| (19) |
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(11) |
EP 0 605 175 B1 |
| (12) |
EUROPEAN PATENT SPECIFICATION |
| (45) |
Mention of the grant of the patent: |
|
13.08.1997 Bulletin 1997/33 |
| (22) |
Date of filing: 21.12.1993 |
|
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| (54) |
A coated article and a method of coating said article
Beschichtetes Werkstück und Verfahren zum Beschichten dieses Werkstückes
Article revêtu et procédé de revêtement de cet article
|
| (84) |
Designated Contracting States: |
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CH DE FR GB IT LI |
| (30) |
Priority: |
30.12.1992 US 998712
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| (43) |
Date of publication of application: |
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06.07.1994 Bulletin 1994/27 |
| (73) |
Proprietor: PRAXAIR S.T. TECHNOLOGY, INC. |
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Danbury,
Connecticut 06810-5113 (US) |
|
| (72) |
Inventor: |
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- Walsh, Patrick Noel
Indianapolis,
Indiana 46208 (US)
|
| (74) |
Representative: W.P. Thompson & Co. |
|
Coopers Building,
Church Street Liverpool L1 3AB Liverpool L1 3AB (GB) |
| (56) |
References cited: :
EP-A- 0 138 228 DE-B- 1 185 034 GB-A- 2 021 641 US-A- 5 149 597
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WO-A-82/01897 FR-A- 2 317 368 GB-A- 2 106 144
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|
| |
|
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- CHEMICAL ABSTRACTS, vol. 103, no. 26, 30 December 1985, Columbus, Ohio, US; abstract
no. 219227h, SHOWA DENKO 'hard alloy powder for thermal spraying' page 246; column
103
|
|
| |
|
| Note: Within nine months from the publication of the mention of the grant of the European
patent, any person may give notice to the European Patent Office of opposition to
the European patent
granted. Notice of opposition shall be filed in a written reasoned statement. It shall
not be deemed to
have been filed until the opposition fee has been paid. (Art. 99(1) European Patent
Convention).
|
[0001] The present invention relates to a coated article and a method of forming a coating
on a substrate.
[0002] More particularly the present invention relates to an article having a wear and corrosion-resistant
coating and a method for forming a wear and corrosion resistant coating on a substrate
in which the coating will not crack when quenched in oil along with its substrate.
[0003] It is known to form a wear and corrosion resistant coating on a metallic substrate
by depositing at least one coating of a metal carbide and binder, particularly tungsten
carbide and cobalt and a nickel based alloy using a plasma, detonation gun or other
thermal spray technique followed by a heat treatment operation. This method is described
in detail in U.S. Patent 4,173,685 issued to M. H. Weatherly on November 6, 1979.
The coating, as taught in the Weatherly patent, may be formed by depositing two successive
layers (the two layer method) on a metallic substrate followed by heat treatment or
by depositing a single layer (the one-layer method) followed by heat treatment. In
the two layer method a metal carbide layer is initially formed on the metallic surface
preferably using a detonation gun followed by the deposition of a nickel based alloy
or mixture of alloys containing boron. The range of boron in the second layer for
the two layer method should be between 3 and 18 wt% when the density of the first
layer is above 95% theoretical and between 6 and 18 wt% when the density of the first-layer
is between 75 and 95% of theoretical. In the one layer method a metal carbide powder
containing a metal binder such as cobalt and a nickel based alloy or mixture of alloys
is mixed and deposited as one layer. The content of the metal carbide and binder is
between 40 wt. % and 75 wt. % of the total composition and the boron content of the
nickel based alloy or mixture of alloys is above 6 wt %. Although suitable wear resistant
coatings may be formed in accordance with the teaching of the aforementioned Weatherly
patent on a wide variety of steel substrates it is not recommended for use on steels
that have to be hardened by oil quenching from elevated temperatures and then optionally
tempered to achieve useful strengths and mechanical properties. If hardened before
coating, such steels will be annealed by the heat treatment that is required in the
aforementioned Weatherly process to develop the optimum wear and corrosion-resistant
properties of the coating (hereinafter referred to as the "Weatherly Coating"). After
the Weatherly coating has been heat-treated it will crack if subjected to reheating
and oil-quenching to develop the most useful properties of the steel. The present
invention provides for forming an article composed of a body and a superimposed coating
that exhibits high wear and corrosion resistance after heat treatment.
[0004] This coating may be used on any body but is especially intended for use on steel
bodies that require heat treatment and oil-quenching after coating because it will
not crack when quenched in oil from high temperature.
