U.S. patent number 3,925,579 [Application Number 05/473,142] was granted by the patent office on 1975-12-09 for method of coating low alloy steels.
This patent grant is currently assigned to Armco Steel Corporation. Invention is credited to Jerry L. Arnold, F. Curtiss Dunbar, Charles Flinchum.
United States Patent |
3,925,579 |
Flinchum , et al. |
December 9, 1975 |
Method of coating low alloy steels
Abstract
A method of fluxless hot dip metallic coating of low alloy steel
strip and sheet containing aluminum, titanium, silicon, chromium,
and/or mixtures thereof. A surface readily wettable by molten
coating metal is obtained by heating the steel to a temperature of
about 1100.degree. to 1675.degree. F in an atmosphere oxidizing to
iron, then further treating under conditions which will reduce the
iron oxide, whereby to form a surface layer comprising a
substantially pure iron matrix containing a uniformly distributed
fine dispersion of oxides of the alloying elements.
Inventors: |
Flinchum; Charles (Trenton,
OH), Dunbar; F. Curtiss (Monroe, OH), Arnold; Jerry
L. (Franklin, OH) |
Assignee: |
Armco Steel Corporation
(Middletown, OH)
|
Family
ID: |
23878370 |
Appl.
No.: |
05/473,142 |
Filed: |
May 24, 1974 |
Current U.S.
Class: |
427/320; 148/276;
427/319; 427/321; 427/431; 427/433; 427/444 |
Current CPC
Class: |
C23C
2/38 (20130101); C21D 1/74 (20130101); C23C
2/02 (20130101) |
Current International
Class: |
C23C
2/36 (20060101); C23C 2/02 (20060101); C23C
2/38 (20060101); C21D 1/74 (20060101); C23C
001/00 () |
Field of
Search: |
;117/51,114R,114C,114A
;148/6,12D ;29/196.2 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Kendall; Ralph S.
Assistant Examiner: Smith; John D.
Attorney, Agent or Firm: Melville, Strasser, Foster &
Hoffman
Claims
The embodiments of the invention in which an exclusive property or
privilege is claimed are defined as follows:
1. A method of enhancing the wettability by a molten coating metal
of the surface of a low alloy steel strip and sheet stock
containing alloying elements more readily oxidizable than iron,
chosen from the group consisting of aluminum, titanium, silicon,
chromium, and mixtures thereof, said alloying elements being
present in amounts greater than the critical contents thereof as
calculated from the following equation wherein aluminum and
aluminum oxide are used as illustrative of the alloying element:
##EQU4## where
comprising the steps of passing said stock continuously through a
furnace in which said stock is heated to a temperature of about
1100.degree. to 1675.degree.F in an atmosphere oxidizing to iron
whereby to form on said stock a surface layer of iron oxide
containing oxides of said alloying elements, dispersed or in solid
solution therein, and subjecting said stock to further heat
treatment in a hydrogen-containing atmosphere having a dewpoint
which makes said atmosphere reducing to iron oxide within the
temperature range of 800.degree. to 1700.degree.F whereby to reduce
said surface layer to a substantially pure iron matrix containing a
uniform fine dispersion of said oxides of said alloying
elements.
2. The method claimed in claim 1, wherein said furnace is heated by
direct combustion of fuel and air therein to produce an atmosphere
of gaseous products of combustion containing 0 to 6% excess oxygen
and no excess combustibles, and wherein said stock is withdrawn
from said furnace while still surrounded by said atmosphere at a
temperature of about 1400.degree. to about 1675.degree.F.
3. The method claimed in claim 2, wherein said coating metal is
aluminum, zinc, or alloys thereof, and wherein said steel, after
withdrawal from said furnace, is brought to a temperature of about
1500.degree.F to about 1700.degree.F in a hydrogen-nitrogen
atmosphere comprising at least about 20% hydrogen.
4. The method claimed in claim 3, wherein said coating metal is
aluminum or alloys thereof, wherein said steel is cooled
approximately to the temperature of the molten coating metal bath
and introduced into said bath while still surrounded by said
hydrogen-nitrogen atmosphere, said atmosphere having a maximum
dewpoint of about 50.degree.F.
5. The method claimed in claim 3, wherein said coating metal is
zinc or alloys thereof, wherein said steel is cooled approximately
to the temperature of the molten coating metal bath while still
surrounded by said hydrogen-nitrogen atmosphere, said atmosphere
having a maximum dewpoint of about 15.degree.F.
6. The method claimed in claim 1, wherein said furnace is heated
without atmosphere control, and wherein said stock is withdrawn
from said furnace into air at a temperature of about 1100.degree.
to about 1400.degree.F.
