Heat Resistant Ferritic Steel And Method For Producing The Same
Abstract:
This ferritic heat resistant steel comprises: a substrate comprising in terms of mass% 0.01 0.3% C 0.01 2% Si 0.01 2% Mn 0.10% or less P 0.03% or less S 7.5 14.0% Cr 0.3% or less sol. Al and 0.005 0.15% N with the remainder being Fe and impurities; and an oxide film which is formed on the substrate and which comprises 25 97% Fe and 3 75% Cr. This ferritic heat resistant steel exhibits excellent selective light absorption properties and oxidation resistance.
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Notices, Deadlines & Correspondence
c/o NIPPON STEEL & SUMITOMO METAL CORPORATION 6 1 Marunouchi 2 chome Chiyoda ku Tokyo
1008071
2. MATSUO Hiroshi
c/o NIPPON STEEL & SUMITOMO METAL CORPORATION 6 1 Marunouchi 2 chome Chiyoda ku Tokyo
1008071
3. OTSUKA Shunichi
c/o NIPPON STEEL & SUMITOMO METAL CORPORATION 6 1 Marunouchi 2 chome Chiyoda ku Tokyo
1008071
Specification
DESCRIPTION
Title of Invention: HEAT RESISTANT FERRITIC STEEL AND
METHOD FOR PRODUCING THE SAME
Technical Field
[0001]
The present invention relates to a heat resistant
steel and a method for producing the steel and, more
particularly, to a heat resistant ferritic steel and a
method for producing the steel.
Background Art
[0002]
In recent years, to achieve energy saving, the
development of highly efficient boilers has been advanced.
For example, an ultra supercritical pressure boiler uses
higher temperature and pressure of steam than those in a
conventional boiler to enhance the energy efficiency.
Also, a boiler using wastes or biomass as a fuel other
than fossil fuels has been developed. Further, there has
been advanced the development of an electric power plant
boiler utilizing solar heat has been developed. In
particular, a solar thermal power plant boiler has
attracted attention from the viewpoints of energy saving
and environmental preservation. As a steel material of
heat exchangers and the like for these boilers, a heat
resistant ferritic steel may be used. The boiler steam
temperature is high, and reaches a temperature close to
600°C in some cases. The heat resistant ferritic steel
used in such an application is required to have excellent
photoselective absorptivity.
[0003]
The photoselective absorptivity is a property such
that absorptivity changes in different wavelength regions.
The term of "excellent photoselective absorptivity" means
that, for light (electromagnetic wave) of visual to nearinfrared
region (wavelength: 0.3 to 1 p , hereinafter
referred to as "low wavelength side"), the absorptivity
is high, and for light (electromagnetic wave) of mediumto
far-infrared region (wavelength: 2.5 to 25 p ,
hereinafter referred to as "high wavelength side"), the
radioactivity is low. In other words, the photoselective
absorptivity means that the reflectance of light on the
low wavelength side is low, and the reflectance of light
on the high wavelength side is high.
[0004]
To attain excellent photoselective absorptivity,
various methods have been proposed so far. JP52-126434A
(Patent Document 1) and JP58-195746A (Patent Document 2)
disclose methods in which the photoselective absorptivity
is enhanced by forming an organic coated film on the
surface of steel material. The paint disclosed in Patent
Document 1 consists of semiconductor particles having an
energy band width of 0.4 to 1.5 eV, a polyvinyl butyral
organic binder, and a solvent. The paint for
photoselective absorbing film disclosed in Patent
Document 2 contains carboxylic acid amide copolymer,
oxides, and solvent-based paint.
[0005] I
JP53-75132A (Patent Document 3), JP60-57157A (Patent
Document 4), and JP62-182553A (Patent Document 5)
disclose methods in which, to attain the photoselective
absorptivity, triiron tetraoxide (FesOl: magnetite) is
formed on the surface of steel by chemical treatment or
the like. Specifically, in Patent Document 3, a
selective absorbing film consisting of magnetite is
formed by immersing a base material consisting mainly of
iron in a high-temperature alkaline solution. In Patent
Document 4, a selective absorbing film consisting of
magnetite is formed by electrooxidizing a base material
consisting mainly of iron in an acidic solution. In
Patent Document 5, a selective absorbing film consisting
of magnetite is formed by electrooxidizing a base
material consisting mainly of iron in an acidic solution
after the surface of base material has been iron-plated.
[0006]
JP55-77667A (Patent Document 6) discloses a method
in which an oxide film consisting mainly of Fe that has a
film thickness of 500 to 2000 angstroms and contains
11.00 to 26.00 wt% of Cr is formed by a chemical
treatment method or the like method, and the surface of
oxide film is mirror-polished. Patent Document 6
describes that the photoselective absorptivity is
enhanced by this method.
[0007]
JP7-325212A (Patent Document 7) discloses a method
in which a film consisting of iron oxide is formed on the
surface of steel by spraying. Patent Document 7
describes that the photoselective absorptivity is
enhanced by this method.
