JP6783643B2 - Carbon material bonding agent and bonding method - Google Patents
Carbon material bonding agent and bonding method Download PDFInfo
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Description
本発明は、黒鉛ブロック材料（押し出し材、竪込め成形材、ＣＩＰ材やＨＩＰ材）、炭素繊維強化炭素材料（Ｃ／Ｃ複合材料）、多孔質炭素材料、膨張黒鉛シート、黒鉛シ−トや膨張黒鉛シ−ト等の炭素材料の接合剤及び接合方法に関する。 The present invention relates to graphite block materials (extruded materials, vertical molding materials, CIP materials and HIP materials), carbon fiber reinforced carbon materials (C / C composite materials), porous carbon materials, expanded graphite sheets, graphite sheets and the like. The present invention relates to a bonding agent and a bonding method for carbon materials such as expanded graphite sheets.
炭素材料を接合するには、炭素材料用の接合剤で仮接合し、加熱によって接合剤を硬化させ、更に熱処理によって炭素化するのが一般的である。炭素材料用の接合剤としては、加熱処理による炭素化中に揮散する成分が少なく、炭素化された後も炭素材を強固に接合することや、更には、炭素材料を接合して製造した製品の使用環境によっては、高温（１０００℃以上）においても接合強度が低下しないということが必要であり、特に半導体製造に使用される高強度炭素材料の接合、高温においても高い接合強度が必要とされる。 In order to bond carbon materials, it is common to temporarily join them with a bonding agent for carbon materials, cure the bonding agent by heating, and then carbonize by heat treatment. As a bonding agent for carbon materials, there are few components that volatilize during carbonization by heat treatment, and even after carbonization, the carbon materials are firmly bonded, and further, products manufactured by bonding carbon materials. Depending on the usage environment, it is necessary that the bonding strength does not decrease even at high temperatures (1000 ° C or higher), and in particular, bonding of high-strength carbon materials used in semiconductor manufacturing and high bonding strength even at high temperatures are required. To.
従来、炭素材料の接合は、炭素前駆体として樹脂単独、あるいは樹脂にタール、又はピッチを添加した混合物とコークス粉末又は黒鉛粉末から成るカーボンセメントを接合剤として炭素材に塗布して接合し、加熱によって接合剤中の樹脂を硬化させ、次いで非酸化性雰囲気中で炭素化することによっておこなっている。
炭素（または黒鉛）をマトリクスとし、炭素繊維（または黒鉛繊維）を強化材とするＣ／Ｃ複合材料は、その機械的強度が著しく高いので、各種の構造部材として利用されている。また、導電性を有することから抵抗発熱体としても使用されている。
Ｃ／Ｃ複合材料の個々の部材を接合して、目的形状の製品に組立てがおこなわれており、組立体が常温において使用される場合にはＣ／Ｃ複合材料部材間を接合強度の大きい各種合成樹脂の接合剤を用いて接合するだけでも充分であるが、組立体が、発熱体として使用される場合には各部材間の接合部は高温に曝され、しかも導電性でなければならないということから、前記の合成樹脂系の接合剤による接合では要求が満たされない。
このような場合の接合においては、接合剤として炭素（または黒鉛）粉末とフェノール樹脂のような合成樹脂を所定の割合で混合した液状またはペースト状の接合剤を選定し、この接合剤をＣ／Ｃコンポジット部材の接合部に塗布して両部材を圧着し、その状態を保持して焼成して合成樹脂を炭化するという方法が採られている。
Conventionally, carbon materials are bonded by applying a carbon cement as a bonding agent to the carbon material alone, or a mixture of a mixture of tar or pitch added to the resin and coke powder or graphite powder as a carbon precursor, and then heating. This is done by curing the resin in the cementing agent and then carbonizing it in a non-oxidizing atmosphere.
A C / C composite material using carbon (or graphite) as a matrix and carbon fibers (or graphite fibers) as a reinforcing material is used as various structural members because of its extremely high mechanical strength. It is also used as a resistance heating element because it has conductivity.
Individual members of the C / C composite material are joined to assemble a product of the desired shape, and when the assembly is used at room temperature, various types of C / C composite material members with high joining strength are connected. It is sufficient to join using a synthetic resin bonding agent, but when the assembly is used as a heating element, the joints between the members must be exposed to high temperatures and must be conductive. Therefore, the requirement is not satisfied by the bonding with the synthetic resin-based bonding agent.
In such a case, a liquid or paste-like bonding agent in which carbon (or graphite) powder and a synthetic resin such as phenol resin are mixed at a predetermined ratio is selected as the bonding agent, and this bonding agent is used as C /. A method is adopted in which the coating is applied to the joint portion of the C composite member, both members are pressure-bonded, the state is maintained, and the synthetic resin is carbonized.
また、炭素材料の接合部に炭素繊維と炭素前駆体である樹脂とからなるプリプレグを介在させ、炭素材料と一体化させた状態でプリプレグを加圧しながら加熱して樹脂を硬化させて接合した後、非酸化性雰囲気中にて焼成する接合方法も知られている。 Further, after a prepreg composed of carbon fiber and a resin which is a carbon precursor is interposed in the joint portion of the carbon material and heated while pressurizing the prepreg in a state of being integrated with the carbon material, the resin is cured and joined. , A bonding method of firing in a non-oxidizing atmosphere is also known.
これらの接合方法において用いる樹脂としては、炭素材料との濡れ性が良く、しかも高い炭化収率を示すことが必要なことから、フェノール樹脂、フラン樹脂、あるいはタール又はピッチ相溶性のフェノール樹脂等が用いられていた。タールやピッチは、炭化収率を稼ぐための増量剤として使用されるものである。
しかし、その接合部には空隙が認められ、接合部の強度は基材強度より低く、電気抵抗値は基材より高く導電性の低いものであり、炭素材料の設計上の自由度は高いとは言えなかった。
As the resin used in these bonding methods, a phenol resin, a furan resin, a tar- or pitch-compatible phenol resin, or the like is used because it is necessary to have good wettability with a carbon material and to show a high carbonization yield. It was used. Tar and pitch are used as bulking agents to increase the carbonization yield.
