JP4853954B2 - Multifunctional material with carbon-doped hafnium oxide layer - Google Patents
Multifunctional material with carbon-doped hafnium oxide layer Download PDFInfo
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- 229910000449 hafnium oxide Inorganic materials 0.000 title claims description 76
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 title claims description 76
- 239000007777 multifunctional material Substances 0.000 title claims description 25
- 239000010410 layer Substances 0.000 claims description 85
- 229910001029 Hf alloy Inorganic materials 0.000 claims description 54
- 229910052735 hafnium Inorganic materials 0.000 claims description 44
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 44
- 239000000758 substrate Substances 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- 239000002344 surface layer Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 6
- 239000002346 layers by function Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 description 37
- 238000002485 combustion reaction Methods 0.000 description 23
- 239000007789 gas Substances 0.000 description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 17
- 239000001301 oxygen Substances 0.000 description 17
- 229910052760 oxygen Inorganic materials 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
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- 150000002430 hydrocarbons Chemical class 0.000 description 11
- 239000000567 combustion gas Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 9
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 8
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
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- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- -1 oxygen Chemical compound 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
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- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000007545 Vickers hardness test Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
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- 239000002585 base Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical class [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- NDRKISKJOAQGIO-UHFFFAOYSA-N cobalt hafnium Chemical compound [Co].[Hf] NDRKISKJOAQGIO-UHFFFAOYSA-N 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- HDLKRBKBZRWMHV-UHFFFAOYSA-N copper hafnium Chemical compound [Cu].[Hf] HDLKRBKBZRWMHV-UHFFFAOYSA-N 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- HGWOBERUERISLJ-UHFFFAOYSA-N hafnium iron Chemical compound [Fe].[Fe].[Hf] HGWOBERUERISLJ-UHFFFAOYSA-N 0.000 description 1
- KNIXSICLZCCLEE-UHFFFAOYSA-N hafnium nickel Chemical compound [Ni].[Hf] KNIXSICLZCCLEE-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
Description
本発明は炭素がドープされた炭素ドープ酸化ハフニウム層又は炭素ドープハフニウム合金酸化物層（両者を、単に炭素ドープ酸化ハフニウム層ということもある）を有する多機能材に関し、より詳しくは、炭素がＨｆ−Ｃ結合の状態でドープされており、耐久性（高硬度、耐スクラッチ性、耐摩耗性、耐薬品性、耐熱性）に優れ且つ光触媒として機能する炭素ドープ酸化ハフニウム層を有する多機能材に関する。 The present invention relates to a multifunctional material having a carbon-doped carbon-doped hafnium oxide layer or a carbon-doped hafnium alloy oxide layer (both may be simply referred to as a carbon-doped hafnium oxide layer). The present invention relates to a multifunctional material having a carbon-doped hafnium oxide layer that is doped in a -C bond state, has excellent durability (high hardness, scratch resistance, abrasion resistance, chemical resistance, heat resistance) and functions as a photocatalyst. .
ハフニウムは、耐酸性、機械的特性、耐熱性に優れているが、熱中性子吸収断面積がジルコニウムの約６００倍である１０５バーンと大きいので、中性子を吸収させる原子力の制御材として用いられている。また、酸化ハフニウムはガラス等に成膜することにより屈折率の高い光学膜として利用されている。 Hafnium is excellent in acid resistance, mechanical properties, and heat resistance, but its thermal neutron absorption cross section is as large as 105 burns, which is about 600 times that of zirconium, so it is used as a nuclear control material that absorbs neutrons. . Further, hafnium oxide is used as an optical film having a high refractive index by forming a film on glass or the like.
このようなハフニウムは、その他の用途として電球のフィラメントや合金としてジェットエンジンの部品として用いられている。また、ハフニウムは、耐熱性の特性から、ジルコニア系セラミックスを溶射して形成される皮膜の成分として用いられることが提案され（特許文献１参照）、あるいは親水性の被覆皮膜の成分としての使用が提案されている（特許文献２参照）が、ハフニウムを主体とした用途は確立されていない。 Such hafnium is used as a part of a jet engine as a filament or alloy of a light bulb for other uses. Further, hafnium has been proposed to be used as a component of a film formed by thermal spraying zirconia ceramics (see Patent Document 1) or used as a component of a hydrophilic coating film because of its heat resistance characteristics. Although it has been proposed (see Patent Document 2), an application mainly using hafnium has not been established.
本発明は、表面層として耐久性（高硬度、耐スクラッチ性、耐摩耗性、耐薬品性、耐熱性）に優れた酸化ハフニウム層を有する多機能材を提供することを目的としている。 An object of the present invention is to provide a multifunctional material having a hafnium oxide layer having excellent durability (high hardness, scratch resistance, wear resistance, chemical resistance, heat resistance) as a surface layer.
本発明者は上記の目的を達成するために鋭意検討した結果、所定の条件下で炭素ドープした酸化ハフニウム層が耐久性（高硬度、耐スクラッチ性、耐摩耗性、耐薬品性、耐熱性）に優れ且つ光触媒として機能することを知見し、本発明を完成させた。 As a result of intensive investigations to achieve the above object, the present inventor has shown that the hafnium oxide layer doped with carbon under a predetermined condition is durable (high hardness, scratch resistance, wear resistance, chemical resistance, heat resistance). And the present invention was completed.