7. The method claimed in claim 6, wherein said coating metal is
aluminum, zinc, or alloys thereof, and wherein said steel, after
contacting air, is brought to a temperature of about 1500.degree.
to about 1700.degree. F in a hydrogen-nitrogen atmosphere
comprising at least about 20% hydrogen.
8. The method claimed in claim 7, wherein said coating metal is
aluminum or alloys thereof, wherein said steel is cooled
approximately to the temperature of the molten coating metal bath
and introduced into said bath while still surrounded by said
hydrogen-nitrogen atmosphere, said atmosphere having a maximum
dewpoint of about 50.degree.F.
9. The method claimed in claim 7, wherein said coating metal is
zinc or alloys thereof, wherein said steel is cooled approximately
to the temperature of the molten coating metal bath while still
surrounded by said hydrogen-nitrogen atmosphere, said atmosphere
having a maximum dewpoint of about 15.degree.F.
10. The method of claim 1, wherein said low alloy steel contains up
to about 3% aluminum, up to about 1% titanium, up to about 2%
silicon, and up to about 5% chromium.
11. The method of claim 10, wherein said furnace is heated by
direct combustion of fuel and air therein to produce an atmosphere
of gaseous products of combustion containing 0% to 6% excess oxygen
and no excess combustibles, and wherein said stock is withdrawn
from said furnace while still surrounded by said atmosphere at a
temperature of about 1400.degree. to about 1675.degree.F.
12. The method claimed in claim 10, wherein said furnace is heated
without atmosphere control, and wherein said stock is withdrawn
from said furnace into air at a temperature of about 1100.degree.
to about 1400.degree.F.
13. The method claimed in claim 10, wherein said coating metal is
aluminum, zinc, or alloy thereof.
14. In the method of fluxless hot dip metallic coating of low alloy
steel strip and sheet stock containing at least one alloying
element in uncombined form chosen from the group consisting of up
to about 3% aluminum, up to about 1% titanium, up to about 2%
silicon, up to about 5% chromium, and mixtures thereof, said
alloying element being present in an amount greater than the
critical content thereof as calculated from the following equation
wherein aluminum and aluminum oxide are used as illustrative of the
alloying element: ##EQU5## where
wherein the surface of said stock is prepared for coating by a
continuous preliminary treatment involving heating under conditions
producing an oxide coating on said surface, followed by further
heat treatment under conditions reducing to iron oxide, and wherein
the stock is thereafter passed into a molten metal coating bath
while surrounded by a protective atmosphere, the improvement which
comprises heating said stock in the first said heating step to a
temperature of about 1100.degree. to about 1675.degree. F in an
atmosphere oxidizing to iron whereby to produce a surface layer of
iron oxide containing a uniform dispersion or solid solution of
oxides of said alloying elements.
15. The method of claim 14, wherein said first heating step is
conducted in a furnace heated by direct combustion of fuel and air
therein and in an atmosphere of gaseous products of combustion
containing 0 to 6% oxygen and no excess combustibles, and wherein
said stock is withdrawn from said furnace while still surrounded by
said atmosphere at a temperature of about 1400.degree. to about
1675.degree. F.
16. The method claimed in claim 14, wherein said first heating step
is conducted in a furnace without atmosphere control, and wherein
said stock is withdrawn from said furnace into air at a temperature
of about 1100.degree. to about 1400.degree. F.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to improvements in the process of hot dip
metallic coating of low alloy steel strip and sheet material
whereby to enhance the wettability of the surfaces thereof by
molten coating metals such as zinc, zinc alloys, aluminum, aluminum
alloys and terne, and to insure good adherence of the coating. Low
alloy steels which may be treated by the process of the present
invention include those containing up to about 3% aluminum, up to
about 1% titanium, up to about 2% silicon, or up to about 5%
chromium, and mixtures thereof, with the remainder of the
composition typical of a carbon steel, as defined by Steel Products
Manual, Carbon Sheet Steel -- page 7 (May 1970) -- published by
American Iron and Steel Institute.
2. Description of the Prior Art
In the hot dip metallic coating of steel strip and sheet material
without a flux, it is necessary to subject the sheet and strip to a
preliminary treatment which provides a clean surface free of iron
oxide scale which is readily wettable by the molten coating metal
and to which the coating metal will adhere after solidification
thereof. Two types of anneal-in-line preliminary treatments are
commonly used in this country, one being the so-called Sendzimir
process and the other so-called Selas process. Detailed
descriptions of these two types of processes may be found in U.S.
Pat. No. 2,110,893, issued Mar. 15, 1938 to T. Sendzimir, and U.S.
Pat. No. 3,320,085, issued May 16, 1967 to C. A. Turner, Jr.,
respectively.