However, voids are found in the joint, the strength of the joint is lower than the strength of the base material, the electrical resistance value is higher than that of the base material and the conductivity is low, and the degree of freedom in designing the carbon material is high. I couldn't say.
従来の接合剤では、焼成後の接合部に空隙が観察され、このため接合強度は基材の炭素材料より低く、接合部を挟んだ炭素材料の電気抵抗値は基材の炭素材料よりも高くなって導電性が低下するという問題がある。
本発明は、炭素材料の接合部の強度を炭素材料自体の強度と同等以上とし、また、接合部の電気抵抗値を基材炭素材料の電気抵抗値と同等以下とする接合剤及び接合方法を提供することにある。
In the conventional bonding agent, voids are observed in the joint after firing, so that the bonding strength is lower than that of the carbon material of the base material, and the electric resistance value of the carbon material sandwiching the joint is higher than that of the carbon material of the base material. There is a problem that the conductivity is lowered.
The present invention provides a bonding agent and a bonding method in which the strength of the joint portion of the carbon material is equal to or higher than the strength of the carbon material itself, and the electrical resistance value of the joint portion is equal to or lower than the electrical resistance value of the base carbon material. To provide.
カーバイド生成触媒の金属Ｆｅ粉末、炭素源の熱硬化性樹脂及び希釈剤としてのアルコールとの混合物である炭素材料用の接合剤であって、カーバイド生成触媒である金属粉末と炭素源である熱硬化性樹脂中の炭素との配合比率が、モル比で６以上である炭素材料用の接合剤である。 A bonding agent for carbon materials, which is a mixture of metal Fe powder of a carbide formation catalyst, a thermosetting resin of a carbon source, and alcohol as a diluent, and thermosetting of the metal powder of a carbide formation catalyst and a carbon source. It is a bonding agent for carbon materials in which the blending ratio with carbon in the sex resin is 6 or more in terms of molar ratio.
半導体製造設備等に使用される炭素材料の接合品の場合、炭素材料（黒鉛）は高純度であることが要求されるので、接合後に純化処理を必要とするため、純化処理を実施しても接合部の強度が低下せず、接合部に不具合が生ずることなくなく純化される接合剤であることが必要である。このため、カーバイドを経由して炭素結合部を形成させるＣＤＣ（Ｃａｒｂｉｄｅ−ｄｅｒｉｖｅｄ ｃａｒｂｏｎ）接合が適切であると考え、カーバイド生成触媒である金属Ｆｅ粉末と樹脂等の炭素源及びアルコール等の分散媒からなる接合剤が課題を解決するものであることを見出したのである。 In the case of a bonded product of carbon material used in semiconductor manufacturing equipment, etc., the carbon material (graphite) is required to have high purity, and a purification treatment is required after bonding. Therefore, even if the purification treatment is performed. It is necessary that the bonding agent is purified without reducing the strength of the joint and without causing any trouble in the joint. Therefore, we consider that CDC (Carbide-developed carbon) bonding that forms a carbon bond via carbide is appropriate, and from a carbon source such as metal Fe powder and resin, which is a carbide generation catalyst, and a dispersion medium such as alcohol. We found that the bonding agent was a solution to the problem.
カーバイドを形成する金属粉末は、Ｓｉ、Ｆｅ、Ａｌ、Ｃａ、Ｃｒ他が知られているが、金属Ｆｅ粉末が取扱い上の安全性、廃棄物の環境に対する影響、価格、カーバイド生成温度、分解温度、接合時の機械的強度等を考慮すると最適である。金属Ｆｅ粉末の平均粒径は２０μｍ以下、好ましくは１０μｍ以下である。
一般に平均粒子径が２０μｍ以上になると最大粒子径が５５μｍを超える場合が多く、接合剤中で沈降しやすくなり、安定した分散状態を保つことが困難となり好ましくない。
As the metal powder forming carbide, Si, Fe, Al, Ca, Cr and others are known, but the metal Fe powder is safe in handling, impact on the environment of waste, price, carbide formation temperature, decomposition temperature. , Optimal considering the mechanical strength at the time of joining. The average particle size of the metal Fe powder is 20 μm or less, preferably 10 μm or less.
Generally, when the average particle size is 20 μm or more, the maximum particle size often exceeds 55 μm, which is not preferable because it tends to settle in the bonding agent and it is difficult to maintain a stable dispersed state.
三酸化二鉄（Ｆｅ２Ｏ３）のような金属酸化物は、６Ｆｅ２Ｏ３+１３Ｃ→４Ｆｅ３Ｃ＋９ＣＯ２の反応式に示すように、酸素により炭素が消費され、炭酸ガスが放出されるため接合の効果が十分に得られない。すなわち、接合部に空隙が多数生成し、接合部の強度が低下したり、接合部に不具合が生ずることや、接合部の電気抵抗値が高くなって電導度が低下するので好ましくない。 Metal oxides such as ferric oxide (Fe 2 O 3), as shown in the reaction scheme 6Fe 2 O 3 + 13C → 4Fe 3 C + 9CO 2, carbon is consumed by oxygen, carbon dioxide is released Therefore, the effect of joining cannot be sufficiently obtained. That is, it is not preferable because a large number of voids are generated in the joint portion, the strength of the joint portion is lowered, a defect occurs in the joint portion, and the electric resistance value of the joint portion is increased to reduce the electric conductivity.
炭素源となる樹脂は、熱硬化性樹脂であるフェノール樹脂、エポキシ樹脂、ユリア樹脂、メラミン樹脂、不飽和ポリエステル樹脂、シリコン樹脂、ポリウレタン樹脂、ポリイミド樹脂、ジアリルフタレート樹脂、ビニルエステル樹脂等が挙げられるが、２０００℃以上にまで熱処理した際の炭素収率が高いこと、希釈に用いる溶剤が安価で比較的沸点が低く蒸発除去しやすいことからフェノール樹脂が好ましい。 Examples of the resin serving as a carbon source include thermosetting resins such as phenol resin, epoxy resin, urea resin, melamine resin, unsaturated polyester resin, silicon resin, polyurethane resin, polyimide resin, diallyl phthalate resin, and vinyl ester resin. However, phenolic resins are preferable because they have a high carbon yield when heat-treated to 2000 ° C. or higher, and the solvent used for dilution is inexpensive, has a relatively low boiling point, and is easily removed by evaporation.
