U.S. patent application number 15/100809 was filed with the patent office on 2016-10-06 for method for processing a dispersion-hardened platinum composition.
This patent application is currently assigned to HERAEUS DEUTSCHLAND GMBH & CO. KG. The applicant listed for this patent is HERAEUS DEUTSCHLAND GMBH & CO. KG. Invention is credited to Dirk MAIER.
Application Number | 20160289808 15/100809 |
Document ID | / |
Family ID | 52101298 |
Filed Date | 2016-10-06 |
United States Patent
Application |
20160289808 |
Kind Code |
A1 |
MAIER; Dirk |
October 6, 2016 |
METHOD FOR PROCESSING A DISPERSION-HARDENED PLATINUM
COMPOSITION
Abstract
A method for processing a dispersion-hardened platinum
composition is provided. A three-dimensional body of a
dispersion-hardened platinum composition containing at least 70% by
weight platinum and maximally 29.95% by weight other precious
metals, as well as 0.05% by weight to 0.5% by weight of at least
one partially-oxidized non-precious metal selected from zirconium,
cerium, scandium, and yttrium is provided and cold formed, whereby
the cross-sectional area of the three-dimensional body is reduced
by maximally 20% during the cold forming, Subsequently a
temperature treatment is performed on the cold-formed
three-dimensional body, in which the cold-formed product is
tempered at at least 1,100.degree. C. for at least one hour. A
method for producing a product made of a dispersion-hardened
platinum composition, a dispersion-hardened platinum material
obtained according to the processing method, and the use of a
dispersion-hardened platinum material are also described.
Inventors: |
MAIER; Dirk; (Offenbach,
DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
HERAEUS DEUTSCHLAND GMBH & CO. KG |
Hanau |
|
DE |
|
|
Assignee: |
HERAEUS DEUTSCHLAND GMBH & CO.
KG
Hanau
DE
|
Family ID: |
52101298 |
Appl. No.: |
15/100809 |
Filed: |
December 4, 2014 |
PCT Filed: |
December 4, 2014 |
PCT NO: |
PCT/EP2014/076600 |
371 Date: |
June 1, 2016 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B22F 2999/00 20130101;
B22F 2999/00 20130101; C22F 1/14 20130101; C22C 5/04 20130101; C22C
32/0021 20130101; B22F 2003/248 20130101; C22C 1/1078 20130101;
B22F 3/18 20130101; B22F 2003/248 20130101 |
International
Class: |
C22F 1/14 20060101
C22F001/14; C22C 5/04 20060101 C22C005/04 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 6, 2013 |
DE |
10 2013 225 187.4 |
Claims
1.-15. (canceled)
16. A method for processing a dispersion-hardened platinum
composition, comprising: providing a three-dimensional body of a
dispersion-hardened platinum composition comprising at least 70% by
weight platinum, maximally 29.95% by weight other precious metals,
and 0.05% by weight to 0.5% by weight of at least one
partially-oxidized non-precious metal selected from zirconium,
cerium, scandium, and yttrium; cold forming the dispersion-hardened
platinum composition to form a cold-pressed three-dimensional body,
wherein a cross-sectional area of the three-dimensional body is
reduced by maximally 20% during the cold forming; and subsequently
performing a temperature treatment on the cold-formed
three-dimensional body by tempering at a temperature of at least
1,100.degree. C. for at least one hour.
17. The method according to claim 16, further comprising before the
cold forming step, forming the dispersion-hardened platinum
composition by a hot forming process at a temperature of at least
800.degree. C.
18. The method according to claim 16, wherein multiple consecutive
cold forming steps are performed and the cross-sectional area of
the three-dimensional body is reduced by more than 20% by the cold
forming steps, wherein each individual cold forming step reduces a
cross-sectional area of the three-dimensional body by maximally
20%, and wherein a temperature treatment is performed on the
cold-formed three-dimensional body between each cold forming step
by tempering at a temperature of at least 1,100.degree. C. for at
least one hour.
19. The method according to claim 18, wherein the tempering
comprises tempering at a temperature of at least 1,550.degree. C.
for at least 24 hours, at a temperature of at least 1,600.degree.
C. for at least 12 hours, at a temperature of at least
1,650.degree. C. for at least one hour, or at a temperature of
1,690.degree. C. to 1,740.degree. C. for at least 30 minutes during
the last temperature treatment after the last cold forming
step.
20. The method according to claim 16, wherein the cold forming
comprises drawing, pushing, pressing, or rolling a wire, sheet or
tube of the dispersion-hardened platinum composition, wherein a
cross-sectional area of the wire, the sheet, or the tube, or a
thickness of the sheet is reduced by maximally 20% during the cold
forming step.
21. The method according to claim 16, wherein the cold forming is
performed at a temperature of 500.degree. C. or less.
22. The method according to claim 16, wherein the temperature
treatment heals defects of the three-dimensional body.
23. The method according to claim 16, wherein the tempering is
performed at a temperature of at least 1,250.degree. C. for at
least one hour.
24. The method according to claim 16, wherein the
dispersion-hardened platinum composition is produced from a
composition comprising at least 70% by weight platinum, maximally
29.95% by weight other precious metals, and 0.05% by weight to 0.5%
by weight of at least one non-precious metal selected from
ruthenium, zirconium, cerium, scandium, and yttrium by at least
partial oxidation of the at least one non-precious metal.