[0005] According to the present invention there is provided a coated article which comprises
a steel body and a superimposed coating with said coating having an as-deposited porosity
of less than 5% and a composition consisting of a metal carbide, metal binder and
fraction, said metal carbide consisting essentially of one or more carbides selected
from tungsten, chromium, vanadium, hafnium, titanium, zirconium, niobium, molybdenum
and tantalum carbides and compounds thereof along with a metal binder selected from
Co, Ni, Fe and alloys thereof and a fraction consisting of a nickel-based boron containing
alloy of such composition that boron constitutes 1.3 and 3.0 wt% of the coating, said
metal carbide (s) and metal binder fraction constituting between 50 wt % and 75 wt
% of the entire composition, with said metal binder being up to 25 wt % of the metal
carbide plus binder fraction and with said nickel based boron-containing alloy representing
the balance of the composition, with a boron content in said nickel based boron-containing
alloy in a range of between 4wt% and 5wt%.
[0006] According to a further aspect of the present invention there is provided a method
for coating a steel body to form an article with a wear and corrosion resistant surface
comprising the steps of: preparing a powder composition consisting of a metal carbide,
metal binder and fraction, wherein said metal carbide consists essentially of at least
one metal carbide selected from tungsten, chromium, vanadium, hafnium, titanium, zirconium,
niobium, molybdenum and tantalum carbides and compounds thereof, the metal binder
is selected from the class consisting of cobalt, nickel, iron and alloys thereof,
and the fraction consists of a nickel based boron-containing alloy in which the metal
carbide and the metal binder in the powder composition comprise between 50 and 75wt%
of the powder composition with the metal binder being up to 25 wt% of the composition
of said fraction and with said nickel based boron containing alloy representing the
balance of the composition, with a boron content in said at least one metal-based
boron-containing alloy in a range of between 4wt% and 5wt%, depositing said powder
composition by a thermal spray process and heating the coating layer to a temperature
above 950 °C to produce a coated layer with less than 5% included porosity and such
that the boron content of the coating lies in the range of 1.3wt% to 3.0wt% of the
total coating composition.
[0007] The present invention will now be further described by way of example, with reference
to the accompanying single figure of drawings which shows the relationship between
the metal carbide-metal binder component and the boron content of the nickel-based
alloy in the powder formulation...
[0008] The powder composition of the present invention includes a metal carbide-binder fraction
comprising tungsten, chromium, vanadium, hafnium, titanium, zirconium, niobium, molybdenum
or tantalum carbide or mixtures or compounds thereof and up to 25 wt % of a metal
binder such as Co, Ni and Fe and a fraction comprising a nickel-based alloy containing
boron. The preferred metal carbide is tungsten carbide and the preferred metal binder
is cobalt in a range of preferably between above 0 and 15 wt %.
[0009] The powder formulation must be applied to the body by a thermal spray process, capable
of producing a coating with less than 5% included porosity. The nickel alloy fraction
of the powder mix must have a boron content such that, upon deposition by such method
capable of producing a coating with less than 5% porosity, the boron content of the
coating lies in the range of 1.3 to 3.0 wt% of the total coating composition. Commercial
thermal spray processes which may be used to provide the required high density coating
include the detonation gun, hypersonic combustion or high velocity oxy-fuel spray
coating processes and other "high velocity" spray coating processes. The detonation
gun process is the preferred process and is well known and fully described in U.S.
Patent No. 2,714,563, 4,173,685 and 4,519,840, respectively. In the detonation gun
process oxygen, acetylene and nitrogen are fed into a gun barrel along with the charge
of material being coated and ignited. The resultant detonation wave accelerates the
powder while heating it close to or above its melting point. When the powder formulation
is applied to the body using the detonation gun technique, it is most advantageous
if the nickel-alloy fraction of the powder mix has a boron content such that the boron
content of the total powder mix is between 1.0 and 2.7 wt%.
[0010] It is crucial to the present invention that the as-deposited coating have a porosity
of less than 5%. The powder composition of the present invention when deposited with
this low porosity using an appropriate thermal spray process and subjected to a heat
treatment at above 950°C (hereinafter referred to as the "primary heat treatment")
forms a hard, ductile, impervious coating that is able to survive, without cracking,
oil-quenching from above 800°C. During the primary heat treatment, the porosity will
reduce to 0 to 90% of its as-coated value and the original powder components will
convert to a mixture of carbides and borides dispersed in a nickel alloy matrix. After
primary heat treatment,a coating with the specified as-deposited composition and density
will exhibit a hardness of greater than 900kg/mm
2 when measured by the Vickers method with 300 gram load and will exhibit a total porosity
of less than 5%, preferably less than 2%, with no through porosity, i.e. any voids
are closed.
[0011] The coating resulting from the primary heat treatment has excellent wear and corrosion
resistance and no further processing is needed to take advantage of these properties,
though the coating may be ground or otherwise finished to favorably modify its surface
characteristics. In addition, the primary heat treatment may be followed by a secondary
heat treatment designed to modify the mechanical properties of the supporting body
without detriment to the coating. This heat treatment may be, for example, an aging
heat treatment or an oil-quenching treatment appropriate to the substrate. A third
heat treatment, to temper the quenched steel, as is common practice in heat treating,
may also be applied without detriment to the coating. Each heat treatment may be carried
out in a vacuum or in an appropriate atmosphere. The secondary heat treatment may
be carried out as a continuation of the primary heat treatment or separately from
the primary heat treatment. In fact, the coating can be cooled and reheated and then
quenched.
