to 40°C/hr. If the slow cooling rate is excessively
high, copper (Cu) forming a rich layer may not sufficiently move, and thus it may
be difficult to form a rich layer having a sufficient thickness. Therefore, it may
be preferable that the slow cooling rate be within the range of 40°C/hr or less. However,
if the slow cooling rate is less than 30°C/hr, the size of grains may increase excessively,
and thus, the strength of the hot-rolled steel sheet may decrease. Thus, the slow
cooling rate may preferably be within the range of 30°C/hr to 40°C/hr. In addition,
if the cooling finish temperature is lower than 350°C, properties of the hot-rolled
steel sheet such as ductility may deteriorate, and productivity may decrease. Conversely,
if the cooling finish temperature is higher than 400°C, a rich layer having a sufficient
thickness may not be formed, and thus the hot-rolled steel sheet may have poor corrosion
resistance. Therefore, the cooling finish temperature may preferably be within the
range of 350°C to 400°C.
[Mode for Invention]
[0033] Hereinafter, the present disclosure will be described more specifically through examples.
However, the following examples should be considered in a descriptive sense only,
and are not for purposes of limitation. The scope of the present invention is defined
by the appended claims, and modifications and variations may be reasonably made therefrom.
(Examples)
[0034] Steel ingots, manufactured through a melting process and having compositions as illustrated
in Table 1 below, were maintained in a heating furnace for one hour at 1200°C and
were subjected to a hot rolling process. In this case, finish hot rolling was performed
at 900°C, and hot-rolled steel sheets having a thickness of 4.5 mm were ultimately
manufactured. Thereafter, the hot-rolled steel sheets were cooled, coiled, and maintained
under the conditions shown in Table 2 below. Thereafter, the hot-rolled steel sheets
were slowly cooled to 380°C at a rate of 35°C/h, thereby completing the manufacturing
of the hot-rolled steel sheets.
[0035] To observe corrosion characteristics of the hot-rolled steel sheets, specimens of
the hot-rolled steel sheets were placed in a solution having a temperature of 60°C
and containing 16.9 volume% sulfuric acid and 0.35 volume% hydrochloric acid for 6
hours, and subsequently, the corrosion loss of each specimen was measured as shown
in Table 2 below.
[0036] In addition, after the immersion in the sulfuric acid-hydrochloric acid composite
corrosive environment, the thickness of an oxide layer (corrosion-resistant layer)
of each hot-rolled steel sheet was measured as shown in Table 2.
[Table 1]
| Steels |
Composition (wt%) |
| C |
Mn |
P |
S |
Al |
Cu |
Sb |
| Inventive Steel 1 |
0.075 |
0.69 |
0.012 |
0.009 |
0.033 |
0.32 |
0.08 |
| Inventive Steel 2 |
0.068 |
0.67 |
0.011 |
0.009 |
0.029 |
0.39 |
0.06 |
| Inventive Steel 3 |
0.074 |
0.75 |
0.009 |
0.01 |
0.029 |
0.44 |
0.05 |
| Comparative Steel 1 |
0.069 |
0.74 |
0.012 |
0.011 |
0.035 |
0.28 |
- |
[Table 2]
| Steels |
Cooling Rate |
Coiling Temperature |
Corrosion Loss |
Thickness of Oxide |
Examples |
| |
(°C/s) |
(°C) |
(mg/cm2/hr) |
Layer (nm) |
|
| Inventive Steel 1 |
130 |
700 |
1.8 |
420 |
Inventive Example 1 |
| |
130 |
500 |
4.5 |
57 |
Comparative Example 1 |
| 10 |
700 |
3.8 |
63 |
Comparative Example 2 |
| Inventive Steel 2 |
130 |
700 |
1.6 |
440 |
Inventive Example 2 |
| |
10 |
700 |
3.6 |
69 |
Comparative Example 3 |
| Inventive Steel 3 |
130 |
700 |
1.4 |
460 |
Inventive Example 3 |
| |
10 |
700 |
3.2 |
75 |
Comparative Example 4 |
| Comparative Steel 1 |
130 |
700 |
8.8 |
220 |
Comparative Example 5 |
[0037] As shown in Tables 1 and 2, Inventive Examples 1 to 3 satisfying the alloying composition
and manufacturing conditions proposed in the present disclosure had a corrosion loss
of 2.0 mg/cm
2/hr or less in the sulfuric acid-hydrochloric acid corrosive environment owing to
the formation of oxide layers having a thickness of 400 nm or greater. That is, Inventive
Examples 1 to 3 had high corrosion resistance.