Disclosure of the Invention
[0008]
In recent years, to increase power generation
efficiency, the boiler steam temperature in solar power
generation is as high as 500 to 600°C, and in the future,
it is expected that the boiler steam temperature will
become much higher. In such a high-temperature
environment, it is difficult to maintain the
photoselective absorptivity. Since the coated film
described in Patent Documents 1 and 2 is organic, the
coated film is less applicable in the above-described
high-temperature environment. The oxide film described
in Patent Documents 3 to 5 consists of magnetite.
Therefore, the radioactivity at high temperatures, that
is, the radioactivity on the high wavelength side is high,
and the photoselective absorptivity is poor. The oxide
film described in Patent Document 6 may have low
photoselective absorptivity at high temperatures. The
oxide film described in Patent Document 7 may have high
radioactivity especially at high temperatures, that is,
high radioactivity on the high wavelength side.
[0009]
An objective of the present invention is to provide
a heat resistant ferritic steel excellent in
photoselective absorptivity.
[OOlO]
The heat resistant ferritic steel in accordance with
the present invention includes a base material comprising,
by mass percent, C: 0.01 to 0.3%, Si: 0.01 to 2%, Mn:
0.01 to 28, P: at most 0.10%, S: at most 0.03%, Cr: 7.5
to 14.0%, sol.Al: at most 0.3%, and N: 0.005 to 0.15%,
the balance being Fe and impurities, and an oxide film
which is formed on the base material and whose chemical
composition excluding oxygen and carbon contains 25 to
97% of Fe and 3 to 75% of Cr. The oxide film contains
spinel-type oxides and Cr203.
[0011]
The heat resistant ferritic steel in accordance with
the present invention is excellent in photoselective
absorptivity.
Best Mode for Carrying Out the Invention
[0012]
An embodiment of the present invention will now be
described in detail. The symbol " % " for the content of
each element means "% by mass" unless otherwise noted.
[0013]
The present inventors conducted researches and
studies on the heat resistant ferritic steel excellent in
photoselective absorptivity. As a result, the present
inventors obtained the following findings.
[0014]
(1) Among various oxides, triiron tetraoxide
(hereinafter, referred to as magnetite), which is an Febased
oxide, exhibits excellent absorptivity for light
(electromagnetic wave) of visual to near-infrared region
(wavelength: 0.3 to 1 p , "low wavelength side").
However, for light (electromagnetic wave) of medium- to
far-infrared region (wavelength: 2.5 to 25 p , "high
wavelength side"), magnetite has a high radioactivity.
That is to say, in a high-temperature environment of 500
to 600°C, magnetite is liable to radiate heat.
[0015]
(2) If the magnetite is made thin, the radioactivity
for the light (electromagnetic wave) on the high
wavelength side decreases. However, even if the oxide
film consisting of very thin magnetite is formed, in
high-temperature environments, Fe diffuses from the base
material to the oxide film, and the oxide film grows and
becomes thick. If the oxide film becomes thick, the
photoselective absorptivity decreases.
[0016]
(3) In the case where the oxide film contains Febased
oxides and Cr-based oxides, or in the case where
the Fe-based oxides themselves in the oxide film contain
Cr, the radioactivity on the high wavelength side can be
restrained. Chromium in the oxide film further restrains
the growth of oxide film in high-temperature environments.
Therefore, Cr can maintain the photoselective
absorptivity of the oxide film for a long period of time.
[0017]
(4) If the chemical composition of oxide film
contains 25 to 97% of Fe and 3 to 75% of Cr, a heat
resistant ferritic steel excellent in photoselective
absorptivity can be obtained.
[0018]
(5) Preferably, the oxide film contains spinel-type
oxides and Cr203 (chromia) . In this description, the
spinel-type oxides include magnetite as well. The
spinel-type oxides other than magnetite are oxides that
contain, for example, Fe and Cr, and have spinel-type
structures.
[0019]
Chromia (Cr203) enhances the reflectance on the high
wavelength side, and restrains the heat radiation of
steel. Further, Cr203 enhances the oxidation resistance.
Therefore, if the oxide film contains not only spineltype
oxides but also Cr203, the heat resistant ferritic
steel having that oxide film is excellent in oxidation
resistance, and also is excellent in photoselective
absorptivity. Specifically, the reflectance of light
(electromagnetic wave) on the low wavelength side is low,
and the reflectance of light on the high wavelength side
is high.
[0020]
(6) Further preferably, in the case where the
maximum diffraction peak intensity of spinel-type oxides
obtained by X-ray surface analysis (XRD) is defined as Is,
and the maximum diffraction peak intensity of Cr203 is
defined as Ic, if Formula (1) is satisfied, the heat
resistant ferritic steel attains excellent photoselective
absorptivity. This is because, if Formula (1) is
satisfied, Cr203 of an amount sufficient to enhance the
reflectance on the high wavelength side is contained in
the oxide film.
0.010 I Ic/Is I 10 . . . (1)
[0021]
(7) Still further preferably, Fez03 (hematite)
contained in the oxide film is restrained. If a large
amount of Fe203 is contained in the oxide film, the
reflectance of light (electromagnetic wave) on the low
wavelength side of the oxide film is high, and the
reflectance of light on the high wavelength side is low.