かかる本発明は、基体の少なくとも表面層が炭素ドープ酸化ハフニウム層又は炭素ドープハフニウム合金酸化物層からなる多機能層とハフニウム、ハフニウム合金、ハフニウム合金酸化物又は酸化ハフニウムの何れかで構成されている下層とを具備し、前記炭素ドープ酸化ハフニウム層又は炭素ドープハフニウム合金酸化物層が前記下層から連続して一体的に形成された柱状結晶であることを特徴とする多機能材にある。 In the present invention, at least the surface layer of the substrate is composed of a multi-functional layer composed of a carbon-doped hafnium oxide layer or a carbon-doped hafnium alloy oxide layer and any of hafnium, hafnium alloy, hafnium alloy oxide, or hafnium oxide. And a carbon-doped hafnium oxide layer or a carbon-doped hafnium alloy oxide layer which is a columnar crystal formed integrally and continuously from the lower layer .
本発明の多機能層は、例えば、少なくとも表面層がハフニウム、ハフニウム合金、ハフニウム合金酸化物又は酸化ハフニウムからなる基体の表面を、炭素、酸素を含む化学種が当該表面に供給される雰囲気下で加熱処理することにより形成できる。かかる多機能層は、セラミックの溶射により形成されたコーティング層とは異なり、緻密な層である。 The multi-functional layer of the present invention is, for example, a surface of a substrate having at least a surface layer made of hafnium, a hafnium alloy, a hafnium alloy oxide, or hafnium oxide in an atmosphere in which chemical species containing carbon and oxygen are supplied to the surface. It can be formed by heat treatment. Such a multifunctional layer is a dense layer unlike a coating layer formed by thermal spraying of ceramic.
また、かかる多機能層は、炭素がＨｆ−Ｃ結合した状態でドープされているのが好ましい。すなわち、多機能層において炭素が酸化ハフニウムＨｆＯ2の酸素を置換するようにドープされているのであり、Ｈｆ−Ｃ結合が生成されている。このようにＨｆ−Ｃ結合が存在することにより、耐久性が著しく向上し、光触媒としての特性が向上する。 Moreover, it is preferable that this multifunctional layer is doped in a state where carbon is Hf-C bonded. That is, in the multifunctional layer, carbon is doped so as to replace oxygen of hafnium oxide HfO 2 , and an Hf—C bond is generated. The presence of the Hf—C bond in this way significantly improves the durability and improves the characteristics as a photocatalyst.
本発明の多機能層は、ハフニウム、ハフニウム合金、酸化ハフニウム又はハフニウム合金酸化物以外の材質からなる基体の表面に設けられていてもよいし、ハフニウム、ハフニウム合金、ハフニウム合金酸化物又は酸化ハフニウムの何れかで構成されている下層上に設けられていてもよい。何れにしても、基体を金属で形成したその表面に多機能層を連続的に設けることができるため、従来のハフニウムを含有するセラミックとは全く異なった特性を有するものである。 The multifunctional layer of the present invention may be provided on the surface of a substrate made of a material other than hafnium, hafnium alloy, hafnium oxide or hafnium alloy oxide, or may be made of hafnium, hafnium alloy, hafnium alloy oxide or hafnium oxide. You may be provided on the lower layer comprised by either. In any case, since the multi-functional layer can be continuously provided on the surface of the substrate formed of metal, it has completely different characteristics from the conventional ceramic containing hafnium.
例えば、ハフニウム、ハフニウム合金、酸化ハフニウム又はハフニウム合金酸化物以外の材質からなる基体の表面にハフニウム、ハフニウム合金、ハフニウム合金酸化物又は酸化ハフニウムからなる表面層を設け、これを炭素、酸素を含む化学種が当該表面に供給される雰囲気下で加熱処理することにより、表面層全体を炭素ドープ酸化ハフニウム層とすると、ハフニウム、ハフニウム合金、酸化ハフニウム又はハフニウム合金酸化物以外の材質からなる基体の表面に多機能層を形成した状態となり、また、表面層の表面側の一部を多機能層とすると、多機能層の下層はハフニウム、ハフニウム合金、酸化ハフニウム又はハフニウム合金酸化物となる。なお、基体全体がハフニウム、ハフニウム合金、酸化ハフニウム又はハフニウム合金酸化物からなる場合も、多機能層の下層はハフニウム、ハフニウム合金、酸化ハフニウム又はハフニウム合金酸化物となる。このように多機能層はその下層のハフニウム、ハフニウム合金、酸化ハフニウム又はハフニウム合金酸化物と連続的且つ一体的に形成される緻密な層であり、剥離等の問題がないものである。 For example, a surface layer made of hafnium, a hafnium alloy, a hafnium alloy oxide, or hafnium oxide is provided on the surface of a substrate made of a material other than hafnium, a hafnium alloy, hafnium oxide, or a hafnium alloy oxide. When the entire surface layer is a carbon-doped hafnium oxide layer by heat treatment in an atmosphere in which seeds are supplied to the surface, the surface of the substrate made of a material other than hafnium, hafnium alloy, hafnium oxide, or hafnium alloy oxide is formed. When a multifunctional layer is formed and a part of the surface layer on the surface side is a multifunctional layer, the lower layer of the multifunctional layer is hafnium, hafnium alloy, hafnium oxide, or hafnium alloy oxide. Even when the entire substrate is made of hafnium, a hafnium alloy, hafnium oxide, or a hafnium alloy oxide, the lower layer of the multifunctional layer is made of hafnium, hafnium alloy, hafnium oxide, or hafnium alloy oxide. As described above, the multifunctional layer is a dense layer formed continuously and integrally with the underlying hafnium, hafnium alloy, hafnium oxide, or hafnium alloy oxide, and has no problems such as peeling.