[0038] Although Comparative Example 1 satisfied the alloying composition of the present
disclosure, the coiling temperature of Comparative Example 1 was low, 500°C. Thus,
an oxide layer was not sufficiently formed, resulting in corrosion loss of 4.5 mg/cm
2/hr. That is, Comparative Example 1 had poor corrosion resistance.
[0039] Although Comparative Examples 2 to 4 satisfied the alloying composition of the present
disclosure, the cooling rate of Comparative Example 2 to 4 was low, 10°C/s. Thus,
oxide layers were not sufficiently formed, resulting in a corrosion loss of 3.2 mg/cm
2/hr or greater. That is, Comparative Examples 2 to 4 had poor corrosion resistance.
[0040] Although Comparative Example 5 satisfied the manufacturing conditions of the present
disclosure, antimony (Sb) was not added to Comparative Example 5, resulting in a corrosion
loss of 8.8 mg/cm
2/hr in the sulfuric acid-hydrochloric acid corrosive environment. That is, Comparative
Example 5 had poor corrosion resistance. The reason for this is that a Cu-Sb composite
oxide having high corrosion resistance was not formed in an oxide layer.
[0041] While exemplary embodiments have been shown and described above, it will be apparent
to those skilled in the art that modifications and variations could be made without
departing from the scope of the present invention as defined by the appended claims.
1. A hot-rolled steel sheet having high composite corrosion resistance to sulfuric acid
and hydrochloric acid, the hot-rolled steel sheet comprising, by wt%, carbon (C):
0.05% to 0.1%, manganese (Mn): 0.5% to 1.5%, phosphorus (P): 0.02% or less, sulfur
(S): 0.02% or less, aluminum (Al): 0.01% to 0.1%, copper (Cu): 0.2% to 0.6%, antimony
(Sb): 0.05% to 0.1%, and a balance of iron (Fe) and inevitable impurities, wherein
copper (Cu) and antimony (Sb) are concentrated in a region from a surface to a 500-nm
position in a thickness direction of the hot-rolled steel sheet, and the hot-rolled
steel sheet has a corrosion loss of 2.0 mg/cm2/hr in 6 hours or less in a solution of 16.9 volume% sulfuric acid and 0.35 volume%
hydrochloric acid having a temperature of 60°C.
2. The hot-rolled steel sheet of claim 1, wherein the inevitable impurities comprise
tungsten (W), molybdenum (Mo), cobalt (Co), and nickel (Ni) in a total amount of less
than 10 ppm.
3. The hot-rolled steel sheet of claim 1, wherein the concentrated copper (Cu) and antimony
(Sb) form an oxide layer comprising a Cu-Sb composite oxide in a corrosive environment
containing sulfuric acid and hydrochloric acid.
4. The hot-rolled steel sheet of claim 3, wherein the oxide layer has a thickness of
400 nm to 500 nm from the surface of the hot-rolled steel sheet in the thickness direction
of the hot-rolled steel sheet.
5. A method for manufacturing a hot-rolled steel sheet having high composite corrosion
resistance to sulfuric acid and hydrochloric acid, the method comprising:
reheating a steel slab to 1100°C to 1300°C, the steel slab comprising, by wt%, carbon
(C): 0.05% to 0.1%, manganese (Mn): 0.5% to 1.5%, phosphorus (P): 0.02% or less, sulfur
(S): 0.02% or less, aluminum (Al): 0.01% to 0.1%, copper (Cu): 0.2% to 0.6%, antimony
(Sb): 0.05% to 0.1%, and a balance of iron (Fe) and inevitable impurities;
obtaining a hot-rolled steel sheet by hot rolling the reheated steel slab and finish
hot rolling the steel slab at a temperature of 850°C to 950°C;
rapidly cooling the hot-rolled steel sheet at a rate of 120°C/s to 150°C/s;
coiling the cooled hot-rolled steel sheet at a temperature of 650°C to 750°C; and
slowly cooling the coiled hot-rolled steel sheet at a rate of 30°C/hr to 40°C/hr to
a cooling finish temperature of 350°C to 400°C.
