CA1130570A - Method for producing a platinoid comprising a dispersed phase of a refractory oxide - Google Patents
Method for producing a platinoid comprising a dispersed phase of a refractory oxideInfo
- Publication number
- CA1130570A CA1130570A CA330,077A CA330077A CA1130570A CA 1130570 A CA1130570 A CA 1130570A CA 330077 A CA330077 A CA 330077A CA 1130570 A CA1130570 A CA 1130570A
- Authority
- CA
- Canada
- Prior art keywords
- oxide
- powder
- platinum
- metal
- spraying device
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
- C22C1/1042—Alloys containing non-metals starting from a melt by atomising
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0021—Matrix based on noble metals, Cu or alloys thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
Abstract
ABSTRACT OF THE DISCLOSURE
The present invention concerns a method for producing a metal from crude platinum or one of its alloys, comprising very fine particles, in dispersed phase form, of at least one refractory oxide, in the proportion of 0.1 to 5°/? by weight with respect to the weight of the said metal, wherein the molten host metallic material containing the said oxide is sprayed on a target by means of a device delivering a jet of pressurized gas.
The present invention concerns a method for producing a metal from crude platinum or one of its alloys, comprising very fine particles, in dispersed phase form, of at least one refractory oxide, in the proportion of 0.1 to 5°/? by weight with respect to the weight of the said metal, wherein the molten host metallic material containing the said oxide is sprayed on a target by means of a device delivering a jet of pressurized gas.
Description
~L36~si~
A method for producing a pla~inold co~npri.~ing ~ di~per~ed phase of refractory ox1de.
The present inven-tion relates -to a method for producing a platinoid comprising a dispersed phase of a refractory oxide.
The platinoids, (or PLATINUM me-tals) and alloys are widely used in industry to produce parts which are subjected, to high operating temperatures on the one hand, and to very corrosive atmospheres, on the other; such parts are, for example, glass-melting crucibles and spinnere-ts for producing glassfibres.
The main property of these parts which - it is desirable to improve as much as possible is their resistance to hot creep.
And precisely to improve -that resistance to hot extrusion, it has already been proposed to incorporate to the me-tal die constitutive of the said parts, small quan-tities of ref`ractory addi~
tives and mainly, finely dispersed refractory oxides.
A conventional method to produce such parts consists in using the technique of powder metallur~y.
Despite the advances made, it is not possible with said method to obtain~ industrially and in reproducible manner, a part which shows an homogeneous distribution of the ~xide phase dispersed inside it~
The production of basic powders remains very difficult to control, esp~cially because of the fineness required from the dispersed pha~e ancl oL`
the low contents involvedO During the preparatio of the coprecipitated powders for example, an agglotneration of ultra-fine particles of oxides can be noted at the very beginning of the precipitation~, which agglomeration lead~ to a growth oP the phase and, AS à result, to a loss o~ the mech~nical pro-perties of the sintered material growth of the elementary particles also occurs during the densifying of the compressed block and subsequent treatments of hot working ancl transformation. In practice, it has proved ~ery difficult to avoid this phenomenon and to obtain, within the same batch or the same sample, a fine enough distribution .
of oxide particles. However it would seem, that particles with a diameter greater than 0.1 ~Im ha~e little action on the resistance to creep.
rhe wet or dry methods for mixing ultrafine particles are virtually never used because o~ the very poor results they give. I
Another process consists in oxidizing then sintering a powder of a platinum alloy with the doping agent (zirconlum for example).
But, with the very low diffusibility of the oxygen in liquid platinum, it i3 not posslble to entlrely oxidize the doping agent dissolved in the die, whi¢h means therefore that no acceptable homogeneity can be obtained reproduciblyO
Another method consists in spraying ;
on a target~ a molten host material, such as platinum for example, and a reactive constltuent, through an atmosphere eonverting said constltuent into a refractory addltlve forming a dlspersed phase contained in the host materlal when said latter settles on the target.
Said method has pro~ed a substantial ad~an~e in the reproducibility of the method and of the resist~nce to hot creep, but it requires the use of reagents meant to form refractory additi~es in the conditions set by the method~ and especially in the condition of temperature of the flame, which llmits the additi~es that can be used~
Also, with particular reagents, only : ~ : , - . . . . .
~L~3~5~
a very poor or a partial conversion of the reactive product into reEractory product can be obtained.
Moreover, the distribution of additive particles in the ingot obtained is sometimes heterogenous and the diameter of the particles may also be too large.
; The object of the present invention is to propose a method for producing a metal which may be from platinum or an alloy thereof comprising a dispersed phase of at least one refractory oxide in the form of very fine particles, and with none of the disadvantages of the methods known under the prior art.
