Technical Field
[0001] An embodiment of the present invention relates to a tungsten alloy part, and a discharge
lamp, a transmitting tube, and a magnetron using the same.
Background Art
[0002] A tungsten alloy part is used in various fields utilizing the high-temperature strength
of tungsten. Examples thereof include a discharge lamp, a transmitting tube, and a
magnetron. The tungsten alloy part is used for a cathode electrode, an electrode supporting
rod, and a coil part or the like in the discharge lamp (HID lamp). The tungsten alloy
part is used for a filament and a mesh grid or the like in the transmitting tube.
The tungsten alloy part is used for the coil part or the like in the magnetron. These
tungsten alloy parts include a sintered body having a predetermined shape, a wire
rod and a coil part obtained by processing the wire rod into a coil form.
[0003] Conventionally, as described in Jpn. Pat. Appln. KOKAI Publication No.
2002-226935 (Patent Literature 1), a tungsten alloy containing thorium (or a thorium compound)
is used for these tungsten alloy parts. In the tungsten alloy of Patent Literature
1, deformation resistance is improved by finely dispersing thorium particles and thorium
compound particles so that the average particle diameter thereof is set to 0.3 µm
or less. Since the thorium-containing tungsten alloy has excellent emitter characteristics
and mechanical strength at a high temperature, the thorium-containing tungsten alloy
is used in the above fields.
[0004] However, since thorium or the thorium compound is a radioactive material, a tungsten
alloy part using no thorium is desired in consideration of the influence on the environment.
In Jpn. Pat. Appln. KOKAI Publication No.
2011-103240 (Patent Literature 2), a tungsten alloy part containing boride lanthanum (LaB
6) has been developed as the tungsten alloy part using no thorium.
[0005] On the other hand, a short arc type high-pressure discharge lamp using a tungsten
alloy containing lanthanum trioxide (La
2O
3) and HfO
2 or ZrO
2 is described in Patent Literature 3. According to the tungsten alloy described in
Patent Literature 3, sufficient emission characteristics are not obtained. This is
because lanthanum trioxide has a low melting point of about 2300°C, and lanthanum
trioxide is evaporated in an early stage when a part is subjected to a high temperature
by increasing an applied voltage or a current density, which causes deterioration
in emission characteristics.
Citation List
Patent Literatures
[0006]
Patent Literature 1: Jpn. Pat. Appln. KOKAI Publication No. 2002-226935
Patent Literature 2: Jpn. Pat. Appln. KOKAI Publication No. 2011-103240
Patent Literature 3: Jpn. Pat. Publication No. 4741190
Summary of Invention
[0007] For example, discharge lamps, parts of which use a tungsten alloy, are roughly divided
into two kinds (a low-pressure discharge lamp and a high-pressure discharge lamp).
Examples of the low-pressure discharge lamp include various arc-discharge type discharge
lamps such as for general lighting, special lighting used for a road or a tunnel or
the like, a curing apparatus for coating material, a UV curing apparatus, a sterilizer,
and a light cleaning apparatus for a semiconductor or the like. Examples of the high-pressure
discharge lamp include a processing apparatus for water supply and sewerage, general
lighting, outdoor lighting for a stadium or the like, a UV curing apparatus, an exposure
device for a semiconductor and a printed circuit board or the like, a wafer inspection
apparatus, a high-pressure mercury lamp such as a projector, a metal halide lamp,
an extra high pressure mercury lamp, a xenon lamp, and a sodium lamp.
[0008] A voltage of 10 V or more is applied to the discharge lamp according to the application.
When a voltage is less than 100 V, a life equal to that of the thorium-containing
tungsten alloy is obtained for the tungsten alloy containing boride lanthanum described
in Patent Literature 2. However, if the voltage is a high value of 100 V or more,
the emission characteristics are deteriorated. As a result, the life is also largely
decreased.
[0009] Similarly, there is a problem that sufficient characteristics are not obtained also
for the transmitting tube or the magnetron if the applied voltage is increased.
[0010] It is an object of the present invention to provide a tungsten alloy part exhibiting
characteristics equal to or higher than those of a thorium-containing tungsten alloy
part without using thorium which is a radioactive material, and a discharge lamp,
a transmitting tube, and a magnetron using the tungsten alloy part.
[0011] According to an embodiment, a tungsten alloy part containing tungsten and at least
two kinds of components (hereinafter, referred to as a Zr component) selected from
the group consisting of Zr, ZrO
2, ZrC, and C is provided. The tungsten alloy part contains 0.1 to 5 wt% of the Zr
component in terms of ZrO
2. The tungsten alloy part preferably contains 0.1 to 3 wt% of the Zr component in
terms of ZrO
2. When contents of Zr and O are converted into ZrO
x, x < 2 is preferably set; and 0 < x < 2 is more preferably set.
[0012] The tungsten alloy part may further contain 0.01 wt% or less of at least one element
selected from the group consisting of K, Si, and Al. The tungsten alloy may contain
2 wt% or less of at least one kind of Ti, Hf, V, Nb, Ta, Mo, and rare earth elements.
Particularly, when the content of Zr is defined as 100 parts by mass, the tungsten
alloy part may contain 15 parts by mass or less of Hf.
[0013] The primary particles of ZrO
2 preferably have an average particle diameter of 15 µm or less, and more preferably
have an average particle diameter of 5 µm or less and a maximum diameter of 15 µm
or less. Secondary particles of ZrO
2 preferably have a maximum diameter of 100 µm or less.
[0014] The Zr component preferably exists as two kinds (ZrO
2 and metal Zr). At least a part of metal Zr is preferably solid-solved in tungsten.
Metal Zr preferably exists on a surface of the tungsten alloy part. When the total
content of Zr is defined as 100 parts by mass, the content of Zr contained in ZrO
2 is preferably 30 to 98 parts by mass.
[0015] The tungsten alloy part preferably has a wire diameter of 0.1 to 30 mm. The tungsten
alloy part preferably has a Vickers hardness Hv of 330 or more, and particularly preferably
330 to 700.
[0016] The discharge lamp electrode part preferably has a tip part having a tapered tip
and a cylindrical body part. When the crystal structure of the transverse section
(radial section) of the body part is observed, the area ratio of the tungsten crystals
having a crystal particle diameter of 1 to 80 µm per unit area (e.g., 300 µm × 300
µm) is preferably 90% or more. When the crystal structure of the vertical section
of the body part is observed, the area ratio of the tungsten crystals having a crystal
particle diameter of 2 to 120 µm per unit area (e.g., 300 µm × 300 µm) is preferably
90% or more.
[0017] The tungsten alloy part of the embodiment is used for a discharge lamp part, a transmitting
tube part, or a magnetron part, for example.
[0018] A discharge lamp of an embodiment includes the tungsten alloy part of the embodiment.
A transmitting tube of an embodiment includes the tungsten alloy part of the embodiment.
A magnetron of an embodiment includes the tungsten alloy part of the embodiment.
[0019] When the tungsten alloy part of the embodiment is applied to an electrode of the
discharge lamp, an applied voltage to the electrode is preferably 100 V or more. Since
the tungsten alloy part of the embodiment included in the discharge lamp electrode
does not contain thorium (or thorium oxide) which is a radioactive material, the tungsten
alloy part does not exert a bad influence on the environment. In addition, the discharge
lamp electrode including the tungsten alloy part of the embodiment has characteristics
equal to or higher than those of an electrode containing a thorium-containing tungsten
alloy. For this reason, the discharge lamp including the tungsten alloy part of the
embodiment is environment-friendly.
Brief Description of Drawings
[0020]
FIG. 1 shows an example of a discharge lamp electrode part of an embodiment.
FIG. 2 shows another example of the discharge lamp electrode part of the embodiment.
FIG. 3 shows an example of a discharge lamp of an embodiment.
FIG. 4 shows an example of a magnetron part of an embodiment.
FIG. 5 shows an example of a discharge lamp electrode part of an embodiment.
FIG. 6 shows another example of the discharge lamp electrode part of the embodiment.
FIG. 7 shows an example of a transverse section of a body part of the discharge lamp
electrode part of the embodiment.
FIG. 8 shows an example of a vertical section of the body part of the discharge lamp
electrode part of the embodiment.
FIG. 9 shows an example of a discharge lamp of an embodiment.
FIG. 10 shows the relationship between an emission current density and an applied
voltage of Example 1 and Comparative Example 1.
Description of Embodiments
[0021] A tungsten alloy part of an embodiment contains tungsten and at least two kinds of
components selected from the group consisting of Zr, ZrO
2, ZrC, and C. The tungsten alloy part contains 0.1 to 5 wt% of Zr in terms of ZrO
2. The tungsten alloy part preferably contains 0.1 to 3 wt% of Zr in terms of ZrO
2.
[0022] The tungsten alloy part contains 0.1 to 5 wt% of Zr (zirconium) in terms of ZrO
2 (zirconium oxide), and thereby characteristics such as emission characteristics and
a strength can be improved. That is, when the content of Zr is less than 0.1 wt% in
terms of ZrO
2, the addition effect of Zr is insufficient. When the content of Zr is more than 3
wt%, the characteristics are deteriorated. The content of Zr is preferably 0.5 to
2.5 wt% in terms of ZrO
2.
[0023] The tungsten alloy part of the embodiment contains at least two kinds of components
selected from the group consisting of Zr, ZrO
2, ZrC, and C. Specifically, the tungsten alloy part contains a combination of Zr and
ZrO
2, a combination of ZrO
2 and ZrC (zirconium carbide), a combination of ZrO
2 and C (carbon), a combination of Zr, ZrO
2, and ZrC, a combination of ZrO
2, ZrC and C, a combination of Zr, ZrO
2, and C, or a combination of Zr, ZrO
2, ZrC and C (carbon) as the ZrO
2 component. When the melting points are compared, the melting points of metal Zr,
ZrO
2, ZrC, and tungsten are respectively 1850°C, 2720°C, 3420°C, and 3400°C (see Iwanami
Shoten "Rikagakujiten (Dictionary of Physics and Chemistry)"). The melting points
of metal thorium and thorium oxide (ThO
2) are respectively 1750°C and 3220 ± 50°C. Since zirconium has a melting point higher
than that of thorium, the tungsten alloy part of the embodiment can have a strength
at high-temperature equal to or higher than that of a thorium-containing tungsten
alloy part.
