JPH03279254A - Copper oxide based conductive ceramics and production thereof - Google Patents
Copper oxide based conductive ceramics and production thereofInfo
- Publication number
- JPH03279254A JPH03279254A JP2078380A JP7838090A JPH03279254A JP H03279254 A JPH03279254 A JP H03279254A JP 2078380 A JP2078380 A JP 2078380A JP 7838090 A JP7838090 A JP 7838090A JP H03279254 A JPH03279254 A JP H03279254A
- Authority
- JP
- Japan
- Prior art keywords
- copper oxide
- based conductive
- nitrate
- copper
- chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 61
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims description 42
- 239000005751 Copper oxide Substances 0.000 title claims description 41
- 229910000431 copper oxide Inorganic materials 0.000 title claims description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- 229910052738 indium Inorganic materials 0.000 claims abstract description 6
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 6
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 6
- 229910052716 thallium Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052733 gallium Inorganic materials 0.000 claims abstract 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 16
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 10
- 150000001805 chlorine compounds Chemical class 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 4
- 150000002823 nitrates Chemical class 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims 3
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 5
- 229960003280 cupric chloride Drugs 0.000 description 5
- 229910002483 Cu Ka Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001960 metal nitrate Inorganic materials 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000005571 anion exchange chromatography Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- HVDZMISZAKTZFP-UHFFFAOYSA-N indium(3+) trinitrate trihydrate Chemical compound O.O.O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HVDZMISZAKTZFP-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004323 axial length Effects 0.000 description 1
- 210000000078 claw Anatomy 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- LACHWJIJRQDEJY-UHFFFAOYSA-N scandium(3+) trinitrate tetrahydrate Chemical compound O.O.O.O.[N+](=O)([O-])[O-].[Sc+3].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] LACHWJIJRQDEJY-UHFFFAOYSA-N 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
- Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は銅酸化物系導電性セラミックス及びその製造方
法に係り、特に、容易かつ安価に人手可能な原料を用い
て、比較的低温での加熱により製造することができる銅
酸化物系導電性セラミックス及びその製造方法に関する
。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to copper oxide-based conductive ceramics and a method for producing the same, and in particular, the present invention relates to a copper oxide-based conductive ceramic and a method for producing the same. The present invention relates to copper oxide-based conductive ceramics that can be produced by heating and a method for producing the same.
［従来の技術］
導電性セラミックスは、セラミックス特有の耐食性、耐
熱性等の優れた特性を利用して、従来より、電極、発熱
体等どして広い分野で使用されている。例えば、塩素工
業において、Ｒｕ Ｏ２は電力消費量が小さく、しかも
耐腐食性等に優れるなどの特性から、電極材料として特
に好適である。[Prior Art] Conductive ceramics have been used in a wide range of fields, such as electrodes and heating elements, by taking advantage of their excellent characteristics such as corrosion resistance and heat resistance, which are unique to ceramics. For example, in the chlorine industry, RuO2 is particularly suitable as an electrode material because of its low power consumption and excellent corrosion resistance.
このＲｕＯ２はまた、最近では熱転写プリンターのサー
マルヘッドにも利用されている。This RuO2 has also recently been used in thermal heads of thermal transfer printers.
更に、導電性セラミックスの他の用途例としては、ＩＴ
Ｏ（Ｉｎ−３ｎ−０系）セラミックスの透明電極への通
用、ＰＬＺＴ （ｐｂ−Ｌａ−Ｚｎ−Ｔｉ系）セラミッ
クスの光スィッチ、光シヤツターへの適用など、その応
用分野は拡大しつつある。その他、導電性セラミックス
は、外部環境の変化を電気的な信号に変換するための各
種センサーの電極としても利用されている。また、セラ
ミックスの耐熱性を考慮すれば、Ｌａ−Ｃｒ−０系又は
Ｌａ−Ｃｏ−０系セラミツクスは、炉用発熱体、燃料電
池電極としても有用である。Furthermore, other applications of conductive ceramics include IT
The field of application is expanding, such as the application of O (In-3n-0 series) ceramics to transparent electrodes and the application of PLZT (pb-La-Zn-Ti series) ceramics to optical switches and optical shutters. In addition, conductive ceramics are also used as electrodes for various sensors that convert changes in the external environment into electrical signals. Furthermore, considering the heat resistance of ceramics, La-Cr-0 or La-Co-0 ceramics are useful as heating elements for furnaces and fuel cell electrodes.
