JPH06144811A - Metal-coated carbonaceous spring - Google Patents
Metal-coated carbonaceous springInfo
- Publication number
- JPH06144811A JPH06144811A JP4299828A JP29982892A JPH06144811A JP H06144811 A JPH06144811 A JP H06144811A JP 4299828 A JP4299828 A JP 4299828A JP 29982892 A JP29982892 A JP 29982892A JP H06144811 A JPH06144811 A JP H06144811A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- spring
- metal
- organic
- coated
- 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.)
- Withdrawn
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、種々の化学合成装
置、航空宇宙環境利用装置、原子炉、核融合炉、センサ
ー、示差熱天秤、ケミカルポンプ、エンジン用部材、等
に適用されるように全表面を金属で被覆された炭素系ス
プリングに関する。INDUSTRIAL APPLICABILITY The present invention is applied to various chemical synthesis equipment, aerospace environment utilization equipment, nuclear reactors, nuclear fusion reactors, sensors, differential thermal balances, chemical pumps, engine parts, etc. The present invention relates to a carbon-based spring whose entire surface is coated with metal.
【０００２】[0002]
【従来の技術】金属製のバネは、バネ定数の温度依存性
が大きく、一般的に常用されるのは２００℃以下であり
耐熱性も６００℃が限度で急激に強度が低下する。ま
た、錆や化学薬品などに対する耐腐食性に乏しい。2. Description of the Related Art Metal springs have a large temperature dependence of spring constant, and are generally used at 200 ° C. or lower, and their heat resistance is drastically reduced at a limit of 600 ° C. Also, it has poor corrosion resistance to rust and chemicals.
【０００３】一方セラミックス製のバネでも耐熱性は１
０００℃が限度で、耐熱衝撃性に乏しい。金属、セラミ
ックス共に比重が高いので部材重量が大きくなる。等の
不都合な点があった。On the other hand, a ceramic spring has a heat resistance of 1
It has a limit of 000 ° C and poor thermal shock resistance. Since the specific gravity of both metal and ceramics is high, the weight of the member becomes large. There were some inconveniences.
【０００４】本願発明者は、炭素材料が、バネ定数の温
度依存性が小さく、高温で溶融、変形することの無い優
れた耐熱性及び弾性係数を維持すること、化学薬品に侵
されることの無い耐薬品性、耐腐食性を持つこと、電気
伝導性や軽量で高い弾性率を持つことに着目して、全炭
素質から成る炭素系のコイルスプリングの製造方法を以
前に提案した。（特公平１−４４６７１）The inventor of the present application has found that the carbon material has a small temperature dependence of the spring constant, maintains excellent heat resistance and elastic modulus without being melted or deformed at high temperature, and is not affected by chemical agents. We have previously proposed a method for manufacturing a carbon-based coil spring consisting of all carbonaceous matter, focusing on its chemical resistance, corrosion resistance, electrical conductivity, light weight, and high elastic modulus. (Japanese Patent Publication 1-44671)
【０００５】この炭素系スプリングは、極めて高い加工
精度で後加工を必要とせず、非酸化性の雰囲気において
は優れた耐熱性及び耐腐食性を有し、高い強度と信頼性
のある精度高い弾性率を保有するものであった。This carbon-based spring does not require post-processing with extremely high processing accuracy, has excellent heat resistance and corrosion resistance in a non-oxidizing atmosphere, and has high strength, reliability, high accuracy and elasticity. It had a rate.
【０００６】しかし、一般に炭素材料は、金属材料に比
べ導電性が悪く、複合マトリックスの材質によっては濡
れ性が悪く接着が困難であり、カーボンの種類・形態に
よっては耐摩耗性が劣る。Generally, however, carbon materials have poor conductivity as compared with metal materials, have poor wettability depending on the material of the composite matrix, and are difficult to bond, and have poor wear resistance depending on the type and form of carbon.
【０００７】耐熱性も非酸化性雰囲気に於てであって、
酸素存在下では腐食が進み物理的特性や外観が損なわれ
る恐れがある。また、黒色であることから用途によって
は、装飾性や美観に欠ける。The heat resistance is also in a non-oxidizing atmosphere,
Corrosion proceeds in the presence of oxygen, which may impair physical properties and appearance. In addition, because it is black, it lacks decorativeness and aesthetics depending on the application.