[0024] When the contents of Zr and 0 are expressed in ZrO
x, × < 2 is preferably set. x < 2 means that the ZrO
2 component contained in the tungsten alloy does not wholly exist as stoichiometric
ZrO
2, and a part thereof exists as metal Zr and ZrC. Since the work function of metal
Zr is 4.1, and greater than the work function (3.4) of metal Th, the emission characteristics
are considered to be deteriorated. However, this is not particularly problematic in
the application for the discharge lamp or the like. Since metal zirconium forms a
solid solution with tungsten, metal zirconium is a component effective in enhancing
a strength. When the contents of Zr and O are expressed in ZrO
x, 0 < x < 2 is preferably set. X < 2 is described above. 0 < x means that either ZrC
or C exists in the tungsten alloy. ZrC or C has a deoxidation effect for removing
an oxygen impurity contained in the tungsten alloy. Since the electrical resistance
value of the tungsten alloy part can be decreased by reducing the oxygen impurity,
the tungsten alloy part has improved characteristics as an electrode. When x of ZrO
x is within the above-mentioned range, metal Zr, ZrO
2, ZrC, or C exists in a good balance, to improve characteristics such as emission
characteristics, a strength, electrical resistance, and a life.
[0025] The contents of Zr, ZrO
2, ZrC, and 0 in the tungsten alloy part can be measured by using an ICP analysis method
and an inert gas fusion-infrared absorption method. In the ICP analysis method, an
amount of Zr obtained by adding an amount of metal Zr and an amount of Zr of ZrO
2 and ZrC can be measured. An amount of oxygen obtained by adding an amount of O (oxygen)
of ZrO
x and an amount of oxygen which independently exists or an amount of oxygen which exists
as another oxide can be measured by the inert gas fusion-infrared absorption method.
In the embodiment, the amount of Zr and the amount of O are measured by the ICP analysis
method and the inert gas fusion-infrared absorption method, and expressed in ZrO
x.
[0026] The tungsten alloy part of the embodiment may contain 0.01 wt% or less of at least
one element selected from the group consisting of K, Si, and Al. K (potassium), Si
(silicon), and Al (aluminum) are so-called dope materials. Recrystallization characteristics
can be improved by adding these dope materials. The recrystallization characteristics
are improved, and thereby a uniform recrystallized structure is likely to be obtained
when a recrystallization heat treatment is performed. Although the lower limit of
the content of the dope material is not particularly limited, the content is preferably
0.001 wt% or more. When the content is less than 0.001 wt%, the addition effect is
small. When the content is more than 0.01 wt%, sinterability and processability are
deteriorated, which may cause a decrease in a mass production property.
[0027] The tungsten alloy part of the embodiment preferably contains 15 parts by mass or
less of Hf when the content of Zr is 100 parts by mass. The content of Zr represents
the total amount of Zr in Zr, ZrO
2, and ZrC. Since Hf (hafnium) has a high melting point of 2207°C, Hf hardly exerts
an adverse influence even when Hf is contained in the tungsten alloy part. Commercially
available Zr powder may contain Hf of several percent depending on the grade. It is
effective to use high-purity Zr powder or high-purity ZrO
2 powder from which impurities have been removed in order to improve the characteristics.
On the other hand, highly purified raw material causes a cost increase. If the content
of Hf (hafnium) is 15 parts by mass or less when the content of Zr is defined as 100
parts by weight, excessive deterioration of the characteristics can be prevented.
[0028] When the amount of carbon in a surface part in the tungsten alloy part of the embodiment
is defined as C1 (wt%) and the amount of carbon in a central part is defined as C2
(wt%), C1 < C2 is preferably set. The surface part means a portion located between
the surface of the tungsten alloy part and a point distant by 20 µm from the surface.
The central part is a central portion in the section of the tungsten alloy part. The
amount of carbon is a value obtained by adding both carbon of a carbide such as ZrC,
and independently existing carbon, and can be analyzed by the inert gas fusion-infrared
absorption method. The amount of carbon C1 in the surface part is smaller than the
amount of carbon C2 in the central part means that carbon in the surface part is oxidized
into CO
2, which is discharged to the outside of the system. When the amount of carbon in the
surface part is decreased, the amount of Zr in the surface part is relatively increased.
For this reason, it is particularly effective when Zr is used as an emitter material.
[0029] The tungsten alloy part of the embodiment preferably contains tungsten crystals having
an average crystal particle diameter of 1 to 100 µm. The tungsten alloy part is preferably
a sintered body. When the tungsten alloy part is the sintered body, parts having various
shapes can be prepared by utilizing a molding process. The sintered body is subjected
to a forging process, a rolling process, and a wiredrawing process or the like, and
thereby the sintered body is likely to be processed into a wire rod (including a filament)
and a coil part or the like. The tungsten crystals of the sintered body have an isotropic
crystal structure in which the ratio of crystals having an aspect ratio of less than
3 is 90% or more. When the sintered body is subjected to the wiredrawing process,
the tungsten crystals have a flat crystal structure in which the ratio of crystals
having an aspect ratio of 3 or more is 90% or more. The particle diameters of the
tungsten crystals can be obtained as follows. First, a photograph of a crystal structure
is taken by a metallurgical microscope or the like. A maximum Feret diameter is measured
for one tungsten crystal existing in the section, and defined as a particle diameter.
The measurement is performed for 100 arbitrary tungsten crystals, and the average
value thereof is defined as an average crystal particle diameter.
[0030] When the average of the maximum Feret diameters of the tungsten crystals is a small
value of less than 1 µm, it is difficult to form a uniform dispersion state of a dispersed
component such as Zr, ZrO
2, ZrC, or C. This is because the grain boundary is small when the average of the maximum
Feret diameters of the tungsten crystals is a small value of less than 1 µm, which
makes it difficult to uniformly disperse the dispersed component in the grain boundary
between the tungsten crystals. On the other hand, when the average of the maximum
Feret diameters of the tungsten crystals is a large value of more than 100 µm, the
strength as the sintered body is decreased. Therefore, the average of the maximum
Feret diameters of the tungsten crystals is preferably 1 to 100 µm, and more preferably
10 to 60 µm.
[0031] From the viewpoint of uniform dispersion, the average value of the maximum Feret
diameters of the dispersed component such as Zr, ZrO
2, ZrC, or C is preferably smaller than the average value of the maximum Feret diameters
of the tungsten crystals. Specifically, when the average value of the maximum Feret
diameters of the tungsten crystals is defined as A (µm) and the average value of the
maximum Feret diameters of the dispersed component is defined as B (µm), B/A ≤ 0.5
is preferably set. The dispersed component such as Zr, ZrO
2, ZrC, or C exists in the grain boundary between the tungsten crystals, and functions
as an emitter material or a grain boundary reinforcing material. The average particle
diameter of the dispersed component is decreased to 1/2 or less of the average crystal
particle diameter of tungsten, and thereby the dispersed component is likely to be
uniformly dispersed in the grain boundary between the tungsten crystals, which can
reduce variation in the characteristics.
[0032] The above tungsten alloy part is preferably used for at least one kind of a discharge
lamp part, a transmitting tube part, and a magnetron part.
[0033] Examples of the discharge lamp part include a cathode electrode, an electrode supporting
rod, and a coil part which are used for a discharge lamp. FIG. 1 and FIG. 2 show an
example of a discharge lamp cathode electrode. In FIG. 1 and FIG. 2, numeral number
1 designates a cathode electrode; numeral number 2 designates an electrode body part;
and numeral number 3 designates an electrode tip part. The cathode electrode 1 is
formed by the sintered body of the tungsten alloy. The electrode tip part 3 may have
a tip having a truncated cone shape as shown in FIG. 1 or a tip having a cone shape
as shown in FIG. 2. The tip part is subjected to polishing processing if needed. Preferably,
the electrode body part 2 has a cylindrical shape, and has a diameter of 2 to 35 mm
and a length of 10 to 600 mm.
[0034] FIG. 3 shows an example of the discharge lamp. In FIG. 3, numeral number 1 designates
a cathode electrode; numeral number 4 designates a discharge lamp; numeral number
5 designates an electrode supporting rod; and numeral number 6 designates a glass
tube. In the discharge lamp 4, the pair of cathode electrodes 1 are disposed in a
state where electrode tip parts face each other. The cathode electrode 1 is joined
to the electrode supporting rod 5. A phosphor layer which is not shown is provided
on the inner surface of the glass tube 6. A mercury, halogen, or argon gas (or neon
gas) or the like is enclosed in the glass tube 6 if needed. When the tungsten alloy
part of the embodiment is used as the electrode supporting rod 5, the whole electrode
supporting rod may be the tungsten alloy of the embodiment. The tungsten alloy of
the embodiment may be used for a portion of the electrode supporting rod to be joined
to the cathode electrode and the remaining portion may be joined to another lead material.
[0035] The coil part may be attached to the electrode supporting rod depending on the kind
of the discharge lamp, to produce the electrode. The tungsten alloy of the embodiment
can also be applied to the coil part.
[0036] The tungsten alloy part of the embodiment is used for the discharge lamp of the embodiment.
The kind of the discharge lamp is not particularly limited. The discharge lamp can
be applied to both a low-pressure discharge lamp and a high-pressure discharge lamp.
Examples of the low-pressure discharge lamp include various arc-discharge type discharge
lamps such as for general lighting, special lighting used for a road or a tunnel or
the like, a curing apparatus for coating material, a UV curing apparatus, a sterilizer,
and a light cleaning apparatus for a semiconductor or the like. Examples of the high-pressure
discharge lamp include a processing apparatus for water supply and sewerage, general
lighting, outdoor lighting for a stadium or the like, a UV curing apparatus, an exposure
device for a semiconductor and a printed circuit board or the like, a wafer inspection
apparatus, a high-pressure mercury lamp such as a projector, a metal halide lamp,
an extra high pressure mercury lamp, a xenon lamp, and a sodium lamp.
[0037] The tungsten alloy part of the embodiment is suitable also for the transmitting tube
part. Examples of the transmitting tube part include a filament and a mesh grid. The
mesh grid may be obtained by knitting a wire rod in a mesh form or forming a plurality
of holes in a sintered body plate. Since the tungsten alloy part of the embodiment
is used as the transmitting tube part in the embodiment, the transmitting tube has
excellent emission characteristics or the like.
[0038] The tungsten alloy part of the embodiment is suitable also for the magnetron part.