Briefly, the conventional Sendzimir process for preparation of
carbon steel strip and sheet material for hot dip metallic coating
involves passing the material through an oxidizing furnace heated,
without atmosphere control, to a temperature of about
1600.degree.F, by combustion, electric resistance, electric
induction, or other conventional means, the residence time being
sufficient to cause the material to reach a temperature of about
700.degree. to 900.degree. F, withdrawing the material from the
furnace into air, forming a controlled surface oxide layer varying
in appearance from light yellow to blue, introducing the material
into a reducing furnace containing a hydrogen and nitrogen
atmosphere, the residence time being sufficient to bring the
material to a temperature of about 1350.degree. to 1700.degree. F.
The controlled oxide layer is completely reduced, and the material
is then cooled to approximately the temperature of the molten metal
coating bath and led beneath the surface of the bath while
surrounded by the hydrogen-nitrogen protective atmosphere.
In the conventional Selas method of treating carbon steel strip and
sheet material, the steps comprise passing the material through a
furnace heated to a temperature of at least about 2200.degree.F by
direct combustion of fuel and air therein, the furnace containing
an atmosphere of gaseous products of combustion having no free
oxygen and at least about 3% excess combustibles, the residence
time of the material being sufficient to cause it to reach a
temperature of about 800.degree. to 1300.degree. F, while
maintaining bright steel surfaces completely free from oxidation,
withdrawing the material from the furnace while still surrounded by
gaseous products of combustion, introducing the material directly
into a reducing section having a hydrogen and nitrogen atmosphere,
in which the material may be further heated from 800.degree. to
1700.degree. F and/or cooled to approximately molten coating metal
bath temperature, and then leading the material beneath the surface
of the bath while surrounded by the hydrogen-nitrogen protective
atmosphere.
It has been found that the above-conventional processes, while
satisfactory for treatment of carbon steel strip and sheet
material, may not satisfactorily prepare the surfaces of low alloy
strip and sheet material for hot dip metallic coating. More
specifically, it has been found that low alloy steels containing
aluminum, titanium, silicon, chromium and/or mixtures thereof in
appreciable amounts are not wettable by molten coating metals such
as aluminum and zinc when treated under the above-described
conditions. The final product is thus completely unacceptable since
large areas have no caoting whatever or a coating which does not
adhere to the base metal.
Moreover, in carbon steel containing relatively small amounts of
alloying elements, e.g., about 0.05% acid-soluble aluminum, it has
been found that poor adherence of the solidified coating matal to
the base metal occasionally occurs even though the material appears
to have been wetted by the molten coating metal. In other words,
although the metallic coating is continuous, adherence is poor in
some areas thereof, thus resulting in high rejection rates.
It is thus apparent that a definite need exists for a reliable
process of fluxless hot dip metallic coating of low alloy steels
which avoids the problems described above.
SUMMARY
It is a principal object of the present invention to provide a
method for the hot dip metallic coating of low alloy strip and
sheet material which enhances the wettability of the surface of the
material by molten coating metal and which insures good adherence
of the coating metal to the base material after solidification
thereof.
In low alloy steels of the type defined above, the alloying element
aluminum (in uncombined form) is most easily oxidized, followed in
order by titanium, silicon, chromium, and iron. Conversely, iron
oxide is the most easily reduced of these elements followed in
order by the oxides of chromium, silicon, titanium and aluminum.
While not wishing to be bound by theory, it is applicants' belief
that conditions can exist in the conventional processing which
would first result in the formation of an external skin of aluminum
oxide, a refractory compound, which is not wettable either by
molten zinc or by molten aluminum. If other elements such as
titanium, silicon and chromium are present instead of aluminum,
these may also diffuse or migrate to the surface and be oxidized to
form a stable oxide layer which may not be wetted by the molten
coating metal. Since aluminum oxide is extremely difficult to
reduce, any subsequent treatment under conventional carbon steel
reducing conditions is ineffective in producing a reduced surface
layer which is wettable by the molten coating metal.
The present invention constitutes a discovery that subjecting the
surface of a low alloy steel containing alloying elements more
readily oxidizable than iron to strongly oxidizing conditions in
the pretreatment processing results in formation of a surface layer
of iron oxide containing a dispersion of oxides of the alloying
elements either in the form of relatively small, uniformly
dispersed precipitates, or in solid solution. This is followed by
subjecting the steel to a conventional reducing treatment in a
hydrogen-containing atmosphere which reduces the surface layer to a
substantially pure iron matrix containing a uniformly distributed
fine dispersion of oxides of the alloying elements.
