EP0628368B1 - Polymer-Metallverbundgussstücke - Google Patents

Polymer-Metallverbundgussstücke Download PDF

Info

Publication number
EP0628368B1
EP0628368B1 EP19940108167 EP94108167A EP0628368B1 EP 0628368 B1 EP0628368 B1 EP 0628368B1 EP 19940108167 EP19940108167 EP 19940108167 EP 94108167 A EP94108167 A EP 94108167A EP 0628368 B1 EP0628368 B1 EP 0628368B1
Authority
EP
European Patent Office
Prior art keywords
metal
insert
melt processable
aluminum
polyimide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP19940108167
Other languages
English (en)
French (fr)
Other versions
EP0628368A1 (de
Inventor
James Francis Mcnamara
David Mark Pentenburg
Edward Anthony Miller
Arnold Wayne Raymond
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0628368A1 publication Critical patent/EP0628368A1/de
Application granted granted Critical
Publication of EP0628368B1 publication Critical patent/EP0628368B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D19/00—Casting in, on, or around objects which form part of the product
    • B22D19/12—Casting in, on, or around objects which form part of the product for making objects, e.g. hinges, with parts which are movable relatively to one another
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D19/00—Casting in, on, or around objects which form part of the product
    • B22D19/08—Casting in, on, or around objects which form part of the product for building-up linings or coverings, e.g. of anti-frictional metal

Definitions

  • Polyimides and similar polymers have long been used in a variety of applications in which high temperatures are encountered. Accordingly, shaped articles of polyimide have been used as bushings, seals, electrical insulators, compressor vanes, piston rings, gears, thread guides, brake linings, and clutch facings. In view of the high cost of polyimide materials, and for greater flexibility in performance characteristics, it is often desirable to combine polyimide with other materials such as metal. In this context, a continuing need exists for economical and efficient methods of combining polyimide with metals.
  • the present invention provides articles comprising non-melt processable high temperature polymers and metal which can be easily and economically fabricated.
  • the instant invention provides an article comprising:
  • the invention further provides a process for the preparation of non-melt processable polymer articles comprising:
  • the figures are cross sectional illustrations of cast metal-polymeric articles according to the present invention.
  • Non-melt processable polymers which can be used in the present invention include those that have no melting point below their decomposition temperature or a melting point greater than about 370°C.
  • Such polymers include, for example, polyimides and polybenzimidazoles.
  • polyimides can be used in the present invention, including those described in Edwards, U.S. Patent 3,179,614, hereby incorporated by reference.
  • the polyimides described therein are prepared from at least one diamine and at least one anhydride.
  • Preferred diamines which can be used include m-phenylene diamine (MPD), p-phenylene diamine (PPD), oxydianiline (ODA), methylene dianiline (MDA) and toluene diamine (TDA).
  • Preferred anhydrides which can be used include benzophenone tetracarboxylic dianhydride (BTDA), biphenyl dianhydride (BPDA), trimellitic anhydride (TMA), pyromellitic dianhydride (PMDA), maleic anhydride (MA) and nadic anhydride (NA).
  • BTDA benzophenone tetracarboxylic dianhydride
  • BPDA biphenyl dianhydride
  • TMA trimellitic anhydride
  • PMDA pyromellitic dianhydride
  • MA maleic anhydride
  • NA nadic anhydride
  • Preferred polyimides which can be used in the present invention include those prepared from the following combinations of anhydride and diamine: BTDA-MPD, MA-MDA, BTDA-TDA-MDA, BTDA-MDA-NA, TMA-MPD & TMA-ODA, BPDA-ODA & BPDA-PPD, BTDA-4,4'-diaminobenzophenone, and BTDA-bis (p-aminophenoxy)-p,p'-biphenyl.
  • An especially satisfactory polyimide in the present invention is that prepared from pyromellitic dianhydride and 4,4'-oxydianiline.
  • the polymeric component of the present invention can also contain fillers of the type typically used in polyimide compositions, such as graphite. Typically such fillers are used in quantities up to about 45% of the total polymeric composition.
  • Particularly preferred graphites which can be used in the present invention are those which are substantially free from reactive impurities, that is, those impurities which have an adverse effect on the oxidative stability of blends with polyimides.
  • the graphite should have less than about 0.15 wt. % of such reactive impurities, and preferably less than about 0.10 wt. %.
  • Typical of such reactive impurities are metal oxides and sulfides, and particularly ferric sulfide, barium sulfide, calcium sulfide, copper sulfide, barium oxide, calcium oxide, and copper oxide.
  • the non-melt processable polymer is formed into a shaped insert.
  • the shape will necessarily vary with the intended use for the polyimide.
  • cylinders of substantially circular cross section are formed.
  • a central aperture is formed within the cylinder.
  • the cast metal contains the insert.
  • the cast metal substantially surrounds the insert.
  • non-melt processable polymer 1 is the general form of a right circular cylinder.
  • Aperture 2 is formed in the middle of the cylinder.
  • Cast metal 3 substantially surrounds the cylinder.
  • retaining means 4 is provided on the outer diameter of the cylinder. This prevents movement of the polymer component in relation to the cast metal in a circumferential direction.
  • Other non-circular shapes or perimetral irregularities for the insert can be used to provide an interlocking configuration of the polymeric and cast metal component, and thus prevent an circumferential movement, as will be evident to those skilled in the art.
  • Figure 2 is a cross-sectional illustration of an article of the present invention shown in Figure 1 taken parallel to the central aperture.
  • the non-melt processable polymer insert 11 has its corners 12 chamfered so that the cast metal 13 is prevented from longitudinal movement relative to the insert.
  • Figure 3 is a cross-sectional illustration of an article of the present invention in which the non-melt processable polymer is intended as a wear strip. There, the non-melt processable polymer 21 is in a trapezoidal configuration. Corners 22 of the polymer are contained by cast metal 23.
  • Metals which can be used in the present invention include those having a melting point of at least about 400°C. Such metals include, for example, aluminum, antimony, barium, magnesium, and zinc, as well as castable alloys of one or more of the above. Aluminum and its alloys have been found to be particularly satisfactory in the present invention. Alloys are typically formulated to balance the flow properties in the molten state and the physical properties of the alloy in its final configuration.
  • the metal is cast to contain the non-melt processable polymer.
  • such containment can be in the form of substantially complete encapsulation, for example, where the polymer is in the form of a cylindrical bearing.
  • such containment can be partial, such as the situation in which the metal contains a corner of the shaped polymer insert or a retaining tab.
  • the high temperature, non-melt fabricable polymer can be formed into the desired shape by the techniques usually used for such materials, such as direct forming, direct forming with secondary machining, or molding of particulate resin with elevated temperature and pressure.
  • the cast metal in the finished articles is characterized by the dendritic crystalline structure characteristic of cast metals.
  • the dendrites are a configuration that has a tree-like branching pattern.
  • the dendrites are formed as the metal cools through the solidifying stage.
  • the casting process can be carried out by a variety of conventional casting operations. For example, sand or investment casting techniques can be used. Typically, however, die casting into metal molds has been found particularly effective for the present invention.
  • the present invention permits the preparation of articles combining metal and non-melt fabricable polymer in an efficient and cost-effective manner.
  • the contact of the polymer with the molten metal has been found to not depreciate the polymer to a significant extent, so long as the polymer is present in the required minimum cross-sectional thickness of about 1 mm.
  • the required thickness for example, in a cylindrical bearing component, is measured as the thickness of the wall of the cylindrical component as opposed to the overall diameter of the bearing.
  • An insert of polyimide prepared from oxydianiline and pyromellitic dianhydride was machined from a solid direct formed blank.
  • the insert had the following nominal dimensions; 24 mm outside diameter x 21 mm inside diameter x 9.5 mm thickness.
  • Chamfers were machined at the outside diameter on each face. Two flats, 180° apart, were machined on the outside diameter. The latter two machining steps were done to prevent axial and rotational movement of the insert relative to the die casted metal.
  • the polyimide insert was then placed on a metal core-pin in a die casting mold.
  • the mold was closed, capturing the insert inside.
  • the mold was preheated to a temperature of 204°C.
  • the inside diameter was measured. Measurements showed the metal shrinkage caused the inside diameter of the insert to be reduced by a nominal 0.33 mm. The inside diameter also had a taper of 0.15 mm to 0.18 mm. It is believed the taper is caused by the two different metal masses of the die cast part, the larger mass causing the inside diameter to be reduced more than the smaller mass. Inspection of the finished part indicated no effect on the surface finish of the inside diameter of the polyimide.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Sliding-Contact Bearings (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)