As a result, the photoselective absorptivity decreases.
Therefore, the amount of Fe203 (hematite) in the oxide
film is preferably smaller.
[0022]
More specifically, in the case where the maximum
diffraction peak intensity of Fe103 is defined as Ih,
Formula (2) is preferably satisfled. If the oxide film
of the produced heat resistant ferritic steel satisfies
Formula (2), since Cr203 of an amount sufficient to
enhance the reflectance on the high wavelength side is
contained in the oxide film with respect to the content
of Fe203, excellent photoselective absorptivity can be
attained.
Ih/ (Is + Ic) < 0.05 . . . (2)
[0023]
(8) The oxide film of the heat resistant ferritic
steel is formed by oxidation treatment. In the oxidation
treatment, if the oxygen partial pressure Po2 (atm) in a
gas atmosphere satisfies Formula (3) , Fez03 is restrained
effectively. More specifically, if the oxygen partial
pressure Po2 (atm) satisfies Formula (3), the formed
oxide film satisfies Formula (2) :
Po2 i 2.76 x 1015 x expi-493.6 x ~o~/(RT).). . (3)
where R is a gas constant whose unit is ~.~-'*mol-'a,n d T
is a temperature whose unit is K.
[0024]
The heat resistant ferritic steel in accordance with
this embodiment, completed on the basis of the above
findings, and the method for producing the steel are as
described below.
[0025]
The heat resistant ferritic steel includes a base
material and an oxide film. The base material comprises,
by mass percent, C: 0.01 to 0.35, Si: 0.01 to 2%, Mn:
0.01 to 2%, P: at most 0.10%, S: at most 0.03%, Cr: 7.5
to 14.0%, sol.Al: at most 0.3%, and N: 0.005 to 0.15%,
the balance being Fe and impurities. The oxide film is
formed on the base material and has a chemical
composition, excluding oxygen and carbon in the oxide
film, containing 25 to 97% of Fe and 3 to 75% of Cr. The
oxide film contains spinel-type oxides and Cr203.
[0026]
In this case, the heat resistant ferritic steel has
excellent photoselective absorptivity.
[0027]
Preferably, in the case where the maximum
diffraction peak intensity of Cr203 obtained by X-ray
diffraction is defined as Ic, and the' maximum diffraction
peak intensity of spinel-type oxides obtained by the Xray
diffraction is defined as IS, the following Formula
(1)' is satisfied.
0.010 < Ic/Is < 10 . . . (1)
[0028]
In this case, excellent photoselective absorptivity
can be attained.
[0029]
The above-described base material of the heat
resistant ferritic steel may further comprises one or
more elements selected from first to fourth groups in
lieu of some of Fe.
First group: Cu: at most 5 % , Ni: at most 5%, and Co:
at most 5%
Second group: Ti: at most 1.0%, V: at most 1.0%, Nb:
at most 1.0%, Zr: at most 1.0%, and Hf: at most 1.0%
Third group: Mo: at most 5%, Ta: at most 5%, W: at
most 5%, and Re: at most 5%
Fourth group: Ca: at most 0.1%, Mg: at most 0.1%, B:
at most 0.1%, and rare earth metal (REM): at most 0.1%
[0030]
The method for producing the heat resistant steel in
accordance with this embodiment includes a step of
preparing the base material having the above-described
chemical composition, and a step of forming an oxide film
on the base material by oxidizing the base material at a
temperature of 500 to 1150°C in a gas atmosphere in which
the oxygen partial pressure Po2 (atm) satisfies Formula
(3) :
Po2 -< 2.76 x 1015 x exp{-493.6 x ~o~/(R)T ). . . (3)
where R is a gas constant whose unit is ~.~-'.mol-', and T
is a temperature whose unit is K.
[ 0 0 3 1 ]
The heat resistant ferritic steel produced by this
production method has excellent photoselective
absorptivity.
[0032]
In the following, the details of the heat resistant
ferritic steel in accordance with this embodiment are
explained.
[0033]
[Configuration of heat resistant ferritic steel]
The heat resistant ferritic steel in accordance with
this embodiment includes a base material and an oxide
film formed on the base material.
[0034]
[Configuration of base material]
The base material has the following chemical
composition.
[0035]
C: 0.01 to 0.3%
Carbon (C) is an austenite stabilizing element for
making the base material martensitic. Furthermore, C
enhances the high-temperature strength of steel by
forming carbides. On the other hand, if the C content is
too high, carbides precipitate excessively, and therefore
the workability and weldability of steel are decreased.
Therefore, the C content is set to 0.01 to 0.3%. The
lower limit of C content is preferably higher than 0.01%,
further preferably 0.03%. The upper limit of C content
is preferably lower than 0.3%, further preferably 0.15%.
