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Phoenix Global Mining
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[wstirrup] 28/2/2012 23:45

Well it's heading back up now!!!

W.

[jackpipe] 12/12/2008 14:27

looks like palladium has taken over from silver as a shorter's paradise.

[jackpipe] 20/11/2008 01:38

Looks like a good shake of palladium just prior to options expiry - down more than 15% since yesterday?

[sbs] 24/10/2008 17:06

Bairds will make you anything, though with gold prices where they are, they are probably concentrating on this market.

[jackpipe] 10/10/2008 11:07

anyone know where to get palladium jewellery? There only seem to be wedding rings commonly available, but the fabrication markup seems ridiculous - eg 12g wedding band (about $80 in metal) for GBP 350. Obviously a chunkier bracelet or necklace might have a better percentage intrinsic metal value?

[sbs] 18/9/2008 17:21

Yes - I have a smidgeon of Pd, which is down a lot. If the Russians are short of cash, it may go down further, but increasing energy costs encourage me to think price can't drop too low.

Tempted by Pt, having sold 488ccs at $2200/oz earlier in the year.

[jackpipe] 18/9/2008 12:04

also LCT didn't do any favours by pumping this incessantly for a few weeks at the top, only to see the price crash soon after.
Might be a bargain at this price, but this market is all a bit murky, IMHO - platinum looking like a bargain, only just off it's low, and a bit less cloak and dagger.

[holism] 18/9/2008 09:11

I agree its all a question of price and volume.The two are seldom in equilibrium. Which was the chartist who wrote books on the subject who has gone bust recently?

[pecker1] 15/8/2008 20:47

Rigger,

It's gone quiet because the premise that the charts foretold a mega palladium bull market has proved to be utter tosh. Charts don't foretell anything as nobody can predict the future one minute from now let alone days, weeks or months ahead. Get it right and it's pure chance but chartists then claim it was all in the charts. Get it wrong and chartists seem to vanish into thin air. I suspect its success rate is about as good as tossing a coin - heads or tails.

[riggerbeautz] 15/8/2008 20:32

This threads gone very quiet. Got stopped out of SWC, but just wondering if LCT or anyone has any further thoughts on Palladium prices to demand into next year?

[sbs] 09/7/2008 07:37

I think we're all waiting for the Russian stockpile to be sold down. Then supply will probably be significantly less than demand - as happened with platinum earlier this year.

[le couteau tombant] 02/7/2008 09:53

Palladium ETF LSE:PHPD Physical Holding up to 2,369,832 1 /10ths of toz ie 236,983.20 toz



ETFS Physical Palladium 2,369,832

[le couteau tombant] 02/7/2008 09:20

Palladium is used in many Titanium super alloys, but percentage used is small still consider automotive demand from Asia reason Palladium is a very strong long, followed by hydrogen storage, alternative energy/portable power usages.

Shell Hydrogen LLC deal with Hydrogenics Inc HYGS is tip of the Iceberg in potential demand to store Hydrogen.



I don't think anyone doubts Palladium will be twice current levels by this this time 2009 who has researched it in any depth.

[le couteau tombant] 02/7/2008 09:17

Bammbamm some info on superalloys I trust interesting.



US Patent 6982059 - Rhodium, platinum, palladium alloy
US Patent Issued on January 3, 2006
Abstract Claims Description Full Text

Description


BACKGROUND OF INVENTION

The present invention relates to materials designed to withstand high temperatures.
More particularly, this invention relates to heat-resistant alloys for high-temperature
applications, such as, for instance, gas turbine engine components of aircraft
engines and power generation equipment.

There is a continuing demand in many industries, notably in the aircraft engine
and power generation industries where efficiency directly relates to operating
temperature, for alloys that exhibit sufficient levels of strength and oxidation
resistance at increasingly higher temperatures. Gas turbine airfoils on such components
as vanes and blades are usually made of materials known in the art as "superalloys."
The term "superalloy" is usually intended to embrace iron-, cobalt-, or nickel-based
alloys, which include one or more additional elements to enhance high temperature
performance, including such non-limiting examples as aluminum, tungsten, molybdenum,
titanium, and iron. The term "based" as used in, for example, "nickel-based superalloy"
is widely accepted in the art to mean that the element upon which the alloy is
"based" is the single largest elemental component by weight in the alloy composition.
Generally recognized to have service capabilities limited to a temperature of about
1100° C., conventional superalloys used in gas turbine airfoils often operate
at the upper limits of their practical service temperature range. In typical jet
engines, for example, bulk average airfoil temperatures range between about 900°
C. to about 1000° C., while airfoil leading and trailing edge and tip temperatures
can reach about 1150° C. or more. At such elevated temperatures, the oxidation
process consumes conventional superalloy parts, forming a weak, brittle metal oxide
that is prone to chip or spall away from the part. Maximum temperatures are expected
in future applications to be over about 1300° C., at which point many conventional
superalloys begin to melt. Clearly, new materials must be developed if the efficiency
enhancements available at higher operating temperatures are to be exploited.

