JP3595036B2 - 研磨材ボデー - Google Patents

研磨材ボデー Download PDF

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JP3595036B2
JP3595036B2 JP20890895A JP20890895A JP3595036B2 JP 3595036 B2 JP3595036 B2 JP 3595036B2 JP 20890895 A JP20890895 A JP 20890895A JP 20890895 A JP20890895 A JP 20890895A JP 3595036 B2 JP3595036 B2 JP 3595036B2
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mixture
group
abrasive particles
abrasive
carbide
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JPH08174427A (ja
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シガラス イアコボス
アネット ロバーツ ブロンウィン
リーデル ラルフ
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デ ビアス インダストリアル ダイアモンド デイビジヨン (プロプライエタリイ) リミテツド
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B24GRINDING; POLISHING
    • B24DTOOLS FOR GRINDING, BUFFING OR SHARPENING
    • B24D3/00Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents
    • B24D3/02Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent
    • B24D3/04Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially inorganic
    • B24D3/06Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially inorganic metallic or mixture of metals with ceramic materials, e.g. hard metals, "cermets", cements
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    • C04B35/6325Organic additives based on organo-metallic compounds
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    • B24D3/14Physical features of abrasive bodies, or sheets, e.g. abrasive surfaces of special nature; Abrasive bodies or sheets characterised by their constituents the constituent being used as bonding agent and being essentially inorganic ceramic, i.e. vitrified bondings
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Description

【0001】
【発明の属する技術分野】
本発明は、摩耗部品、切削差込み工具等として用いるための研磨材ボデーに関する。
【0002】
【従来の技術】
研磨材成形体(compact)は、切削、ミリング、研磨、削孔、及び他の研磨操作で広く用いられている。それらは一般に第二相マトリックス中に分散させた超硬度研磨材粒子を含んでいる。マトリックスは金属か又はセラミックである。超硬度研磨材粒子は、ダイヤモンド又は立方晶系窒化硼素(CBN)でもよい。これらの粒子は一般に用いられている高圧高温圧搾製造工程中、互いに結合して多結晶質物体を形成することが知られている。そのようにして製造したボデーは、PCD又はPCBNとしても知られている。
【0003】
ダイヤモンド及び立方晶系窒化硼素研磨材成形体の例は、米国特許第3,745,623号、第3,767,371号、第3,743,489号、及び第4,334,928号明細書に記載されている。
【0004】
例えば、米国特許第4,334,928号明細書は、80〜20体積%の高圧型窒化硼素、及び残余の、周期表第IVa族又は第Va族遷移金属の炭化物、窒化物、炭窒化物、硼化物、及び珪化物、それらの混合物、及びそれらの固溶体化合物からなる群から選択した少なくとも一種類の結合剤化合物材料のマトリックスから本質的になる工具用焼結成形体を教示しており、そのマトリックスは焼結ボデー中の連続結合構造体を形成しており、高圧窒化硼素が連続マトリックス中に分散している。
【0005】
耐火セラミックは、有機前駆物質を熱分解することにより比較的低い温度で周囲圧力で合成されてきた。種々の形の焼結セラミックボデーは、この経路を用いることにより製造することができる。次の文献はそのような方法を記載している。
