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JP2006245695

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DESCRIPTION JP2006245695
An ultrasonic horn having a carbon-doped titanium oxide layer and a carbon-doped titanium
oxide layer having excellent durability and functioning as a visible light responsive photocatalyst.
I will provide a. A main component of a hydrocarbon is a surface of an ultrasonic output side end
portion of which at least a surface layer is made of titanium, titanium alloy, titanium alloy oxide
or titanium oxide so that the surface temperature becomes 900 to 1500 ° C. Directly on the
surface of the ultrasonic output side with a combustion flame of hydrocarbon-based gas directly
on the surface of the ultrasonic output side, and the surface temperature of the ultrasonic output
side is 900 ° to 1500 ° It is obtained by heat treatment so as to be C. [Selected figure] Figure 1
Ultrasonic horn
[0001]
A first invention relates to an ultrasonic horn for giving an ultrasonic signal to an object to be
treated, wherein at least a part of an ultrasonic output side end is a layer consisting of titanium
oxide or titanium alloy oxide in which at least a surface layer is carbon-doped. And the carbon is
doped in the form of Ti-C bonds. More specifically, at least a part of the ultrasonic output side
end is doped with carbon in the form of Ti-C bond, and the durability (high hardness, scratch
resistance, abrasion resistance, chemical resistance, heat resistance) Ultrasonic horn that
functions as a visible light responsive photocatalyst. The second invention relates to an ultrasonic
horn for giving an ultrasonic signal to an object to be treated, more specifically, at least a part of
the ultrasonic output side end is oxidized titanium oxide or titanium alloy on at least a part of the
surface Since it has a large number of projections made of organic substances, volatile organic
02-05-2019
1
compounds (VOCs) can be easily adsorbed, its surface area is large and it is carbon-doped, so its
activity as a photocatalyst is high and it functions as a visible light responsive photocatalyst Also,
the present invention relates to an ultrasonic horn which is high in hardness and excellent in
peeling resistance, abrasion resistance, chemical resistance and heat resistance.
[0002]
Conventionally, titanium dioxide TiO 2 (in the present specification, claims, simply referred to as
titanium oxide) is known as a substance exhibiting a photocatalytic function. As a method of
forming a titanium oxide film on titanium metal, a method of forming a titanium oxide film by
anodic oxidation on titanium metal since the 1970s, thermally titanium oxide on a titanium metal
plate in an electric furnace supplied with oxygen A method of forming a film, a method of
forming a titanium oxide film on titanium metal by heating a titanium plate in a 1100-1400 ° C.
flame of city gas, and the like are known (see Non-Patent Document 1).
[0003]
In the case of producing a photocatalytic product in which an effect of deodorizing, antibacterial,
antifogging or antifouling is obtained by such a photocatalytic function, generally, titanium oxide
sol is applied onto a substrate by spray coating, spin coating, dipping or the like. However, since
the film thus formed is susceptible to peeling and abrasion, it has been difficult to use the film
over a long period of time. In addition, the method of forming a photocatalyst film into a film by
sputtering method is also known (for example, refer patent documents 4-5).
[0004]
In addition, in order for titanium oxide to function as a photocatalyst, ultraviolet light having a
wavelength of 400 nm or less is required, but many studies have been conducted on titanium
oxide photocatalysts that are doped with various elements and function by visible light. For
example, there is a report that nitrogen-doped titanium oxide is superior as a visible light
responsive photocatalyst by comparing titanium oxides doped with F, N, C, S, P, Ni, etc.,
respectively (see Non-Patent Document 2) .
[0005]
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In addition, as a titanium oxide photocatalyst doped with other elements in this manner, a
titanium compound formed by substituting oxygen sites of titanium oxide with atoms such as
nitrogen, or doping atoms such as nitrogen between lattices of crystals of titanium oxide The
photocatalyst which consists of a titanium compound which distributes atoms, such as nitrogen,
in the grain boundary of the polycrystalline aggregate of titanium oxide or a titanium oxide
crystal, is proposed (for example, refer to patent documents 6-9 grade). However, such
photocatalysts are not always satisfactory in terms of durability such as abrasion resistance.
Furthermore, for example, n-TiO2-xCx, which is a chemically modified titanium oxide, is applied
to a titanium metal by applying a natural gas combustion flame whose temperature is maintained
around 850 ° C. by adjusting the flow rates of natural gas and oxygen. There is a report that it
absorbs light of 535 nm or less (see Non-Patent Document 3).
[0006]
Furthermore, crystal nuclei prepared by various manufacturing methods such as CVD method or
PVD method are put in a sol solution composed of an inorganic metal compound or an organic
metal compound, or a sol solution is applied to the crystal nuclei, solidified, and heat treated It is
known that, by growing a titanium oxide crystal from the crystal nucleus, a highly active
photocatalytic function can be obtained when the crystal shape of the titanium oxide crystal
grown from the crystal nucleus forms a columnar crystal (for example, Patent Documents 10 to
12). However, in that case, since the columnar crystals grow only from the seed crystals placed
on the substrate, the formed columnar crystals have insufficient adhesion strength to the
substrate, so they were produced as such The photocatalyst is not always satisfactory in terms of
durability such as abrasion resistance.
[0007]
The ultrasonic horn used to efficiently give ultrasonic signals to the object to be treated in an
ultrasonic processing machine such as an ultrasonic welding machine is formed of a metallic
substance such as steel, titanium, titanium alloy, etc. However, it is known that the surface on the
ultrasonic output side in contact with the object to be treated is easily worn away. For example,
when an ultrasonic horn is used in a liquid, it is known that abrasion called erosion occurs on the
surface on the ultrasonic output side. Patent Document 1: Japanese Patent Application
Publication No. 09-241038 Patent Document 2: Japanese Patent Application Publication No. 09262481 Patent Document 2: Japanese Patent Application Publication No. 10-053437 Patent
02-05-2019
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Document 2: Japanese Patent Application Publication No. 11-012720 Patent Document 2:
Japanese Patent Application Publication 2001-205105 Japanese Patent Application Publication
2001-205103 Patent Document 1: Japanese Patent Application Laid-Open No. 2002-50976
Patent Document 2: Japanese Patent Application Laid-Open No. 2002/105953 Patent Document
2: International Patent Publication No. 01/10553 Patent Document 2: Japanese Patent
Application Laid-Open No. 2002-253975 Patent Document 2 Japanese Patent Application LaidOpen No. 2002-370027 Patent Document 1: JP-A-2002-370034 A. Fujishima et al., J.
Electrochem. Soc. Vol. 122、No. 11, p. 1487-1489, November 1975 R. Asahi et al., SCIENCE Vol.
293、2001July 13, p. 269-271 Shahed U. M. Khan et al., SCIENCE Vol. 297、2002September
27, p. 2243-2245
[0008]
Here, the conventional titanium oxide-based photocatalysts have problems in durability (high
hardness, scratch resistance, abrasion resistance, chemical resistance, heat resistance) both in the
ultraviolet light responsive type and the visible light responsive type. , Had become a bottleneck
in terms of practical use.
[0009]
On the other hand, the conventional ultrasonic horn is formed of a metallic substance such as
steel, titanium, titanium alloy and has a problem that the surface on the ultrasonic output side is
easily abraded, so it is excellent in durability Is required.
[0010]
Therefore, the first invention is excellent in durability (high hardness, scratch resistance, abrasion
resistance, chemical resistance, heat resistance) as a surface layer on at least a part of the
ultrasonic output side end portion in the ultrasonic horn Another object of the present invention
is to provide an ultrasonic horn having a carbon-doped titanium oxide layer which functions as a
visible light responsive photocatalyst.
[0011]
The second invention can easily adsorb VOC, has a large surface area, and is carbon-doped, so it
has a high activity as a photocatalyst and functions as a visible light responsive photocatalyst,
and has peeling resistance, abrasion resistance, and abrasion resistance. An object of the present
invention is to provide an ultrasonic horn having an ultrasonic wave output side end which is
excellent in chemical properties and heat resistance.