[0036]
Si: 0.01 to 2%
Silicon (Si) deoxidizes the steel. Furthermore, Si
enhances the steam oxidation resistance of steel. On the
other hand, if the Si content is too high, the toughness
of steel is decreased. Further, since the oxide film
contains Si, if the Si content is too high, the steel
becomes liable to dissipate heat, and the photoselective
absorptivity decreases. Therefore, the Si content is set
t o 0.01 t o 2%. The lower l i m i t of S i content is
p r e f e r a b l y higher than 0.01%, f u r t h e r p r e f e r a b l y 0.05%,
and s t i l l f u r t h e r p r e f e r a b l y 0.1%. The upper l i m i t of S i
content is p r e f e r a b l y lower than 2%, f u r t h e r p r e f e r a b l y
1.0%, and s t i l l f u r t h e r p r e f e r a b l y 0.5%.
[0037]
Mn: 0.01 t o 2%
Manganese (Mn) deoxidizes t h e s t e e l . Furthermore,
Mn forms MnS by combining with S i n t h e base m a t e r i a l ,
and t h e r e f o r e enhances t h e hot w o r k a b i l i t y of steel. On
t h e o t h e r hand, i f t h e Mn content is too high, t h e steel
is e m b r i t t l e d , and a l s o t h e high-temperature s t r e n g t h of
steel is decreased. Therefore, t h e Mn content is set t o
0.01 t o 2%. The lower l i m i t of Mn content is p r e f e r a b l y
higher than 0.01%, f u r t h e r p r e f e r a b l y 0.05%, and s t i l l
f u r t h e r p r e f e r a b l y 0.1%. The upper l i m i t of Mn content
is p r e f e r a b l y lower than 2%, f u r t h e r p r e f e r a b l y 1.0%, and
s t i l l f u r t h e r p r e f e r a b l y 0.8%.
[0038]
P: a t most 0.10%
S: a t most 0.03%
Phosphorus ( P ) and s u l f u r (S) a r e i m p u r i t i e s . P and
S s e g r e g a t e a t c r y s t a l g r a i n boundaries i n the base
m a t e r i a l , and decrease t h e hot workability of s t e e l .
Furthermore, P and S concentrate a t t h e i n t e r f a c e between
t h e oxide film and t h e base m a t e r i a l , and decrease t h e
adhesiveness of oxide f i l m . Therefore, t h e P content and
t h e S content a r e p r e f e r a b l y a s low as p o s s i b l e . The P
content is set to at most 0.10%, and the S content is set
to at most 0.03%. The P content is preferably at most
0.03%, and the S content is preferably at most 0.015%.
[0039]
Cr: 7.5 to 14.0%
Chromium (Cr) enhances the oxidation resistance of
steel. Furthermore, Cr is contained in the oxide film,
and enhances the photoselective absorptivity of steel.
In particular, Cr enhances the reflectance on the high
wavelength side, and contributes to the suppression of
heat radiation of steel. Furthermore, Cr enhances the
adhesiveness of steel relative to the oxide film. On the
other hand, if the Cr content is too high, the amount of
delta ferrite is increased, and therefore the strength
and toughness of steel are decreased. Furthermore, much
Cr203 is contained in the oxide film on the base material
by oxidation treatment, and in particular, the light
absorption on the low wavelength side is decreased.
Therefore, the Cr content is set to 7.5 to 14.0%. The
lower limit of Cr content is preferably higher than 7.5%,
further preferably 7.7%, and still further preferably
8.0%. The upper limit of Cr content is preferably lower
than 14.0%, further preferably 12.0%, and still further
preferably 10.0%.
[0040]
so1.A:: at most 0.3%
Aluminum (Al) deoxidizes the steel. On the other
hand, if the A1 content is too high, the cleanliness of
steel is decreased, and the hot workability of steel is
decreased. Therefore, the sol.Al content is set to at
most 0.3%. The lower limit of sol.Al content is
preferably 0.001%. The upper limit of sol.Al content is
preferably lower than 0.3%, further preferably 0.1%. The
sol.Al means acid soluble Al.
[0041]
N: 0.005 to 0.15%
Nitrogen (N) solid-solution strengthens the steel.
Furthermore, N forms nitrides and/or carbo-nitrides, and
therefore precipitation strengthens the steel. On the
other hand, if the N content is too high, the nitrides
and carbo-nitrides are coarsened, and the toughness of
steel is decreased. Therefore, the N content is set to
0.005 to 0.15%. The lower limit of N content is
preferably higher than 0.005%, further preferably 0.01%.
The upper limit of N content is preferably lower than
0.15%, further preferably 0.10%.
[0042]
The balance of the base material of the heat
resistant ferritic steel in accordance with this
embodiment consists of Fe and impurities. The term
"impurities" so referred to in this description indicates
the elements that are mixed on account of ore or scrap
used as a raw material of steel, environments in the
process of production, and the like. An impurity is, for
example, oxygen ( 0 ) .
[0043]
Furthermore, the base material of the heat resistant
ferritic steel in accordance with this embodiment may
contain one or more elements selected from the following
first to fourth groups in lieu of some of Fe.