Examples of the magnetron part include a coil part. FIG. 4 shows a magnetron cathode
structure as an example of the magnetron part. In FIG. 4, numeral number 7 designates
a coil part; numeral number 8 designates an upper supporting member; numeral number
9 designates a lower supporting member; numeral number 10 designates a supporting
rod; and numeral number 11 designates a magnetron cathode structure. The upper supporting
member 8 and the lower supporting member 9 are integrated with each other with the
supporting rod 10 provided therebetween. The coil part 7 is disposed around the supporting
rod 10, and integrated with the upper supporting member 8 and the lower supporting
member 9. The magnetron part is suitable for a microwave oven. A tungsten wire material
having a wire diameter of 0.1 to 1 mm is preferably used for the coil part. The diameter
of the coil part is preferably 2 to 6 mm. When the tungsten alloy part of the embodiment
is used for the magnetron part, the magnetron part exhibits excellent emission characteristics
and excellent strength at high-temperature. Therefore, the reliability of the magnetron
including the magnetron part can be improved.
[0039] Next, a method for producing the tungsten alloy part of the embodiment will be described.
As long as the tungsten alloy part of the embodiment has the above constitution, the
method for producing the tungsten alloy part is not particularly limited. However,
examples of the method for efficiently producing the tungsten alloy part include the
following method.
[0040] First, tungsten powder used as a raw material is prepared. The average particle diameter
of the tungsten powder is preferably 1 to 10 µm. When the average particle diameter
is less than 1 µm, the tungsten powder is apt to be aggregated, which makes it difficult
to uniformly disperse the ZrO
2 component. When the average particle diameter is more than 10 µm, the average crystal
particle diameter as the sintered body may be more than 100 µm. Although the purity
of the tungsten powder depends on the application, the tungsten powder preferably
has a high purity of 99.0 wt% or more, and more preferably 99.9 wt% or more.
[0041] Next, ZrO
2 powder is prepared as the Zr component. ZrC powder is prepared as the ZrC component.
A mixture of Zr powder and carbon powder may be used instead of the ZrC powder. Instead
of ZrC powder, a mixture obtained by mixing one or two kinds selected from the Zr
powder and the carbon powders with the ZrC powder may be used. Among these, the ZrO
2 powder or the ZrC powder is preferably used. The ZrC powder is partially decomposed
in a sintering process to produce carbon, and the carbon reacts with an oxygen impurity
in the tungsten powder to be oxidized into carbon dioxide. Carbon dioxide is discharged
to the outside of the system. The ZrC powder contributes to the uniformity of the
tungsten alloy, which is preferable. When the mixed powder of the Zr powder and carbon
powder is used, a load in a production process is increased since both the Zr powder
and the carbon powder are uniformly mixed. Since metal Zr is apt to be oxidized, the
ZrC powder is preferably used.
[0042] The primary particles of the ZrO
2 powder preferably have an average particle diameter of 15 µm or less, and more preferably
0.5 to 5 µm, as described below. When the average particle diameter is less than 0.5
µm, the agglomerate of the ZrO
2 powder is large, which makes it difficult to uniformly disperse the ZrO
2 powder. When the average particle diameter is more than 15 µm, it is difficult to
uniformly disperse the ZrO
2 powder in the grain boundary between the tungsten crystals. The ZrC powder preferably
has an average particle diameter of 0.5 to 5 µm. When the average particle diameter
is less than 0.5 µm, the agglomerate of the ZrC powder is large, which makes it difficult
to uniformly disperse the ZrC powder. When the average particle diameter is more than
5 µm, it is difficult to uniformly disperse the ZrC powder in the grain boundary between
the tungsten crystals. From the viewpoint of obtaining a uniform dispersion, the average
particle diameter of the ZrO
2 powder or ZrC powder is preferably equal to or smaller than the average particle
diameter of the tungsten powder.
[0043] As described above, when the amount of Zr of the ZrO
2 powder, ZrC powder, and Zr powder is defined as 100 parts by mass, the amount of
Hf is preferably 15 parts by mass or less, and more preferably 10 parts by mass or
less. Although the amount of Hf is preferably small, highly purified raw material
causes a cost increase. Therefore, the amount of Hf is more preferably 0.1 to 3 parts
by mass.
[0044] At least one dope material selected from the group consisting of K, Si, and Al is
added if needed. The addition amount is preferably 0.01 wt% or less.
[0045] Next, raw powders are uniformly mixed. A mixing process is preferably performed by
using a mixing machine such as a ball mill. The mixing process is preferably performed
for 8 hours or more, and more preferably 20 hours or more. The raw powders may be
mixed with an organic binder or an organic solvent if needed to produce a slurry.
A granulation process may be performed if needed.
[0046] Next, the raw powders are pressed in a mold to prepare a molded body. The molded
body is subjected to a degreasing process if needed. Next, a sintering process is
performed. The sintering process is preferably performed under a hydrogen atmosphere,
an inert atmosphere such as a nitrogen atmosphere, or in a vacuum. Sintering is preferably
performed at a temperature of 1400 to 3000°C for 1 to 20 hours. When the sintering
temperature is less than 1400°C or the sintering time is less than 1 hour, the sintering
is insufficient, which decreases the strength of the sintered body. When the sintering
temperature is more than 3000°C or the sintering time is more than 20 hours, the tungsten
crystals may overgrow. Carbon in the surface part of the sintered body is likely to
be discharged to the outside of the system by sintering under a hydrogen atmosphere,
under an inert atmosphere, or in a vacuum. The sintering can be performed by electric
sintering, pressureless sintering, and pressure sintering or the like, and is not
particularly limited thereto.
[0047] Next, a process of processing the sintered body into a part is performed. Examples
of the processing process include a forging process, a rolling process, a wiredrawing
process, a cutting process, and a polishing process. Examples of the processing process
when the sintered body is processed into a coil part include a coiling process. Examples
of the processing process when the mesh grid is prepared as the transmitting tube
part include a process of weaving the filament in a mesh form.
[0048] Next, the processed part is subjected to a stress relief heat treatment if needed.
The stress relief heat treatment is preferably performed at 1300 to 2500°C under an
inert atmosphere or in a vacuum. The stress relief heat treatment is performed, and
thereby an internal stress generated in the processing process to the part can be
suppressed, which can enhance the strength of the part.
[0049] It is preferable that the tungsten alloy part of the embodiment contains 0.1 to 5
wt% of Zr in terms of ZrO
2 and the primary particles of the ZrO
2 particles have an average particle diameter of 15 µm or less.
[0050] The tungsten alloy part preferably contains two kinds (ZrO
2 and Zr). The atomic ratio of O/Zr for ZrO
2 (hafnium oxide) is not limited to 2, and may be within a range of 1.6 to 2. The tungsten
alloy part contains 0.1 to 5 wt% of Zr in terms of ZrO
2 (O/Zr atomic ratio = 2). Zr is a component functioning as an emitter material in
the discharge lamp electrode part. When the content of Zr is less than 0.1 wt% in
terms of ZrO
2, emission characteristics are insufficient. When the content of Zr is more than 5
wt%, a strength decrease or the like may be caused. Therefore, the amount of Zr is
preferably 0.3 to 3.0 wt% in terms of ZrO
2, and more preferably 0.5 to 2.5 wt%.
[0051] Preferably, ZrO
2 exists in a particle form, and the primary particles of ZrO
2 have an average particle diameter of 15 µm or less. The ZrO
2 particles exist in the grain boundary between the tungsten crystal particles. Therefore,
when the ZrO
2 particles are too large, a clearance between the tungsten crystal particles is enlarged,
which causes a density decrease and a strength decrease. When the ZrO
2 particles exist in the grain boundary between the tungsten crystal particles, the
ZrO
2 particles function as not only an emission material but also a dispersion reinforcing
material. Therefore, the ZrO
2 particles are advantageous in the strength enhancement of an electrode part.
[0052] The primary particles of the ZrO
2 particles preferably have an average particle diameter of 5 µm or less and a maximum
diameter of 15 µm or less. Further, the primary particles of the ZrO
2 particles preferably have an average particle diameter of 0.1 µm or more and 3 µm
or less and a maximum diameter of 1 µm or more and 10 µm or less. The small ZrO
2 particles having an average particle diameter of less than 0.1 µm or a maximum diameter
of less than 1 µm may be consumed quickly and disappear due to emission. The ZrO
2 particles preferably have an average particle diameter of 0.1 µm or more or a maximum
diameter of 1 µm or more in order to achieve a life improvement of the electrode.
[0053] For the dispersion state of the ZrO
2 particles in the tungsten alloy part, 2 to 30 particles preferably exist on an arbitrary
straight line having a length of 200 µm. When the number of the ZrO
2 particles is less than 2 (0 to 1 particle) per straight line having a length of 200
µm, the ZrO
2 particles are partially decreased, which increases the variation in emission. On
the other hand, when the number of the ZrO
2 particles is more than 30 (31 particles or more) per straight line having a length
of 200 µm, a part of the ZrO
2 particles may be excessively increased, to cause an adverse influence such as a strength
decrease. The dispersion state of the ZrO
2 particles is investigated by subjecting the arbitrary section of the tungsten alloy
to magnification photographing. The magnification ratio of the magnified photograph
is set to 1000 times or more. An arbitrary straight line having a length of 200 µm
(line thickness: 0.5 mm) is drawn on the magnified photograph, and the number of the
ZrO
2 particles existing on the line is counted.
[0054] The secondary particles of the ZrO
2 preferably have a maximum diameter of 100 µm or less. The secondary particle of ZrO
2 is an agglomerate of the primary particles. When the diameter of the secondary particle
is more than 100 µm, the strength of the tungsten alloy part is decreased. Therefore,
the maximum diameter of the secondary particles of the ZrO
2 particles is preferably 100 µm or less, more preferably 50 µm or less, and still
more preferably 20 µm or less.
[0055] Zr (metal Zr) of the Zr component has various dispersion states.
[0056] In a first dispersion state, metal Zr exists as particles. Metal Zr particles exist
in the grain boundary between the tungsten crystal particles as in the ZrO
2 particles. The metal Zr particles exist in the grain boundary between the tungsten
crystal particles, and thereby the metal Zr particles also function as the emission
material and the dispersion reinforcing material. Therefore, the primary particles
of metal Zr preferably have an average particle diameter of 15 µm or less, more preferably
10 µm or less, and still more preferably 0.1 to 3 µm. The primary particles of metal
Zr preferably have a maximum diameter of 15 µm or less, and more preferably 10 µm
or less. When the tungsten alloy is prepared, the ZrO
2 particles and the metal Zr particles may be previously mixed, or the ZrO
2 particles may be deoxidized in the production process to prepare the metal Zr particles.