02-05-2019
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[0012]
As a result of intensive studies to achieve the above object, the inventor of the present invention
has found that the combustion flame of a hydrocarbon-based gas is the surface of a substrate
whose surface layer is composed of titanium, titanium alloy, titanium alloy oxide or titanium
oxide. Carbon is doped in the form of Ti-C bond by heat treatment at a high temperature using
Mg, and has excellent durability (high hardness, scratch resistance, abrasion resistance, chemical
resistance, heat resistance) and A member useful for applying to an ultrasonic horn having a
carbon-doped titanium oxide layer functioning as a visible light responsive photocatalyst as a
surface layer (hereinafter referred to as “multifunctional material”.
) Was obtained, and the present invention has been completed.
[0013]
That is, in the first ultrasonic horn of the present invention, at least a part of the surface layer of
the ultrasonic output side end portion is made of a carbon-doped titanium oxide layer, and the
carbon is doped in a Ti-C bond state, It is characterized in that it is formed of a multifunctional
material (first multifunctional material) which is excellent in durability and functions as a visible
light responsive photocatalyst.
[0014]
Furthermore, as a result of intensive investigations by the inventor to achieve the above object,
combustion of unsaturated hydrocarbon, particularly acetylene, on the surface of a substrate at
least the surface layer of which is titanium, titanium oxide, titanium alloy or titanium alloy oxide
The flame is applied directly and heat-treated under specific conditions, or the surface of the
substrate is heat-treated under specific conditions in a combustion exhaust gas atmosphere of
unsaturated hydrocarbon, particularly acetylene, inside the surface layer. A layer of fine columns
made of titanium oxide or titanium alloy oxide is formed, and a layer of the fine columns is cut in
a direction along the surface layer to at least a part of the substrate. A member in which a layer
in which fine columns consisting of titanium oxide or titanium alloy oxide stand is exposed, and a
plurality of continuous narrow projections made of titanium oxide or titanium alloy oxide on a
thin film And a member having exposed fine columns standing on the protrusions, that is, both of
them have many protrusions made of titanium oxide or titanium alloy oxide on at least a part of
the surface. The fact that they are both useful multi-functional materials, and because the fine
pillars which are projections made of the titanium oxide or titanium alloy oxide and the
continuous narrow projections are carbon-doped, It has high photocatalytic activity, functions as
a visible light responsive photocatalyst, can adsorb VOC easily, has high hardness, and is able to
02-05-2019
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obtain a multifunctional material excellent in peeling resistance, abrasion resistance, chemical
resistance and heat resistance. And completed the present invention.
[0015]
That is, the second ultrasonic horn of the present invention has a large number of projections
made of titanium oxide or titanium alloy oxide on at least a part of the surface of the ultrasonic
output side end, for example, at least A layer in which a fine column consisting of titanium oxide
or titanium alloy oxide is partially exposed is exposed or a large number of continuous narrow
projections consisting of titanium oxide or titanium alloy oxide on the thin film and the
projection The fine pillars standing on the top are exposed, and the protrusions, for example, the
fine pillars, the narrow protrusions are formed of a carbon-doped multifunctional material
(second multifunctional material). It features.
[0016]
According to the present invention, at least a part of the ultrasonic wave output side end of the
ultrasonic horn is formed of the first multifunctional material or the second multifunctional
material.
[0017]
The first multifunctional material has excellent durability (high hardness, scratch resistance,
abrasion resistance, chemical resistance, heat resistance) and functions as a visible light
responsive photocatalyst, so it is used as a visible light responsive photocatalyst Not only that, it
can be significantly used for various ultrasonic horns in which hard chromium plating has been
used conventionally.
In addition, application to an ultrasonic horn intended for preventing pitting corrosion, general
corrosion, stress corrosion cracking and the like by reducing the potential of the base material
can be expected.
[0018]
The second multifunctional material has high photocatalytic activity, functions as a visible light
responsive photocatalyst, can easily adsorb VOC, has high hardness, is excellent in peeling
resistance, abrasion resistance, chemical resistance, and heat resistance. ing.
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[0019]
Therefore, not only weight reduction can be achieved by forming at least a part of the ultrasonic
wave output side end of the ultrasonic horn with the first multifunctional material or the second
multifunctional material, but also the hardness, etc. It is possible to provide an ultrasonic horn
that has excellent durability and has the excellent effect of a visible light responsive
photocatalyst.
[0020]
In addition, it is preferable to use the first multifunctional material if durability is important, and
it is preferable to use the second multifunctional material if height of photocatalytic activity is
important.
[0021]
Hereinafter, the best mode for carrying out the present invention will be described.
[0022]
The ultrasonic horn of the present embodiment is characterized in that a predetermined
multifunctional material is used for at least a part of the members of the ultrasonic output side
end.
Therefore, in the following, first, the multifunctional material will be described in detail, and then,
an ultrasonic horn using the multifunctional material will be described.
[0023]
[Regarding Multifunctional Material] The first multifunctional material used in the ultrasonic
horn of the present invention is, for example, carbonized at least on the surface of a substrate
whose surface layer is composed of titanium, titanium alloy, titanium alloy oxide or titanium
oxide. It can be produced by heat treatment at a high temperature using a combustion flame of a
gas containing hydrogen as its main component, but at least this surface layer is a substrate
composed of titanium, a titanium alloy, a titanium alloy oxide or titanium oxide The whole of the
base may be made of titanium, titanium alloy, titanium alloy oxide or titanium oxide, or may be
02-05-2019
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made of a surface portion forming layer and a core material, and their materials may be different.
In addition, with regard to the shape of the substrate, the final product shape (flat plate or solid
shape) where durability such as high hardness, scratch resistance, abrasion resistance, chemical
resistance, heat resistance etc. is desired, or visible light on the surface It may be a final product
shape that is desired to have a responsive photocatalytic function.
[0024]
In the case where the base having at least the surface layer of titanium, titanium alloy, titanium
alloy oxide or titanium oxide is composed of the surface portion forming layer and the core
material and their materials are different, the thickness of the surface portion forming layer The
thickness may be the same as the thickness of the carbon-doped titanium oxide layer to be
formed (that is, the entire surface-forming layer is a carbon-doped titanium oxide layer) or may
be thick (ie, the thickness of the surface-forming layer) A part of the direction becomes a carbondoped titanium oxide layer, and a part remains as it is).
Further, the material of the core material is not particularly limited as long as it does not burn,
melt or deform during the heat treatment in the production method of the first invention.
For example, iron, iron alloy, non-ferrous alloy, ceramics, other ceramics, high temperature heat
resistant glass, etc. can be used as the core material.
Examples of a base composed of such a thin film surface layer and core material include a
method such as sputtering, vapor deposition, thermal spraying, etc. of a film consisting of
titanium, titanium alloy, titanium alloy oxide or titanium oxide on the surface of core material.
And those obtained by applying a commercially available titanium oxide sol on a surface of a
core material by spray coating, spin coating or dipping, and the like.
[0025]
The first multifunctional material is composed of a layer comprising carbon-doped titanium oxide
or titanium alloy oxide, an intermediate layer and a core material, and the intermediate layer is
made of titanium, titanium alloy, titanium alloy oxide or It may be titanium oxide, and the core
02-05-2019
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material may be made of materials other than titanium, a titanium alloy and titanium oxide.
[0026]
Various titanium alloys known as the above-mentioned titanium alloys can be used without
particular limitation.
For example, Ti-6Al-4V, Ti-6Al-6V-2Sn, Ti-6Al-2Sn-4Zr-6Mo, Ti-10V-2Fe-3Al, Ti-7Al-4Mo, Ti-5Al2.5Sn, Ti- 6Al-5Zr-0.5Mo-0.2Si, Ti-5.5Al-3.5Sn-3Zr-0.3Mo-1Nb-0.3Si, Ti-8Al-1Mo-1V, Ti-6Al-2Sn4Zr- 2Mo, Ti-5Al-2Sn-2Zr-4Mo-4Cr, Ti-11.5Mo-6Zr-4.5Sn, Ti-15V-3Cr-3Al-3Sn, Ti-15Mo-5Zr-3Al,
Ti-15Mo-5Zr, Ti-13V-11Cr-3Al etc. can be used.