［発明が解決しようとする課題］
このような導電性セラミックスの通用分野は多岐にわた
り、その有用性が重視されていることから、導電性セラ
ミックスをより安価にかつより容易に製造する技術の出
現が常に望まれている。[Problem to be solved by the invention] As such conductive ceramics are used in a wide variety of fields and their usefulness is emphasized, it is desirable to develop a technology to manufacture conductive ceramics more cheaply and more easily. always desired.
本発明は上記従来の実情に鑑みてなされたものであり、
容易かつ安価に入手可能な原料を用いて、比較的低温で
加熱することにより、工業的に有利に製造することがで
きる銅酸化物系導電性セラミックス及びその製造方法を
提供することを目的とする。The present invention has been made in view of the above-mentioned conventional situation,
The purpose of the present invention is to provide copper oxide-based conductive ceramics that can be industrially advantageously produced by heating at relatively low temperatures using easily and inexpensively available raw materials, and a method for producing the same. .
［課題を解決するための手段」
請求項（１）の銅酸化物系導電性セラミックスは、下記
一般式［１］で示されることを特徴とする。[Means for Solving the Problems] The copper oxide-based conductive ceramic of claim (1) is characterized by being represented by the following general formula [1].
（Ｍ。(M.
Ｃｕ。Cu.
） ０゜ Ａ。) 0° A.
［ ■ ］ 請求項（２） の銅酸化物系導電性セラミックス は下記一般式 ［ で示されることを特徴とす る。[ ■ ] Claim (2) copper oxide conductive ceramics is the following general formula [ is characterized by Ru.
Ｃｕ７ ０゜ Ａ。Cu7 0゜ A.
・・・ ［ＩＩ］
請求項（３）の銅酸化物系導電性セラミックスの製造方
法は、請求項（１）の銅酸化物系導電性セラミックスを
製造する方法であって、Ｉ ｎ、Ｓｃ、Ｙ、Ｔｌ及びＧ
ａよりなる群から選ばれる１種又は２種以上の金属の硝
酸塩群から選ばれる１種又は２種以上の硝酸塩群から選
ばれる１種又は塩化物とからなる混合物（但し、該金属
の硝酸塩と硝酸銅、該金属の塩化物と塩化銅との組み合
わせを除く。）を２００〜６００℃で加熱することによ
り特許請求の範囲第１項に記載の銅酸化物系導電性セラ
ミックスを製造する方法を特徴とする請求項（４）の銅
酸化物系導電性セラミックスの製造方法は、請求項（２
）の銅酸化物系導電性セラミックスを製造する方法であ
って、硝酸銅と塩化銅との混合物を２００〜６００℃で
加熱することを特徴とする。... [II] The method for manufacturing a copper oxide-based conductive ceramic according to claim (3) is a method for manufacturing the copper oxide-based conductive ceramic according to claim (1), wherein In, Sc, Y, Tl and G
A mixture consisting of one or more metal nitrates selected from the group consisting of one or two or more metal nitrates or a chloride (however, a mixture consisting of one or two or more metal nitrates selected from the group consisting of A method for producing copper oxide-based conductive ceramics according to claim 1 by heating copper nitrate (excluding combinations of chlorides of the metal and copper chloride) at 200 to 600°C. The method for producing copper oxide-based conductive ceramics according to claim (4), characterized in that
) is a method for producing copper oxide-based conductive ceramics, which is characterized by heating a mixture of copper nitrate and copper chloride at 200 to 600°C.
以下に本発明の詳細な説明する。The present invention will be explained in detail below.
本発明の銅酸化物系導電性セラミックスは下記一般式［
Ｉ］で示され、
（ＭＸ ｃ ｕ、）７０． Ａ、＋＋ ［Ｉコ式中、
Ｍ： Ｉ ｎ、Ｓｃ％Ｙ、Ｔｉｔ及びＧ８よりなる群か
ら選ばれる１種又は２種以上の元素
Ａ ： Ｃｕ、或いは、ＣＩｌ及びＮｏ。The copper oxide conductive ceramic of the present invention has the following general formula [
I], (MX cu,)70. A, ++ [In the formula, M: one or more elements selected from the group consisting of In, Sc%Y, Tit and G8 A: Cu, or CII and No.
