JPH0378194B2 - - Google Patents
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- Publication number
- JPH0378194B2 JPH0378194B2 JP8853987A JP8853987A JPH0378194B2 JP H0378194 B2 JPH0378194 B2 JP H0378194B2 JP 8853987 A JP8853987 A JP 8853987A JP 8853987 A JP8853987 A JP 8853987A JP H0378194 B2 JPH0378194 B2 JP H0378194B2
- Authority
- JP
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- Prior art keywords
- adhesive material
- bonding
- powder
- adhesive
- component
- Prior art date
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- 239000000853 adhesive Substances 0.000 claims description 61
- 230000001070 adhesive effect Effects 0.000 claims description 61
- 239000000463 material Substances 0.000 claims description 60
- 239000000843 powder Substances 0.000 claims description 44
- 239000002245 particle Substances 0.000 claims description 18
- 239000002131 composite material Substances 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 101710195817 Envelope protein H3 Proteins 0.000 claims 1
- 238000000034 method Methods 0.000 description 26
- 229910052751 metal Inorganic materials 0.000 description 23
- 239000002184 metal Substances 0.000 description 23
- 239000000919 ceramic Substances 0.000 description 18
- 239000000758 substrate Substances 0.000 description 17
- 238000005304 joining Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 239000010949 copper Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000003466 welding Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012634 fragment Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000012790 adhesive layer Substances 0.000 description 3
- 238000005219 brazing Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 230000013011 mating Effects 0.000 description 3
- 238000005551 mechanical alloying Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 2
- 239000004484 Briquette Substances 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229910000952 Be alloy Inorganic materials 0.000 description 1
- 229910017770 Cu—Ag Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- -1 bonding strength Substances 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
- 238000010273 cold forging Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Ceramic Products (AREA)
- Powder Metallurgy (AREA)
Description
（産業上の利用分野）
本発明は金属と金属、金属とセラミツク、セラ
ミツクとセラミツクの接合用に好適な接着用材料
に関するものである。
（従来の技術）
従来より、金属と金属、セラミツクとセラミツ
クのように同一材質間の接合法、或いは金属とセ
ラミツクの異材質間の接合法としては様々な接合
法が知られている。
例えば、金属と金属の接合法としては電気溶
接、ガス溶接、摩擦溶接等々の融接法があり、基
材を溶融しない方法としてロウ付け処理や有機接
着剤による接着法がある。
また、セラミツクとセラミツクの接合法として
は有機接着剤による接着法や耐熱金属法（特開昭
61−58870号参照）などがある。
これらの同一材質間の接合に対し、金属とセラ