When a method for deoxidizing the ZrO
2 particles is used, an effect for discharging oxygen in tungsten to the outside of
the system is also obtained, which is preferable. When the deoxidation is possible,
the electrical resistance of the tungsten alloy can be decreased, which improves the
conductivity of the electrode.
[0057] In a second dispersion state, metal Zr exists on the surfaces of the ZrO
2 particles. As in the first dispersion state, when the sintered body of the tungsten
alloy is prepared, oxygen is removed from the surfaces of the ZrO
2 particles, which leads to a state in which a metal Zr film is formed on the surface.
Even the ZrO
2 particles with the metal Zr film exhibit excellent emission characteristics. The
primary particles of ZrO
2 with the metal Zr film preferably have an average particle diameter of 15 µm or less,
more preferably 10 µm or less, and still more preferably 0.1 to 3 µm. The primary
particles of ZrO
2 with the metal Zr film preferably have a maximum diameter of 15 µm or less, and more
preferably 10 µm or less.
[0058] In a third dispersion state, metal Zr is partly or wholly solid-solved in tungsten.
Metal Zr forms a solid solution with tungsten. The strength of the tungsten alloy
can be enhanced by forming the solid solution. The presence or absence of the solid
solution can be determined by XRD analysis. First, the contents of the Zr component
and oxygen are measured. The contents of Zr and oxygen are expressed in ZrO
x, to confirm x < 2. Next, the XRD analysis is performed to confirm that the peak of
metal Zr is not detected. Thus, although x of ZrO
x is smaller than 2, and zirconium which is not contained in stoichiometric zirconium
oxide exists, the peak of metal Zr is not detected. This means that metal Zr is solid-solved
in tungsten.
[0059] On the other hand, x of ZrO
x is smaller than 2; zirconium which is not contained in stoichiometric zirconium oxide
exists; and the peak of metal Zr is detected. This case means the first dispersion
state where metal Zr is not solid-solved and exists in the grain boundary between
the tungsten crystals. The second dispersion state can be analyzed by using EPMA (electron
beam microanalyzer) or TEM (transmission electron microscope).
[0060] The dispersion state of metal Zr may be any one kind or a combination of two or more
kinds of the first dispersion state, the second dispersion state, and the third dispersion
state.
[0061] When the total content of Zr is defined as 100 parts by mass, the ratio of Zr contained
in the ZrO
2 particles is preferably 30 to 98 parts by mass. Zr may be wholly contained in the
ZrO
2 particles. The emission characteristics are obtained by use of the ZrO
2 particles. On the other hand, the conductivity and strength of the tungsten alloy
can be enhanced by dispersing metal Zr. However, when Zr is wholly metal Zr, the emission
characteristics and the strength at high-temperature are decreased. Metal Zr has a
melting point of 1850°C; ZrO
2 has a melting point of 2720°C; and metal tungsten has a melting point of 3400°C.
Since ZrO
2 has a higher melting point than that of metal Zr, the high-temperature strength of
the tungsten alloy part containing ZrO
2 is enhanced. Since ZrO
2 has a surface current density nearly equal to that of ThO
2, electric current equal to that of a thorium oxide-containing tungsten alloy part
can be passed through the tungsten alloy part of the embodiment. Therefore, when the
tungsten alloy part of the embodiment is applied to the electrode of the discharge
lamp, a current density equal to that of a thorium oxide-containing tungsten alloy
electrode can be set, which eliminates the design change of a control circuit or the
like. From these viewpoints, when the total content of the Zr component is defined
as 100 parts by mass, the content of Zr contained in ZrO
2 is preferably 30 to 98 parts by mass, and more preferably 60 to 95 parts by mass.
[0062] The contents of ZrO
2 and metal Zr in the tungsten alloy can be analyzed as follows. The total amount of
Zr in the tungsten alloy is measured according to the ICP analysis method. Next, the
total amount of oxygen in the tungsten alloy is measured by an inert gas fusion-infrared
absorption method. When the tungsten alloy is a binary system containing tungsten
and Zr, the measured total amount of oxygen may be considered to substantially or
wholly be contained in ZrO
2. Therefore, the amount of ZrO
2 can be calculated based on the measured total amount of Zr and total amount of oxygen.
In the case of using this method, the amount of ZrO
2 is calculated as O/Zr = 2.
[0063] For the sizes of the ZrO
2 particles, a magnified photograph of an arbitrary section of the tungsten alloy sintered
body is taken, and the longest diagonal line of the ZrO
2 particles existing on the section is measured, to define the length of the diagonal
line as the particle diameter of the primary particle of ZrO
2. This measurement is performed for 50 ZrO
2 particles, to define the average value thereof as the average particle diameter of
the primary particles of ZrO
2. The maximum value of the particle diameters (the longest diagonal lines) of the
primary particles of ZrO
2 is defined as the maximum diameter of the primary particles of ZrO
2.
[0064] The tungsten alloy part of the embodiment may contain 2 wt% or less of at least one
element selected from the group consisting of Ti, V, Nb, Ta, Mo, and rare earth elements.
The at least one element selected from the group consisting of Ti, V, Nb, Ta, Mo,
and rare earth elements exist in any form of a metal simple substance, oxide, and
carbide. The tungsten alloy part may contain two or more kinds of these elements.
Even if the tungsten alloy part contains two or more kinds of elements, the total
amount thereof is preferably 2 wt% or less. These elements mainly function as the
dispersion reinforcing material. Since the ZrO
2 particles function as the emission material, the ZrO
2 particles are consumed when the discharge lamp is used for a long time. On the other
hand, since Ti, V, Nb, Ta, Mo, and rare earth elements have weak emission characteristics,
these elements are less consumed by emission, and can maintain their function as a
dispersion reinforcing material over a long period of time. Although the lower limits
of the contents of these elements are not particularly limited, the contents are preferably
0.01 wt% or more. Among these elements, the rare earth elements are preferable. Since
the rare earth elements have a large atomic radius of 0.16 nm or more, the rare earth
elements advantageously increase the surface current density. In other words, a metal
simple substance containing an element having an atomic radius of 0.16 nm or more
or a compound thereof is preferably used as the dispersion reinforcing material.
[0065] FIG. 5 and FIG. 6 show an example of a discharge lamp electrode part of an embodiment.
In FIG. 5 and FIG. 6, numeral number 21 designates a discharge lamp electrode part;
numeral number 22 designates a discharge lamp electrode part having a taper-shaped
tip part; numeral number 23 designates a tip part; and numeral number 24 designates
a body part. The discharge lamp electrode part 21 has a cylindrical shape. The tip
part 23 of the discharge lamp electrode part 21 is tapered to produce the discharge
lamp electrode part 22. Although the discharge lamp electrode part 21 before being
tapered usually has a cylindrical shape, the discharge lamp electrode part 21 may
have a quadrangular prism shape.
[0066] The discharge lamp electrode part preferably has a tip part having a tapered tip
and a cylindrical body part. The characteristics of the discharge lamp electrode part
are improved by tapering, that is, sharpening the tip part. As shown in FIG. 6, the
ratio of the length of the tip part 23 to that of the body part 24 is not particularly
limited, and is appropriately set in accordance with the application.
[0067] The wire diameter ϕ of the discharge lamp electrode part is preferably 0.1 to 30
mm. When the wire diameter ϕ is less than 0.1 mm, the strength of the electrode part
cannot be maintained, which may lead to breakage of the electrode part when the electrode
part is incorporated into the discharge lamp or breakage of the electrode part when
the tip part is tapered. When the wire diameter ϕ is a large value of more than 30
mm, it is difficult to control the uniformity of the tungsten crystal structure as
described below.
[0068] When the crystal structure of the transverse section (radial section) of the body
part is observed, the area ratio of the tungsten crystals having a crystal particle
diameter of 1 to 80 µm per unit area (e.g., 300 µm × 300 µm) is preferably 90% or
more. FIG. 7 shows an example of the transverse section of the body part. In FIG.
7, numeral number 24 designates a body part; and numeral number 25 designates a transverse
section. In order to measure the crystal structure of the transverse section, a magnified
photograph of the radial section in the center of the length of the body part is taken.
When the wire diameter is thin, and a unit area of, for example, 300 µm × 300 µm cannot
be photographed in one viewing field, an arbitrary transverse section is photographed
a plurality of times. In the magnified photograph, the longest diagonal line of the
tungsten crystal particles existing in the section of the magnified photograph is
defined as the maximum diameter. In the section, the area ratio of the tungsten crystal
particles having a maximum diameter falling within a range of 1 to 80 µm is calculated.
[0069] The area ratio of the tungsten crystals having a crystal particle diameter of 1 to
80 µm per unit area of the transverse section of the body part is 90% or more. This
shows that the small tungsten crystals having a crystal particle diameter of less
than 1 µm and the large tungsten crystals having a crystal particle diameter of more
than 80 µm are few. When the tungsten crystals of less than 1 µm are too many, the
grain boundary between the tungsten crystal particles is too small. When the ratio
of the ZrO
2 particles is increased in the grain boundary between the tungsten crystal particles,
and the ZrO
2 particles are consumed by emission, large defects are formed, which decreases the
strength of the tungsten alloy. On the other hand, when the number of large tungsten
crystal particles of more than 80 µm is increased, the grain boundary is too large,
which decreases the strength of the tungsten alloy. The area ratio of the tungsten
crystals having a crystal particle diameter of 1 to 80 µm per unit area of the transverse
section of the body part is preferably 96% or more, and more preferably 100%.
[0070] The average particle diameter of the tungsten crystal particles in the transverse
section is preferably 50 µm or less, and more preferably 20 µm or less. The average
aspect ratio of the tungsten crystal particles in the transverse section is preferably
less than 3. The aspect ratio is calculated as follows. A magnified photograph of
unit area (e.g., 300 µm × 300 µm) is taken; the maximum diameter (Feret diameter)
of the tungsten crystal particles existing in the section is defined as a major axis
L; the particle diameter vertically extending from the center of the major axis L
is defined as a minor axis S; and major axis L/minor axis S (the major axis L is divided
by the minor axis S) = aspect ratio is set. This measurement is performed for 50 tungsten
crystal particles, and the average value thereof is defined as the average aspect
ratio. (Major axis L + minor axis S)/2 (total of the major axis L and minor axis S
is divided by 2) = particle diameter is set, and the average value of the 50 tungsten
crystal particles is defined as the average particle diameter.