ｘ＋ｙ＝１
０≦ｘ ／ ｙ≦１０、好ましくは０≦ｘ／ｙ≦１０≦
Ｚ≦８．１≦Ｗ≦９
である。x+y=1 0≦x/y≦10, preferably 0≦x/y≦10≦
Z≦8.1≦W≦9.
このような本発明の銅酸化物系導電性セラミックスのＸ
線回折スペクトルのピークとしては、２θで
１６．０〜１６．８° ２９．５〜３４．０° ３７．
８〜３９．５゜５４．６〜５７．０°のピークが特徴的
である。これらのピークは立方晶系の結晶の面指数
１１１．２２２，４００，４４０
に帰属される。軸長ａは約９．２〜９．８Ａである。X of such copper oxide-based conductive ceramics of the present invention
The peaks of the line diffraction spectrum are 16.0 to 16.8 degrees 29.5 to 34.0 degrees in 2θ 37.
The peaks at 8-39.5° and 54.6-57.0° are characteristic. These peaks are assigned to cubic system crystal plane indices of 111.222, 400, and 440. The axial length a is approximately 9.2 to 9.8A.
このような本発明の銅酸化物系導電性セラミックスのう
ち、請求項（１）の銅酸化物系導電性セラミックスは、
例えば、請求項（３）の方法に従フて、次のようにして
製造することができる。Among such copper oxide-based conductive ceramics of the present invention, the copper oxide-based conductive ceramics of claim (1) include:
For example, according to the method of claim (3), it can be manufactured as follows.
即ち、まずＭの硝酸塩群から選ばれる１種又は塩化物と
、硝酸銅群から選ばれる１種又は塩化銅との所定量（但
し、Ｍの硝酸塩と硝酸銅、Ｍの塩化物と塩化銅の組み合
わせを除く。）を混合し、次いで、得られた混合物を２
００〜６００℃で加熱することにより、本発明の銅酸化
物系導電性セラミックスを得る。ここで、加熱温度が６
００℃を超えると絶縁性セラミックスであるＣｕＯ又は
Ｍ２０２が分解生成し、導電性セラミックスの生成割合
が減少し、更に高温の場合には全て絶縁性セラミックス
となるため好ましくない。一方、加熱温度が２００℃未
満では硝酸塩の分解反応が効率的に進行しない。That is, first, a predetermined amount of one selected from the nitrate group of M or a chloride and one selected from the copper nitrate group or copper chloride (however, a predetermined amount of M nitrate and copper nitrate, M chloride and copper chloride) ), and then the resulting mixture is mixed with 2
By heating at 00 to 600°C, the copper oxide-based conductive ceramic of the present invention is obtained. Here, the heating temperature is 6
If the temperature exceeds 00° C., CuO or M202, which are insulating ceramics, will be decomposed and produced, and the proportion of conductive ceramics produced will decrease, and if the temperature is higher than that, all the insulating ceramics will become insulating ceramics, which is not preferable. On the other hand, if the heating temperature is less than 200°C, the nitrate decomposition reaction will not proceed efficiently.
この加熱時間は１分〜５０時間程度の間で適宜選定され
、加熱は電気炉等の通常の加熱装置を用いて、酸素又は
空気中にて行なうことができる。The heating time is appropriately selected from about 1 minute to about 50 hours, and the heating can be performed in oxygen or air using a normal heating device such as an electric furnace.
なお、使用される硝酸塩及び塩化物にはその水和物も当
然含まれ、また、硝酸銅としては、塩基性硝酸銅ＣＬＩ
２ （ＯＨ） ３ （ＮＯ３）も使用可能である。Ｍ
及び銅の硝酸塩群から選ばれる１種又は塩化物の原料化
合物の混合法としては、各々の原料化合物をボールミル
等で粉砕混合する方法、又は、各々の原料化合物水溶液
を混合した後、蒸発乾固して水を除去する方法等を採用
することができる。Note that the nitrates and chlorides used naturally include their hydrates, and the copper nitrate includes basic copper nitrate CLI.