25. The method according to claim 24, wherein the oxidation of the
at least one non-precious metal is performed at a temperature
between 600.degree. C. and 1,600.degree. C. in an oxidizing
atmosphere.
26. A dispersion-hardened platinum material produced by the method
according to claim 16.
27. A cylindrical three-dimensional body made of the
dispersion-hardened platinum material according to claim 26,
wherein the body withstands a tensile strain of 9 MPa in a
direction of the length of the three-dimensional body at a
temperature of 1,600.degree. C. for at least 40 hours without
tearing.
28. A sheet metal made of the dispersion-hardened platinum material
according to claim 26, wherein the sheet has a rectangular
cross-section of 0.85 mm.times.3.9 mm and a length of 140 mm, and
wherein the sheet sags by less than 40 mm after 40 hours in a oven
chamber at 1,650.degree. C. on two parallel-arranged cylindrical
rods with a circular cross-section and a diameter of 2 mm at a
distance of 100 mm when the middle of the sheet metal is exposed to
a load of 30 g.
29. A sheet metal, a tube, a wire, or a product formed from a wire,
tube, and/or sheet metal comprising the dispersion-hardened
platinum material according to claim 26.
30. The dispersion-hardened platinum material according to claim
26, wherein the dispersion-hardened platinum material comprises
0.05% by weight to 0.3% by weight of at least one at least
partially-oxidized non-precious metal selected from zirconium,
cerium, scandium, and yttrium.
31. A device comprising a dispersion-hardened platinum material
produced according to the method of claim 16.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Section 371 of International
Application No. PCT/EP2014/076600, filed Dec. 4, 2014, which was
published in the German language on Jun. 11, 2015 under
International Publication No. WO 2015/082630 A1 and the disclosure
of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] Form bodies made of platinum are commonly used in
high-temperature processes, in which the material must possess high
corrosion resistance. For example, components made of platinum
exposed to mechanical loads, such as, for example, stirrers or
glass fiber jet troughs, are used in the glass industry. However,
its low mechanical strength at high temperatures is a disadvantage
of platinum when used as a material. For this reason,
dispersion-hardened platinum compositions are generally used in the
high-temperature processes referred to above.
[0003] The production and processing of these materials are known,
for example, from printed specifications GB 1 340 076 A, GB 2 082
205 A, EP 0 683 240 A2, EP 1 188 844 A1, and EP 1 964 938 A1.
[0004] The production of components from dispersion-hardened
platinum compositions generally starts with generating an ingot
that is being hot rolled. The semi-finished product thus obtained
can then be cold-formed.
[0005] Forming at low temperatures enables inexpensive adaptation
to individual requirements. However, it has been evident that the
mechanical properties of dispersion-hardened materials are not yet
sufficiently good or, at least, could be better in these forming
techniques. The components have too-short service lives for some
applications or need to be replaced more frequently than desired.
This replacement is associated with high costs. However, forming at
high temperatures (so-called hot forming) is very expensive and
difficult since the machinery used for this purpose is very
elaborate.
BRIEF SUMMARY OF THE INVENTION
[0006] Accordingly, it is the object of the invention to overcome
the disadvantages of the prior art. In particular, the method is to
enable inexpensive adaptation of components made of platinum
compositions to individual requirements while improving the
mechanical properties. Concurrently, the components thus obtained
are to have a long service life and show as little wear and tear as
possible. Moreover, the method should be easy and inexpensive to
implement. In addition, the formed components should show good
processing properties, in particular, welding properties.
[0007] The invention thus relates to a method for processing a
dispersion-hardened platinum composition. Moreover, the present
invention describes a method for producing a product from a
dispersion-hardened platinum composition. Moreover, the present
invention relates to a product obtained from this method and the
use of these platinum compositions.
[0008] The objects of the invention are solved by a method for
processing of a dispersion-hardened platinum composition
characterized by the steps of:
Providing a three-dimensional body of a dispersion-hardened
platinum composition comprising at least 70% by weight platinum and
maximally 29.95% by weight other precious metals, as well as 0.05%
by weight to 0.5% by weight of at least one partially-oxidized
non-precious metal selected from zirconium, cerium, scandium, and
yttrium; cold forming the dispersion-hardened platinum composition,
whereby the cross-sectional area of the three-dimensional body made
of the dispersion-hardened platinum composition is reduced by
maximally 20% during the cold forming; and subsequently performing
a temperature treatment on the cold-formed three-dimensional body,
in which the cold-formed product is tempered at a temperature of at
least 1,100.degree. C. for at least one hour.
DETAILED DESCRIPTION OF THE INVENTION
[0009] In the scope of the invention, cross-sectional area shall be
understood to be the surface area of the surface formed by an
(imaginary) section through the three-dimensional body. The plane
defined by the cross-sectional area does not necessarily have to be
situated perpendicular or essentially perpendicular to the longest
extension of the three-dimensional body.
[0010] The percent by weight specifications given above add up to
100%, whereby the weight of the non-precious metals relates to the
weight of metal.
[0011] Preferably, the non-precious metal or non-precious metals
are oxidized with oxygen at a level of at least 70%, preferably at
least 90%. In this context, all oxidation stages of the
non-precious metals are taken into consideration, such that,
preferably, at most 30 atom-%, particularly preferably at most 10
atom-%, of the non-precious metal are present as metal, i.e., in
the formal oxidation stage of 0.
