KR100444894B1 - 플라스틱 슬라이딩층을 갖는 미끄럼 베어링용 복합재료의 제조방법 및 이에 적합한 페이스트 - Google Patents

플라스틱 슬라이딩층을 갖는 미끄럼 베어링용 복합재료의 제조방법 및 이에 적합한 페이스트 Download PDF

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KR100444894B1
KR100444894B1 KR1019970705968A KR19970705968A KR100444894B1 KR 100444894 B1 KR100444894 B1 KR 100444894B1 KR 1019970705968 A KR1019970705968 A KR 1019970705968A KR 19970705968 A KR19970705968 A KR 19970705968A KR 100444894 B1 KR100444894 B1 KR 100444894B1
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fluorine
plastic
parent
paste
composite material
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KR1019970705968A
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KR19980702562A (ko
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아담 아힘
만 홀스트
푸체스베르게르 스테판
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페데랄-모굴 비스바덴 게엠베하 운트 코. 카게
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Abstract

본 발명에 따른 방법에 따라서 플라스틱슬라이드층의 제조를 위해 무엇보다도 페이스트가 플라스틱분산물과 충진재로부터 만들어진다. 상기 페이스트는 유기용매를 포함하지 않으며, 소결된 다공성 금속층에 도포된다. 생산된 다층재료는 그다음 소결된다. 유기용매가 사용되지 않으므로 건강상의 위험과 화재의 위험이 경감된다. 더구나 본 발명에 따라 제조된 복합재료는 뛰어난 공동화 내성을 보인다. 베어링과 같이 종래의 윤활제가 없는 적용에 추가하여 이들 복합재료들은 특히 기어펌프 및 충격흡수기에서 결과적으로 사용될 수 있다.

Description

플라스틱 슬라이딩층을 갖는 미끄럼 베어링용 복합재료의 제조방법 및 이에 적합한 페이스트
본 발명은 청구범위 제 1 항의 전제부에 따른 플라스틱 피복층을 갖는 미끄럼 베어링용 복합재료의 제조방법 및 유기 용매를 포함하지 않는 상기 제조에 요구되는 페이스트에 관한 것이다. 본 발명은 또한 상기 복합재료의 이용에 관한 것이다.
자기-윤활 베어링 재료들은 이미 공지되어 있다. 이것들의 가장 일반적인 형태에서 이것들은 강철지지부(steel backing)에 적용된 다공성의 소결된 주석 또는 납-청동 합금들(lead-bronze alloys)로 구성된다. 여러가지 충진재들을 가지는 플루오로 폴리머들의 혼합물들은, 이것들이 소결된 지지부상에서 10 내지 30㎛의 층을 형성하도록 상기 다공성의 소결된 층으로 가공된다.
자기-윤활 베어링을 제조하는 방법은 DE-PS-1 132 710 호에 기술되어 있다. 상기 방법에서 PTFE 분산물(폴리테트라플루오로에틸렌 분산물)과 충진재로부터 제조된 페이스트(paste)는 압력하에서 다공질의 청동층 내의 공동들속으로 삽입되며, 그 다음 금속이 소결된다. DE-PS-1 132 710 호는 또한 PTFE 충진재 페이스트의 제조를 기술한다. 상기 충진재는 5 와 60％사이의 농도에 있는 PTFE 분산물과 혼합되며, 여기서 분산물을 안정화시키는 이온습윤제와 불용성 화합물을 형성하는 염의도움으로, 그 다음 PTFE의 응고제가 첨가된 충진재의 균일한 개재물과 함께 일어난다. 상기 방법에서는, 예를들면, 톨루엔과 같은 휘발성의 유기용매와, 선택적으로, 에틸페닐폴리글리콜 에테르 또는 지방질 알킬 술포네이트와 같은 계면활성물질이 추가적으로 사용될 수 있는 것으로 언급될 것이다. 상기 계면활성물질은 더욱 우수한 습윤과 이로 인한 상기 충진재의 더욱 균일한 상호혼합을 위해 사용된다. 상기 유기용매는, 완성된 부분에서 10 내지 30㎛ 두께의 필요한 작은 피복층의 달성을 가능케하는 상기 페이스트의 요구되는 점조도(consistency)를 얻기 위해 사용된다.