[0027]
In the production of the first multifunctional material, it is possible to use a combustion flame of
a hydrocarbon, particularly a gas containing acetylene as a main component, and in particular, it
is desirable to use a reduction flame.
In the production of the first multifunctional material, this hydrocarbon-based gas means a gas
containing at least 50% by volume of hydrocarbon, for example, containing at least 50% by
volume of acetylene, and optionally air, It means a gas mixed with hydrogen, oxygen and the like.
In the production of the multifunctional material, the gas containing hydrocarbon as a main
component preferably contains 50% by volume or more of acetylene, and the hydrocarbon is
most preferably 100% of acetylene.
In the case of using unsaturated hydrocarbons, particularly acetylene having a triple bond,
unsaturated bonds are decomposed to form an intermediate radical substance in the process of
combustion, particularly in the reduction flame, to form an intermediate radical substance. It is
considered that carbon doping is likely to occur because the activity is strong.
02-05-2019
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[0028]
In the production of the first multifunctional material, when the surface layer of the substrate to
be heat-treated is titanium or a titanium alloy, oxygen for oxidizing the titanium or titanium alloy
is necessary, and air or oxygen is contained accordingly. Need to be
[0029]
In the production of the first multifunctional material, the surface of a substrate whose surface
layer is composed of titanium, titanium alloy, titanium alloy oxide or titanium oxide is heated at a
high temperature using a combustion flame of a hydrocarbon-based gas In this case, even if a
combustion flame of a hydrocarbon-based gas is directly applied to the surface of the substrate
and heat-treated at a high temperature, the surface of such a substrate is a hydrocarbon-based
gas The heat treatment may be performed at a high temperature in a combustion gas
atmosphere, and the heat treatment can be performed, for example, in a furnace.
When the combustion flame is directly applied and heat treatment is performed at a high
temperature, the fuel gas as described above may be burned in a furnace and the combustion
flame may be applied to the surface of the substrate.
When heat treatment is performed at high temperature in a combustion gas atmosphere, the fuel
gas as described above is burned in a furnace, and the high temperature combustion gas
atmosphere is used.
[0030]
In the heat treatment, the surface temperature of the substrate is 900 to 1500 ° C., preferably
1000 to 1200 ° C., and a carbon-doped titanium oxide layer in which carbon is doped in the
form of Ti-C bonds is formed as the surface layer of the substrate. It is necessary to carry out
heat treatment to
In the case of heat treatment in which the surface temperature of the substrate is less than 900
° C., the durability of the obtained substrate having a carbon-doped titanium oxide layer is
insufficient, and the photocatalytic activity under visible light is also insufficient. On the other
hand, in the case of heat treatment where the surface temperature of the substrate exceeds 1500
02-05-2019
10
° C., exfoliation of an extremely thin film occurs from the surface portion of the substrate upon
cooling after heat treatment, and the durability (high hardness) targeted in the first invention ,
Scratch resistance, abrasion resistance, chemical resistance, heat resistance) can not be obtained.
In addition, even in the case of heat treatment in which the surface temperature of the substrate
is in the range of 900 to 1500 ° C., if the heat treatment time is long, peeling of the very thin
film occurs from the surface portion of the substrate upon cooling after heat treatment. Since the
effect of durability (high hardness, scratch resistance, abrasion resistance, chemical resistance,
heat resistance) aimed at in the first invention is not obtained, the surface of the substrate is
cooled at the time of cooling after heat treatment. It is necessary that the time be such as not to
cause peeling. That is, the heat treatment time is a time sufficient to form the surface layer into a
carbon-doped titanium oxide layer in which carbon is doped in the form of Ti-C bonds, but the
electrode from the surface portion of the substrate is cooled after heating. It should be time that
does not lead to thin film peeling. Although the heat treatment time is correlated with the heating
temperature, it is preferably about 400 seconds or less.
[0031]
In the production of the first multifunctional material, carbon containing 0.3 to 15 at%,
preferably 1 to 10 at% of carbon is doped in the form of Ti-C bond by adjusting the heating
temperature and the heating time. A carbon-doped titanium oxide layer can be obtained relatively
easily. When the amount of carbon doping is small, the carbon-doped titanium oxide layer is
transparent, and as the amount of carbon doping increases, the carbon-doped titanium oxide
layer becomes semitransparent and opaque. Therefore, by forming a transparent carbon-doped
titanium oxide layer on a transparent sheet core, it is excellent in durability (high hardness,
scratch resistance, abrasion resistance, chemical resistance, heat resistance) and visible light
response Can be obtained as a transparent plate that functions as a mold photocatalyst, and
durability (high hardness, scratch resistance, abrasion resistance) can be obtained by forming a
transparent carbon-doped titanium oxide layer on a plate having a colored pattern on the
surface. It is possible to obtain a decorative board which is excellent in chemical resistance and
heat resistance and which functions as a visible light responsive photocatalyst. When at least the
surface layer of the base composed of titanium, titanium alloy, titanium alloy oxide or titanium
oxide is composed of the surface forming layer and the core material, and the thickness of the
surface forming layer is 500 nm or less, When the surface portion forming layer is heated to the
vicinity of the melting point, a large number of small island-like undulations floating in the sea
are formed on the surface and become translucent.
[0032]
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In a multifunctional material having a carbon-doped titanium oxide layer in which carbon is
doped in the form of a Ti-C bond, the thickness of the carbon-doped titanium oxide layer is
preferably 10 nm or more, and has high hardness, scratch resistance, and resistance It is more
preferable that the thickness be 50 nm or more in order to achieve the wear resistance. When
the thickness of the carbon-doped titanium oxide layer is less than 10 nm, the durability of the
resulting multifunctional material having a carbon-doped titanium oxide layer tends to be
insufficient. The upper limit of the thickness of the carbon-doped titanium oxide layer needs to
be considered in terms of cost and the effect to be achieved, but is not particularly limited.
[0033]
The carbon-doped titanium oxide layer of the first multifunctional material is formed by doping
chemically modified titanium oxide as described in Non-Patent Document 3 described above, or
various atoms or anions X conventionally proposed. Unlike titanium oxide containing the
titanium compound Ti̶O̶X, it contains a relatively large amount of carbon and doped carbon
is contained in the form of Ti̶C bonds. As a result, mechanical strength such as scratch
resistance and wear resistance is improved, and Vickers hardness is considered to be
significantly increased. In addition, the heat resistance is also improved.
[0034]
The carbon-doped titanium oxide layer of the first multifunctional material has a Vickers
hardness of 300 or more, preferably 500 or more, more preferably 700 or more, and most
preferably 1000 or more. The Vickers hardness of 1000 or more is harder than the hardness of
hard chromium plating. Therefore, the first multifunctional material can be significantly used for
various materials in which hard chromium plating has conventionally been used.
[0035]
The carbon-doped titanium oxide layer of the first multifunctional material responds to not only
ultraviolet light but also visible light having a wavelength of 400 nm or more, and effectively
functions as a photocatalyst. Therefore, the first multifunctional material can be used as a visible
light responsive photocatalyst, and exhibits a photocatalytic function indoors as well as outdoors.
The carbon-doped titanium oxide layer of the first multifunctional material exhibits
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superhydrophilicity with a contact angle of 3 ° or less.
[0036]
Furthermore, the carbon-doped titanium oxide layer of the first multifunctional material is also
excellent in chemical resistance, and after being immersed in each aqueous solution of 1 M
sulfuric acid and 1 M sodium hydroxide for one week, the film hardness, wear resistance and
light When the current density was measured and compared with the measurement value before
treatment, no significant change was observed. Incidentally, in the case of a commercially
available titanium oxide film, generally, the binder dissolves in acid or alkali depending on its
type, so that the film peels off, and there is almost no acid resistance or alkali resistance.
[0037]
The second multifunctional material used in the ultrasonic horn of the present invention is, for
example, the combustion of unsaturated hydrocarbon, particularly acetylene, on the surface of a
substrate at least the surface layer of which is titanium, titanium oxide, titanium alloy or titanium
alloy oxide. Heat treatment with flame is performed to form a layer in which fine columns
consisting of titanium oxide or titanium alloy oxide stand in the surface layer, and then, for
example, thermal stress, shear stress, tensile force are applied to the fine layer. The pillared layer
is cut along the surface layer in a direction along the surface layer to form at least a part of the
substrate, usually a large column of the titanium oxide or titanium alloy oxide on the substrate. A
member in which a layer standing in a forest is exposed, a large number of continuous narrow
projections made of titanium oxide or titanium alloy oxide on a thin film, and fine columns
standing in a forest on the projections By obtaining a member It can be granulated.