As used herein, the term "internal oxidation " will be understood
to designate the formation of a dispersion of oxides of alloying
elements in an iron matrix adjacent the surface, when processed
conventionally. The term "external oxidation " will be used to
designate the formation of an external skin or layer of stable
oxides of alloying elements more readily oxidizable than iron, when
subjected to conventional processing. However, these terms will not
be applied to the process of the present invention.
In current commercial in-line-anneal hot dip metallic coating
lines, the required high degree of oxidizing potential may be
achieved as follows:
When practicing the Sendzimir process, the temperature of the strip
and sheet material upon exiting the oxidizing furnace is increased
to a range of about 1100.degree. to about 1400.degree. F (rather
than the conventional 700.degree. to 900.degree. F). In the Selas
process, the temperature of the strip and sheet material exiting
the direct fired preheat furnace is increased to about 1400.degree.
to 1675.degree. F (rather than the conventional 800.degree. to
1300.degree. F). Moreover, the atmosphere in the direct fired
preheat furnace is modified so as to contain 0 to 6% excess oxygen
and no excess combustibles.
The present application discloses that an external skin of
unreducible oxide will form in the reducing sections of both the
conventional Selas-type and Sendzimir processes if a critical level
of alloying elements is exceeded. As hereinafter explained in
detail, Auger analysis showed that this external oxidation also
takes place in the pretreatment furnace of the conventional Selas
process. In the conventional Sendzimir pretreatment processing the
maximum temperature reached (900.degree.F) is believed to be too
low for significant diffusion of the oxidizing element to occur.
Many of the alloy steels mentioned in this invention are very
resistant to oxidation, and, in fact, when a steel containing
approximately 2% Al, 1, 2% Cr, 1% Si, 0.5% Ti is subjected to the
conventional Sendzimir pretreatment practice, the maximum
recommended temperature of 900.degree.F is insufficient to produce
a visible oxide film.
The process of the present invention is unsuitable for a carbon
steel which does not contain substantial amounts of the more easily
oxidized alloying elements because the iron surface would be scaled
to such an extent that a conventional reducing treatment would not
convert all of the thickness of the scale surface, and poor coating
adherence would result. It would likewise follow that a treatment
for alloy levels considerably lower than the above-mentioned 2% Al,
1, 2% Cr, 1% Si, 0.5% Ti steel, but yet beyond the carbon steel
level, would require preoxidation treatment conditions between the
maximum tolerable for carbon steel and that required for the above
cited example of a low alloy steel.
The above theory also explains the previously-discussed problem of
poor adherence of coating metal to a carbon steel base metal
containing relatively small amounts of acid-soluble aluminum, e.g.,
as little as 0.03% in some instances. Here again the diffusion of
aluminum to the surface accompanied by oxidation thereof, while not
forming an aluminum oxide layer of sufficient thickness or
continuity to prevent complete wetting of the surface by the molten
coating metal, nevertheless sometimes prevents good adherence of
the coating metal after solidification by reason of the refractory
nature of the aluminum oxide areas on the surface.
In its broadest aspect, thee method of the invention can be relied
upon to enhance to wettability by a molten coating metal of, and to
insure adherence of the coating metal (after solidification
thereof) to, the surface of a low alloy steel containing one or
more alloying elements more readily oxidizable than iron. This is
effected by first heating the steel to a temperature of about
1100.degree. to about 1675.degree. F in an atmosphere oxidizing to
iron, and subjecting the steel to further treatment under
conditions which reduce the iron oxide, whereby to reduce the
surface layer to a substantially pure iron matrix containing a
uniform dispersion of oxides of the alloying elements.
BRIEF DESCRIPTION OF THE DRAWINGS
Reference is made to the accompanying drawing wherein:
FIGS. 1A, 1B and 1C are diagrammatic representations of surface
conditions at indicated processing stages of an iron alloy
containing an element Me, which forms an oxide more stable than
iron oxide, in an amount less than the critical content under
conventional Selas-type pretreatment conditions;
FIG. 1D is a graphic representation of the surface condition of the
alloy of FIG. 1C;
FIGS. 2A, 2B and 2C are diagrammatic representations of surface
conditions at indicated processing stages of an iron alloy
containing an element Me, which forms an oxide more stable than
iron oxide, in an amount greater than the critical content under
conventional Selas-type pretreatment conditions;
FIG. 2D is a graphic representation of the surface condition of the
alloy of FIG. 2C;
FIGS. 3A, 3B and 3C are diagrammatic representations of surface
conditions at indicated stages of the process of the present
invention of an iron alloy containing an element Me, which forms an
oxide more stable than iron oxide, in an amount greater than the
critical content as calculated for conventional Selas-type
pretreatment;
FIG. 3D is a graphic representation of the surface condition of the
alloy of FIG. 3C; and
FIG. 4 is a graphic representation of the relation between the
critical aluminum content of a low alloy steel and the hydrogen
content and dew point of the treatment atmosphere.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
As stated above, according to applicants' theory, in conventional
pretreatment of a low alloy steel containing an element which forms
an oxide more stable than iron oxide, a surface layer of this more
stable oxide is formed which is not reduced in the reducing section
nor in the molten coating bath. Hence, very little wetting of the
surface of the low alloy steel occurs. In the following discussion,
it should be kept in mind that it is necessary to qualify the term
oxidizing to indicate whether it means oxidizing to iron. On the
other hand, when the term reducing is used, this will mean that it
is reducing to iron unless otherwise specified.