2 (OH) 3 (NO3) can also be used. M
The method of mixing raw material compounds selected from the group of copper nitrates and chlorides is to grind and mix each raw material compound in a ball mill or the like, or to mix the aqueous solutions of each raw material compound and then evaporate to dryness. A method of removing water by removing water can be adopted.
請求項（２）の銅酸化物系導電性セラミックスは、上記
請求項（３）の方法において、Ｍの硝酸塩、塩化物を用
いずに硝酸銅及び塩化銅のみを原料として同様に２００
〜６００℃で加熱することにより製造することができる
。The copper oxide-based conductive ceramic according to claim (2) is produced by using the method according to claim (3) using only copper nitrate and copper chloride as raw materials without using M nitrate or chloride.
It can be produced by heating at ~600°C.
［作用］
本発明の銅酸化物系導電性セラミックスのＸ線回折スペ
クトルのパターンから、本発明の銅酸化物系導電性セラ
ミックスは、Ａｇ７０ａ（ＮＯ３）類似組成を有する立
方晶系の結晶であると認められる。この結晶においては
、立方晶の酸素が一部欠損したものも含まれ、Ｍ及び銅
の酸化数は＋１〜＋３の混合価数であると考えられ、こ
れが導電性に寄与するものと推定される。[Function] From the X-ray diffraction spectrum pattern of the copper oxide conductive ceramic of the present invention, it can be concluded that the copper oxide conductive ceramic of the present invention is a cubic crystal having a composition similar to Ag70a (NO3). Is recognized. In this crystal, some cubic crystal oxygen is partially deficient, and the oxidation number of M and copper is thought to be a mixed valence of +1 to +3, which is presumed to contribute to electrical conductivity. .
しかして、このような本発明の銅酸化物系導電性セラミ
ックスは、本発明の方法に従って、硝酸塩や塩化物とい
った安価で容易に入手可能な原料を用いて、２００〜６
００℃といった比較的低い加熱温度にて容易かつ効率的
に製造することができる。Therefore, such copper oxide-based conductive ceramics of the present invention can be produced using inexpensive and easily available raw materials such as nitrates and chlorides according to the method of the present invention.
It can be easily and efficiently manufactured at a relatively low heating temperature of 00°C.
［実施例コ 以下に実施例を挙げて本発明をより具体的に説明する。[Example code] EXAMPLES The present invention will be explained in more detail with reference to Examples below.
実施例１
硝酸インジウム三水和物１．７９７ｇと塩化第二銅二水
和物０．８６３ｇと硝酸銅三水和物７．３４ｇ （モル
比１：１：６）を良く混合し、混合物を空気中、４２０
℃で１θ分間加熱した。Example 1 1.797 g of indium nitrate trihydrate, 0.863 g of cupric chloride dihydrate, and 7.34 g of copper nitrate trihydrate (molar ratio 1:1:6) were mixed well, and the mixture was in the air, 420
It was heated at ℃ for 1θ minutes.
これをベレットに成型し、金ホイルに包み５２０℃で３
０分間加熱した。Form this into a pellet, wrap it in gold foil and heat it at 520℃ for 3 hours.
Heated for 0 minutes.
その結果、第１図に示すような立方晶系のＸ線回折パタ
ーン（Ｃｕ Ｋａ線線用用を有する銅酸化物系導電性
セラミックスが得られた。このＸ線回折スペクトルから
、本実施例により（Ｉ ｎｒ／ａ Ｃｕｔ７ａ ） ７
０ｘ Ｃｊ２ｖが生成したことが確認された。この銅酸
化物系導電性セラミックスの温度−比抵抗曲線を第２図
に示す。第２図より得られた銅酸化物系導電性セラミッ
クスは良好な導電性を示すことが明らかである。As a result, a copper oxide-based conductive ceramic having a cubic X-ray diffraction pattern (for Cu Ka rays) as shown in FIG. 1 was obtained. From this X-ray diffraction spectrum, it was found that (I nr/a Cut7a) 7
It was confirmed that 0x Cj2v was generated. FIG. 2 shows a temperature-resistivity curve of this copper oxide conductive ceramic. It is clear from FIG. 2 that the copper oxide conductive ceramic obtained exhibits good conductivity.