【０００８】[0008]
【発明が解決しようとする課題】本発明の目的は、前記
した炭素材料の欠点を補い問題を解決すべく、すなわ
ち、酸素存在下の高温でも優れた耐熱性及び耐腐食性を
有し、高い強度と信頼性のある精度高い弾性率を保有
し、金属材料に匹敵する導電性、接着性、耐摩耗性、美
観を有し、軽量である等の優れた機能を持つ新しい複合
機能性炭素スプリングを提供することである。SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned drawbacks of carbon materials and solve the problems, namely, to have excellent heat resistance and corrosion resistance even at high temperature in the presence of oxygen, A new multi-functional carbon spring that possesses strength, reliability, high precision elastic modulus, electrical conductivity, adhesion, abrasion resistance, aesthetics comparable to metal materials, and excellent features such as being lightweight. Is to provide.
【０００９】[0009]
【課題を解決するための手段】本願発明者は、以前に提
案した、全炭素質から成る炭素系のコイルスプリング
（特公平１−４４６７１）すなわち、有機質線状体或
は、これに炭素繊維、黒鉛ウイスカー、黒鉛粉体、非晶
質炭素粉体を均一に分散し、高度に複合強化した有機質
線状体をコイル状の任意の形態に賦形した後、必要に応
じて炭素前駆体処理を施し、さらに不活性雰囲気中に加
熱処理して炭素化した炭素系コイルスプリングが、バネ
定数の温度依存性が小さく、高温で溶融、変形すること
の無い耐薬品性、耐腐食性を持つこと、電気伝導性や軽
量で高い弾性率を持つことに着目して、この全炭素質か
ら成る炭素系のコイルスプリングを基材として、その全
表面を所望する機能に応じて選択された金属で、被覆す
ることによって、使用の適用範囲を広くした新しい複合
機能性炭素スプリングを作製できることに想到し、本発
明を完成した。The inventor of the present invention has previously proposed a carbon-based coil spring composed of all carbonaceous material (Japanese Patent Publication No. 1-44671), that is, an organic linear body or carbon fiber, Graphite whiskers, graphite powder, and amorphous carbon powder are evenly dispersed, and a highly complex-reinforced organic linear material is shaped into a coil shape, and then a carbon precursor treatment is performed if necessary. The carbon-based coil spring that has been subjected to heat treatment and carbonization by heating in an inert atmosphere has a small temperature dependence of spring constant and has chemical resistance and corrosion resistance that does not melt or deform at high temperatures. Focusing on its electrical conductivity, light weight, and high elastic modulus, this carbon-based coil spring consisting of all-carbonaceous material is used as the base material, and its entire surface is coated with a metal selected according to the desired function. Used by Conceive that a new multifunction carbon spring to widen the application range can be prepared, thereby completing the present invention.
【００１０】すなわち本発明は、次の通りである。 （１） 有機質線状体をスプリング形状に賦形した後、
炭素化させてなる実質的に炭素から成り、炭素固有の性
質を有する炭素系コイルスプリングの表面が、金属皮膜
によって被覆されてなる金属被覆された炭素系スプリン
グ。That is, the present invention is as follows. (1) After shaping the organic linear body into a spring shape,
A metal-coated carbon-based spring in which the surface of a carbon-based coil spring, which is substantially carbonized and has inherent properties of carbon, is coated with a metal film.
【００１１】（２） 該有機質線状体が、熱可塑性樹
脂、熱硬化性樹脂、リグニン、セルロース、トラガント
ガム、アラビアガム、天然ガム及びその誘導体、糖類、
キチン、キトサンを含む縮合多環芳香族を分子の基本構
造に持つ化合物、ナフタリンスルフォン酸のホルマリン
縮合物、インダンスレン系建染染料及びその中間体、及
びピッチ類、乾留ピッチ類よりなる群より選んだ少なく
とも１種を線状に成形した線状体である前項（１）記載
の金属被覆された炭素系スプリング。(2) The organic linear material is a thermoplastic resin, thermosetting resin, lignin, cellulose, tragacanth gum, gum arabic, natural gum and its derivatives, sugars,
From the group consisting of compounds having condensed polycyclic aromatic compounds containing chitin and chitosan in the basic structure of the molecule, formalin condensates of naphthalene sulfonic acid, indanthrene-based vat dyes and their intermediates, and pitches and carbonized pitches. The metal-coated carbon-based spring according to the above (1), which is a linear body formed by linearly molding at least one selected.