[0012] A relationship exists in the coating composition between the metal carbide-metal
binder component and the boron content of the nickel-based alloy which in concert
with the method of application must be satisfied to produce acceptable coating characteristics
in terms of high stress abrasive wear resistance, low porosity and ability to sustain
oil quenching without cracking. Typically the interdependence between the metal carbide-metal
binder and the nickel based alloy is shown in Figure 1 using a composition of a WC-CO
powder containing 4.4%C, 9.4%Co, 0.6%Fe, balance W and a Ni-B alloy which is composed
of a combination of two nickel-based alloy components identified as Ni-B alloy 1 and
Ni-B alloy 2, respectively. The nominal composition of Ni-B alloy 1 is: 14 wt % B,
2 wt. % Fe, balance Ni, and the nominal composition of the Ni-B alloy 2 is: 3% B,
3% Fe, 4% Si, 7% Cr, balance Ni. In Figure 1, the ordinate represents the percentage
of the WC-Co powder in the powder mix and the abscissa the percentage of Ni-B alloy
1. The proportions of Ni-B alloy I and Ni-B alloy 2 control the boron content of the
powder formulation. The circled data points in Figure 1 define the boundaries of a
triangular-like geometry and correspond to the data identified in the following Tables
I and II respectively. In Table I, the boron content of each of the mixtures is specified
as the percentage of boron in the combined Ni-B alloy independent of the wt. % of
the metal carbide. Table II shows the weight percent of boron in the powder and coating
from which it should be noted that the boron content in the coating is not only retained
but is enhanced from that in the powder.
Table I
| --Mix Composition-- |
| wt. percent |
| WC-Co |
Ni-B Alloy 1 |
Ni-B Alloy 2 |
% B in Ni-B Alloys |
| 75.0 |
6.0 |
19.0 |
5.64 |
| 65.0 |
6.0 |
29.0 |
4.88 |
| 50.0 |
6.0 |
44.0 |
4.32 |
| |
| 71.0 |
5.0 |
24.0 |
4.90 |
| 65.0 |
5.0 |
30.0 |
4.57 |
| 57.0 |
5.0 |
38.0 |
4.28 |
| |
| 67.0 |
4.0 |
29.0 |
4.33 |
| 65.0 |
4.0 |
31.0 |
4.26 |
| 63.0 |
4.0 |
33.0 |
4.19 |
| |
| 65.0 |
3.6 |
31.4 |
4.13 |
Table II
| --Powder Mix Comp-- |
| wt. percent |
| WC-Co |
Ni-B Alloy 1 |
Ni-B Alloy 2 |
Percent Boron |
| |
|
|
In Pwdr |
In Ctng |
| 75 |
6.0 |
19.0 |
1.4 |
1.9 |
| 65 |
6.0 |
29.0 |
1.7 |
2.2 |
| 50 |
6.0 |
44.0 |
2.2 |
2.6 |
| |
| 71 |
5.0 |
24.0 |
1.4 |
1.8 |
| 65 |
5.0 |
30.0 |
1.6 |
2.0 |
| 57 |
5.0 |
38.0 |
1.9 |
2.3 |
| |
| 67 |
4.0 |
29.0 |
1.5 |
1.9 |
| 65 |
4.0 |
31.0 |
1.5 |
1.9 |
| 63 |
4.0 |
33.0 |
1.6 |
2.0 |
| |
| 65 |
3.6 |
31.4 |
1.5 |
1.9 |
[0013] The area within the triangle formed in Figure 1 delineates the range of powder compositions
which will form a coating having properties of high wear resistance, low porosity
and the ability to withstand oil quenching without cracking. The optimum boron content
range is between 4 wt. % and 5 wt. %. A boron content of above 6 wt % in the nickel
boron alloy powder formulation results in a coating which cracks when quenched in
oil. The range of the metal carbide-metal binder is also limited to between 50 and
75 wt % of the total mixture and preferably between 55 and 65 wt%. The percent of
boron must be correlated to the percent of the metal carbide-metal binder to remain
within the triangular region. The region above line A-B of Figure 1 designates a region
of high wear resistance and a microhardness above 900 HV.3, whereas in the region
above line A-C the porosity will be too high and the coating will exhibit interconnected
porosity. The content of boron in the coating should be between 1.8 and 2.6 wt % in
the case exemplified in figure 1 and between about 1.3 to 3.0 wt % in the most general
case. When deposition of the coating is done by means of a detonation gun, as is assumed
in Tables 1 and 2 and figure 1, the content of the metal carbide and binder must lie
between 40 and 65 wt % and the percent of boron in the powder between 1.4 and 2.2
wt %. The article of the present invention is particularly suitable for high stress
abrasive wear environments such as, for example, a steel guide or work roll. The coating
formed in accordance with the present invention is particularly suitable as a bearing
surface for any type of bearing and for use in providing a surface coating for a valve
seat or valve gate.
