Background of the Invention and Related Art Statement
[0001] The present invention relates to a metal-made seamless pipe and a process for producing
such a pipe. More particularly, the present invention relates to a metal-made seamless
pipe which is low in processability but can be produced in a small thickness and a
small inner diameter, which is superior in mechanical strengths and gastightness,
and which can be suitably used, for example, as a sealing member of a translucent
vessel (e.g. a ceramic-made translucent vessel) of, for example, a high-pressure discharge
lamp (e.g. a metal halide lamp); as well as to a process for producing such a metal-made
seamless pipe.
[0002] As shown in Fig. 5, a translucent ceramic pipe 20 (a translucent pipe) is used as
a translucent vessel of a high-pressure discharge lamp 10 (e.g. a metal halide lamp),
because the translucent vessel contains a light emitting material (e.g. dysprosium
iodide) of high corrosivity and accordingly requires corrosion resistance.
[0003] In order to seal the translucent ceramic pipe 20 (a translucent pipe) used as a translucent
vessel, a metal-made pipe 30 (e.g. a Mo pipe) was proposed as a sealing member (European
Patent Publication EP 0982278A1).
[0004] The metal (e.g. Mo or W) used in such a metal-made pipe, however, is generally low
in processability and there has been a limit in producing the pipe in a small thickness
and a small inner diameter.
[0005] Since the metal is low in processability and its cutting is difficult, production
of a metal-made pipe therefrom has been conducted ordinarily by sintering a metal
ingot and subjecting the sintered metal ingot to rolling, drawing or the like to obtain
a pipe-shaped material.
[0006] In such a production process, it has been extremely difficult to obtain a metal-made
pipe of small thickness and small diameter.
[0007] In view of the above-mentioned problems, the object of the present invention is to
provide a metal-made seamless pipe which is low in processability but can be produced
in a small thickness and a small inner diameter, which is superior in mechanical strengths
and gastightness, and which can be suitably used, for example, as a sealing member
of a translucent vessel (e.g. a ceramic-made translucent vessel) of, for example,
a high-pressure discharge lamp (e.g. a metal halide lamp); and a process for producing
such a metal-made seamless pipe.
Summary of the Invention
[0008] The present invention provides a metal-made seamless pipe as set out in claim 1,
and a process for production thereof as set out in claim 4.
[0009] Preferably, the metals contained in the pipe each having a melting point of 2,600°C
or more and are selected from Mo, W and Re.
[0010] Preferably, the pipe further contains, in addition to the metal, at least one kind
of oxide selected from the group consisting of Al
2O
3, Y
2O
3 Dy
2O
3, Gd
2O
3, Ho
2O
3 and Tm
2O
3, in an amount of 0.02 to 5% by volume relative to 100% of the total of the metal
and the oxide.
[0011] In preparation of the mixture in the process, there is preferably further added,
in addition to the components used, at least one kind of oxide selected from the group
consisting of Al
2O
3, Y
2O
3, Dy
2O
3, Gd
2O
3, Ho
2O
3 and Tm
2O
3, in an amount of 0.02 to 5% by volume relative to 100% of the total of the metal
and the oxide.
[0012] Preferably drying of the pipe-shaped material is conducted in an atmosphere containing
the vapor of the solvent.
Brief Description of the Drawings
[0013]
Fig. 1 is a graph showing a reflation of porosity and gastightness in metal-made seamless
pipe.
Fig. 2 is a sectional view schematically showing a peeling test which comprises peeling
a thin W plate attached to an alumina plate via an Al2O3-Y2O3-Dy2O3-La2O3 type ceramic composition, from the alumina plate at a given force.
Fig. 3 is a graph showing the gastightnesses when Mo, W, Re, Ti, Hf and Zr were used
and their porosities were all fixed at 5%..
Fig. 4 is a graph showing a relation of thickness. inner diameter and gastightness
in metal-made seamless pipe.
Fig. 5 is a sectional view schematically showing a state in which a metal-made seamless
pipe is used as a sealing member for the ceramic-made translucent vessel of a high-pressure
discharge lamp (e.g. a metal halide lamp).