【００１２】（３） 該有機質線状体が、熱可塑性樹
脂、熱硬化性樹脂、リグニン、セルロース、トラガント
ガム、アラビアガム、天然ガム及びその誘導体、糖類、
キチン、キトサンを含む縮合多環芳香族を分子の基本構
造に持つ化合物、ナフタリンスルフォン酸のホルマリン
縮合物、インダンスレン系建染染料及びその中間体及び
ピッチ類、乾留ピッチ類よりなる群より選んだ少なくと
も１種の有機物材料をマトリックス炭素の出発原料と
し、これに炭素繊維、黒鉛ウィスカー、黒鉛粉体、非晶
質炭素粉体の少なくとも１種を均一に分散し、高度に複
合強化した上で線状に成形した線状体である前項（１）
記載の金属被覆された炭素系スプリング。(3) The organic linear material is a thermoplastic resin, thermosetting resin, lignin, cellulose, tragacanth gum, gum arabic, natural gum and its derivatives, sugars,
Selected from the group consisting of compounds having condensed polycyclic aromatic compounds containing chitin and chitosan in the basic structure of the molecule, formalin condensates of naphthalene sulfonic acid, indanthrene-based vat dyes and their intermediates and pitches, and dry-distilled pitches. At least one organic material is used as a starting material for the matrix carbon, and at least one of carbon fiber, graphite whiskers, graphite powder, and amorphous carbon powder is uniformly dispersed in the matrix carbon, and highly composite strengthened. The above (1), which is a linear body formed into a linear shape
A metal-coated carbon-based spring as described.
【００１３】マトリックス炭素の有機物材料としては、
後記の熱可塑性樹脂、及び熱硬化性樹脂をはじめ、リグ
ニン、セルロース、トラガントガム、アラビアガム、天
然ガム及びその誘導体、糖類、キチン、キトサン等のご
とき縮合多環芳香族を分子の基本構造内に持つ化合物及
びナフタレンスルフォン酸のホルマリン縮合物、ジニト
ロナフタレン、ピレン、ピラントロン、ビオラントロ
ン、ベンゾアントロン等から誘導されるインダンスレン
系建染染料及びその中間体及びピッチ類である。As the matrix carbon organic material,
In addition to the thermoplastic resin and thermosetting resin described below, it has condensed polycyclic aromatic compounds such as lignin, cellulose, tragacanth gum, gum arabic, natural gum and its derivatives, sugars, chitin and chitosan in the basic structure of the molecule. Compounds and indanthrene-based vat dyes derived from formalin condensates of naphthalene sulfonic acid, dinitronaphthalene, pyrene, pyranthrone, violanthrone, benzanthrone, and the like, and intermediates and pitches thereof.
【００１４】熱可塑性樹脂類としては、ポリ塩化ビニ
ル、ポリアクリロニトリル、ポリ塩化ビニリデン、後塩
素化ポリ塩化ビニル、ポリ酢酸ビニル、ポリビニルアル
コール、ポリビニルピロリドン、エチルセルロース、カ
ルボキシメチルセルロース、ポリ塩化ビニル・酢酸ビニ
ル共重合体、等の通常の熱可塑性樹脂及びポリフェニレ
ンオキサイド、ポリパラキシレン、ポリスルフォン、ポ
リイミド、ポリアミドイミド、ポリベンツイミダゾー
ル、ポリオキサジアゾール、等の耐熱性熱可塑性樹脂を
用い、Examples of the thermoplastic resins include polyvinyl chloride, polyacrylonitrile, polyvinylidene chloride, post-chlorinated polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polyvinylpyrrolidone, ethyl cellulose, carboxymethyl cellulose, polyvinyl chloride / vinyl acetate. Polymers, such as ordinary thermoplastic resins such as polyphenylene oxide, polyparaxylene, polysulfone, polyimide, polyamideimide, polybenzimidazole, polyoxadiazole, etc. using heat-resistant thermoplastic resin,
【００１５】熱硬化性樹脂としては、フェノール樹脂、
フラン樹脂、エポキシ樹脂、キシレン樹脂、コプナ樹
脂、等が用いられ加熱により、流動すると共に、分子間
架橋を生じ三次元化して硬化し、特別の炭素前駆体化処
理を行うことなく高い炭素残査収率を示すものである。As the thermosetting resin, phenol resin,
Furan resin, epoxy resin, xylene resin, copuna resin, etc. are used and they flow when heated, and at the same time they undergo intermolecular cross-linking and become three-dimensional and harden, resulting in a high carbon residue yield without special carbon precursor treatment. It shows the rate.