FR-A-2563468 호에 일 방법이 공지되는데, 여기서는 먼저 PTFE 스트립이 제조되고, 이것은 일측면상에 쌍축적으로 배향된 폴리에틸렌 테레프탈레이트로 구성된 재료를 가지며, 타측면상에는 여과지를 갖는다. 이러한 PTFE 스트립은 PTFE 페이스트 및 충진재로 구성되고, 수성 분산물이 사용된다. 약간의 물은 진공펌프에 의해 스트립의 제조 동안 상기 여과지를 통하여 흡입 제거된다. 이렇게 제조된 상기 스트립이 감기기 전에, 상기 여과지는 제거되는데, 이는 상기 페이스트가 물의 제거로 인해 상당한 정도로 이미 경화되었기 때문이다. 상기 스트립은 그것의 자유 측면을 가지고 다공성의 소결된 층에 적용되고 상기 지지재료는 동시에 제거된다, 상기 PTFE 재료의 물 함량은 매우 낮다. 결과적인 PTFE 피복층은 예를 들면 0.15 mm 두께이다.
DE 41 05 657 A1 호에는 슬라이딩 재료가 공지되는데, 이것은 지지금속 및 거기에 적용된 다공성 금속층을 포함하고 그 표면속으로 함침 코팅 조성물이 도입된다. 이러한 함침 조성물은 PFA, EPE 및 FEP 뿐만 아니라 납으로 구성되고, 나머지는 PTFE 이다. 내마찰성 및 내마모성 그리고 공동화 내성의 요구되는 개선은 폴리머 합금 및 납 분말에 의존한다. DE 41 05 657 A1 은 상기 사용된 함침 조성물이 용매를 포함하는지 포함하지 않는지 여부는 언급하지 않는다.
EP 0 430 324 A1 호는 PTFE, 청동, 흑연 그리고 PVDF 로 구성되는 플라스틱 재료의 제조를 기술한다. 상기 PVDF 분말은 추가적인 성분들과 혼합되고 2 mm 두께의 밴드로서 압출되고, 이로부터 입상재료가 제조된다. 상기 입상재료로부터 그 다음 스트립이 제조되고 이것은 상기 미끄럼 베어링 재료의 다공성 청동층에 적용된다.
US-4,208,472 호는 용매를 포함하는 함침 페이스트를 기술한다.
EP 0 043 182 A1 호는 요지로서 금속성 용기들의 제조와 관련된 윤활제 조성물을 갖는다. 상기 미끄럼 베어링의 제조는 언급되지 않았다.
무겁게 부하된 미끄럼 베어링에 있어서 공동화작용을 통하여 종종 공동들이 발생하는데, 이 공동들은 잠시후 다시 파열되며 이에 따라 에너지를 방출한다. 이렇게 방출된 에너지는 상기 재료의 국부적인 파괴를 가져오며 이에 따라 상기 재료로 구성된 부품들의 사용수명들은 현저하게 감소된다.
FR-A-2563468 호로부터 시작하는, 본 발명이 기초로 하는 과제는, 따라서, 결함없는 플라스틱 피복층, 특히 20 ㎛ 이하의 피복층이 제조될 수 있는, 더 긴 사용수명 및 개선된 공동화 내성을 나타내는, 플라스틱 피복층을 갖는 미끄럼 베어링용 복합재료를 제조하는 방법 및 페이스트를 제공하는 것이다.
이러한 과제는 유기용매를 포함하지 않는 페이스트가 사용되는 플라스틱 피복층을 갖는 미끄럼 베어링용 복합재료의 제조 방법에 의해 해결되는데, 상기 복합재료의 제조를 위해서는 비이온성 습윤제가 사용되고 이에 따라 상기 플라스틱 슬라이딩층은 30㎛ 이하의 두께를 나타낸다.