また、その基体の形状については、高硬度、耐スクラッチ性、耐摩耗性、耐薬品性、耐熱性等の耐久性が望まれる最終商品形状（平板状や立体状）や、表面に光触媒機能を有することが望まれる最終商品形状であっても、或いは粉末状であってもよい。 As for the shape of the substrate, the final product shape (flat or three-dimensional) where durability such as high hardness, scratch resistance, abrasion resistance, chemical resistance, and heat resistance is desired, and the surface has a photocatalytic function. It may be the final product shape that it is desired to have, or it may be in powder form.
なお、多機能層は、十分な厚さで形成すれば、表面を研磨して寸法出しを行うことも可能である。 Note that if the multifunctional layer is formed with a sufficient thickness, the surface can be polished and dimensioned.
本発明の多機能材は、耐久性（高硬度、耐スクラッチ性、耐摩耗性、耐薬品性、耐熱性）に優れ且つ光触媒として機能するので、種々の技術分野にも有意に利用できる。 Since the multifunctional material of the present invention is excellent in durability (high hardness, scratch resistance, abrasion resistance, chemical resistance, heat resistance) and functions as a photocatalyst, it can be used significantly in various technical fields.
本発明の多機能材は、少なくとも表面層がハフニウム、ハフニウム合金、ハフニウム合金酸化物又は酸化ハフニウムからなる基体の表面を、炭素、酸素を含む化学種が当該表面に供給される雰囲気下で加熱処理することにより形成できる。 The multifunctional material of the present invention is a heat treatment of at least the surface of a substrate whose surface layer is made of hafnium, a hafnium alloy, a hafnium alloy oxide, or hafnium oxide in an atmosphere in which chemical species including carbon and oxygen are supplied to the surface. Can be formed.
ここで、炭素、酸素を含む化学種が表面に供給される雰囲気下で加熱処理するとは、例えば、炭素及び酸素を含む化合物を含むガス（炭素原子と酸素原子がガス雰囲気中に存在していればよく、炭素を含む化合物を含むと共に酸素を含むガス、炭素及び酸素の両者を含む化合物を含むと共に必要に応じて酸素を含むガスなどをいう）の燃焼炎を用いて加熱処理すること、又はこのような燃焼炎の雰囲気ガスを表面に供給しながら必要に応じて加熱処理することである。すなわち、炭素、酸素を含む化学種、すなわち、活性化された炭素原子又は炭素原子を含む原子団、活性化された酸素又は酸素原子を含む原子団、炭素及び酸素を含む原子団などが表面に供給される状態で加熱処理をすればよく、好適には燃焼炎を用いて直接表面を加熱処理するか、燃焼炎の雰囲気ガスを表面に供給しながら加熱処理することにより、表面を酸化しつつ炭化するという複雑な表面改質を実現し、炭素を表面にドープして炭素ドープ酸化ハフニウム層を形成する。 Here, heat treatment in an atmosphere in which chemical species including carbon and oxygen are supplied to the surface means, for example, a gas containing a compound containing carbon and oxygen (if carbon atoms and oxygen atoms exist in the gas atmosphere). Heat treatment using a combustion flame containing a compound containing carbon and a gas containing oxygen, a compound containing both carbon and oxygen, and a gas containing oxygen if necessary), or It is heat-treating as needed while supplying the atmosphere gas of such a combustion flame to the surface. That is, carbon, chemical species including oxygen, that is, activated carbon atoms or atomic groups including carbon atoms, activated oxygen or atomic groups including oxygen atoms, atomic groups including carbon and oxygen, and the like are present on the surface. Heat treatment may be performed in the supplied state, and preferably the surface is oxidized by directly heat-treating the surface using a combustion flame, or by heat treatment while supplying the atmosphere gas of the combustion flame to the surface. A complicated surface modification of carbonization is realized, and carbon is doped on the surface to form a carbon-doped hafnium oxide layer.
具体的には、基体の表面にガスの燃焼炎を直接当てて高温で加熱処理しても、そのような基体の表面を燃焼ガスの雰囲気中で加熱処理してもよく、この加熱処理は例えば炉内で実施することができる。燃焼炎を直接当てて高温で加熱処理する場合には、上記のようなガスを炉内で燃焼させ、その燃焼炎を該基体の表面に当てればよい。燃焼ガス雰囲気中で加熱処理する場合には、上記のようなガスを炉内で燃焼させ、その高温の燃焼ガス雰囲気を利用する。なお、少なくとも表面層がハフニウム、ハフニウム合金、酸化ハフニウム又はハフニウム合金酸化物からなる基体が粉末状である場合には、そのような粉末を火炎中に導入し、火炎中に所定時間滞留させて加熱処理するか、或いはそのような粉末を流動状態の高温の燃焼ガス中に流動床状態に所定時間維持することにより粒子全体を炭素ドープ酸化ハフニウムとするか、表面が炭素ドープ酸化ハフニウム層を有する粉末とすることができる。 Specifically, a gas combustion flame may be directly applied to the surface of the substrate and heat treatment may be performed at a high temperature, or such a substrate surface may be heat-treated in a combustion gas atmosphere. It can be carried out in a furnace. When heat treatment is performed at a high temperature by directly applying a combustion flame, the above gas may be burned in a furnace, and the combustion flame may be applied to the surface of the substrate. When heat treatment is performed in a combustion gas atmosphere, the above gas is burned in a furnace and the high-temperature combustion gas atmosphere is used. In addition, when at least the surface layer is made of hafnium, hafnium alloy, hafnium oxide, or hafnium alloy oxide in a powder form, such a powder is introduced into the flame and heated by being retained in the flame for a predetermined time. Powders having a carbon-doped hafnium oxide layer on the surface, or the entire particle is made into carbon-doped hafnium oxide by maintaining such a powder in a fluidized hot combustion gas in a fluidized bed state for a predetermined time. It can be.