【００１６】ピッチ類、乾留ピッチ類とは、石油ピッ
チ、コールタールピッチ、アスファルト、及び、これら
のピッチ類や合成樹脂などの炭化水素化合物の乾留ピッ
チ（４００℃以下の処理物で、炭素残査収率が７５％〜
９５％）である。Pitches and carbonized pitches are petroleum pitch, coal tar pitch, asphalt, and carbonized carbonaceous pitches of hydrocarbon compounds such as these pitches and synthetic resins (treated products at 400 ° C. or less. The rate is 75% ~
95%).
【００１７】本発明において、マトリックス炭素の出発
原料である有機物材料に複合して用いられる複合強化用
黒鉛微粉末について説明を加える。スプリング機能を良
好に発現させるには、高度に発達した黒鉛の結晶端面
（エッジ面）がスプリング線の軸方向に平行に整列する
ように組織配向した複合炭素材料を作製することが重要
である。それ故、黒鉛ウイスカ、高配向性気相熱分解黒
鉛（ＨＯＰＧ）、キッシュ黒鉛、結晶質天然黒鉛が好ま
しく用いられる。黒鉛微粉末の粒度は、目的とするスプ
リングの直径によっても異なるが、最大粒径が数μｍ以
下であることが好ましい。In the present invention, the fine graphite powder for composite reinforcement used in combination with the organic material which is the starting material of the matrix carbon will be described. In order to exhibit the spring function well, it is important to prepare a composite carbon material in which the crystal end faces (edge faces) of highly developed graphite are texture-oriented so that they are aligned parallel to the axial direction of the spring wire. Therefore, graphite whiskers, highly oriented vapor phase pyrolytic graphite (HOPG), quiche graphite, and crystalline natural graphite are preferably used. The particle size of the fine graphite powder varies depending on the diameter of the target spring, but the maximum particle size is preferably several μm or less.
【００１８】第一工程として、本発明の有機質線状体
は、有機高分子物質である、熱可塑性樹脂、熱硬化性樹
脂、天然高分子、合成高分子及びピッチ類、乾留ピッチ
類の内一種または、二種以上を直接熔融させるか、また
は溶剤、可塑剤、炭化促進触媒、架橋剤、重合開始剤、
等を添加して、良く分散させた後ペレット化し、押し出
し成形機等を用いて所望の直径に押し出し成形して製造
される。In the first step, the organic linear material of the present invention is one of organic polymer materials such as thermoplastic resins, thermosetting resins, natural polymers, synthetic polymers and pitches, and carbonized pitches. Alternatively, two or more kinds are directly melted, or a solvent, a plasticizer, a carbonization accelerating catalyst, a crosslinking agent, a polymerization initiator,
Etc. are added and well dispersed, then pelletized, and extruded to a desired diameter using an extrusion molding machine or the like to manufacture.
【００１９】また、複合強化された有機質線状体を得る
には、上記配合物に、目的に応じて、炭素繊維、黒鉛ウ
イスカ、黒鉛粉体、非晶質炭素粉体の一種もしくは二種
以上を高速ブレンダーで均一に分散し、加圧ニーダー、
二本ロールなどの高剪断力が掛けられる混練機を用い
て、十分に混合分散を施し、ペレタイザーにより顆粒化
した後、スクリュー式やプランジャー式等の押出機によ
り所望の直径に高速に押出成形して、押し出し方向に複
合した黒鉛の結晶が良く配列するように配向操作を加え
ることにより得られる。Further, in order to obtain a composite-reinforced organic linear body, one or more kinds of carbon fiber, graphite whiskers, graphite powder, and amorphous carbon powder are added to the above-mentioned composition depending on the purpose. Evenly with a high speed blender, press kneader,
Using a kneading machine such as a two-roll machine with high shearing force, thoroughly mix and disperse, granulate with a pelletizer, and then extrude at a high speed to a desired diameter with an extruder such as a screw type or a plunger type. Then, an orientation operation is performed so that the composite graphite crystals are well aligned in the extrusion direction.
【００２０】第二工程として、コイル状に賦形するに
は、得られた有機線状体及び複合強化有機線状体を所望
のコイル内径を外径とする表面の滑らかな耐熱性材料の
円柱（棒）、またはパイプを形状支持基材として、これ
にコイル状に巻き付けその両端を固定する。In the second step, in order to shape it into a coil shape, the obtained organic linear body and composite reinforced organic linear body are formed into a cylinder of a heat-resistant material having a desired coil inner diameter and a smooth surface. A (rod) or a pipe is used as a shape-supporting base material, and the shape-supporting base material is wound around the shape-supporting base material and fixed at both ends thereof.