상기의 페이스트를 제조하기 위하여, 첨가된 이온성 습윤제와 또한 물을 가지는 60중량％까지의 플루오로서머플라스틱으로 구성된 분산물이 플루오로서머플라스틱의 부피 기준으로 5 내지 50 부피％의 충진재와, 플루오로서머플라스틱의 양을 기준으로 0.1 내지 1.5 중량％의 비이온성 습윤제와, 그리고 과량의 물과 혼합되며, 그 다음 침전제로 침전되며, 과량의 물은 제거되고, 상기 페이스트는 지지재료를 피복하는 소결된 다공성 금속층에 도포되며, 이렇게 제조된 다층재료는 그 다음에 소결되는 것이 바람직하다. 상기 분산물중의 이온성 습윤제의 비율은 플루오로서머플라스틱의 양을 기준으로 1 내지 5 중량％의 범위에 있는 것이 바람직하다.
사용된 플루오로서머플라스틱 분산물에 명확하게 일치되는 양의 비이온성 습윤제를 사용함에 의해, 상기 침전 공정후 상기 페이스트에 의한 물의 방출은 지연된다. 비이온성 습윤제의 전체 농도가 플루오로서머플라스틱의 양을 기준으로 0.1 과 1.5 중량％ 사이, 바람직하게는 0.1 내지 1.0 중량％에 놓이는 좁은 범위안에서 유지되는 경우, 상기 플루오로서머플라스틱의 응고 후 및 교반 공정 동안, 상기 페이스트는 결함을 갖지 않으며 어떠한 소정의 요구되는 두께로 상기 다공성 금속지지부에 도포될 수 있는 상태에 도달될 것이다. 알킬폴리글리콜에테르가 비이온성 습윤제로서 사용되는 것이 바람직하다. 그러나, 알킬아릴폴리글리콜에테르, 알킬아미노폴리글리콜에테르, 아실폴리글리콜에테르, 알킬아미노옥사이드 또는 폴리 알콜의 지방산에스테르의 사용이 또한 가능하다.
이온성 계면활성 물질들의 이용은 이러한 목적에 부적합한데, 이는 불용성 화합물들의 형성에 의하여 침전과정 동안에 상기 이온성 계면활성 물질들이 불활성화되며 이에 따라 더 이상 페이스트의 점조도에 영향을 줄 수 없기 때문이다.
플루오로서머플라스틱은, 예를들면, PTFE(폴리테트라플루오로에틸렌), PFA(폴리(테트라플루오로에틸렌-코-퍼플루오로비닐메틸에테르)), FEP(폴리(테트라플루오로에틸렌-코-헥사플루오로프로필렌)), ETFE(폴리(에틸렌-알트-테트라플루오로에틸렌)) 또는 이들의 혼합물일 수 있다. 본 발명에 따르면, PTFE 가 바람직하다. 상기 분산물 내에 포함된 이온성 습윤제는 예를들면 소듐라우릴설페이트이다. 충진재의 예들은 몰리브데늄디설파이드, 납, 납산화물, 흑연, 코크스, 카본블랙, 청동, 플라스틱, 섬유질 재료 및 이들 재료들의 혼합물들이다. 상기 지지재료는 강철, 청동 또는 알루미늄을 포함할 수 있으며 여기에 바람직하게는 청동으로 구성된 다공성 금속층이 적용된다.
이러한 방법의 특별한 장점은 유기용매의 사용이 필요없게 되며, 이에 따라 제조에 관여하는 사람들에 대한 건강상의 위험과 높은 화재의 위험이 현저하게 감소되는 것이다. 이것은 또한 제조공장 및 작업장소의 안전예방에 드는 비용을 현저하게 절감시킨다.
이하, 실시예들을 기초로, 다양한 PTFE/충진재 혼합물들로 코팅된 복합 재료들이 시험되며, 여기서 다양한 충진재들 및 습윤재들이 사용되었다.
실시예 1.