このように炭素ドープ酸化ハフニウム層を形成する条件は、表面改質する表面の素材や処理方法によって異なり、一概に設定することはできない。すなわち、例えば、加熱処理の温度や時間は、表面に供給される炭素、酸素を含む化学種の種類や濃度の違い、例えば、燃焼炎を用いる場合には、燃焼ガスの種類や燃焼炎の用い方により異なるが、炭素ドープ酸化ハフニウム層、特に、Ｈｆ−Ｃ結合が形成される炭素ドープ酸化ハフニウム層が形成できる条件を選択する必要がある。 Thus, the conditions for forming the carbon-doped hafnium oxide layer vary depending on the surface material to be surface-modified and the processing method, and cannot be set unconditionally. That is, for example, the temperature and time of the heat treatment are different in the type and concentration of chemical species including carbon and oxygen supplied to the surface, for example, in the case of using a combustion flame, the type of combustion gas and the use of the combustion flame Depending on the method, it is necessary to select conditions under which a carbon-doped hafnium oxide layer, particularly a carbon-doped hafnium oxide layer in which an Hf-C bond is formed, can be formed.
このような炭素ドープ酸化ハフニウム層は、詳細は後述するが、図１に示すように、柱状結晶からなるものであり、柱状結晶は下層のハフニウム層から連続して一体的に形成されている。なお、かかる炭素ドープ酸化ハフニウム層の厚さは加熱処理の温度及び時間により変化するものである。 Although the carbon-doped hafnium oxide layer will be described in detail later, as shown in FIG. 1, the carbon-doped hafnium oxide layer is composed of columnar crystals, and the columnar crystals are continuously formed integrally from the lower hafnium layer. Note that the thickness of the carbon-doped hafnium oxide layer varies depending on the temperature and time of the heat treatment.
このような多機能層の好ましい形成方法としては、炭素、酸素を含む化合物を含む燃焼ガス、例えば、アルコール系化合物、炭化水素などを含むガスの燃焼炎を用いて加熱処理するのが望ましい。 As a preferred method for forming such a multifunctional layer, it is desirable to perform heat treatment using a combustion gas containing a compound containing carbon and oxygen, for example, a combustion flame containing a gas containing an alcohol compound or hydrocarbon.
このような燃焼炎を用いて加熱処理して本発明の多機能層を得る場合、特に、炭化水素、好ましくは不飽和結合を含む炭化水素、特にアセチレンを、主成分とするガスの燃焼炎、特に還元炎を利用することが望ましい。炭化水素含有量が少ない燃料を用いる場合には、炭素のドープ量が不十分であったり、皆無であったりし、その結果として硬度が不十分となる。 In the case of obtaining the multifunctional layer of the present invention by heat treatment using such a combustion flame, in particular, a combustion flame of a gas mainly containing hydrocarbons, preferably hydrocarbons containing unsaturated bonds, particularly acetylene, In particular, it is desirable to use a reducing flame. When a fuel having a low hydrocarbon content is used, the carbon doping amount is insufficient or not at all, and as a result, the hardness becomes insufficient.
ここで、炭化水素を主成分とするガスとは、炭化水素、好ましくは不飽和炭化水素、特にアセチレンを、少なくとも３０容量％、好ましくは少なくとも５０容量％含有するガスを意味し、例えば、アセチレンを３０容量％以上、好ましくは５０容量％以上含有し、適宜、空気、水素、酸素等を混合したガスを意味する。このような多機能材の製造においては、炭化水素を主成分とするガスがアセチレンを５０容量％以上含有することが好ましく、炭化水素がアセチレン１００％であることが最も好ましい。不飽和炭化水素、特に三重結合を有するアセチレンを用いた場合には、その燃焼の過程で、特に還元炎部分で、不飽和結合部分が分解して中間的なラジカル物質が形成され、このラジカル物質は活性が強いので炭素ドープが生じ易いと考えられる。 Here, the hydrocarbon-based gas means a gas containing at least 30% by volume, preferably at least 50% by volume of hydrocarbon, preferably unsaturated hydrocarbon, particularly acetylene, for example, acetylene. It means a gas containing 30% by volume or more, preferably 50% by volume or more and appropriately mixed with air, hydrogen, oxygen or the like. In the production of such a 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% acetylene. When unsaturated hydrocarbons, especially acetylene having a triple bond, are used, in the process of combustion, especially in the reducing flame part, the unsaturated bond part decomposes to form an intermediate radical substance. It is considered that carbon doping is likely to occur because of its high activity.
なお、このように燃焼炎を用いて多機能材を製造する場合、加熱処理する基体の表面層がハフニウム又はハフニウム合金である場合には、該ハフニウム又はハフニウム合金を酸化する酸素が必要であり、その分だけ空気又は酸素を含んでいる必要がある。 When producing a multifunctional material using a combustion flame in this way, when the surface layer of the substrate to be heat-treated is hafnium or a hafnium alloy, oxygen that oxidizes the hafnium or hafnium alloy is required, It is necessary to contain air or oxygen accordingly.