Detailed Description of Preferred Embodiments
[0014] The preferred embodiments of the metal-made seamless pipe and the process for production
thereof, both of the present invention are specifically described below with reference
to the accompanying drawings.
[0015] The metal-made seamless pipe of the present invention contains, as a main component,
at least one kind of metal selected from the group consisting of metals each having
a melting point of 1,600°C or more, and has a porosity of 0.3 to 25% when the porosity
is defined as an areal proportion of the open pores not perforating in the thickness
direction of the pipe, present at the outer surface of the pipe, to the total area
(100%) of the outer surface of the pipe.
[0016] The metal-made seamless pipe of the present invention has higher reliability to leak-free
(breakage) than pipes having seams, because it has no seam. When a metal-made pipe
having a seam is used as a sealing member for translucent vessel of high-pressure
discharge lamp (e.g. metal halide lamp), leakage (breakage) tends to occur therefrom
because the translucent vessel inside becomes several atm. during the operation of
the tube, resulting in lower reliability than in the case of seamless pipe.
[0017] As to the kind of the metal having a melting point of 1,600° C or more, used in the
present invention, there is no particular restriction. As preferable examples of the
metal, there can be mentioned at least one kind of metal selected from Mo (melting
point: 2,623°C), W (melting point: 3,422°C), Re (melting point: 3,186°C), Ti (melting
point: 1,668°C), Hf (melting point: 2,233°C) and Zr (melting point: 1,855°C), all
having corrosion resistance to the substance sealed into translucent vessel.
[0018] Incidentally, Mo and W have a body-centered cubic crystal structure, have a high
melting point as mentioned above, and have a very high Vickers hardness of 200 to
450. Re, Ti, Hf and Zr have a close-packed cubic crystal structure, have a high melting
point, and are low in crystal slip. Therefore, these metals are very low in processability.
[0019] In the present invention, "open pores other than through-pores" refer to pipe-surface
pores not perforating (not causing leakage) in the thickness direction of pipe. Such
open pores can be confirmed by conducting a He leakage test and making an image analysis
for outer surface porosity.
[0020] As shown in Table 1, when the porosity of metal-made seamless pipe exceeds 25%, its
gastightness is low.
[0021] Herein, "gastightness" is measured by fitting a metal-made pipe of 1 mm in outer
diameter, 0.7 mm in inner diameter (therefore, 0.3 mm in thickness) and 100 mm in
length to a He detector. When the pipe sample number is 10 and all the samples are
gastight, the gastightness of the pipe is taken as 100%. "Gastight" refers to that
in the He leakage test, the leakage rate is 1.0x10
-10 atm.cc/sec or less.
[0022] The lower limit of the outer surface porosity is determined by the wettability toward
other substance, particularly, cement, ceramic, glass or the like. A lower limit smaller
than 0.3% is not preferred as is clear from the results of the following peeling test.
Peeling test
[0023] As shown in Fig. 2, a thin W plate 3 was attached to an alumina plate 1 via an Al
2O
3-Y
2O
3-Dy
2O
3-La
2O
3 type ceramic composition; the thin W plate 3 was peeled from the alumina plate 1;
the sites of breakage and the evaluations are shown in Table 1.
Table 1
|
Site of breakage |
Evaluation |
Porosity of thin W plate (%) |
0.1 |
Thin W plate surface No breakage of ceramic |
× |
0.2 |
Thin W plate surface No breakage of ceramic |
× |
0.3-0.5 |
Thin W plate surface Ceramic on W plate: small |
Δ |
1.0 |
Ceramic on W plate: small to medium |
Δ - ○ |
3.0 |
Ceramic on W plate: medium |
○ |
5.0 |
Ceramic on W plate: large |
○ |
[0024] As is clear from Table 1, the presence of ceramic on W plate (the remaining of ceramic
composition on the surface side of thin W plate contacting with ceramic composition
when the thin W plate was peeled) indicates high wettability, i.e. high adhesivity
between thin W plate and ceramic composition. Therefore, a large amount of ceramic
on W plate was rated as ○. No ceramic on W plate was rated as X, and the intermediate
between them was rated as Δ. It is appreciated form Table 1 that a porosity of less
than 0.3% gives low adhesivity.