ミツクとの異材質間の接合法としては、有機接着
剤による接着法や活性金属法、焼きばめ法、固相
反応法などがあり、またセラミツク基材にMoや
Ｗなどでメタライズした後にニツケルメツキを施
し、金属基材と半田付けする耐熱金属法があり、
最近の技術では酸化物系の無機接着剤を使用して
水和化合物をつくるなどの化学反応による接合法
も出現している。
（発明が解決しようとする問題点）
しかし、上記各種接合法のうち、金属同志の固
有な接合法である融接法を除けば、いずれも熱に
弱く、接着強度も充分でないという欠点がある。
一方、僅かに、蒸着、スパツタリング、溶射等
による接合技術や箔状のインサート材を使用する
接合技術も提案されているが、接着力に乏しいと
いう欠点があるばかりでなく、使用範囲が限定さ
れるなどのため、実用性に乏しく、経済性でも満
足し得る接合法とは言えない。
本発明は、上記従来技術の欠点を解消し、耐熱
性を有すると共に接着強度が高く、特に冷熱繰返
し使用に耐え、しかも金属、セラミツクの同一材
質間の接合のみならず、金属とセラミツクの異材
質間の接合にも簡便に利用でき、実用性、経済性
を満足する新規な接着用材料を提供することを目
的とするものである。
（問題点を解決するための手段）
上記目的を達成するため、本発明者は、耐熱性
を確保するためにまず接着材を金属質のものと
し、この金属質の接着材において特に接着強度を
高め得る方策について鋭意研究したところ、従来
の金属ロウの如く（例、特公昭61−10235号）、単
にその化学成分を調整するだけではその用途が制
限され、しかも耐熱性、接着強度の向上の要請に
対して限界があることが判明し、したがつて、化
学成分の調整はもとより、加えて接着材の物理的
構造面に重点をおいて実験研究を重ねた結果、
Agを必須成分として含む特定組成であつて、し
かも接着材の構造として各成分を混合状態で、か
つ共存せしめた複合粉末構造とすることにより、
上記目的が達成できることを見い出した。
しかし、かゝる金属質接着材を用いて接合した
基材を繰返し使用した場合、接着層の接着力に難
がある場合があることに鑑み、一層接着力の向上
を図るために更に研究を重ねた結果、接着層の熱
膨張率を調整するために特定成分を適量添加すれ
ばよいことが判明し、ここに本発明をなしたもの
である。
すなわち、本発明に係る接着用材料は、Cu及
びNiのうちの少なくとも１種を10〜60％、Ti、
Nb及びZrのうちの少なくとも１種を10〜80％
（但し、下記希土類元素を含むときは７〜80％）、
必要に応じて希土類元素（Ｙを含む）のうちの少
なくとも１種を5ppm〜３％含み、更に5μｍ以下
のAl2O3、Mo及びSiO2のうちのいずれか１種を
１〜10％含み、残部が実質的にAg35〜45％であ
る組成を有し、かつ、少なくとも、各成分粒子が
メカニカルアロイングされた複合粉末を含有して
いることを特徴とするものである。かゝる接着用
材料は粉末状体、シート状成形体、ペースト状
等々の任意の態様で使用することが可能である。
以下に本発明を実施例に基づいて詳細に説明す
る。
本発明者は、従来の金属ロウの主な成分系とし
て知られている銀ロウ、ニツケルロウ、銅ロウな
どの主成分を参酌し、Cu−Ti−Agの三成分系を
ベース組成としてその物理的構造について種々の
実験研究を行つた。
まず、上記３成分を溶融合金化状態、或いは粉
末状態とし、粉末状態の中でも単に３成分が混合
している単純混合粉末状態と３成分微粉をメカニ
カルアロイングせしめた複合粉末状態とに区分
し、これらの各状態における接合温度（使用温
度）と物理的構造の変化の可能性について調べ、
接合効果を考察した。
その結果、溶融合金化した場合及び単純な粉末
混合状態の場合には特に接合効果の向上は見られ
ず、接合温度と有機的な関係がなかつたのに対
し、複合粉末状態の場合には接合温度を適切に選
ぶならば接合強度が顕著に向上することを発見し
た。これは、各成分の微粉がメカニカルアロイン
グされているため、接合温度において緻密に隣接
する各成分微粉が表面で溶融して粒子間結合が強
固になり、これが一種のノリの役目を果たして接
合強度が増大するものと考えられる。因みに、そ
のような適切な接合温度を超える高温で各成分溶
融合金化した状態で使用した場合には、その効果
が低下する現象がみられた。また単独混合状態で
は各成分が分離した混合状態にあるために加熱し
ても上記効果は期待できなかつた。
以上の基礎実験に基づき、上記３成分系の組成
範囲、他元素の添加等々について更に実験研究を
重ね、ここに接着用材料として使用し得る化学成
分を確定したものである。
次に、本発明の接着用材料における各成分の限
定理由を示す。
Cu及び／又はNiとAgは、Cu−Ag系やNi−
Ag系或いはCu−Ni−Ag系のロウ材的役目を果
たし、接合強度を高めるために必要である。更
に、Niは特に銅板を使用して金属基材との組合
せで接合する場合、接合後の冷却時に金属基材側
が剥離するのを防止するのに有効で、熱膨張率を
緩和するのを防止する作用があり、またCuは接
合温度を低くするのに有効である。これらのため
には、Cu及びNiのうちの少なくとも１種を10〜
60％、好ましくは20〜50％添加し、またAgはこ
れらの成分並びに以下に示す各成分の含有量合計
の残部、好ましくは35〜45％添加する。
Tiは接合強度等の接着用材料としての性能向
上のために上記Cu、NiとAgとの関連から少なく
とも10％以上添加する必要がある。しかし、80％
を超えると接合層の硬度が高くなり、熱シヨツク
に弱くなるので、好ましくない。したがつて、
Tiは10〜80％、好ましくは10％を超え60％以下
の範囲で添加する。但し、後述の希土類元素を添
加するときは下限値を７％とする。
Tiの代りにNb又はZr、或いはこれらを複数使
用しても同じ効果が得られる。
また、上記成分系に対し、必要に応じて希土類
元素（Ｙを含む）のうちの少なくとも１種を添加
することができる。添加する量は5ppm〜3wt％