[0014] The following are examples which illustrate the invention and its advantage over
the prior art:
Example I
[0015] A powder mix (Powder Mix 1) was prepared of a WC-Co powder containing 86% W, 9.5%
Co, 4.5% C with an alloy containing 83% Ni, 14% B, 2% Fe (Ni-B Alloy 1) and another
alloy containing 83% Ni, 3% B, 7% Cr, 4% si, 3% Fe (Ni-B Alloy 2) in such proportions
as to net 1.7% B in the mix. Powder Mix 1 was deposited by means of a detonation gun
onto 1.27cms x 1.91cms (1/2"x 3/4") x 2.711 blocks of AISI 1018 steel. This detonation
gun coating exhibited an as-deposited porosity of less than 5%. The resultant coating
(Coating 11) had a microhardness greater than 900 HV.3 and a porosity of less than
1% after primary heat treatment to a temperature in excess of 1000°C. A coating made
on a similar block of AISI 1018 steel using the same powder through a plasma torch
was less than 95% dense though otherwise appearing to be of high quality in the as-deposited
state, but was found to contain more than 10% porosity after primary heat treatment
and its microhardness could not be measured accurately because of the high porosity.
When deposited on the large faces of a 111 x 31, x 611 4140 steel block later heated
to over 1000°C for 1 hr and subsequently reheated to 850°C and quenched in oil, Coating
#1 did not crack. The plasma torch coating could not be oil quenched without cracking.
Example II
[0016] It is an essential part of the concept of the present invention that the boron be
retained in the coating at specific levels throughout the deposition and heat treatment.
Coating #1 was deposited onto a 211 diameter, 611 long aluminum tube from which it
was broken off by crushing the tube. The chemical composition of this coating was
determined by standard methods of chemical analysis. Essentially identical results
were obtained when the coating was deposited on a flat plate made of low carbon steel
and again broken off mechanically. Coating #1 is made from Powder Mix 1, which contains
1.7% boron, but when removed from the substrate and analyzed it was found to contain
2.1% B. The apparent increase in B content is a result of preferential loss of other
constituents during coating. In contrast, a coating made by the spray and fuse process
from Stellite SF6 powder, which also contains 1.7% B, was found by analysis to contain
only 1.2% B.
Example III
[0017] A 511 0.D., 1.91cms (3/4") wall tube made of AISI 4140 steel was coated with 0.01611
of Coating #1 and primary heat-treated, then subsequently reheated to 850°C, oil quenched
and tempered. The coating did not crack.
Example IV
[0018] Flat plates, 1.211 x 311 x 811, of AISI 4130 steel were coated on the two large faces
with 0.01411 - 0.01611 of Coating #1 and then subjected to the primary heat-treatment
for the coating. Following this, they were oil quenched and tempered to harden the
substrate to 40 HRC at the surface (20 HRC at the center). Fluorescent penetrant inspection
of the coatings revealed no cracking.
Example V
[0019] The foregoing experiment was repeated on two plates of similar size made of AISI
4140 steel and on a valve gate, 10.16cms x 17.78cms x 4.57cms (4" x 7" x 1.8") made
of AISI 4130 steel. No cracking of the coating was observed subsequent to oil quenching
and tempering of any of these.
Example VI
[0020] A tube of AISI 52100 steel, 211 in outside diameter x 611 long, with a 0.32cms (1/8")
wall thickness, coated with 0.01211 of Coating #1 and put through the usual successive
heat treatments also survived oil quenching without the coating cracking.
Example VII
[0021] Coating #1 was applied to the O.D. of a centrifugally cast steel mill work roll of
nominal composition 1.7% C, 1.5% Ni, 1.1% Cr, 0.5% Mo, balance Fe and impurities and
given the primary heat-treatment for the coating, but no secondary heat treatment.
It is inherent in the operation of such rolls that each area of the surface is alternately
heated and quenched as it moves into and out of contact with the hot steel. The coating
was then ground and the roll installed in the finishing station of an I-beam shaping
line. Three hundred tons of product was successfully rolled before the coating was
penetrated. Penetration occurred in an area where the grinding had substantially reduced
the coating thickness as a result of some out-of-roundness that developed during heat-treatment.
It was evident from inspection of the coating on the remainder of the roll that the
coating had survived numerous impacts by the leading edges of the beams that were
being shaped. Moreover, furrows observed in the coating indicated that significant
drag had developed between the coating and the I-beam at times during rolling, but
the coating had neither cracked nor delaminated. It was also observed that neither
the coating nor the substrate exposed by penetration of the coating exhibited the
typical thermal fatigue patterns (firecracking) that usually degrade these rolls.