接合剤の配合割合は、金属Ｆｅ粉末と樹脂中の炭素がカーバイド化する反応、３Ｆｅ+Ｃ→Ｆｅ３Ｃを基にＦｅ／Ｃのモル比Ｆｅ／Ｃ＝３／１＝３を基準としてＦｅ量を増加させて検討した。Ｆｅ／Ｃが６以上で体積抵抗率が接合される炭素材料と同等且つ接合部の曲げ強度が同等以上となるので、モル比６以上とするのが好ましい。 The mixing ratio of the binder, the metal Fe powder and carbon in the resin is carbide reaction, 3Fe + C → Fe 3 molar ratio of C based on the Fe / C Fe / C = 3 /1 = 3 Fe as a reference The amount was increased and examined. When Fe / C is 6 or more, the volume resistivity is equivalent to that of the carbon material to be bonded and the bending strength of the bonded portion is equivalent or more. Therefore, the molar ratio is preferably 6 or more.
上記接合剤を用いて得られた接合部の厚みは、２０μｍ以下であり、接合による炭素材料の設計上の寸法計算から大きく狂うことはなく、設計自由度向上に寄与することができる。
接合しようとする炭素材料の面の加工精度が悪く、炭素材料同士を合わせた際に隙間ができ、接合剤を塗布しても接合部に隙間ができてしまう場合、接合部に隙間が発生するのを防ぐために最大粒子径１５０μｍ以下の黒鉛粉末や炭素繊維粉末を添加混合して用いることが有効である。添加する黒鉛粉末や炭素繊維粉末の最大粒子径が１５０μｍを超えると接合部が厚くなり、接合による炭素材料の設計上において煩雑となり好ましくない。
The thickness of the joint portion obtained by using the above-mentioned bonding agent is 20 μm or less, and there is no significant deviation from the design dimensional calculation of the carbon material by bonding, which can contribute to the improvement of the degree of freedom in design.
If the processing accuracy of the surface of the carbon material to be joined is poor, a gap is created when the carbon materials are combined, and a gap is created at the joint even when the bonding agent is applied, a gap is generated at the joint. It is effective to add and mix graphite powder and carbon fiber powder having a maximum particle size of 150 μm or less in order to prevent the above. If the maximum particle size of the graphite powder or carbon fiber powder to be added exceeds 150 μm, the joint portion becomes thick, which is not preferable because it complicates the design of the carbon material by joining.
黒鉛粉末や炭素繊維粉末を予め本発明の接合剤に添加混合して用いる場合でもＦｅ／Ｃは、６以上とすることが必要であり、金属Ｆｅ粉末に対するフェノール樹脂中の炭素（Ｃ）と添加された黒鉛粉末乃至炭素繊維粉末中の炭素（Ｃ） の合計のＣの比が６以上になるように調節する。 Even when graphite powder or carbon fiber powder is added and mixed with the bonding agent of the present invention in advance, Fe / C needs to be 6 or more, and carbon (C) in the phenol resin is added to the metal Fe powder. The ratio of the total C of carbon (C) in the graphite powder to the carbon fiber powder is adjusted to be 6 or more.
接合剤中の固形分濃度は、塗料として塗工しやすい粘度に希釈材を用いて適宜調整する。刷毛を用いる場合は、４０％程度が好適である。 The solid content concentration in the bonding agent is appropriately adjusted by using a diluent to have a viscosity that makes it easy to apply as a paint. When a brush is used, about 40% is preferable.
本発明の接合剤によれば、得られる接合部の強度及び電気抵抗値は炭素材料と同等またはそれより優れたものとなり、接合部は、炭素材料と均一に一体化された炭素であり、接合したことで炭素材料の特性には変化が認められず、また、半導体製造用に使用するために高純度化処理をおこなってもこの特性は失われることはない。
本発明の接合剤は、炭素材料を接合する場合、一方の炭素材料に塗布した後、もう一方の炭素材料を塗布面に重ね合わせ圧着し、１５０〜２５０℃で接合剤を硬化させた後、２０００℃以上で熱処理を行うことで接合部に空隙のない強固な炭素からなる接合部を得ることができる。
本発明の接合剤によればＣ／Ｃコンポジット部材の相互間を極めて強固に接合することができ、しかも、その接合部は耐熱性、耐食性、導電性を有するので、Ｃ／Ｃコンポジットを発熱体とした複雑形状の発熱装置、腐食雰囲気中で使用する発熱装置の組立て時に適用して極めて有用である。
According to the bonding agent of the present invention, the strength and electric resistance value of the obtained joint portion are equal to or superior to those of the carbon material, and the joint portion is carbon uniformly integrated with the carbon material, and the joint is bonded. As a result, no change is observed in the characteristics of the carbon material, and this characteristic is not lost even if a high purification treatment is performed for use in semiconductor manufacturing.
When joining carbon materials, the bonding agent of the present invention is applied to one carbon material, then the other carbon material is superposed on the coated surface and pressure-treated, and the bonding agent is cured at 150 to 250 ° C. By performing heat treatment at 2000 ° C. or higher, a joint made of strong carbon with no voids in the joint can be obtained.
According to the bonding agent of the present invention, the C / C composite members can be bonded to each other extremely strongly, and the bonded portion has heat resistance, corrosion resistance, and conductivity. Therefore, the C / C composite is a heating element. It is extremely useful when assembling a heating device with a complicated shape and a heating device used in a corrosive atmosphere.