[0012] Preferably, the dispersion-hardened platinum composition
contains 0.05% by weight to 0.5% by weight, particularly preferably
0.1% by weight to 0.4% by weight, and specifically preferably 0.15%
by weight to 0.3% by weight of the at least partially-oxidized
non-precious metal.
[0013] High fractions of non-precious metal oxides lead to longer
service lives of the three-dimensional bodies when exposed to
mechanical strain. Three-dimensional bodies having low fractions of
non-precious metal oxides show advantages with regard to the
processing properties, for example welding properties, of the
three-dimensional bodies.
[0014] A three-dimensional body is provided in the method according
to the present invention. The term three-dimensional body shall be
understood comprehensively in this context. Preferably, a
three-dimensional body can take the shape of a sheet metal, a tube
or a wire.
[0015] In this context, the extension of the three-dimensional body
in the three directions of space is not subject to any particular
limitations, but can be selected according to the requirements.
[0016] Accordingly, the sheet metals, tubes or wires provided can
have a thickness in the range of 0.1 mm to 10 mm, preferably 0.3 mm
to 5 mm. In this context, thickness refers to the minimal extension
of a three-dimensional body. In the case of a wire, this is the
diameter, and in the case of a tube, this is the difference between
outer and inner radius, which is also called wall thickness of the
tube.
[0017] The platinum composition that can be used according to the
invention comprises at least 70% by weight platinum and maximally
29.95% by weight of other precious metals. Accordingly, the
composition can essentially consist of platinum and the at least
partially-oxidized non-precious metals specified above.
Accordingly, the platinum material can be pure platinum other than
common impurities with the at least partially-oxidized non-precious
metals admixed to it. Moreover, the platinum composition can
further comprise other precious metals, in which case the platinum
composition is a platinum alloy.
[0018] The invention can provide other precious metals to be
selected from ruthenium, rhodium, gold, palladium, and iridium.
[0019] The three-dimensional body provided is cold-formed according
to the method according to the invention. The term "cold forming"
is known in professional circles, whereby this forming takes place
at relatively low temperatures below the recrystallization
temperature of the platinum composition and comprises, in
particular, drawing, pressing, deep drawing, cold rolling, cold
hammering, and pushing. Forming comprises an extensive deformation
of the three-dimensional body. Preferably, the invention can
provide at least 50%, particularly preferably at least 75%, and
specifically preferably at least 95% of the volume of the
three-dimensional body to be subjected to a deformation.
Accordingly, if the three-dimensional body is, for example, a sheet
metal, preferably at least 50%, particularly preferably at least
75%, and specifically preferably at least 95% of the surface of the
sheet metal are exposed to a force and/or a pressure, for example
by rolling. In the case of a sheet metal, the surface can be
simplified to be the surfaces that are perpendicular to the minimal
extension of the three-dimensional body (thickness). If the
three-dimensional body is, for example, a wire or a tube,
preferably at least 50%, particularly preferably at least 75%, and
specifically preferably at least 95% of the length of the wire or
tube are exposed to a force, for example by drawing.
[0020] It is essential to the invention that only a relatively low
forming takes place during cold forming. The cross-sectional area
of the three-dimensional body made of the dispersion-hardened
platinum composition is reduced by maximally 20%, particularly
preferably by maximally 18%, and specifically preferably by
maximally 15%. These values are related to the cross-sectional area
of the three-dimensional body, which is reduced maximally. In the
case of a sheet metal, which is being rolled in one direction only,
the reduced cross-sectional area results, for example, from the
thickness and the non-extended extension of the three-dimensional
body. In the case of a wire or a tube, the reduction of the
cross-sectional area results from the change of the diameter and/or
wall thickness. Since the volume of the body does not change due to
the forming, at least one cross-sectional area must be enlarged
during a forming process. For example, the length of a sheet metal,
tube or wire will increase during a forming process such that the
surface area in the direction in which the length increases will
increase as well. The directions in which the forming forces act,
engage, in particular, parallel or perpendicular to the plane
defined by the cross-sectional area.
[0021] A preferred embodiment provides the cross-sectional area of
the three-dimensional body made of the dispersion-hardened platinum
composition to be reduced by at least 5%, preferably by at least
8%, and particularly preferably by at least 10% during cold
forming.
[0022] It has been found that the internal damage to the
dispersion-hardened three-dimensional body upon forming which is
associated with a reduction of the cross-sectional area of less
than 5% and subsequent annealing does not contribute significantly
to an improvement of the creep strength. The lower the change of
the cross-sectional area per forming step in the specified range,
the lesser is the impact on the improvement of the creep strength
as compared to forming processes associated with a reduction of the
cross-sectional area of 5% to 20%, preferably of 8% to 18%, and
specifically preferably of 10% to 15%.
[0023] Moreover, the invention can provide a wire to be drawn or
pressed during cold forming, whereby the cross-sectional area of
the wire made of the dispersion-hardened platinum composition is
reduced by maximally 20%, particularly preferably by maximally 18%,
and specifically preferably by maximally 15% during the cold
forming, or a sheet metal to be rolled, drawn, pressed or pushed
during cold forming, whereby the cross-sectional area of the sheet
metal or the thickness of the sheet metal is reduced by maximally
20%, particularly preferably by maximally 18%, and specifically
preferably by maximally 15% during cold forming, or a tube to be
rolled, drawn or pressed during cold forming, whereby the
cross-sectional area of the tube made of the dispersion-hardened
platinum composition is reduced by maximally 20%, particularly
preferably by maximally 18%, and specifically preferably by
maximally 15% during cold forming.