An aspect o~ the invention is as Eollows:
Method for producing a metal from platinoids, platinum or an alloy thereof comprising, particles of at least one refractory oxide having a diameter less than about 1 ~m, in the form of a dispersed phase and in the proportion of 0.1 to 5/Oo by weight of the weight of said metal, wherein the molten host material contained in the said oxide is sprayed on a target by means of a device delivering a jet of pressurized gas. ~In the above text /OO = for thousand).
According to the invention, the metal used as host metal may be from platinum or one of its alloys, i.e. mainly platinum, alloyed with the main platinoids, rhodium, iridium, palladium. By alloys are especially meant the various combina-~5 tions of those alloys together, such as for example, the common-ly u~ed Pt-Rh alloys.
The invention gives some particularly interesting results with pure platinum, and also with platinum-rhodium and platinum-iridium alloys.
: , . ~ :
.. . :- : .
.
It iq possible with the method according to the il~vention to obtain, in easy and reproducible manner, a very homogeneous dispersion of fine particle~ of refractory oxide~ in the metal die and, consequently, to produce a part which is more resistant to hot creepu Compared with -the known methods, which call on internal oxidizing of the platinwm and of its alloys, the method according to the invention is essentially characterized by the use of a basic product comprising an already oxidized and finely dispersed strengthening phase~
According to the invention, the refractory oxide is used in the form of very fin~e particles, in the proportion of between Ool and 5/00 by weight with respect to the weight of the metallic host material and preferably, between 0.2 and l~/oo especially in the case of yttrium oxide. It is most desirable for the oxide to have a melting point higher than that of the host metal~ ;
Preferred rare earth and refractory oxides are yttrium oxides as well as thoseis~ued from the elements of columns IIA and IVA of the periodical classification of elements (AFNOR-norm)~ The preferred oxide is yttrium oxide, but the zirconium, thorium, titanium, calciuml aluminium and hafnium oxides can also be advantageougly used.
- By very fine particles of refractory oxides are meant particle~ with pre~erably a diameter less than 1 ~m.
Already known techniques for pressurized blowing of molten metals, so-called flame, plasma or arc techniques can be used as spraying techniques~
Flame blowing, using an oxyacetylene gun, is the preferred technique.
5~
It is also desirable, according to a preferred embodiment, for the oxide a-t the outlet of the spraying device, to be also in th~ molten state and not dissociated into metal and oxygenO
According to the invention, the spraying device is directly supplied by at least ;`
one powder containing the metallic host material and the oxide, or by a metallic wire prepared by the powder metallurgy technique ~rom the said powder.
To produce the powder, it is preferable to use a physico-chemical method which permits to obtain, homogeneously, either a close mixture of powder from the host material with very ~ine oxide powder, or a powder from an alloy of the metallic hos-t material which comprises already the dispersed phase of refractory oxideO
The following well-known methods may be used to produce such powders:
a) Co-precipitating a salt of -the host metal and a salt of the metal of the oxide.
b) Suspending a powder of the host metal in a solution containing the metal of the oxide and then precipitating the re~ractory oxide in fin~ particle form, which particles are adsorbed on the powder of the host metal. A preferred powder may be prepared by suspending a fine platinum powder (of Fisher average diameter less than 2 ~m) in a solution o~ yttrium nitrate and then precipitating the yttrium oxide adsorbed on the platinum by adding an alkaline base such as soda.
c) Calcinating a homogeneous mixture of powder from the host metal with a salt from the metal of the re~ractory oxide~
It is also possible to start with a . ,.
.~ , ,.
mixture of powders and to subject this to the so~
called "metal alloying" process, consisting in producing an alloy by mechanical meansO This ~- comprises the steps of mixing up ultrafine po~ders in a bowl filled with steel balls and stirring ; very strongly, In certain experimental condition~;
some very fine metallurgical structures are obtained in which smallest particles cannot be seen under an optical microscope.
Tlle blowingdevice may be directly supplied with the suitable mixture of powder introd-uced in a combustible sheath, which may be an advantage whenever the host material includes metals which get partially sintered at high temperatures such as rhodium and iridiumO
It is also possible to produce from the said mixture, when using the powder metallurgy method, a metallic wire with which the blowing device is supplied.
According to the invention and due to the fact that before the blowing operation, a mixture or homogeneous and close combination of fine particles of the host material and of the oxide is used, it is possible to obtain, in reproducible manner, on the target, an ingot with a particularly homogeneous phase disper~ed inside the host material.