페이스트가 물 16ℓ, 알킬폴리글리콜에테르 50g 그리고 몰리브데늄설파이트 5kg을 40％ PTFE 분산물 21.6kg과 균일하게 혼합하고, 그 다음 20％의 알루미늄나이트레이트 400g 으로 침전시켜 제조되었다. 5분의 정치시간 후에 과량의 물이 제거되고 상기 제조된 페이스트는 15㎛ 두께의 층의 금속 스트립에 도포되었다; 마지막으로 상기 다층재료는 소결되고 종래의 방법으로 조정되었다. 본 발명에 따르는 복합재료(1)가 얻어졌다.
본 발명의 효과를 명확히 하기 위해 3개의 추가적인 페이스트-기초 복합재료들이 제조되었다.
실시예 2.
복합재료(2)가 실시예 1 에서와 같이 제조된다. 제조가 요구되는 페이스트는 PTFE의 부피를 기준으로 20 부피％의 MoS2과, 톨루엔 및 이온성 습윤제 소듐라우릴설페이트를 포함한다. 비이온성 습윤제는 첨가되지 않는다.
실시예 3.
본 발명에 따른 복합재료(3)가 실시예 1 에서와 같이 제조되었으며, 여기서 페이스트는 PTFE와, PTFE의 부피 기준으로 20 부피％의 Pb, 그리고 비이온성 습윤제 알킬폴리글리콜에테르를 포함한다. 유기용매는 사용되지 않는다.
실시예 4.
종래기술에 상응하는 복합재료(4)가 실시예 3 에서와 같이 제조되었으며, 여기서 비이온성 습윤제가 사용되었으나, 톨루엔 및 소듐라우릴설페이트가 상기 페이스트에 첨가되었다.
상술한 목적, 특징 및 장점들 및 다른 목적, 특징 및 장점들은 이하 첨부된 도면을 참조로 설명을 통하여 더욱 용이하게 명확화될 것이다.
도 1 은 본 발명에 따라 준비된 미끄럼 베어링용 복합재료의 사용수명과 종래기술에 따라 준비된 복합재료의 사용수명을 비교하는 막대 그래프이다.
비교시험에서, 상기 복합재료들은 공동화 내성에 대하여 시험되었다. 이 시험은 2000N의 측방 부하와, 40mm의 진폭 및 1Hz의 경사축방향의 운동 하에 있는 충격 흡수기에서 22mm의 내경을 가지는 10mm 폭의 부싱에서 수행되었다. 제 1도는 이러한 시험의 결과를 제시한다.
본 발명에 따른 복합재료의 공동화 내성은 종래 재료들에 비하여 상당히 개선되었음을 볼 수 있다.
상기 결과들은 상기 페이스트로부터의 더욱 완전한 물 제거와, 그에 따른 롤링-인 공정(rolling-in process) 동안의 플라스틱 조성물의 더욱 효과적인 압축의 결과이다. 잔존하는 물이 증발하는 동안, 상기 플라스틱층에서는 유기용매들의 추가적인 함량들을 가지는 경우 보다 더 적은 다공성이 부여되며, 이에 따라 PTFE입자 접촉 표면의 더 높은 비율에 의하여 더욱 완전한 소결공정이 가능해진다. 이에 따라, 벗겨진 표면 샘플들은 현저하게 더 강인하다. 충격흡수기 또는 유압펌프에서 일어나는 것과 같은 공동화 응력하에서 상기 층 내부의 이렇게 강화된 결합은 표면 파편들을 걸러내는 것을 방지하며 따라서 상기 구성 부품들의 신뢰성을 증가시킨다.
베어링과 같은 종래의 윤활제를 포함하지 않는 적용들에 추가하여, 이들 복합재료들은 결과적으로 특히 기어펌프 및 충격흡수기에 또한 사용될 수 있다.