[0025] When a metal of relatively low melting point is used, sintering takes place at an
early timing and proceeds before the binder gas is released; pores generate inside
in a large amount and easily become through-pores; as a result, gastightness tends
to be low before a porosity of 25% (the upper limit of specified range) is reached.
[0026] Gastightnesses when Mo, W, Re, Ti, Hf and Zr are used, are compared by fixing the
porosity at 5% for all cases. As shown in Fig. 3, of these metals, preferred are metals
having a melting point of 2,600°C or more, i.e. Mo (melting point = 2,623°C), W (melting
point = 3,422°C) and Re (melting point = 3,186).
[0027] The metal-made seamless pipe of the present invention preferably has an inner diameter
of 0.4 to 3.0 mm and a thickness of 0.05 to 1.0 mm.
[0028] As shown in Fig. 4, no leakage occurs (therefore, superior gastightness is obtained)
in a certain region wherein the inner diameter and the thickness are in the above
ranges.
[0029] For example, when the inner diameter is 3 mm and the thickness is 0.05 mm, the inner
diameter is too large and no sufficient increase in density takes place during molding;
thus, leakage occurs when the thickness is as small as 0.05 mm.
[0030] When the inner diameter is 0.4 mm and the thickness is 1.0 mm, the thickness is too
large and non-uniformity in drying speed arises after molding; as a result, drying
cracks (microcracks) appear and leakage is incurred.
[0031] Preferably, the metal-made seamless pipe of the present invention further contains,
in addition to the metal, at least one kind of oxide selected from the group consisting
of Al
2O
3, Y
2O
3, Dy
2O
3, Gd
2O
3, Ho
2O
3 and Tm
2O
3, in an amount of 0.02 to 5% by volume, preferably 0.05 to 2% by volume relative to
100% of the total of the metal and the oxide, for improvement in strength. When the
amount of the oxide is less than 0.02% by volume, the effect of strength improvement
is low. When the amount of the oxide is more than 5% by volume, adverse effects such
as reduction in gastightness, brittleness and the like may appear. Of the above oxides,
Al
2O
3 is preferred for the corrosion resistance.
[0032] The process for producing a metal-made seamless pipe according to the present invention
comprises preparing a mixture containing (1) 80 to 98% by weight of a powder of at
least one kind of metal selected from the group consisting of metals each having a
melting point of 1,600°C or more and (2) a binder in a solvent; kneading the mixture
for 0 to 3 hours, preferably 1 to 2 hours and then extruding the kneaded material
to form a pipe-shaped material; drying the pipe-shaped material at -5 to 25°C (preferably
-2 to 15°C) for 10 hours (shortest) to 48 hours (preferably 24 hours) (longest) from
the completion of the extrusion and thereafter at 30 to 120°C, preferably 80 to 100°C
for 0 to 8 hours, preferably 0.5 to 4 hours; then, firing the dried material at a
lower temperature selected from a temperature between 1,000 to 2,100°C and a temperature
lower by 300°C than the melting point of the metal.
[0033] Thus, in the present process for producing a metal-made seamless pipe, mild drying
is conducted for a given length of time from the completion of the extrusion. This
mild drying is necessary to remove the extrusion strain, etc. remaining right after
the extrusion (at the start of drying). In drying of, in particular, a pipe-shaped
material, the drying speed is inevitably higher than that of a solid (non-hollow)
material and, therefore, its drying right after extrusion need be mild. Residual extrusion
stress becomes a main cause for firing deformation, etc.
[0034] As to the preparation of the mixture, there is no particular restriction. In this
step, when the content of the metal powder is less than 80% by weight, drying cracks
may appear; when the content of the metal powder is more than 98% by weight, the dispersion
of the metal particles may be insufficient.
[0035] There is no particular restriction, either, as to the method of kneading and extrusion
in the extrusion step.