実施例２
硝酸インジウム三水和物１．７９７ｇと塩化第二銅二水
和物０．４３２ｇと硝酸銅三水和物７．３４ｇ （モル
比１：０．５：６）に水１０ｍＩｔを加えて溶解し、こ
れを空気中、４８０℃で１０分間加熱した。Example 2 10 ml of water was added to 1.797 g of indium nitrate trihydrate, 0.432 g of cupric chloride dihydrate, and 7.34 g of copper nitrate trihydrate (molar ratio 1:0.5:6). This was heated in air at 480° C. for 10 minutes.
その結果、Ｎ３図に示すような立方晶系のｘｇ回折パタ
ーン（Ｃｕ Ｋａ線線用用を有する銅酸化物系導電性
セラミックスが得られた。As a result, a copper oxide conductive ceramic having a cubic xg diffraction pattern (for Cu Ka lines) as shown in the N3 diagram was obtained.
このＸ線回折スペクトルから、本実施例により（Ｉ ｎ
２／ｌｌＩＣｕ ＋５ｙｒｓ）７０ ｔ Ｃ１１ｗが
生成したことが確認された。なお、陰イオンクロマトグ
ラフィー分析の結果、Ｎの存在は認められず、Ｃｌのみ
の存在が認められた。この銅酸化物系導電性セラミック
スの比抵抗（室温）は９Ｘ１０−’Ω・ｃｍであった。From this X-ray diffraction spectrum, according to this example, (I n
It was confirmed that 2/llICu +5yrs)70t C11w was produced. Note that as a result of anion chromatography analysis, the presence of N was not observed, and only Cl was observed. The specific resistance (at room temperature) of this copper oxide-based conductive ceramic was 9×10 −′Ω·cm.
実施例３
硝酸スカンジウム四水和物１．５７５ｇと塩化第二銅二
水和物０．８８６ｇと硝酸銅三水和物７．５３８ｇ （
モル比ｔ：１：６）を良く混合し、混合物を空気中、４
８０℃で３０分間加熱した。Example 3 1.575 g of scandium nitrate tetrahydrate, 0.886 g of cupric chloride dihydrate, and 7.538 g of copper nitrate trihydrate (
Molar ratio t: 1:6) was mixed well, and the mixture was placed in air at 4
Heated at 80°C for 30 minutes.
その結果、第４図に示すような立方晶系のＸ線回折パタ
ーン（Ｃｕ Ｋａ線線用用を有する銅酸化物系導電性
セラミックスが得られた。このＸ線回折スペクトルから
、本実施例により（Ｓ ｅ ｌ／Ｉ！ｌ Ｃｕｔ７ａ）
フＯｘ Ｃｌａｗが生成したことが確認された。なお、
陰イオンクロマトグラフィー分析の結果、Ｎの存在は認
められず、Ｃｌ２のみの存在が認められた。この銅酸化
物系導電性セラミックスの比抵抗（室温）は８Ｘ１０−
’Ω・Ｃｍであった。As a result, a copper oxide conductive ceramic having a cubic X-ray diffraction pattern (for Cu Ka rays) as shown in FIG. 4 was obtained. From this X-ray diffraction spectrum, it was found that (S e l/I!l Cut7a)
It was confirmed that Ox Claw was generated. In addition,
As a result of anion chromatography analysis, the presence of N was not observed, and only Cl2 was observed. The specific resistance (room temperature) of this copper oxide conductive ceramic is 8X10-
'Ω・Cm.
実施例４
塩化第二銅二水和物１．０５２ｇと硝酸銅三水和物８．
９４８ｇ （モル比１：６）を良く混合し、酸素気流中
、２３０℃で６時間加熱した。Example 4 1.052 g of cupric chloride dihydrate and copper nitrate trihydrate 8.
948 g (molar ratio 1:6) were mixed well and heated at 230° C. for 6 hours in an oxygen stream.
その結果、第５図に示すような立方晶系のＸ線回折パタ
ーン（Ｃｕ Ｋ α 線用用 ）を有する生成物が
得られた。このＸ線回折スペクトルから、本実施例によ
りＣｕ７ｅ。As a result, a product having a cubic X-ray diffraction pattern (for Cu K α rays) as shown in FIG. 5 was obtained. From this X-ray diffraction spectrum, Cu7e was determined according to this example.