【0006】
1. Wright, J.K. and Evans, J.R.G., Br. Ceram. Trans. J., 89, 163−167, 1990.
2. Interrante L.V. et al, Mat. Res. Soc. Symp. Proc. Vol. 249, 31, 1992.
3. Paine R.T. et al, Polymer Preprints, Vol. 34 No. 1, 336, 1993.
4. Seyferth D. et al, J. Am. Ceram. Soc., 75(5), 1300, 1992.
5. Bouillon E. et al, J. of Mat. Sci., 26 1333, 1991.
6. Soraru G.D., et al, J. of Mat. Sci., 25 3886, 1990.
7. Gilbert M. Brown and Leon Maya T., Amer. Ceram. Ceram. Soc. 71, 78−82 (1988).
【0007】
一群のダイヤモンド粒子をセラミックマトリックス中に分散させたものからなるダイヤモンド砥石車も当分野で知られている。
【0008】
【発明が解決しようとする課題】
ダイヤモンド又は立方晶系窒化硼素(CBN)のような超硬度研磨材粒子が、セラミックマトリックス中に分散した研摩材の製造方法を提供する。
【0009】
【課題を解決するための手段】
本発明による研磨材ボデー製造方法は、
(i) 熱分解してセラミック粒子を生成することができる有機金属重合体と一群の研磨材粒子とからなる混合物を与え、
(ii) 前記混合物に熱を加えて前記重合体を熱分解し、そして
(iii) 熱分解した混合物を凝集研磨材ボデーへ焼結する、
諸工程を含む。
【0010】
本発明の方法により製造される焼結研磨材ボデーは、第二相材料中に研磨材粒子が分散したものからなる。第二相材料は、セラミックであり、好ましくは耐火セラミックである。適当なセラミックの例は、炭化珪素、窒化珪素、炭窒化珪素、二酸化珪素、窒化硼素、炭化硼素、窒化アルミニウム、炭化タングステン、炭化チタン、窒化チタン、及び一般に遷移金属の種々の炭化物、窒化物、硼化物である。
【0011】
隣合った研磨材粒子は一般に互いに結合していないが、取り巻く第二相材料には強く結合しており、その第二相は連続相を形成している。研磨材粒子は、ダイヤモンド及び立方晶系窒化硼素又はその混合物を含む群から選択するのが好ましい。
【0012】
生成した焼結研磨材ボデーは強靭で耐摩耗性をもち、例えば、ベアリング表面又は差込み工具のような耐摩耗性表面として用いるのに適している。研磨材粒子が立方晶系窒化硼素(CBN)である場合、ボデーは、鉄合金又は鉄ニッケル基合金又はニッケル基超合金を切削又は機械加工するのに用いることができる。研磨材粒子がダイヤモンドの場合、ボデーは工学及び鉱業での種々の切削、機械加工及び削孔の用途で用いることができる。例えば、木工業用、或はアルミニウム珪素合金の機械加工に、或は繊維補強重合体又は金属マトリックス複合体の機械加工での耐摩耗性作動切削工具として用いることができる。また、コーリング(coring)又は油削孔バイトで切削又は計器保持具(gauge keeping element)として用いることができる。
【0013】
【発明の実施の形態】
本発明の方法の工程(i)で、熱分解してセラミック粒子を生成することができる有機金属重合体と一群の研磨材粒子とからなる混合物を与える。これは、種々の方法で達成することができ、その例を下に記載する。
【0014】
1 混合物は次のようにして調製することができる。容器中で適当な溶媒中に重合体の有機金属前駆物質を溶解する。次に研磨材粒子をその溶液に添加する。次にその混合物を加熱し、溶媒を蒸発し、続いて有機金属前駆物質を重合する。重合は、含まれる前駆物質により、一般に100℃〜500℃(両端の数字を含む)の範囲の温度で行う。得られた混合物は、凝集固体状になっており、容器の形に従った形になっているが、重合体中に研磨材粒子が分散したものからなる。次にその混合物をボールミルにかける。
【0015】