[0036] There is no particular restriction, either, as to the method of drying.
[0037] The firing in the firing step is conducted in a non-oxidizing atmosphere or in vacuum.
In the firing step, when the firing temperature is lower than a lower temperature
selected from 1,000°C and a temperature lower by 300°C than the melting point of the
metal, insufficient sintering may take place; when the firing temperature is higher
than a lower temperature selected from 2,100°C and a temperature lower by 300°C than
the melting point of the metal, firing deformation may take place depending upon the
kind of the metal used.
[0038] By employing such a production process, it is possible to easily obtain a thin, small-diameter
seamless which has been difficult to obtain with conventional processes; therefore,
productivity improvement and consequent cost reduction can be achieved.
[0039] The drying of the pipe-shaped material is preferably conducted in an atmosphere containing
the vapor of the solvent used in the mixture.
[0040] By employing such a production process, mild drying becomes possible and extrusion
strain can be reduced.
[0041] The present invention is specifically described below by way of Examples. However,
the present invention is in no way restricted by these Examples.
Example 1
[0042] To 1,000 g of a powder of W (melting point = 3,422°C were added 12 g of ethyl cellulose
(a binder), 30 g of butylcarbitol acetate (a solvent) and 10 g of additives including
Al
3O
3. The mixture was passed through a tri-roll mill ten times.
[0043] The mixture was molded by an extruder. The extrudate was dried in the air at 80°C
for 2 hours.
[0044] The dried material was fired in hydrogen at 1,900°C for 3 hours. To remove the binder
while preventing the oxidation of Mo, moistening was made to obtain a dew point of
0°C.
[0045] By the above treatment, there was produced a Mo pipe having a porosity of 8% and
a leakage rate of 1.0x10
-10 atm. cc/sec or less in the He leakage test.
[0046] As described above, the present invention can provide a metal-made seamless pipe
which is low in processability but can be produced in a small thickness and a small
inner diameter, which is superior in mechanical strengths and gastightness, and which
can be suitably used, for example, as a sealing member of a translucent vessel (e.g.
a ceramic-made translucent vessel) of, for example, a high-pressure discharge lamp
(e.g. a metal halide lamp); and a process for producing such a metal-made seamless
pipe. The metal-made seamless pipe of the present invention can preferably be used
suitably particularly as a sealing member of translucent pipe of, for example, high-pressure
discharge lamp (e.g. ceramic-made metal halide lamp). The present metal-made seamless
pipe can also be used suitably as a metal pipe produced from a metal of low processability
and having a small thickness and a small inner diameter, high heat resistance, high
mechanical strengths and superior gastightness, for example, a fine pipe of, for example,
heat exchangers used in extreme situations such as space, aviation, military and the
like.
1. A metal-made seamless pipe containing, as a main component, at least one kind of metal
having a melting point of 1,600°C or more, and selected from Mo, W, Re, Ti, Hf and
Zr, which pipe has a porosity of 0.3 to 25% when the porosity is defined as an areal
proportion of the open pores present at the outer surface of the pipe, to the total
area (100%) of the outer surface of the pipe, the pores not perforating in the thickness
direction of the pipe, and wherein the pipe has an inner diameter of 0.4 to 3.0 mm
and a thickness of 0.05 to 1.0 mm.
2. A metal-made seamless pipe according to claim 1, wherein the at least one kind of
metal is selected from Mo, W and Re, with a melting point of 2,600°C or more.
3. A metal-made seamless pipe according to claims 1 and 2, which further contains, in
addition to the metal, at least one kind of oxide selected from the group consisting
of Al2O3, Y2O3, Dy2O3 Gd2O3, Ho2O3 and Tm2O3, in an amount of 0.02 to 5% by volume relative to 100% of the total of the metal
and the oxide.