6. The method of claim 5, wherein during the coiling of the cooled hot-rolled steel sheet,
a surface of the hot-rolled steel sheet reaches a temperature of 720°C to 750°C through
a heat recuperation phenomenon.
1. Warmgewalztes Stahlblech mit hoher kombinierter Korrosionsbeständigkeit gegen Schwefelsäure
und Salzsäure, wobei das warmgewalzte Stahlblech in Gew.-% umfasst, Kohlenstoff (C):
0,05 % bis 0,1 %, Mangan (Mn): 0,5 % bis 1,5 %, Phosphor (P): 0,02 % oder weniger,
Schwefel (S): 0,02 % oder weniger, Aluminium (AI): 0,01 % bis 0,1 %, Kupfer (Cu):
0,2 % bis 0,6 %, Antimon (Sb): 0,05 % bis 0,1 %, und einen Rest aus Eisen (Fe) und
unvermeidlichen Verunreinigungen, wobei Kupfer (Cu) und Antimon (Sb) in einem Bereich
ausgehend von einer Oberfläche zu einer 500 nm-Position in einer Dickenrichtung des
warmgewalzten Stahlblechs konzentriert sind, und das warmgewalzte Stahlblech einen
Korrosionsverlust von 2,0 mg/cm2/h in 6 Stunden oder weniger in einer Lösung aus 16,9 Volumen-% Schwefelsäure und
0,35 Volumen-% Salzsäure mit einer Temperatur von 60° C hat.
2. Warmgewalztes Stahlblech nach Anspruch 1, wobei die unvermeidlichen Verunreinigungen
Wolfram (W), Molybdän (Mo), Cobalt (Co) und Nickel (Ni) in einer Gesamtmenge von weniger
als 10 ppm umfassen.
3. Warmgewalztes Stahlblech nach Anspruch 1, wobei das konzentrierte Kupfer (Cu) und
Antimon (Sb) eine ein Cu-Sb-Verbundoxid umfassende Oxidschicht in einer Schwefelsäure
und Salzsäure enthaltenden korrosiven Umgebung bilden.
4. Warmgewalztes Stahlblech nach Anspruch 3, wobei die Oxidschicht eine Dicke von 400
nm bis 500 nm ausgehend von der Oberfläche des warmgewalzten Stahlblechs in der Dickenrichtung
des warmgewalzten Stahlblechs hat.
5. Verfahren zum Herstellen eines warmgewalzten Stahlblechs mit hoher kombinierter Korrosionsbeständigkeit
gegen Schwefelsäure und Salzsäure, wobei das Verfahren umfasst:
Wiedererwärmen einer Stahlbramme auf 1100° C bis 1300 ° C, wobei die Stahlbramme in
Gew.-% umfasst, Kohlenstoff (C): 0,05 % bis 0,1 %, Mangan (Mn): 0,5 % bis 1,5 %, Phosphor
(P): 0,02 % oder weniger, Schwefel (S): 0,02 % oder weniger, Aluminium (AI): 0,01
% bis 0,1 %, Kupfer (Cu): 0,2 % bis 0,6 %, Antimon (Sb): 0,05 % bis 0,1 %, und einen
Rest aus Eisen (Fe) und unvermeidlichen Verunreinigungen;
Erlangen eines warmgewalzten Stahlblechs durch Warmwalzen der wiedererwärmten Stahlbramme
und Endwarmwalzen der Stahlbramme bei einer Temperatur von 850° C bis 950° C;
schnelles Abkühlen des warmgewalzten Stahlblechs mit einer Rate von 120° C/s bis 150°
C/s;
Aufwickeln des warmgewalzten Stahlblechs bei einer Temperatur von 650° C bis 750°
C; und
langsames Abkühlen des aufgewickelten warmgewalzten Stahlblechs mit einer Rate von
30° C/h bis 40° C/h auf eine Abkühlendtemperatur von 350° C bis 400° C.