2 重合体の有機金属前駆物質と一群の研磨材粒子とを一緒にミリングし、前駆物質を重合し、次に任意に混合物をミリングすることにより微粉末状の混合物を製造する。
【0016】
3 重合体の有機金属前駆物質と一群の研磨材粒子とを同時に混合及び重合し、次に任意にその混合物をミリングすることにより、微粉末状の混合物を製造する。
【0017】
4 重合体と一群の研磨材粒子とをミリングすることにより微粉末状の混合物を製造する。
【0018】
混合物中の研磨材粒子の濃度は、最終的焼結研磨材ボデー中のそれらの濃度が30体積%〜90体積%(両端の数字を含む)の範囲、好ましくは50体積%〜80体積%(両端の数字を含む)の範囲になるような濃度にすべきである。
【0019】
本発明の方法は、工程(i)と工程(ii)との間に、工程(ii)のための未焼成ボデーを形成するために工程(i)の混合物をプレスする工程を含んでいてもよい。
【0020】
本発明の方法の工程(ii)で、工程(i)の混合物、又は中間工程の未焼成ボデーに熱を加えて重合体を熱分解する。
【0021】
熱分解工程では、混合物を300℃〜1000℃(両端の数字を含む)の範囲の温度に加熱し、重合体を分解し、ガス状副生成物を除去する。
【0022】
工程(ii)は、
(ii)(a) 混合物を、温度が約300℃に到達するまで急速に、例えば、10℃/分までの加熱速度で加熱する;
(ii)(b) 次に温度が約300℃から約800℃まで、混合物をゆっくり、例えば、10℃〜20℃/時(両端の数字を含む)の加熱速度で加熱し;そして
(ii)(c) 次に温度が約1000℃に到達するまで混合物を急速に、例えば、10℃/分までの加熱速度で加熱する;
の三つの段階で行うことができる。
【0023】
混合物は最終的温度で重合体の熱分解を確実に行わせる時間維持してもよい。例えば、混合物を最終的温度に4時間保持してもよい。
【0024】
加熱速度を変化させる理由は、中間温度でゆっくり加熱することが必要だからである。なぜなら、未焼成ボデーの熱分解中、H、CH、及び他の揮発性物が主に300℃〜800℃で一時的な開口気孔を通って蒸発するからである。
【0025】
工程(ii)は、窒素又は窒素混合物の不活性雰囲気中で行うのが好ましい。
【0026】
工程(ii)の結果、セラミック粒子が得られ、その結晶子粒径は10〜500nmの程度であり、それと研磨材粒子はよく混合されている。そのようなセラミック粒子は通常大きな表面積をもち、それに伴う大きな活性度を有する特徴を持つ。
【0027】
本発明の方法の工程(iii )では、熱分解した混合物を凝集研磨材ボデーに焼結する。
【0028】
混合物の焼結は、研磨材粒子上の表面不純物を除去し、セラミック粒子中或は上の反応部位と結合するそれらの傾向を増大する。
【0029】
セラミック/研磨材粒子混合物の焼結は、一般に1000℃〜1400℃(両端の数字を含む)の温度で行う。混合物中の研磨材粒子がダイヤモンドである場合、1000℃〜1100℃(両端の数字を含む)の温度を用いる。混合物中の研磨材粒子がCBNである場合、1000℃〜1400℃(両端の数字を含む)の温度を用いる。
【0030】
用いる温度は最終的焼結研磨材ボデーの組成を決定する。焼結温度範囲の下端では、無定形マトリックスが形成されるのに対し、その範囲の上端では結晶化マトリックスが形成する。
【0031】
研磨材ボデーの密度を増大するため、焼結は加圧下で行なってもよい。圧力は一般に20kバールを越えない。好ましい圧力範囲は10バール〜10kバールである。比較的低い圧力或は非加圧焼結したを用いることにより、従来法に勝る利点を与える。圧力を加える場合、その適用後、加圧焼結ボデー中の研磨材粒子の含有量は90体積%程の高さになる。
【0032】
本発明の方法で用いるのに好ましい有機金属重合体は、NCP200〔ヘキスト社(Hoechst Aktiengesellschat)の製品〕のような重合したポリオルガノシラザンであり、それは無定形炭窒化珪素セラミックマトリックスに転化することができる。
【0033】
本発明を次の実施例により例示する。
【0034】
【実施例】
例1