【００２１】次に、この生成形体を固定したまま１８０
℃に加熱されたエアー・オーブン中にて、１０時間処理
してプリ・カーサー（炭素前駆体）材料とする。Next, with the green body fixed, 180
A pre-cursor (carbon precursor) material is obtained by processing for 10 hours in an air oven heated to 0 ° C.
【００２２】更に、支持用基材に固定したまま窒素ガス
中で昇温速度を制御しつつ１０００℃迄徐々に加熱し
て、炭素化を終了させ目的とする炭素系スプリングを得
る。Further, while being fixed to the supporting base material, the material is gradually heated to 1000 ° C. in nitrogen gas while controlling the temperature rising rate, and the carbonization is completed to obtain the desired carbon-based spring.
【００２３】目的によっては、更に真空中またはアルゴ
ン気相中で２２００℃まで加熱処理を施し全体を緻密化
することも行われる。Depending on the purpose, a heat treatment may be further performed up to 2200 ° C. in vacuum or in an argon gas phase to densify the whole.
【００２４】次に、得られた炭素質或いは黒鉛質の炭素
系コイルスプリングを基材として、この表面に、所望す
る機能に応じた金属膜を、ＣＶＤ法、イオンプレーティ
ング法、真空蒸着法、イオンスパッタ法、等の乾式法、
電解鍍金法、化学鍍金法、等の湿式法、を利用して堆積
させることにより金属被覆を構築して、全表面が金属被
覆された炭素系スプリングとして完成する。Next, using the obtained carbonaceous or graphitic carbon-based coil spring as a base material, a metal film corresponding to a desired function is formed on the surface thereof by a CVD method, an ion plating method, a vacuum deposition method, Dry method such as ion sputtering method,
A metal coating is constructed by depositing it using a wet method such as an electrolytic plating method, a chemical plating method, etc., and a carbon-based spring having the entire surface metal-coated is completed.
【００２５】[0025]
【実施例】以下に実施例によって、本発明を更に具体的
に説明するが、本発明は、この実施例によって何等限定
されるものではない。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
【００２６】実施例１ 平均重合度７００のストレート塩化ビニル樹脂１００重
量％、に対し、ジオクチルフタレート３０重量％をヘン
シェルミキサー中にて均一分散を行う。次に、加熱ニー
ダーにて材料温度を１５０℃に保ちながら十分に混練す
る。ついで、素材をペレタイザーによってペレット化し
成形用組成物を得た。このペレットをスクリュー型押出
機で直径０．８mmのダイスを用い、脱気を行いつつ１３
０℃で押し出し、ポリ塩化ビニル線状体を得た。これを
平滑な表面を有する、直径１０mmの炭素質ボビンに巻き
付けた。次に、これを空気存在下１００℃１０時間、更
に１８０℃２４時間保持して、不溶、不融のプリ・カー
サー（炭素前駆体）線材とした。次に、これを窒素ガス
中で５００℃までを１０℃／時、５００℃から１０００
℃迄を５０℃／時の昇温速度で昇温し、その後１５００
℃迄を１００℃／時で昇温し、１５００℃で３時間保持
した後、自然冷却して焼成を完了し、支持ボビンより賦
形物を離型して、線径０．４mm、ピッチ０．４mm、コイ
ル内径１０mm、のガラス状炭素質スプリングを得た。次
に、このガラス状炭素質スプリングをＨＣＤ（中空陰極
放電）式イオンプレーティング装置に入れ、１０-4Ｔｏ
ｒｒでＡｒガスをソースガスとして金属チタン（Ｔｉ）
をガラス状炭素質スプリング表面上に１μｍの膜厚で均
一に堆積させた。密着性の良い、ピンホールの無い、良
好な皮膜が形成され、目的とする、金属チタン被覆炭素
スプリングが得られた。Example 1 30% by weight of dioctyl phthalate was uniformly dispersed in 100% by weight of a straight vinyl chloride resin having an average degree of polymerization of 700 in a Henschel mixer. Next, the material is sufficiently kneaded with a heating kneader while keeping the material temperature at 150 ° C. Then, the material was pelletized by a pelletizer to obtain a molding composition. This pellet was degassed with a screw type extruder using a 0.8 mm diameter die.
It was extruded at 0 ° C. to obtain a polyvinyl chloride linear body. This was wound around a carbonaceous bobbin having a smooth surface and a diameter of 10 mm. Next, this was kept in the presence of air at 100 ° C. for 10 hours and further at 180 ° C. for 24 hours to obtain an insoluble and infusible pre-cursor (carbon precursor) wire. Next, this is heated in nitrogen gas up to 500 ° C. at 10 ° C./hour, 500 ° C. to 1000 ° C.