[0071] When the crystal structure of the vertical section of the body part is observed,
the area ratio of the tungsten crystals having a crystal particle diameter of 2 to
120 µm per unit area (e.g., 300 µm × 300 µm) is preferably 90% or more. FIG. 8 shows
an example of the vertical section. In FIG. 8, numeral number 24 designates a body
part; and numeral number 26 designates a vertical section. In order to measure the
crystal structure of the vertical section, a magnified photograph of the vertical
section passing through the center of the diameter of the body part is taken. When
a unit area of, for example, 300 µm × 300 µm cannot be photographed in one viewing
field, an arbitrary vertical section is photographed a plurality of times. In the
magnified photograph, the longest diagonal line of the tungsten crystal particles
existing in the section of the magnified photograph is defined as the maximum diameter.
In the section, the area ratio of the tungsten crystal particles having a maximum
diameter falling within a range of 2 to 120 µm is calculated.
[0072] The area ratio of the tungsten crystals having a crystal particle diameter of 2 to
120 µm per unit area of the vertical section of the body part is 90% or more. This
shows that the small tungsten crystals having a crystal particle diameter of less
than 2 µm and the large tungsten crystals having a crystal particle diameter of more
than 120 µm are few. When the tungsten crystals of less than 2 µm are too many, the
grain boundary between the tungsten crystal particles is too small. When the ratio
of the ZrO
2 particles is increased in the grain boundary between the tungsten crystal particles,
and the ZrO
2 particles are consumed by emission, large defects are formed, which decreases the
strength of the tungsten alloy. On the other hand, when the number of large tungsten
crystal particles of more than 120 µm is increased, the grain boundary is too large,
which decreases the strength of the tungsten alloy. The area ratio of the tungsten
crystals having a crystal particle diameter of 2 to 120 µm per unit area of the vertical
section of the body part is preferably 96% or more, and more preferably 100%.
[0073] The average particle diameter of the tungsten crystal particles in the vertical section
is preferably 70 µm or less, and more preferably 40 µm or less. The average aspect
ratio of the tungsten crystal particles in the vertical section is preferably 3 or
more. A method for measuring the average particle diameter and the average aspect
ratio is the same as that used for the transverse section.
[0074] As described above, a tungsten alloy having excellent discharge characteristics and
strength, particularly strength at high-temperature can be provided by controlling
the sizes of the tungsten crystal particles, and the sizes and ratio of the ZrO
2 particles. Therefore, the characteristics of the discharge lamp electrode part are
also improved.
[0075] The tungsten alloy part preferably has a relative density of 95.0% or more, and more
preferably 98.0% or more. When the relative density is less than 95.0%, air bubbles
are increased, which may cause adverse influences such as a strength decrease and
partial discharge. The relative density is obtained by the calculation of (measured
density/theoretical density) × 100 (%) = relative density from a measured density
according to an Archimedes method and a theoretical density. The theoretical density
is obtained by calculation from the density and mass ratio of a known component. Herein,
the density of tungsten is 19.3 g/cm
3; the density of zirconium is 6.51 g/cm
3; and the density of zirconium oxide is 6.52 g/cm
3. For example, in the case of a tungsten alloy containing 1 wt% of ZrO
2, 0.2 wt% of Zr, and the remainder being tungsten, the theoretical density is 6.52
× 0.01 + 6.51 × 0.002 + 19.3 × 0.988 = 19.14662 g/cm
3. When the theoretical density is calculated, the existence of impurities need not
be considered.
[0076] The tungsten alloy part of the embodiment preferably has a Vickers hardness of Hv
330 or more, and more preferably Hv 330 to 700. When the Vickers hardness is less
than Hv 330, the tungsten alloy is too soft, which decreases the strength. On the
other hand, when the Vickers hardness is more than Hv 700, the tungsten alloy is too
hard, which makes it difficult to process the tip part into a taper shape. When the
tungsten alloy is too hard, an electrode part having a long body part has no flexibility,
and may be apt to be broken. When the Vickers hardness Hv is 330 or more, the three
point bending strength of the tungsten alloy can be increased to 400 MPa or more.
[0077] When the tungsten alloy part of the embodiment is applied to the discharge lamp electrode,
a surface roughness Ra is preferably 5 µm or less. Particularly, the tip part preferably
has a surface roughness Ra of 5 µm or less, and more preferably 3 µm or less. When
surface unevenness is large, emission characteristics are deteriorated.
[0078] The above tungsten alloy part can be applied to various discharge lamps. The discharge
lamps are not particularly limited to the low-pressure discharge lamp and the high-pressure
discharge lamp or the like. Therefore, even if a large voltage of 100 V or more is
applied, a long life can be achieved. The wire diameter of the body part is within
a range of 0.1 to 30 mm. The wire diameter capable of being applied is a thin size
of 0.1 mm or more and 3 mm or less, a medium size of more than 3 mm and 10 mm or less,
and a thick size of more than 10 mm and 30 mm or less. The length of the electrode
body part is preferably 10 to 600 mm.
[0079] FIG. 9 shows an example of the discharge lamp. In FIG. 9, numeral number 22 designates
an electrode part (having a tapered tip part); numeral number 27 designates a discharge
lamp; numeral number 28 designates an electrode supporting rod; and numeral number
29 designates a glass tube. In the discharge lamp 27, the pair of electrode parts
22 are disposed in a state where electrode tip parts face each other. The electrode
parts 22 are joined to the electrode supporting rod 28. A phosphor layer which is
not shown is provided on the inner surface of the glass tube 29. A mercury, halogen,
or argon gas (or neon gas) or the like is enclosed in the glass tube 29 if needed.
[0080] The tungsten alloy part of the embodiment is used for the discharge lamp of the embodiment.
The kind of the discharge lamp is not particularly limited. The discharge lamp can
be applied to both a low-pressure discharge lamp and a high-pressure discharge lamp.
Examples of the low-pressure discharge lamp include various arc-discharge type discharge
lamps such as for general lighting, special lighting used for a road or a tunnel or
the like, a curing apparatus for coating material, a UV curing apparatus, a sterilizer,
and a light cleaning apparatus for a semiconductor or the like. Examples of the high-pressure
discharge lamp include a processing apparatus for water supply and sewerage, general
lighting, outdoor lighting for a stadium or the like, a UV curing apparatus, an exposure
device for a semiconductor and a printed circuit board or the like, a wafer inspection
apparatus, a high-pressure mercury lamp such as a projector, a metal halide lamp,
an extra high pressure mercury lamp, a xenon lamp, and a sodium lamp. Since the strength
of the tungsten alloy is improved, the discharge lamp can also be applied to a field
involving movement (vibration) such as an automotive discharge lamp.
[0081] Next, a production method will be described. As long as the tungsten alloy part of
the embodiment has the above constitution, the production method is not particularly
limited. However, examples of the production method for efficiently obtaining the
tungsten alloy part include the following method.
[0082] First, tungsten alloy powder containing a Zr component is prepared. ZrO
2 powder is prepared as the Zr component. The primary particles of the ZrO
2 powder preferably have an average particle diameter of 15 µm or less, and more preferably
an average particle diameter of 5 µm or less. Preferably, ZrO
2 powder having a maximum diameter of more than 15 µm is previously removed by using
a sieve. When a maximum diameter is desired to be set to 10 µm or less, large ZrO
2 particles are removed by using a sieve having a predetermined mesh diameter. When
the ZrO
2 particles having a small particle diameter are desired to be removed, the ZrO
2 particles are removed by using a sieve having a predetermined mesh diameter. Before
sieving, the ZrO
2 particles are preferably subjected to a pulverizing process in a ball mill or the
like. Since the aggregate can be broken by performing the pulverizing process, particle
diameter control according to sieving is likely to be performed.
[0083] Next, metal tungsten powder is mixed. The metal tungsten powder preferably has an
average particle diameter of 0.5 to 10 µm. The metal tungsten powder preferably has
a purity of 98.0 wt% or more, an oxygen content of 1 wt% or less, and an impurity
metal component of 1 wt% or less. It is preferable that the metal tungsten powder
is previously pulverized in a ball mill or the like as for the ZrO
2 particles, and small particles and large particles are removed in a sieving process.
[0084] The metal tungsten powder is added so that a Zr content is set to 0.1 to 5 wt% in
terms of ZrO
2. A mixed powder of ZrO
2 particles and metal tungsten powder is put into a mixing vessel, and the mixing vessel
is rotated, to uniformly mix the mixed powder. At this time, the mixed powder can
be smoothly mixed by using a cylindrical mixing vessel as the mixing vessel, and rotating
the cylindrical mixing vessel in a circumferential direction. The tungsten powder
containing the ZrO
2 particles can be prepared by this process. In consideration of deoxidation during
a sintering process to be described below, a small amount of carbon powder may be
added.
[0085] Next, a molded body is produced by using the obtained tungsten powder containing
the ZrO
2 particles. When the molded body is formed, a binder is used if needed. When a cylindrical
molded body is formed, the diameter of the molded body is preferably set to 0.1 to
40 mm. When a molded body is cut out from a plate-like sintered body as described
below, the size of the molded body is arbitrary. The length (thickness) of the molded
body is arbitrary.
[0086] Next, the molded body is presintered. The presintering is preferably performed at
1250 to 1500°C. A presintered body can be obtained by this process. Next, the presintered
body is subjected to electric sintering. The electric sintering is preferably performed
under a condition where the temperature of the sintered body is set to 2100 to 2500°C.
When the temperature is less than 2100°C, the sintered body cannot be sufficiently
densified, which decreases the strength. When the temperature is more than 2500°C,
the ZrO
2 particles and the tungsten particles overgrow, and the intended crystal structure
is not obtained.
[0087] In another method, the molded body may be sintered at a temperature of 1400 to 3000°C
for 1 to 20 hours. When the sintering temperature is less than 1400°C or the sintering
time is less than 1 hour, the sintering is insufficient, which decreases the strength
of the sintered body. When the sintering temperature is more than 3000°C or the sintering
time is more than 20 hours, the tungsten crystals may overgrow.