[0024] The invention can provide no micro-fissures or pores to
arise or less than 100 micro-features and/or less than 1,000 pores
per cubic millimeter to arise on the inside of the
dispersion-hardened platinum composition during the cold
forming.
[0025] After the cold forming of the three-dimensional body, a
temperature treatment of the cold-formed three-dimensional body
follows, in which the cold-formed product is tempered at a
temperature of at least 1,100.degree. C. for at least one hour. The
tempering can preferably take place over a period of time of at
least 90 minutes, more preferably at least 120 minutes,
particularly preferably at least 150 minutes, and specifically
preferably at least 180 minutes. The temperature at which the
tempering is performed can preferably be at least 1,200.degree. C.,
particularly preferably at least 1,250.degree. C., more
particularly preferably at least 1,300.degree. C., and specifically
preferably at least 1,400.degree. C.
[0026] Moreover, the invention can provide the cold-formed
three-dimensional body to be tempered at a temperature of at least
1,250.degree. C. for at least one hour, preferably at a temperature
of 1,400.degree. C. for one to three hours during the temperature
treatment.
[0027] The longer the tempering process and the higher the
temperature at which the temperature treatment is performed, the
better are the mechanical properties of the cold-formed form body.
However, the improvement of the mechanical properties reaches
saturation at some point and there is a risk of strong grain
growth, which deteriorates the mechanical properties again.
Moreover, the costs of the method increase with the duration and
the tempering temperature. The minimal temperature of the tempering
process is 1,100.degree. C. The highest temperature of the
tempering process is 20.degree. C. below the melting temperature of
the respective dispersion-hardened platinum composition.
[0028] Preferably, the invention can provide the temperature
treatment or temperature treatments on the cold-formed
three-dimensional body to be used in order to heal defects of the
three-dimensional body.
[0029] Methods according to the invention can just as well provide
multiple consecutive cold forming processes to be performed and the
cross-sectional area of the three-dimensional body to be reduced by
more than 20% by the cold forming processes, whereby each
individual cold forming process reduces the cross-sectional area of
the three-dimensional body made of the dispersion-hardened platinum
composition by maximally 20%, particularly preferably by maximally
18%, and specifically preferably by maximally 15%, and a
temperature treatment to be performed on the cold-formed
three-dimensional body between each cold forming process, in the
course of which the cold-formed product is tempered at a
temperature of at least 1,100.degree. C. for at least one hour.
[0030] In this context, "between each cold forming process" shall
be understood to mean that a temperature treatment is preferably
performed at a temperature of at least 1,100.degree. C. for at
least one hour after each cold forming process, such that the
number of cold forming steps and the number of tempering steps are
equal.
[0031] Performing multiple cold forming processes and temperature
treatments is advantageous in that the cold forming processes and
temperature treatments, which are relatively easy and simple to
perform, allow even major forming processes to be implemented
without weakening the dispersion-hardened platinum composition,
i.e., without reducing, e.g., the creep strength of the alloy. It
has even been evident, surprisingly, that the creep strength
steadily improves with an increasing number of forming and
annealing steps.
[0032] A preferred embodiment of the invention provides for the
case of multiple consecutive cold forming processes. Each
individual cold forming process reduces the cross-sectional area of
the three-dimensional body made of the dispersion-hardened platinum
composition by at least 5%, preferably by at least 8%, and
particularly preferably by at least 10%.
[0033] Forming steps that comprise only minor reduction of the
cross-sectional area of the dispersion-hardened three-dimensional
body of less than 5% per forming step and subsequent annealing do
not contribute significantly to an improvement of the creep
strength. The lower the change of the cross-sectional area per
forming step in the specified range, the lesser is the impact on
the improvement of the creep strength as compared to forming
processes associated with a reduction of the cross-sectional area
of 5% to 20%. Moreover, having multiple consecutive forming and
annealing steps renders the method elaborate and therefore
uneconomical. This is even more pronounced with a larger number of
requisite forming steps in order to attain the desired final
dimension of the dispersion-hardened three-dimensional body. It is
preferred to reach the final dimension in a total of eight forming
steps. This number of forming steps is a good compromise of
economic efficiency and improvement of the mechanical
properties.
[0034] Preferably, the invention can provide the cold-formed
product to be tempered at a temperature of at least 1,550.degree.
C. for at least 24 h, at a temperature of at least 1,600.degree. C.
for at least 12 hours, at a temperature of at least 1,650.degree.
C. for at least one hour or to be tempered at a temperature of
1,690.degree. C. to 1,740.degree. C. for at least 30 minutes during
the last temperature treatment after the last cold forming of the
three-dimensional body.
[0035] This last step largely removes the minor defects
to-be-healed of the dispersion-hardened platinum composition in
their final form, and the thus generated product therefore exhibits
a very high creep strength.