As indicated above, the manner in which aluminum oxide is formed in
a low alloy steel is of great significance. With low aluminum
concentrations, e.g., less than about 0.05% acid-soluble aluminum,
and a relatively high oxidizing potential (such as that obtained by
heating to about 1800.degree.F in a 20% hydrogen atmosphere having
a dew point of about 120.degree.F) internal oxidation of the
aluminum has been observed. Under these circumstances a precipitate
of aluminum oxide is dispersed uniformly in a relatively pure iron
matrix, and the surface of the alloy remains predominantly pure
iron. However, as the concentration of aluminum is increased, or as
the oxidizing potential is decreased, the rate of penetration of
the internal oxide is decreased. At some combination of aluminum
content and relatively low surface oxidizing potential, a
transition from internal to external oxidation will occur. This
external oxidation results in the formation of the previously
mentioned aluminum oxide layer or skin which acts as a barrier to
prevent wetting by a molten coating metal. Calculations will be set
forth hereinafter showing the relation between aluminum contents
and oxidizing potential which causes the formation of such an
aluminum oxide layer, but which can be avoided successfully in
accordance with the present invention.
As explained above, the essential feature of the present invention
is to conduct the "oxidizing" treatment under conditions which are
highly oxidizing to iron. This results in the formation of a
surface layer or scale on the low alloy steel strip and sheet which
is primarily iron oxide (Fe.sub.3 O.sub.4) in which oxides of
alloying elements such as aluminum, titanium, silicon and chromium
are present either as finely dispersed precipitates or in a solid
solution with iron oxide. In either event these stable oxides of
the alloying elements are present as a minor volume fraction of the
surface layer and are uniformly dispersed throughout the layer. In
other words, diffusion or migration of the alloying elements to the
surface is avoided. When material having a surface layer in this
form is passed through the reducing furnace, the iron oxide portion
is readily reduced. The more stable oxides of the alloying elements
are not reduced and remain uniformly dispersed in a substantially
pure iron matrix. In this condition the low alloy steel surface is
readily wettable by a molten coating metal such as zinc or
aluminum.
It is unlikely that a layer of aluminum oxide could subsequently
form on the outer surface of the steel in the reducing section
since this could occur only if aluminum diffuses from the unreacted
matrix out through the freshly formed substantially pure iron layer
to the surface. Reaction kinetics would dictate against such an
occurrence.
After reduction of the iron oxide the hot dip coating process is
conducted in conventional manner with the strip and sheet material
being led beneath the surface while surrounded by a protective
atmosphere. Coating and finishing are effected by any conventional
method.
A sample from a heat of a low alloy steel having a nominal
composition of about 0.05% carbon, 2% chromium, 2% aluminum, 1%
silicon, 0.5% titanium, about 0.3% manganese and remainder
substantially iron, was subjected to a conventional Selas process
of heating to about 1200.degree.F with an atmosphere containing 3%
excess combustibles, followed by treatment in a reducing section at
about 1600.degree.F for three minutes in an atmosphere of 25%
hydrogen and 75% nitrogen, having a dew point of -60.degree.F.
Another sample of the same heat was treated in accordance with the
method of the present invention by heating to a temperature of
1500.degree.F in a direct fired furnace having no combustibles and
2% excess O.sub.2, followed by the same treatment in the reducing
furnace as that set forth above.
These samples were subjected to surface analysis by an Auger
Spectrometer made by Physical Electronics, Inc. An Auger spectrum
was obtained for each sample surface. Each sample was then sputter
etched with an argon ion gun, and simultaneously the amounts of
certain elements present were monitored using the multi-plexing
feature of the system. This gave an elemental concentration profile
as a function of depth from the surface of each sample. After a
certain period of sputter etching a second Auger spectrum was run
for comparison with the initial surface spectrum.
The most marked difference between the two Auger spectra of the
initial surfaces of each sample was that the surface of the
conventionally treated sample showed about 10 times more aluminum,
less iron and slightly more oxygen present than did the surface of
the sample treated in accordance with the present invention. After
sputter etching for 15 minutes at a nominal 80 A/min rate, the
conventionally treated sample showed significantly less aluminum
and oxygen and more iron than the initial surface of that sample.