The spray of molten host material issued from the nozzle of the gun is generally in the form of a flux of fine droplets. By crashing at impact speeds greater than 50 m/secs, they coat the surface of the mold, so as to constitute a stack of strata about 10 ~um thickl each creating an ingot the sizes of which are given by the targetO The target is generally made of copper and is cooled. After being removed from the mold, the ingot is machined and heat forged until a . . ~ - . : - : .
.
~:~3~D5~
rough-shape i~ obtain~d with nonrly the ~h~oretlcal densit;y. Saicl rough~sllap~ i~ subsequently cold-rolled bofore bein,~, subjected to a tr~atmont for stablli~ins t'he grain.
In the case of Qpplications requirin~r a high resistance to hot creep, the metals prcpar~d by the process accordins to the in~ontion have excellerlt properties and can be used ad~antageously in th~ glass industry to produce the commonly used apparatus, suoh as: spinnerets for the production of glass~fihres intended for heat illsulation and soundproof:ins and for reinforcing plastics, glass fusing crucib:les~
optical glass refining equipment 7 molten gla~s agitators, etc.... The metals prepared by the method according to the invention also find interesting applications iII the field of containers for laboratory use, and of catalytic gauzes~
Other advantages and characteris-tics of the invention will emerge on reading the following example given non-res~ictively (all the percentages indicated are given by weight).
a) A platinum powder containing 005/OO
by weight of yttrium oxide is prepared as follows:
~ a fine platinum powder is suspended (average Fischer diameter: 1~5 um) in a solution of yttrium nitrate, and then a soda solution is added whilst stirring~
The yttrium oxide precipitate is adsorbed on the -~
platinumO The doped powder of platinum is washed and then dried at 800CD
b) The powder is compacted and sintered for 2h at :L100-1300C. The sintered block is forged at 1100C and then drawn into a ~ire of 1.5 mm diam-ete~.
c) The wire produced according to a) ... ~ .
and b) i..s spray~d ~y me~n~ o~` ~n oxy~acetyl.~rle blowplpe of the Schoop type emd the b~own mater:ial is recoverecl in th~ copper mold which is si-tua-ted opposite the ~pray-gun~ The pres~ure o~` tlle o.xygen and of the acetylene are controlled so as to prevent the dissociation of the oxide and al~o to lceep the flame hot enough to allou the melting o~ all the particlos of Y203~ The wire i.s pulveri~ed unti.l thc in~ot reache~ the desi.red dimensions. In the c~se of experimental insots~ the c~rentdimensions are 50 x :~
20 x 10 mm.
d) The ingot iq cold-rolled on the surface, heat ~orged at 1150C until total densi~ying.
e) The ~orged ingot is cold-ro:Lled with no intermediate annealing until cold rolling reduction (~e 100) are approaching 80%.
f) The roush shapes ~re.annealed ~or 30 minutes at lOOO~C and then cold~rolled again by 30%.
Table I below gives the typical values, obtained in cold conditions 9 for the limit of elasticity (E), the ultimate strength, elongation (A~/o) ~ Vickers hardness under 5 kg (HV5) on test pieces 1 mm thick, o~ pure platinum, of platinum-rhodium at L0%, and of the alloy of example 1 according to the inventionO
Table II below gives the typical values in hours of resistance to hot creep of platinum-rhodium at 10%, and of the alloy of example 1 according to the invention.
The remarkable and unexpected resistance to hot creep of the alloy according to the invention is to be not.ed, in relation to the Pt(Rh 10%)~
Examples 2 to 4:
The same mode of operation as in . . .
~r' . . .
i7~
.
example 1 is used except that the contents of Y203 are different.
The results obtained are given in table III below, in which are indicated the typical values of resistance to hot creep in hours at 1000C, under a load of 3.85 kg/mm2 and of Vickers hardness un~er 5 kg (H~5) on test pieces, 1 mm thick, of alloy accordin~ to the invention.
.
. ~i .
:. ~ , ,. . : -~o TABLE I
,_ ~
. . . M~t~llur~ical ~ E R A% l1V
State l ~kg/mmZ) tkg/mm2) tkg~mm2) .
Platinum Cold-rollsd te- xlOOa80%)34 34 0,8 8a Annsaled 7 13 28 38 Pt-Rh 10% Cold-rolled. 53 53 0,6 . lB0 t~ xlO0=80%) . .
eO
Annealed 13 29 21 A8 10 ~ ~Anne~led _ ~ 53 3 143 . . _ . , . . ~ :' TAdLE II
Temperature 1000C 1300C 1 1450C
~ . _ . . I
\ 3 3,85 l,i 2,5 0,5 1,3 1,7 Brea-\ Load g \ tkg/ .
.Time. \ mm2) .. ~. _ . .
Pt-RH 10%20-30 4-8 2,2 2,6 Alloy of Example 1 . .
oo-?oo 20-40 lQ0-20010-15 ,? ~00 ,20-40 _ 10-20 TABLE III
. .