とし、ミツシユメタルを使用してもよい。希土類
元素を添加することによりTi、Nb、Zrの添加率
の下限値を７％に下げることがでか、特にTi等
の添加率を小さくしても接着力を得ることができ
るほか、特にSiCなどのセラミツク基材を接合す
る場合に添加すると効果が顕著である。
更に、本発明では、接合層の熱膨張率を調整
し、冷熱繰り返し使用に対しても接着力を維持す
るために、Al2O3、Mo及びSiO2のうちのいずれ
か１種を１〜10％添加する。１％未満ではそのよ
うな効果が得られず、10％を超えて多く添加する
と接着力が低下するので、好ましくない。これら
の成分の添加に際しては、5μｍ以下、好ましく
は2μｍ以下の粉末を用いる必要がある。
上記化学成分を有する接着用材料は、いわゆる
メカニカルアロイ法によつて製造することがで
き、各成分の粉末を擂潰機、ボールミル、アトラ
イター等の撹拌機を用いて高速、高エネルギー下
で所要時間混合撹拌して粉砕することにより、各
成分粒子がメカニカルアロイングしたいわゆるメ
カニカルアロイ形態の複合粉末が得られる。この
複合粉末の粒度は44μｍ以下、好ましくは10μｍ
以下のものが50wt％以上である微粉末が望まし
い。
メカニカルアロイ法（メカニカルアロイング）
は成分粉末を機械的に（すなわち、非溶融状態又
は固相状態で）合金化する方法であり、高速、高
エネルギーを与え得る撹拌機によつて粗粒の成分
粉末を微粉砕し、これが展伸（冷間鍛造）作用に
より破片化し、相対的に延性のある成分破片によ
り他の成分破片が畳み込まれ絡み合つて凝着した
層状構造となり、更に展伸作用を受け、遂には光
学顕微鏡では見分けがつかないほどに均質化、す
なわち、合金化した粒子が得られる。この粒子は
各成分の破片粒子間の凝着作用を利用した固相状
態における合金粒子ということができ、Ｘ線回折
により合金化していることを容易に確認できる。
本発明の接着用材料は、このような複合粉末形
態の粒子を少なくとも含有しているもので、種々
の態様で使用可能であり、粉末状体、シート状成
形体、ブリケツトとして、或いはペースト状にし
て使用できる。
粉末状態の好ましい使用態様としては、まず金
属、セラミツク等の基板上に薄い枠をセツトした
後、該粉末を充填して接着面に挟み込んだ状態と
し、次いで非酸化性雰囲気中又は10-3Torr以下
の減圧下で１〜100Kg／cm2の荷重のもとに600〜
900℃に所要時間加熱し、接合する。なお、900℃
を超える温度上で熱処理すると接着用材料が溶融
合金化し接合効果が低下するので、この点に留意
する必要がある。
粉末状成形体の場合、例えば、上記各成分の粉
末をポツトミル等でよく混合し、圧粉成形機によ
り200〜400Kgｆ／mm3程度の加圧成形し、圧粉体を
得る。圧粉体の形状はシート状、ブリケツト等で
あつて、接着態様に合致した形状にすればよい。
なお、原料粉末として前記の複合粉末を使用する
ときは、そのまま加圧成形する。
成形体の他の形態としては、上記圧粉体を焼結
することにより焼結体とすることができる。焼結
体とするには、例えば、圧粉体を680〜810℃で非
酸化性雰囲気中で行うのが好ましい。焼結温度を
高くして溶融合金化が開始すると接着用材料とし
ての性能、すなわち接合効果が急に低下し、また
Ti、Nb、Zr等を含む成分系の場合には酸化しや
すいので、これらの点に留意する必要がある。
また、更に成形体の他の態様として、上記焼結
体を圧延して焼結圧延体とすることもできる。焼
結圧延体は厚さ１mm以下のシート状にすれば更に
使用し易くなる利点がある。
これらの成形体の好ましい使用態様としては、
まず、金属、セラミツク等の基材に接着用材料で
ある成形体を挟み込んだ状態とし、次いで非酸化
性雰囲気中又は10-3Torr以下の減圧下で１〜100
Kg／cm2の荷重のもとに600〜900℃に所要時間加熱
し、接合する。なお、900℃を超える温度上で熱
処理すると接着用材料が溶融合金化し接合効果が
低下するので、この点に留意して接着温度を決め
る必要がある。
ペースト状で使用する場合は、接着用材料の粉
末を有機溶媒中に分散させる。有機溶媒として
は、テレピネオール、ブチルカルビトール。テキ
サノール、ブチルカルビトールアセテートなどを
使用することができ、またペースト中の粉量は60
〜90wt％とするのが適当である。なお、有機溶
媒の他に界面活性剤（例、ロジン・ワツクス）を
少量添加したり、またバインダーとしてエチルセ
ルロースなどを添加してもよい。
上記ペーストの好ましい使用態様としては、ま
ず金属、セラミツク等の基材の一方又は双方の接
着面に接着ペーストを所要量塗布し、乾燥後、不
活性雰囲気下で550〜600℃で焼成してバインダー
分を揮散させ、次いで非酸化性雰囲気中又は
10-3Torr以下の減圧下で１〜100Kg／cm2の荷重の
もとに600〜900℃に所要時間加熱し、接合する。
塗布量は焼成後の膜厚が10〜30μｍ程度が良い。
あまり薄いと拡散不充分となり接着強度が上がら
ない。また、500μｍ以上に厚くなりすぎるとセ
ラミツク基板に使用した場合、熱膨張差の影響が
大きくなり、セラミツク板に亀裂が生ずるように
なる。なお、加熱温度については、フエライトを
接着する場合は600℃程度の比較的低温でも接着
力を発揮する。これはフエライト表面がTi、Zr、
Nb等によつて還元されFe相を生ずるためと思わ
れる。一般には830〜900℃が好ましい。800℃以
下では接合力が低く、950℃以上になると接合材
料のソリが大きくなり、900℃を超える温度上で
熱処理すると接着用材料が溶融合金化し接合効果
が低下するので、この点に留意して接着温度を決
める必要がある。接着用材料がペースト状の場合
は、これを印刷工程により接着面に印刷し、基材
を接合すれば、多量処理も可能である。
次に本発明の実施例を示す。
（実施例）
原料粉末として、
スポンジチタン（−20μｍに分級）粉末 20部
銀粉末（平均粒径1.6μｍ） 40部
銅粉末（平均粒径1.5μｍ） 40部