The so-called "refractory superalloys," as described in Koizumi et al., U.S.
Pat. No. 6,071,470, represent a class of alloys designed to operate at higher temperatures
than those of conventional superalloys. According to Koizumi et al., refractory
superalloys consist essentially of a primary constituent selected from the group
consisting of iridium (Ir), rhodium (Rh), and a mixture thereof, and one or more
additive elements selected from the group consisting of niobium (Nb), tantalum
(Ta), hafnium (Hf), zirco ium (Zr), uranium (U), vanadium (V), titanium (Ti), and
aluminum (Al). The refractory superalloys have a microstructure containing an FCC
(face-centered cubic)-type crystalline structure phase and an L12 type
crystalline structure phase, and the one or more additive elements are present
in a total amount within the range of from 2 atom % to 22 atom %.

SUMMARY OF INVENTION

Although the refractory superalloys have shown potential to become replacements
for conventional superalloys in present and future gas turbine engine designs,
it has been shown that many alloys of this class do not meet all of the desired
performance criteria for high-temperature applications. Therefore, the need persists
for alloys with improved high-temperature properties.

The present invention provides several embodiments that address this need. One
embodiment is an alloy comprising


palladium, in an amount ranging from about 1 atomic percent to about
41 atomic percent;
platinum, in an amount that is dependent upon the amount of palladium,
such that

a. for the amount of palladium ranging from about 1 atomic percent
to about 14 atomic percent, the platinum is present up to about an amount defined
by the formula (40+X) atomic percent, wherein X is the amount in atomic percent
of the palladium, and
b. for the amount of palladium ranging from about 15 atomic percent
up to about 41 atomic percent, the platinum is present in an amount up to about
54 atomic percent; and


the balance comprising rhodium, wherein the rhodium is present in an
amount of at least 24 atomic percent;
wherein the alloy comprises a microstructure that is essentially free
of L12-structured phase at a temperature greater than about 1000° C.



A second embodiment is an alloy comprising from about 5 atomic percent to about
40 atomic percent platinum and the balance comprising rhodium, wherein the alloy
further comprises a microstructure that is essentially free of L12-structured phase
at a temperature greater than about 1000° C.

A third embodiment is a gas turbine engine component comprising an alloy, the
alloy comprising:


palladium, in an amount ranging from about 1 atomic percent to about
41 atomic percent;
platinum, in an amount that is dependent upon said amount of palladium,
such that

a. for said amount of palladium ranging from about 1 atomic percent
to about 14 atomic percent, said platinum is present up to about an amount defined
by the formula (40+X) atomic percent, wherein X is the amount in atomic percent
of said palladium, and
b. for said amount of palladium ranging from about 15 atomic percent
up to about 41 atomic percent, said platinum is present in an amount up to about
54 atomic percent;


from about 0 atomic percent to about 5 atomic percent of a metal selected
from the group consisting of zirconium, hafnium, titanium, and mixtures thereof;
from about 0 atomic percent to about 5 atomic percent ruthenium; and
the balance comprising rhodium, wherein said rhodium is present in an
amount of at least 24 atomic percent;
wherein said alloy of said gas turbine engine component further comprises
a microstructure that is essentially free of L12-structured phase at a temperature
greater than about 1000° C.



BRIEF DESCRIPTION OF DRAWINGS

These and other features, aspects, and advantages of the present invention
will become better understood when the following detailed description is read with
reference to the accompanying drawings in which like characters represent like
parts throughout the drawings, wherein:

FIGS. 1-3 each depict a Pt-Rh-Pd ternary composition diagram, and

FIG. 4 is a schematic representation of an airfoil.

DETAILED DESCRIPTION

The discussion herein employs examples taken from the gas turbine industry, particularly
the portions of the gas turbine industry concerned with the design, manufacture,
operation, and repair of aircraft engines and power generation turbines. However,
the scope of the invention is not limited to only these specific industries, as
the embodiments of the present invention are applicable to many and various applications
that require materials resistant to high temperature and aggressive environments.
Unless otherwise noted, the temperature range of interest where statements and
comparisons are made concerning material properties is from about 1000° C.
to about 1300° C. The term "high temperature" as used herein refers to temperatures
above about 1000° C.