[0038]
In the base having at least the surface layer of titanium, titanium oxide, titanium alloy or titanium
alloy oxide, the whole of the base may be composed of any of titanium, titanium oxide, titanium
alloy or titanium alloy oxide, Alternatively, it may be composed of a surface portion forming layer
made of titanium, titanium oxide, titanium alloy or titanium alloy oxide, and a core made of
another material.
In addition, the shape of the substrate may be any final product shape (flat plate or solid shape)
where photocatalytic activity and / or superhydrophilicity is desired.
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[0039]
A base having at least a surface layer of titanium, titanium oxide, titanium alloy or titanium alloy
oxide is composed of a surface portion forming layer of titanium, titanium oxide, titanium alloy
or titanium alloy oxide and a core material of other materials In this case, the thickness (quantity)
of the surface layer-forming layer is equivalent to the amount of the layer in which fine columns
consisting of titanium oxide or titanium alloy oxide are standing ( That is, the entire surface
portion forming layer is a layer in which fine columns consisting of titanium oxide or titanium
alloy oxide stand on the surface) or may be thicker (that is, a part of the surface portion forming
layer in the thickness direction) The fine columns made of titanium oxide or titanium alloy oxide
form a forested layer, and the remaining portion remains unchanged. Further, the material of the
core material is not particularly limited as long as it is not burned, melted or deformed during the
heat treatment in the production of the second multifunctional material. For example, iron, iron
alloy, non-ferrous alloy, glass, ceramics, and other pottery can be used as the core material. As
the substrate composed of such a thin film surface layer and core material, the same ones as
those described in the first invention can be used. The thickness of the surface layer is preferably
0.5 μm or more, more preferably 4 μm or more.
[0040]
As the titanium alloy, various known titanium alloys can be used without being particularly
limited, and the same one as the first multifunctional material can be used.
[0041]
In the production of the second multifunctional material, for example, it is desirable to use a
combustion flame of a gas containing unsaturated hydrocarbon, particularly acetylene as a main
component, and in particular, to use a reduction flame.
In the production of the second multifunctional material, a gas containing at least 50% by volume
of unsaturated hydrocarbon, for example, a gas containing at least 50% by volume of acetylene
and appropriately mixing air, hydrogen, oxygen, etc. preferable. In the production of the second
multifunctional material, the fuel component is most preferably 100% of acetylene. In the case of
using unsaturated hydrocarbons, particularly acetylene having a triple bond, unsaturated bonds
are decomposed to form an intermediate radical substance in the process of combustion,
02-05-2019
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particularly in the reduction flame, to form an intermediate radical substance. Since the activity is
strong, carbon doping tends to occur, and the doped carbon is included in the state of Ti-C bond.
Thus, when carbon is doped in the fine column, the hardness of the fine column is increased, and
as a result, the mechanical strength such as the hardness and the abrasion resistance of the
multifunctional material is improved, and the heat resistance is also improved.
[0042]
In the production of the second multifunctional material, a combustion flame is directly applied
to the surface of a substrate whose surface layer is composed of titanium, titanium oxide,
titanium alloy or titanium alloy oxide for heat treatment, or the surface of the substrate is burned
The heat treatment is carried out in an exhaust gas atmosphere, but this heat treatment can be
carried out, for example, by means of a gas burner or in a furnace. When the combustion flame is
directly applied and heat treatment is performed at a high temperature, the combustion flame
may be applied to the surface of the substrate by a gas burner. When heat treatment is
performed at a high temperature in a combustion exhaust gas atmosphere, the fuel gas as
described above may be burned in a furnace and an atmosphere including the high temperature
combustion exhaust gas may be used.
[0043]
With regard to heat treatment, a layer is formed in which fine columns consisting of titanium
oxide or titanium alloy oxide stand on the inside of the surface layer, at least the surface layer
consisting of titanium, titanium oxide, titanium alloy or titanium alloy oxide, and then For
example, thermal stress, shear stress, and tensile force are applied to cut the layer in which the
micro pillars stand in the direction along the surface layer to form the titanium oxide or titanium
alloy oxide on at least a part of the substrate. A member in which the layer in which the fine
pillars are standing is exposed, a large number of continuous narrow projections made of the
titanium oxide or titanium alloy oxide on the thin film, and the fine stands being held on the
projections It is necessary to adjust the heating temperature and the heating time so that it is
possible to obtain a member in which the column is exposed. The heat treatment is preferably
performed at a temperature of 600 ° C. or higher.
[0044]
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By heating under such conditions, the height of the layer in which the fine pillars stand is about 1
to 20 μm, the thickness of the thin film thereon is about 0.1 to 10 μm, and the fine pillars An
intermediate having an average thickness of about 0.2 to 3 μm is formed. Thereafter, the
titanium oxide or the titanium oxide or the titanium oxide layer is formed on at least a part of the
substrate by, for example, applying thermal stress, shear stress, tensile force to cut the layer in
which the micro pillars stand along the surface layer. A member in which a layer in which fine
columns consisting of titanium alloy oxide are standing is exposed (that is, all or most of the thin
film present on the layer in which fine columns on the substrate stand) However, a part of the
thin film which was present on the layer where the fine pillars are standing may remain without
peeling), and a large number of continuous narrow widths consisting of titanium oxide or
titanium alloy oxide on the thin film A protrusion and a member on which the fine column
standing on the protrusion is exposed are obtained.
[0045]
In the case of applying thermal stress to cut a layer in which fine columns are standing in a
direction along the surface layer, for example, either the surface or the back surface of the
substrate is cooled or the surface of the substrate is heated. Provide a temperature difference
between the and the back side. As this cooling method, for example, either the front surface or
the back surface of the above-mentioned hot intermediate is brought into contact with a cooling
object such as a stainless steel block, or cold air (air at normal temperature) is made to either the
front surface or the back surface of the above-mentioned hot intermediate Spray. Even if the
above-mentioned hot intermediate is allowed to cool, thermal stress occurs, but to a lesser extent.
[0046]
In the case where shear stress is applied to cut the layer in which the fine pillars stand up in the
direction along the surface layer, for example, the surface and the back surface of the abovementioned intermediate are applied with a relatively reverse force due to frictional force. In
addition, in the case of applying tensile force to cut the layer in which fine columns are standing
in the direction along the surface layer, for example, using a vacuum suction disk etc. Pull in the
opposite direction in the vertical direction. In the case where only a member in which a layer on
which a fine column consisting of titanium oxide or titanium alloy oxide stands is exposed is used
on at least a part of the substrate, oxidation is performed on the thin film of the above
intermediate. It is also possible to remove a large number of continuous narrow projections made
of titanium or titanium alloy oxide and a portion corresponding to a member on which the fine
02-05-2019
16
pillars standing on the projections are exposed by polishing, sputtering or the like.
[0047]
In a member in which a layer in which fine columns made of titanium oxide or titanium alloy
oxide stand is exposed on at least a part of the substrate obtained as described above, the layer in
which the fine columns are formed is Although the height of the layer in which the fine pillar
stands is changed depending on the height position of the fine column cut in the direction along
the surface layer, the height of the layer in which the fine pillar stands is generally 1 to The
average thickness of the fine columns is about 0.5 to 3 μm. This member can easily adsorb VOC
and has a large surface area, so it has high activity as a photocatalyst, and it is also a
multifunctional material with high film hardness and excellent peeling resistance, abrasion
resistance, chemical resistance, and heat resistance. is there.
