JPS62222097A - Oxide film coated tungsten wire and its production - Google Patents
Oxide film coated tungsten wire and its productionInfo
- Publication number
- JPS62222097A JPS62222097A JP6486686A JP6486686A JPS62222097A JP S62222097 A JPS62222097 A JP S62222097A JP 6486686 A JP6486686 A JP 6486686A JP 6486686 A JP6486686 A JP 6486686A JP S62222097 A JPS62222097 A JP S62222097A
- Authority
- JP
- Japan
- Prior art keywords
- tungsten wire
- oxide film
- oxide
- coated tungsten
- wire
- 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.)
- Pending
Links
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 13
- 239000008151 electrolyte solution Substances 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 2
- 239000010935 stainless steel Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 description 3
- -1 oxygen ions Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、酸化皮膜タングステン線に関し、特に、コロ
ナ放電用の帯電線に適する酸化皮膜タングステン線に関
する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an oxide coated tungsten wire, and particularly to an oxide coated tungsten wire suitable for a charging wire for corona discharge.
従来のコロナ放電用の帯電線に適する酸化皮膜タングス
テン線及びその製造方法に関しては、特公昭５３−２８
０９９号公報に記載されている。Regarding an oxide coated tungsten wire suitable for a charging wire for conventional corona discharge and its manufacturing method, Japanese Patent Publication No. 53-28
It is described in Publication No. 099.
即ち、該公報に記載された酸化皮膜タングステン線は、
大気中において、細いタングステン線ヲ。That is, the oxide coated tungsten wire described in the publication is
A thin tungsten wire in the atmosphere.
４００〜５００℃に加熱し、大気中の酸素分子をタング
ステン線の表面に取り込むことによシ、酸化皮膜を生成
させる。所謂間接加熱方法を用いて製造されている。The tungsten wire is heated to 400 to 500°C and oxygen molecules in the atmosphere are taken into the surface of the tungsten wire to form an oxide film. It is manufactured using a so-called indirect heating method.
しかしながら、斯かる間接加熱方法による酸化皮膜タン
グステン及びその製造方法には、下記の種々の問題点が
ある。However, the oxide-coated tungsten and its manufacturing method using such indirect heating methods have the following various problems.
酸化皮膜を生成するタングステン酸化物は、タングステ
ン線への加熱温度の微妙な変化の影響を受は易く、シか
も、大気中の酸素濃度は常に一定ではないことから、タ
ングステン酸化物に組成成分のパラつき及び生成量の不
均一が生じ易い欠点がある。まだ、加熱温度及び大気中
の酸素濃度を管理することは、事実上困難であシ、製品
の歩留りを劣化させる欠点がある。The tungsten oxide that forms the oxide film is easily affected by subtle changes in the heating temperature of the tungsten wire, and since the oxygen concentration in the atmosphere is not always constant, the composition of the tungsten oxide may vary. It has the disadvantage that it tends to cause unevenness and non-uniformity in the amount produced. However, it is actually difficult to control the heating temperature and the oxygen concentration in the atmosphere, and there is a drawback that the yield of the product is degraded.
よって、このように不安定な加熱による酸化物の生成方
法では、酸化物の組成成分をコロナ放電雰囲気中で最も
安定な酸化物であるＷＯ２に到達させることが難しく、
不安定な高温酸化物であるＷＯ及びＷ１８Ｏ４９等を多
量に生成してしまい。Therefore, in this method of generating an oxide by unstable heating, it is difficult to make the composition of the oxide reach WO2, which is the most stable oxide in the corona discharge atmosphere.
A large amount of unstable high temperature oxides such as WO and W18O49 are produced.
安定したコロナ放電を得ることができない。Unable to obtain stable corona discharge.
また、安定した最終酸化物Ｗｏ２を重量比で９０−以上
得るために、長時間の加熱を与えたとしても酸化皮膜の
膜厚が不可避的に厚＜（１，５〜３．５μｍ）なってし
まい、却ってコロナ放電性を劣化させるものである。In addition, in order to obtain a stable final oxide Wo2 with a weight ratio of 90 or more, even if heating is applied for a long time, the thickness of the oxide film inevitably becomes less than (1.5 to 3.5 μm). This actually deteriorates the corona discharge properties.
