JP4825001B2 - Thermal spray deposition method for super engineering plastics laminated film - Google Patents
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Description
本発明は、ＰＥＥＫ、ＰＰＳまたはＰＥＫの単体材料もしくは複合材料を基材にフレーム溶射して上記複合材料の被膜を形成する方法およびそれにより得られたスーパーエンプラ積層膜に関するものである。 The present invention relates to a method for forming a coating film of a composite material by flame spraying a single material or composite material of PEEK, PPS or PEK on a base material, and a super engineering plastic laminated film obtained thereby.
従来、ＰＥＥＫ複合材料の溶射適用方法として、例えば特開２０００−９６２０３に、ＨＶＯＦプロセスを用いた方法が開示されている。
この方法では、基材としてのステンレス鋼に、前処理としてクリーニング及びグリットブラストする。
次に、約７０％のＰＥＥＫを約２０％のＰＴＦＥ及び約１０％のカーボンと混合して、ＰＥＥＫ複合材料を調整する。この際に最適の粒径は、ＰＥＥＫについては約７０μｍ、ＰＴＦＥについては約５３μｍ、カーボン粒子については約６μｍとする。
そして、前記ステンレス鋼には、ニッケル−アルミニウム合金等の一層の金属材料をアーク噴霧して基材上に結合層を一体に形成する。
次に、ＨＶＯＦプロセスを使用し、ＰＥＥＫ複合材料混合物を基材及び結合層に適用し、ＰＥＥＫ複合材料層を形成させる。
付着後、焼鈍プロセスによりＰＥＥＫ複合材料層を含む全体を約４００℃まで加熱し、その温度に約３０分間に亘って保持し、約２７０℃に冷却して１０分間保持し、その後約６０℃以下に冷却しコーティングを完了する。
In this method, cleaning and grit blasting are performed on stainless steel as a base material as a pretreatment.
Next, about 70% PEEK is mixed with about 20% PTFE and about 10% carbon to prepare a PEEK composite. The optimum particle size at this time is about 70 μm for PEEK, about 53 μm for PTFE, and about 6 μm for carbon particles.
Then, a single layer of a metal material such as a nickel-aluminum alloy is arc sprayed on the stainless steel to integrally form a bonding layer on the substrate.
Next, using a HVOF process, the PEEK composite mixture is applied to the substrate and tie layer to form a PEEK composite layer.
After deposition, the entire PEEK composite layer including the PEEK composite layer is heated to about 400 ° C. by an annealing process, held at that temperature for about 30 minutes, cooled to about 270 ° C. and held for 10 minutes, and then about 60 ° C. or less. Cool to complete the coating.
前記従来構成では、溶射の前に結合層を設ける必要があり、また溶射の後にも高温での長時間の加熱が必要となり、工程数が多く繁雑であると共に、高温によってＰＥＥＫ複合樹脂層の密着性が劣化し、厚みの範囲で３５０〜４６０μｍに限られる欠点があった。
この発明は上記問題点を解決するものであって、その主たる課題は、プライマーを基材に塗って焼成し、成膜後にＰＥＥＫ単体材料もしくは複合材料、ＰＰＳ単体材料もしくは複合材料、ＰＥＫ単体材料もしくは複合材料のいずれか１つを粉末式フレーム溶射によって生成されるスーパーエンプラ積層膜の溶射成膜法を提供することにある。
これは、基材の素材が限定されることなく、フレーム溶射によって簡単にＰＥＥＫ、ＰＰＳまたはＰＥＫの単体材料もしくは複合材料を成膜することができ、且つ密着性が高まるので、被膜の厚みを薄くも厚くも設計することができ、滑性、耐久性、耐摩耗性に優れたスーパーエンプラ積層膜の溶射成膜法を提供することにある。
In the conventional configuration, it is necessary to provide a bonding layer before spraying, and it is necessary to heat for a long time at a high temperature after spraying, and the number of processes is complicated, and the adhesion of the PEEK composite resin layer due to the high temperature. The properties deteriorated and the thickness is limited to 350 to 460 μm.
The present invention solves the above-mentioned problems, and the main problem is that a primer is applied to a substrate and baked, and after film formation, a PEEK simple material or composite material, a PPS simple material or composite material, a PEK simple material or An object of the present invention is to provide a method for thermal spray deposition of a super engineering plastic laminated film produced by powder flame spraying of any one of the composite materials.
This is because the material of the base material is not limited, and PEEK, PPS or PEK simple material or composite material can be easily formed by flame spraying, and the adhesion is increased, so the thickness of the coating is reduced. both can be designed thicker to provide lubricity, durability, thermal spray deposition method excellent super engineering plastics laminate film in wear resistance.