[0036] Any dispersion-hardened platinum composition is suitable as
a starting product for the present processing method. However,
surprising advantages result from the use of semi-finished products
that have generally been subjected to a hot forming process. Before
the cold forming, the dispersion-hardened platinum composition can
be formed by a hot forming process at a temperature of at least
800.degree. C., preferably at a temperature of at least
1,000.degree. C., particularly preferably at a temperature of at
least 1,250.degree. C.
[0037] A further subject matter of the present invention is a
method for producing a product from a dispersion-hardened platinum
composition, which is characterized in that, before providing the
dispersion-hardened platinum composition, it is produced from a
composition of at least 70% by weight platinum and maximally 29.95%
by weight other precious metals, as well as 0.05% by weight to 0.5%
by weight of at least one non-precious metal selected from
ruthenium, zirconium, cerium, scandium, and yttrium by at least
partial oxidation of the non-precious metal or non-precious
metals.
[0038] Preferably, the non-precious metal or non-precious metals
are converted to metal oxides at a level of at least 70%,
preferably at least 90%.
[0039] The treatment of the non-precious metal or non-precious
metals can preferably take place at a temperature between
600.degree. C. and 1,600.degree. C. in an oxidizing atmosphere,
preferably between 800.degree. C. and 1,000.degree. C. in an
oxidizing atmosphere.
[0040] The method for producing a product made of a
dispersion-hardened platinum composition can preferably be combined
with the previously described method for processing and the
embodiments thereof that are described herein as being
preferred.
[0041] Another subject matter of the present invention is a
dispersion-hardened platinum material that can be obtained through
a method for processing and/or through a method for producing a
product from a dispersion-hardened platinum composition. This
subject matter provides excellent mechanical properties in
combination with excellent processing properties and/or an
inexpensive and simple production.
[0042] Preferably, the invention can provide a cylindrical
three-dimensional body made of the dispersion-hardened platinum
material to withstand a tensile strain of 9 MPa in the direction of
the length of the three-dimensional body at a temperature of
1,600.degree. C. for at least 40 hours without tearing, preferably
to withstand at least 50 hours without tearing, particularly
preferably to withstand at least 100 hours without tearing and/or a
sheet metal made of the dispersion-hardened platinum material,
which has a rectangular cross-section of 0.85 mm.times.3.9 mm and a
length of 140 mm and is placed in an oven chamber at 1,650.degree.
C. on two parallel-arranged cylindrical rods with a circular
cross-section and a diameter of 2 mm at a distance of 100 mm,
whereby the middle of the sheet metal is exposed to a load of 30 g,
to sag by less than 40 mm, preferably to sag by less than 30 mm,
particularly preferably to sag by less than 20 mm, more
particularly preferably to sag by less than 14 mm after 40
hours.
[0043] According to the present invention, a cylindrical
three-dimensional body shall be understood to be a straight
cylinder-like body, in particular a cylinder, or a cylinder-like
body with a non-circular or round footprint. In particular, the
cylindrical three-dimensional body is a cuboid (i.e., a
cylinder-like body with a rectangular footprint) with edge lengths
in the range of 0.5 mm to 5 mm.
[0044] The length of the cylindrical three-dimensional body shall
be understood to be the longest extension. In the case of a wire or
a tube, the direction of the length is the axis of the cylindrical
three-dimensional body, whereas, in the case of a sheet metal, it
is one extension in the plane of the sheet metal.
[0045] Moreover, a dispersion-hardened platinum material having the
mechanical properties described above of a cylindrical
three-dimensional body is a subject matter of the present
invention.
[0046] Preferably, the invention can provide the
dispersion-hardened platinum material to comprise 0.05% by weight
to 0.4% by weight, specifically preferably 0.05% by weight to 0.3%
by weight of at least one at least partially oxidized non-precious
metal selected from zirconium, cerium, scandium, and yttrium. This
embodiment allows, in particular, a material with excellent
mechanical properties and very good processing properties to be
provided.
[0047] In a special embodiment, the dispersion-hardened platinum
material can be a sheet metal, a tube or a wire or a product formed
from a wire, tube and/or sheet metal.
[0048] Another subject matter of the present invention is a use of
a dispersion-hardened platinum material or of a formed
three-dimensional body made of a platinum composition that can be
obtained or is obtained through a method according to the invention
for processing and/or through a method according to the invention
for producing a product made of a dispersion-hardened platinum
composition, for devices for use in the glass industry or in a
laboratory.
[0049] The invention is based on finding, surprisingly, that
keeping the degree of cold forming low (at most 20% change of the
cross-sectional area) also keeps low the structural damage, such
as, e.g., crystal lattice displacements, which are introduced into
the dispersion-hardened platinum composition such that the
subsequent temperature treatment successfully heals the damage to
the extent that the stability of the formed platinum composition is
significantly higher than in known methods for cold forming of
dispersion-hardened platinum compositions. If more extensive
forming is desired, this can be attained either with an upstream
hot forming process or multiple consecutive low-level cold forming
processes, whereby the structural damage is healed through a
temperature treatment between each cold forming process. According
to an insight obtained in the scope of the present invention, the
mechanical weakening of cold-formed dispersion-hardened platinum
compositions arises from an excessive number of major defects, such
as micro-fissures, delamination of the particle/matrix boundaries,
and pores on grain boundaries, and these are caused by an
excessively high degree of forming and/or excessive reduction of
the cross-sectional area.