The Weatherly coating, when applied to this substrate, blistered and cracked during
primary heat treatment.
Example VIII
[0022] In comparison with the present invention spray and fuse coatings were prepared by
an outside source from Stellite SF6 powder and from Stellcar Composite 1 powder. The
composition of the former is nominally 1.7% B, 19% Cr, 13.5% Ni, 7.5% W, 2.3% Si,
3% Fe, balance Co; Stellcar Composite 1 is a mix of 60% WC and 40% of a Ni-base alloy.
Both are standard commercial spray and fuse coatings. These coatings as supplied to
us by a commercial vendor on 111 x 311 x 611 blocks of 4140 steel, were much more
porous than coatings of the subject invention. By examination of mounted cross sections
the porosity of the Stellcar Composite 1 coating was estimated as being 15 - 25 percent,
while that of the Stellite SF6 coating was 6 8 percent. When subjected to oil quenching
on 311 x 611 x 111 blocks of 4140 steel, the Stellite SF6 coating developed cracks
just under the surface running parallel to the surface. The Composite 1 coating developed
numerous cracks that ran completely through the coating from the surface to the substrate.
While the cracking of the Stellite SF6 coating was relatively minor, it should be
noted that this coating is significantly lower in hardness than the coatings of this
invention, measuring only 450-500 HV.3.
Example IX
[0023] Samples of Coating #1 were prepared by coating Powder Mix 1 onto low carbon steel
substrates for wear rate and mechanical property determinations and then tested in
parallel with similarly prepared specimens coated using a plasma torch with a coating
composition as taught in Weatherly containing tungsten carbide-cobalt and a nickel
based alloy with about 8.5 wt% B and having about 3.4 wt% B in the coating. The results
of these wear measurements are shown in Table III as indicated below where it is evident
that the two coatings are essentially equivalent in the properties tested. The Weatherly
coating, however, cracked when quenched in oil on pieces of the same size, shape,
and composition as those on which Coating #1 survived.
Table III
| Test |
Coating of Invention |
Weatherly Coating |
| High Stress Abrasion (a) |
3.9 |
3.2 - 5.0 |
| 300 Erosion (A'203) (b) |
19 |
19 - 25 |
| 900 Erosion (A'203) (b) |
85 |
90 - 95 |
| Sand Abrasion (c) |
1.7 - 1.8 |
1.3 - 2.0 |
(a) mil/min
(b) µmlg
(c) mm3/1000 revolutions |
Example X
[0024] In comparison with the present invention a coating containing roughly the same B,
C, Ni and W content as Coating 11, of Example 1, was prepared from another powder
mix, using a plasma torch instead of the detonation gun used to deposit Coating #1.
The porosity in this coating ranged from 3% to 6% in different samples, making it
substantially inferior to coating #1.
Example XI
[0025] Coatings were prepared by detonation gun deposition of mixtures of the WC-CO powder
described in Example I with varying amounts of Ni-B alloy 1 and Ni-B alloy 2 on the
two large faces of 2.54cms x 7.62cms x 15.24cms(1" x 3" X 6") blocks of AISI 4140
steel, then heat treated first at over 1000°C to treat the coating and subsequently
reheated to about 850°C, quenched in oil, reheated again at a lower temperature to
temper the steel to about HRC 30 and examined for cracks using fluorescent penetrant.
No cracks were found in any of these coatings. The specific compositions of these
coatings are listed in the following Table IV. Each of these coatings was not measurably
different from Coating #1 in resistance to high stress abrasion and had no more porosity
than Coating II.
TABLE IV
| -----Mix Composition----- |
| WC-Co |
Ni-B Alloy 1 |
Ni-B Alloy 2 |
Wt % B in Ni-B Alloys |
Percent Boron |
| |
|
|
|
In Pwdr |
In Ctng |
| **65.0 |
6.0 |
29.0 |
4.88 |
1.7 |
2.2 |
| 65.0 |
5.0 |
30.0 |
4.57 |
1.6 |
2.0 |
| 62.0 |
5.0 |
33.0 |
4.45 |
1.7 |
2.2 |
| 60.0 |
5.0 |
35.0 |
4.38 |
1.8 |
2.3 |
| 57.0 |
5.0 |
38.0 |
4.28 |
1.9 |
2.3 |
| 67.0 |
4.0 |
29.0 |
4.33 |
1.5 |
1.9 |
| ** This composition is designated Coating #1 in the text. |
1. A coated article which comprises a steel body and a superimposed coating with said
coating having an as-deposited porosity of less than 5% and a composition consisting
of a metal carbide, metal binder and fraction, said metal carbide consisting essentially
of one or more carbides selected from tungsten, chromium, vanadium, hafnium, titanium,
zirconium, niobium, molybdenum and tantalum carbides and compounds thereof along with
a metal binder selected from Co, Ni, Fe and alloys thereof and a fraction consisting
of a nickel-based boron containing alloy of such composition that boron constitutes
1.3 and 3.0 wt% of the coating, said metal carbide (s) and metal binder fraction constituting
between 50 wt % and 75 wt % of the entire composition, with said metal binder being
up to 25 wt % of the metal carbide plus binder fraction and with said nickel based
boron-containing alloy representing the balance of the composition, with a boron content
in said nickel based boron-containing alloy in a range of between 4wt% and 5wt%.