この発明は、上記課題を解決するために、請求項１のスーパーエンプラ積層膜の溶射成膜法の発明では、
基材に所定のプライマーを塗布して焼成し、成膜後にＰＥＥＫ、ＰＰＳ、またはＰＥＫの単体材料もしくは複合材料を粉末式フレーム溶射によって付着させたスーパーエンプラ積層膜の溶射成膜法において、
プライマーが粉末式フレーム溶射に用いる母材樹脂と同じＰＥＥＫ樹脂、ＰＰＳ樹脂またはＰＥＫ樹脂からなるディスパージョンポリマーであり、
前記基材に上記プライマーをコーティングし焼成して１０〜５０μｍの厚みのプライマー薄膜層を形成し、
該プライマー薄膜層に、粉体形態で前記母材樹脂となるＰＥＥＫ、ＰＰＳ、またはＰＥＫの単体材料もしくは複合材料を粉末式フレーム溶射によって付着し焼鈍することなく１００μｍ〜３ｍｍの厚みの範囲内で単体材料層または複合材料層を形成してなることを特徴とする。
In order to solve the above-described problems, the present invention provides a thermal engineering film- forming method for a super engineering plastic laminate film according to
In a thermal spray film-forming method of a super engineering plastic laminate film in which a predetermined primer is applied to a substrate and baked, and PEEK, PPS, or a single material or composite material of PEK is attached by powder-type flame spraying after film formation,
The primer is a dispersion polymer made of the same PEEK resin, PPS resin or PEK resin as the base resin used for powder flame spraying,
The primer is coated on the substrate and baked to form a primer thin film layer having a thickness of 10 to 50 μm,
A single material or composite material of PEEK, PPS, or PEK that becomes the matrix resin in powder form is attached to the primer thin film layer by powder-type flame spraying, and is alone within a thickness range of 100 μm to 3 mm without annealing. A material layer or a composite material layer is formed.
請求項２の発明では、
基材が、ステンレス、鉄、アルミニウムの金属またはセラミックからなることを特徴とする。
In the invention of
The substrate is made of stainless steel, iron, aluminum metal or ceramic.
この発明は、プライマー層を設けることで金属酸化防止及び密着強度の強化が得られ、簡単に処理でき、更にコストパフォーマンスを高めることができる。
また、基材に溶射されたＰＥＥＫ複合材料層は炭化せず、酸化度が低いので緻密性、密着性が高く、滑性、耐久性、耐摩耗性にすぐれる。
また、溶射方法として粉末式フレーム溶射を用いることができる。
さらに、複合材料として、ＰＥＥＫ樹脂、ＰＰＳ樹脂、またはＰＥＫ樹脂のいずれか１つにセラミックを添加することで、硬度や滑りなどの性能的付加価値を有することができる。
単体材料層および複合材料層を形成した積層膜の膜厚を３ｍｍまで成形することができる。
In the present invention, by providing the primer layer, the metal oxidation prevention and the adhesion strength can be enhanced, the treatment can be easily performed, and the cost performance can be further improved.
In addition, the PEEK composite material layer sprayed onto the base material is not carbonized and has a low degree of oxidation, so it has high density and high adhesion, and is excellent in lubricity, durability and wear resistance.
Further, powder flame spraying can be used as a spraying method.
Further, by adding ceramic to any one of the PEEK resin, the PPS resin, and the PEK resin as the composite material, performance added values such as hardness and slip can be obtained.
The thickness of the laminated film on which the single material layer and the composite material layer are formed can be molded up to 3 mm.
以下に、この発明を、ＰＥＥＫ樹脂を用いた場合の単体材料または複合材料の溶射方法およびＰＥＥＫ単体材料層及び複合材料層についての好適実施例について説明する。 Below, this invention is demonstrated about the suitable example about the spraying method of the single-piece | unit material or composite material at the time of using PEEK resin, and a PEEK single-material layer and a composite material layer.
本実施例では、以下の基材にＰＥＥＫ単体材料またはＰＥＥＫ複合材料を溶射する方法からなる。
ここで基材１は、ＰＥＥＫ樹脂の溶融温度（約３５０℃）に耐えられる素材であれば特に限定されるものではないが、例えばステンレス、鉄、アルミニウムなどの金属や、セラミックなどであってもよい。
In this embodiment, the following base material consists of a method of spraying a PEEK simple substance or a PEEK composite material.