を準備し、これらの合計50grに対し、第１表に示
す割合（wt％）でAl2O3粉末（平均粒径1.6μｍ）、
Mo微粉（平均粒径3.8μｍ）又はSiO2粉末（アロ
エジル）を準備した。
まず、前処理として、これらを擂潰機を用いて
５時間混合粉砕し、複合粉末とした。混合粉砕
後、フイツシヤー・サブ・シーブ・サイザーで平
均粒径を測定したところ、1.3μｍであつた。
次いで、この混合粉砕粉末を次の割合で配合
し、擂潰機を使用して５時間、予備混練した。予
備混練の目的は、粉末表面を活性にし、ビヒクル
と接触させることにより、分散性をよくするため
である。
上記混合粉砕粉末 80重量部
エチルセルロース 1.5 〃
テキサノール 16.7 〃
界面活性剤 1.8 〃
予備混練が終了した後、３本ロール・ミルを用
いて本混練を行い、ペースト状の接着用材料とし
た。
なお、上記混合粉砕粉末の一部については、ブ
リケツトにし、接着用材料とした。
次に、基材として、約2.5mm口×0.635mmｔの寸
法の96％Al2O3基板、AlN基板及びSiC基板の各
基板と、25mm口×0.5mmｔ寸法の銅板、SUS304板
及びSS34板の相手基材のそれぞれの片側全面に、
200メツシユ、バイアス張り、エマルジヨン厚さ
45μｍのスクリーンを使用して、スクリーン印刷
機により上記ペーストを印刷した。
印刷後、120℃で30分間乾燥し、600℃で窒素気
流中にて20分間脱脂処理した。
次いで、第１表に示す基材組合せにて、850℃、
窒素気流中で上記基板を中心にサンドイツチ構造
となるように相手基材を重ね、貼り合せて接合し
た。
接合後、ミーク加工機により10mm口のサンプル
を切り出し、接合強度を測定した。なお、接合強
度の測定法は、サンプルを第１図に示すようにセ
ツトし、プツシユ・プル・テスターにより強度を
測定した。同図中、１は基板、２は基板１を中心
にサンドイツチした相手基材板で、これらの基材
が接合層３で接着されており、一方の基材板２に
銅板４を半田付けし、他方の基材板２に銅リベツ
ト（10mmφ）５を半田付けし、上記テスターによ
り強度を測定した。接合強度の判定は、基材が全
く接合されなかつた場合と基板が破壊した場合を
除き、接合面で破断したときの破断時の荷重で示
した。
また、冷熱サイクル試験も行つた。この試験で
は、接合した上記サンプルをそのまま冷熱サイク
ル試験装置に装着し、−55℃×30分間保持と、＋
150℃×30分間保持とを１サイクルとして、基板
が破壊するまでのサイクル数にてチエツクした。
以上の結果を第１表に併記する。同表より明ら
かなとおり、Al2O3、Mo又はSiO2のいずれも添
加しない場合（No.１）或いは少量添加した場合
（No.２）には、一応接合強度は確保されるものの、
冷熱サイクル数が小さく、また適量添加でも粒径
が大きすぎる場合（No.５）は接合強度が不充分で
あると共に冷熱サイクル数が小さく、多量に添加
した場合（No.４）は接合そのものができなくな
る。これに対し、本発明例はいずれも接合強度が
充分確保されると共に冷熱サイクル数が大きく、
各種の基材組合せにおいても熱膨張率が効果的に
調整されていることがわかる。また接着材料の利
用態様が異なつても同様の結果が得られる。
(Field of Industrial Application) The present invention relates to an adhesive material suitable for joining metals to metals, metals to ceramics, and ceramics to ceramics. (Prior Art) Various joining methods have been known for joining the same materials, such as metal to metal, ceramic to ceramic, or joining different materials, such as metal to ceramic. For example, methods for joining metals include fusion welding methods such as electric welding, gas welding, and friction welding, and methods that do not melt the base materials include brazing and bonding methods using organic adhesives. In addition, the bonding methods for ceramics and ceramics include the bonding method using organic adhesives and the heat-resistant metal method (Japanese Patent Application Laid-open No.
61-58870). In contrast to these bonding methods between the same materials, methods for bonding dissimilar materials such as metal and ceramic include adhesive methods using organic adhesives, active metal methods, shrink fitting methods, and solid phase reaction methods. There is a heat-resistant metal method in which the base material is metallized with Mo, W, etc., then nickel plated and soldered to the metal base material.