First group: Cu: at most 5%, Ni: at most 5%, and Co:
at most 5%
Second group: Ti: at most 1.0%, V: at most 1.0%, Nb:
at most 1.0%, Zr: at most 1.0%, and Hf: at most 1.0%
Third group: Mo: at most 5%, Ta: at most 5%, W: at
most 5%, and Re: at most 5%
Fourth group: Ca: at most 0.1%, Mg: at most 0.1%, B:
at most 0.1%, and rare earth metal (REM): at most 0.1%
[0044]
First group: Cu: at most 5%, Ni: at most 5%, and Co: at
most 5%
All of copper (Cu), nickel (Ni), and cobalt (Co) are
selective elements. These elements are austenite
stabilizing elements, and restrain the formation of delta
ferrite. If at least one of these elements is contained
even a little, the above-described effect can be achieved.
On the other hand, if the contents of these elements are
too high, the creep strength on the long time side is
decreased. Therefore, the Cu content is set to at most
5%, the Ni content is set to at most 5%, and the Co
content is set to at most 5%. The lower limit of the
content of each of these elements is preferably 0.005%.
The upper limit of each of these elements is preferably
lower than 5%, further preferably 3%, and still further
preferably 1%.
[0045]
Second group: Ti: at most 1.0%, V: at most 1.0%, Nb: at
most 1.0%, Zr: at most 1.0%, and Hf: at most 1.0%
All of titanium (Ti), vanadium (V), niobium (Nb),
zirconium (Zr) , and Hafnium (Hf) are selective elements.
These elements form carbides, nitrides, and carbonitrides,
and precipitation strengthen the steel. If at
least one of these elements is contained even a little,
the above-described effect can be achieved. On the other
hand, if the contents of these elements are too high, the
workability of steel is decreased. Therefore, the Ti
content is set to at most 1.0%, the V content is set to
at most 1.0%, the Nb content is set to at most 1.0%, the
Zr content is set to at most 1.0%, and the Hf content is
set to at most 1.0%. The lower limit of the content of
each of these elements is preferably 0.01%. The upper
limit of the content of each of these elements is
preferably lower than 1.0%, further preferably 0.8%, and
still further preferably 0.4%.
[0046]
Third group: Mo: at most 5%, Ta: at most 5%, W: at most
5%, and Re: at most 5%
All of molybdenum (Mo), tantalum (Ta), tungsten (W),
and rhenium (Re) are selective elements. All of these
elements enhance the strength of steel. If at least one
of these elements is contained even a little, the abovedescribed
effect can be achieved. On the other hand, if
the contents of these elements are too high, the
toughness, ductility, and workability of steel are
decreased. Therefore, the Mo content is set to at most
5%, the Ta content is set to at most 5%, the W content is
set to at most 5%, and the Re content is set to at most
5%. The lower limit of the content of each of these
elements is preferably 0.01%, further preferably 0.1%.
The upper limit of the content of each of these elements
is preferably lower than 5%, further preferably 4%, and
still further preferably 3%.
[0047]
Fourth group: Ca: at most 0.1%, Mg: at most 0.1%, B: at
most 0.1%, and rare earth metal (REM): at most 0.1%
All of calcium (Ca), magnesium (Mg), boron (B), and
rare earth metal (REM) are 'selective elements. All of
these elements enhance the strength, workability, and
oxidation resistance of steel. If at least one of these
elements is contained even a little, the above-described
effects can be achieved. On the other hand, if the
contents of these elements are too high, the toughness
and weldability of steel are decreased. Therefore, the
Ca content is set to at most 0.1%, the Mg content is set
to at most 0.1%, the B content is set to at most 0.1%,
and the REM content is set to at most 0.1%. The lower
limit of the content of each of these elements is
preferably 0.0015%. The upper limit of the content of
each of these elements is preferably lower than 0.1%,
further preferably 0.05%. The "REM" is the general term
of seventeen elements in which yttrium (Y) and scandium
(Sc) are added to the elements ranging from lanthanum
(La) of atomic number 57 to lutetium (Lu) of atomic
number 71 in the periodic table.
[0048]
[Oxide film]
The oxide film of the heat resistant ferritic steel
in accordance with this embodiment is formed on the base
material. The heat resistant ferritic steel in
accordance with this embodiment has excellent
photoselective absorptivity because of having the oxide
film explained below.
[0049]
[Chemical composition of oxide film]
The oxide fiim consists of oxides. The chemical
composition of oxide film contains 25 to 97% of Fe and 3
to 75% of Cr. The content of chemical composition of
oxide film described here is a content excluding oxygen
(0) and carbon (C) . Other than Fe and Cr, about 5% or
less of an element of Al, Si, Ti, Mn, Nb or the like
having a high affinity to oxygen may be contained. The
heat resistant ferritic steel can attain excellent
oxidation resistance and photoselective absorptivity
because the oxide film has the above-described chemical
composition, especially because the Cr content meets the
condition of the above-described content range.
[0050]
The chemical composition of oxide film can be
measured by subjecting the base material having the oxide
film to EDX (energy dispersive X-ray spectroscopy) from
the surface thereof. The chemical composition is
determined from the detected elements excluding oxygen
(0) and carbon (C) as described above.
[0051]
The preferable chemical composition contains 50 to
95% of Fe and 5 to 50% of Cr. The further preferable
chemical composition contains 70 to 95% of Fe and 5 to
30% of Cr.