In several high temperature applications, such as, for example, gas turbines,
the selection of structural materials is made based upon the performance of materials
for a number of different properties. For gas turbine components, including, for
example, turbine blades (also known as "buckets") and vanes (also known as "nozzles"),
where the maximum metal temperatures typically range from about 1000° C. to
over about 1200° C. in present systems and temperatures over about 1300°
C. are envisioned for future applications, the properties that are considered include,
for example, oxidation resistance, melting temperature (the temperature at which
liquid metal begins to form as the material is heated), strength, coefficient of
thermal expansion, modulus of elasticity, and cost.

The term "oxidation resistance" is used in the art to refer to the amount of
damage sustained by a material when exposed to oxidizing environments, such as,
for example, high temperature gases containing oxygen. Oxidation resistance is
related to the rate at which the weight of a specimen changes per unit surface
area during exposure at a given temperature. In many cases, the weight change is
measured to be a net loss in weight as metal is converted to oxide that later detaches
and falls away from the surface. In other cases, a specimen may gain weight if
the oxide tends to adhere to the specimen, or if the oxide forms within the specimen,
underneath the surface, a condition called "internal oxidation." A material is
said to have "higher" or "greater" oxidation resistance than another if the material's
rate of weight change per unit surface area is closer to zero than that of the
other material for exposure to the same environment and temperature. Numerically,
oxidation resistance can be represented by the time over which an oxidation test
was run divided by the absolute value of the weight change per unit area.

"Strength" as used herein refers to the ultimate tensile strength of a
material, which is defined in the art to mean the maximum load sustained by a specimen
in a standard tensile test divided by the original cross-sectional area (i.e.,
the cross-sectional area of the specimen prior to applying the load).

Coefficient of thermal expansion (α) is the change in unit length
exhibited by a specimen of material per degree change in temperature. Modulus of
elasticity (E) is the ratio of tensile stress divided by tensile strain for elastic
deformation. These two quantities are considered in turbine material design and
selection because the product of these two quantities is proportional to the amount
of elastic stress generated between joined materials of differing thermal expansion
coefficients. Therefore, to minimize stresses, the product of E and α (herein
referred to as "E-alpha factor") is kept as low as possible.

Refractory superalloys, with their high content of highly environmentally
resistant elements such as iridium and rhodium, represent a class of materials
with potential for use in high temperature applications. However, as the data in
Table 1 indicate, several refractory superalloys with compositions according to
aforementioned U.S. Pat. No. 6,071,470 do not approach the oxidation resistance
of a standard nickel-based superalloy at a temperature of about 1200° C.


TABLE 1






Oxidation resistance for selected alloys








Oxidation Resistance



Alloy Designation (composition
(hr-cm2/mg)



numbers refer to atomic percent)
100 hr. test at about 1200° C.











1-A (Nickel-based superalloy)
16.7



1-B (15Zr + bal. Ir)
0.9



1-C (7Zr + bal. Rh)
7.1



1-D (10Zr + 6Nb + bal. Rh)
1.2








In refractory superalloy systems, oxidation resistance is primarily derived from
the presence of certain metals selected from the so-called "platinum group" in
the FCC phase. The platinum group comprises platinum (Pt), palladium (Pd), rhodium
(Rh), iridium (Ir), rhenium (Re), ruthenium (Ru), and osmium (Os). Where the primary
constituent of a refractory superalloy is rhodium, iridium, or mixtures thereof,
strength is primarily derived by the addition of elements that promote the formation
of the L12-structured phase. Because the L12-structured phase
usually forms in these alloys by a precipitation mechanism from the supersaturated
FCC ("matrix") phase, the elements that promote the formation of the L12-structured
phase are referred to herein as "precipitate strengthening metals." Such metals
include, for example, zirconium (Zr), niobium (Nb), tantalum (Ta), titanium (Ti),
hafnium (Hf), and mixtures thereof. The L12-structured phase has a generic
chemical formula of M3X, where M is a platinum group metal and X is
a precipitate strengthening metal. As the proportion of precipitate strengthening
metal in the alloy increases, the volume fraction of L12-structured
phase increases, which increases the strength of the alloy. However, as the volume
fraction of L12-structured phase increases, the amount of platinum group
metal present in the FCC matrix phase to provide oxidation resistance decreases-it
is "tied up" in the L12-structured phase. Refractory superalloys, therefore,
sacrifice a certain amount of oxidation resistance to enhance strength.

In contrast to the refractory superalloys of Koizumi et al., certain embodiments
of the present invention are alloys that are essentially free of the L12-structured
phase at a temperature greater than about 1000° C., and so the oxidation-resistant
elements present are not significantly tied up in precipitate phases. The term
"essentially free of the L12-structured phase" as used herein means
that an alloy microstructure contains less than about 5 volume percent of the L12-structured
phase. Formulation of alloys for high-temperature use is dependent upon an understanding
of the property requirements needed for particular applications, and the relationship
between alloy composition and properties. Some embodiments of the present invention
represent a specific "window" of composition based upon such an understanding.