Recent technologies include bonding methods based on chemical reactions, such as the creation of hydrated compounds using oxide-based inorganic adhesives. (Problems to be Solved by the Invention) However, among the various joining methods mentioned above, all of them, except for fusion welding, which is a unique method for joining metals together, have the drawbacks of being weak against heat and lacking in adhesive strength. . On the other hand, a few bonding techniques using vapor deposition, sputtering, thermal spraying, etc., and bonding techniques using foil insert materials have been proposed, but they not only have the disadvantage of poor adhesive strength, but also have a limited range of use. For these reasons, it is not practical and cannot be said to be a satisfactory joining method in terms of economy. The present invention eliminates the drawbacks of the above-mentioned prior art, has heat resistance, high adhesive strength, and is particularly resistant to repeated cold and hot use, and is not only suitable for bonding between the same materials such as metal and ceramic, but also for bonding different materials between metal and ceramic. The object of the present invention is to provide a new adhesive material that can be easily used for bonding between materials and is practical and economical. (Means for Solving the Problems) In order to achieve the above object, the present inventors first made the adhesive material metallic in order to ensure heat resistance, and in particular, the adhesive strength of the metallic adhesive material was improved. As a result of intensive research on ways to improve heat resistance and adhesive strength, we found that simply adjusting the chemical composition of conventional metal solders (e.g., Japanese Patent Publication No. 61-10235) limits its use, and that it is difficult to improve heat resistance and adhesive strength. It became clear that there was a limit to the requirements, and as a result of repeated experimental research focusing not only on adjusting the chemical components, but also on the physical structure of the adhesive.
By having a specific composition that includes Ag as an essential component, and having a composite powder structure in which each component is mixed and coexisting as an adhesive structure,
It has been found that the above objectives can be achieved. However, when substrates bonded using such metallic adhesives are repeatedly used, the adhesive strength of the adhesive layer may be impaired, so further research is being conducted to further improve the adhesive strength. As a result of stacking the adhesive layers, it was found that an appropriate amount of a specific component should be added to adjust the coefficient of thermal expansion of the adhesive layer, and the present invention was thus made. That is, the adhesive material according to the present invention contains 10 to 60% of at least one of Cu and Ni, Ti,
10-80% of at least one of Nb and Zr
(However, if the following rare earth elements are included, 7 to 80%)
Contains 5 ppm to 3% of at least one rare earth element (including Y) as necessary, and further contains 1 to 10% of any one of Al 2 O 3 , Mo, and SiO 2 of 5 μm or less. The composition is characterized by having a composition in which the balance is substantially 35 to 45% Ag, and containing at least a composite powder in which each component particle is mechanically alloyed. Such an adhesive material can be used in any form such as a powder, a sheet-like molded product, or a paste. The present invention will be explained in detail below based on examples. The present inventor took into consideration the main components known as the main component systems of conventional metal solders, such as silver wax, nickel wax, and copper wax, and based on the three-component system of Cu-Ti-Ag, the physical We conducted various experimental studies on the structure. First, the three components are in a molten alloyed state or a powder state, and the powder state is divided into a simple mixed powder state in which the three components are simply mixed, and a composite powder state in which the three component fine powders are mechanically alloyed, We investigated the possibility of changes in junction temperature (operating temperature) and physical structure in each of these states,
The bonding effect was considered. As a result, no particular improvement in the joining effect was observed in the case of molten alloy or in the case of a simple powder mixture state, and there was no organic relationship with the joining temperature, whereas in the case of a composite powder state, there was no improvement in the joining effect. It was discovered that the bonding strength can be significantly improved if the temperature is selected appropriately. This is because the fine powder of each component is mechanically alloyed, so at the bonding temperature, the closely adjacent fine powder of each component melts on the surface, strengthening the bond between the particles, which acts as a kind of glue and strengthens the bond. is expected to increase. Incidentally, when used in a state in which each component was molten and alloyed at a high temperature exceeding such an appropriate bonding temperature, a phenomenon was observed in which the effectiveness was reduced. In addition, since each component is in a separated mixed state in a single mixed state, the above-mentioned effect could not be expected even if heated. Based on the above basic experiments, we conducted further experimental research on the composition range of the three-component system, the addition of other elements, etc., and determined the chemical components that can be used as adhesive materials. Next, reasons for limiting each component in the adhesive material of the present invention will be shown. Cu and/or Ni and Ag are Cu-Ag system and Ni-
It is necessary to serve as a brazing material for Ag-based or Cu-Ni-Ag-based brazing materials and to increase bonding strength. Furthermore, Ni is particularly effective in preventing the metal substrate side from peeling off during cooling after bonding, especially when bonding copper plates in combination with metal substrates, and prevents the coefficient of thermal expansion from being moderated. In addition, Cu is effective in lowering the junction temperature. For these purposes, at least one of Cu and Ni must be added to
Ag is added in an amount of 60%, preferably 20 to 50%, and the balance of the total content of these components and each component shown below, preferably 35 to 45%, is added. In order to improve performance as an adhesive material such as bonding strength, Ti needs to be added in an amount of at least 10% due to the relationship with Cu, Ni and Ag mentioned above. But 80%