Claims (14)

  1. 다음 단계들을 포함하는, 플라스틱 슬라이딩층을 갖는 미끄럼 베어링용 복합재료의 제조방법:
    (a) 다음을 포함하며 유기 용매를 포함하지 않는 분산 수용액을 제조하는 단계:
    (1) 플루오로서모플라스틱의 분산 수용액;
    (2) 플루오로서모플라스틱의 양을 기준으로, 0.1 내지 1.5 중량％의 비이온성 습윤제;
    (3) 플루오로서모플라스틱의 양을 기준으로, 1 내지 5 중량％의 이온성 습윤제;
    (4) 플루오로서모플라스틱의 부피에 대하여 5 내지 50 부피％의 충진재; 그리고
    (5) 물;
    (b) 단계 (a) 에 따라 형성된 상기 분산 수용액에 침전제를 첨가하여 상기 분산 수용액을 침전시키고 침전된 페이스트를 가라앉히는 단계;
    (c) 어떠한 요구되는 두께에서도 결함없이, 소결된 다공성 금속층에 적용될 수 있는 페이스트를 얻기 위해, 단계 (b) 에 따라 침전된 상기 페이스트로부터 단지 과량의 물을 제거하는 단계;
    (d) 단계 (c) 후에, 상기 다공성 금속층에 플루오로서모플라스틱 피복층을얻고 이에 따라 다층 재료를 형성하기 위해 상기 페이스트를 소결된 다공성 금속층에 적용하는 단계; 그리고
    (e) 상기 소결된 다공성 금속층 상의 플루오로서모플라스틱 피복층의 두께가 30 마이크론 보다 작은 미끄럼 베어링 플루오로서모플라스틱 복합재료를 얻기 위해 단계 (d)에서 형성된 상기 다층 재료를 소결하는 단계.
  2. 제 1 항에 있어서,
    단계 (a)에서, 상기 플루오로서모플라스틱의 분산 수용액은 60 중량％ 까지의 플루오로서모플라스틱을 함유하는 것을 특징으로 하는 플라스틱 슬라이딩층을 갖는 미끄럼 베어링용 복합재료의 제조방법.
  3. 제 1 항에 있어서,
    단계 (a)에서, 상기 플루오로서모플라스틱은, 폴리테트라플루오로에틸렌, {폴리(테트라플루오로에틸렌-코-퍼플루오로비닐메틸에테르)}, {폴리(테트라플루오로에틸렌-코-헥사플루오로프로필렌)}, {폴리(에틸렌-알트-테트라플루오로에틸렌)} 및 이것들의 혼합물로 구성되는 그룹으로부터 선택되는 것을 특징으로 하는 플라스틱 슬라이딩층을 갖는 미끄럼 베어링용 복합재료의 제조방법.
  4. 제 1 항에 있어서,
    단계 (a) 에서, 상기 비이온성 습윤제는, 알킬 폴리글리콜 에테르, 알킬 아릴 폴리글리콜 에테르, 아실 폴리글리콜 에테르, 알킬아민 옥사이드 및 폴리알콜의 지방산 에스테르로 구성되는 그룹으로부터 선택되는 것을 특징으로 하는 플라스틱 슬라이딩층을 갖는 미끄럼 베어링용 복합재료의 제조방법.
  5. 제 1 항에 있어서,
    단계 (a) 에서, 상기 비이온성 습윤제의 비율은 상기 플루오로서모플라스틱의 양에 대하여 0.1 내지 1.0 중량％ 사이의 범위인 것을 특징으로 하는 플라스틱 슬라이딩층을 갖는 미끄럼 베어링용 복합재료의 제조방법.
  6. 제 1 항에 있어서,
    단계 (a) 에서, 상기 충진재는, 몰리브데넘 설파이드, 납, 산화납, 흑연, 코크스, 카본 블랙, 청동, 플라스틱 재료, 섬유 재료, 및 이것들의 혼합물로 구성되는 그룹으로부터 선택되는 것을 특징으로 하는 플라스틱 슬라이딩 층을 갖는 미끄럼 베어링용 복합재료의 제조방법.
  7. 제 1 항에 있어서,
    단계 (a) 에서, 상기 충진재는 상기 플루오로서모플라스틱에 대하여 15 내지 40 부피％의 양으로 첨가되는 것을 특징으로 하는 플라스틱 슬라이딩층을 갖는 미끄럼 베어링용 복합재료의 제조방법.