本発明の多機能材の製造においては、表面層がハフニウム、ハフニウム合金、酸化ハフニウム又はハフニウム合金酸化物からなる基体の表面を、炭化水素を主成分とするガスの燃焼炎を用いて高温で加熱処理するが、この場合に、基体の表面に炭化水素を主成分とするガスの燃焼炎を直接当てて高温で加熱処理しても、そのような基体の表面を炭化水素を主成分とするガスの燃焼ガス雰囲気中で加熱処理してもよく、この加熱処理は例えば炉内で実施することができる。燃焼炎を直接当てて高温で加熱処理する場合には、上記のような燃料ガスを炉内で燃焼させ、その燃焼炎を該基体の表面に当てればよい。燃焼ガス雰囲気中で加熱処理する場合には、上記のような燃料ガスを炉内で燃焼させ、その高温の燃焼ガス雰囲気を利用する。なお、少なくとも表面層がハフニウム、ハフニウム合金、ハフニウム合金酸化物又は酸化ハフニウムからなる基体が粉末状である場合には、そのような粉末を火炎中に導入し、火炎中に所定時間滞留させて加熱処理するか、或いはそのような粉末を流動状態の高温の燃焼ガス中に流動床状態に所定時間維持することにより粒子全体を炭素がＨｆ−Ｃ結合の状態でドープされた炭素ドープ酸化ハフニウムとするか、炭素がＨｆ−Ｃ結合の状態でドープされた炭素ドープ酸化ハフニウム層を有する粉末とすることができる。 In the production of the multifunctional material of the present invention, the surface of the substrate whose surface layer is made of hafnium, hafnium alloy, hafnium oxide, or hafnium alloy oxide is heated at a high temperature using a combustion flame of a gas mainly composed of hydrocarbons. In this case, even if the combustion flame of a gas mainly composed of hydrocarbon is directly applied to the surface of the substrate and the heat treatment is performed at a high temperature, the surface of such a substrate is a gas mainly composed of hydrocarbon. The heat treatment may be performed in a combustion gas atmosphere, and this heat treatment can be performed in a furnace, for example. When heat treatment is performed at a high temperature by directly applying a combustion flame, the above-described fuel gas may be burned in a furnace and the combustion flame may be applied to the surface of the substrate. When heat treatment is performed in a combustion gas atmosphere, the above fuel gas is burned in a furnace and the high-temperature combustion gas atmosphere is used. In addition, when the substrate having at least the surface layer made of hafnium, hafnium alloy, hafnium alloy oxide or hafnium oxide is in the form of powder, such powder is introduced into the flame and heated by being retained in the flame for a predetermined time. By treating or maintaining such powder in a fluidized hot combustion gas in a fluidized bed for a predetermined time, the entire particle is carbon-doped hafnium oxide doped with carbon in Hf-C bonds. Or it can be set as the powder which has the carbon dope hafnium oxide layer by which carbon was doped in the state of the Hf-C bond.
アセチレンを主成分とするガスの燃焼炎を用いた加熱処理の場合には、基体の表面温度が４００〜２２００℃、好ましくは５５０〜２０００℃、さらに好ましくは７００〜１８００℃となり、基体の表面層が炭素ドープ酸化ハフニウム層となるように加熱処理する必要がある。加熱処理が不十分の場合には、炭素ドープ酸化ハフニウム層とはならず、基体の耐久性は不十分となり、且つ光触媒活性も不十分となる。 In the case of heat treatment using a gas combustion flame containing acetylene as a main component, the surface temperature of the substrate is 400 to 2200 ° C., preferably 550 to 2000 ° C., more preferably 700 to 1800 ° C. It is necessary to heat-treat so that becomes a carbon-doped hafnium oxide layer. When the heat treatment is insufficient, the carbon-doped hafnium oxide layer is not formed, the durability of the substrate is insufficient, and the photocatalytic activity is also insufficient.
本発明の多機能材の多機能層は、炭素を、例えば、０.１〜１０ａｔ％含有するものである。かかる炭素含有量は、加熱処理の条件、表面層の材質などによって異なり、特に限定されないが、炭素含有量が上昇するほど耐久性等の特性の向上が見られる傾向となる。 The multifunctional layer of the multifunctional material of the present invention contains carbon, for example, 0.1 to 10 at%. Such carbon content varies depending on the conditions of the heat treatment, the material of the surface layer, and the like, and is not particularly limited.
本発明の多機能層の厚さは、１０ｎｍ以上であることが好ましく、高硬度、耐スクラッチ性、耐摩耗性を達成するためには５０ｎｍ以上であることが一層好ましい。炭素ドープ酸化ハフニウム層の厚さが１０ｎｍ未満である場合には、得られる炭素ドープ酸化ハフニウム層を有する多機能材の耐久性は不十分となる傾向がある。炭素ドープ酸化ハフニウム層の厚さの上限については、コストと達成される効果とを考慮する必要があるが、特に制限されるものではない。 The thickness of the multifunctional layer of the present invention is preferably 10 nm or more, and more preferably 50 nm or more in order to achieve high hardness, scratch resistance and wear resistance. When the thickness of the carbon-doped hafnium oxide layer is less than 10 nm, the resulting multifunctional material having the carbon-doped hafnium oxide layer tends to be insufficient. The upper limit of the thickness of the carbon-doped hafnium oxide layer needs to be considered in terms of cost and effect to be achieved, but is not particularly limited.