Here, the
実施例１は、図１に示すように、まず第１工程として基材１に前処理を施す工程からなる。
この工程中、好ましくは、コーティングが施されるべき表面から塵埃、水分、オイル、及び他の汚染物を除去することによって基材をクリーニングする。
更に、付着性を向上させるため、コーティングが施されるべき表面を公知のブラスト処理により粗くすることが望ましい。
As shown in FIG. 1, Example 1 includes a step of pretreating the
During this process, the substrate is preferably cleaned by removing dust, moisture, oil, and other contaminants from the surface to be coated.
Furthermore, in order to improve adhesion, it is desirable to roughen the surface to be coated by a known blasting process.
次に、第２工程として、上記基材１に、プライマーとして、溶射の母材樹脂と同じ樹脂としてのＰＥＥＫ樹脂からなるディスパ−ジョンポリマーをスプレーでコーティングし、１０〜５０μｍ程度の厚みのＰＥＥＫ薄膜層２を形成する。
本実施例では、塗布したＰＥＥＫ樹脂を公知の方法で塗装及び焼成を行った。
ここでプライマーの焼成温度は上記実施例に限定されるものではない。
Next, as a second step, the
In this example, the applied PEEK resin was painted and baked by a known method.
Here, the firing temperature of the primer is not limited to the above embodiment.
そして、第３工程では、上記プライマーの焼成による成膜後に、前記粉体状のＰＥＥＫ複合材料を前記基材１のＰＥＥＫ薄膜層２上に溶射によって適用する。
これにより成膜されたＰＥＥＫ単体材料層およびＰＥＥＫ複合材料層３は基材との密着性が極めて高いので、１００μｍ〜３ｍｍの厚みの範囲内で設定することができる。
In the third step, the powdery PEEK composite material is applied onto the PEEK
Since the PEEK simple substance layer and the PEEK
ここで溶射は、アセチレン（プロパン）炎を熱源とし、ＰＥＥＫ単体材料またはＰＥＥＫ複合材料の粉末材を溶融噴射し基材のＰＥＥＫ薄膜層２上に前記ＰＥＥＫ単体材料またはＰＥＥＫ複合材料の皮膜を形成する粉末式フレーム溶射を用いることを特徴としている。
Here, thermal spraying uses an acetylene (propane) flame as a heat source, melts and jets a powder of PEEK simple material or PEEK composite material, and forms a film of the PEEK simple material or PEEK composite material on the PEEK
この粉末式フレーム溶射法では、前記ＰＥＥＫ単体材料またはＰＥＥＫ複合材料を所定の設計厚みまで溶射した後、フュージング（溶融）処理によって開孔気孔を無くし、緻密性を高めることができる。 In this powder-type flame spraying method, after the PEEK single material or PEEK composite material is sprayed to a predetermined design thickness, the pores are eliminated by fusing (melting), thereby improving the denseness.
従来構成では、ＨＶＯＦシステムの処理後に、付着後焼鈍プロセスとして４００℃で３０分程度維持し、約２７０℃に冷却して１０分間保持し、その後約６０℃以下に冷却する必要があるが、本発明ではそのような加熱をしなくとも成膜することができる。
必要に応じて、加熱をする場合であっても、溶射後に３８０℃以上加熱すればよい。
In the conventional configuration, after the treatment of the HVOF system, it is necessary to maintain the post-adhesion annealing process at 400 ° C. for about 30 minutes, cool to about 270 ° C., hold for 10 minutes, and then cool to about 60 ° C. or less. In the invention, the film can be formed without such heating.
Even if it is a case where it heats as needed, what is necessary is just to heat 380 degreeC or more after thermal spraying.
溶射に際して、基材１のコーティングとして使用するためのポリマー材料として粉体形態のＰＥＥＫ複合材料を調製する（この調製は、第３工程の溶射の前であればよく、第１工程や第２工程の前に予め行ってもよい）。
本実施例では、ＰＥＥＫ樹脂単体またはＰＥＥＫ樹脂とセラミックの混合物からなっている。
At the time of thermal spraying, a PEEK composite material in powder form is prepared as a polymer material to be used as a coating for the substrate 1 (this preparation may be performed before the thermal spraying in the third step, and the first step and the second step) May be done in advance).
In this embodiment, it is made of PEEK resin alone or a mixture of PEEK resin and ceramic.
この発明では、セラミックと共に、あるいはセラミックに替えてアルミナ（Ａｌ２Ｏ３）、バナジウム（ＢＮ）、ジルコニア（Ｚｒ）、タングステン、トルマリンなどのいずれか１または複数を用いることができる。
ＰＥＥＫ樹脂に対するこれらの混合割合は１〜５０％の範囲内であって、混合物と用途に応じて適宜に混合割合を変更することができる。
In the present invention, any one or more of alumina (Al 2 O 3 ), vanadium (BN), zirconia (Zr), tungsten, tourmaline and the like can be used together with or in place of ceramic.