Up to ℃ at a heating rate of 50 ℃ / hour, then 1500
After heating up to 100 ° C at 100 ° C / hour and holding at 1500 ° C for 3 hours, complete cooling by natural cooling and releasing the shaped object from the supporting bobbin, wire diameter 0.4mm, pitch 0 A glassy carbonaceous spring having a diameter of 0.4 mm and a coil inner diameter of 10 mm was obtained. Next, this glassy carbonaceous spring was placed in an HCD (hollow cathode discharge) type ion plating device and 10 −4 To
Metallic titanium (Ti) with Ar gas as source gas at rr
Was uniformly deposited on the surface of the glassy carbonaceous spring in a film thickness of 1 μm. A good film having good adhesion and no pinhole was formed, and the intended metal titanium-coated carbon spring was obtained.
【００２７】実施例２ フラン樹脂（日立化成社製 ヒタフランＶＦ−３０２）
２０重量％、と塩素含有率６５％の塩素化塩化ビニル樹
脂粉末（（株）日本カーバイド社製 ニカテンプＴ−０
２５）４０重量％、に平均粒度２μｍの天然黒鉛粉末
（（株）日本黒鉛社製 ＣＳＳＰ）４０重量％及び可塑
剤として、ジオクチルフタレート１０重量％を加え、ヘ
ンシェル・ミキサーを用いて分散した後、表面温度を１
２０℃に保ったミキシング用二本ロールを用いて十分に
混練を繰り返してシート状組成物を得、プランジャー型
油圧押し出し成形機により、５ｍ／秒の吐出速度で真空
押し出し成形を行い、直径３mmの黒鉛強化有機質線状体
を得た。これを平滑な表面を有する、直径１３mmの炭素
質ボビンに巻き付けた。この後の処理は実施例1と同様に
行って、炭素化させ支持ボビンより賦形物を離型し、線径
２mm、ピッチ１．５mm、コイル内径１３mm、の黒鉛複合炭
素質スプリングを得た。次に、市販工業用クロムめつき
浴（日本エムアンドティー（株）社製 ＨＥＥＦ浴）を
満たした鍍金槽中に黒鉛複合炭素質スプリングを浸漬
し、浴温５０℃、電流密度５０Ａ／ｄｍ2で電気鍍金を
行って、平均膜厚２μｍの金属クロムで被覆された目的
とする金属クロム被覆炭素スプリングが得られた。Example 2 Furan resin (Hitafuran VF-302 manufactured by Hitachi Chemical Co., Ltd.)
Chlorinated vinyl chloride resin powder with 20% by weight and chlorine content of 65% (Nikatemp T-0 manufactured by Nippon Carbide Co., Ltd.)
25) 40% by weight, 40% by weight of natural graphite powder having an average particle size of 2 μm (CSSP manufactured by Nippon Graphite Co., Ltd.) and 10% by weight of dioctyl phthalate as a plasticizer were added and dispersed using a Henschel mixer. Surface temperature is 1
A sheet-like composition was obtained by sufficiently kneading using a two-roll mixing roll kept at 20 ° C., and a plunger-type hydraulic extrusion molding machine was used to perform vacuum extrusion molding at a discharge speed of 5 m / sec to obtain a diameter of 3 mm. A graphite-reinforced organic linear body of was obtained. This was wound around a carbonaceous bobbin having a smooth surface and a diameter of 13 mm. The subsequent treatment was carried out in the same manner as in Example 1 to carbonize and release the shaped product from the supporting bobbin to obtain a graphite composite carbonaceous spring having a wire diameter of 2 mm, a pitch of 1.5 mm and a coil inner diameter of 13 mm. . Next, the graphite composite carbonaceous spring is immersed in a plating tank filled with a commercially available industrial chromium plating bath (HEEF bath manufactured by Nippon M & T Co., Ltd.), and the bath temperature is 50 ° C. and the current density is 50 A / dm 2. Was electroplated to obtain a target metal-chrome-coated carbon spring coated with metal chromium having an average film thickness of 2 μm.