本発明の多機能層は、上述したとおり、ハフニウム、ハフニウム合金、酸化ハフニウム又はハフニウム合金酸化物以外の材質からなる基体の表面に設けられていてもよいし、ハフニウム、ハフニウム合金、ハフニウム合金酸化物又は酸化ハフニウムの何れかで構成されている下層上に設けられていてもよく、この場合の下層の下地はハフニウム、ハフニウム合金、酸化ハフニウム又はハフニウム合金酸化物以外の材質となる。 As described above, the multifunctional layer of the present invention may be provided on the surface of a substrate made of a material other than hafnium, a hafnium alloy, hafnium oxide, or a hafnium alloy oxide, or hafnium, a hafnium alloy, or a hafnium alloy oxide. Alternatively, it may be provided on a lower layer made of either hafnium oxide. In this case, the lower layer is made of a material other than hafnium, a hafnium alloy, hafnium oxide, or a hafnium alloy oxide.
ここで、ハフニウム、ハフニウム合金、酸化ハフニウム又はハフニウム合金酸化物以外の材質からなる基体とは、上述したような製造方法における加熱処理の際に燃焼したり、溶融したり、変形したりするものでなければ、特に制限されることはない。このような基体としては、鉄、鉄合金、非鉄合金、セラミックス、その他の陶磁器、高温耐熱性ガラス等を用いることができる。このような基体上に形成される薄膜状の表面層は、ハフニウム、ハフニウム合金、酸化ハフニウム又はハフニウム合金酸化物からなる皮膜をスパッタリング、蒸着、溶射等の方法で形成したもの等を挙げることができが、緻密で下層との密着力の優れた層とするのが好ましい。 Here, the substrate made of a material other than hafnium, a hafnium alloy, hafnium oxide, or a hafnium alloy oxide is one that burns, melts, or deforms during the heat treatment in the manufacturing method as described above. If not, there is no particular limitation. As such a substrate, iron, iron alloy, non-ferrous alloy, ceramics, other ceramics, high-temperature heat-resistant glass, or the like can be used. Examples of such a thin film-like surface layer formed on the substrate include a film formed of hafnium, a hafnium alloy, hafnium oxide or a hafnium alloy oxide by a method such as sputtering, vapor deposition, or thermal spraying. However, it is preferable to use a dense layer having excellent adhesion to the lower layer.
また、少なくとも表面層がハフニウム、ハフニウム合金、酸化ハフニウム又はハフニウム合金酸化物からなる基体が粉末状である場合には、その粉末の粒径が小さい場合に上記のような加熱処理により粒子全体を炭素ドープ酸化ハフニウムとすることが可能であるが、本発明においては表面層のみが炭素ドープ酸化ハフニウムとなれば良いのであり、従って、粉末の粒径については何ら制限されることはない。しかし、加熱処理の容易性、製造の容易性を考慮すると１５ｎｍ以上であることが好ましい。 In addition, when the base layer is made of at least a surface layer made of hafnium, hafnium alloy, hafnium oxide, or hafnium alloy oxide, and the powder is small, the entire particle is carbonized by heat treatment as described above. Although it is possible to use doped hafnium oxide, in the present invention, only the surface layer should be carbon-doped hafnium oxide, and therefore the particle size of the powder is not limited at all. However, considering the ease of heat treatment and the ease of production, it is preferably 15 nm or more.
さらに、本発明において、ハフニウム合金としては、公知の種々のハフニウム合金を用いることができ、特に制限されることはない。例えば、ハフニウム鉄合金、ハフニウム銅合金、ハフニウムコバルト合金、ハフニウムニッケル合金などを挙げることができる。 Furthermore, in the present invention, various known hafnium alloys can be used as the hafnium alloy and is not particularly limited. For example, a hafnium iron alloy, a hafnium copper alloy, a hafnium cobalt alloy, a hafnium nickel alloy, etc. can be mentioned.
本発明の多機能材の炭素ドープ酸化ハフニウム層は、酸化ハフニウム層よりも優れたビッカース硬度を有し、酸化ハフニウム層より２０％程度高いビッカース硬度を有する。 The carbon-doped hafnium oxide layer of the multifunctional material of the present invention has a Vickers hardness superior to that of the hafnium oxide layer, and has a Vickers hardness of about 20% higher than that of the hafnium oxide layer.
また、本発明の多機能材の炭素ドープ酸化ハフニウム層は、酸化ハフニウム層と同様に耐薬品性にも優れており、１Ｍ硫酸及び１Ｍ水酸化ナトリウムのそれぞれの水溶液に一週間浸漬した後、皮膜硬度、耐摩耗性及び光電流密度を測定し、処理前の測定値と比較したところ、有為な変化はみられなかった。 Further, the carbon-doped hafnium oxide layer of the multifunctional material of the present invention is excellent in chemical resistance like the hafnium oxide layer, and after being immersed in respective aqueous solutions of 1M sulfuric acid and 1M sodium hydroxide for one week, When the hardness, abrasion resistance and photocurrent density were measured and compared with the measured values before treatment, no significant change was observed.
本発明の多機能材の炭素ドープ酸化ハフニウム層は、光触媒として有効に作用するものである。 The multifunctional carbon-doped hafnium oxide layer of the present invention effectively functions as a photocatalyst.
以上説明したように、本発明の炭素ドープ酸化ハフニウム層からなる多機能層は、緻密であり、下層と連続的に形成されるので、下層との密着性も良好である。従って、従来、酸化ハフニウムを溶射、ＰＶＤ、ＣＶＤなどにより形成したコーディング層の代替品として使用した場合、より緻密で、下層との密着性の高い多機能層を形成できるので、各種用途に使用可能である。 As described above, the multifunctional layer composed of the carbon-doped hafnium oxide layer of the present invention is dense and is formed continuously with the lower layer, and therefore has good adhesion to the lower layer. Therefore, when using hafnium oxide as an alternative to a coating layer formed by thermal spraying, PVD, CVD, etc., it is possible to form a multifunctional layer that is denser and has higher adhesion to the lower layer, so it can be used for various applications. It is.