_ * t Hvtkg/mm2
A method for producing a pla~inold co~npri.~ing ~ di~per~ed phase of refractory ox1de.
The present inven-tion relates -to a method for producing a platinoid comprising a dispersed phase of a refractory oxide.
The platinoids, (or PLATINUM me-tals) and alloys are widely used in industry to produce parts which are subjected, to high operating temperatures on the one hand, and to very corrosive atmospheres, on the other; such parts are, for example, glass-melting crucibles and spinnere-ts for producing glassfibres.
The main property of these parts which - it is desirable to improve as much as possible is their resistance to hot creep.
And precisely to improve -that resistance to hot extrusion, it has already been proposed to incorporate to the me-tal die constitutive of the said parts, small quan-tities of ref`ractory addi~
tives and mainly, finely dispersed refractory oxides.
A conventional method to produce such parts consists in using the technique of powder metallur~y.
Despite the advances made, it is not possible with said method to obtain~ industrially and in reproducible manner, a part which shows an homogeneous distribution of the ~xide phase dispersed inside it~
The production of basic powders remains very difficult to control, esp~cially because of the fineness required from the dispersed pha~e ancl oL`
the low contents involvedO During the preparatio of the coprecipitated powders for example, an agglotneration of ultra-fine particles of oxides can be noted at the very beginning of the precipitation~, which agglomeration lead~ to a growth oP the phase and, AS à result, to a loss o~ the mech~nical pro-perties of the sintered material growth of the elementary particles also occurs during the densifying of the compressed block and subsequent treatments of hot working ancl transformation. In practice, it has proved ~ery difficult to avoid this phenomenon and to obtain, within the same batch or the same sample, a fine enough distribution .
of oxide particles. However it would seem, that particles with a diameter greater than 0.1 ~Im ha~e little action on the resistance to creep.
rhe wet or dry methods for mixing ultrafine particles are virtually never used because o~ the very poor results they give. I
Another process consists in oxidizing then sintering a powder of a platinum alloy with the doping agent (zirconlum for example).
But, with the very low diffusibility of the oxygen in liquid platinum, it i3 not posslble to entlrely oxidize the doping agent dissolved in the die, whi¢h means therefore that no acceptable homogeneity can be obtained reproduciblyO
Another method consists in spraying ;
on a target~ a molten host material, such as platinum for example, and a reactive constltuent, through an atmosphere eonverting said constltuent into a refractory addltlve forming a dlspersed phase contained in the host materlal when said latter settles on the target.
Said method has pro~ed a substantial ad~an~e in the reproducibility of the method and of the resist~nce to hot creep, but it requires the use of reagents meant to form refractory additi~es in the conditions set by the method~ and especially in the condition of temperature of the flame, which llmits the additi~es that can be used~
Also, with particular reagents, only : ~ : , - . . . . .
~L~3~5~
a very poor or a partial conversion of the reactive product into reEractory product can be obtained.
Moreover, the distribution of additive particles in the ingot obtained is sometimes heterogenous and the diameter of the particles may also be too large.
; The object of the present invention is to propose a method for producing a metal which may be from platinum or an alloy thereof comprising a dispersed phase of at least one refractory oxide in the form of very fine particles, and with none of the disadvantages of the methods known under the prior art.
An aspect o~ the invention is as Eollows:
Method for producing a metal from platinoids, platinum or an alloy thereof comprising, particles of at least one refractory oxide having a diameter less than about 1 ~m, in the form of a dispersed phase and in the proportion of 0.1 to 5/Oo by weight of the weight of said metal, wherein the molten host material contained in the said oxide is sprayed on a target by means of a device delivering a jet of pressurized gas. ~In the above text /OO = for thousand).
According to the invention, the metal used as host metal may be from platinum or one of its alloys, i.e. mainly platinum, alloyed with the main platinoids, rhodium, iridium, palladium. By alloys are especially meant the various combina-~5 tions of those alloys together, such as for example, the common-ly u~ed Pt-Rh alloys.
The invention gives some particularly interesting results with pure platinum, and also with platinum-rhodium and platinum-iridium alloys.
: , . ~ :
.. . :- : .
.