One embodiment of the present invention is an alloy comprising rhodium, platinum,
and palladium, wherein the alloy comprises a microstructure that is essentially
free of L12-structured phase at a temperature greater than about 1000°
C. Some physical properties of these three elements, along with those of nickel
(Ni) for comparison, are given in Table 2.





Property
units
Rh
Pt
Pd
Ni













Melting Point
° C.
1966
1769
1552
1453


Density
g/cc
12.4
21.4
12
8.9


Linear Expansion
10-8/K
8.3
9.1
11.6
13.3


Coeff


Young's Modulus
GPa
414
171
117
207


Tensile Strength
MPa
758
138
228
827







Each of the elements platinum, palladium, and rhodium have a face-centered cubic
(FCC) crystal structure, and are soluble in each other such that the FCC structure
is maintained even when the three elements are mixed to form alloys. In terms of
oxidation resistance, at a temperature of about 1300° C. and using the oxidation
resistance of Pt as a baseline, Rh is about 2.5 times as resistant, and Pd is about
60% as resistant. By comparison, Ir is only about 2% as resistant as Pt at this
temperature, and nickel-based superalloys are close to or past their incipient
melting points (i.e., the lowest temperature at which localized melting of the
alloy occurs) and thus are very susceptible to oxidation.

The alloy embodiments of the present invention represent formulations designed
to balance the properties of the resulting alloy, by carefully controlling the
alloy composition, such that the alloy has properties that are acceptable for use
in a high temperature application, for example, a gas turbine engine. The formulation
of such an alloy comprising Pt, Pd, and Rh represents an optimization driven by
a series of compromises. For example, Pd is the least expensive element of the
three, so an alloy that is relatively rich in Pd is less expensive than an alloy
that is relatively lean in Pd. However, Pd also has the lowest oxidation resistance
of the three elements, and so the advantageous cost of the Pd-rich alloys is offset
by reduced oxidation resistance. Embodiments of the present invention have been
formulated using an analysis of this and several other alloy property trade-offs.
The factors considered during the analysis included, for example, oxidation resistance,
strength, cost, E-alpha factor, ease of alloy processing, reliability of joint
between the alloy and a typical nickel-based superalloy (i.e., the ability to form
a joint with acceptable strength and microstructure), and amount of diffusion interaction
between the alloy and a nickel-based superalloy substrate. These last two factors
are considered because in certain embodiments of the present invention, the alloy
is in direct contact with gas turbine airfoil materials, such as, for example,
nickel-based superalloys, and thus the reliability of the joint is one of several
important factors. The amount of diffusion interaction with a nickel-based superalloy
structure is also one of several important factors in these embodiments, where
the amount of interaction is desired to be as low as possible to avoid significantly
changing the local alloy chemistry at the interface between the alloy of the present
invention and the nickel-based alloy. If such a change occurs, low-melting-point
phases may form which will severely degrade the performance of the overall component.
For the alloy of the present invention, one interaction that is considered potentially
detrimental is that between palladium and nickel, where incorporation of 10 atomic
percent Pd into nickel, for example, reduces the melting point by over 100°
C. In addition, elements diffusing from the airfoil material into the alloy of
the present invention will lower the inherent oxidation resistance of the alloy.
Those skilled in the art will appreciate, therefore, that the need to mitigate
the diffusion interaction property enhances the appeal of keeping the Pd concentration
in the alloy as low as the combination of desired properties will allow.

In certain embodiments, the alloy of the present invention has an oxidation resistance
of at least about 16 hour-cm2/mg at a temperature of about 1200° C., which
is at least about as high as the oxidation resistance of the baseline nickel-based
superalloy in Table 1. Certain embodiments are provided in which the alloy has
an ultimate tensile strength greater than about 100 megapascals (MPa) at a temperature
of about 1200° C., and in some embodiments, the alloy has an E-alpha factor
less than about 3.6 MPa/° C. at a temperature of about 1000° C.

Certain embodiments of the present invention provide that the alloy of the
present invention further comprises a metal selected from the group consisting
of zirconium, hafnium, titanium, and mixtures thereof, and in some embodiments,
the alloy comprises from about 0 atomic percent to about 5 atomic percent of a
metal selected from the group consisting of zirconium, hafnium, titanium, and mixtures
thereof, herein referred to as "strengtheners". Particular embodiments provide
that the metal comprises zirconium. In the alloys of the present invention, these
elements serve to improve alloy strength, but not by forming the L12-structured
phase of the refractory superalloys. The amount of strengtheners added to the alloys
of the present invention is controlled to be below the solubility limit at about
1000° C. for these elements in the FCC Pt-Rh-Pd solid solution.
Controlling the amount of strengtheners in this way ensures that the alloys of
the present invention remain essentially free of L12-structured phase
at a temperature greater than about 1000° C. The strengthening is instead
achieved through solid solution strengthening, wherein the strengthening element
remains dissolved in the FCC phase and hardens the FCC phase by straining the surrounding
FCC crystal structure. Additionally, as an alloy of the present invention comprising
strengtheners is exposed to high-temperature service conditions, the strengtheners
oxidize to form a uniform dispersion of very small, very hard oxide particles that
reinforce the FCC alloy.