2. An article as claimed in claim 1, wherein said nickel-based boron-containing alloy
comprises a first and second component with said first component containing 13 to
14 wt % boron and constituting 4 to 8 wt % of the coating composition and with said
second component containing 2 to 4 wt % boron and alloying elements selected from
the class consisting of chromium, iron and silicon.
3. An article as claimed in any one of claims 1 and 2, wherein the coating upon heat
treatment to above a heat treatment temperature of at least 950°C forms a nickel alloy
matrix containing compounds of one or more carbide (s) and boride (s) with said heat
treated coating having a hardness above 8,82 GPa (900 Kg/mm2) Hv.3, being metallurgically bonded to the said body, and having a porosity of 0
to 90% of the as-deposited coating said porosity being present only in the form of
isolated enclosed pores.
4. An article as claimed in any one of the preceding claims, wherein said body is selected
from the class consisting of a guide or work roll for use in guiding steel, a bearing
and a valve component.
5. A process for coating a steel body to form an article with a wear and corrosion resistant
surface comprising the steps of: preparing a powder composition consisting of a metal
carbide, metal binder and fraction, wherein said metal carbide consists essentially
of at least one metal carbide selected from tungsten, chromium, vanadium, hafnium,
titanium, zirconium, niobium, molybdenum and tantalum carbides and compounds thereof,
the metal binder is selected from the class consisting of cobalt, nickel, iron and
alloys thereof, and the fraction consists of a nickel based boron-containing alloy
in which the metal carbide and the metal binder in the powder composition comprise
between 50 and 75wt% of the powder composition with the metal binder being up to 25
wt% of the composition of said fraction and with said nickel based boron containing
alloy representing the balance of the composition, with a boron content in said at
least one metal-based boron-containing alloy in a range of between 4wt% and 5wt%,
depositing said powder composition by a thermal spray process and heating the coating
ranges to a temperature above 950 °C to produce a coated range with less than 5% included
porosity and such that the boron content of the coating lies in the range of 1.3wt%
to 3.0wt% of the total coating composition.
6. A process as claimed in claim 5, wherein deposition is by means of a detonation gun
and the boron content of the powder is between 1.0 and 2.7 wt %.
7. A process as claimed in claim 6, in which the boron content is between 1.4 and 2.2wt%.
8. A process as claimed in claim 6, in which said metal carbide(s) comprise tungsten
carbide(s) and said metal binder consists essentially of cobalt.
9. A process as claimed in claim 6, in which said metal binder constitutes between 6
and 15 wt% of the carbide and binder fraction.
10. A process as claimed in claim 9 in which said boron-containing alloy comprises a first
and second component with said first component containing 13 to 14 wt% boron and constituting
about 3.6 to 6wt% of the powder and with said second component containing 2 to 4 wt%
boron and also containing alloying elements selected from the class consisting of
chromium, iron and silicon.
1. Beschichteter Gegenstand mit einem Stahlkörper und einem darüber aufgebrachten Überzug,
wobei der Überzug eine Porosität im aufgebrachten Zustand von weniger als 5 % und
eine Zusammensetzung aufweist, die ein Metallkarbid, Metallbindemittel und eine Fraktion
aufweist, wobei das Metallkarbid im wesentlichen aus einem oder mehreren Karbiden
besteht, die aus Wolfram-, Chrom-, Vanadium-, Hafnium-, Titan-, Zirkon-, Niob-, Molybdän-
und Tantal-Karbiden und Verbindungen daraus ausgewählt sind, zusammen mit einem Metallbindemittel,
das aus Co, Ni, Fe und deren Legierungen ausgewählt ist, und einer Fraktion, die aus
einer borhaltigen Nickelbasislegierung von solcher Zusammensetzung besteht, daß Bor
1,3 bis 3,0 Gew.% des Überzugs ausmacht, wobei das Metallkarbid bzw. die Metallkarbide
und die Metallbindemittelfraktion zwischen 50 Gew.% und 75 Gew.% der gesamten Zusammensetzung
ausmachen, wobei das Metallbindemittel bis zu 25 Gew.% des Metallkarbids plus der
Bindemittelfraktion ausmacht und wobei die borhaltige Nickelbasislegierung den Rest
der Zusammensetzung ausmacht, wobei der Borgehalt in der borhaltigen Nickelbasislegierung
im Bereich von 4 Gew.% bis 5 Gew.% liegt.