  8. 베어링을 포함하는 충격 흡수기 또는 기어펌프의 제조에서, 베어링으로서 제 1 항에 따른 상기 소결된 다층 미끄럼 베어링 플루오로서모플라스틱 복합재료를 이용하는 방법.
  9. 유기 용매를 포함하지 않고 다음 단계를 포함하는 공정에 의해 제조되는, 미끄럼 베어링용 플라스틱 피복층의 제조를 위한 페이스트:
    (a) 유기용매를 포함하지 않으며 다음을 포함하는 분산 수용액을 제조하는 단계:
    (1) 플루오로서모플라스틱의 분산 수용액;
    (2) 플루오로서모플라스틱의 양을 기준으로, 0.1 내지 1.5 중량％의 비이온성 습윤제;
    (3) 플루오로서모플라스틱의 양을 기준으로, 1 내지 5 중량％의 이온성 습윤제;
    (4) 플루오로서모플라스틱의 부피에 대하여 5 내지 50 부피％의 충진재; 그리고
    (5) 물;
    (b) 단계 (a) 에 따라 형성된 상기 분산 수용액에 침전제를 첨가하여 상기 분산 수용액을 침전시키고 침전된 페이스트를 가라앉히는 단계;
    (c) 어떠한 요구되는 두께에서도 결함없이, 소결된 다공성 금속층에 적용될 수 있는 페이스트를 얻기 위해, 단계 (b) 에 따라 침전된 상기 페이스트로부터 단지 과량의 물을 제거하는 단계.
  10. 제 9 항에 있어서,
    상기 비이온성 습윤제는, 알킬 폴리글리콜 에테르, 알킬 아릴 폴리글리콜 에테르, 아실 폴리글리콜 에테르, 알킬아민 옥사이드 및 폴리알콜의 지방산 에스테르로 구성되는 그룹으로부터 선택되는 것을 특징으로 하는 페이스트.
  11. 제 9 항에 있어서,
    상기 비이온성 습윤제의 비율은 상기 플루오로서모플라스틱의 양에 대하여 0.1 내지 1.0 중량％ 사이의 범위인 것을 특징으로 하는 페이스트.
  12. 제 9 항에 있어서,
    상기 플루오로서모플라스틱은, 폴리테트라플루오로에틸렌, {폴리(테트라플루오로에틸렌-코-퍼플루오로비닐메틸에테르)}, {폴리(테트라플루오로에틸렌-코-헥사플루오로프로필렌)}, {폴리(에틸렌-알트-테트라플루오로에틸렌)} 및 이것들의 혼합물로 구성되는 그룹으로부터 선택되는 것을 특징으로 하는 페이스트.
  13. 제 9 항에 있어서,
    상기 충진재는, 몰리브데넘 설파이드, 납, 산화납, 흑연, 코크스, 카본 블랙, 청동, 플라스틱 재료, 섬유 재료, 및 이것들의 혼합물로 구성되는 그룹으로부터 선택되는 것을 특징으로 하는 페이스트.
  14. 제 9 항에 있어서,
    상기 충진재는 상기 플루오로서모플라스틱에 대하여 15 내지 40 부피％의 양으로 존재하는 것을 특징으로 하는 페이스트.
KR1019970705968A 1995-03-01 1996-02-23 플라스틱 슬라이딩층을 갖는 미끄럼 베어링용 복합재료의 제조방법 및 이에 적합한 페이스트 KR100444894B1 (ko)

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Publication number Publication date
EP0813452A1 (de) 1997-12-29
JPH11514386A (ja) 1999-12-07
JP4065558B2 (ja) 2008-03-26
DE19507045C2 (de) 1998-10-15
WO1996026793A1 (de) 1996-09-06
KR19980702562A (ko) 1998-07-15
US5948479A (en) 1999-09-07
DE59600967D1 (de) 1999-01-21
EP0813452B1 (de) 1998-12-09
DE19507045A1 (de) 1996-09-12
ES2126388T3 (es) 1999-03-16

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