[0048]
On the other hand, on the thin film obtained as described above, a large number of continuous
narrow projections made of titanium oxide or titanium alloy oxide and members exposed with
fine pillars standing on the projections are small. The height of the protrusions on each piece is
about 2 to 12 μm, and the height of the micro pillars is the height of the micro pillars obtained
by cutting the layer in which the micro pillars stand in the direction along the surface layer The
height of the layer in which the fine pillars stand is generally about 1 to 5 μm, and the average
thickness of the fine pillars is about 0.2 to 0.5 μm, although it changes depending on the height
position. However, depending on the conditions for cutting the layer in which the fine pillars
stand up in the direction along the surface layer, there may be a case where a large number of
continuous narrow projections are exposed without very few fine pillars. This member can also
adsorb VOC and has a large surface area, so its activity as a photocatalyst is high. Further, this
member can be used as it is or pulverized, and the pulverized product can also easily adsorb
VOC, and since the surface area is large, the activity as a photocatalyst is high.
[0049]
In the second multifunctional material, the fine columns made of titanium oxide or titanium alloy
oxide, many continuous narrow projections, and the fine pillars standing on the projections are
carbon-doped, so that ultraviolet light is emitted. Of course, it responds to visible light with a
wavelength of 400 nm or more, acts particularly effectively as a photocatalyst, can be used as a
visible light responsive photocatalyst, and exhibits a photocatalytic function both indoors and
02-05-2019
17
outdoors.
[0050]
The shape of each of the fine pillars of the layer in which the fine pillars of titanium oxide or
titanium alloy oxide constituting the second multifunctional material stand is as judged from the
photomicrographs of FIGS. 10 and 13. , Prismatic, cylindrical, pyramidal, conical, inverted
pyramidal, etc. which extend straight in a direction perpendicular or inclined to the surface of the
substrate, or which extends while curving or bending , Branched and extending in a branched
manner, and a complex thereof.
Moreover, as the whole shape, it can show with various expressions, such as a frost pillar shape,
a raising carpet shape, a bowl shape, a row pillar shape, a pillar shape assembled with blocks, etc.
In addition, the thickness, height, the size of the root (bottom surface), and the like of the fine
columns change depending on the heating conditions and the like.
[0051]
A large number of continuous narrow projections consisting of titanium oxide or titanium alloy
oxide in a thin film form and a member with exposed fine columns standing on the projections
are judged from the photomicrograph of FIG. The large number of continuous narrow projections
can be seen as the appearance of the outside of a walnut shell, the appearance of pumice stone,
and each continuous narrow projection can be shaped like a spit It can be seen that the pattern is
bent. Also, the shape of the fine pillars standing on the protrusions is the same as the shape of
each fine pillar of the layer on which the fine pillars stand on the above-mentioned substrate, but
the joint between the fine pillars and the thin film Since many of them are cut off, the density of
fine pillars standing on the protrusions is generally smaller than the density of the fine pillars of
the layer on which the fine pillars stand on the above-mentioned substrate.
[0052]
Hereinafter, the present invention will be described in more detail based on examples and
comparative examples.
[0053]
02-05-2019
18
[Examples 1 to 3] By using a combustion flame of acetylene and heating the titanium plate
having a thickness of 0.3 mm so that the surface temperature thereof becomes about 1100 ° C.,
the carbon becomes Ti̶C bond as a surface layer In this state, a titanium plate having a carbondoped titanium oxide layer doped is formed.
The carbon doping amount and the thickness of the carbon-doped titanium oxide layer by
adjusting the heat treatment time at 1100 ° C. to 5 seconds (Example 1), 3 seconds (Example 2)
and 1 second (Example 3), respectively. A titanium plate having different carbon-doped titanium
oxide layers was formed.
[0054]
The carbon content of the carbon-doped titanium oxide layer doped with carbon formed in
Examples 1 to 3 in the state of Ti̶C bond was determined by a fluorescent X-ray analyzer.
Assuming that the molecular structure of TiO2-xCx is based on its carbon content, the carbon
content of 8 at%, TiO1. 76The carbon content of C0.24, Example 2 was about 3.3 at%, TiO 1.90 C
0.10, and the carbon content of Example 3 was 1.7 at%, TiO 1.95 C0.05. Further, the carbondoped titanium oxide layer doped with carbon formed in Examples 1 to 3 in the state of Ti̶C
bond was superhydrophilic having a contact angle with water droplets of about 2 °.
[0055]
[Comparative Example 1] A commercially available titanium oxide sol (STS-01 manufactured by
Ishihara Sangyo Co., Ltd.) is spin-coated on a titanium plate having a thickness of 0.3 mm, and
then heated to improve adhesion. It formed.
[0056]
Comparative Example 2 A commercial product in which titanium oxide is spray-coated on a SUS
plate was used as a substrate having the titanium oxide film of Comparative Example 2.
[0057]
Test Example 1 (Vickers Hardness) A nanohardness tester (NHT) (made by CSM Instruments of
02-05-2019
19
Switzerland) was used for the carbon-doped titanium oxide layer in which the carbon of Example
1 was doped in the Ti-C bond state and the titanium oxide film of Comparative Example 1. Film
hardness was measured under the conditions of indenter: Belkovich type, test load: 2 mN, load
unloading rate: 4 mN / min, and carbon of Example 1 was doped with Ti-C bond. The doped
titanium oxide layer had a high Vickers hardness of 1340.
On the other hand, the Vickers hardness of the titanium oxide film of Comparative Example 1
was 160.
[0058]
These results are shown in FIG.
For reference, reference values of Vickers hardness of hard chromium plating layer and nickel
plating layer (from Tomono, “Practical plating manual”, Chapter 6, cited from Ohmsha (1971))
are also shown. It is apparent that the carbon-doped titanium oxide layer doped with carbon in
the Ti-C bond of Example 1 has a higher hardness than the nickel plating layer or hard chromium
plating layer.
[0059]
Test Example 2 (Scratch Resistance) For the carbon-doped titanium oxide layer doped with
carbon in the Ti-C bond of Example 1 and the titanium oxide film of Comparative Example 1, a
micro scratch tester (MST) (CSM Instruments, Switzerland) Made by indenter: Rockwell
(diamond), tip radius 200 μm, initial load: 0 N, final load: 30 N, loading speed: 50 N / min,
scratch length: 6 mm, stage speed: 10.5 mm / min A scratch resistance test was performed. A
"detachment initiation" load at which small film peeling occurs in the scratch marks and a "full
surface peeling" load at which film peeling occurs throughout the scratch marks were
determined. The results are as shown in Table 1.
[0060]
As apparent from this table, it can be seen that the carbon-doped titanium oxide surface layer of
Example A is superior in scratch resistance to the titanium oxide film of Comparative Example 1.
02-05-2019
20
[0061]
Test Example 3 (Abrasion Resistance) A high temperature tribometer (HT-TRM) (Switzerland) was
used for the carbon-doped titanium oxide layer in which carbon in Example 1 was doped in the
Ti-C bond state and the titanium oxide film of Comparative Example 1. Test temperature: room
temperature and 470 ° C., ball: SiC ball of diameter 12.4 mm, load: 1 N, sliding speed: 20 mm /
sec, radius of rotation: 1 mm, test rotation speed: 1000 rotation conditions. The wear test was
carried out below.
[0062]
As a result, for the titanium oxide film of Comparative Example 1, peeling occurred at both room
temperature and 470 ° C., but for the carbon-doped titanium oxide layer in which carbon of
Example 1 was doped in the state of Ti̶C bond No significant trace wear was detected under
both room temperature and 470 ° C. conditions.
[0063]
Test Example 4 (Chemical Resistance) The titanium plate having a carbon-doped titanium oxide
layer doped with carbon in the Ti-C bond state in Example 1 was immersed in 1 M aqueous
sulfuric acid solution and 1 M aqueous sodium hydroxide solution for 1 week at room
temperature. Thereafter, the film hardness, the abrasion resistance, and the photocurrent density
described later were measured. As a result, no significant difference was observed in the results
before and after immersion.
That is, it was found that the carbon-doped titanium oxide layer doped with carbon in the Ti-C
bond of Example 1 has high chemical resistance.
[0064]
Test Example 5 (Structure of a carbon-doped titanium oxide layer doped with carbon in the form
of a Ti̶C bond) With respect to a carbon-doped titanium oxide layer in which carbon in Example
1 is doped in the form of a Ti̶C bond With a spectroscope (XPS), an accelerating voltage: 10 kV,
a target: Al, Ar ion sputtering was performed for 2700 seconds, and analysis was started.