（ＩＱ、Ｎｏ、）ｗの銅酸化物系導電性セラミックスが
得られたことが確認された。この化合物の赤外線吸収ス
ペクトルは約１３６０〜１３８０ｃｍ−’に吸収ピーク
を有しており、ＮＯ３基の存在を示した。得られた銅酸
化物系導電性セラミックスの比抵抗（室温）はｌＸｌ０
−’Ω・ｃｍであった。It was confirmed that a copper oxide-based conductive ceramic of (IQ, No.)w was obtained. The infrared absorption spectrum of this compound had an absorption peak at about 1360-1380 cm-', indicating the presence of NO3 groups. The specific resistance (room temperature) of the obtained copper oxide conductive ceramic is lXl0
-'Ω·cm.
実施例５
塩化第二銅二水和物０．３４５ｇと硝酸銅三水和物２．
９３６ｇ（モル比１：１３）に水１０ｍ１を加えて溶解
し、酸素気流中、２３０℃で６時間加熱した。Example 5 0.345 g of cupric chloride dihydrate and copper nitrate trihydrate 2.
936 g (molar ratio 1:13) was dissolved in 10 ml of water, and heated at 230° C. for 6 hours in an oxygen stream.
その結果、第６図に示すような立方晶系のＸ線回折パタ
ーン（Ｃｕ Ｋａ線線用用を有する銅酸化物系導電性
セラミックスが得られた。このＸ線回折スペクトルから
、本実施例によりＣｕ７０Ｈ（Ｃｌ２．Ｎ０３）ｖが生
成したことが確認された。この化合物の赤外線吸収スペ
クトルは約１３６０〜１３８０ｃｍ−’に吸収ピークを
有しており、ＮＯ３基の存在を示した。この銅酸化物系
導電性セラミックスの比抵抗（室温）はｌＸｌ０−’Ω
・ａｍであった。As a result, a copper oxide-based conductive ceramic having a cubic X-ray diffraction pattern (for Cu Ka rays) as shown in FIG. 6 was obtained. From this X-ray diffraction spectrum, it was found that It was confirmed that Cu70H(Cl2.N03)v was produced.The infrared absorption spectrum of this compound had an absorption peak at about 1360 to 1380 cm-', indicating the presence of NO3 groups.This copper oxide The specific resistance (room temperature) of the system conductive ceramics is lXl0-'Ω
・It was am.
［発明の効果］
以上詳述した通り、本発明の銅酸化物系導電性セラミッ
クスによれば、セラミックスの耐熱性、耐食性、機械的
特性と、導電性とを兼備する高特性導電性セラミックス
であって、安価で入手し易い原料を用いて、比較的低温
の加熱により容易かつ効率的に製造することができる銅
酸化物系導電性セラミックスが提供される。[Effects of the Invention] As detailed above, the copper oxide-based conductive ceramic of the present invention is a high-performance conductive ceramic that has both the heat resistance, corrosion resistance, mechanical properties, and electrical conductivity of ceramics. Thus, there is provided a copper oxide-based conductive ceramic that can be easily and efficiently manufactured by heating at a relatively low temperature using inexpensive and easily available raw materials.
このような本発明の銅酸化物系導電性セラミックスは、
各種の電極、発熱体材料として好適に適用可能であり、
また、近年技術進歩の著しい超伝導体を製造するため原
料としても工業的に極めて有用である。Such a copper oxide-based conductive ceramic of the present invention is
It can be suitably applied as various electrodes and heating element materials,
It is also industrially extremely useful as a raw material for producing superconductors, which have undergone remarkable technological advances in recent years.