It iq possible with the method according to the il~vention to obtain, in easy and reproducible manner, a very homogeneous dispersion of fine particle~ of refractory oxide~ in the metal die and, consequently, to produce a part which is more resistant to hot creepu Compared with -the known methods, which call on internal oxidizing of the platinwm and of its alloys, the method according to the invention is essentially characterized by the use of a basic product comprising an already oxidized and finely dispersed strengthening phase~
According to the invention, the refractory oxide is used in the form of very fin~e particles, in the proportion of between Ool and 5/00 by weight with respect to the weight of the metallic host material and preferably, between 0.2 and l~/oo especially in the case of yttrium oxide. It is most desirable for the oxide to have a melting point higher than that of the host metal~ ;
Preferred rare earth and refractory oxides are yttrium oxides as well as thoseis~ued from the elements of columns IIA and IVA of the periodical classification of elements (AFNOR-norm)~ The preferred oxide is yttrium oxide, but the zirconium, thorium, titanium, calciuml aluminium and hafnium oxides can also be advantageougly used.
- By very fine particles of refractory oxides are meant particle~ with pre~erably a diameter less than 1 ~m.
Already known techniques for pressurized blowing of molten metals, so-called flame, plasma or arc techniques can be used as spraying techniques~
Flame blowing, using an oxyacetylene gun, is the preferred technique.
5~
It is also desirable, according to a preferred embodiment, for the oxide a-t the outlet of the spraying device, to be also in th~ molten state and not dissociated into metal and oxygenO
According to the invention, the spraying device is directly supplied by at least ;`
one powder containing the metallic host material and the oxide, or by a metallic wire prepared by the powder metallurgy technique ~rom the said powder.
To produce the powder, it is preferable to use a physico-chemical method which permits to obtain, homogeneously, either a close mixture of powder from the host material with very ~ine oxide powder, or a powder from an alloy of the metallic hos-t material which comprises already the dispersed phase of refractory oxideO
The following well-known methods may be used to produce such powders:
a) Co-precipitating a salt of -the host metal and a salt of the metal of the oxide.
b) Suspending a powder of the host metal in a solution containing the metal of the oxide and then precipitating the re~ractory oxide in fin~ particle form, which particles are adsorbed on the powder of the host metal. A preferred powder may be prepared by suspending a fine platinum powder (of Fisher average diameter less than 2 ~m) in a solution o~ yttrium nitrate and then precipitating the yttrium oxide adsorbed on the platinum by adding an alkaline base such as soda.
c) Calcinating a homogeneous mixture of powder from the host metal with a salt from the metal of the re~ractory oxide~
It is also possible to start with a . ,.
.~ , ,.
mixture of powders and to subject this to the so~
called "metal alloying" process, consisting in producing an alloy by mechanical meansO This ~- comprises the steps of mixing up ultrafine po~ders in a bowl filled with steel balls and stirring ; very strongly, In certain experimental condition~;
some very fine metallurgical structures are obtained in which smallest particles cannot be seen under an optical microscope.
Tlle blowingdevice may be directly supplied with the suitable mixture of powder introd-uced in a combustible sheath, which may be an advantage whenever the host material includes metals which get partially sintered at high temperatures such as rhodium and iridiumO
It is also possible to produce from the said mixture, when using the powder metallurgy method, a metallic wire with which the blowing device is supplied.
According to the invention and due to the fact that before the blowing operation, a mixture or homogeneous and close combination of fine particles of the host material and of the oxide is used, it is possible to obtain, in reproducible manner, on the target, an ingot with a particularly homogeneous phase disper~ed inside the host material.
The spray of molten host material issued from the nozzle of the gun is generally in the form of a flux of fine droplets. By crashing at impact speeds greater than 50 m/secs, they coat the surface of the mold, so as to constitute a stack of strata about 10 ~um thickl each creating an ingot the sizes of which are given by the targetO The target is generally made of copper and is cooled. After being removed from the mold, the ingot is machined and heat forged until a . . ~ - . : - : .
.
~:~3~D5~
rough-shape i~ obtain~d with nonrly the ~h~oretlcal densit;y. Saicl rough~sllap~ i~ subsequently cold-rolled bofore bein,~, subjected to a tr~atmont for stablli~ins t'he grain.
In the case of Qpplications requirin~r a high resistance to hot creep, the metals prcpar~d by the process accordins to the in~ontion have excellerlt properties and can be used ad~antageously in th~ glass industry to produce the commonly used apparatus, suoh as: spinnerets for the production of glass~fihres intended for heat illsulation and soundproof:ins and for reinforcing plastics, glass fusing crucib:les~
optical glass refining equipment 7 molten gla~s agitators, etc.... The metals prepared by the method according to the invention also find interesting applications iII the field of containers for laboratory use, and of catalytic gauzes~
Other advantages and characteris-tics of the invention will emerge on reading the following example given non-res~ictively (all the percentages indicated are given by weight).