【００２８】実施例３ 実施例２で得られた黒鉛複合炭素質スプリングを基材と
して、ＣＶＤ反応槽である管状炉中でセットし、基材に
直接通電して抵抗発熱させ７００℃に保ち、反応槽中を
真空にしてから、一方よりキャリアガスとして水素を六
塩化タングステン（ＷＣｌ6）の入った２９０℃の気化
室に送り、水素と共に気化したＷＣｌ6を反応槽内に導
入してＷＣｌ6を熱分解及び還元反応させて、基材表面
に金属タングステンを堆積させた。この反応式は、以下
の通りである。 ＷＣｌ6＋３Ｈ2−−−−> Ｗ＋６ＨＣｌ （７００
℃） 基材との密着性は、良好であり、密度も高く、素地への
倣い性が良く炭素表面に、平均膜厚０．５μｍの金属タ
ングステンが被覆された目的とする金属タングステン被
覆炭素スプリングが得られた。Example 3 Using the graphite composite carbonaceous spring obtained in Example 2 as a base material, the graphite composite carbonaceous spring was set in a tubular furnace, which is a CVD reaction tank, and the base material was directly energized to generate resistance heat and kept at 700 ° C. the reaction vessel after the vacuum, whereas more hydrogen feed to the vaporization chamber containing a 290 ° C. of tungsten hexachloride (WCl 6) as the carrier gas, WCl 6 vaporized together with hydrogen is introduced into the reaction vessel WCl 6 Was thermally decomposed and reduced to deposit metallic tungsten on the surface of the substrate. This reaction formula is as follows. WCl 6 + 3H 2 −−−−> W + 6HCl (700
℃) Adhesion to the base material is good, the density is high, the conformability to the substrate is good, and the target metal tungsten-coated carbon spring in which the carbon surface is coated with metal tungsten having an average film thickness of 0.5 μm was gotten.
【００２９】[0029]
【発明の効果】本願発明の金属被覆炭素系スプリング
は、金属やセラミックスのスプリングに比べ軽量で、空
気中で９００℃迄のバネ定数の変化が極めて小さく温度
依存性は殆ど無視でき、応力−歪の関係はフックの法則
に従った。基材の炭素系スプリングは、アルゴンガスな
どの不活性気相中では、各々の焼成温度以下の温度では
全く劣化が観察されず、精度高いバネ定数を維持した
が、２５０℃の空気中では６ケ月間で曲げ強度が初期の
２０％程度まで低下する。金属クロム被覆炭素スプリン
グでは殆ど変化が見られず、３×１０6サイクルの繰り
返し伸縮テストの結果でも何等異常は認められなかっ
た。また、表面は金属光沢のある滑らかな美観を備えて
いる。更に、電気伝導度は、基材炭素よりも二桁以上も
向上し、金属に近いものとなった。この様に、本願発明
は、基材炭素スプリングに金属被覆を施すことによっ
て、炭素材料の持つ欠点を補い、その長所を遺憾なく発
揮させることを可能とするものである。The metal-coated carbon-based spring of the present invention is lighter in weight than metal or ceramic springs, has a very small change in spring constant up to 900 ° C. in air, and its temperature dependence can be neglected. The relationship followed Hooke's law. The carbon-based spring as the base material did not show any deterioration at temperatures below the respective firing temperatures in an inert gas phase such as argon gas, and maintained a highly accurate spring constant. The bending strength decreases to about 20% of the initial value in a month. Almost no change was observed in the metal chromium-coated carbon spring, and no abnormality was found in the result of the repeated expansion and contraction test of 3 × 10 6 cycles. In addition, the surface has a smooth aesthetic with a metallic luster. Furthermore, the electrical conductivity was improved by more than two orders of magnitude over the carbon base material, and was close to that of metal. As described above, the present invention makes it possible to compensate for the drawbacks of the carbon material and fully exert its advantages by applying a metal coating to the base carbon spring.
Claims (3)
た後、炭素化させてなる実質的に炭素から成り、炭素固
有の性質を有する炭素系コイルスプリングの表面が、金
属皮膜によって被覆されてなる金属被覆された炭素系ス
プリング。1. A surface of a carbon-based coil spring, which is formed by shaping an organic linear body into a spring shape and then carbonizing the carbon material, and has a characteristic peculiar to carbon, is coated with a metal film. A carbon-based spring coated with metal.
化性樹脂、リグニン、セルロース、トラガントガム、ア
ラビアガム、天然ガム及びその誘導体、糖類、キチン、
キトサンを含む縮合多環芳香族を分子の基本構造に持つ
化合物、ナフタリンスルフォン酸のホルマリン縮合物、 インダンスレン系建染染料及びその中間体、及びピッチ
類、乾留ピッチ類よりなる群より選んだ少なくとも１種
を線状に成形した線状体である請求項１記載の金属被覆
された炭素系スプリング。2. The organic linear material is a thermoplastic resin, a thermosetting resin, lignin, cellulose, tragacanth gum, gum arabic, natural gum and its derivatives, sugars, chitin,
Selected from the group consisting of compounds having condensed polycyclic aromatics including chitosan in the basic structure of the molecule, formalin condensate of naphthalene sulfonic acid, indanthrene-based vat dyes and their intermediates, and pitches and carbonized pitches The metal-coated carbon-based spring according to claim 1, which is a linear body in which at least one kind is formed into a linear shape.