[0052]
[Structure of oxide film]
The oxide film contains a plurality of oxides.
Preferably, the oxide film mainly contains spinel-type
oxides and Cr203. The term "mainly" described here means
that, in the case where the cross section in the
thickness direction of oxide film is microscopically
observed, the area ratio of the spinel-type oxides and
Cr203 is 60% or more of the whole oxide film.
[0053]
The oxide film may contain oxides containing Al, Si,
Ti, Mn, and Nb in addition to spinel-type oxides and
Cr203. If the oxide film contains spinel-type oxides and
Cr203, the heat resistant ferritic steel can have
excellent photoselective absorptivity. More specifically,
by causing the oxide film to contain Cri03, the
reflectance on the high wavelength side is further
enhanced, and the radiation of heat in high-temperature
environments is restrained.
[0054]
The oxides in the oxide film are identified by XRD
(X-ray diffractometry) in which X-rays are applied to the
surface of the base material having the oxide film (heat
resistant ferritic steel). In the XRD, a Co bulb may be
used as an X-ray bulb, or any other bulbs may be used.
[0055]
Preferably, the heat resistant ferritic steel
satisfies Formula (1) :
0.010 I Ic/Is I 10 . . . (1)
where Is means the maximum diffraction peak intensity of
spinel-type oxides in the oxide film, which is obtained
by XRD. The symbol Ic means the maximum diffraction peak
intensity of Cr203 in the oxide film. The maximum
diffraction peak intensity so referred to in this
description corresponds, for spinel-type oxides, to the
intensity on the (311) plane, and corresponds, for Crz03,
to the intensity on the (104) plane. Generally, the
volume ratio of each of oxides is determined from the
integration of peak intensities. However, as described
above, if the oxide film satisfies Formula (1) defined by
the maximum diffraction peak intensity ratio, the heat
resistant ferritic steel exhibits excellent
photoselective absorptivity.
I00561
It is defined that IR1 = Ic/Is. If IR1 is less than
0.010, the ratio of Cr203 in the oxide film is
excessively low. Therefore, the photoselective
absorptivity decreases. In particular, the reflectance
on the high wavelength side decreases. Furthermore, the
oxidation resistance of the heat resistant ferritic steel
decreases.
[ 0 0 5 7 1
On the other hand, if IR1 exceeds 10, the ratio of
Cr203 in the oxide film is excessively high. In this case,
although the oxidation resistance of the heat resistant
ferritic steel increases, the photoselective absorptivity
decreases remarkably.
[0058]
If IR1 satisfies Formula (I), the heat resistant
ferritic steel is liable to absorb light, and is less
liable to dissipate heat. Specifically, the reflectance
on the low wavelength side decreases, and the reflectance
on the high wavelength side increases. The lower limit
of IR1 is preferably higher than 0.010, further
preferably 0.020, and still further preferably 0.050.
The upper limit of IR1 is preferably lower than 10,
further preferably 7, and still further preferably 5.
[0059]
For the oxide film in accordance with this
embodiment, the content of Fez03 is preferably lower. If
the content of Fe203 is high, the reflectance of light
(electromagnetic wave) on the low wavelength side of
oxide film increases, and the reflectance of light on the
high wavelength side decreases. That is to say, the
photoselective absorptivity of oxide film decreases.
Therefore, the content of Fe203 is preferably lower.
[0060]
More specifically, the oxide film of the heat
resistant ferritic steel preferably satisfies Formula
(2) :
Ih/ (Is + Ic) 5 0.05 . . . (2)
where Ih means the maximum diffraction peak intensity of
Fe203 in the oxide film. The maximum diffraction peak
intensity so referred to in this description corresponds,
for Fe203, to the intensity on the (104) plane. Generally,
the volume ratio of each of oxides is determined from the
integration of peak intensities. However, as described
above, if the oxide film satisfies Formula (2) defined by
the maximum diffraction peak intensity ratio, the heat
resistant ferritic steel exhibits quite excellent
photoselective absorptivity.
[0061]
It is defined that IRh = Ih/(Is + Ic). If IRh is
0.05 or less, the ratio of Fe203 in the oxide film is
sufficiently low. Therefore, the heat resistant ferritic
steel is liable to absorb light, and less liable to
dissipate heat. Specifically, the reflectance on the low
wavelength side decreases, and the reflectance on the
high wavelength side increases. The lower limit of ;Rh
is preferably lower than 0.05, further preferably 0.010,
and still further preferably 0.005.
[0062]
The oxide film in accordance with this embodiment
may contain FeO (wustite). Wustite is less liable to
appear on the surface of oxide film because it is formed
on the base material side as compared with magnetite,
which is a spinel-type oxide. That is to say, wustite is
less liable to be formed in the outermost layer of oxide
film. Therefore, wustite does not substantially exert an
influence on the photoselective absorptivity. Therefore,
the oxide film may contain or need not contain wustite.
[0063]
[Production method]
There is explained one example of a method for
producing the heat resistant ferritic steel in accordance
with this embodiment.