After sputter etching the sample treated in accordance with the
method of the invention for 12 minutes at a nominal 25 A/min rate,
this sample showed little change in the aluminum content as
compared to its initial surface, although iron increased and oxygen
decreased substantially.
Reference is made to FIG. 2C, which represents diagrammatically,
and to FIG. 2D, which represents graphically, the surface condition
of the above sample subjected to conventional Selas-type treatment,
derived from the data of the Auger spectra. It will be noted that a
layer of oxides of the alloying elements is formed on the surface
of the sample (i.e., external oxidation), whereas the alloy content
drops sharply to a lower value of short distance inwardly from the
surface (FIG. 2D). This shows the diffusion or migration of
alloying elements to the surface. Thereafter, as distance from the
surface increases, the content of the alloying elements gradually
increases, thus showing some tendency for alloying elements in the
internal lattice of the steel to diffuse to the surface. This is to
be contrasted with FIGS. 1C and 1D showing the behavior of a sample
containing less than a critical content and thus exhibiting
internal oxidiation.
Reference is made to FIG. 3B representing diagrammatically the
surface condition of the above sample after heating in an
atmosphere oxdizing to iron in accordance with the process of the
invention. A surface layer is formed comprising iron oxide and
oxides of the alloying elements uniformly dispersed, or in solid
solution, in the iron oxide layer. FIG. 3C represents
diagrammatically, and FIG. 3D represents graphically, the surface
condition after the reducing treatment, derived from the data of
the Auger spectra. FIG. 3D shows that the concentration of alloying
elements at the surface is substantially less than in the
corresponding stage of the conventional treatment shown in FIG.
2D.
The mathematics for internal oxidation have been established in the
following articles:
C. wagner, "Zeit. Elekrochem.", 63, pp 772-790 (1959)
R. a. rapp, "Corrosion", 21, pp 382-401 (1965)
J. h. swisher, "Oxidation of Metals and Alloys", pp 235-267, ASM
(1971)
In order to permit simplification in the mathematics, a special
case will be assumed in which aluminum is the alloying element and
in which: ##EQU1## where N.sub.0.sup. (s) = oxygen mole fraction
established at the surface
N.sub.al = original mole fraction soluble Al
D.sub.al = diffusivity of Al
D.sub.0 = diffusivity of O
The rate of internal oxidation is given by
where
It has been determinled experimentally in the above-mentioned
article by Rapp that when the volume fraction of aluminum oxide is
less than 0.3 internal oxidation results, but when the volume
fraction of aluminum oxide is greater than this value, external
oxidation occurs with formation of an aluminum oxide layer on the
surface. The final working equation which determines the critical
content of aluminum tolerable without the occurrence of external
oxidation is as follows: ##EQU3## where
Assuming a temperature of 1600.degree.F and an atmosphere of 25%
hydrogen and 75% nitrogen with a dew point of -60.degree.F the
oxygen partial pressure is calculated to be 1.08 .times. 10.sup.-24
atmosphere. Using results published in an article by J.H. Swisher
and E.G. Turkdogon in Trans. Met. Soc. AIME, 239, pp. 426-431
(1967) on the solubility of oxygen in body-centered-cubic iron, a
value of equilibrium oxygen solubility (N.sub.O.sup.(s)) of 2.73
.times. 10.sup.-9 is obtained, Using puslished data* for D.sub.O,
D.sub.Al, V.sub.Fe, and V.sub.Al .sbsb.2 O.sbsb.3, a value of 0.05%
aluminum is calculated which represents the critical level for the
above operating conditions. More than 0.05% aluminum would result
in an external aluminum oxide layer or scale, while less than 0.05%
aluminum would produce an internal oxide of aluminum oxide
precipitated uniformly in an iron matrix.
As will be apparent from the above equation, an increase in the dew
point of the gas (which would increase N.sub.O.sup.(s)) would
result in an increase in the critical aluminum content which could
be tolerated and still avoid formation of an external aluminum
oxide scale. In other words, a higher oxidizing potential raises
the critical aluminum content.
Reference is made to FIG. 4 which is a graphic representation of
the relation of hydrogen content and dew point to the critical
aluminum content in body-centered-cubic iron at a temperature of
1600.degree.F. An aluminum content in the area beneath each curve
results in internal oxidation, while an aluminum content above each
curve results in external oxidation with consequent formation of a
difficulty reducible oxide layer or scale. The curves of FIG. 4 are
plotted from equation (1) above. It is apparent that relatively
slight increases in the hydrogen content sharply reduce the
critical aluminum content at the lower hydrogen levels.
