[0001] This invention relates to a method of surface treatment of a member of heat-resistant
alloy for use in turbines, blowers, boilers or the like to render it- resistant to
high temperature oxidation as well as to high temperature corrosion.
[0002] In industrial gas turbines using petroleum or natural gas as the fuel, gas temperature
at the turbine inlet tends to become higher as the turbine efficiency is improved.
On the other hand, as the available fuel supply has changed for the worse in recent
years, the fuels used for the turbines have been diversified and the content of corrosive
impurities in the fuels such as sulphur (S), sodium (Na), vanadium (V), and so forth
has tended to increase. As a result, so-called "hot parts" such as the blades and
burners of turbines, that are exposed to these high temperature gases, are subjected
to extremely severe high temperature oxidation as well as high temperature corrosion.
[0003] These hot parts have conventionally been made primarily of heat-resistant alloys.
In particular turbine blades consist of Ni- and Co-based alloys called "ultra-alloys".
However, since high temperature strength is generally a top priority requirement for
these ultra-alloys, they have the drawback that their corrosion resistance and oxidation
resistance are not satisfactory. Various attempts have therefore been made to provide
these heat-resistant alloys with oxidation resistance and corrosion resistance and
various surface treatment methods using for example chemical and physical techniques
have been employed. However, none of these methods has been really satisfactory as
regards efficiency and cost.
[0004] The present invention is directed to providing a method which overcomes the deficiences
of the previous methods. Accordingly, in order to provide a member of heat-resistant
alloy with high temperature oxidation resistance and high temperature corrosion resistance,
the present invention provides a surface treatment method which is characterized by
the steps of coating by spraying onto the surface of said member in the form of a
substrate, a heat-resistant material of metals such as Ni and Cr or Ni-Cr alloys or
their compounds as a first layer, then applying, as a second layer, a liquid coating
containing metals such as AL, Si, Vr, Ts and the like or their alloys or compounds
as the corrosion-resistant material by means of spray-coating, brush-coating or the
like, and heat-treating the coated surface.
[0005] The surface treatment method of the present invention provides the characterizing
features as illustrated in Table 1 in comparison with the conventional methods.
[0006] The present invention will be now described in more detail by reference to an example
in accordance therewith.
[0007] A substrate of Udimet 520 (by weight 19% Cr, 12% Co, 6% Mo, 3% Ti, 2% Aℓ, 1% Fe,
Ni-Bal), widely used as an ultra-alloy for the hot parts of a gas turbine, was treated
in the following sequence:
(1) After the surface of the substrate had been cleaned with an alkaline emulsion
cleaning agent, steam cleaning was carried out using a Fluron type solvent. The surface
was further blasted using an Aℓ2O3 blast.
(2) A Ni-Cr (50/50 by weight) alloy was applied as a coating to form a first layer
having a thickness of about 50η by plasma spraying.
(3) The surface of the sprayed-on first layer was blasted using Aℓ 2O3 to remove any oxide film formed on its outermost surface.
(4) The surface of the sprayed-on first layer was coated by spraying on a coating
slurry formed by dispersing Aℓ. and Si02, each having a particle size of about 0.1 to 1η, in an organic carrier (alcohol,
solvent naphtha, etc) to form a second layer.
(5) After these treatments, the substrate was placed in an electric furnace and was
held at 800C. (± 5°C) for 20 minutes to evaporate and remove the liquid. After being further
held at 330°C (± 50C) for 15 minutes, the substrate was withdrawn from the furnace.
(6) The substrate was held at 1,080°C for 4 hours inside a hydrogen furnace, was cooled
in the furnace and was then withdrawn.
[0008] Above mentioned step (4) could be carried out using a mixture of fine. Aℓ particles
with Aℓ
2O
3 powder in a mixing ratio by weight of 80/20 or 50/50 or a mixture of Aℓ with Si0
2 in a mixing ratio by weight of 80/20 or 50/50. Also step (6) could be carried out
using a vacuum furnace in place of the hydrogen furnace.
[0009] Although in this example Udimet 520 has been treated by the method of the invention
by way of example, similar excellent results can also be obtained when treating the
surfaces of other substrates such Ni-based alloy, Co-based alloy and stainless steel.
[0010] The coated surface of the substrate provided by the above described method had an
extremely smooth and flat surface and Aℓ and Si from the second layer sufficiently
penetrated by diffusion into the first layer, thereby completely eliminating the fine
pores of the first layer. Hence, the composite coating was. rendered wholly homogeneous.
[0011] In other words, since the melting point of Aℓ is 660
0C., Aℓ was fused due to the heat-treatment and penetrated into the fine pores, thus
presumably rendering the surface smooth and flat. Further, it was confirmed that a
part of AL and Si reached and was diffused also into the substrate.
[0012] Table 2 illustrates the results of fly-ash errosion resistance test, corrosion resistance
test, and practical application test using gas turbine blades, each test being applied
to a member treated by a method in accordance with the present invention and a member
treated by a conventional method. The composite coating produced by the method in
accordance with the present invention had a better performance in comparison with
that produced by the conventional method in the fly-ash errosion resistance test and
the corrosion resistance test. In the practical application test using gas turbine
blades, too, the coated blade produced using the method of the present invention exhibited
the tendency that the deposition amount of the fuel ash became smaller. In a thermal
inpact test comprising holding the testpiece at 1,100°C, for 15 minutes, then charging
it into the water at 20°C. and repeating these procedures five times, the composite
coating produced by the method of the present invention did not suffer peeling or
cracking and had extremely good adhesion.

1. A method of surface treatment of a member made of heat-resistant alloy characterised
by the steps of spraying onto the surface of said member a coating of a heat-resistant
material, applying a liquid coating containing a corrosion-resistant material onto
the sprayed-on coating and then heat treating said member to effect penetration by
diffusion of one coating into the other.
2. A method according to claim 1, characterised in that said sprayed-on coating comprises
Ni or Cr or a Ni-Cr alloy or a compound of Ni and/or Cr.
3. A method according to Claim 1 or Claim 2, characterised in that said liquid coating
comprises a slurry.
4. A method according to any preceding claim, characterised in that said liquid coating
contains at least one of the following, Aℓ, Si, Vr, Ts, or an alloy thereof or a compound
thereof.
5. A method according to Claim 4, characterised in that the liquid coating comprises
a slurry formed by dispersing Aℓ and Si02 in a liquid carrier.
6. A method according to Claim 5, characterised in that said Aℓ and Si02 have a particle size of about 0.1η to 1η.
7. A method according to Claim 4, characterised in that the liquid coating comprises
a slurry formed by dispersing Aℓ and Aℓ 2O3 in a liquid carrier.
8. A method according to any preceding claim, characterised in that the heat treatment
includes the step of holding the member at about 10800C for several hours.
9. A method according to Claim 8, wherein said step in the heat treatment is preceded
by a heating step to evaporate the liquid, followed by a relatively short heat treatment
at about 330°C.
10. A method of surface treatment of a member made of heat resistant alloy, substantially
as hereinbefore described by way of example.