4. A process for producing a metal-made seamless pipe according to any one of claims
1 to 3, which comprises:
preparing a mixture containing (1) 80 to 98% by weight of a powder of at least one
kind of metal selected from Mo, W, Re, Ti, Hf and Zr, having a melting point of 1,600°C
or more and (2) a binder in a solvent,
kneading the mixture for 0 to 3 hours and then extruding the kneaded material to form
a pipe-shaped material, and
drying the pipe-shaped material at -5 to 25°C for 10 hours to 48 hours from the completion
of the extrusion and thereafter at 30 to 120°C for 0.5 to 8 hours and then firing
the dried material at a temperature in a range between 1,000°C and the lower of: either
2,100°C or a temperature 300°Clower than the melting point of the metal.
5. A process for producing a metal-made seamless pipe according to claim 4, wherein the
at least one kind of metal is selected from Mo, W and Re with a melting point of 2,600°C
or more.
6. A process for producing a metal-made seamless pipe according to claim 4 or 5, wherein
in preparation of the mixture, there is further added, in addition to the components
used, at least one kind of oxide selected from the group consisting of Al2O3, Y2O3, Dy2O3, Gd2O3, Ho2O3 and Tm2O3, in an amount of 0.02 to 5% by volume relative to 100% of the total of the metal
and the oxide.
7. A process for producing a metal-made seamless pipe according to any one of claims
4 to 6, wherein the drying of the pipe-shaped material is conducted in an atmosphere
containing the vapor of the solvent.
1. Nahtloses Metallrohr, umfassend als Hauptkomponente zumindest eine Art von Metall,
das einen Schmelzpunkt von 1.600 °C oder mehr aufweist und aus Mo, W, Re, Ti, Hf und
Zr ausgewählt ist, wobei das Rohr eine Porosität von 0,3 bis 25 % aufweist, wenn die
Porosität als Flächenverhältnis zwischen den offenen Poren an der Außenfläche des
Rohrs und der Gesamtfläche (100 %) der Außenfläche des Rohrs definiert ist, wobei
die Poren das Rohr in die Dickerichtung nicht perforieren, und worin das Rohr einen
Innendurchmesser von 0,4 bis 3,0 mm und eine Dicke von 0,05 bis 1,0 mm aufweist.
2. Nahtloses Metallrohr nach Anspruch 1, worin die zumindest eine Art von Metall aus
Mo, W und Re ausgewählt ist und einen Schmelzpunkt von 2.600 °C oder mehr aufweist.
3. Nahtloses Metallrohr nach Anspruch 1 und 2, das neben dem Metall außerdem eine Art
von Oxid, das aus der aus Al2O3, Y2O3, Dy2O3, Gd2O3, Ho2O3 und Tm2O3 bestehenden Gruppe ausgewählt ist, in einer Menge von 0,02 bis 5 Vol.-%, bezogen
auf 100 % der Gesamtmenge des Metalls und des Oxids, umfasst.
4. Verfahren zur Herstellung eines nahtlosen Metallrohrs nach einem der Ansprüche 1 bis
3, umfassend:
die Herstellung eines Gemischs, das (1) 80 bis 98 Gew.-% eines Pulvers aus zumindest
einer Art von Metall, das aus Mo, W, Re, Ti, Hf und Zr ausgewählt ist und einen Schmelzpunkt
von 1.600 °C oder mehr aufweist, und (2) ein Bindemittel in einem Lösungsmittel umfasst,
das 0- bis 3-stündige Kneten des Gemischs, gefolgt vom Extrudieren des gekneteten
Materials, um ein rohrförmiges Material zu bilden, und
das Trocknen des rohrförmigen Metalls bei -5 bis 25 °C für eine Dauer von 10 Stunden
bis 48 Stunden nach Beendigung der Extrusion, anschließend 0,5 bis 8 Stunden lang
bei 30 bis 120°C, gefolgt vom Brennen des getrockneten Materials bei einer Temperatur
in einem Bereich zwischen 1.000 °C und dem niedrigeren Wert von entweder 2.100 °C
oder einer Temperatur, die 300 °C unter dem Schmelzpunkt des Metalls liegt.
5. Verfahren zur Herstellung eines nahtlosen Metallrohrs nach Anspruch 4, worin die zumindest
eine Art von Metall aus Mo, W und Re ausgewählt ist und einen Schmelzpunkt von 2.600
°C oder mehr aufweist.