そこで２本発明の目的は、上記欠点を鑑み１重量比で９
０％以上の高純度のＷＯ２からなる均一で膜厚の薄い（
０，１〜０．５μｍ）酸化皮膜を有するタングステン線
と、その製造方法を提供するものである。Therefore, in view of the above-mentioned drawbacks, the object of the present invention is to
A uniform and thin film made of 0% or higher purity WO2 (
The present invention provides a tungsten wire having an oxide film (0.1 to 0.5 μm) and a method for manufacturing the same.
本発明によれば、タングステン線に酸化皮膜を形成した
酸化皮膜タングステン線において、電解液中で形成され
たＷＯ□からなる酸化皮膜を有することを特徴とする酸
化皮膜タングステン線を得る。According to the present invention, there is obtained an oxide film tungsten wire having an oxide film formed on a tungsten wire, which is characterized in that it has an oxide film made of WO□ formed in an electrolytic solution.
好ましくは、酸化皮膜は１重量比で９０〜９５−の量の
ｗｏ と、残余をＷ１８Ｏ４９とＷ１８Ｏ４９との混
合物とから形成することを特徴とする酸化皮膜タングス
テン線を得る。Preferably, the oxide film is formed from WO in an amount of 90 to 95 - by weight, and the remainder is a mixture of W18O49 and W18O49 to obtain an oxide film tungsten wire.
さらに１本発明によれば、タングステン線を陽極側に設
けて、湿式電解を施したことを特徴とする酸化皮膜タン
グステン線の製造方法が得られる。Furthermore, according to the present invention, there is obtained a method for producing an oxide coated tungsten wire, characterized in that the tungsten wire is provided on the anode side and subjected to wet electrolysis.
好ましくは、タングステン線は、予め電解表面仕上を施
した後に陽極側に設け、印加電流を１．６〜１．８Ａと
し、印加電圧を１８〜２２Ｖとし２通電時間を８〜１０
秒としたことを特徴とする酸化皮膜タングステン線の製
造方法を得る。Preferably, the tungsten wire is provided on the anode side after being subjected to an electrolytic surface finishing in advance, and the applied current is 1.6 to 1.8 A, the applied voltage is 18 to 22 V, and the tungsten wire is energized for 8 to 10 hours.
A method for manufacturing an oxide coated tungsten wire is obtained, characterized in that the process is performed in seconds.
本発明について２図面を参照して説明する。 The present invention will be explained with reference to two drawings.
第１図において、係る酸化皮膜タングステン線は、電解
液槽１に満たされた濃度４チの水酸化ナトリウム溶液か
らなる電解液２の中で製造される。In FIG. 1, such an oxide-coated tungsten wire is manufactured in an electrolytic solution 2 which is filled in an electrolytic solution tank 1 and is made of a sodium hydroxide solution with a concentration of 4%.
電解液２中には、ステンレスからなる陰極３と。In the electrolyte 2 is a cathode 3 made of stainless steel.
直径φ０．１ ｔａｘのタングステン線４によって形成
すれる陽極５とが浸漬されている。陰極３と陽極５とに
は各々、整流器５によって特徴付けられた直流電源のｅ
端子との端子とに接続されている。An anode 5 formed of a tungsten wire 4 having a diameter of φ0.1 tax is immersed therein. The cathode 3 and the anode 5 are each connected to a DC power source e, characterized by a rectifier 5.
Connected to the terminal and the terminal.
今、整流器５から、印加電流１．８Ａ、印加電圧２０Ｖ
をそれぞれの極板３・５に１０秒間通電させることによ
り、膜厚０，１〜０．５μｍの薄く均一なＷＯ２の酸化
皮膜６を得ることができる。Now, from the rectifier 5, the applied current is 1.8 A, and the applied voltage is 20 V.
By energizing each of the electrode plates 3 and 5 for 10 seconds, a thin and uniform WO2 oxide film 6 having a thickness of 0.1 to 0.5 μm can be obtained.
すなわち、電解液２中に遊離したマイナスイオンである
酸素イオンが、プラスに帯電したタングステン線の表面
に取り込まれて、高純度のＷＯ□からなる酸化皮膜６を
形成することになる。That is, oxygen ions, which are negative ions liberated in the electrolytic solution 2, are taken into the positively charged surface of the tungsten wire, forming an oxide film 6 made of highly pure WO□.