It is desired to emphasize at this point that the above equation
and the graph of FIG. 4 are not a definition of or limitation on
the present invention. Rather, these make it possible to predict in
a quantitative manner when and why external oxidation may occur in
conventional fluxless hot dip metallic coating operations. The
present invention makes it possible to avoid external oxidation
when the critical aluminum content exceeds that which could be
tolerated under conventional or normal conditions. In other words,
the equation and graph of FIG. 4 can be used to ascertain whether a
steel of any given composition may be processed in conventional
manner or whether it must be processed in accordance with the
present invention in order to obtain good wettability by the molten
coating metal and good adherence of the coating.
The above equation, while not exact, can also be utilized (with
appropriate substitutions) to calculate the concentrations of other
elements such as titanium, silicon and chromium, which form oxides
more stable than iron oxide. If more than one of such elements is
present, the critical content of the element which forms the most
stable oxide (aluminum) should first be calculated, followed in
order by calculations of the critical contents of titanium, silicon
and chromium. If none is present in an amount near the critical
content, external oxidation should not occur under conventional
processing conditions unless two or more elements exhibit a
synergistic or cumulative effect, with the fractions of critical
contents adding up to a total greater than the critical content of
any one element.
A coil of strip of the above 2% Cr - 2% Al - 1% Si-0.5% Ti steel
treated in accordance with the method of the invention was coated
in a Selas-type commercial aluminum coating line. The strip surface
was readily wetted by the molten aluminum, and the solidified
coating exhibited excellent adherence to the base metal strip.
For comparison, another coil of the same low alloy steel was
subjected to conventional pretreatment followed by coating in the
same commercial aluminum coating line. This strip was not wettable
by the molten aluminum, and the final product was thus
unacceptable. The treatment conditions for these coils are
summarized in Table I.
TABLE 1
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Low Alloy Strip .050 in thickness .times. 48 in Width - nominal 2%
Cr, 2% Al, 1% Si, 0.5% Ti, 0.5% C, 0.3% Mn, balance Fe
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Pretreatment Present Invention Conventional Conditions 1st Trial
2nd Trial Practice
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(1) Combustion Ratios 2.6% excess O.sub.2 2.8% excess O.sub.2 4%
excess gas preheat section (combustible) (2) Strip Temp. after
1550.degree.F 1500.degree.F 1200.degree.F preheater (3) Radiant
Tube Zones 1800.degree.F 1800.degree.F 1750.degree.F (4) Line Speed
150 fpm 145 fpm 193 fpm (5) Strip Temp. after 1750.degree.F
1750.degree.F 1500.degree.F Radiant Tube (6) Hydrogen in Re- 5000
cfh 5000 cfh 3500 cfh ducing Section (7) Dew Point at bottom
+15.degree.F -20.degree.F -20.degree.F of Slow Cool Zone
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A series of nine laboratory heats was prepared with pure iron as a
base and to each of which a different amount of aluminum or silicon
was added. These samples were then rolled to strip thickness and
coated with molten aluminum in a Selas-type continuous coating
line. Furnace conditions were in accordance with conventional
practice in that the direct fired preheat furnace atmosphere
contained 6% combustibles and the temperature to which the strips
were heated in the preheat furnace was 1275.degree.F. Critical
contents of aluminum and silicon were calculated from equation (1)
above for the furnace conditions.
Metallographic examination of the coated samples showed that in all
instances where the aluminum or silicon content was less than the
theoretical critical amount, as determined from equation (1), the
materials were completely wetted by the molten aluminum of the
coating bath. In all cases where the aluminum or silicon content
was equal to or greater than the theoretical critical content,
metallurgical examination showed a lack of wetting as evidenced by
areas which did not contain an iron-aluminum intermetallic alloy
layer.
Additional samples from all nine heats were then coated on the same
Selas-type coating line under furnace conditions contemplated in
the process of the present invention. The preheater was adjusted to
provide 3% excess O.sub.2 and no combustibles in the furnace
atmosphere and samples were heated to slightly above 1500.degree.F,
thereby creating conditions strongly oxidizing to iron. These
furnace conditions resulted in complete wetting by molten aluminum
of all heats, even those which exhibited uncoated areas under
conventional processing conditions. The results of these tests are
summarized in Table II.
It is apparent from these tests that merely heating a steel to a
temperature above that used in conventional processing is not
effective if the atmosphere is not oxidizing to iron at the
temperature involved. It is further evident from the Auger spectra
reported above that the process is equally effective for
aluminum-and/or-silicon-killed steels and for steels containing
greater amounts of alloying elements, e.g., up to about 3%
aluminum, up to about 5% chromium, up to about 2% silicon, up to
about 1% titanium, and mixtures thereof. Moreover, although the
process of the invention has particular utility in aluminizing
steels containing the specific alloying elements recited above, it
is not so limited and is effective for fluxless hot-dip coating by
any commonly-used coating metal of a ferrous metal strip or sheet
containing an alloying element or elements more readily oxidizable
than iron.