[0088] Examples of the sintering atmosphere include an inert atmosphere such as a nitrogen
or argon atmosphere, a reducing atmosphere such as a hydrogen atmosphere, and a vacuum.
Under any of these atmospheres, carbon in the ZrO
2 particles is removed during the sintering process. Since an oxygen impurity in the
tungsten powder is also removed during decarbonization, the oxygen content in the
tungsten alloy can be decreased to 1 wt% or less, and further to 0.5 wt% or less.
When the oxygen content in the tungsten alloy is decreased, the conductivity is improved.
[0089] A Zr-containing tungsten sintered body can be obtained by the sintering process.
When the presintered body has a cylindrical shape, the sintered body is also a cylindrical
sintered body (ingot). In the case of the plate-like sintered body, the cylindrical
sintered body (ingot) can be obtained by a process of cutting out the plate-like sintered
body into a predetermined size.
[0090] Next, the cylindrical sintered body (ingot) is subjected to forging processing, rolling
processing, and wiredrawing processing or the like, to adjust the wire diameter. A
processing ratio in that case is preferably within a range of 30 to 90%. When the
sectional area of the cylindrical sintered body before processing is defined as A
and the sectional area of the cylindrical sintered body after processing is defined
as B, the processing ratio is obtained by the processing ratio of [(A - B)/A] × 100%.
The wire diameter is preferably adjusted by a plurality of such processes. The pores
of the cylindrical sintered body before processing can be crushed by performing the
plurality of such processes, to obtain a high-density electrode part.
[0091] Next will be described a case where a cylindrical sintered body having a diameter
of 25 mm is processed into a cylindrical sintered body having a diameter of 20 mm,
for example. Since the sectional area A of a circle having a diameter of 25 mm is
460.6 mm
2 and the sectional area B of a circle having a diameter of 20 mm is 314 mm
2, the processing ratio is [(460.6 - 314)/460.6] × 100 = 32%. At this time, the diameter
of the cylindrical sintered body to be processed is preferably set to 20 mm from 25
mm by a plurality of wiredrawing processings or the like.
[0092] When the processing ratio is a low value of less than 30%, the crystal structure
is not sufficiently stretched in the processing direction, which makes it difficult
to set the tungsten crystals and the ZrO
2 particles at the intended size. When the processing ratio is a small value of less
than 30%, the pores in the cylindrical sintered body before processing are not sufficiently
crushed, and may remain as is. The remaining internal pores cause a decrease in the
durability or the like of a cathode part. On the other hand, when the processing ratio
is a large value of more than 90%, the sintered body is excessively processed, which
may cause disconnections and decrease the yield. For this reason, the processing ratio
is preferably 30 to 90%, and more preferably 35 to 70%. When the relative density
of the sintered tungsten alloy is 95% or more, the sintered tungsten alloy may not
be necessarily processed at the above processing ratio.
[0093] After the wire diameter of the sintered body is processed to 0.1 to 30 mm, the electrode
part can be prepared by cutting the sintered body to a required length. The tip part
is processed into a taper shape if needed. Polishing processing, a heat treatment
(recrystallization heat treatment or the like), and shape processing are performed
if needed.
[0094] The recrystallization heat treatment is preferably performed at 1300 to 2500°C under
a reducing atmosphere, under an inert atmosphere, or in a vacuum. The effect of the
stress relief heat treatment suppressing the internal stress generated in the processing
process to the electrode part is obtained by performing the recrystallization heat
treatment, and the strength of the part can be enhanced.
[0095] The above production method can efficiently produce the discharge lamp electrode
part of the embodiment. Examples
(Example 1)
[0096] As raw powders, 1.5 wt% of ZrO
2 powder (purity: 99.0%) having an average particle diameter of 2 µm was added to tungsten
powder (purity: 99.99 wt%) having an average particle diameter of 2 µm. When the amount
of Zr for the ZrO
2 powder was defined as 100 parts by mass, the amount of impurity Hf was 1.0 part by
mass.
[0097] The raw powders were mixed in a ball mill for 10 hours, to prepare a mixed raw powder.
Next, the mixed raw powder was put into a mold, to produce a molded body. The obtained
molded body was subjected to furnace sintering in hydrogen at 1800°C for 10 hours.
A sintered body having a height of 16 mm, a width of 16 mm, and a length of 420 mm
was obtained by the process.
[0098] A rod having a square section or a circular section was prepared by forging processing
or the like. Next, a cylindrical sample having a diameter of 2.4 mm and a length of
150 mm was cut out. The sample was subjected to centerless polishing processing, to
set a surface roughness Ra to 5 µm or less. Next, a stress relief heat treatment was
performed in hydrogen at 1600°C.
[0099] Thereby, an electrode for measuring emission characteristics was prepared as a tungsten
alloy part according to Example 1, and emission current measurement was performed.
(Comparative Example 1)
[0100] A discharge lamp cathode part was prepared, which was made of a tungsten alloy containing
2 wt% of ThO
2 and had the same size.
[0101] The content of ZrO
2, the amounts of carbon in a surface part and a central part, and the average particle
diameter of tungsten crystals were investigated for the tungsten alloy part of Example
1. For the analysis of the content of ZrO
2, the amount of Zr and the amount of oxygen were analyzed by ICP analysis and an inert
gas fusion-infrared absorption method, and expressed in ZrO
x. The amounts of carbon in the surface part and the central part were analyzed as
follows. Measurement samples were cut out from a cylindrical section and a range between
a surface and a position distant by 10 µm from the surface, and the amounts of carbon
were measured by a combustion-infrared absorption method. The average value of the
crystal particle diameters of 100 tungsten crystals measured in an arbitrary sectional
structure was defined as the average crystal particle diameter of tungsten crystal
particles. The results are shown in Table 1.
[Table 1]
Table 1
|
In terms of ZrO2 (wt%) |
x value when expressed in ZrOx |
Amount of carbon in surface part (wt%) |
Amount of carbon in central part (wt%) |
Average crystal particle diameter of tungsten (µm) |
Example 1 |
1.5 |
1.82 |
0.001 |
0.002 |
30 |
[0102] Next, there were investigated the emission characteristics of the discharge lamp
cathode parts according to Example 1 and Comparative Example 1. For the measurement
of the emission characteristics, emission current densities (mA/mm
2) were measured by changing an applied voltage (V) to 100 V, 200 V, 300 V, and 400
V. The emission current densities were measured under conditions of an electric current
load of 18 ± 0.5 A/W applied to the cathode part and an applied time of 20 ms. The
results are shown in FIG. 10.
[0103] As can be seen from FIG. 10, it was found that Example 1 has more excellent emission
characteristics than those of Comparative Example 1. Thus, it is found that the discharge
lamp cathode part of Example 1 exhibits excellent emission characteristics without
using thorium oxide which is a radioactive material. The temperature of the cathode
part was 2100 to 2200°C during measurement. For this reason, it is found that the
cathode part according to Example 1 has excellent strength at high-temperature and
an excellent life or the like.
(Examples 2 to 6)
[0104] Next, there were prepared raw mixed powders in which the addition amount of ZrO
2, the addition amount of ZrC, and the addition amount of K as a dope material were
changed as shown in Table 2. The raw mixed powders were subjected to metal molding,
and sintered in hydrogen at 1500 to 1900°C for 7 to 16 hours, to obtain sintered bodies.
In Examples 2 and 3, a cutting-out process was performed under a condition where the
size of the sintered body was the same as that of Example 1. In Examples 4 and 5,
the sizes of the molded bodies were adjusted, to directly obtain sintered bodies having
a diameter of 2.4 mm and a length of 150 mm. In Example 6, 0.5 wt% of ZrC powder (purity:
99.0%) having an average particle diameter of 2 µm was added. When the Zr amount of
ZrO
2 powder was defined as 100 parts by mass, the amount of impurity Hf was 1.0 part by
mass. When the ZrO
2 powder and ZrC powder of Example 6 were used, and the Zr amount was defined as 100
parts by mass, the amount of impurity Hf was 1.0 part by mass.
[0105] Each of the samples was subjected to centerless polishing processing to set a surface
roughness Ra to 5 µm or less. Next, a tip part was processed into a conic shape having
an inclination angle of 45 degrees. Next, a stress relief heat treatment was performed
in hydrogen at 1400 to 1700°C. Thereby, discharge lamp cathode parts according to
Examples 2 to 5 were prepared, and measured in the same manner as in Example 1. The
results are shown in Table 3.
[Table 2]
Table 2
|
Addition amount of ZrO2 |
Addition amount of K |
Addition amount of ZrC |
Example 2 |
0.5 |
None |
None |
Example 3 |
1.0 |
None |
None |
Example 4 |
2.3 |
0.005 |
None |
Example 5 |
1.2 |
None |
None |
Example 6 |
1.0 |
None |
0.5 |
Table 3
|
In terms of ZrO2 (wt%) |
x value when expressed in ZrOx |
Amount of carbon in surface part (wt%) |
Amount of carbon in central part (wt%) |
Average crystal particle diameter of tungsten (µm) |
Example 2 |
0.5 |
1.85 |
0.001 |
0.002 |
60 |
Example 3 |
1.0 |
1.83 |
0.001 |
0.002 |
40 |
Example 4 |
2.3 |
1.86 |
0.002 |
0.003 |
50 |
Example 5 |
1.2 |
1.81 |
0.001 |
0.002 |
30 |
Example 6 |
1.5 |
0.95 |
0.005 |
0.009 |
10 |
[0106] Next, emission characteristics were estimated under the same condition as that of
Example 1. The results are shown in Table 4.
[Table 4]
Table 4
|
Emission current density (mA/mm2) |
Applied voltage 100V |
Applied voltage 200V |
Applied voltage 300V |
Applied voltage 400V |
Example 2 |
2.0 |
29.7 |
42.0 |
43.8 |
Example 3 |
1.7 |
31.7 |
44.8 |
45.8 |
Example 4 |
6.7 |
36.0 |
48.1 |
50.0 |
Example 5 |
2.5 |
31.6 |
47.0 |
48.5 |
Example 6 |
2.4 |
36.4 |
41.2 |
51.8 |
[0107] As can be seen from Table 4, the discharge lamp cathode parts according to the Examples
exhibited excellent characteristics. The temperatures of the cathode parts were 2100
to 2200°C during measurement. For this reason, it is found that the cathode parts
according to Examples 2 to 6 have excellent high-temperature strength and an excellent
life or the like. Example 1 contained two kinds (Zr and ZrO
2). Examples 6 contained three kinds (Zr, ZrO
2, and ZrC).