実際に形成された酸化皮膜の組成成分は１重量比で９０
〜９５％のＷＯと、残余をＷ１８Ｏ４９とＷ１８Ｏ４９
との混合物とからなるものであった。The composition of the oxide film actually formed is 90% by weight.
~95% WO and the rest W18O49 and W18O49
It consisted of a mixture of
ここで、大気中の酸素に比べて、電解液中の酸素イオン
は、常に一定の雰囲気をタングステン線に及ぼすことが
容易であると共に、タングステン線自身は、加熱等の手
段を用いずに、印加する電流によって、容易に一定の反
応エネルギーを与えられることになる。このため、不安
定な酸化物であるＷ１８０，９．Ｗ１８Ｏ４９等の生成
が抑制され、最終酸化物Ｗｏ３に次いで安定な酸化物で
あるＷＯ２が最終生成物として、酸化皮膜を形成するこ
とができる。Here, compared to oxygen in the atmosphere, it is easier for oxygen ions in the electrolyte to always exert a constant atmosphere on the tungsten wire, and the tungsten wire itself can be heated without using any means such as heating. A certain amount of reaction energy can be easily given by the current. For this reason, the unstable oxide W180,9. The generation of W18O49 and the like is suppressed, and WO2, which is the second most stable oxide after the final oxide Wo3, can form an oxide film as a final product.
次に、第２の実施例は、第２図に示すとおシ。Next, a second embodiment is shown in FIG.
電解液２・２を満たした電解槽１・１に、陰極３と陽極
５とをそれぞれ浸漬させである。この２つの電解槽１・
１中の電解液２・２に、タングステン線４を浸漬させ、
整流器５からの電流ｔタングステン線４を介して通電さ
せることにより、陽電極５側で、タングステン線に、上
述したとおシ酸化皮膜６が形成される。尚、酸化皮膜６
を連続的に生成する場合は３図中の矢印のとおり、タン
グステン線４を陰極３から陽極５に移動させるものであ
る。A cathode 3 and an anode 5 are immersed in electrolytic baths 1 and 1 filled with electrolytes 2 and 2, respectively. These two electrolytic cells 1.
The tungsten wire 4 is immersed in the electrolyte 2.2 in 1,
By passing current t from the rectifier 5 through the tungsten wire 4, the above-described oxidized film 6 is formed on the tungsten wire on the positive electrode 5 side. In addition, the oxide film 6
In order to continuously generate the tungsten wire 4, the tungsten wire 4 is moved from the cathode 3 to the anode 5 as indicated by the arrow in FIG.
尚、一般にタングステン線は、カーボンコーティングを
施されて製品化されている場合が多く。Generally, tungsten wire is often commercialized with carbon coating.
また、タングステン線の表面の汚れを落とすことも必要
であることから、予め電解表面仕上を施して、タングス
テン線の表面をクリーンにした後。It is also necessary to remove dirt from the surface of the tungsten wire, so after applying an electrolytic surface finish to the surface of the tungsten wire to clean it.
電解液中に浸漬することが好ましい。Preferably, it is immersed in an electrolyte.
以上の湿式陽極酸化による酸化皮膜タングステン線の製
造方法の結果、膜厚が０．１〜０．５μｍの酸化皮膜を
均一に、且つ短時間（１０秒程度）に形成できた。As a result of the above-described method for producing an oxide coated tungsten wire by wet anodization, an oxide coat having a thickness of 0.1 to 0.5 μm could be formed uniformly and in a short time (about 10 seconds).
ここで２本発明に係る酸化タングステン線と従来との性
能比較試験結果を第３図〜第５図に示す。Here, the results of a performance comparison test between the tungsten oxide wire according to the present invention and the conventional wire are shown in FIGS. 3 to 5.
即ち９本発明に係る製造方法である所謂湿式陽極酸化方
法による酸化皮膜タングステン線（第３図）と、大気中
で高温酸化させる従来の所謂間接加熱方法による酸化皮
膜タングステン線（第４図）と。That is, 9 oxide-coated tungsten wires produced by the so-called wet anodic oxidation method (FIG. 3), which is a manufacturing method according to the present invention, and oxide-coated tungsten wires produced by the conventional so-called indirect heating method (FIG. 4), which are oxidized at high temperatures in the atmosphere. .