a) A platinum powder containing 005/OO
by weight of yttrium oxide is prepared as follows:
~ a fine platinum powder is suspended (average Fischer diameter: 1~5 um) in a solution of yttrium nitrate, and then a soda solution is added whilst stirring~
The yttrium oxide precipitate is adsorbed on the -~
platinumO The doped powder of platinum is washed and then dried at 800CD
b) The powder is compacted and sintered for 2h at :L100-1300C. The sintered block is forged at 1100C and then drawn into a ~ire of 1.5 mm diam-ete~.
c) The wire produced according to a) ... ~ .
and b) i..s spray~d ~y me~n~ o~` ~n oxy~acetyl.~rle blowplpe of the Schoop type emd the b~own mater:ial is recoverecl in th~ copper mold which is si-tua-ted opposite the ~pray-gun~ The pres~ure o~` tlle o.xygen and of the acetylene are controlled so as to prevent the dissociation of the oxide and al~o to lceep the flame hot enough to allou the melting o~ all the particlos of Y203~ The wire i.s pulveri~ed unti.l thc in~ot reache~ the desi.red dimensions. In the c~se of experimental insots~ the c~rentdimensions are 50 x :~
20 x 10 mm.
d) The ingot iq cold-rolled on the surface, heat ~orged at 1150C until total densi~ying.
e) The ~orged ingot is cold-ro:Lled with no intermediate annealing until cold rolling reduction (~e 100) are approaching 80%.
f) The roush shapes ~re.annealed ~or 30 minutes at lOOO~C and then cold~rolled again by 30%.
Table I below gives the typical values, obtained in cold conditions 9 for the limit of elasticity (E), the ultimate strength, elongation (A~/o) ~ Vickers hardness under 5 kg (HV5) on test pieces 1 mm thick, o~ pure platinum, of platinum-rhodium at L0%, and of the alloy of example 1 according to the inventionO
Table II below gives the typical values in hours of resistance to hot creep of platinum-rhodium at 10%, and of the alloy of example 1 according to the invention.
The remarkable and unexpected resistance to hot creep of the alloy according to the invention is to be not.ed, in relation to the Pt(Rh 10%)~
Examples 2 to 4:
The same mode of operation as in . . .
~r' . . .
i7~
.
example 1 is used except that the contents of Y203 are different.
The results obtained are given in table III below, in which are indicated the typical values of resistance to hot creep in hours at 1000C, under a load of 3.85 kg/mm2 and of Vickers hardness un~er 5 kg (H~5) on test pieces, 1 mm thick, of alloy accordin~ to the invention.
.
. ~i .
:. ~ , ,. . : -~o TABLE I
,_ ~
. . . M~t~llur~ical ~ E R A% l1V
State l ~kg/mmZ) tkg/mm2) tkg~mm2) .
Platinum Cold-rollsd te- xlOOa80%)34 34 0,8 8a Annsaled 7 13 28 38 Pt-Rh 10% Cold-rolled. 53 53 0,6 . lB0 t~ xlO0=80%) . .
eO
Annealed 13 29 21 A8 10 ~ ~Anne~led _ ~ 53 3 143 . . _ . , . . ~ :' TAdLE II
Temperature 1000C 1300C 1 1450C
~ . _ . . I
\ 3 3,85 l,i 2,5 0,5 1,3 1,7 Brea-\ Load g \ tkg/ .
.Time. \ mm2) .. ~. _ . .
Pt-RH 10%20-30 4-8 2,2 2,6 Alloy of Example 1 . .
oo-?oo 20-40 lQ0-20010-15 ,? ~00 ,20-40 _ 10-20 TABLE III
. .
_ * t Hvtkg/mm2
2~ ~ _ r _ .
Y O ~ L~ Bi~ annea- B L~ BL ~annsaling a~
Exam- 2 3 ling at 1000C 1000C and col~-plesContents . and cold-rol-. rolled30% ~:
led 30%
- ~_ _ . . __ _ .
20,280 /OO 25-50 50-100 50-5A 55-65 3o i 3-0,360 /OO 20-60 j- 50~100 50-60 55-65 ;
_ _ _ , 40,850 /O0 17-25 25-55 48-50 45~48 ~ ., ~ tr : resistance to extrusion at 1000C under a load of 3.850 kg/mm2 in h.
35~ ~ BL: as laminated .. .. .
., ;, . ~ . . ~ - .
,: - ., ~ ~ , . . . .
::
Y O ~ L~ Bi~ annea- B L~ BL ~annsaling a~
Exam- 2 3 ling at 1000C 1000C and col~-plesContents . and cold-rol-. rolled30% ~:
led 30%
- ~_ _ . . __ _ .
20,280 /OO 25-50 50-100 50-5A 55-65 3o i 3-0,360 /OO 20-60 j- 50~100 50-60 55-65 ;
_ _ _ , 40,850 /O0 17-25 25-55 48-50 45~48 ~ ., ~ tr : resistance to extrusion at 1000C under a load of 3.850 kg/mm2 in h.