6. Verfahren nach Anspruch 5, wobei eine Oberfläche des warmgewalzten Stahlblechs während
des Aufwickelns des abgekühlten warmgewalzten Stahlblechs durch ein Wärmerückgewinnungsphänomen
eine Temperatur von 720° C bis 750° C erreicht.
1. Tôle d'acier laminée à chaud ayant une résistance combinée élevée à la corrosion par
l'acide sulfurique et l'acide hydrochlorique, la tôle d'acier laminée à chaud comprenant,
en % de poids, du carbone (C) : 0,05 % à 0,1 %, du manganèse (Mn) : 0,5 % à 1,5 %,
du phosphore (P) : 0,02 % ou moins, du soufre (S) : 0,02 % ou moins, de l'aluminium
(Al) : 0,01 % à 0,1 %, du cuivre (Cu) : 0,2 % à 0,6 %, de l'antimoine (Sb) : 0,05
% à 0,1 %, et un solde de fer (Fe) et d'impuretés inévitables, sachant que le cuivre
(Cu) et l'antimoine (Sb) sont concentrés dans une région allant d'une surface à une
position de 500 nm dans une direction d'épaisseur de la tôle d'acier laminée à chaud,
et la tôle d'acier laminée à chaud a une perte par corrosion de 2,0 mg/cm2/h en 6 heures ou moins dans une solution de 16,9 % en volume d'acide sulfurique et
de 0,35 % en volume d'acide hydrochlorique ayant une température de 60 °C.
2. La tôle d'acier laminée à chaud de la revendication 1, sachant que les impuretés inévitables
comprennent du tungstène (W), du molybdène (Mo), du cobalt (Co), et du nickel (Ni)
dans une quantité totale de moins de 10 ppm.
3. La tôle d'acier laminée à chaud de la revendication 1, sachant que le cuivre (Cu)
et l'antimoine (Sb) concentrés forment une couche d'oxyde comprenant un oxyde composite
Cu-Sb dans un environnement corrosif contenant de l'acide sulfurique et de l'acide
hydrochlorique.
4. La tôle d'acier laminée à chaud de la revendication 3, sachant que la couche d'oxyde
a une épaisseur de 400 nm à 500 nm depuis la surface de la tôle d'acier laminée à
chaud dans la direction d'épaisseur de la tôle d'acier laminée à chaud.
5. Procédé de fabrication d'une tôle d'acier laminée à chaud ayant une résistance combinée
élevée à la corrosion par l'acide sulfurique et l'acide hydrochlorique, le procédé
comprenant :
le réchauffage d'une brame d'acier à 1100 °C à 1300 °C, la brame d'acier comprenant,
en % en poids, du carbone (C) : 0,05 % à 0,1 %, du manganèse (Mn) : 0,5 % à 1,5 %,
du phosphore (P) : 0,02 % ou moins, du soufre (S) : 0,02 % ou moins, de l'aluminium
(Al) : 0,01 % à 0,1 %, du cuivre (Cu) : 0,2 % à 0,6 %, de l'antimoine (Sb) : 0,05
% à 0,1 %, et un solde de fer (Fe) et d'impuretés inévitables ;
l'obtention d'une tôle laminée à chaud par laminage à chaud de la brame d'acier réchauffée
et laminage à chaud de finition de la brame d'acier à une température de 850 °C à
950 °C ;
le refroidissement rapide de la tôle d'acier laminée à chaud à un taux de 120 °C/s
à 150 °C/s ;
le bobinage de la tôle d'acier laminée à chaud refroidie à une température de 650
°C à 750 °C ; et
le refroidissement lent de la tôle d'acier laminée à chaud bobinée à un taux de 30
°C/h à 40 °C/h à une température de finition de refroidissement de 350 °C à 400 °C.
6. Le procédé de la revendication 5, sachant que pendant le bobinage de la tôle d'acier
laminée à chaud refroidie, une surface de la tôle d'acier laminée à chaud atteint
une température de 720 °C à 750 °C par un phénomène de récupération de chaleur.