(Examples 11 to 20 and Comparative Example 11)
[0108] Tungsten powder (purity: 99.0 wt% or more) and ZrO
2 powder shown in Table 5 were prepared as raw powders. The powders were sufficiently
loosened in a ball mill, and subjected to a sieving process so that the maximum diameters
thereof were set to values shown in Table 5 if needed.
[Table 5]
Table 5
|
Tungsten powder |
ZrO2 powder |
Average particle diameter (µm) |
Maximum diameter (µm) |
Oxygen content (wt%) |
Carbon content (wt%) |
Average particle diameter of primary particles (µm) |
Maximum diameter of secondary particles (µm) |
Example 11 |
1 |
5 |
0.2 |
<0.01 |
1.2 |
7.0 |
Example 12 |
2 |
8 |
0.2 |
<0.01 |
2.5 |
8.0 |
Example 13 |
3 |
10 |
0.2 |
<0.01 |
4.5 |
10.0 |
Example 14 |
5 |
18 |
0.8 |
<0.01 |
4.7 |
10.0 |
Example 15 |
8 |
30 |
0.8 |
<0.01 |
8.3 |
13.0 |
Example 16 |
2 |
10 |
0.5 |
<0.01 |
2.4 |
6.0 |
Example 17 |
3 |
12 |
0.5 |
<0.01 |
3.2 |
8.5 |
Example 18 |
2 |
7 |
0.1 |
<0.01 |
0.7 |
3.3 |
Example 19 |
2 |
7 |
0.1 |
<0.01 |
0.7 |
3.3 |
Example 20 |
2 |
7 |
0.1 |
<0.01 |
0.7 |
3.3 |
Comparative Example 11 |
5 |
40 |
0.8 |
<0.01 |
20 |
50 |
[0109] Next, the tungsten powder and the ZrO
2 powder were mixed at ratios shown in Table 6, and mixed in the ball
[0110] mill again. Next, the mixtures were molded to prepare molded bodies. Next, a sintering
process was performed under conditions shown in Table 6. Sintered bodies having a
height of 16 mm, a width of 16 mm, and a length of 420 mm were obtained.
[Table 6]
Table 6
|
Amount of Zr (in terms of ZrO2, wt%) |
Sintering process |
Example 11 |
0.5 |
Under nitrogen atmosphere, presintering, 1400°C → Electric sintering, 2300°C |
Example 12 |
1.0 |
Under hydrogen atmosphere, presintering, 1350°C → Electric sintering, 2200°C |
Example 13 |
1.5 |
Under hydrogen atmosphere, furnace sintering, 1900°C |
Example 14 |
2.0 |
Under nitrogen atmosphere, presintering, 1450°C → Electric sintering, 2200°C |
Example 15 |
2.5 |
Under hydrogen atmosphere, furnace sintering, 1800°C |
Example 16 |
1.5 |
Under hydrogen atmosphere, presintering, 1400°C → Electric sintering, 2250°C |
Example 17 |
1.0 |
Under hydrogen atmosphere, furnace sintering, 1950°C |
Example 18 |
0.8 |
Under hydrogen atmosphere, presintering, 1380°C → Electric sintering, 2260°C |
Example 19 |
0.2 |
Under hydrogen atmosphere, furnace sintering, 1930°C |
Example 20 |
4.2 |
Under hydrogen atmosphere, furnace sintering, 2000°C |
Comparative Example 11 |
2.5 |
Under hydrogen atmosphere, furnace sintering, 1800°C |
[0111] Next, cylindrical sintered bodies (ingots) were cut out of from the obtained tungsten
alloy sintered bodies, and the wire diameters were adjusted by appropriately combining
forging processing, rolling processing, and wiredrawing processing. Processing ratios
were as shown in Table 7. The wire diameters were adjusted. Then, the sintered bodies
were cut to a predetermined length, and the tip parts were processed into a taper
shape. Then, the sintered bodies were subjected to surface polishing, to set surface
roughnesses Ra to 5 µm or less. Next, the sintered bodies were subjected to a recrystallization
heat treatment at 1600°C under a hydrogen atmosphere. Thereby, discharge lamp electrode
parts were completed.
[Table 7]
Table 7
|
Cylindrical sintered body (ingot) |
Wire diameter of electrode part (mm) |
Processing ratio(%) |
Kind of cylindrical sintered body |
Diameter mm x length mm |
|
|
Example 11 |
Example 11 |
5mm×50mm |
3mm |
64 |
Example 12 |
Example 12 |
10mm×100mm |
8mm |
36 |
Example 13 |
Example 13 |
20mm×100mm |
16mm |
36 |
Example 14 |
Example 14 |
26mm×100mm |
20mm |
41 |
Example 15 |
Example 15 |
35mm×100mm |
25mm |
49 |
Example 16 |
Example 16 |
22.4mm×100mm |
10mm |
80 |
Example 17 |
Example 17 |
1.2mm×50mm |
1mm |
70 |
Example 18 |
Example 18 |
5mm×50mm |
3mm |
64 |
Example 19 |
Example 19 |
10mm×100mm |
8mm |
36 |
Example 20 |
Example 20 |
35mm×100mm |
25mm |
49 |
Comparative Example 11-1 |
Comparative Example 11 |
10mm×50mm |
3mm |
91 |
Comparative Example 11-2 |
Comparative Example 11 |
9mm×100mm |
8mm |
21 |
[0112] Next, magnified photographs of the transverse section and vertical section of the
body part of each of the discharge lamp electrode parts were taken. The average particle
diameter and maximum diameter of the ZrO
2 component, and the ratio, average particle diameter and aspect ratio of the tungsten
crystal particles were then measured. For the magnified photographs, the circumferential
and vertical slices were made through the center of the body part, and arbitrary unit
areas of 300 µm x 300 µm were investigated. The results are shown in Table 8. [Table
8]
Table 8
|
Tungsten crystal particle diameter |
ZrO2 particles |
Transverse section |
Vertical section |
Average particle diameter of primary particles µm |
Maximum diameter of primary particles µm |
Maximum diameter of secondary particles µm |
Ratio of 1 to 80 µm % |
Average particle diameter µm |
Average aspect ratio |
Ratio of 2 to 120 µm % |
Average particle diameter µm |
Average aspect ratio |
Example 11 |
100 |
12.8 |
2.7 |
100 |
22.3 |
4.5 |
1.2 |
2.7 |
7.0 |
Example 12 |
100 |
24.4 |
2.2 |
100 |
35.7 |
3.4 |
2.5 |
4.7 |
8.0 |
Example 13 |
98 |
36.3 |
2.4 |
97 |
44.7 |
3.5 |
4.5 |
6.0 |
10.0 |
Example 14 |
94 |
46.1 |
2.6 |
93 |
72.2 |
4.0 |
4.7 |
6.3 |
10.0 |
Example 15 |
90 |
55.3 |
2.8 |
92 |
78.8 |
4.2 |
8.3 |
11.1 |
13.0 |
Example 16 |
100 |
27.7 |
2.6 |
100 |
35.7 |
4.6 |
2.4 |
3.8 |
6.0 |
Example 17 |
100 |
31.5 |
2.6 |
100 |
53.2 |
4.3 |
3.2 |
4.5 |
8.5 |
Example 18 |
100 |
26.7 |
2.5 |
100 |
29.2 |
4.3 |
0.7 |
1.8 |
3.3 |
Example 19 |
100 |
27.8 |
2.4 |
100 |
39.0 |
3.5 |
0.7 |
1.8 |
3.3 |
Example 20 |
100 |
29.1 |
2.6 |
100 |
42.2 |
3.6 |
0.7 |
1.8 |
3.3 |
Comparative Example 11-1 |
74 |
52.0 |
3.8 |
68 |
108.3 |
5.3 |
20 |
28.7 |
50 |
Comparative Example 11-2 |
90 |
57.6 |
1.8 |
93 |
55.6 |
2.0 |
20 |
28.7 |
50 |
[0113] Next, the ratio of ZrO
2 in the Zr component was measured for each of the discharge lamp electrode parts.
[0114] An oxygen content, a relative density (%), a Vickers hardness (Hv), and a three point
bending strength were obtained.
[0115] The ratio of ZrO
2 in the Zr component was obtained by measuring the amount of Zr in the tungsten alloy
according to an ICP analysis method and the amount of carbon in the tungsten alloy
according to a combustion-infrared absorption method. Carbon in the tungsten alloy
may be considered to be contained in ZrO
2. Therefore, the detected total amount of Zr was defined as 100 parts by weight, and
the amount of Zr contained in ZrO
2 was converted. The mass ratio thereof was obtained. The oxygen content in the tungsten
alloy was analyzed by an inert gas combustion-infrared absorption method. The relative
density was obtained by dividing a measured density analyzed by an Archimedes method
by a theoretical density. The theoretical density was obtained by the above calculation.
The Vickers hardness (Hv) was obtained according to JIS-Z-2244. The three point bending
strength was obtained according to JIS-R-1601. The results are shown in Table 9.
[Table 9]
Table 9
|
x value when expressed in ZrOx |
Parts by mass of Zr contained in ZrO2 when the total amount of Zr is defined as 100 parts by mass |
Oxygen content in tungsten alloy (wt%) |
Relative density (%) |
Vickers hardness (Hv) |
Three point bending strength (MPa) |
Example 11 |
0.19 |
96 |
0.1 |
99.0 |
483 |
502 |
Example 12 |
0.18 |
90 |
<0.01 |
96.5 |
419 |
446 |
Example 13 |
0.14 |
70 |
<0.01 |
96.9 |
437 |
464 |
Example 14 |
0.12 |
60 |
0.4 |
98.2 |
476 |
474 |
Example 15 |
0.16 |
80 |
<0.01 |
99.2 |
483 |
500 |
Example 16 |
0.18 |
92 |
<0.01 |
99.6 |
497 |
515 |
Example 17 |
0.19 |
94 |
<0.01 |
99.2 |
492 |
501 |
Example 18 |
0.18 |
91 |
<0.01 |
99.1 |
490 |
507 |
Example 19 |
0.18 |
88 |
<0.01 |
97.8 |
433 |
460 |
Example 20 |
0.17 |
86 |
<0.01 |
99.3 |
477 |
491 |
Comparative Example 11-1 |
0.19 |
96 |
0.2 |
99.2 |
820 |
382 |
Comparative Example 11-2 |
0.19 |
96 |
0.2 |
92.0 |
280 |
323 |
[0116] The discharge lamp electrode parts according to the Examples had high density and
an excellent ickers hardness (Hv). This was because a part of ZrO
2 was deoxidized. The Zr component which was not contained in ZrO
2 was in any state of a state of metal Zr particles, a state where a part of surfaces
of ZrO
2 particles were metal Zr, and a state of a solid solution of tungsten and hafnium.