以下に、実施例及び比較例に基づいて本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail based on examples and comparative examples.
（実施例１）
アセチレンの燃焼炎を用い、厚さ０．５０ｍｍのハフニウム板（ニコラ社ＨＦ−１８３４６１、純度：９９．５％）をその表面温度が約５５０℃となるように３０分間加熱処理することにより、表面層として炭素ドープ酸化ハフニウム層を有するハフニウム板を形成した。
Example 1
By using an acetylene combustion flame, a 0.50 mm thick hafnium plate (Nicola HF-183461, purity: 99.5%) is heated for 30 minutes so that its surface temperature is about 550 ° C. A hafnium plate having a carbon-doped hafnium oxide layer as a layer was formed.
（実施例２〜６）
加熱処理する際の表面温度及び加熱処理時間を下記表１の通りに変更した以外は実施例１と同様にして、実施例２〜６の炭素ドープ酸化ハフニウム層を有するハフニウム板を形成した。
(Examples 2 to 6)
A hafnium plate having the carbon-doped hafnium oxide layers of Examples 2 to 6 was formed in the same manner as in Example 1 except that the surface temperature and the heat treatment time during the heat treatment were changed as shown in Table 1 below.
（実施例７）
メタンガスの燃焼炎を用い、実施例１と同様なハフニウム板をその表面温度が約９００℃となるように３０分間加熱処理することにより、実施例７の炭素ドープハフニウム層を有するハフニウム板を形成した。
(Example 7)
A hafnium plate having the carbon-doped hafnium layer of Example 7 was formed by heat-treating a hafnium plate similar to that of Example 1 for 30 minutes using a combustion flame of methane gas so that the surface temperature was about 900 ° C. .
（比較例１）
加熱処理していないハフニウム板を比較例１のハフニウム板とした。
(Comparative Example 1)
The hafnium plate that was not heat-treated was used as the hafnium plate of Comparative Example 1.
（比較例２〜６）
比較例１と同一のハフニウム板を加熱炉で所定の加熱温度及び加熱時間で大気酸化して表面に酸化ハフニウム層を形成した。加熱処理温度及び加熱処理時間は表１に示すとおりであり、室温から加熱処理温度に達するまでの時間は加熱処理時間に換算しないで加熱処理時間を設定した。
(Comparative Examples 2-6)
The same hafnium plate as in Comparative Example 1 was oxidized in the air at a predetermined heating temperature and heating time in a heating furnace to form a hafnium oxide layer on the surface. The heat treatment temperature and the heat treatment time are as shown in Table 1, and the heat treatment time was set without converting the time from the room temperature to the heat treatment temperature being converted into the heat treatment time.
試験例１（ビッカース硬度）
各実施例及び比較例の表面硬度を、マイクロビッカース硬度計により、圧子：ダイヤモンド圧子、試験力：２４５．２ｍＮ、荷重保持時間：１５ｓｅｃの条件下で皮膜硬度を測定したところ、表１の結果が得られた。
Test Example 1 (Vickers hardness)
The surface hardness of each example and comparative example was measured with a micro Vickers hardness tester under the conditions of indenter: diamond indenter, test force: 245.2 mN, load holding time: 15 sec. Obtained.
これらの結果から明らかなように、アセチレンの燃焼炎により加熱処理した炭素ドープ酸化ハフニウム層を有する実施例１〜６のハフニウム板及びメタンガスの燃焼炎により加熱処理したハフニウム板は、加熱炉を用いて同温度・同時間だけ加熱処理した比較例と比較すると、硬度が２０％程度向上していることが確認された。 As is clear from these results, the hafnium plate of Examples 1 to 6 having the carbon-doped hafnium oxide layer heat-treated by the acetylene combustion flame and the hafnium plate heat-treated by the methane gas combustion flame were obtained using a heating furnace. It was confirmed that the hardness was improved by about 20% as compared with the comparative example in which the heat treatment was performed only at the same temperature and for the same time.
試験例２（結晶構造と結合状態）
実施例３の炭素ドープ酸化ハフニウム層についてＸＲＤ（Ｘ線回折分析）をした結果を図２に示す。比較のために比較例４の大気酸化による酸化ハフニウム層の分析結果も併せて示す。なお、測定条件は以下の通りである。
Test Example 2 (Crystal structure and bonding state)
The result of XRD (X-ray diffraction analysis) of the carbon-doped hafnium oxide layer of Example 3 is shown in FIG. For comparison, the analysis result of the hafnium oxide layer by atmospheric oxidation in Comparative Example 4 is also shown. Measurement conditions are as follows.
測定機器：Ｐｈｉｌｌｉｐｓ社製 ＰＷ３０４０
管球：Ｃｕ
出力：４０ｋＶ−５０ｍＡ
スキャン速度：１°／ｍｉｎ
スキャン範囲：２θ＝ ２〜８０°
スリット：ＤＳ・ＳＳ； 照射範囲が１５ｍｍ一定となるよう自動調整
ｍａｓｋ； １０ｍｍ
Measuring instrument: PW3040 manufactured by Phillips
Tube: Cu
Output: 40kV-50mA
Scan speed: 1 ° / min
Scan range: 2θ = 2-80 °
Slit: DS / SS; Automatic adjustment to keep the irradiation range constant at 15 mm
mask; 10mm
また、ＸＰＳ（Ｘ線光電子分光分析）の結果を図３に示す。 The results of XPS (X-ray photoelectron spectroscopy) are shown in FIG.