或る量の微粉砕テトラキス(ジメチルアミド)チタンを、0.5〜2μmの範囲の粒径を有する或る量のCBN粒子と混合した。次にその混合物をヘリウム雰囲気中で反応容器中に入れ、今度はそれを真空導管に接続し、蒸留により液体アンモニアで満たした。反応容器を真空中で密封し、混合物を室温へ暖めた。れんが色のチタンアンモノリシス生成物が実質的に直ちに析出するが、それにも拘わらず反応容器を時々振りながら4日以上放置した。析出物を沈降させ、上澄み液を傾瀉して除去した。アンモニアを蒸留して固体に戻し、それを洗浄し、そしてその傾瀉・蒸留・洗浄工程を数回繰り返した。アンモニア及び残留ジアルキルアミンを蒸留により除去し、微細に分散したCBNを含有する固体チタン化合物をポンプにより一晩乾燥した。固体アンモノリシス生成物は、Ti(N(CH)(NH(N)の実験式を持つことが判明した その化合物は重合体であり、窒素を含む官能基(ニトリド、イミド、アミド)により架橋されていた。
【0035】
次に混合物を真空中で熱分解した。400℃より低い温度で殆どのガス状生成物〔主にNH(CH及びNH〕が放出されるので、混合物を800℃まで加熱した。チタン重合体生成物は分解してTiNになり、緊密なTiN/CBN混合物を与えた。この熱分解は化学量論的であり、式:
Ti(N(CH)(NH(N) Δ TiN+NH(CH)+NH
と記述される。
【0036】
TiN生成物中には、残留炭素がTiC又は無定形炭素として残っていた。
【0037】
得られた混合物を加圧容器中に入れ、1100℃及び10kバールまで15分間加熱した。そのプレスから取り出すと、気孔率が5%未満である凝集ボデーが形成されていることが判明した。そのボデーの組成は、58体積%CBN、35体積%のTiN及び7体積%のTiCであった。
【0038】
例2
例1と同様な方法により、トルエンに溶解したビニルシラン及びダイヤモンド粉末(粒径範囲平均0.5〜2μ)の混合物を調製した。溶媒を蒸発した後、混合物を局限しない不活性雰囲気中で徐々に加熱し、ビニルシランを重合し、次に800℃でポリビニルシランを熱分解した。更に10kバールの圧力で1100℃に加熱することにより、混合物を焼結し、1質量%より低い遊離珪素含有量を有する研磨材ボデーにした。そのボデーを一辺が5mmの大きさの三角形にレーザーで切断し、マトリックスドリルバイトを製造するのに従来用いられているろう付け合金により結合炭化タングステン支柱にろう付けした。冷却すると、研磨材ボデーは炭化物支柱から剥離しなかった。
【0039】
例3
ジエチルアルミニウムアミド、EtAlNHを、トリエチルアルミニウムとアンモニアとを炭化水素溶媒中で次の反応:
AlEt+NH→EtAlNH+C
に従い反応させることにより製造した。
【0040】
エタンを除去し、高度に揮発性の三量体EtAlNH中間体を残した。次にこの中間体の溶液を或る量の0.5〜2μm粒径の立方晶系窒化硼素微粉末と混合した。その粉末を極めてゆっくり混合し、次に超音波撹拌することにより均質にした。混合物を不活性雰囲気中の入ったグローブボックス(glovebox)中の反応容器中に入れ、真空導管に接続した。容器を150℃に加熱し、そこで混合物を固化し、アルミニウム中間体を分解して名目上EtAlNHとして記述される生成物にした。この生成物は種々の組成(その熱履歴による)を持つが、広い分布の分子量を持つ不溶性重合体として分類される。
【0041】
更に400℃まで加熱すると、アルミニウム生成物は熱分解:
EtAlNH Δ AlN+C
によりAlNへ転化した。
【0042】
得られたAlN/CBN混合物をプレス中に入れ、10kバールの圧力で1000℃へ加熱し、気孔を除去した。得られたボデーは窒化アルミニウムマトリックス中に主にばらばらのCBN粒子を60体積%含んでいた。
【0043】
例4
例3と同じ手順を繰り返した。但しCBN粉末を混合した後、SiCウィスカーを10体積%添加した。得られた生成物は、例3の非補強生成物と比較して向上した靭性を持っていた。
【0044】
例5
この例ではポリオルガノシラザンを無定形炭窒化珪素セラミックマトリックスへ転化した。このセラミックマトリックスは、ハイブリッド処理と呼ばれている重合体からセラミックへの転化法により生成させた。
【0045】