単に電解表面仕上を施されて、自然酸化したタングステ
ン線（第５図）とを用いて、高温高湿の大気内でコロナ
放電させた場合における印加電圧の変化をそれぞれ比較
するものである。図中の上段のグラフＡは、初期のコロ
ナ放電中の印加電圧の変化を表し、下段のグラフＢは、
５０時間継続してコロナ放電させた後の印加電圧の変化
を表している。尚、グラフの縦軸は印加電圧Ｖであシ、
横軸は時間Ｔである。Using a naturally oxidized tungsten wire (FIG. 5) that has simply been given an electrolytic surface finish, the changes in applied voltage are compared when a corona discharge is caused in a high temperature, high humidity atmosphere. Graph A in the upper part of the figure represents the change in applied voltage during the initial corona discharge, and graph B in the lower part represents the change in applied voltage during the initial corona discharge.
It shows the change in applied voltage after corona discharge continued for 50 hours. Note that the vertical axis of the graph is the applied voltage V,
The horizontal axis is time T.
第３図に示すとおシ２本発明に係る酸化皮膜タングステ
ン線は、５０時間経過すると印加電圧が周期的に変化す
るものの、変化の振幅は極めて小さく、５０時間経過後
も最も安定したコロナ放電が行えた。As shown in Figure 3, although the applied voltage of the oxide-coated tungsten wire according to the present invention changes periodically after 50 hours, the amplitude of the change is extremely small, and even after 50 hours, the most stable corona discharge is maintained. I was able to do it.
第４図では、従来の間接加熱方法による酸化皮膜タング
ステン線は、印加電圧の振幅が大きく。In FIG. 4, the amplitude of the applied voltage is large for the oxide coated tungsten wire produced by the conventional indirect heating method.
本発明のものに比べ、コロナ放電の安定性が著しく劣る
ことがわかる。It can be seen that the stability of corona discharge is significantly inferior to that of the present invention.
第５図では、電解仕上げを施した自然酸化のタングステ
ン線は、印加電圧の振幅が極めて大きくコロナ放電が０
に近い場合もある。Figure 5 shows that the electrolytically finished naturally oxidized tungsten wire has an extremely large amplitude of applied voltage and zero corona discharge.
In some cases, it is close to .
このように、印加電圧の振幅が大きいと、実際の複写機
等に用いた場合１画像が乱れ、使用に耐えない。As described above, if the amplitude of the applied voltage is large, one image will be distorted when used in an actual copying machine, etc., making it unusable.
以上説明のとおり２本発明によれば、最終酸化物Ｗ０３
に次いで、安定した酸化物であるＷＯ７を主成分とし、
均一で薄膜な酸化皮膜を、短時間で。As explained above, according to the present invention, the final oxide W03
Next, the main component is WO7, which is a stable oxide,
Creates a uniform and thin oxide film in a short time.
タングステン線に施すことができるから、極めて安定し
たコロナ放電をすることが可能である。Since it can be applied to tungsten wire, extremely stable corona discharge can be achieved.
しかも２本発明の湿式陽極酸化方法によれば。Moreover, according to the wet anodic oxidation method of the present invention.
不安定な大気中の酸素に影響されず、又、微妙な制御が
難しい加熱等のエネルギーを用いないから。This is because it is not affected by the unstable oxygen in the atmosphere, and does not use energy such as heating, which is difficult to delicately control.
安定した品質を提供することができ、その管理も簡便で
ある。It can provide stable quality and is easy to manage.