Claims (10)

  1. Verfahren zur Herstellung von Gegenständen aus nichtschmelzverarbeitbarem Polymerem, umfassend:
    (A) das Bilden eines geformten Einbettungsteils aus nichtschmelzverarbeitbarem Polymerem mit einer Dicke von wenigstens etwa 1 mm; und
    (B) das Gießen von geschmolzenem Metall um das Einbettungsteil herum, um das Einbettungsteil einzufassen, wobei das Metall einen Schmelzpunkt von wenigstens etwa 400°C besitzt.
  2. Verfahren nach Anspruch 1, bei welchem das nichtschmelzverarbeitbare Polymere im wesentlichen aus Polyimid besteht.
  3. Verfahren nach Anspruch 2, bei welchem das Polyimid aus Oxydianilin und Pyromellitsäuredianhydrid hergestellt ist.
  4. Verfahren nach Anspruch 1, bei welchem das Metall ausgewählt wird aus der Gruppe bestehend aus Aluminium, Antimon, Barium, Magnesium und Zink sowie gießbaren Legierungen von diesen.
  5. Verfahren nach Anspruch 4, bei welchem das Metall im wesentlichen aus Aluminium oder einer gießbaren Legierung von Aluminium besteht.
  6. Gegenstand aus nichtschmelzverarbeitbarem Polymerem, umfassend:
    (A) ein formgestaltetes Einbettungsteil aus nichtschmelzverarbeitbarem Polymerem mit einer Querschnittsdicke von wenigstens 1 mm; und
    (B) Gußmetall, das das Einbettungsteil enthält; wobei das Einbettungsteil und das Gußmetall eine ineinandergreifende Konfiguration besitzen.
  7. Gegenstand nach Anspruch 6, bei welchem das nichtschmelzverarbeitbare Polymere im wesentlichen aus Polyimid besteht.
  8. Gegenstand nach Anspruch 7, bei welchem das Polyimid aus Oxydianilin und Pyromellitsäuredianhydrid hergestellt ist.
  9. Gegenstand nach Anspruch 6, bei welchem das Metall ausgewählt ist aus einer Gruppe bestehend aus Aluminium, Antimon, Barium, Magnesium und Zink sowie gießbaren Legierungen von diesen.
  10. Gegenstand nach Anspruch 8, bei welchem das Metall im wesentlichen aus Aluminium oder einer gießbaren Legierung von Aluminium besteht.
EP19940108167 1993-06-07 1994-05-27 Polymer-Metallverbundgussstücke Expired - Lifetime EP0628368B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US7280193A 1993-06-07 1993-06-07
US72801 1993-06-07
US72901 2008-02-28