[0050] In particular, the gentle, low level cold forming prevents
internal damage, such as micro-fissures, delamination of the
particle/matrix boundaries, and pores on grain boundaries, that
cannot be healed at all or only with great effort. Micro-fissures
and pores arising on the grain boundaries due to the forming are
particularly damaging since they impair the mechanical stability of
the dispersion-hardened platinum composition to a particularly
strong extent. Using the method according to the invention, this
damage can be prevented. Accordingly, this is the first successful
attempt to generate a dispersion-hardened platinum composition with
very high mechanical stability and excellent processing properties,
in particular welding properties, which is also being claimed.
[0051] Further exemplary embodiments of the invention shall be
illustrated in the following on the basis of some examples, though
without limiting the scope of the invention.
Semi-Finished Precursor 1: Production of a Semi-Finished Precursor
With a sheet Thickness of 2 mm Through Internal Oxidation by Zr and
Y
[0052] Following the method specified in Example 1 of EP 1 964 938
A1, an ingot containing PtRh10 (alloy made of 90% by weight Pt and
10% by weight Rh) and 2200 ppm non-precious metals (1800 ppm Zr and
400 ppm Y) was cast. The ingot was then subjected to mechanical and
thermal treatment. Accordingly, it was rolled to a sheet thickness
of 2.2 mm, then recrystallization-annealed, and subsequently rolled
to a sheet thickness of 2 mm. The sheet-metal was then oxidized at
900.degree. C. for 18 days and subsequently ductility-annealed at
1400.degree. C. for 6 h.
Semi-Finished Precursor 2: Production of a Semi-Finished Precursor
With a Sheet Thickness of 3 mm Through Internal Oxidation by Zr and
Y
[0053] Following the method specified in Example 1 of EP 1 964 938
A1, an ingot containing PtRh10 (alloy made of 90% by weight Pt and
10% by weight Rh) and 2200 ppm non-precious metals (1800 ppm Zr and
400 ppm Y) was cast. The ingot was then subjected to mechanical and
thermal treatment. Accordingly, it was rolled to a sheet thickness
of 3.3 mm, then recrystallisation-annealed, and subsequently rolled
to a sheet thickness of 3 mm. The sheet-metal was then oxidized at
900.degree. C. for 27 days and subsequently ductility-annealed at
1400.degree. C. for 6 h.
Semi-Finished Precursor 3: Production of a Semi-Finished Precursor
With a Sheet Thickness of 3 mm Through Internal Oxidation by Zr, Y,
and Sc
[0054] Following the method specified in Example 1 of EP 1 964 938
A1, an ingot containing PtRh10 (alloy made of 90% by weight Pt and
10% by weight Rh) and 2120 ppm non-precious metals (1800 ppm Zr,
270 mm Y, and 50 ppm Sc) was cast. The ingot was then subjected to
mechanical and thermal treatment. Accordingly, it was rolled to a
sheet thickness of 3.3 mm, then recrystallization-annealed, and
subsequently rolled to a sheet thickness of 3 mm. The sheet-metal
was then oxidized at 900.degree. C. for 24 days and subsequently
ductility-annealed at 1400.degree. C. for 6 h.
EXAMPLE 1
[0055] The semi-finished precursor 1 with a thickness of approx. 2
mm obtained according to the procedure described above was then
processed further, according to the invention, according to the
following rolling and annealing steps.
[0056] The sheet metal was rolled to 1.7 mm and subsequently
annealed at 1,400.degree. C. for 4 h. Then, the sheet metal was
rolled to 1.4 mm and annealed at 1,400.degree. C. for 2 h. Then,
the sheet metal was rolled further to 1.2 mm and annealed again at
1,400.degree. C. for 2 h. Then, the sheet metal was rolled to 1 mm
and annealed again at 1,400.degree. C. Subsequently, the sheet
metal was rolled to its final thickness of 0.85 mm and a final
annealing at 1,100.degree. C. for 4 h was performed. The reduction
of the cross-sectional area per rolling step was 20%.
EXAMPLE 2
[0057] Example 1 was essentially repeated, except that a final
annealing was performed at 1,700.degree. C. for 1 h after rolling
to a final thickness of 0.85 mm.
EXAMPLE 3
[0058] The semi-finished precursor 2 with a thickness of approx. 3
mm obtained according to the procedure described above was then
processed further, according to the invention, according to the
following rolling and annealing steps.
[0059] The sheet metal was rolled to 2.4 mm and subsequently
annealed at 1,150.degree. C. for 4 h. Then, the sheet metal was
rolled to 1.92 mm and annealed at 1,150.degree. C. for 4 h. Then,
the sheet metal was rolled to 1.53 mm and annealed again at
1,150.degree. C. for 4 h. The rolling and annealing steps were
repeated thrice, whereby the sheet metal was rolled first to 1.22
mm, then to 0.99 mm, and subsequently to 0.8 mm and annealed at
1,150.degree. C. for 4 h after each rolling step. The reduction of
the cross-sectional area per rolling step was 20%.
EXAMPLE 4
[0060] The semi-finished precursor 2 with a thickness of approx. 3
mm obtained according to the procedure described above was then
processed further, according to the invention, according to the
following rolling and annealing steps.
[0061] The sheet metal was rolled to 2.4 mm and subsequently
annealed at 1300.degree. C. for 4 h.