In some embodiments, the alloy of the present invention further comprises from
about 0 atomic percent to about 5 atomic percent ruthenium. This element has been
found to enhance the ability of high temperature alloys to resist both internal
and external oxidation, when present in an amount consistent with the above composition range.

Referring to FIG. 1 (a Pt-Rh-Pd ternary composition diagram),
in certain embodiments of the alloy of the present invention, the Pd is present
in an amount ranging from about 1 atomic percent (composition boundary 1)
to about 41 atomic percent (composition boundary 2); the Pt is present in
an amount that is dependent upon the amount of palladium, such that


a. for the amount of palladium ranging from about 1 atomic percent to
about 14 atomic percent, the platinum is present up to about an amount defined
by the formula (40+X) atomic percent (composition boundary 3), wherein X
is the amount in atomic percent of the palladium, and
b. for the amount of palladium ranging from about 15 atomic percent
up to about 41 atomic percent, the platinum is present in an amount up to about
54 atomic percent (composition boundary 4); and
the balance comprising rhodium, wherein the rhodium is present in an
amount of at least 24 atomic percent (composition boundary 5). The alloys
according to the above embodiment are therefore contained in the composition field
6 as shown in FIG. 1.



Referring to FIG. 2, in particular embodiments the platinum is present
up to the lesser of about 52 atomic percent and an amount defined by the formula
(30+X) atomic percent (composition boundary 21), wherein X is the amount
of the palladium; the palladium is present in an amount that is dependent on the
amount of the platinum, such that


a. for the amount of platinum ranging from about 0 to about 21 atomic
percent, the palladium is present in an amount ranging from about 1 atomic percent
(composition boundary 22) to about an amount defined by the formula (15+Y)
atomic percent (composition boundary 23), wherein Y is the amount in atomic percent
of the platinum, and
b. for the amount of platinum ranging from about 22 atomic percent to
about 52 atomic percent, the palladium is present in an amount ranging from about
1 atomic percent (composition boundary 22) to about 36 atomic percent (composition
boundary 24); and
the balance comprises rhodium, wherein the rhodium is present in an
amount ranging from about 26 atomic percent (composition boundary 25) to
the lesser of about 95 atomic percent and about an amount defined by the formula
(85+2Y) atomic percent (composition boundary 26), wherein Y is the amount
in atomic percent of the platinum. The alloys according to the above embodiment
are therefore contained in the composition field 27 as shown in FIG. 2.



Referring to FIG. 3, in particular embodiments, the alloy of the present
invention comprises from about 21 atomic percent platinum (point A) to about 52
atomic percent platinum (point B); from about 22 atomic percent palladium (composition
boundary 31) to about 36 atomic percent palladium (composition boundary
32); and the balance comprises rhodium, wherein the rhodium is present in
an amount ranging from about 26 atomic percent rhodium (composition boundary 33)
to about 43 percent rhodium (composition boundary 34). The alloys according
to the above embodiment are therefore contained in the composition field 35
as shown in FIG. 3.

In other particular embodiments, the alloy of the present invention comprises
from about 3 atomic percent platinum (point C) to about 29 atomic percent platinum
(point D); from about 1 atomic percent palladium (composition boundary 36)
to about 6 atomic percent palladium (composition boundary 37); and the balance
comprises rhodium, wherein the rhodium is present in an amount ranging from about
70 atomic percent (composition boundary 38) to the lesser of about 94 atomic
percent and about an amount defined by the formula (85+2Y) atomic percent (composition
boundary 39), wherein Y is the amount in atomic percent of the platinum.
The alloys according to the above embodiment are therefore contained in the composition
field 40 as shown in FIG. 3.

The alloys of composition field 35 are comparatively rich in Pd and lean
in Rh when compared to the alloys of composition field 40. The alloys of
composition field 35 are optimized compositions wherein factors such as,
for example, cost and ductility are weighted more heavily than for the alloys of
composition field 40 in an optimization analysis. The alloys of composition
field 40 are optimized compositions wherein oxidation resistance is weighted
comparatively heavily in an optimization analysis. It will be appreciated by those
skilled in the art, therefore, that alloys of composition field 40 are,
for example, more oxidation resistant, more expensive, and less ductile than the
alloys of composition field 35, and that the selection of any particular
alloy composition is done based upon the particular requirements of the application
for which the alloy is being selected.