[0064]
The method for producing the heat resistant ferritic
steel in accordance with this embodiment includes a step
of preparing the base material (base material preparing
step) and a step of oxidizing the prepared base material
to form the oxide film on the base material (oxidizing
step). In the following, the base material preparing
step and the oxidizing step are described in detail.
[0065]
[Base material preparing step?
A starting material having the above-described
chemical composition is prepared. The starting material
may be a slab, bloom, or billet produced by the
continuous casting process (including the round
continuous casting). Also, the starting material may be
a billet produced by hot-working an ingot produced by the
ingot-making process, or may be a billet produced by hotworking
a slab or bloom.
[0066]
The prepared starting material is charged into a
heating furnace or a soaking pit, and is heated. The
heated starting material is hot-worked to produce the
base material. For example, as the hot working, the
Mannesmann process is carried out. Specifically, the
starting material is piercing-rolled by using a piercing
machine to form a material pipe. Successively, the
starting material is elongation-rolled and sized by using
a mandrel mill and a sizing mill to produce the base
material as a seamless steel pipe. As the hot working,
the hot-extrusion process or the hot forging process may
be carried out to produce the base material. As
necessary, the base material produced by hot working may
be subjected to heat treatment, or may be subjected to
cold working. The cold working is, for example, cold
rolling or cold drawing. By the above-described step,
the base material as a seamless pipe is produced.
[ 0 0 6 7 ]
The base material may be a steel plate. In this
case, the base material used as a steel plate is produced
by hot-working the starting material. Also, the base
material used as a bar steel may be produced by hot
working. Further, the base material used as a welded
steel pipe may be produced by welding a steel plate.
[0068]
[Oxidizing step]
Successively, the oxide film is formed on the
produced base material. The oxide film is produced, for
example, by the method described below.
[0069]
The base material is subjected to oxidation
treatment. The oxidation treatment is performed in a gas
atmosphere of, for example, mixed gas or combustion gas.
The preferable oxidation treatment temperature is 1'1500~
or lower, and the preferable oxidation treat time is 3
hours or shorter.
[0070]
If the oxidation treatment temperature is too high,
the ratio of the spinel-type oxides in the oxide film
increases excessively, and the ratio of Cr203 decreases
excessively. If the oxidation treatment temperature is
too low, the oxide film is formed unevenly on the base
material, and in some cases, the oxide film cannot cover
the base material. For this reason, the photoselective
absorptivity decreases. Therefore, the preferable
oxidation treatment temperature is 500°C to 1150°C.
[0071]
Preferably, by controlling the gas atmosphere of
oxidation treatment, and by changing the structure of
oxide film, an oxide film satisfying Formula (2) can be
obtained. More specifically, it is preferable that the
oxygen partial pressure Po2 (atm) in the gas atmosphere
of oxidation treatment satisfy Formula (3).
Po2 < 2.76 x 1015 x expi-493.6 x 103/(RT)) . . . (3)
[0072]
If Po2 satisfies Formula (3), the oxygen partial
pressure in the gas atmosphere thermodynamically becomes
lower than the oxygen partial pressure necessary for
steady formation of Fe203. Therefore, the formation of
Fe203 is restricted. In the case where composition
fluctuations caused by a gas flow in the gas atmosphere
and composition fluctuations on account of combustion
state are considered, further preferably, the oxygen
partial pressure Po2 satisfies Formula (4).
Po2 5 1.00 x 1014 x expi-493.6 x 103/(RT)) . . . (4)
[0073]
Concerning the gas atmosphere of oxidation treatment,
for example, the air-fuel ratio of combustion gas may be
controlled. Specifically, if the air-fuel ratio is
controlled, the gas composition in the gas atmosphere
changes. Based on the gas composition in the oxidation
treatment gas atmosphere, the oxygen partial pressure is
determined. Based on the gas composition, the oxygen
partial pressure can be calculated by using, for example,
the thermodynamic computation software "MALT-2 for WIN".
[0074]
As a fuel, natural gas, methane, propane, butane, or
the like may be used. Also, a mixed gas such as H2-H20 or
CO-C02 may be used. Further, an oxidation treatment gas
atmosphere in which these gases are mixed may be used.
[0075]
Oxidation treatment that doubles as normalizing
treatment (normalizing) may be performed. In this case,
the cold-rolled base material is normalized. The
preferable oxidation treatment temperature in this case
is 900°C or higher. The oxidation treatment time is
preferably 30 minutes or shorter, further preferably 20
minutes or shorter. If the oxidation treatment
temperature is too high and if the oxidation treatment
time is too long, the oxide film becomes excessively
thick. In this case, the adhesiveness between oxide film
and base material decreases, and the oxide film sometimes
peels off. For this reason, the photosensitive
absorptivity of the heat resistant ferritic steel
decreases.
[0076]
Oxidation treatment that doubles as tempering
treatment (low-temperature annealing) may be performed.
In this case, the normalized base material is subjected
to the oxidation treatment that doubles as tempering
treatment. In this case, the preferable oxidation
treatment temperature is 650 to 850°c,'and the preferable
oxidation treatment time is 2 hours or shorter.