6. Verfahren zur Herstellung eines nahtlosen Metallrohrs nach Anspruch 4 oder 5, worin
bei der Herstellung des Gemischs neben den verwendeten Komponenten außerdem zumindest
eine Art von Oxid, das aus der aus Al2O3, Y2O3, Dy2O3, Gd2O3, Ho2O3 und Tm2O3 bestehenden Gruppe ausgewählt ist, in einer Menge von 0,02 bis 5 Vol.-%, bezogen
auf 100 % der Gesamtmenge des Metalls und des Oxids, zugesetzt wird.
7. Verfahren zur Herstellung eines nahtlosen Metallrohrs nach einem der Ansprüche 4 bis
6, worin das Trocknen des rohrförmigen Materials in einer Atmosphäre durchgeführt
wird, die den Dampf des Lösungsmittels enthält.
1. Tuyau sans soudure composé de métal contenant, en tant que composant principal, au
moins un type de métal ayant un point de fusion de 1 600 °C ou plus, et choisi parmi
Mo, W, Re, Ti, Hf et Zr, lequel tuyau a une porosité de 0,3 à 25 % lorsque la porosité
est définie comme proportion surfacique des pores ouverts présents à la surface externe
du tuyau sur l'aire totale (100 %) de la surface externe du tuyau, les pores ne transperçant
pas dans la direction de l'épaisseur du tuyau, et dans lequel le tuyau a un diamètre
interne de 0,4 à 3,0 mm et une épaisseur de 0,05 à 1,0 mm.
2. Tuyau sans soudure composé de métal selon la revendication 1, dans lequel le au moins
un type de métal est choisi parmi Mo, W et Re, avec un point de fusion de 2 600 °C
ou plus.
3. Tuyau sans soudure composé de métal selon les revendications 1 et 2, qui contient
en outre, en plus du métal, au moins un type d'oxyde choisi dans le groupe constitué
par Al2O3, Y2O3, Dy2O3, Gd2O3, Ho2O3 et Tm2O3, en une quantité de 0,02 à 5 % en volume par rapport à 100 % du total du métal et
de l'oxyde.
4. Procédé de production d'un tuyau sans soudure composé de métal selon l'une quelconque
des revendications 1 à 3, qui comprend :
la préparation d'un mélange contenant (1) 80 à 98 % en poids d'une poudre d'au moins
un type de métal choisi parmi Mo, W, Re, Ti, Hf et Zr, ayant un point de fusion de
1 600 °C ou plus et (2) un liant dans un solvant,
le malaxage du mélange pendant 0 à 3 heures, puis l'extrusion du matériau malaxé pour
former un matériau en forme de tuyau et
le séchage du matériau en forme de tuyau à - 5 à 25°C pendant 10 heures à 48 heures
à partir de l'achèvement de l'extrusion et par la suite à 30 à 120°C pendant 0,5 à
8 heures, puis la cuisson du matériau séché à une température dans une gamme comprise
entre 1 000°C et la plus basse parmi : soit 2 100 °C, soit une température de 300
°C inférieure au point de fusion du métal.
5. Procédé de production d'un tuyau sans soudure composé de métal selon la revendication
4, dans lequel le au moins un type de métal est choisi parmi Mo, W et Re avec un point
de fusion de 2 600 °C ou plus.
6. Procédé de production d'un tuyau sans soudure composé de métal selon la revendication
4 ou 5, dans lequel lors de la préparation du mélange, il est en outre ajouté, en
plus des composants utilisés, au moins un type d'oxyde choisi dans le groupe constitué
par Al2O3, Y2O3, Dy2O3, Gd2O3, Ho2O3 et Tm2O3, en une quantité de 0,02 à 5 % en volume par rapport à 100 % du total du métal et
de l'oxyde.
7. Procédé de production d'un tuyau sans soudure composé de métal selon l'une quelconque
des revendications 4 à 6, dans lequel le séchage du matériau en forme de tuyau est
conduit dans une atmosphère contenant la vapeur du solvant.