第１図は２本発明に係る酸化皮膜生テスト装置の概略図
、第２図は２本発明に係る工業化装置の概略図、第３図
は２本発明に係る酸化皮膜タングステン線のコロナ放電
中における印加電圧の変化を示すグラフ、第４図及び第
５図は、従来の酸化皮膜タングステン線のコロナ放電中
における印加電圧の変化を示すグラフ。
１・・・電解液槽、２・・・電解液、３・・・陰極板、
４・・・タングステン線、５・・・陽極板、６・・・酸
化皮膜。
第２図
第３図
第４図
第５図Fig. 1 is a schematic diagram of the oxide film raw test device according to the present invention, Fig. 2 is a schematic diagram of the industrialization equipment according to the present invention, and Fig. 3 is a schematic diagram of the oxidized film tungsten wire according to the present invention during corona discharge. FIGS. 4 and 5 are graphs showing changes in applied voltage during corona discharge of a conventional oxide-coated tungsten wire. 1... Electrolyte tank, 2... Electrolyte, 3... Cathode plate,
4... Tungsten wire, 5... Anode plate, 6... Oxide film. Figure 2 Figure 3 Figure 4 Figure 5
Claims (1)
グステン線において、電解液中で形成されたＷＯ＿２か
らなる酸化皮膜を有することを特徴とする酸化皮膜タン
グステン線。 ２）前記酸化皮膜は、重量比で、９０〜９５％の量のＷ
Ｏ＿２と、残余をＷ＿１＿８Ｏ＿４＿９とＷ＿２＿Ｏ＿
５＿８との混合物とから形成されていることを特徴とす
る特許請求の範囲第１項記載の酸化皮膜タングステン線
。 ３）酸化皮膜の膜厚は、０．１〜０．５μｍに形成され
ていることを特徴とする特許請求の範囲第２項記載の酸
化皮膜タングステン線。 ４）タングステン線を陽極側に設けて、湿式電解を施し
たことを特徴とする酸化皮膜タングステン線の製造方法
。 ５）タングステン線は、予め電解表面仕上を施した後に
陽極側に設けたことを特徴とする特許請求の範囲第４項
記載の酸化皮膜タングステン線の製造方法。 ６）湿式電解は、印加電流を１．６〜１．８Ａとし、印
加電圧を１８〜２２Ｖとし、通電時間を８〜１０秒とし
たことを特徴とする特許請求の範囲第５項記載の酸化皮
膜タングステン線の製造方法。[Scope of Claims] 1) An oxide film tungsten wire having an oxide film formed on a tungsten wire, which has an oxide film made of WO_2 formed in an electrolytic solution. 2) The oxide film contains W in an amount of 90 to 95% by weight.
O_2 and the remainder W_1_8O_4_9 and W_2_O_
The oxide coated tungsten wire according to claim 1, characterized in that it is formed from a mixture of 5_8 and 5_8. 3) The oxide film tungsten wire according to claim 2, wherein the oxide film has a thickness of 0.1 to 0.5 μm. 4) A method for manufacturing an oxide coated tungsten wire, characterized in that the tungsten wire is provided on the anode side and subjected to wet electrolysis. 5) The method for manufacturing an oxide-coated tungsten wire according to claim 4, wherein the tungsten wire is provided on the anode side after being subjected to electrolytic surface finishing in advance. 6) The oxidation according to claim 5, wherein the wet electrolysis is performed using an applied current of 1.6 to 1.8 A, an applied voltage of 18 to 22 V, and a current application time of 8 to 10 seconds. Method for manufacturing coated tungsten wire.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6486686A JPS62222097A (en) | 1986-03-25 | 1986-03-25 | Oxide film coated tungsten wire and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6486686A JPS62222097A (en) | 1986-03-25 | 1986-03-25 | Oxide film coated tungsten wire and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62222097A true JPS62222097A (en) | 1987-09-30 |
Family
ID=13270504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6486686A Pending JPS62222097A (en) | 1986-03-25 | 1986-03-25 | Oxide film coated tungsten wire and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62222097A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6605165B2 (en) * | 1999-05-28 | 2003-08-12 | Canon Kabushiki Kaisha | Method of manufacturing discharge wire |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5126567A (en) * | 1974-08-30 | 1976-03-04 | Suwa Seikosha Kk | TOKEI YOGA ISOBUHIN |
| JPS5321050A (en) * | 1976-08-11 | 1978-02-27 | Seiko Instr & Electronics | Dial face of timepiece |
-
1986
- 1986-03-25 JP JP6486686A patent/JPS62222097A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5126567A (en) * | 1974-08-30 | 1976-03-04 | Suwa Seikosha Kk | TOKEI YOGA ISOBUHIN |
| JPS5321050A (en) * | 1976-08-11 | 1978-02-27 | Seiko Instr & Electronics | Dial face of timepiece |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6605165B2 (en) * | 1999-05-28 | 2003-08-12 | Canon Kabushiki Kaisha | Method of manufacturing discharge wire |
| US6917776B2 (en) | 1999-05-28 | 2005-07-12 | Canon Kabushiki Kaisha | Discharge wire, method of manufacturing discharge wire and electrification device |
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