第一の段階では、ポリシラザンとダイヤモンド又はCBN研磨材粒子とからなる混合物を与えるため、三つの異なった経路が研究された。
(a) CBN又はダイヤモンドをドープしたポリシラザンNCP200をボールミルにかける。重合(架橋とも呼ばれている)後、複合体微粉末を生成させるのに更にボールミルにかける必要があった。
(b) ポリシラザンNCP200及び或る量の研磨材粒子の混合及び重合を同時に行う。NCP200は液体で、重合中発砲するので、研磨材粒子は重合後、重合体中に均一に分布する。次にボールミルにかけることにより粉末が生成する。
(c) 重合したNCP200/研磨材粒子混合物をボールミルにかける。
【0046】
Si又はSiCの如き種子粒子を混合段階中に添加してもよい。
【0047】
得られた粉末を32μm篩を通して篩い分け、630MPaでコールドアイソスタティックプレスにかけ、円柱状の未焼成ボデーを得た。
【0048】
次にその未焼成ボデーをAr中で熱処理にかけた。熱分解工程の加熱計画は、300℃までの10℃/分の大きな加熱速度、300℃〜800℃の間で10℃〜20℃/時の低下した加熱速度、及び1000℃までの10℃/分の加速した加熱速度を用いることにより、全処理時間に対して最適にした。最終温度での等温保持は4時間であった。中間的温度でのゆっくりした加熱は、未焼成ボデーの熱分解中、H及びCHが主に300℃〜800℃で一時的開口気孔を通って揮発するので必要であった。
【0049】
然る後、ボデーを1100℃〜1400℃で更に熱処理にかけ、セラミックマトリックスを結晶化し、焼結した。この場合も、混合物中の研磨材粒子がダイヤモンドである場合、1000℃〜1100℃の温度を用い、研磨材粒子がCBNである場合、1000℃〜1400℃の温度を用いた。
【0050】
純粋なポリシラザンから誘導された炭窒化珪素は、1400℃より高い温度で結晶化するので、Si又はSiCの如き種子粒子を存在させた場合の結晶化開始温度の低下が研究された。即ち、二種類の異なったセラミック複合体を形成した:ダイヤモンド又はCBNを無定形Si−C−Nマトリックス中に埋込んだもの、又はダイヤモンド又はCBNを多結晶質Si/SiCマトリックス中に埋込んだもの。

Claims (18)

  1. (i) 熱分解してセラミック粒子を生成することができる有機金属重合体及び一群の研磨材粒子を含む混合物を、
    (a)重合体の有機金属前駆物質を一群の研磨材粒子と共にミリングし、前記前駆物質を重合し、次に前記混合物をミリングする;又は
    (b)重合体の有機金属前駆物質と、一群の研磨材粒子とを同時に混合及び重合し、次にその混合物をミリングする;又は
    (c)重合体と一群の研磨材粒子とを一緒にミリングする;
    ことにより与え、
    (ii) 前記混合物に熱を加えて前記重合体を熱分解し、そして
    (iii) 熱分解した混合物を凝集研磨材ボデーへ焼結する、
    諸工程を有する研磨材ボデーの製造方法。
  2. 工程(i)で、混合物中の研磨材粒子の濃度が、最終的凝集研磨材ボデー中のそれらの濃度が30体積%〜90体積%(両端の数字を含む)の範囲に入る濃度である、請求項1に記載の方法。
  3. 工程(i)で、混合物中の研磨材粒子の濃度が、最終的凝集研磨材ボデー中のそれらの濃度が50体積%〜80体積%(両端の数字を含む)の範囲に入る濃度である、請求項2に記載の方法。
  4. 工程(i)と工程(ii)の間に、工程(i)の混合物をプレスして工程(ii)のための未焼成ボデーを形成する工程を含む、請求項1に記載の方法。
  5. 工程(ii)で、混合物を300℃〜1000℃(両端の数字を含む)の範囲の温度に加熱し、重合体を熱分解させる、請求項1に記載の方法。
  6. 工程(ii)で、加熱を、
    (ii)(a) 混合物を、温度が約300℃に到達するまで急速に加熱する;
    (ii)(b) 次に温度が約300℃〜約800℃の間にある時、混合物をゆっくり加熱し;そして
    (ii)(c) 次に温度が約1000℃に到達するまで混合物を急速に加熱する;
    の三つの段階で行う、請求項5に記載の方法。