化性樹脂、リグニン、セルロース、トラガントガム、ア
ラビアガム、天然ガム及びその誘導体、糖類、キチン、
キトサンを含む縮合多環芳香族を分子の基本構造に持つ
化合物、ナフタリンスルフォン酸のホルマリン縮合物、
インダンスレン系建染染料及びその中間体及びピッチ
類、乾留ピッチ類よりなる群より選んだ少なくとも１種
の有機物材料をマトリックス炭素の出発原料とし、これ
に炭素繊維、黒鉛ウィスカー、黒鉛粉体、非晶質炭素粉
体の少なくとも１種を均一に分散し、高度に複合強化し
た上で線状に成形した線状体である請求項１記載の金属
被覆された炭素系スプリング。3. The organic linear material is a thermoplastic resin, thermosetting resin, lignin, cellulose, tragacanth gum, gum arabic, natural gum and its derivatives, sugars, chitin,
A compound having a condensed polycyclic aromatic compound containing chitosan in the basic structure of the molecule, a formalin condensate of naphthalene sulfonic acid,
At least one organic material selected from the group consisting of indanthrene-based vat dyes and their intermediates, pitches, and carbonized pitches is used as a starting material for matrix carbon, and carbon fiber, graphite whiskers, graphite powder, The metal-coated carbon-based spring according to claim 1, which is a linear body in which at least one kind of amorphous carbon powder is uniformly dispersed, highly composite-reinforced, and then linearly molded.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4299828A JPH06144811A (en) | 1992-11-10 | 1992-11-10 | Metal-coated carbonaceous spring |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4299828A JPH06144811A (en) | 1992-11-10 | 1992-11-10 | Metal-coated carbonaceous spring |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06144811A true JPH06144811A (en) | 1994-05-24 |
Family
ID=17877415
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4299828A Withdrawn JPH06144811A (en) | 1992-11-10 | 1992-11-10 | Metal-coated carbonaceous spring |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06144811A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1988004922A1 (en) * | 1986-12-25 | 1988-07-14 | Teysan Pharmaceuticals Co., Ltd. | Slowly soluble granule and persistently effective composite granule prepared therefrom |
| EP2017241A2 (en) | 2007-06-07 | 2009-01-21 | Ibiden Co., Ltd. | Graphite material and a method of producing graphite material |
| JP2009242196A (en) * | 2008-03-31 | 2009-10-22 | Ibiden Co Ltd | Graphite elastic body and its manufacturing method |
| CN104372313A (en) * | 2014-09-29 | 2015-02-25 | 上海科慧太阳能技术有限公司 | Preparation method of back electrode of thin film solar cell and thin film solar cell |
| CN112812801A (en) * | 2021-01-13 | 2021-05-18 | 中国石油大学(华东) | Preparation process of mesophase pitch and pitch-based carbon fiber |
-
1992
- 1992-11-10 JP JP4299828A patent/JPH06144811A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1988004922A1 (en) * | 1986-12-25 | 1988-07-14 | Teysan Pharmaceuticals Co., Ltd. | Slowly soluble granule and persistently effective composite granule prepared therefrom |
| EP2017241A2 (en) | 2007-06-07 | 2009-01-21 | Ibiden Co., Ltd. | Graphite material and a method of producing graphite material |
| US8048515B2 (en) | 2007-06-07 | 2011-11-01 | Ibiden Co., Ltd. | Graphite material and a method of producing graphite material |
| US8367196B2 (en) | 2007-06-07 | 2013-02-05 | Ibiden Co., Ltd. | Graphite material |
| JP2009242196A (en) * | 2008-03-31 | 2009-10-22 | Ibiden Co Ltd | Graphite elastic body and its manufacturing method |
| CN104372313A (en) * | 2014-09-29 | 2015-02-25 | 上海科慧太阳能技术有限公司 | Preparation method of back electrode of thin film solar cell and thin film solar cell |
| CN112812801A (en) * | 2021-01-13 | 2021-05-18 | 中国石油大学(华东) | Preparation process of mesophase pitch and pitch-based carbon fiber |
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| A300 | Withdrawal of application because of no request for examination |
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