2. Gegenstand nach Anspruch 1, wobei die borhaltige Nickelbasislegierung eine erste und
eine zweite Komponente aufweist, wobei die erste Komponente 13 bis 14 Gew.% Bor enthält
und 4 bis 8 Gew.% der Überzugszusammensetzung ausmacht, und wobei die zweite Komponente
2 bis 4 Gew.% Bor enthält und wobei ferner legierende Elemente vorgesehen sind, die
aus der aus Chrom, Eisen und Silizium bestehenden Klasse ausgewählt sind.
3. Gegenstand nach einem der Ansprüche 1 oder 2, wobei der Überzug bei einer Wärmebehandlung
auf eine Wärmebehandlungstemperatur von mindestens 950 °C eine Nickellegierungsmatrix
bildet, welche Verbindungen von einem oder mehreren Karbid(en) und Borid(en) enthält,
wobei der wärmebehandelte Überzug eine Härte von über 8,82 GPa HV0.3 (900 kg/mm2) aufweist, mit dem Körper metallurgisch verbunden ist und eine Porosität von 0 bis
90 % des Überzugs im aufgebrachten Zustand aufweist, wobei die Porosität nur in Form
von isolierten eingeschlossenen Poren vorliegt.
4. Gegenstand nach einem der vorhergehenden Ansprüche, wobei der Körper aus der aus einer
Führungs- oder Arbeitsrolle zum Gebrauch beim Führen von Stahl, einem Lager und einer
Ventilkomponente bestehenden Klasse ausgewählt ist.
5. Verfahren zum Beschichten eines Stahlkörpers zur Bildung eines Gegenstandes mit einer
verschleiß- und korrosionsbeständigen Oberfläche, wobei im Zuge des Verfahrens: eine
Pulverzusammensetzung bestehend aus einem Metallkarbid, Metallbindemittel und einer
Fraktion hergestellt wird, wobei das Metallkarbid im wesentlichen aus mindestens einem
Metallkarbid besteht, welches aus Wolfram-, Chrom-, Vanadium-, Hafnium-, Titan-, Zirkon-,
Niob-, Molybdän- und Tantal-Karbiden und Verbindungen daraus ausgewählt ist, wobei
das Metallbindemittel aus der aus Kobalt, Nickel, Eisen und Legierungen derselben
bestehenden Klasse ausgewählt ist, und wobei die Fraktion aus einer borhaltigen Nickelbasislegierung
besteht, bei welcher das Metallkarbid und das Metallbindemittel in der Pulverzusammensetzung
zwischen 50 und 75 Gew.% der Pulverzusammensetzung ausmachen, wobei das Metallbindemittel
bis zu 25 Gew.% der Zusammensetzung der Fraktion ausmacht und wobei die borhaltige
Nickelbasislegierung den Rest der Zusammensetzung darstellt, wobei die mindestens
eine borhaltige Metallbasislegierung einen Borgehalt im Bereich von 4 Gew.% bis 5
Gew.% aufweist, wobei die Pulverzusammensetzung mittels eines thermischen Spritzverfahrens
und mittels Erwärmen der Beschichtung auf eine Temperatur von über 950 °C abgeschieden
wird, um einen beschichteten Bereich mit einer eingeschlossenen Porosität von weniger
als 5 % zu erzeugen, wobei der Borgehalt des Überzugs im Bereich von 1,3 Gew.% bis
3,0 Gew.% der gesamten Überzugszusammensetzung liegt.
6. Verfahren nach Anspruch 5, bei welchem die Abscheidung mittels einer Detonationskanone
erfolgt und der Borgehalt des Pulvers zwischen 1,0 und 2,7 Gew.% liegt.
7. Verfahren nach Anspruch 6, bei welchem der Borgehalt zwischen 1,4 und 2,2 Gew.% liegt.
8. Verfahren nach Anspruch 6, bei welchem das (die) Metall-Karbid(e) Wolframkarbid(e)
aufweist und das Metallbindemittel im wesentlichen aus Kobalt besteht.
9. Verfahren nach Anspruch 6, bei welchem das Metallbindemittel zwischen 6 und 15 Gew.%.
der Karbid- und Bindemittelfraktion ausmacht.
10. Verfahren nach Anspruch 9, bei welchem die borhaltige Legierung eine erste und eine
zweite Komponente aufweist, wobei die erste Komponente 13 bis 14 Gew.% Bor enthält
und etwa 3,6 bis 6 Gew.% des Pulvers ausmacht und wobei die zweite Komponente 2 bis
4 Gew.% Bor sowie legierende Elemente enthält, die aus der aus Chrom, Eisen und Silizium
bestehenden Klasse ausgewählt sind.