Referring again to FIG. 1, in particular embodiments, the alloy of the
present invention consists essentially of palladium, in an amount ranging from
about 1 atomic percent (composition boundary 1) to about 41 atomic percent
(composition boundary 2); platinum, in an amount that is dependent upon
the amount of palladium, such that


a. for the amount of palladium ranging from about 1 atomic percent to
about 14 atomic percent, the platinum is present up to about an amount defined
by the formula (40+X) atomic percent (composition boundary 3), wherein X
is the amount in atomic percent of the palladium, and
b. for the amount of palladium ranging from about 15 atomic percent
up to about 41 atomic percent, the platinum is present in an amount up to about
54 atomic percent (composition boundary 4);
from about 0 atomic percent to about 5 atomic percent of a metal selected
from the group consisting of zirconium, hafnium, titanium, and mixtures thereof;
from about 0 atomic percent to about 5 atomic percent ruthenium; and
the balance rhodium, wherein the rhodium is present in an amount of at least 24
atomic percent (composition boundary 5); wherein the alloy further comprises
a microstructure that is essentially free of L12-structured phase at
a temperature greater than about 1000° C.



Those skilled in the art will appreciate that additions of carbon and boron
to the embodiments of the present invention may marginally improve strength and
other properties as they do in many other alloy systems, and that such additions
are generally up to about 0.25 atomic percent for each of these two elements. Furthermore,
incidental impurities, such as nickel, cobalt, chromium, iron, and other metals,
are often present in processed alloys and may be present in alloys provided by
the present invention in amounts of up to about 0.5 atomic percent, for example.

Other embodiments of the present invention provide an alloy comprising from
about 5 atomic percent to about 40 atomic percent platinum and the balance comprising
rhodium (herein referred to as a "Rh-Pt alloy"), wherein the alloy further
comprises a microstructure that is essentially free of L12-structured
phase at a temperature greater than about 1000° C. The alternatives for properties
and the presence of strengtheners and ruthenium, as described for above embodiments,
are also applicable to this embodiment. In certain embodiments, the alloy comprises
from about 5 atomic percent to about 30 atomic percent platinum and the balance
comprises rhodium, and in particular embodiments, the alloy comprises from about
5 atomic percent to about 10 atomic percent platinum; and the balance comprises
rhodium. Certain embodiments provide an alloy consisting essentially of from about
5 atomic percent to about 40 atomic percent platinum; from about 0 atomic percent
to about 5 atomic percent of a metal selected from the group consisting of zirconium,
hafnium, titanium, and mixtures thereof; from about 0 atomic percent to about 5
atomic percent ruthenium; and the balance rhodium; wherein said alloy comprises
a microstructure that is essentially free of L12-structured phase at
a temperature greater than about 1000° C. The Rh-Pt alloy compositions
described are optimized to provide a high level of oxidation resistance and strength,
suitable for use in a high-temperature application, for example, a gas turbine
engine component.

Another embodiment of the present invention provides a gas turbine engine
component comprising the alloy of the present invention. The alternatives for composition
and properties of the alloy in these gas turbine engine component embodiments are
the same as discussed above for the alloy embodiments.

In some embodiments, the gas turbine engine component is a blade of an aircraft
engine, a vane of an aircraft engine, a bucket of a power generation turbine engine,
or a nozzle of a power generation turbine. Referring to FIG. 4, in particular embodiments
the gas turbine engine component comprises an airfoil 10, and the airfoil
comprises the alloy. Specific embodiments provide that the airfoil 10 comprises
a tip section 11, a leading edge section 12, and a trailing edge
section 13, and wherein at least one of said tip section 11, said
leading edge section 12, and said trailing edge section 13 comprises
said alloy. Having only particular sections (i.e., those sections known to experience
the most aggressive stress-temperature combinations) of the airfoil comprise the
alloy of the present invention minimizes certain drawbacks of alloys comprising
significant amounts of rhodium, platinum, or palladium, including their high cost
and high density in comparison to conventional airfoil materials. These drawbacks
have a reduced effect on the overall component because the rhodium-based high temperature
alloy comprises only a fraction of the overall surface area of the component. The
properties of the component are thus "tailored" to the expected localized environments,
reducing the need for compromise during the design process and increasing the expected
operating lifetimes for new and repaired components. As described above, E-alpha
factor and diffusion interaction are considered to be two of several important
factors in the selection of a suitable alloy for embodiments where the alloy is
to comprise only particular sections of a gas turbine component, because the alloy
is to be in direct contact with a nickel-based alloy as in, for example, a coating
or a brazed or welded joint.