These mixing ratios with respect to the PEEK resin are in the range of 1 to 50%, and the mixing ratio can be appropriately changed according to the mixture and the application.
上記実施例１で成膜されたＰＥＥＫ単体材料層またはＰＥＥＫ複合材料層３は、溶射温度が低く高温に長時間さらされることがないので、炭化せず、酸化度が低くなり、緻密性を高めることができる。
これにより、極めて低有孔度のコーティングをおこなうことができると共に、摩擦係数が低く、耐蝕性、耐摩耗性に優れる。
The PEEK single material layer or the PEEK
As a result, it is possible to perform coating with a very low porosity, a low friction coefficient, and excellent corrosion resistance and wear resistance.
また、後加工として、表面平滑性を出すために、電気炉または真空炉にて焼き戻しを行うことが効果的であることが確認された。
更に、製品を５％の希硫酸の溶液中に浸漬し、８時間加熱して７０〜９０℃とし、１６時間保温するサイクル試験を行った結果、１ヶ月以上異常は見られなかった。これにより耐蝕性があることも確認された。
In addition, it was confirmed that it is effective to perform tempering in an electric furnace or a vacuum furnace in order to obtain surface smoothness as post-processing.
Furthermore, the product was immersed in a 5% dilute sulfuric acid solution, heated for 8 hours to 70-90 ° C., and kept for 16 hours. As a result, no abnormality was observed for more than one month. Thereby, it was also confirmed that there was corrosion resistance.
その他、この発明は上記各実施例に限定されるものではなく、要するにこの発明の要旨を変更しない範囲で種々設計変更しうる。 In addition, the present invention is not limited to the above embodiments, and various design changes can be made without departing from the scope of the present invention.
この発明では、プライマーとして、粉末式フレーム溶射に用いる熱可塑性樹脂複合材料の母材樹脂と同じ樹脂を用いることが好ましいが、基材と溶射する熱可塑性樹脂複合材料との密着性を有するものであれば他の樹脂を用いてもよい。
その他、この発明は上記各実施例に限定されるものではなく、要するにこの発明の要旨を変更しない範囲で種々設計変更しうる。
In this invention, it is preferable to use the same resin as the base resin of the thermoplastic resin composite material used for powder flame spraying as the primer, but it has adhesion between the base material and the thermoplastic resin composite material to be sprayed. Other resins may be used as long as they are present.
In addition, the present invention is not limited to the above embodiments, and various design changes can be made without departing from the scope of the present invention.
１ 基材
２ ＰＥＥＫ薄膜層
３ ＰＥＥＫ複合材料層
DESCRIPTION OF
Claims (2)
プライマーが粉末式フレーム溶射に用いる母材樹脂と同じＰＥＥＫ樹脂、ＰＰＳ樹脂またはＰＥＫ樹脂からなるディスパージョンポリマーであり、
前記基材に上記プライマーをコーティングし焼成して１０〜５０μｍの厚みのプライマー薄膜層を形成し、
該プライマー薄膜層に、粉体形態で前記母材樹脂となるＰＥＥＫ、ＰＰＳ、またはＰＥＫの単体材料もしくは複合材料を粉末式フレーム溶射によって付着し焼鈍することなく１００μｍ〜３ｍｍの厚みの範囲内で単体材料層または複合材料層を形成してなることを特徴とするスーパーエンプラ積層膜の溶射成膜法。 In a thermal spray film-forming method of a super engineering plastic laminate film in which a predetermined primer is applied to a substrate and baked, and PEEK, PPS, or a single material or composite material of PEK is attached by powder-type flame spraying after film formation,
The primer is a dispersion polymer made of the same PEEK resin, PPS resin or PEK resin as the base resin used for powder flame spraying,
The primer is coated on the substrate and baked to form a primer thin film layer having a thickness of 10 to 50 μm,
A single material or composite material of PEEK, PPS, or PEK that becomes the matrix resin in powder form is attached to the primer thin film layer by powder-type flame spraying, and is alone within a thickness range of 100 μm to 3 mm without annealing. A method for thermal spraying a super engineering plastic laminated film, comprising forming a material layer or a composite material layer.
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| JP2003043306A (en) * | 2001-07-31 | 2003-02-13 | Takahiko Mukoda | Connector component for multicore optical fiber and manufacturing method |
| JP3905730B2 (en) * | 2001-08-07 | 2007-04-18 | 日建塗装工業株式会社 | Composite resin film and method of forming composite resin film |
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| JP2014128862A (en) * | 2012-12-28 | 2014-07-10 | Shuji Iwata | Disc-shaped carrier |
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