[0077]
The oxidation treatment may be performed after the
normalizing treatment and tempering treatment. In this
case, it is preferable that the base material structure
formed by the normalizing treatment and tempering
treatment be not changed in property. For this reason,
the preferable oxidation treatment temperature is not
higher than the tempering treatment temperature. Since
the oxidation treatment temperature is as low as not
higher than the tempering treatment temperature, the
oxidation rate is low. Therefore, the oxidation
treatment time may be long. However, considering the
productivity, the preferable oxidation treatment time is
3 hours or shorter.
[0078]
The oxide film may be formed on the whole surface of
base material. However, the oxide film may be formed
only on the surface required to be excellent in
photoselective absorptivity, such as the outer peripheral
surface of a pipe, which is the base material.
[0079]
The above-described oxidation treatment may be
performed one time or a plurality of times. After each
step of normalizing treatment, tempering treatment, and
oxidation treatmen:, straightening or the like may be
performed mechanically. In the case where oil or dirt
sticks to the surface of oxide film formed on the base
material, even if the treatment of degreasing or cleaning
is performed, the properties of oxide film are not
changed.
[0080]
In the above-described oxidation treatment, the
composition of oxide film can be changed by controlling
the concentration of combustion gas. By following the
above-described steps, the heat resistant ferritic steel
having the base material and the oxide film of this
embodiment can be produced.
[0081]
In the above-described oxidation treatment step, if
Fe203 (hematite) is formed on the outermost layer of
oxide film as the result that the oxygen partial pressure
Po2 in the gas atmosphere of oxidation treatment does not
satisfy Formula (3), the Fe203 (hematite) may be removed
by shotblasting treatment. Even in this case, the oxide
film containing magnetite, spinel-type oxides, and Cr203
of this embodiment is formed.
Example 1
[0082]
Heat resistant ferritic steels having various
chemical compositions were produced, and the
photoselective absorptivity thereof was examined.
[0083]
[Examination method]
Heat resistant ferritic steels of steel Nos. 1 to 9
having the chemical compositions given in Table 1 were
melted to produce ingots.
[0084]
[Table 11
Referring to Table 1, for steels of steel Nos. 1 to
7, the chemical composition of base material was within
the range of chemical composition of the present
invention. On the other hand, for steels of steel Nos. 8
and 9, the chemical composition of base material was out
of the range of chemical composition of the present
invention. Specifically, the Cr content of steel No. 8
exceeded the upper limit of Cr content of the base
material of the present invention. The Cr content of
steel No. 9 was lower than the lower limit of Cr co'ntent
of the base material of the present invention.
[0086]
Each of the produced ingots was hot-rolled and coldrolled
to produce a base material. In this example, the
base material was a steel plate. The produced base
material was subjected to oxidation treatment under
various conditions to form an oxide film on the surface
of base material. Table 2 gives steel No. used in each
of test Nos. and oxidation treatment conditions.
[0087]
[Table 21
I-'
I-'
I-'
.Ln
'l.,,k~,E
r
?:st
No .
/
1
5
u
3
i i.
!I
I 2
1.1
: 4
15
el
P, u
I-'
(D
Reflectonce
I-'
Str.,'l
Nn.
1
!
2
-!
i
2
4
3
7
4
6
4:
8'
9'
0.5 wn
8
2
4
3
6
4
6
4
6
9
8
8
4
19+
4
I-'
I-'
L.C
($1
10 11rn
60
3 3
65
4 6
b2
58
55
4 8
4 6
65
35
37
14'
2 0"
lo*
* -c>icat->L cviatlon :rrm ringe a a ~ c l f i r di n present invention.
Oxidarisn M a x i m d i f f r a c t i o n peak
r reat~rent
Tn:~p~.saturre
t.ine
105OCCx10 n1i.1
10SO°C~10 mi:.
1050"Cx10 a ~ i n
75C*Cx60mia
600°Cx60 min
1050°Cx30 *nln
l1)5O"Cx10 rnlrl
?kOoCx4> n~in
.i20°C*5 rllln
73O0Cx50 min
107O"CxlO m:n
10bO°Cx10 m-n
116uDCx15 min
!9CO"cxlO nrln
lOt.u"ix10 min
Oxide
Chi-l~cal
,.~moositoin ( ?. 1
Fe:50, Cr:46
'i'c:9b, Cr:3
Fe:72, Cr:15
Fe:88,Cr:8
Fc:7Er Cr:22
F?:80, Cr:16
Fe:S.!, Cr: 17
Fe:72, Cr:T5
Fe:10, Cr:iO
Fa:27, Cr:70
Fa:96, Cr:4
Fe:96, Cr:3
F?:J8, Cr:l*
&:lo, Cr:8bb
Fs:99, ir:
Documents
Application Documents
#
Name
Date
1
Notrially attested GPA and Merger Certificate.pdf
2014-06-16
2
Form 5.pdf
2014-06-16
3
Form 3.pdf
2014-06-16
4
English language translations of priority documents.pdf
2014-06-16
5
Cover letter, Form 1, Form 2 with complete specification and Abstract.pdf