Coating metals which may be used include, but are not limited to,
those described in U.S. Pat. No. 2,784,122 issued Mar. 5, 1957 to
N. Cox et al, at column 2, lines 9-33; and in U.S. Pat. 2,839,455,
issued June 17, 1958 to H. La Tour et al, at column 1, lines 68-72
and column 2, lines 1-7. The disclosures of these patents are
incorporated herein by reference.
TABLE II
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Aluminum-Coated Low Alloy Steels Metallographic Examination For
Coating-Base Metal Diffusion
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Layer CONDITION I Samples % Al (0.15% Al Critical)* CONDITION
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II A-1 0.008 Good coating** Good coating A-2 0.036 Good coating
Good coating A-3 0.22 Uncoated areas*** Good coating % Si (0.41% Si
Critical)*
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B-1 1.28 Uncoated areas Good coating B-2 0.18 Good coating Good
coating B-3 0.027 Good coating Good coating % Si (0.41% Si
Critical)*
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C-1 0.70 Uncoated areas Good coating C-2 0.12 Good coating Good
coating C-3 0.003 Good coating Good coating
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TREATMENT CONDITIONS Preheater Reducing Furnace Critical Contents*
STRIP TEMP. MAXIMUM AFTER PREHEATER % COMBUSTIBLES % EXCESS O.sub.2
% H.sub.2 D.P. STRIP TEMP. % Al %
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Si Cond. I 1275F 6 0 100 +15F 1500F 0.15 0.41 Cond. II 1500F 0 3 33
+15F 1700F -- --
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*Critical contents of Al and Si were calculated from equation (1)
above **Continuous normal diffusion layer ***Absence of diffusion
layer indicating no wetting
As indicated above, in its broadest aspects, the method of the
invention comprises heating a low alloy steel containing alloying
elements more readily oxidizable than iron in an atmosphere
oxidizing to iron under conditions which form on the steel a
surface layer of iron oxide containing a dispersion of oxides of
the alloying elements, then further treating the steel under
conditions reducing to iron oxide. When the initial heating step is
carried out in accordance with the Selas-type process, the steel is
preferably heated to a temperature of about 1400.degree.F to about
1600.degree.F in an atmosphere of gaseous products of combustion
containing 0% to 6% excess O.sub.2, preferably about 2% excess
O.sub.2, and no combustibles. In the subsequent reducing section
the steel is preferably brought to a temperature of about
1500.degree. to about 1700.degree. F in an atmosphere containing
hydrogen, preferably at least about 20% hydrogen. The steel is then
cooled to appropriate bath entry temperature while still protected
by the hydrogen-nitrogen atmosphere, the dew point of which must be
consistent with carbon steel practice.
It will be understood that the strip bath entry temperature and
maximum dew point of the hydrogen-nitrogen atmosphere in the
furnace are dependent on the type of coating metal (i.e., the
minimum strip temperature prior to bath entry). In general the
strip is brought to a temperature ranging from slightly less than
to slightly higher than that of the coating metal bath. When
coating with aluminum a dew point not higher than about 50.degree.F
should be observed. When galvanizing, a maximum dew point of about
15.degree.F should be observed because of the lower strip
temperature. For aluminizing, typical strip bath entry temperatures
are about 1250.degree.F to 1350.degree.F, while for galvanizing,
typical strip bath entry temperatures are about 850.degree. to
950.degree. F.
In a new installation the advantages of rapid strip heating,
adaptability to processing different types of steel, and furnace
pressure control clearly favor the use of a Selas-type
installation. However, as indicated above, the method of the
invention is equally applicable to a Sendzimir-type process, and
existing installations of this type can be readily adapted for
operation in accordance with the method of this invention.
Basically, the only difference is to heat the steel in the
oxidizing furnace to a temperature of 1100.degree.F or greater,
preferably to 1300.degree.F. The conditions in the reducing section
remain unchanged.
The lower strip preheat oxidizing temperature range for the
Sendzimir-type process as compared to the Selas-type process is
accounted for by the differences in atmosphere composition to which
the strip is exposed. Thus, to produce a given thickness of surface
oxide, a lower temperature is required when strip is heated in the
Sendzimir oxidizing furnace and exposed to air than with the
Selas-type system where the strip is exposed only to oxidizing
products of combustion prior to direct entry into the reducing
furnace.
* * * * *