35~ ~ BL: as laminated .. .. .
., ;, . ~ . . ~ - .
,: - ., ~ ~ , . . . .
::
Claims (11)
1. Method for producing a metal from platinoids, platinum or an alloy thereof comprising, particles of at least one refractory oxide having a diameter less than about 1 µm, in the form of a dispersed phase and in the proportion of 0.1 to 5°/? by weight of the weight of said metal, wherein the molten host material contained in the said oxide is sprayed on a target by means of a device delivering a jet of pressurized gas.
2. A process as claimed in claim 1, wherein the said oxide has a melting point higher than that of the metallic host material.
3. A process as claimed in claim 1, wherein the said oxide is selected from rare earths and yttrium oxide and from the oxide listed in columns IIA and IVA of the periodical classifi-cation of elements (AFNOR norm).
4. A process as claimed in any one of claims 1, 2 or 3, wherein the said metal is selected from the group consisting of pure platinum, a platinum-rhodium alloy, and a platinum-iridium alloy.
5. A method as claimed in any one of claims 1, 2 or 3, wherein the said oxide is yttrium oxide.
6. A method as claimed in any one of claims 1, 2 or 3, wherein the oxide delivered by the spraying device is also in the molten state.
7. A method as claimed in any one of claims 1, 2 or 3, wherein the oxide, delivered by the spraying device is in a non-disassociated state.
8. A method as claimed in any one of claims 1, 2 or 3, wherein the spraying device is directly supplied by at least one powder containing the metallic host material and the oxide, or by a metallic wire prepared from the powder by the powder metallurgy method.
9. A method as claimed in any one of claims 1, 2 or 3, wherein the said spraying device is an oxy-acetylene flame gun.
10. A method as claimed in any one of claims 1, 2 or 3, wherein the said spraying device is an oxy-acetylene flame gun, and wherein the metal obtained contains between 0.2 and 1°/? of yttrium oxide.
11. A process as claimed in any one of claims 1, 2 or 3, wherein the spraying device is directly supplied by at least one powder containing the metallic host material and the oxide, or by a metallic wire prepared from the powder by the powder metallurgy method, and wherein the said powder is prepared by suspending a fine platinum powder in a solution of yttrium nitrate and by precipitation of the yttrium oxide and adsorption of said latter on the platinum by addition of an alkaline base.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7818441A FR2429264A1 (en) | 1978-06-20 | 1978-06-20 | PROCESS FOR THE MANUFACTURE OF A PLATINOID COMPRISING A DISPERSE PHASE OF A REFRACTORY OXIDE |
| FR7818441 | 1978-06-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1130570A true CA1130570A (en) | 1982-08-31 |
Family
ID=9209751
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA330,077A Expired CA1130570A (en) | 1978-06-20 | 1979-06-19 | Method for producing a platinoid comprising a dispersed phase of a refractory oxide |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US4252558A (en) |
| JP (1) | JPS5547336A (en) |
| BE (1) | BE877074A (en) |
| CA (1) | CA1130570A (en) |
| CH (1) | CH640884A5 (en) |
| DE (1) | DE2924896A1 (en) |
| ES (1) | ES481737A1 (en) |
| FR (1) | FR2429264A1 (en) |
| GB (1) | GB2023667B (en) |
| IT (1) | IT1118983B (en) |
| NL (1) | NL7904828A (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL8100238A (en) * | 1980-01-25 | 1981-08-17 | Johnson Matthey Co Ltd | ALLOY, METHOD FOR PREPARING THE SAME AND USE OF THE ALLOY. |
| ATE67402T1 (en) * | 1985-09-11 | 1991-10-15 | Degussa | MATERIAL FOR FACING DENTAL PROSTHESES. |
| JPH0439564Y2 (en) * | 1985-11-25 | 1992-09-16 | ||
| US4819859A (en) * | 1987-12-18 | 1989-04-11 | Ppg Industries, Inc. | Lamination of oxide dispersion strengthened platinum and alloys |
| DE4417495C1 (en) * | 1994-05-19 | 1995-09-28 | Schott Glaswerke | Prodn. of pure platinum materials reinforced with yttrium oxide |
| DE19531242C1 (en) * | 1995-08-25 | 1996-10-31 | Degussa | Hot strength platinum |