[0062] Then, the sheet metal was rolled to 1.92 mm and annealed at
1,300.degree. C. for 4 h. Then, the sheet metal was rolled to 1.53
mm and annealed again at 1300.degree. C. for 4 h. The rolling and
annealing steps were repeated thrice, whereby the sheet metal was
rolled first to 1.22 mm, then to 0.99 mm, and subsequently to 0.8
mm and annealed at 1300.degree. C. for 4 h after each rolling step.
The reduction of the cross-sectional area per rolling step was
20%.
EXAMPLE 5
[0063] The semi-finished precursor 2 with a thickness of approx. 3
mm obtained according to the procedure described above was then
processed further, according to the invention, according to the
following rolling and annealing steps.
[0064] The sheet metal was rolled to 2.4 mm and subsequently
annealed at 1400.degree. C. for 4 h. Then, the sheet metal was
rolled to 1.92 mm and annealed at 1,400.degree. C. for 4 h. Then,
the sheet metal was rolled to 1.53 mm and annealed again at
1400.degree. C. for 4 h. The rolling and annealing steps were
repeated thrice, whereby the sheet metal was rolled first to 1.22
mm, then to 0.99 mm, and subsequently to 0.8 mm and annealed at
1400.degree. C. for 4 h after each rolling step. The reduction of
the cross-sectional area per rolling step was 20%.
EXAMPLE 6
[0065] The semi-finished precursor 2 with a thickness of approx. 3
mm obtained according to the procedure described above was then
processed further, according to the invention, according to the
following rolling and annealing steps.
[0066] The sheet metal was rolled to 2.55 mm and subsequently
annealed at 1400.degree. C. for 4 h. Then, the sheet metal was
rolled to 2.16 mm and annealed at 1,400.degree. C. for 4 h. Then,
the sheet metal was rolled to 1.84 mm and annealed again at
1400.degree. C. for 4 h. The rolling and annealing steps were
repeated 5 times, whereby the sheet metal was rolled first to 1.56
mm, then to 1.33 mm, then to 1.13 mm, then to 0.96 mm, and
subsequently to 0.8 mm and annealed at 1,400.degree. C. for 4 h
after each rolling step. The reduction of the cross-sectional area
per rolling step was 15%.
EXAMPLE 7
[0067] The semi-finished precursor 3 with a thickness of approx. 3
mm obtained according to the procedure described above was then
processed further, according to the invention, according to the
following rolling and annealing steps.
[0068] The sheet metal was rolled to 2.4 mm and subsequently
annealed at 1150.degree. C. for 4 h.
[0069] Then, the sheet metal was rolled to 1.92 mm and annealed at
1,150.degree. C. for 4 h. Then, the sheet metal was rolled to 1.53
mm and annealed again at 1150.degree. C. for 4 h. The rolling and
annealing steps were repeated thrice, whereby the sheet metal was
rolled first to 1.22 mm, then to 0.99 mm, and subsequently to 0.8
mm and annealed at 1150.degree. C. for 4 h after each rolling step.
The reduction of the cross-sectional area per rolling step was
20%.
EXAMPLE 8
[0070] The semi-finished precursor 3 with a thickness of approx. 3
mm obtained according to the procedure described above was then
processed further, according to the invention, according to the
following rolling and annealing steps.
[0071] The sheet metal was rolled to 2.55 mm and subsequently
annealed at 1400.degree. C. for 4 h. Then, the sheet metal was
rolled to 2.16 mm and annealed at 1,400.degree. C. for 4 h. Then,
the sheet metal was rolled to 1.84 mm and annealed again at
1400.degree. C. for 4 h. The rolling and annealing steps were
repeated 5 times, whereby the sheet metal was rolled first to 1.56
mm, then to 1.33 mm, then to 1.13 mm, then to 0.96 mm, and
subsequently to 0.8 mm and annealed at 1,400.degree. C. for 4 h
after each rolling step. The reduction of the cross-sectional area
per rolling step was 15%.
EXAMPLE 9
[0072] The semi-finished precursor 3 with a thickness of approx. 3
mm obtained according to the procedure described above was then
processed further, according to the invention, according to the
following rolling and annealing steps.
[0073] The sheet metal was rolled to 2.7 mm and subsequently
annealed at 1400.degree. C. for 4 h. Then, the sheet metal was
rolled to 2.43 mm and annealed at 1,400.degree. C. for 4 h. Then,
the sheet metal was rolled to 2.19 mm and annealed again at
1400.degree. C. for 4 h. The rolling and annealing steps were
repeated 9 times, whereby the sheet metal was rolled first to 1.97
mm, then to 1.77 mm, then to 1.44 mm, then to 1.29 mm, then to 1.16
mm, then to 1.05 mm, then to 0.94 mm, and subsequently to 0.85 mm
and annealed at 1,400.degree. C. for 4 h after each rolling step.
The reduction of the cross-sectional area per rolling step was
10%.
EXAMPLE 10
[0074] Example 9 was essentially repeated, except that a final
annealing was performed at 1,700.degree. C. for 1 h after rolling
to a final thickness of 0.85 mm.
EXAMPLE 11
[0075] The semi-finished precursor 3 with a thickness of approx. 3
mm obtained according to the procedure described above was then
processed further, according to the invention, according to the
following rolling and annealing steps.