1. Article revêtu qui comprend un corps en acier et un revêtement superposé, ledit revêtement
ayant une porosité, tel qu'il a été déposé, inférieure à 5 % et une composition consistant
en un carbure métallique, un liant métallique et une fraction, ledit carbure métallique
consistant essentiellement en un ou plusieurs carbures choisis entre des carbures
de tungstène, de chrome, de vanadium, d'hafnium, de titane, de zirconium, de niobium,
de molybdène et de tantale et des composés de ces carbures, le liant métallique étant
choisi entre Co, Ni, Fe et leurs alliages, et la fraction consistant en un alliage
à base de nickel, contenant du bore, ayant une composition telle que le bore représente
1,3 à 3,0 % en poids du revêtement, ledit ou lesdits carbures métalliques et ladite
fraction de liant métallique représentant 50 % en poids à 75 % en poids de la composition
totale, ledit liant métallique représentant une quantité allant jusqu'à 25 % en poids
du carbure métallique plus la fraction de liant, et ledit alliage à base de nickel
contenant du bore, représentant le reste de la composition, la teneur en bore dudit
alliage à base de nickel, contenant du bore, étant comprise dans l'intervalle de 4
% en poids à 5 % en poids.
2. Article suivant la revendication 1, dans lequel l'alliage à base de nickel, contenant
du bore, comprend des premier et second constituants, ledit premier constituant contenant
13 à 14 % en poids de bore et représentant 4 à 8 % en poids de la composition de revêtement,
et ledit second constituant contenant 2 à 4 % en poids de bore et des éléments d'alliage
choisis dans la catégorie consistant en chrome, fer et silicium.
3. Article suivant l'une quelconque des revendications 1 et 2, dans lequel le revêtement,
par traitement thermique à une température supérieure à une température de traitement
thermique d'au moins 950°C, forme une matrice d'alliage de nickel contenant des composés
d'un ou plusieurs carbures et d'un ou plusieurs borures avec ledit revêtement ayant
subi un traitement thermique ayant une dureté supérieure à 8,82 Gpa (900 kg/mm2) HV.3, étant en liaison métallurgique avec ledit corps et ayant une porosité de 0
à 90 % du revêtement tel qu'il a été déposé, ladite porosité étant présente seulement
sous forme de pores clos isolés.
4. Article suivant l'une quelconque des revendications précédentes dans lequel le corps
est choisi dans la catégorie consistant en un guide ou cylindre de travail destiné
à être utilisé dans le guidage de l'acier, un palier et un composant de vanne.
5. Procédé pour le revêtement d'un corps en acier afin de former un article présentant
une surface résistante à l'usure et à la corrosion, comprenant les étapes consistant
:
à préparer une composition de poudre consistant en un carbure métallique, un liant
métallique et une fraction, dans laquelle ledit carbure métallique consiste essentiellement
en au moins un carbure métallique choisi entre les carbures de tungstène, de chrome,
de vanadium, d'hafnium, de titane, de zirconium, de niobium, de molybdène et de tantale
et leurs composés, le liant métallique est choisi dans la catégorie consistant en
cobalt, nickel, fer et leurs alliages, et la fraction consiste en un alliage à base
de nickel contenant du bore, dans lequel le carbure métallique et le liant métallique
dans la composition sous forme de poudre représentent 50 à 75 % en poids de la composition
sous forme de poudre, le liant métallique représentant une quantité allant jusqu'à
25 % en poids de la composition de ladite fraction, et ledit alliage à base de nickel
contenant du bore représentant le reste de la composition, la teneur en bore de l'alliage
à base d'au moins un métal et contenant du bore étant comprise dans l'intervalle de
4 % en poids à 5 % en poids, à déposer ladite composition de poudre par un procédé
de pulvérisation thermique et à chauffer la couche de revêtement à une température
supérieure à 950°C pour produire une couche revêtue avec moins de 5 % de porosité
inclus et de telle sorte que la teneur en bore du revêtement soit comprise dans l'intervalle
de 1,3 % à 3,0 % en poids de la composition de revêtement totale.
6. Procédé suivant la revendication 5, dans lequel le dépôt est effectué au moyen d'un
canon à détonation et la teneur en bore de la poudre est comprise dans l'intervalle
de 1,0 à 2,7 % en poids.
7. Procédé suivant la revendication 6, dans lequel la teneur en bore est comprise dans
l'intervalle de 1,4 à 2,2 % en poids.
8. Procédé suivant la revendication 6, dans lequel le ou les carbures métalliques comprennent
un ou plusieurs carbures de tungstène et le liant métallique consiste essentiellement
en cobalt.
9. Procédé suivant la revendication 6, dans lequel le liant métallique représente 6 à
15 % en poids du carbure et de la fraction de liant.
10. Procédé suivant la revendication 9, dans lequel l'alliage contenant du bore comprend
des premiers et seconds constituants, ledit premier constituant contenant 13 à 14
% en poids de bore et représentant 3,6 à 6 % en poids de la poudre, et ledit second
constituant contenant 2 à 4 % en poids de bore et contenant également des éléments
d'alliage choisis dans la catégorie consistant en chrome, fer et silicium.