| US6338809B1 (en) * | 1997-02-24 | 2002-01-15 | Superior Micropowders Llc | Aerosol method and apparatus, particulate products, and electronic devices made therefrom |
| US7625420B1 (en) * | 1997-02-24 | 2009-12-01 | Cabot Corporation | Copper powders methods for producing powders and devices fabricated from same |
| EP1386708B1 (en) * | 1997-02-24 | 2014-06-18 | Cabot Corporation | Particulate products made by an aerosol method |
| US20050097987A1 (en) * | 1998-02-24 | 2005-05-12 | Cabot Corporation | Coated copper-containing powders, methods and apparatus for producing such powders, and copper-containing devices fabricated from same |
| DE19813988C1 (en) * | 1998-03-28 | 1999-10-28 | Heraeus Gmbh W C | Process for the production of a welded molded body consisting of finely divided, small particles of base metal oxide and strengthened platinum material, in particular a tube, in particular having at least one inner wall |
| JP3778338B2 (en) * | 2000-06-28 | 2006-05-24 | 田中貴金属工業株式会社 | Method for producing oxide dispersion strengthened platinum material |
| JP3776296B2 (en) * | 2000-06-28 | 2006-05-17 | 田中貴金属工業株式会社 | Oxide dispersion strengthened platinum material and method for producing the same |
| DE10046456C2 (en) * | 2000-09-18 | 2003-04-10 | Heraeus Gmbh W C | Through finely divided, small particles of base metal oxide, dispersion-strengthened, gold-free platinum material |
| JP6275533B2 (en) * | 2014-04-11 | 2018-02-07 | 株式会社フルヤ金属 | Glass melting stirrer and glass melting furnace |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR856363A (en) * | 1939-06-01 | 1940-06-12 | Degussa | Process for making homogeneous mixtures from two or more different substances |
| IT460208A (en) * | 1942-02-07 | |||
| US2476222A (en) * | 1944-03-10 | 1949-07-12 | Int Nickel Co | Production of powdered metal mixtures for sintering |
| US3378392A (en) * | 1963-07-24 | 1968-04-16 | Metco Inc | High temperature flame spray powder and process |
| GB1139897A (en) | 1965-01-15 | 1969-01-15 | Johnson Matthey Co Ltd | Improvements in and relating to the treatment of platinum group metals and alloys |
| GB1280815A (en) * | 1968-07-12 | 1972-07-05 | Johnson Matthey Co Ltd | Improvements in and relating to the dispersion strengthening of metals |
| US3598635A (en) * | 1969-02-24 | 1971-08-10 | Corning Glass Works | Plasma spraying protective coating on refractory |
| JPS5112615Y2 (en) * | 1971-05-18 | 1976-04-05 | ||
| US3713270A (en) * | 1971-05-24 | 1973-01-30 | Nat Res Dev | Hydrogen diffusion membranes |
| GB1461176A (en) * | 1974-04-11 | 1977-01-13 | Plessey Inc | Method of producing powdered materials |
| DE2807587A1 (en) * | 1977-02-23 | 1978-08-24 | Johnson Matthey Co Ltd | PLATINUM ALLOY |
-
1978
- 1978-06-20 FR FR7818441A patent/FR2429264A1/en active Granted
-
1979
- 1979-06-08 CH CH537879A patent/CH640884A5/en not_active IP Right Cessation
- 1979-06-15 US US06/048,805 patent/US4252558A/en not_active Expired - Lifetime
- 1979-06-18 JP JP7573479A patent/JPS5547336A/en active Granted
- 1979-06-18 GB GB7921116A patent/GB2023667B/en not_active Expired
- 1979-06-19 IT IT68302/79A patent/IT1118983B/en active
- 1979-06-19 CA CA330,077A patent/CA1130570A/en not_active Expired
- 1979-06-19 BE BE2/57878A patent/BE877074A/en not_active IP Right Cessation
- 1979-06-20 ES ES481737A patent/ES481737A1/en not_active Expired
- 1979-06-20 NL NL7904828A patent/NL7904828A/en not_active Application Discontinuation
- 1979-06-20 DE DE19792924896 patent/DE2924896A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| IT7968302A0 (en) | 1979-06-19 |
| DE2924896A1 (en) | 1980-01-17 |
| GB2023667A (en) | 1980-01-03 |
| CH640884A5 (en) | 1984-01-31 |
| DE2924896C2 (en) | 1989-08-31 |
| JPS6223063B2 (en) | 1987-05-21 |
| GB2023667B (en) | 1983-04-27 |
| US4252558A (en) | 1981-02-24 |
| IT1118983B (en) | 1986-03-03 |
| JPS5547336A (en) | 1980-04-03 |
| FR2429264B1 (en) | 1982-01-15 |
| BE877074A (en) | 1979-12-19 |
| FR2429264A1 (en) | 1980-01-18 |
| ES481737A1 (en) | 1980-06-16 |
| NL7904828A (en) | 1979-12-27 |
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