02-05-2019
21
Assuming that the sputtering rate is 0.64 Å / s, which is equivalent to that of the SiO 2 film, the
depth is about 173 nm.
The results of the XPS analysis are shown in FIG. The highest peak appears when the binding
energy is 284.6 eV. It is judged that this is a C̶H (C) bond generally found in Cls analysis. The
next highest peak is seen when the binding energy is 281.7 eV. Since the bonding energy of the
Ti-C bond is 281.6 eV, it is determined that C is doped as a Ti-C bond in the carbon-doped
titanium oxide layer of Example 1. In addition, as a result of conducting XPS analysis at 11
different positions in the depth direction of the carbon-doped titanium oxide layer, similar peaks
appeared near 281.6 eV at all points.
[0065]
Moreover, Ti-C bond was also confirmed in the boundary of a carbon dope titanium oxide layer
and a base | substrate. Therefore, the hardness is increased by the Ti-C bond in the carbon-doped
titanium oxide layer, and the film peeling strength is significantly increased by the Ti-C bond at
the boundary between the carbon-doped titanium oxide layer and the substrate. Is expected.
[0066]
Test Example 6 (Wavelength Response) The wavelength response of the carbon-doped titanium
oxide layer doped with carbon in the Ti-C bond of Examples 1 to 3 and the titanium oxide film of
Comparative Examples 1 and 2 is monochrome of Oriel Co. It measured using the meter.
Specifically, a voltage of 0.3 V was applied between each layer and the film in a 0.05 M aqueous
solution of sodium sulfate with a counter electrode to measure the photocurrent density.
[0067]
The results are shown in FIG. FIG. 3 shows the obtained photocurrent density jp with respect to
the irradiation wavelength. The wavelength absorption edge of the carbon-doped titanium oxide
layer doped with carbon in the Ti-C bond of Examples 1 to 3 extends to 490 nm, and the
photocurrent density increases with the increase of the carbon doping amount. Was recognized.
Although not shown here, it was found that when the carbon doping amount exceeds 10 at%, the
current density tends to decrease, and when it exceeds 15 at%, the tendency becomes
02-05-2019
22
remarkable. Therefore, it was recognized that the carbon doping amount has an optimum value
at about 1 to 10 at%. On the other hand, in the titanium oxide films of Comparative Examples 1
and 2, it was recognized that the photocurrent density was extremely small and the wavelength
absorption edge was also about 410 nm.
[0068]
Test Example 7 (Light Energy Conversion Efficiency) For the carbon-doped titanium oxide layer
in which carbon in Examples 1 to 3 is doped in the form of Ti̶C bond and the titanium oxide
film of Comparative Examples 1 and 2, the formula η = jp (Ews) The light energy conversion
efficiency η defined by −Eapp) / I was determined. Here, E ws is a theoretical decomposition
voltage of water (= 1.23 V), E app is an applied voltage (= 0.3 V), and I is an irradiation light
intensity. The results are shown in FIG. FIG. 4 shows the light energy conversion efficiency η
with respect to the irradiation light wavelength.
[0069]
As apparent from FIG. 4, the light energy conversion efficiency of the carbon-doped titanium
oxide layer doped with carbon in the Ti-C bond state in Examples 1 to 3 is extremely high, and
the conversion efficiency at a wavelength of around 450 nm is a comparative example. It was
found that the conversion efficiency in the ultraviolet region (200 to 380 nm) of the titanium
oxide films of 1 and 2 was superior. In addition, the water splitting efficiency of the carbondoped titanium oxide layer doped with carbon in the Ti-C bond state of Example 1 is about 8% at
a wavelength of 370 nm, and an efficiency exceeding 10% can be obtained at 350 nm or less. I
understand.
[0070]
Test Example 8 (Deodorizing Test) A deodorizing test was conducted on the carbon-doped
titanium oxide layer in which carbon in Examples 1 and 2 was doped in the form of Ti-C bond
and the titanium oxide film of Comparative Example 1. Specifically, after acetaldehyde, which is
generally used in the deodorizing test, is enclosed in a 1000 ml glass container together with a
substrate having a carbon-doped titanium oxide layer, the influence of concentration reduction
due to initial adsorption can be ignored. The visible light was irradiated with a fluorescent lamp
with a UV cut filter, and the acetaldehyde concentration was measured by gas chromatography
02-05-2019
23
every predetermined irradiation time. The surface area of each film was 8.0 cm <2>.
[0071]
The results are shown in FIG. FIG. 5 shows the acetaldehyde concentration versus the elapsed
time after visible light irradiation. The acetaldehyde decomposition rate of the carbon-doped
titanium oxide layers of Examples 1 and 2 is about 2 times or more as high as the acetaldehyde
decomposition rate of the titanium oxide film of Comparative Example 1, and the carbon doping
amount is large. It was found that the carbon-doped titanium oxide layer of Example 1 having
high energy conversion efficiency had a higher decomposition rate compared to the carbondoped titanium oxide layer of Example 2.
[0072]
Test Example 9 (Antifouling Test) An antifouling test was conducted on the carbon-doped
titanium oxide layer of Example 1 and the titanium oxide film of Comparative Example 1. Each
film was placed in a smoking room in the Central Research Institute of Electric Power Industry,
and surface dirt was observed after 145 days. There is no direct incidence of sunlight in this
smoking room.
[0073]
A photograph showing this result is shown in FIG. Although oil adhered to the surface of the
titanium oxide film of Comparative Example 1 and exhibited a pale yellow color, no particular
change was observed in the surface of the carbon-doped titanium oxide layer of Example 1, and
the surface was kept clean. It was found that the antifouling effect was sufficiently exhibited.
[0074]
[Examples 4 to 7] As in Examples 1 to 3, using a combustion flame of acetylene, a 0.3 mm-thick
titanium plate was heated at the surface temperatures shown in Table 2 for the times shown in
Table 2 As a result, a titanium plate having a carbon-doped titanium oxide layer as a surface
layer was formed.
02-05-2019
24
[0075]
Comparative Example 3 Using a combustion flame of natural gas, a 0.3 mm-thick titanium plate
was heat-treated at the surface temperature shown in Table 2 for the time shown in Table 2.
[0076]
Test Example 10 The carbon-doped titanium oxide layers of Examples 4 to 7 and the coating of
Comparative Example 3 were measured for Vickers hardness (HV) in the same manner as in Test
Example 1 described above.
The results are shown in Table 2.
The carbon-doped titanium oxide layers formed in Examples 4 to 11 were superhydrophilic
having a contact angle with water droplets of about 2 °.
[0077]
As apparent from the data shown in Table 2, when heat treatment was performed so that the
surface temperature was 850 ° C. with combustion gas of natural gas, only a film having a
Vickers hardness of 160 was obtained, but the surface temperature was 1000 In the case of
Examples 4-7 heat-processed using the combustion gas of an acetylene so that it may become
more than ° C, the carbon dope titanium oxide layer of Vickers hardness 1200 was obtained.
[0078]
Test Example 11 For the carbon-doped titanium oxide layers of Examples 4 to 7 and the titanium
oxide films of Comparative Examples 1 and 3, as in Test Example 6, a voltage of 0. The
photocurrent density was measured by applying 3 V and irradiating light of 300 nm to 520 nm.
The results are shown in FIG. In FIG. 7, the obtained photocurrent density jp is compared with
the potential ECP (V vs. SSE is shown.
[0079]
02-05-2019
25
The carbon-doped titanium oxide layers of Examples 4 to 6 obtained by heat treatment using
acetylene combustion gas to have a surface temperature of 1000 to 1200 ° C. are relatively
excellent in relatively large photocurrent density I understand. On the other hand, the titanium
oxide of Comparative Example 3 obtained by heating the surface temperature to 850 ° C. and
the carbon-doped titanium oxide layer of Example 7 obtained by heating the surface temperature
to 1500 ° C. It was found that the photocurrent density is relatively small.