Alloys set forth herein as embodiments of the present invention are made using
any of the various traditional methods of metal production and forming. Traditional
casting, powder metallurgical processing, directional solidification, and single-crystal
solidification are non-limiting examples of methods suitable for forming ingots
of these alloys. Thermal and thermo-mechanical processing techniques common in
the art for the formation of other alloys are suitable for use in manufacturing
and strengthening the alloys of the present invention. For embodiments where the
alloy of the present invention comprises strengtheners, the alloy may be given
a heat-treatment in air at a temperature suitable to form a dispersion of oxide
particles as described above. For situations where alloys of the present invention
are joined to a Ni-base superalloy or other conventional material, heat treatments
are limited to temperatures below those that will degrade or melt the conventional material.

The examples presented below are intended to demonstrate results obtained with
alloys of the present invention and are not to be considered as limiting the scope
of the present invention in any way.

EXAMPLE 1

Several alloys with compositions according to embodiments of the present
invention were prepared for an oxidation test to be run for 100 hours at a temperature
of about 1300° C. The tested compositions are presented in Table 3. The test
specimens were cylindrical pins with a diameter of about 2.5 mm and length of about
30 mm. After exposure, the diameter of each pin was measured and the change in
radius was used as a measure of oxidation resistance. Each of the alloys tested
registered a radius change of less than about 0.003 mm. For comparison, a similar
specimen of a single crystal nickel-based superalloy, tested at a significantly
lower temperature (about 1200° C.) to avoid incipient melting, registered
a radius change of about 0.03 mm.









Composition



Designation
(numbers represent atomic percent)








A
60Rh-20Pt-20Pd



B
60Rh-25Pd-10Pt-2Ru-3Zr



C
40Rh-34.5Pt-25Pd-0.5Zr








EXAMPLE 2

Alloys designated A and B in Table 3, above, were tested for ultimate tensile
strength at about 1200° C., along with a specimen of a single crystal nickel-based
superalloy. The ultimate tensile strength results were as follows: Nickel-based
alloy, 152 MPa; Alloy A, 124 MPa; Alloy B, 152 MPa.

While only certain features of the invention have been illustrated and described
herein, many modifications and changes will occur to those skilled in the art.
It is, therefore, to be understood that the appended claims are intended to cover
all such modifications and changes as fall within the true spirit of the invention.

* * * * *

[bammbamm] 28/6/2008 08:59

Just stumbled across this thread and what a great read it is.

Apologies if it has already been mentioned, I recall a newspaper article a few weeks ago that talked about the use of palladium in the aviation industry and the development of 'greener' engines. The article was basically saying that jet engine manufacturers were buying large quantities of 'ium metals for use in their next generation engines. The use of these metals allowed higher temperatures, better fuel economy and improved emissions.

[chartsmart] 27/6/2008 20:02

Palladium prices climbed to an average of $359.21 in 2007, up 10.7% from the $324.38 averaged in 2006. During the first quarter of this year prices spiked to $600 on an intraday basis, but have since come off. Palladium prices averaged $448.80 through May of this year, up 25.7% from the same period last year.

Total palladium supply declined to 8,509,000 ounces in 2007, down 0.8% from 8,575,000 ounces in 2006. This year total supply is projected to contract further to 8,433,000 ounces. Last year the bulk of the decline came from lower mine output in South Africa. This year lower mine output from South Africa and reduced Russian exports are projected to push total supply lower. Secondary supply surged 13.7% last year and could increase 5.0% this year.

Total fabrication demand rose to 7,960,000 ounces last year, up 7.0% from 7,442,000 ounces in 2006. Demand from the auto sector continued to increase last year, rising 6.2%. Palladium demand in electronics, dental, and other uses also increased, as well as Chinese demand. This year total fabrication demand could rise 5.2% to 8,378,000 ounces. Automotive demand is projected to increase 7.2%. Palladium use in all of the other major sectors is also projected to increase.

The net surplus in the palladium market is projected to decline to 56,000 ounces this year, down sharply from 548,000 ounces in 2007, and just a fraction of 1,133,000 ounces in 2006.

[le couteau tombant] 27/6/2008 13:54

No numbers on Mintage 2007

2005 looks liquid enough.

If I assume China 2008 10,280,000 Vehicle units at

72.50% =7,453,000 Petroleum 85% Palladium assume 6 g PGM=38,010,300 grammes Pd
27.50% 2,827,000 Diesel 5% Palladium assume 6 g PGM=848,100 grammes Pd

I come to 38,858,400 grammes Pd ie 1,249,325.64 toz from China Automotive Demand estimated.