Exceeding this is not preferable because the hardness of the bonding layer increases and it becomes vulnerable to heat shock. Therefore,
Ti is added in a range of 10 to 80%, preferably more than 10% and less than 60%. However, when adding rare earth elements, which will be described later, the lower limit is 7%. The same effect can be obtained by using Nb or Zr, or a plurality of these instead of Ti. Furthermore, at least one rare earth element (including Y) can be added to the above component system as needed. The amount to be added is 5ppm to 3wt%
Mitsushi Metal may also be used. By adding rare earth elements, it is possible to lower the lower limit of the addition rate of Ti, Nb, and Zr to 7%. In particular, it is possible to obtain adhesive strength even with a small addition rate of Ti, etc. It has a remarkable effect when added when bonding ceramic base materials such as. Furthermore, in the present invention, in order to adjust the coefficient of thermal expansion of the bonding layer and maintain adhesive strength even after repeated use of cold and heat, any one of Al 2 O 3 , Mo and SiO 2 is added to the bonding layer. Add 10%. If it is less than 1%, such an effect cannot be obtained, and if it is added in excess of 10%, the adhesive strength decreases, which is not preferable. When adding these components, it is necessary to use powders of 5 μm or less, preferably 2 μm or less. Adhesive materials having the above chemical components can be manufactured by the so-called mechanical alloying method, in which powders of each component are processed at high speed and with high energy using a stirrer such as a crusher, ball mill, or attritor. By mixing, stirring and pulverizing for a period of time, a so-called mechanical alloy composite powder in which each component particle is mechanically alloyed can be obtained. The particle size of this composite powder is 44μm or less, preferably 10μm
A fine powder containing 50wt% or more of the following is desirable. Mechanical alloying method (mechanical alloying)
This is a method of mechanically alloying component powders (that is, in a non-molten state or solid state). Coarse component powders are pulverized using a stirrer that can provide high speed and high energy. It fragments due to the elongation (cold forging) action, and the relatively ductile component fragments fold up other component fragments and intertwine to form a cohesive layered structure, which is further subjected to the elongation action, and finally becomes visible under an optical microscope. Indistinguishably homogenized, ie alloyed, particles are obtained. These particles can be said to be alloy particles in a solid state using the cohesive action between fragment particles of each component, and it can be easily confirmed that they are alloyed by X-ray diffraction. The adhesive material of the present invention contains at least particles in the form of such a composite powder, and can be used in various forms, such as a powder, a sheet-like molded product, a briquette, or a paste. It can be used as The preferred method of using the powder is to first set a thin frame on a substrate made of metal, ceramic, etc., fill it with the powder and sandwich it between adhesive surfaces, and then heat it in a non-oxidizing atmosphere or at 10 -3 Torr. 600~ under a load of 1~100Kg/ cm2 under reduced pressure below
Heat to 900℃ for the required time and bond. In addition, 900℃
If the adhesive material is heat treated at a temperature exceeding 100 mL, the adhesive material will turn into a molten alloy and the bonding effect will decrease, so this point must be kept in mind. In the case of a powder compact, for example, the powders of the above-mentioned components are thoroughly mixed in a pot mill or the like, and the powder is compacted using a compacting machine at a pressure of about 200 to 400 Kgf/mm 3 to obtain a compact. The shape of the green compact may be a sheet, a briquette, or the like, and may be any shape that matches the bonding mode.
In addition, when using the above-mentioned composite powder as a raw material powder, it is press-molded as it is. As another form of the molded body, a sintered body can be obtained by sintering the green compact. In order to obtain a sintered body, it is preferable to perform the compacting at 680 to 810° C. in a non-oxidizing atmosphere, for example. When the sintering temperature is raised and molten alloying begins, the performance as an adhesive material, that is, the bonding effect, suddenly decreases, and
In the case of a component system containing Ti, Nb, Zr, etc., it is easy to oxidize, so these points need to be taken into consideration. Furthermore, as another embodiment of the molded body, the above-mentioned sintered body can be rolled to form a sintered and rolled body. The sintered and rolled body has the advantage of being easier to use if it is shaped into a sheet with a thickness of 1 mm or less. The preferred usage of these molded bodies is as follows:
First, a molded body, which is an adhesive material, is sandwiched between base materials such as metal or ceramic, and then heated to a temperature of 1 to 100 in a non-oxidizing atmosphere or under a reduced pressure of 10 -3 Torr or less.
Weld by heating to 600-900°C for the required time under a load of Kg/ cm2 . Note that heat treatment at a temperature exceeding 900°C will turn the adhesive material into a molten alloy, reducing the bonding effect, so it is necessary to keep this in mind when determining the adhesive temperature. When used in the form of a paste, the powder of the adhesive material is dispersed in an organic solvent. Examples of organic solvents include terpineol and butyl carbitol. Texanol, butyl carbitol acetate, etc. can be used, and the amount of powder in the paste is 60
It is appropriate to set it to ~90wt%. In addition to the organic solvent, a small amount of a surfactant (eg, rosin wax) may be added, or ethyl cellulose or the like may be added as a binder. A preferred method of using the above paste is to first apply the required amount of adhesive paste to the adhesive surface of one or both of the base materials, such as metal or ceramic, and after drying, bake at 550 to 600°C in an inert atmosphere to form a binder. evaporate and then in a non-oxidizing atmosphere or
They are bonded by heating to 600 to 900°C for the required time under a reduced pressure of 10 -3 Torr or less and a load of 1 to 100 Kg/cm 2 .
The coating amount is preferably such that the film thickness after firing is about 10 to 30 μm.