  7. 工程(ii)で、混合物を最終温度に、重合体の熱分解を確実に行わせる時間維持する、請求項5又は6に記載の方法。
  8. 工程(iii)で、熱分解した混合物を1000℃〜1400℃(両端の数字を含む)の温度で焼結する、請求項1に記載の方法。
  9. 工程(iii)で、焼結を加圧下で行う、請求項1に記載の方法。
  10. 研磨材粒子を、ダイヤモンド、立方晶系窒化硼素及びそれらの混合物からなる群から選択する、請求項1に記載の方法。
  11. 生成したセラミックが、炭化珪素、窒化珪素、炭窒化珪素、窒化硼素、炭化硼素、窒化アルミニウム、炭化タングステン、炭化チタン、窒化チタン、及び遷移金属の炭化物、窒化物、及び硼化物からなる群から選択されたものである、請求項1に記載の方法。
  12. 生成したセラミックが、炭化珪素、窒化珪素、炭窒化珪素、二酸化珪素、窒化硼素、炭化硼素、窒化アルミニウム、炭化タングステン、炭化チタン、窒化チタン、及び遷移金属の炭化物、窒化物、及び硼化物からなる群から選択されたものである、請求項1に記載の方法。
  13. 有機金属重合体が重合したポリ有機シラザンである、請求項1に記載の方法。
  14. 一群の研磨材粒子をセラミックマトリックス中に分散したものを含む複合研磨材ボデーにおいて、前記ボデーが、前記研磨材粒子が前記複合研磨材ボデーの50体積%〜80体積%(両端の数字を含む)を占め、前記研磨材粒子が前記複合研磨材ボデー中の連続相を形成するセラミックマトリックスに結合しており、前記セラミックマトリックスが、熱分解してセラミック粒子を生成することができる有機金属重合体と前記一群の研磨材粒子とを含む混合物の熱分解及びひき続いての焼結により形成されていることを特徴とし、前記混合物は:
    (a)重合体の有機金属前駆物質を一群の研磨材粒子と共にミリングし、前記前駆物質を重合し、次に前記混合物をミリングする;又は
    (b)重合体の有機金属前駆物質と、一群の研磨材粒子とを同時に混合及び重合し、次にその混合物をミリングする;又は
    (c)重合体と一群の研磨材粒子とを一緒にミリングする;
    ことにより与えられたものである上記複合研磨材ボデー。
  15. 研磨材粒子を、ダイヤモンド、立方晶系窒化硼素及びそれらの混合物からなる群から選択する、請求項14に記載の複合研磨材ボデー。
  16. セラミックマトリックスを、炭化珪素、窒化珪素、炭窒化珪素、窒化硼素、炭化硼素、窒化アルミニウム、炭化タングステン、炭化チタン、窒化チタン、及び遷移金属の炭化物、窒化物、及び硼化物からなる群から選択する、請求項14又は15に記載の複合研磨材ボデー。
  17. セラミックマトリックスを、炭化珪素、窒化珪素、炭窒化珪素、二酸化珪素、窒化硼素、炭化硼素、窒化アルミニウム、炭化タングステン、炭化チタン、窒化チタン、及び遷移金属の炭化物、窒化物、及び硼化物からなる群から選択する、請求項14又は15に記載の複合研磨材ボデー。
  18. 有機金属重合体が重合されたポリオルガノシラザンである、請求項14に記載の複合研磨材ボデー。
JP20890895A 1994-08-17 1995-08-16 研磨材ボデー Expired - Fee Related JP3595036B2 (ja)

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DE69519408T2 (de) 2001-04-19
ZA956408B (en) 1996-03-11
DE69519408D1 (de) 2000-12-21
EP0698447B1 (en) 2000-11-15
EP0698447A2 (en) 1996-02-28
EP0698447A3 (en) 1996-08-14
CA2156347C (en) 2004-01-06
KR960007507A (ko) 1996-03-22
CA2156347A1 (en) 1996-02-18
US5649984A (en) 1997-07-22
JPH08174427A (ja) 1996-07-09

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