[0080]
[Example 8] A carbon-doped surface layer is oxidized by heat-treating a 0.3 mm thick Ti-6Al-4V
alloy plate using an acetylene combustion flame so that the surface temperature becomes about
1100 ° C. An alloy plate made of a titanium alloy containing titanium was formed. The heat
treatment time at 1100 ° C. was 60 seconds. The layer containing carbon-doped titanium oxide
thus formed is superhydrophilic having a contact angle of about 2 ° with water droplets, and
has the same photocatalytic activity as the carbon-doped titanium oxide layer obtained in
Example 4. showed that.
[0081]
Example 9 A titanium thin film having a thickness of about 500 nm was formed by sputtering on
the surface of a 0.3 mm-thick stainless steel plate (SUS 316). A stainless steel plate having a
carbon-doped titanium oxide layer as a surface layer was formed by heat treatment using a
combustion flame of acetylene so that the surface temperature would be about 900.degree. The
heat treatment time at 900 ° C. was 15 seconds. The carbon-doped titanium oxide layer thus
formed is superhydrophilic having a contact angle with water droplets of about 2 ° and exhibits
the same photocatalytic activity as the carbon-doped titanium oxide layer obtained in Example 4.
The
[0082]
[Example 10] A titanium oxide powder with a particle size of 20 μm is supplied into a
combustion flame of acetylene, retained in the combustion flame for a predetermined time, and
heat-treated so that the surface temperature becomes about 1000 ° C A titanium powder having
02-05-2019
26
a carbon-doped titanium oxide layer as a layer was formed. The heat treatment time at 1000 °
C. was 4 seconds. The titanium powder having the carbon-doped titanium oxide layer thus
formed exhibited the same photocatalytic activity as the carbon-doped titanium oxide layer
obtained in Example 4.
[0083]
[Examples 11 to 12] A titanium thin film having a thickness of about 100 nm was formed by
sputtering on the surface of a 1 mm-thick glass plate (Pyrex (registered trademark)). A glass
having a carbon-doped titanium oxide layer as a surface layer by heat treatment using an
acetylene combustion flame so that the surface temperature is 1100 ° C. (Example 11) or 1500
° C. (Example 12) Formed a board. The heat treatment time at 1100 ° C. or 1500 ° C. was 10
seconds. The carbon-doped titanium oxide layer thus formed was transparent as shown in the
photograph in FIG. 8A when the surface temperature is 1100 ° C. However, when the surface
temperature is 1500 ° C. As shown in FIG. 9, many small island-shaped undulations floating in
the sea were formed on the surface, and became translucent as shown in FIG. 8 (b).
[0084]
[Examples 13 to 16] The surface of a 0.3 mm-thick titanium plate was heat-treated with a
combustion flame of acetylene at the surface layer temperature shown in Table 3 for the time
shown in Table 3. Thereafter, when the surface to which the combustion flame is applied is
cooled by bringing it into contact with the flat surface of a 30 mm thick stainless block, a layer of
fine titanium oxide pillars consisting of white titanium oxide is exposed on most of the titanium
plate surface. And a plurality of continuous narrow projections made of white titanium oxide on a
thin film, and small pieces exposed to fine pillars standing on the projections. That is, in the layer
in which fine columns consisting of titanium oxide formed inside the surface layer by heat
treatment stand, the layer in which the fine columns stand in the subsequent cooling is cut in the
direction along the surface layer. Thus, Examples 13 to 16 were obtained.
[0085]
FIG. 10 is a photomicrograph of the member obtained in Example 13. The layer 2 in which fine
columns made of white titanium oxide stand on the surface of the titanium plate 1 is exposed,
and a white film is formed on the thin film. The figure shows a state in which a large number of
02-05-2019
27
continuous narrow projections made of titanium oxide and small pieces 3 exposed with fine
columns standing on the projections remain on the layer 2. . In addition, although the titanium
plate surface 1 is not exposed in the manufacturing method of Examples 13-16, the
microphotograph of FIG. 10 has shown the state which removed a part of layer 2 in which the
fine pillar stands. FIG. 11 is a photomicrograph showing the state of the thin film side surface of
the small piece member 3 in which a large number of continuous narrow projections made of
white titanium oxide are exposed on the thin film and the micro pillars standing on the
projections are exposed. FIG. 12 shows a large number of continuous narrow projections made of
white titanium oxide on a thin film and a large number of continuous narrow widths of small
pieces 3 exposed with fine pillars standing on the projections. FIG. 13 is a photomicrograph
showing the state of the surface of the protrusion and the fine pillar exposed on the protrusion,
and FIG. 13 is the state of the layer 2 in which the fine pillar of white titanium oxide is stand Is a
photomicrograph showing
[0086]
Example 17 The surface of a 0.3 mm thick Ti-6Al-4V alloy plate was heat treated with a
combustion flame of acetylene at the surface layer temperatures shown in Table 3 for the times
shown in Table 3. Thereafter, when the surface to which the combustion flame is applied is
cooled by bringing it into contact with the flat surface of a 30 mm thick stainless block, a layer of
fine columns made of titanium alloy oxide is exposed on most of the titanium alloy plate surface.
The film was separated into a plurality of continuous narrow projections made of titanium alloy
oxide on the thin film, and small pieces exposed to fine pillars standing on the projections.
[0087]
Example 18 A titanium thin film having a thickness of about 3 μm was formed on the surface of
a 0.3 mm-thick stainless steel plate (SUS 316) by electron beam evaporation. The thin film
surface was heat-treated with the combustion flame of acetylene at the surface layer temperature
shown in Table 3 for the time shown in Table 3. Then, when the surface to which the combustion
flame is applied is cooled by bringing it into contact with the flat surface of a 30 mm thick
stainless block, a layer of fine titanium oxide pillars of white titanium is exposed on most of the
stainless steel sheet surface. And a plurality of continuous narrow projections made of white
titanium oxide on a thin film, and small pieces exposed to fine pillars standing on the projections.
02-05-2019
28
[0088]
Comparative Example 4 A commercially available titanium oxide sol (STS-01 manufactured by
Ishihara Sangyo Co., Ltd.) is spin-coated on a titanium plate having a thickness of 0.3 mm, and
then heated to improve adhesion. It formed.
[0089]
Test Example 12 (Scratch Hardness Test: Pencil Method) JIS K 5600-5-J2 was applied to the
surface on the fine column side of the member in which the layer having fine columns standing
on the surface of the substrate obtained in Examples 13 to 18 is exposed. Based on 4 (1999), a
pencil scratching hardness test was conducted using Uni 1H to 9H pencils manufactured by
Mitsubishi Pencil Co., Ltd.
The results are as shown in Table 3. That is, no damage was observed when using a 9H pencil for
all the test pieces.
[0090]
Test Example 13 (Chemical resistance test) A member in which a layer having fine pillars
exposed on the substrate surface obtained in Examples 13 to 18 is exposed to 1 M aqueous
sulfuric acid solution and 1 M aqueous sodium hydroxide solution respectively at room
temperature 1 After immersion for a week, washing with water and drying, the above-mentioned
scratch hardness test: pencil method was carried out. The results are as shown in Table 3. That is,
no damage was observed even when using a 9H pencil for all the test pieces, and it was found
that they had high chemical resistance.
[0091]
Test Example 14 (Heat Resistance Test) A member in which the layer having fine columns
standing on the surface of the substrate obtained in Examples 13 to 18 is exposed is placed in a
tubular furnace, and it takes 1 hour from room temperature under air atmosphere. The
temperature was raised to 500 ° C., held at a constant temperature of 500 ° C. for 2 hours, and
allowed to stand and cooled to room temperature over 1 hour, and then the above-mentioned
scratch hardness test: pencil method was performed. The results are as shown in Table 3. That is,
02-05-2019
29
no damage was observed even when using a 9H pencil for all the test pieces, and it was found
that they had high heat resistance.