If it is too thin, diffusion will be insufficient and adhesive strength will not increase. Furthermore, if the thickness is too large, exceeding 500 μm, when used on a ceramic substrate, the influence of the difference in thermal expansion becomes large and cracks will occur in the ceramic plate. Regarding the heating temperature, when bonding ferrite, adhesive strength is exhibited even at a relatively low temperature of about 600°C. This is because the ferrite surface is Ti, Zr,
This is thought to be because it is reduced by Nb etc. and produces an Fe phase. Generally, 830 to 900°C is preferred. Below 800°C, the bonding strength is low; above 950°C, the bonding material will warp; heat treatment above 900°C will turn the bonding material into a molten alloy, reducing the bonding effect, so keep this in mind. It is necessary to determine the bonding temperature. If the adhesive material is in the form of a paste, it can be processed in large quantities by printing it on the adhesive surface using a printing process and bonding the base materials. Next, examples of the present invention will be shown. (Example) As raw material powders, prepare 20 parts of sponge titanium powder (classified to -20 μm), 20 parts of silver powder (average particle size 1.6 μm), 40 parts of copper powder (average particle size 1.5 μm), and add them to a total of 50 gr. On the other hand, Al 2 O 3 powder (average particle size 1.6 μm) at the proportions (wt%) shown in Table 1,
Mo fine powder (average particle size 3.8 μm) or SiO 2 powder (Aloesil) was prepared. First, as a pretreatment, these were mixed and pulverized for 5 hours using a crusher to obtain a composite powder. After mixing and pulverizing, the average particle size was measured using a Fisher sub-sieve sizer and found to be 1.3 μm. Next, this mixed pulverized powder was blended in the following proportions and pre-kneaded for 5 hours using a crusher. The purpose of pre-kneading is to improve dispersibility by activating the powder surface and bringing it into contact with the vehicle. The above mixed pulverized powder 80 parts by weight Ethyl cellulose 1.5 Texanol 16.7 Surfactant 1.8 After the preliminary kneading was completed, main kneading was performed using a three-roll mill to obtain a paste-like adhesive material. A part of the mixed pulverized powder was made into briquettes and used as an adhesive material. Next, as base materials, 96% Al 2 O 3 substrate, AlN substrate, and SiC substrate with dimensions of approximately 2.5 mm opening x 0.635 mm t, and copper plate, SUS304 board, and SS34 board with dimensions of 25 mm opening x 0.5 mm t. On the entire surface of each side of the mating base material,
200 mesh, bias tension, emulsion thickness
The paste was printed on a screen printer using a 45 μm screen. After printing, it was dried at 120°C for 30 minutes and degreased at 600°C in a nitrogen stream for 20 minutes. Next, the base material combinations shown in Table 1 were heated at 850°C.
In a nitrogen stream, the mating substrates were stacked and bonded together to form a sandwich structure around the substrate. After bonding, a 10 mm sample was cut out using a Meek cutting machine and the bond strength was measured. The bonding strength was measured by setting the sample as shown in FIG. 1 and measuring the strength using a push-pull tester. In the figure, 1 is a substrate, and 2 is a mating substrate plate sandwiched around the substrate 1. These substrates are bonded with a bonding layer 3, and a copper plate 4 is soldered to one of the substrate plates 2. A copper rivet (10 mmφ) 5 was soldered to the other base plate 2, and its strength was measured using the tester described above. The bonding strength was determined by the load at breakage when the bonded surface was broken, except when the base materials were not bonded at all or when the substrates were broken. A thermal cycle test was also conducted. In this test, the bonded sample was placed in a thermal cycle test device and held at -55℃ for 30 minutes, and then +
One cycle was holding at 150°C for 30 minutes, and the number of cycles until the substrate was destroyed was checked. The above results are also listed in Table 1. As is clear from the table, when neither Al 2 O 3 , Mo nor SiO 2 is added (No. 1) or when a small amount of Al 2 O 3 is added (No. 2), the bonding strength is secured to some extent;
If the number of cooling and heating cycles is small and the particle size is too large even when added in an appropriate amount (No. 5), the bonding strength will be insufficient and the number of cooling and heating cycles will be small, and if a large amount is added (No. 4), the bond itself will be damaged. become unable. On the other hand, in all the examples of the present invention, sufficient joint strength is ensured and the number of cooling/heating cycles is large.
It can be seen that the coefficient of thermal expansion is effectively adjusted even in various base material combinations. Furthermore, similar results can be obtained even if the adhesive material is used in different ways.
【表】
（発明の効果）
以上詳述したように、本発明に係る接着用材料
は、特定成分系でその化学成分を調整すると共に
粉末形態を複合粉末を少なくとも含むものとした
ので、接合が容易で、しかも耐熱性及び接着強度
が優れ、特に冷熱繰り返し使用に耐える接合部を
得ることができ、金属やセラミツクの同一材質間
の接合のみならず、それらの異材質間の接合にも
使用することができる。[Table] (Effects of the Invention) As detailed above, the adhesive material according to the present invention has its chemical components adjusted using a specific component system, and its powder form contains at least a composite powder, so that bonding is possible. It is easy to use, has excellent heat resistance and adhesive strength, and can produce joints that can withstand repeated use of cold and heat.It is used not only for joining the same materials such as metals and ceramics, but also for joining different materials. be able to.