本発明の効果は、接合面の外観観察、及び機械的強度、灰分量の測定によって評価した。測定方法について以下に示す。
＜外観観察＞
接合部の外観は、目視又は金属顕微鏡によって観察した。
＜粒度＞
平均粒径、及び最大粒子径の測定は、日機装株式会社製レーザー回折式粒度分布測定装置ＭＴ３３００ＥＸを用いて水に分散剤として微量の界面活性剤を添加し、試料を超音波分散させた状態で測定した。試験に供される粉体の全体積を１００％として累積カーブを求め、その累積カーブが小粒子径側から大粒子径側に向けて積算したときの５０％、１００％となる点の粒子径をそれぞれ平均粒径、最大粒子径とした。
＜全電気抵抗＞
炭素材料を接合した接合品の全電気抵抗値の測定は、４０ｍｍ×４０ｍｍ×４０ｍｍに切り出した基材の一面に接合剤を塗布し、この面に同じく４０ｍｍ×４０ｍｍ×４０ｍｍに切り出した基材を接合して作成した接合品をテストピースとして用い、４端子法により測定した。接合部が各端子の中点になる位置にセットし、１．００Ａの定電流を流した状態で端子間距離２０ｍｍで電圧を測定することによって求めた。なお、異種材料間での接合では比較用の全抵抗が測定出来ないため、各基材の体積抵抗率を使用した。
The effect of the present invention was evaluated by observing the appearance of the joint surface and measuring the mechanical strength and the amount of ash. The measurement method is shown below.
<Appearance observation>
The appearance of the joint was observed visually or by a metallurgical microscope.
<Granularity>
The average particle size and the maximum particle size are measured by adding a small amount of surfactant as a dispersant to water using the laser diffraction type particle size distribution measuring device MT3300EX manufactured by Nikkiso Co., Ltd. and ultrasonically dispersing the sample. It was measured. The cumulative curve is obtained with the total volume of the powders used in the test as 100%, and the particle size at the point where the cumulative curve is 50% or 100% when integrated from the small particle size side to the large particle size side. Was taken as the average particle size and the maximum particle size, respectively.
<Total electrical resistance>
To measure the total electrical resistance of a bonded product with carbon materials bonded, a bonding agent is applied to one surface of a base material cut out to 40 mm x 40 mm x 40 mm, and the base material cut out to 40 mm x 40 mm x 40 mm is also applied to this surface. The joined product prepared by joining was used as a test piece and measured by the 4-terminal method. It was determined by setting the joint at the midpoint of each terminal and measuring the voltage at a distance of 20 mm between the terminals with a constant current of 1.00 A flowing. Since the total resistance for comparison cannot be measured by joining between different materials, the volume resistivity of each base material was used.
＜黒鉛材：曲げ強度、圧縮強度、引張強度＞
曲げ強度、引張強度、及び圧縮強度の機械的強度測定には、インストロンジャパン カンパニィリミテッド社製、インストロン５９６９型万能材料試験機を用いて室温で測定した。
曲げ強度は、４０ｍｍ×４０ｍｍ×４０ｍｍの基材片を２個接合した８０ｍｍ×４０ｍｍ×４０ｍｍの接合品から８０ｍｍ×４０ｍｍ×８ｍｍの試験片を切り出し、スパン７０ｍｍで接合部がその中央になるようにセットし、試験速度３ｍｍ／ｍｉｎで３点曲げ試験を実施した。
圧縮強度は、接合面が圧縮方向に対し垂直及び平行になるようにφ２０×２０ｍｍの試験片を接合品から切り出し、試験速度３ｍｍ／ｍｉｎで荷重Ｐを作用させて実施した。
引張強度は、接合部１を有する接合品を図１に示すφ２０×４０ｍｍの平行部２を有し両端部に治具に取り付けるためのネジ３が形成してあるダンベル型試験片に加工して引張試験速度３ｍｍ／ｍｉｎで実施した。
<Graphite material: bending strength, compressive strength, tensile strength>
The mechanical strengths of bending strength, tensile strength, and compressive strength were measured at room temperature using an Instron 5969 type universal material tester manufactured by Instron Japan Company Limited.
The bending strength is such that a test piece of 80 mm × 40 mm × 8 mm is cut out from a bonded product of 80 mm × 40 mm × 40 mm in which two pieces of a 40 mm × 40 mm × 40 mm base material are joined, and the joint portion is centered at a span of 70 mm. It was set and a 3-point bending test was performed at a test speed of 3 mm / min.
The compression strength was carried out by cutting out a test piece having a diameter of 20 × 20 mm from the joint product so that the joint surface was perpendicular to and parallel to the compression direction, and applying a load P at a test speed of 3 mm / min.
Tensile strength is obtained by processing a joint product having a joint portion 1 into a dumbbell type test piece having a parallel portion 2 having a diameter of 20 × 40 mm and having screws 3 for attaching to a jig at both ends as shown in FIG. The tensile test was carried out at a tensile test speed of 3 mm / min.
＜Ｃ/Ｃ複合材料の曲げ強度、引張強度、せん断強度＞
曲げ試験、引張試験用には、それぞれ図２、図３に示すＣ/Ｃ複合材の端面同士を接合した試験片を切り出して、黒鉛材の場合に用いたインストロン５９６９型万能材料試験機を用いて同様に実施した。
せん断強度は、図４に示す切込み幅５ｍｍのダブルノッチ型の試験片を切り出して試験速度３ｍｍ／ｍｉｎで同様に実施した。ノッチ４を結ぶ線が接合部であり、ノッチ４の切込み幅は５ｍｍである。
<Bending strength, tensile strength, shear strength of C / C composite material>
For the bending test and the tensile test, a test piece in which the end faces of the C / C composite materials shown in FIGS. 2 and 3 are joined to each other is cut out, and the Instron 5969 type universal material tester used in the case of the graphite material is used. It was carried out in the same manner using.
The shear strength was similarly carried out at a test speed of 3 mm / min by cutting out a double notch type test piece having a depth of cut of 5 mm shown in FIG. The line connecting the notches 4 is the joint portion, and the notch 4 has a notch width of 5 mm.