[0092]
Test Example 15 (Antifouling Test) A member having a surface area of 8 cm <2> in which a layer
in which fine columns stand on the surface of a substrate obtained in Example 16 is exposed as a
sample and the oxidation obtained in Comparative Example 4 The antifouling test was performed
using a titanium plate having a surface area of 8 cm <2> having a titanium film. Specifically,
these samples are immersed in 80 mL of methylene blue aqueous solution adjusted to a
concentration of about 10 μmol / L, respectively, and the influence of concentration reduction
due to the initial adsorption can be ignored, and then Matsushita Electric Industrial Co., Ltd. The
visible light was irradiated with a fluorescent lamp with a UV cut filter made in Japan, and the
absorbance of the methylene blue aqueous solution at a wavelength of 660 nm was measured
with a water quality analyzer DR / 2400 manufactured by HACH every predetermined irradiation
time. The results are as shown in FIG.
[0093]
From FIG. 14, the member in which the layer in which fine columns stand on the surface of the
substrate obtained in Example 16 is exposed is compared to the titanium plate having the
titanium oxide film obtained in Comparative Example 4 with methylene blue It can be seen that
the decomposition rate of is high and the antifouling effect is high.
[0094]
Test Example 16 (Crystal Structure and Bonding State) X-ray analysis (XRD) was performed on a
sample obtained from a fine column of a member in which a layer having a fine column standing
on the substrate surface obtained in Example 15 is exposed. As a result, it turned out that it has a
rutile type crystal structure.
[0095]
In addition, with respect to the fine pillar portion of the member in which the layer having fine
pillars standing on the substrate surface obtained in Example 15 is exposed, acceleration voltage:
10 kV with an X-ray photoelectron spectrometer (XPS), target: With Al as it is, Ar ion sputtering
is performed for 2700 seconds to start analysis.
02-05-2019
30
Assuming that the sputtering rate is 0.64 Å / s, which is equivalent to that of the SiO 2 film, the
depth is about 173 nm.
The results of the XPS analysis were as shown in FIG. The highest peak appears when the binding
energy is 284.6 eV. It is judged that this is a C̶H (C) bond generally found in Cls analysis. The
next highest peak is seen when the binding energy is 281.6 eV. Since the bonding energy of the
Ti-C bond is 281.6 eV, it is judged that C is doped as a Ti-C bond in the fine column of Example
15. In addition, as a result of conducting XPS analysis at 14 points at different positions of the
height position of the fine column, similar peaks appeared near 281.6 eV at all points.
[0096]
[Example 19] A disk with a diameter of 32 mm and a thickness of 0.3 mm was used as a test
piece, and the surface was heated by a combustion flame of acetylene so that the surface
temperature was maintained at about 1150 ° C. The heating of the first test piece was stopped
at a heating time of 120 seconds and allowed to cool. The heating of the second test piece was
stopped at 180 seconds and allowed to cool. The third test piece was heated for 480 seconds,
and the surface to which the combustion flame was applied was immediately brought into
contact with the flat surface of a 30 mm thick stainless block and cooled. By this cooling, the thin
film was peeled off from the surface of the titanium plate, and a member in which a layer in
which fine columns made of white titanium oxide stand from above was exposed was obtained.
About these three test pieces, a 10 μm deep hole of 3 μm × 12 μm is dug in the surface of the
test piece using FIB-SEM apparatus SMI 8400 SE manufactured by Seiko Instruments Inc., and
the side and bottom are observed by SEM apparatus VE7800 manufactured by Keyences Co. Did.
The SEM photograph of the test piece after 120 seconds is FIG. 16, the SEM photograph of the
test piece after 180 seconds is FIG. 17, and the SEM photograph of the test piece after 480
seconds is FIG. In FIG. 17 after 180 seconds, signs of a fine column structure are beginning to
appear in the lower part of the film, and by continuing the flame treatment, it is considered that
the fine column is elongated and a fine column structure as intended in the present invention is
formed. .
[0097]
Specific Example FIG. 19 is a perspective view showing an example of an ultrasonic horn. The
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ultrasonic transducer 10 connected to the ultrasonic horn 20 is also shown in FIG. The end face
of the ultrasonic wave input side end 21 (for example, a dashed hatched portion in FIG. 19) in the
ultrasonic horn 20 is connected to the ultrasonic transducer 10. The ultrasound signal generated
by the ultrasound transducer 10 is input to the ultrasound horn 20 from the end face of the
ultrasound input side end 21, and the ultrasound output end 22 of the ultrasound horn 20 (for
example, in FIG. 19). It is output from the solid hatching portion) and given to the processing
object.
[0098]
As the object to be treated, various substances which differ depending on the apparatus in which
the ultrasonic horn 20 is used correspond, for example, when the ultrasonic horn 20 is used for
metal welding, it is a metal plate and the ultrasonic horn 20 is super When used for sonic fuel oil
reforming, it becomes fuel oil (heavy oil) for diesel engines.
[0099]
The ultrasonic horn 20, together with the ultrasonic transducer 10, may be, for example, an
ultrasonic welding machine, an ultrasonic squeezing machine, an ultrasonic soldering machine,
an ultrasonic cutting machine, an ultrasonic processing machine such as an ultrasonic caulking
machine, or an ultrasonic wave. Used in washing machines, ultrasonic stirrers, etc.
[0100]
In this example, at least a part of the ultrasonic output end 22 of the ultrasonic horn 20 has a
layer at least the surface layer of which is carbon-doped titanium oxide or titanium alloy oxide,
and the carbon is Ti̶C. It is doped in the state of bonding.
The entire ultrasonic wave output side end 22 may be the entire ultrasonic horn 20.
[0101]
Alternatively, at least a part of the ultrasonic output end 22 of the ultrasonic horn 20 has a large
number of projections made of titanium oxide or titanium alloy oxide on at least a part of the
surface, and the projections are carbon It is doped.
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Also in this case, the entire ultrasonic wave output side 22 may be the entire ultrasonic horn 20.
[0102]
With such a configuration, at least the ultrasonic output end 22 side of the ultrasonic horn 20
can be made excellent in durability, and the end face of the ultrasonic output end 22 is easily
worn away. Can be prevented.
[0103]
In the example shown in FIG. 19, the ultrasonic horn 20 is formed in a cylindrical shape on the
ultrasonic input side end 21 side and is formed in a tapered cylindrical shape on the ultrasonic
output side end 22. The shape of the sonic horn 20 may be any shape.
Further, the area occupied by the ultrasonic wave input side end 21 and the area occupied by the
ultrasonic wave output side end 22 in the ultrasonic horn 20 are an example, and are not limited
to the areas shown in FIG.
[0104]
It is a figure which shows the result of the film | membrane hardness test of Experiment 1. FIG. It
is a figure showing the result of the XPS analysis of example 5 of an examination. It is a figure
which shows the wavelength responsiveness of the photoelectric current density of Experiment
6. FIG. It is a figure which shows the test result of the light energy conversion efficiency of
Experimental example 7. FIG. It is a figure which shows the result of the deodorizing test of
Experimental example 8. FIG. 7 is a photograph showing the results of the antifouling test of Test
Example 9. It is a figure showing the result of example 11 of an examination. It is a photograph
which shows the light-transmission state of the carbon dope titanium oxide layer obtained in
Example 11 and 12. 15 is a photograph showing the surface state of the carbon-doped titanium
oxide layer obtained in Example 11. 21 is a micrograph showing the state of the ultrasonic horn
obtained in Example 13. FIG. It is a microscope picture which shows the state of the thin film side
surface of the small-piece member 3 to which the fine pillar which stands on a large number of
continuous narrow protrusion parts and protrusions which consist of white titanium oxide on a
thin film is exposed. A large number of continuous narrow projections made of white titanium
oxide on a thin film, and a large number of continuous narrow projections of a small piece
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member 3 on which the fine pillars standing on the projections are exposed It is a microscope
picture which shows the state of the surface of the side where the fine pillar standing in the
forest is exposed. It is a microscope picture which shows the state of the layer 2 which the fine
pillar which consists of a white titanium oxide stands. It is a graph which shows the result of
Experiment 15 (antifouling test). It is a graph which shows the result of Experiment 16 (crystal
structure and a coupling | bonding state). It is a SEM photograph after heating time 120 seconds
in Example 19. It is a SEM photograph after the heating time in Example 19 180 seconds. It is a
SEM photograph after heating time 480 seconds in Example 19. It is a perspective view showing
an ultrasonic horn with an ultrasonic transducer.
Explanation of sign
[0105]
1 substrate surface 2 fine column 3 thin film
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