第１図は接合層の接合強度測定法を説明する図
である。
FIG. 1 is a diagram illustrating a method for measuring the bonding strength of a bonding layer.
Claims (1)
少なくとも１種を10〜60％、Ti、Nb及びZrのう
ちの少なくとも１種を10〜80％を含み、更に5μ
ｍ以下のAl2O3、Mo及びSiO2のうちのいずれか
１種を１〜10％含み、残部が実質的にAg35〜45
％である組成を有し、かつ、少なくとも、各成分
粒子がメカニカルアロイングされた複合粉末を含
有していることを特徴とする接着用材料。 ２ 前記接着用材料は粉末状体である特許請求の
範囲第１項記載の接着用材料。 ３ 前記接着用材料はシート状成形体である特許
請求の範囲第１項記載の接着用材料。 ４ 前記接着用材料はペースト状をなしている特
許請求の範囲第１項記載の接着用材料。 ５ Cu及びNiのうちの少なくとも１種を10〜60
％、Ti、Nb及びZrのうちの少なくとも１種を７
〜80％、希土類元素（Ｙを含む）のうちの少なく
とも１種を5ppm〜３％含み、更に5μｍ以下の
Al2O3、Mo及びSiO2のうちのいずれか１種を１
〜10％含み、、残部が実質的にAg35〜45％である
組成を有し、かつ、少なくとも、各成分粒子がメ
カニカルアロイングされた複合粉末を含有してい
ることを特徴とする接着用材料。 ６ 前記接着用材料は粉末状体である特許請求の
範囲第５項記載の接着用材料。 ７ 前記接着用材料はシート状成形体である特許
請求の範囲第５項記載の接着用材料。 ８ 前記接着用材料はペースト状をなしている特
許請求の範囲第５項記載の接着用材料。[Claims] 1% by weight (the same applies hereinafter), containing 10 to 60% of at least one of Cu and Ni and 10 to 80% of at least one of Ti, Nb and Zr, 5μ more
Contains 1 to 10% of any one of Al 2 O 3 , Mo and SiO 2 of less than m, and the remainder is substantially Ag35 to 45
%, and contains at least a composite powder in which each component particle is mechanically alloyed. 2. The adhesive material according to claim 1, wherein the adhesive material is a powder. 3. The adhesive material according to claim 1, wherein the adhesive material is a sheet-like molded body. 4. The adhesive material according to claim 1, wherein the adhesive material is in the form of a paste. 5 At least one of Cu and Ni 10 to 60
%, at least one of Ti, Nb and Zr.
~80%, contains at least one rare earth element (including Y) at 5ppm~3%, and has a particle diameter of 5μm or less.
One of Al 2 O 3 , Mo and SiO 2
~10% Ag, the balance being substantially 35-45% Ag, and at least a composite powder in which each component particle is mechanically alloyed. . 6. The adhesive material according to claim 5, wherein the adhesive material is a powder. 7. The adhesive material according to claim 5, wherein the adhesive material is a sheet-like molded body. 8. The adhesive material according to claim 5, wherein the adhesive material is in the form of a paste.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8853987A JPS63256291A (en) | 1987-04-10 | 1987-04-10 | Material for adhesion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8853987A JPS63256291A (en) | 1987-04-10 | 1987-04-10 | Material for adhesion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63256291A JPS63256291A (en) | 1988-10-24 |
| JPH0378194B2 true JPH0378194B2 (en) | 1991-12-12 |
Family
ID=13945649
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8853987A Granted JPS63256291A (en) | 1987-04-10 | 1987-04-10 | Material for adhesion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63256291A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2783577B2 (en) * | 1988-03-04 | 1998-08-06 | 株式会社東芝 | Brazing filler metal paste for metal-ceramics and electronic components |
| JPH04108673A (en) * | 1990-08-27 | 1992-04-09 | Denki Kagaku Kogyo Kk | Brazing filler metal paste and joined body using the same |
| JP2599029B2 (en) * | 1990-11-14 | 1997-04-09 | 三ツ星ベルト株式会社 | Joining method of joining materials selected from metals or ceramics, and joining materials used therefor |
| CN102814600B (en) * | 2012-08-28 | 2015-05-20 | 广州有色金属研究院 | Amorphous foil brazing filler metal for ceramic braze welding |
| WO2015133577A1 (en) | 2014-03-07 | 2015-09-11 | 日本碍子株式会社 | Joint manufacturing method |
| JP6810438B2 (en) * | 2015-02-09 | 2021-01-06 | 国立研究開発法人産業技術総合研究所 | Mixed particles, slurries containing mixed particles, composites, and conjugates |
| CN108620767B (en) * | 2018-05-08 | 2020-05-12 | 哈尔滨工业大学 | Preparation method of composite solder for brazing quartz short fiber reinforced silicon dioxide composite material and Invar alloy |
-
1987
- 1987-04-10 JP JP8853987A patent/JPS63256291A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63256291A (en) | 1988-10-24 |
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