＜灰分＞
予め空焼きした白金ルツボに試料を投入し、電気加熱式の灰化炉にて８５０℃で保持することにより灰化を行った。白金ルツボごと灰化炉から取り出し、放冷後デシケーター内で１５分、更に２３．５℃、湿度５０％に保たれた天秤室内に５分放置した後、重量測定により灰分を計算して求めた。
<Ash>
The sample was put into a platinum crucible that had been air-baked in advance, and ashed by holding it at 850 ° C. in an electric heating type ashing furnace. The platinum crucible was taken out of the ashing furnace, allowed to cool, left in a desiccator for 15 minutes, and then left in a balance chamber kept at 23.5 ° C. and 50% humidity for 5 minutes, and then the ash content was calculated by weight measurement. ..
以下に本発明についての具体例を示すが、本発明は、特許請求の範囲を逸脱しない範囲で接合部の形状、基材（炭素材料）の銘柄等は必要に応じて変更できるものであり、以下の実施例に限定されるものではない。
＜実施例１〜２、比較例１〜３＞
平均粒子径１２μｍ、最大粒子径５５μｍのＪＦＥケミカル株式会社製の鉄粉ＪＩＰ−２８０、不揮発分６０％、残炭率５８％ＤＩＣ株式会社製のレゾール型フェノール樹脂フェノライト５９００、希釈剤としてイソプロピルアルコール（ＩＰＡ）を表１の実施例１、２、比較例１、２、及び３に示す割合で撹拌羽根つき混合器に投入して１０００回転で１０分間混合して塗料化し、接合剤を得た。
等方性黒鉛材（商品名ＩＧＳ―７４３、新日本テクノカーボン株式会社）を４０ｍｍ×４０ｍｍ×４０ｍｍに切り出し、一面に刷毛を用いて接合剤を４５０ｇ／ｃｍ２になるように塗布した。接合剤の塗布面にもう一つの４０ｍｍ×４０ｍｍ×４０ｍｍに切り出した等方性黒鉛材（ＩＧＳ−７４３）を重ね合わせて圧着し、１５０℃で２時間保持し、フェノライト５９００に含まれていた溶剤と希釈に用いたイソプロピルアルコールを蒸発除去し、硬化後、非酸化性雰囲気の減圧下にて２０００℃で３時間保持し熱処理を行った。炭素材料基材が黒色乃至黒鉄色の艶消し状であるのに対し、接合部は、黒い光沢を呈していた。
Specific examples of the present invention will be shown below, but in the present invention, the shape of the joint portion, the brand of the base material (carbon material), etc. can be changed as necessary without departing from the claims. It is not limited to the following examples.
<Examples 1 and 2, Comparative Examples 1 and 3>
Iron powder JIP-280 manufactured by JFE Chemical Co., Ltd. with an average particle diameter of 12 μm and a maximum particle diameter of 55 μm, non-volatile content 60%, residual carbon content 58%, resole-type phenolic resin phenolite 5900 manufactured by DIC Corporation, isopropyl alcohol as a diluent. (IPA) was put into a mixer with stirring blades at the ratios shown in Examples 1 and 2 and Comparative Examples 1, 2 and 3 in Table 1 and mixed at 1000 rpm for 10 minutes to form a paint to obtain a bonding agent. ..
An isotropic graphite material (trade name: IGS-743, Shin Nihon Techno Carbon Co., Ltd.) was cut out to a size of 40 mm × 40 mm × 40 mm, and a bonding agent was applied to one surface at 450 g / cm 2 using a brush. Another 40 mm × 40 mm × 40 mm cut out isotropic graphite material (IGS-743) was superposed on the coated surface of the adhesive and pressure-treated, held at 150 ° C. for 2 hours, and contained in Phenolite 5900. The solvent and isopropyl alcohol used for dilution were evaporated and removed, and after curing, the mixture was held at 2000 ° C. for 3 hours under reduced pressure in a non-oxidizing atmosphere for heat treatment. The carbon material base material had a matte black to black iron color, while the joint had a black luster.
等方性黒鉛材（ＩＧＳ−７４３）同士の接合部は、厚さ２０〜３０μｍで空隙が発生することなく基材である等方性黒鉛材と一体化して接合されていた。
基材の等方性黒鉛材の全抵抗は１２０μΩ、曲げ強度は５７．３ＭＰａであるが、接合物の全抵抗と曲げ強度は、鉄粉と炭素源であるフェノール樹脂を炭化したときに残る炭素量（フェノライト５９００の重量×不揮発分×残炭率）の比Ｆｅ／Ｃが７．１８である実施例１、同様に６．１７である実施例２は、全抵抗がそれぞれ１３０、１４０μΩ、曲げ強度がそれぞれ５４．９、５６．３ＭＰａであり、抵抗値、曲げ強度とも基材と同等であった。
一方、比較例１（Ｆｅ／Ｃ＝５．１５）、比較例２（同４．１２）、比較例３（同３．０９）は、全抵抗は、それぞれ１３０、１５０、１４０μΩであり、基材とほぼ同等であったが、曲げ強度は、それぞれ４７．３、４６．０、４３．６ＭＰａであり、基材より劣っていた。なお、実施例１，２の破断部は接合部ではなく基材の等方性黒鉛材（ＩＧＳ―７４３）に生じていたのに対し、比較例１、２、及び３では接合部が破断していた。
The joint portion between the isotropic graphite materials (IGS-743) had a thickness of 20 to 30 μm and was integrally bonded with the isotropic graphite material as a base material without forming voids.
The total resistance and bending strength of the isotropic graphite material of the base material is 120 μΩ and the bending strength is 57.3 MPa, but the total resistance and bending strength of the bonded material are the carbon remaining when carbonized iron powder and the phenol resin which is the carbon source. In Example 1 in which the ratio Fe / C of the amount (weight of phenolite 5900 × non-volatile content × residual carbonization ratio) is 7.18, and in Example 2 in which the ratio is 6.17, the total resistances are 130 and 140 μΩ, respectively. The bending strength was 54.9 and 56.3 MPa, respectively, and the resistance value and the bending strength were the same as those of the substrate.
On the other hand, in Comparative Example 1 (Fe / C = 5.15), Comparative Example 2 (4.12), and Comparative Example 3 (3.09), the total resistances were 130, 150, and 140 μΩ, respectively. It was almost the same as the material, but the bending strength was 47.3, 46.0, and 43.6 MPa, respectively, which were inferior to the base material. In addition, while the fractured portion of Examples 1 and 2 occurred not in the joint portion but in the isotropic graphite material (IGS-743) of the base material, in Comparative Examples 1, 2 and 3, the joint portion was fractured. Was there.