しかして、このような本発明の銅酸化物系導電性セラミ
ックスは、請求項（３）、（４）の本発明の銅酸化物系
導電性セラミックスの製造方法により、容易かつ効率的
に低コストにて製造される。Therefore, such a copper oxide-based conductive ceramic of the present invention can be easily and efficiently produced at low cost by the method of producing a copper oxide-based conductive ceramic of the present invention according to claims (3) and (4). Manufactured in
【図面の簡単な説明】
第１図は実施例１で得られた銅酸化物系導電性セラミッ
クスのＸ線回折スペクトルを示す図、第２図は同温度−
比抵抗曲線を示す図である。第３図、第４図、第５図及
び第６図は各々、実施例２．３．４及び５で得られた銅
酸化物系導電性セラミックスのＸ線回折スペクトルを示
す図である。[Brief Description of the Drawings] Figure 1 shows the X-ray diffraction spectrum of the copper oxide conductive ceramic obtained in Example 1, and Figure 2 shows the same temperature -
It is a figure showing a resistivity curve. FIG. 3, FIG. 4, FIG. 5, and FIG. 6 are diagrams showing the X-ray diffraction spectra of the cuprate-based conductive ceramics obtained in Examples 2.3.4 and 5, respectively.
Claims (4)
ラミックス。 （Ｍ＿ｘＣｕ＿ｙ）＿７Ｏ＿ｚＡ＿ｗ・・・［Ｉ］［Ｉ
］式中、 ＭはＩｎ、Ｓｃ、Ｙ、Ｔｌ及びＧａより なる群から選ばれる１種又は２種以上の 元素、ＡはＣｌ、或いはＣｌ及びＮＯ＿３ を表わす。 ｘ＋ｙ＝１ ０＜ｘ／ｙ≦１０ ０≦ｚ≦８ １≦ｗ≦９(1) A copper oxide-based conductive ceramic represented by the following general formula [I]. (M_xCu_y)_7O_zA_w...[I][I
] In the formula, M represents one or more elements selected from the group consisting of In, Sc, Y, Tl and Ga, and A represents Cl or Cl and NO_3. x+y=1 0<x/y≦10 0≦z≦8 1≦w≦9
ラミックス。 Ｃｕ＿７Ｏ＿ｚＡ＿ｗ・・・［II］ ［II］式中、ＡはＣｌ、或いはＣｌ及び ＮＯ＿３を表わす。 ０≦ｚ≦８ １≦ｗ≦９(2) A copper oxide-based conductive ceramic represented by the following general formula [II]. Cu_7O_zA_w... [II] [II] In the formula, A represents Cl, or Cl and NO_3. 0≦z≦8 1≦w≦9
ばれる１種又は２種以上の金属の硝酸塩及び／又は塩化
物と、銅の硝酸塩及び／又は塩化物とからなる混合物（
但し、該金属の硝酸塩と硝酸銅、該金属の塩化物と塩化
銅との組み合わせを除く。）を２００〜６００℃で加熱
することにより特許請求の範囲第１項に記載の銅酸化物
系導電性セラミックスを製造する方法。(3) A mixture consisting of a nitrate and/or chloride of one or more metals selected from the group consisting of In, Sc, Y, Tl, and Ga and a nitrate and/or chloride of copper (
However, combinations of nitrates of the metals and copper nitrate, and combinations of chlorides of the metals and copper chloride are excluded. ) at 200 to 600°C.
加熱することにより特許請求の範囲第２項に記載の銅酸
化物系導電性セラミックスを製造する方法。(4) A method for producing the copper oxide-based conductive ceramics according to claim 2 by heating a mixture of copper nitrate and chloride at 200 to 600°C.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2078380A JP2967541B2 (en) | 1990-03-27 | 1990-03-27 | Copper oxide conductive ceramics and method for producing the same |
| US07/639,931 US5112783A (en) | 1990-01-22 | 1991-01-14 | Conductive copper oxide ceramics and process for producing same |
| DE4101761A DE4101761C2 (en) | 1990-01-22 | 1991-01-22 | Electrically conductive copper oxide ceramics and process for their production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2078380A JP2967541B2 (en) | 1990-03-27 | 1990-03-27 | Copper oxide conductive ceramics and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03279254A true JPH03279254A (en) | 1991-12-10 |
| JP2967541B2 JP2967541B2 (en) | 1999-10-25 |
Family
ID=13660411
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2078380A Expired - Lifetime JP2967541B2 (en) | 1990-01-22 | 1990-03-27 | Copper oxide conductive ceramics and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2967541B2 (en) |
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1990
- 1990-03-27 JP JP2078380A patent/JP2967541B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2967541B2 (en) | 1999-10-25 |
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