[0076] The sheet metal was rolled at 1,100.degree. C. (hot forming)
to 1.5 mm and subsequently annealed at 1,400.degree. C. for 4 h.
Then, the sheet metal was rolled to 1.2 mm (1st cold forming) and
subsequently annealed at 1,250.degree. C. for 4 h. Then, the sheet
metal was rolled to 1.02 mm (2nd cold forming) and subsequently
annealed again at 1,250.degree. C. for 4 h. The rolling and
annealing steps were repeated thrice, whereby the sheet-metal was
rolled first to 0.94 mm (3rd cold forming), then to 0.86 mm (4th
cold forming), and subsequently to 0.8 mm (5th cold forming) and
the sheet-metal was annealed at 1,250.degree. C. for 4 h after each
rolling step. The reduction of the cross-sectional area was 50%
during the hot forming step and 20% initially, then 15%, and then
8% each during the cold forming steps.
Reference Example 1
[0077] The semi-finished precursor 1 with a thickness of approx. 2
mm obtained according to the procedure described above was then
processed further according to a conventional method. For this
purpose, the sheet metal was rolled directly to 1 mm and annealed
at 1,000.degree. C. Subsequently, the sheet metal was rolled to
0.85 mm and a final annealing at 1,000.degree. C. for 1 h was
performed.
Reference Example 2
[0078] The semi-finished precursor 2 with a thickness of approx. 3
mm obtained according to the procedure described above was then
processed further according to a conventional method. For this
purpose, the sheet metal was rolled to 1.5 mm and annealed at
1,400.degree. C. for 4 h. Then, the sheet metal was rolled to 0.8
mm. The reduction of the cross-sectional area per rolling step was
50%.
Reference Example 3
[0079] The semi-finished precursor 3 with a thickness of approx. 3
mm obtained according to the procedure described above was then
processed further according to a conventional method. For this
purpose, the sheet metal was rolled to 1.5 mm and annealed at
1,400.degree. C. for 4 h. Then, the sheet metal was rolled to 0.8
mm. The reduction of the cross-sectional area per rolling step was
50%.
Mechanical Properties of the Platinum Materials Thus Obtained
Creep Strength According to Rupture Test:
[0080] To measure the creep strength, a weight corresponding to the
desired load in MPa for the specified cross-section was appended to
a sheet-metal sample with a cross-section of 0.85 mm.times.3.9 mm
and a length of 120 mm (Examples 1, 2, 9, 10 and Reference Example
1) or 0.08 mm.times.3.9 mm and a length of 120 mm (Examples 3, 4,
5, 6, 7, 8, 11 and Reference Examples 2 and 3). The sample was
heated by means of electrical current and controlled to constantly
be at the desired temperature by means of a pyrometer measurement.
The time until rupture of the probe was determined and corresponds
to the creep strength.
TABLE-US-00001 TABLE 1 Creep Strength until Rupture at
1,600.degree. C. and 9 MPa Load Reference example 1 20 h Reference
example 2 35 h Reference example 3 30 h Example 1 50 h Example 2
>120 h Example 3 >100 h Example 4 >100 h Example 5 >100
h Example 6 >100 h Example 7 >100 h Example 8 >100 h
Example 9 >100 h Example 10 >120 h Example 11 >100 h
Creep Strength Values According to the Sagging Test
[0081] The sagging test is another method for estimation of the
creep strength. For this purpose, pieces of sheet metal with a
cross-section of 0.85 mm.times.10 mm and a length of 140 mm
(Examples 1, 2, 9, 10 and Reference Example 1) or with a
cross-section of 0.8 mm.times.10 mm and a length of 140 mm
(Examples 3, 4, 5, 6, 7, 8, 11 and Reference Examples 2 and 3) were
placed on two parallel ceramic rods separated by a distance of 100
mm and the middle of the sheet was exposed to a load of 30 g. The
sample arrangement was then heated to 1,650.degree. C. in a chamber
oven and the sagging of the samples was measured after 40 h.
TABLE-US-00002 TABLE 2 Creep Strength According to the Sagging Test
Reference example 1 Sagging >40 mm Reference example 2 Sagging
35 mm Reference example 3 Sagging 37 mm Example 1 Sagging 18 mm
Example 2 Sagging <12 mm Example 3 Sagging 18 mm Example 4
Sagging 17 mm Example 5 Sagging 18 mm Example 6 Sagging 16 mm
Example 7 Sagging 17 mm Example 8 Sagging 17 mm Example 9 Sagging
16 mm Example 10 Sagging 10 mm Example 11 Sagging 16 mm
[0082] The Examples illustrated above demonstrate that a surprising
improvement in the mechanical properties can be attained through
the measures according to the invention, whereby this improvement
can be increased even more by a tempering step at a temperature
above 1,100.degree. C., in particular above 1,500.degree. C.
[0083] The features of the invention disclosed in the preceding
description, claims, and exemplary embodiments, can be essential
for the implementation of the various embodiments of the invention
both alone and in any combination.
[0084] It will be appreciated by those skilled in the art that
changes could be made to the embodiments described above without
departing from the broad inventive concept thereof. It is
understood, therefore, that this invention is not limited to the
particular embodiments disclosed, but it is intended to cover
modifications within the spirit and scope of the present invention
as defined by the appended claims.
* * * * *