＜圧縮強度試験＞
等方性黒鉛材（ＩＧＳ―７４３）を実施例２の接合剤を用いて実施例２と同様の方法で接合した。得られた接合品から圧縮方向に対して接合部が垂直方向、及び平行方向に接合されたφ２０×２０（ｍｍ）の試験片を作成して圧縮試験を行った。
等方性黒鉛材（ＩＧＳ―７４３）の圧縮強度が、１１８．０ＭＰａであるのに対し、圧縮方向に対し接合面が直角をなす方向の試験片は１１８．６ＭＰａ、接合面が平行となる方向の試験片は１２２．２ＭＰａであった。どちらの接合方向においても、斜めに破断しており、接合部が破断することはなく、接合部の強度は基材と同等以上である結果を得た。
<Compressive strength test>
The isotropic graphite material (IGS-743) was bonded using the bonding agent of Example 2 in the same manner as in Example 2. From the obtained bonded product, a test piece having a diameter of 20 × 20 (mm) in which the joint portion was joined in the direction perpendicular to the compression direction and in the parallel direction was prepared and a compression test was performed.
The compressive strength of the isotropic graphite material (IGS-743) is 118.0 MPa, whereas the test piece in the direction in which the joint surface is perpendicular to the compression direction is 118.6 MPa, in the direction in which the joint surfaces are parallel. The test piece was 122.2 MPa. In either of the joining directions, the joints were broken diagonally, the joints were not broken, and the strength of the joints was equal to or higher than that of the base material.
＜引張強度試験＞
実施例２の接合剤を用いて実施例２と同様の方法で接合した等方性黒鉛材（ＩＧＳ―７４３）を図１に示すダンベル状の形状の試験片に加工した。
等方性黒鉛材の引張強度が３７．５ＭＰａであるのに対し、接合品では３７．４ＭＰａであった。基材部分が、破断し接合部の強度は、基材同等以上であることを確認した。
<Tensile strength test>
An isotropic graphite material (IGS-743) bonded by the same method as in Example 2 using the bonding agent of Example 2 was processed into a dumbbell-shaped test piece shown in FIG.
The tensile strength of the isotropic graphite material was 37.5 MPa, whereas that of the bonded product was 37.4 MPa. It was confirmed that the base material portion broke and the strength of the joint was equal to or higher than that of the base material.
＜物理特性試験＞
実施例２の接合剤を用いて、嵩密度、成型方法、体積抵抗率、熱膨張率のそれぞれ異なる等方性黒鉛材（ＩＧＳ―７４３）、押し出し成形黒鉛材（ＧＲ−１０３）、及び型込め成形黒鉛材（商品名ＭＦ３０７、新日本テクノカーボン株式会社製）の同種材料間、及び異種材料間の接合を実施例２と同様の方法で行った。各黒鉛基材の特性を表２に、接合を実施した接合品の特性を表３に示す。
同種材接合の接合品の体積抵抗率は、基材と同等を示した。また異種材接合品の体積抵抗率は、それぞれの基材代表値から計算した値（基材Ａと基材Ｂの体積抵抗値の和の１／２）と一致した。曲げ強度は、同種材での接合では基材と同等の結果を示した。
試験後の破断部の外観観察によると、破断は、基材部で生じていた。
従って接合品の曲げ強度は基材と同等であることを確認した。異種材接合における曲げ強度は、低強度側の基材と同等となった。破断部の外観観察によると、破断部は低強度基材側に生じていた。従って、異種材接合品の曲げ強度は低強度基材の強度と同等になるといえる。
以上より、本発明の接合剤を使用した接合部の強度は、基材強度よりも高くなっていることを確認した。
<Physical property test>
Using the bonding agent of Example 2, isotropic graphite material (IGS-743), extruded graphite material (GR-103), and embedding, which differ in bulk density, molding method, volume resistance, and coefficient of thermal expansion, respectively. Joining of the molded graphite material (trade name MF307, manufactured by Shin Nihon Techno Carbon Co., Ltd.) between the same kind of materials and between different kinds of materials was carried out in the same manner as in Example 2. Table 2 shows the characteristics of each graphite base material, and Table 3 shows the characteristics of the bonded products that have been bonded.
The volume resistivity of the bonded product of the same kind of material was similar to that of the base material. Further, the volume resistivity of the dissimilar material bonded product was in agreement with the value calculated from each base material representative value (1/2 of the sum of the volume resistivity values of the base material A and the base material B). The bending strength showed the same result as the base material when joining with the same kind of material.
According to the appearance observation of the fractured portion after the test, the fracture occurred in the base material portion.
Therefore, it was confirmed that the bending strength of the bonded product was equivalent to that of the base material. The bending strength in joining dissimilar materials was equivalent to that of the base material on the low strength side. According to the appearance observation of the fractured portion, the fractured portion was generated on the low-strength substrate side. Therefore, it can be said that the bending strength of the dissimilar material bonded product is equivalent to the strength of the low-strength base material.
From the above, it was confirmed that the strength of the joint portion using the bonding agent of the present invention is higher than the strength of the base material.
＜比較例４＞
人造黒鉛粉末と液状フェノール樹脂からなる市販品を接合剤として用いた他は、実施例１と同様の方法で等方性黒鉛材（ＩＧＳ−７４３）を接合した。
接合部には空隙が多数確認され、全抵抗は２６０μΩ、曲げ試験の結果は、曲げ強度は１．７ＭＰａであり、接合部から破断した。
<Comparative example 4>
An isotropic graphite material (IGS-743) was bonded in the same manner as in Example 1 except that a commercially available product composed of artificial graphite powder and liquid phenol resin was used as a bonding agent.
A large number of voids were confirmed at the joint, the total resistance was 260 μΩ, and the result of the bending test was that the bending strength was 1.7 MPa, and the fracture occurred from the joint.