ＸＲＤの結果によると、実施例３の表面層の結晶構造はＨｆＯ2であり、その他に有為なピークは存在しなかったので、構造が酸化ハフニウムと同一であることが確認された。 According to the result of XRD, the crystal structure of the surface layer of Example 3 was HfO 2 , and no other significant peak was present, so it was confirmed that the structure was the same as hafnium oxide.
一方、ＸＰＳにおいて、アルゴンスパッタリングにより、皮膜内部の結合状態を調べた結果、図３に示されるように、実施例３の皮膜では、２８０．８ｅＶ近傍に強度ピークが確認された。このピークはＨｆ−Ｃ結合によるものと考えられる。 On the other hand, in XPS, as a result of examining the bonding state inside the film by argon sputtering, as shown in FIG. 3, in the film of Example 3, an intensity peak was confirmed in the vicinity of 280.8 eV. This peak is considered to be due to the Hf-C bond.
これらの結果より、炭素はＨｆＯ2構造の酸素を置換するようにドープされ、Ｈｆ−Ｃ結合していると考えられる。なお、比較例４、すなわち電気炉中で酸化させた皮膜においては、Ｈｆ−Ｃ結合は確認されなかった。 From these results, it is considered that carbon is doped so as to replace oxygen in the HfO 2 structure and is Hf—C bonded. In Comparative Example 4, that is, in the film oxidized in the electric furnace, no Hf-C bond was confirmed.
試験例３（耐薬品性）
１Ｍ硫酸水溶液および１Ｍ水酸化ナトリウム水溶液それぞれについて、実施例２、３及び比較例３、４のハフニウム板を室温で１週間浸漬した後、ビッカース硬度試験を行なった。
Test Example 3 (Chemical resistance)
The 1M sulfuric acid aqueous solution and 1M sodium hydroxide aqueous solution were immersed in the hafnium plates of Examples 2 and 3 and Comparative Examples 3 and 4 at room temperature for 1 week, and then subjected to a Vickers hardness test.
この結果、実施例の試料については、浸漬前と比較して硬度の減少をほとんど認めなかった。すなわち、高い耐薬品性を有することが認められた。これに対し、比較例の試料については多少の硬度減少が、特にアルカリ浸漬後にものについて認められた。 As a result, with respect to the sample of the example, a decrease in hardness was hardly observed as compared with that before immersion. That is, it was confirmed to have high chemical resistance. On the other hand, with respect to the sample of the comparative example, a slight decrease in hardness was observed particularly after the alkali immersion.
試験例４（短波長照射による自然浸漬電位測定）
実施例３（７００℃、１２０分）の炭素ドープ酸化ハフニウム層及び比較例４（７００℃、１２０分）の酸化ハフニウム皮膜の短波長用ランプ照射による自然浸漬電位を測定した。具体的には、それぞれの皮膜に対し、０．０５Ｍ硫酸ナトリウム水溶液（飽和溶存酸素、常温）中で、参照電極として飽和銀−塩化銀を用いて、電位を測定した。その結果を図４に示す。
Test Example 4 (Measurement of natural immersion potential by short wavelength irradiation)
The natural immersion potential of the carbon-doped hafnium oxide layer of Example 3 (700 ° C., 120 minutes) and the hafnium oxide film of Comparative Example 4 (700 ° C., 120 minutes) by irradiation with a short wavelength lamp was measured. Specifically, the potential of each coating was measured in a 0.05 M aqueous sodium sulfate solution (saturated dissolved oxygen, room temperature) using saturated silver-silver chloride as a reference electrode. The result is shown in FIG.
この結果、実施例の炭素ドープ酸化ハフニウムは２４０ｎｍにおける自然浸漬電位が比較例の酸化ハフニウムより卑下することが認められた。 As a result, it was confirmed that the carbon-doped hafnium oxide of the example had a lower natural immersion potential at 240 nm than the hafnium oxide of the comparative example.
本発明の多機能材は、炭素ドープ酸化ハフニウム層の各種特性を応用して、遮熱性、耐熱性、耐摩耗性、耐薬品性等が求められる各種用途に使用可能である。 The multifunctional material of the present invention can be used in various applications that require heat shielding properties, heat resistance, wear resistance, chemical resistance, etc. by applying various characteristics of the carbon-doped hafnium oxide layer.
Claims (4)
前記多機能層中の炭素がＨｆ−Ｃ結合した状態でドープされていることを特徴とする多機能材。 The multifunctional material according to claim 1,
The multi-functional material is characterized in that carbon in the multi-functional layer is doped with Hf-C bonding.
前記多機能層が、ハフニウム、ハフニウム合金、酸化ハフニウム又はハフニウム合金酸化物以外の材質からなる基体の表面に設けられていることを特徴とする多機能材。 In the multifunctional material according to claim 1 or 2,
A multifunctional material, wherein the multifunctional layer is provided on a surface of a substrate made of a material other than hafnium, a hafnium alloy, hafnium oxide, or a hafnium alloy oxide.
多機能材が粉末状であることを特徴とする多機能材。 In the multifunctional material in any one of Claims 1-3 ,
A multifunctional material characterized in that the multifunctional material is in powder form.
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