Publications (2)

Publication Number Publication Date
EP0628368A1 EP0628368A1 (de) 1994-12-14
EP0628368B1 true EP0628368B1 (de) 1998-08-26

Family

ID=22109838

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19940108167 Expired - Lifetime EP0628368B1 (de) 1993-06-07 1994-05-27 Polymer-Metallverbundgussstücke

Country Status (3)

Country Link
EP (1) EP0628368B1 (de)
JP (1) JP3311494B2 (de)
DE (1) DE69412703T2 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2311518T3 (es) 2001-05-21 2009-02-16 Krosaki Harima Corporation Aparato para el cambio de toberas de inmersion, tobera de inmersion y placa de cierre utilizada para la misma.

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3179614A (en) * 1961-03-13 1965-04-20 Du Pont Polyamide-acids, compositions thereof, and process for their preparation
GB908557A (en) * 1960-06-02 1962-10-17 Hans Joachim Fuchs Improvements in or relating to light metal alloy engine casings
JPH04290693A (ja) * 1991-03-20 1992-10-15 Toyoda Gosei Co Ltd ホース一体化継手
JP3002300B2 (ja) * 1991-07-12 2000-01-24 日本トムソン株式会社 球面滑り軸受及びその製造方法

Also Published As

Publication number Publication date
JP3311494B2 (ja) 2002-08-05
DE69412703D1 (de) 1998-10-01
JPH079112A (ja) 1995-01-13
EP0628368A1 (de) 1994-12-14
DE69412703T2 (de) 1999-04-29

Similar Documents

Publication Publication Date Title
EP0412891B1 (de) Form aus metallpulvergefülltem Epoxyharz und Verfahren zu deren Herstellung
US4807728A (en) Brake member and method of manufacturing same
US5789523A (en) Polyimide compositions with improved wear resistance and friction at high PV (pressure × velocity) conditions
KR100412071B1 (ko) 금형 방법, 다이 캐스트 주조법 및 다이 캐스트 제품
US5119865A (en) Cu-alloy mold for use in centrifugal casting of ti or ti alloy and centrifugal-casting method using the mold
CN1759956A (zh) 双液离心浇注制造双金属复合耐磨管的方法
US4280844A (en) Refractory brick for molding molten steel
US5399417A (en) Cast metal-polymeric articles
EP0628368B1 (de) Polymer-Metallverbundgussstücke
KR20040072737A (ko) 주철관의 연속 주조 몰드 보호용 제품
US5179153A (en) Wear resistant polyimide composition
KR20030069066A (ko) 시효 경화성 구리 합금
JPS60208443A (ja) アルミニウム合金材
US5898048A (en) Polyimide powder and process for producing powder molded body
KR19990023170A (ko) 금형용 아연-기재 합금, 금형용 아연-기재 합금 블록 및 이들의 제조방법
RU2422243C2 (ru) Охлаждающая составная часть литейной формы для заливки литейного материала и применение охлаждающей составной части литейной формы
WO2004101197A3 (de) Verfahren zum schleudergiessen
JPH08104928A (ja) 硬化性銅合金の用途
KR900001097B1 (ko) 플래스틱 성형용 주조금형
US2408341A (en) Alloy
JPS62250125A (ja) ブレ−キ部品とその製造法
JPH0256182B2 (de)
US915727A (en) Process of making castings of aluminum and aluminum alloys.
KR20160145237A (ko) 내마모형 고력황동 및 이의 제조방법
JPS6330105A (ja) カリバ−付圧延用複合スリ−ブ

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): DE GB

17P Request for examination filed

Effective date: 19950607

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 19970806

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE GB

REF Corresponds to:

Ref document number: 69412703

Country of ref document: DE

Date of ref document: 19981001

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20120523

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20120523

Year of fee payment: 19

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20130527

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20131203

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69412703

Country of ref document: DE

Effective date: 20131203

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20130527