＜比較例５〜１１＞
最大粒子径５５μｍのＪＦＥケミカル株式会社製の酸化鉄粉末ＪＣ−Ｎ、不揮発分６０％、残炭率５８％ＤＩＣ株式会社製のレゾール型フェノール樹脂フェノライト５９００、希釈剤としてイソプロピルアルコール（ＩＰＡ）を表４の比較例５〜１１に示す割合で撹拌羽根つき混合器に投入して１０００回転で１０分間混合して塗料化して接合剤を得た。この接合剤を使用して実施例１の接合品に対して実施したのと同様の試験を行った。
<Comparative Examples 5 to 11>
Iron oxide powder JC-N manufactured by JFE Chemical Co., Ltd. with a maximum particle size of 55 μm, non-volatile content 60%, residual carbon content 58%, resole-type phenol resin phenolite 5900 manufactured by DIC Corporation, and isopropyl alcohol (IPA) as a diluent. It was put into a mixer with stirring blades at the ratios shown in Comparative Examples 5 to 11 in Table 4 and mixed at 1000 rpm for 10 minutes to form a paint to obtain a bonding agent. Using this bonding agent, the same test as that performed on the bonded product of Example 1 was performed.
等方性黒鉛材（ＩＧＳ―７４３）同士の接合部の厚さは２０〜４０μｍ程度であり、接合部は基材と一体化していた。
基材である等方性黒鉛材（ＩＧＳ―７４３）の全抵抗は１２０μΩ、曲げ強度は５７．３ＭＰａであるが、比較例の接合物の全抵抗と曲げ強度を測定したところ、Ｆｅ２Ｏ３粉末と炭素源であるフェノール樹脂を炭化したときに残る炭素量（フェノライト５９００の重量×不揮発分×残炭率）の比Ｆｅ２Ｏ３／Ｃが０．７７以上（比較例９〜１１）において基材同等の全抵抗値を示したが、０．７７未満（比較例５〜８）では、基材の全抵抗値より大きかった。
基材である黒鉛材に対する触媒効果が小さく、カーバイド化が十分におこなわれず、接合部に空隙が多数形成されて電気抵抗の上昇を招いたものと考えられる。
一方、曲げ強度は、Ｆｅ２Ｏ３／Ｃ＝０．７７（比較例５〜８）迄はＦｅ２Ｏ３量の増加と共に大きく増加したが、０．７７以上（比較例９〜１１）では微増に留まり、基材強度である５７．３ＭＰａには届かなかった。
The thickness of the joint between the isotropic graphite materials (IGS-743) was about 20 to 40 μm, and the joint was integrated with the base material.
The total resistance of the isotropic graphite material (IGS-743), which is the base material, is 120 μΩ and the bending strength is 57.3 MPa. However, when the total resistance and bending strength of the bonded material of the comparative example were measured, Fe 2 O 3 The ratio of the amount of carbon remaining when the powder and the phenol resin, which is the carbon source, are carbonized (weight of phenolite 5900 x non-volatile content x residual carbon ratio) Fe 2 O 3 / C is 0.77 or more (Comparative Examples 9 to 11). The total resistance value was equivalent to that of the base material, but less than 0.77 (Comparative Examples 5 to 8) was larger than the total resistance value of the base material.
It is probable that the catalytic effect on the graphite material as the base material was small, carbide formation was not sufficiently performed, and a large number of voids were formed at the joints, leading to an increase in electrical resistance.
On the other hand, the bending strength increased significantly with the increase in the amount of Fe 2 O 3 up to Fe 2 O 3 / C = 0.77 (Comparative Examples 5 to 8), but at 0.77 or more (Comparative Examples 9 to 11), it increased significantly. It increased only slightly and did not reach the base material strength of 57.3 MPa.
＜実施例１１〜１６＞
黒鉛粉末添加
実施例１１〜１３は、平均粒子径１２μｍ、最大粒子径５５μｍのＪＦＥケミカル株式会社製の鉄粉ＪＩＰ−２８０、不揮発分６０％、残炭率５８％ＤＩＣ株式会社製のレゾール型フェノール樹脂フェノライト５９００、平均粒子径２７μｍ、最大粒子径１５０μｍの日本カーボン株式会社製人造黒鉛粉末ＥＧ-1Ｃ、希釈剤としてイソプロピルアルコールを表５に示す割合で撹拌羽根付き混合機に投入し、１０００回転／分で１０分間混合して塗料化して接合剤を得た他は、等方性黒鉛材（ＩＧＳ−７４３）を基材として実施例１と同様の方法にて処理した。
実施例１４〜１６は、フェノライト５９００に換えて不揮発分８３％、残炭率５９％住友ベークライト株式会社製のノボラック型フェノール樹脂ＰＲ−５０４０４を用いて、ＰＲ−５０４０４と黒鉛粉末との合計重量１００ｇ当たり硬化剤ＨＰ-４４を５ｍｌ加え、２５℃で２４時間放置した以外は、実施例１１〜１３と同様に行った。
各実施例について接合部の厚さ、曲げ強度を測定した。最大粒子径１５０μｍの黒鉛粉末を骨材として添加したことにより、接合部の厚さは約０．１ｍｍ前後増加した。フェノール樹脂種の違いによる差は無かった。骨材の添加量およびフェノール樹脂種が異なるものであっても強度の低下は認められず、全ての試料は基材部分で破断した。
本実施例によって、接合面の平面度が十分でなく、基材同志を合わせた際に隙間が存在する場合、接合剤に黒鉛粉末を骨材として添加することによって強固な接合部が得られることが判明した。
<Examples 11 to 16>
Addition of graphite powder In Examples 11 to 13, iron powder JIP-280 manufactured by JFE Chemical Co., Ltd. having an average particle diameter of 12 μm and a maximum particle diameter of 55 μm, a non-volatile content of 60%, and a residual carbon content of 58%, a resole-type phenol manufactured by DIC Co., Ltd. Resin phenolite 5900, artificial graphite powder EG-1C manufactured by Nippon Carbon Co., Ltd. with an average particle diameter of 27 μm and a maximum particle diameter of 150 μm, and isopropyl alcohol as a diluent were put into a mixer with stirring blades at the ratio shown in Table 5 and rotated 1000 times. It was treated in the same manner as in Example 1 using an isotropic graphite material (IGS-743) as a base material, except that the mixture was mixed at / min for 10 minutes to form a coating agent to obtain a bonding agent.