[le couteau tombant] 27/6/2008 13:37

Palladium Maple Leaf Coins
Palladium Maple Leaf coins by the Royal Canadian Mint offer the palladium investment community the option of government mint-issued palladium investment coins. Prior to the Palladium Maple Leaf coins' release, 1-oz Credit Suisse and 1-oz PAMP palladium bars were investors' only viable options.

Palladium Maple Leaf coins contain one ounce of 99.95% pure palladium and are $50 legal tender coins in Canada. Palladium Maple Leaf coins are the first palladium coins minted by the Royal Canadian Mint and are presently the only legal tender palladium coins being minted by a major government mint. Palladium Maple Leaf coins will be individually sealed in thermatron, in strips of ten coins.

The first run of Palladium Maple Leaf coins were limited to 40,000 and were dated 2005 (minted early November 2005). This means that 2005-dated Palladium Maple Leaf coins probably will turn out to be a small mintage relative to years during which the coins will be minted for twelve months. Therein lies a unique opportunity for the palladium investment community.

Although the Royal Canadian Mint introduced Palladium Maple Leafs to go after the investment community's interest in palladium coins, because only 40,000 of the 2005-dated coins were minted they could become collectibles. The operative words are "could be" because there is not a good history of palladium coins appealing to collectors.

Still, before the first shipment of Palladium Maple Leaf coins was made, one major wholesaler had already sold most of its allotment. Investors who like palladium coins should move quickly to get a position in 2005-dated Palladium Maple Leafs. The coins are being offered at lower premiums than the Credit Suisse and PAMP 1-oz palladium bars, and the coins may achieve collector status.

If you would like to discuss buying palladium coins or the palladium investment market, call us.

[le couteau tombant] 27/6/2008 13:29

Only 1200 of these across all 4 versions in 2006

[le couteau tombant] 27/6/2008 13:28

Getting some supply numbers of Canadian 1 troy ounce Maple Leaf Coins,apparently only 40,000 minterentd 2005 off to get 2006 and 2007 supply numbers.

Royal Canadian Mint Introduces Palladium Maple Leaf Coins
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In early November, the Royal Canadian Mint struck for the first time legal tender palladium coins. The Royal Canadian Mint is one of the world's premier mints, and the Palladium Maple Leafs ad to the Mint's stellar line of coins. (The Mint's Gold Maple Leafs are the world's best-selling 24-karat gold bullion coins.) The first run of Palladium Maple Leafs will be dated 2005 and limited to 40,000 coins.

Only one size of Palladium Maple Leaf coins will be minted: a one ounce coin with a legal tender value of $50. The coins will be 99.95% pure, which is standard for palladium investment products, including the popular Credit Suisse 1-oz bars and the PAMP 1-oz bars.

Palladium Maple Leaf coins will be individually sealed in thermatron, in strips of ten coins. The new coins are the only legal tender palladium bullion coins being minted by a major government mint.

The 2005-dated Palladium Maple Leaf coins stand a chance of achieving collector premiums with only 40,000 being minted. That is because the 40,000 2005-dated coins probably will turn out to be a small mintage relative to years during which the coins will be minted for twelve months.

However, buyers looking for Palladium Maple Leafs to pick up collector premiums need to be aware that there is not a good history of palladium coins appealing to collectors. Yet before the first shipment of Palladium Maple Leaf coins was made, one major wholesaler had already sold most of its allotment.

Palladium is a member of a six-metal group called the Platinum Group Metals and is a by-product of platinum and nickel mining. Because palladium has similar chemical characteristics to platinum, it is often used as a substitute for platinum when cost effective to do so.

The primary demand for palladium is the manufacture of catalytic converters for auto emissions control. Other uses include electronics, dental, chemical, and jewelry. The palladium market is relatively small compared with the markets for gold, silver, and platinum, the best-known and most popular precious metals investments.

Investors who like palladium should move quickly to get a position in 2005-dated Palladium Maple Leafs. The coins are being offered at lower premiums than the Credit Suisse 1-oz palladium bars and the PAMP 1-oz palladium bars, and coins stand an outside chance of picking up collector premiums.

Bill Haynes heads CMI Gold & Silver Inc, one of the nation's oldest precious metals dealers. See CMIGS' website at This article may be reprinted provided this signature remains intact, including the direct link to CMI Gold & Silver Inc.

Article by: Bill Haynes

[le couteau tombant] 26/6/2008 14:10

Precious Metals especially PGMs going up very fast!

[le couteau tombant] 26/6/2008 14:03

Precious Metals Really beginning to take off now!

[le couteau tombant] 26/6/2008 12:35

Tim,

Someone's accumulating.

ETF Securities Pd ETF PHPD up another 20,000 toz in last 2 days Long Holding, ie 9.60% increase in Long Position.



Palladium per 22/06/2008 2,084,338 1/10th toz



ETFS Physical Palladium

2,284,338