(Examples 21 to 25)
[0117] Next, the same tungsten powder and ZrO
2 powder as those in Example 12 were used, and a second component changed to a composition
shown in Table 10 was prepared. These were subjected to furnace sintering at 2000°C
under a sintering condition of a hydrogen atmosphere, to obtain ingots. The ingots
were processed at a processing ratio of 50%, to obtain electrode parts having a wire
diameter of 10 mm. The electrode parts were subjected to a recrystallization heat
treatment at 1600°C under a hydrogen atmosphere. The same measurement was performed
for each of the Examples. The results were shown in Tables 10 to 12.
[Table 10]
Table 10
|
Amount of Zr component (in terms of ZrO2, wt%) |
Addition component (material/wt%) |
Example 21 |
1.0 |
K/0.005 |
Example 22 |
1.0 |
Hf/0.01 |
Example 23 |
1.0 |
Hf/0.5 |
Example 24 |
1.0 |
HfC/0.1 |
Example 25 |
1.0 |
Ta/0.2 |
[Table 11]
Table11
|
Tungsten crystal particle diameter |
ZrO2 particles |
Transverse section |
Vertical section |
Average particle diameter of primary particles µm |
Maximum diameter of primary particles µm |
Maximum diameter of secondary particles µm |
Ratio of 1 to 80 µm % |
Average particle diameter µm |
Average aspect ratio |
Ratio of 2 to 120 µm % |
Average particle diameter µm |
Average aspect ratio |
Example 21 |
100 |
25.8 |
2.3 |
100 |
36.1 |
3.4 |
2.5 |
4.0 |
8.0 |
Example 22 |
100 |
26.7 |
2.4 |
100 |
36.5 |
3.3 |
2.5 |
4.0 |
8.0 |
Example 23 |
100 |
25.1 |
2.4 |
100 |
35.2 |
3.6 |
2.5 |
4.0 |
8.0 |
Example 24 |
100 |
26.5 |
2.4 |
100 |
36.7 |
3.5 |
2.5 |
4.0 |
8.0 |
Example 25 |
100 |
27.0 |
2.4 |
100 |
35.7 |
3.5 |
2.5 |
4.0 |
8.0 |
[Table 12]
Table 12
|
x value when expressed in ZrOx |
Parts by mass of Zr contained in ZrO2 when the total amount of Zr is defined as 100 parts by mass |
Oxygen content in tungsten alloy (wt%) |
Relative density (%) |
Vickers hardness (Hv) |
Three point bending strength (MPa) |
Example 21 |
0.18 |
92 |
<0.01 |
98.1 |
423 |
450 |
Example 22 |
0.18 |
90 |
<0.01 |
98.4 |
426 |
447 |
Example 23 |
0.18 |
91 |
<0.01 |
98.7 |
424 |
452 |
Example 24 |
0.18 |
88 |
<0.01 |
98.5 |
430 |
454 |
Example 25 |
0.18 |
90 |
<0.01 |
98.3 |
424 |
454 |
[0118] As can be seen from Tables 10 to 12, since the use of the addition elements strengthened
a dispersion strengthening function and suppressed the grain growth of the tungsten
crystals, the enhancement of the strength was observed.
(Examples 11A to 25A, Comparative Examples 11-1A to 11-2A, and Comparative Example
12)
[0119] The emission characteristics of discharge lamp electrode parts of Examples 11 to
25, Comparative Example 11-1, and Comparative Example 11-2 were investigated. For
the measurement of the emission characteristics, emission current densities (mA/mm
2) were measured by changing an applied voltage (V) to 100 V, 200 V, 300 V, and 400
V. The emission current densities were measured under conditions of an electric current
load of 18 ± 0.5 A/W applied to the discharge lamp electrode part and an applied time
of 20 ms.
[0120] A discharge lamp electrode part which was made of a tungsten alloy containing 2 wt%
of ThO
2 and had a wire diameter of 8 mm was prepared as Comparative Example 12. The results
are shown in Table 13.
[Table 13]
Table 13
|
Electrode part |
Emission current density(mA/mm2) |
Applied voltage 100V |
Applied voltage 200V |
Applied voltage 300V |
Applied voltage 400V |
Example 11A |
Example 11 |
3.0 |
28.1 |
36.5 |
40.8 |
Example 12A |
Example 12 |
3.2 |
29.5 |
38.5 |
42.4 |
Example 13A |
Example 13 |
3.3 |
29.8 |
38.8 |
43.0 |
Example 14A |
Example 14 |
3.3 |
30.1 |
39.3 |
44.5 |
Example 15A |
Example 15 |
3.5 |
32.5 |
40.7 |
45.9 |
Example 16A |
Example 16 |
3.3 |
30.6 |
39.5 |
44.0 |
Example 17A |
Example 17 |
3.3 |
30.6 |
39.3 |
43.7 |
Example 18A |
Example 18 |
3.1 |
29.3 |
37.8 |
42.1 |
Example 19A |
Example 19 |
3.3 |
30.6 |
39.1 |
42.4 |
Example 20A |
Example 20 |
3.3 |
31.2 |
39.3 |
42.6 |
Example 21A |
Example 21 |
3.2 |
29.7 |
38.6 |
43.2 |
Example 22A |
Example 22 |
3.2 |
29.8 |
38.7 |
43.6 |
Example 23A |
Example 23 |
3.2 |
29.7 |
38.5 |
43.5 |
Example 24A |
Example 14 |
3.2 |
29.7 |
38.6 |
43.6 |
Example 25A |
Example 15 |
3.2 |
29.6 |
38.7 |
43.7 |
Comparative Example 11-1A |
Comparative Example 11-1 |
3.1 |
27.0 |
34.6 |
38.8 |
Comparative Example 11-2A |
Comparative Example 11-2 |
2.6 |
23.7 |
29.0 |
32.5 |
Comparative Example 12A |
Comparative Example 12 |
1.1 |
31.1 |
43.0 |
45.0 |
[0121] The discharge lamp electrode parts according to the Examples do not use thorium oxide.
The discharge lamp electrode parts according to the Examples exhibited emission characteristics
equal to or higher than those of Comparative Example 2 using thorium oxide. The temperatures
of the electrode parts were 2100 to 2200°C during measurement. For this reason, the
discharge lamp electrode parts according to Examples have excellent strength at high-temperature.
(Examples 26 to 28)
[0122] Next, there were prepared Example 26 (the recrystallization heat treatment condition
of Example 11 was changed to 1800°C), Example 27 (the recrystallization heat treatment
condition of Example 13 was changed to 1800°C), and Example 28 (the recrystallization
heat treatment condition of Example 18 was changed to 1800°C) produced by the same
production method except that the recrystallization heat treatment condition was changed
to 1800°C in the discharge lamp electrode parts of Example 11, Example 13, and Example
18. The same measurement was performed. The results are shown in Tables 14 and 15.
[Table 14]
Table 14
|
Tungsten crystal particle diameter |
ZrO2 particles |
Transverse section |
Vertical section |
Average particle diameter of primary particles µm |
Maximum diameter of primary particles µm |
Maximum diameter of secondary particles µm |
Ratio of 1 to 80 µm % |
Average particle diameter µm |
Average aspect ratio |
Ratio of 2 to 120 µm % |
Average particle diameter µm |
Average aspect ratio |
Example 26 |
100 |
15.0 |
2.8 |
100 |
25.8 |
4.6 |
1.2 |
2.7 |
7.0 |
Example 27 |
98 |
38.1 |
2.9 |
97 |
46.2 |
3.9 |
4.5 |
6.0 |
10.0 |
Example 28 |
100 |
28.5 |
2.6 |
100 |
30.4 |
4.5 |
0.7 |
1.8 |
3.3 |
[Table 15]
Table 15
|
x value when expressed in ZrOx |
Parts by mass of Zr contained in ZrO2 when the total amount of Zr is defined as 100 parts by mass |
Oxygen content in tungsten alloy (wt%) |
Relative density (%) |
Vickers hardness (Hv) |
Three point bending strength (MPa) |
Example 26 |
0.19 |
94 |
0.1 |
99.0 |
483 |
502 |
Example 27 |
0.13 |
66 |
<0.01 |
96.9 |
437 |
464 |
Example 28 |
0.18 |
88 |
<0.01 |
99.1 |
490 |
507 |
[0123] The discharge lamp electrode parts according to the present Examples had high density,
an excellent Vickers hardness (Hv), and an excellent three point bending strength.
This was because a part of ZrO
2 was deoxidized. As a result of analyzing the Zr component which was not contained
in ZrO
2, the Zr component became a solid solution of tungsten and zirconium. That is, two
kinds (Zr and ZrO
2) existed as the Zr component. For this reason, when the recrystallization heat treatment
temperature was set to 1700°C or more, metal Zr was found to be likely to be solid-solved
in tungsten. The emission characteristics were measured by the same method.
[Table 16]
Table 16
|
Electrode part |
Emission current density(mA/mm2) |
Applied voltage 100V |
Applied voltage 200V |
Applied voltage 300V |
Applied voltage 400V |
Example 26A |
Example 26 |
3.2 |
29.3 |
38.1 |
43.1 |
Example 27A |
Example 27 |
3.6 |
30.7 |
40.0 |
45.3 |
Example 28A |
Example 28 |
3.3 |
30.4 |
39.5 |
44.3 |
[0124] It was found that metal Zr is wholly solid-solved in tungsten as described above,
which improves the emission characteristics. This is considered to be because the
existence of metal Zr on the surface of the tungsten alloy is likely to be caused
by the solid solution.
[0125] Since the present invention has excellent emission characteristics as described above,
the present invention can be used for not only the discharge lamp electrode part but
also fields such as the magnetron part (coil part) and the transmitting tube part
(mesh grid) requiring the emission characteristics.