In Examples 14 to 16, the total weight of PR-50404 and graphite powder was used in place of Fenolite 5900 using a novolak-type phenolic resin PR-50404 manufactured by Sumitomo Bakelite Co., Ltd. with a non-volatile content of 83% and a residual carbon content of 59%. The same procedure as in Examples 11 to 13 was carried out except that 5 ml of the curing agent HP-44 was added per 100 g and the mixture was left at 25 ° C. for 24 hours.
The thickness and bending strength of the joint were measured for each example. By adding graphite powder having a maximum particle size of 150 μm as an aggregate, the thickness of the joint portion increased by about 0.1 mm. There was no difference due to the difference in phenolic resin type. No decrease in strength was observed even when the amount of aggregate added and the phenolic resin type were different, and all the samples broke at the base material portion.
According to this embodiment, when the flatness of the joint surface is not sufficient and there is a gap when the base materials are combined, a strong joint can be obtained by adding graphite powder as an aggregate to the joint agent. There was found.
＜実施例１７〜１８＞
実施例２の接合剤を用いてＣ/Ｃ複合材料（商品名ＣＣＭ−１９０Ｃ、ＣＣＭ−４００Ｃ、日本カーボン株式会社製）の接合を行い図２〜４に示す試験片を作製し、強度測定を行った。ＣＣＭ−１９０Ｃの曲げ強度は１６０ＭＰａ、引張強度は２６０ＭＰａ、せん断強度は６ＭＰａ、ＣＣＭ-４００Ｃではそれぞれ１４０ＭＰａ、９５ＭＰａ、１２ＭＰａである。
端面同士の接合強度を測定する曲げ及び引張試験において、接合部は炭素繊維で強化されていないため、接合強度は基材以下となった。しかし、曲げ強度は基材強度の約８０％の値を示しており、実用的には問題がないといえる。
一方、表面同士の接合強度を測定したせん断強度は基材同等以上を示した。試験片は基材で破断されており、表面同士の接合強度は基材強度以上であった。
表６は、Ｃ/Ｃ複合材料の特性値を示すものである。
<Examples 17-18>
C / C composite materials (trade names CCM-190C, CCM-400C, manufactured by Nippon Carbon Co., Ltd.) are bonded using the bonding agent of Example 2 to prepare the test pieces shown in FIGS. 2 to 4, and the strength is measured. went. The bending strength of CCM-190C is 160 MPa, the tensile strength is 260 MPa, the shear strength is 6 MPa, and the CCM-400C is 140 MPa, 95 MPa, and 12 MPa, respectively.
In the bending and tensile tests for measuring the joint strength between the end faces, the joint strength was lower than that of the base material because the joint was not reinforced with carbon fibers. However, the bending strength shows a value of about 80% of the base material strength, and it can be said that there is no problem in practical use.
On the other hand, the shear strength obtained by measuring the bonding strength between the surfaces was equal to or higher than that of the base material. The test piece was broken by the base material, and the bonding strength between the surfaces was equal to or higher than the base material strength.
Table 6 shows the characteristic values of the C / C composite material.
＜実施例１９＞
実施例２の接合剤のみを硬化後、非酸化性雰囲気の減圧下にて２０００℃で３時間保持し熱処理を行い、灰分を測定したところ２３０ｐｐｍであり、実施例２の接合剤に使用したフェノール樹脂のみを同様に熱処理して灰分測定を実施した結果の２５０ｐｐｍと同等であった。
<Example 19>
After curing only the bonding agent of Example 2, the ash content was measured by holding at 2000 ° C. for 3 hours under reduced pressure in a non-oxidizing atmosphere for 3 hours, and the ash content was 230 ppm. The phenol used in the bonding agent of Example 2 was obtained. It was equivalent to 250 ppm as a result of heat-treating only the resin in the same manner and measuring the ash content.
＜実施例２０＞
実施例２と同様にして接合し、同様の熱処理を行い、４０ｍｍ×４０ｍｍ×５ｍｍに切り出した。接合面は４０ｍｍ×４０ｍｍの面である。この接合品を、塩化水素ガスの流量３５ｌ/ｍｉｎの雰囲気中、２０００℃で３時間保持して純化処理を行った。灰分測定をしたところ、等方性黒鉛材（ＩＧＳ−７４３）のみを同様に純化処理した場合の３ｐｐｍと同様３ｐｐｍであった。一方、等方性黒鉛材（ＩＧＳ−７４３）の灰分は、３５１ｐｐｍ、接合品は４１１ｐｐｍであった。
また、接合品を純化処理したものの曲げ強度は、５４．１ＭＰａであり、未純化品と同様に基材部分で破断し、接合部は十分な接合強度を保持していることが確認された。純化処理前後で強度及び灰分に差は無いことから、本発明によって製造された炭素材料の接合品は高純度化処理が必須である半導体製造用途にも使用可能であることが確認できた。
<Example 20>
They were joined in the same manner as in Example 2, subjected to the same heat treatment, and cut out to a size of 40 mm × 40 mm × 5 mm. The joint surface is a surface of 40 mm × 40 mm. This bonded product was kept at 2000 ° C. for 3 hours in an atmosphere of a hydrogen chloride gas flow rate of 35 l / min for purification treatment. When the ash content was measured, it was 3 ppm, which was the same as 3 ppm when only the isotropic graphite material (IGS-743) was similarly purified. On the other hand, the ash content of the isotropic graphite material (IGS-743) was 351 ppm, and that of the bonded product was 411 ppm.
Further, it was confirmed that the bending strength of the purified product was 54.1 MPa, which was broken at the base material portion as in the unpurified product, and the joint portion maintained a sufficient joint strength. Since there is no difference in strength and ash content before and after the purification treatment, it was confirmed that the bonded product of carbon material produced by the present invention can also be used for semiconductor manufacturing applications where high purification treatment is essential.
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