EP0417081A1 - Procede d'emboutissage isostatique a chaud de corps en nitrure de silicium renforces par des fibres et des barbes de carbure - Google Patents

Procede d'emboutissage isostatique a chaud de corps en nitrure de silicium renforces par des fibres et des barbes de carbure

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Publication number
EP0417081A1
EP0417081A1 EP88902464A EP88902464A EP0417081A1 EP 0417081 A1 EP0417081 A1 EP 0417081A1 EP 88902464 A EP88902464 A EP 88902464A EP 88902464 A EP88902464 A EP 88902464A EP 0417081 A1 EP0417081 A1 EP 0417081A1
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EP
European Patent Office
Prior art keywords
carbide
nitrogen
partial pressure
silicon nitride
pressure
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.)
Ceased
Application number
EP88902464A
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German (de)
English (en)
Inventor
Peter Greil
Klaus Nickel
Michael Hoffmann
Günter Petzow
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.)
Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
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Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
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Application filed by Max Planck Gesellschaft zur Foerderung der Wissenschaften eV filed Critical Max Planck Gesellschaft zur Foerderung der Wissenschaften eV
Publication of EP0417081A1 publication Critical patent/EP0417081A1/fr
Ceased legal-status Critical Current

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Definitions

  • the invention relates to a method for hot isostatic pressing (HIPen) of carbide fiber and carbide whisker-reinforced silicon nitride bodies.
  • silicon nitride ceramics are of great importance as materials in engine construction, e.g. B. for use in heat engines, and as a forming and cutting tool in metalworking.
  • the electrical and mechanical properties can be significantly improved by introducing carbide fibers or carbide whiskers (US-A-4 507 224).
  • the manufacture of silicon nitride ceramics reinforced with carbide fibers or carbide whiskers is therefore of great importance.
  • the high sintering temperatures require increased nitrogen pressures to prevent decomposition of the Si 3 N 4 matrix in silicon and nitrogen. It is therefore necessary to use temperatures below 1900 ° C. in the case of pressure-less sintering in order to decompose the Si 3 N 4 material during sintering in accordance with the reaction
  • silicon nitride remains stable up to very high temperatures (e.g. up to over 2700 ° C at 100 MPa) .
  • the object of the present invention was therefore to provide a process for the hot isostatic pressing of carbide-fiber and carbide-whisker-reinforced silicon nitride bodies, with which the disadvantages mentioned above can be avoided and with which carbide-fiber and whisker-reinforced silicon nitride bodies can be produced in a simple and economical manner, which because of their mechanical, chemical and electrical properties and because of their. Stability fully meets the high requirements.
  • the invention therefore relates to a process for hot isostatic pressing (HIPen) of silicon nitride shaped bodies reinforced with carbide fiber or carbide whiskers from the group SiC, HfC, NbC, TaC, TiC, VC or ZrC, which is characterized in that the non-pressurized Pre-sintered molded bodies in a nitrogenous atmosphere without encapsulation at temperatures between 1000 and 3000 ° C in a nitrogen protective gas atmosphere under a nitrogen partial pressure which is the equation
  • Nitrogen as a gas cannot be dispensed with during sintering, since when the nitrogen partial pressure is reduced, the upper limit of the sintering temperature drops drastically due to equation (1).
  • the nitrogen partial pressure which must be set for the hot isostatic pressing of carbide fiber or whisker reinforced Si 3 N 4 composite materials without destroying the matrix or fiber / whisker, must therefore be between an upper and a lower limit for the respective carbide. It has now been found that the respective limit is determined by the equation
  • T s is the sintering or HIP temperature in ° K (K).
  • the upper limit of the nitrogen partial pressure that can be used is determined by the reaction reactions (equations 3 to 9) 2 HfC + N 2 ⁇ 2 HfN + 2 C (3)
  • Table 1 shows the parameters a, b and c from which the upper limit of the nitrogen partial pressure (P N2 ) can be calculated for the carbide used according to equation (2). These values are known from the literature (see Chase et al. (1975), JANAF thermochemical tables; Storms, EK (1967) The refractory carbides, Refractory materials 3, Academic Press, NY, USA; Toth, LE (1971) Transition metal carbides and nitrides, Refractory materials 7, Academic Press, NY, USA).
  • Parameters a, b and c to calculate the upper limit of the applicable nitrogen partial pressure.
  • the lower temperature limit is determined by the stability in the presence of nitrogen of the carbide to be used as fiber or whisker. This means that the reactions according to equations (3) to (9) must be avoided.
  • FIGS. 1a to 1g graphically represent the nitrogen partial pressures (P N2 ) and temperature (T) conditions which are possible for the carbides used according to the invention and at which one can work according to the invention.
  • the hatched area illustrates the possible area.
  • 1a shows the P N2 -T region for the HIPen of NbC fiber / - whisker-reinforced Si 3 N 4 ;
  • 1b shows the P N2 -T region for the HIPen of TaC fiber / - whisker-reinforced Si 3 N 4 ;
  • 1c shows the P N2 -T region for the HIPen of SiC fiber / - whisker-reinforced Si 3 N 4
  • 1d shows the P N2 -T region for the HIPen of HfC fiber / - whisker-reinforced Si 3 N 4 ;
  • 1e shows the P N2 -T region for the HIPen of TiC fiber / - whisker-reinforced Si 3 N 4 ;
  • Fig. 1g the P N2 -T area for the HIPen of VC fiber / - Whisker reinforced Si 3 N 4 .
  • the protective gas is preferably an inert gas, such as Ar, He, Ne, Xe, or a mixture thereof.
  • composition of the nitrogen protective gas atmosphere is as follows:
  • Total pressure necessary for hot isostatic pressing is the reason. Size lies in the usual pressure range used for the hot isostatic pressing (HIP) process.
  • a total gas pressure P Hip of at least 1000 bar is preferably used.
  • the proportion of carbide fibers and / or carbide whiskers can be up to 50% by weight, based on the starting mixture.
  • the lower limit of the carbide content is in generally around 0.1% by weight, preferably 0.5% by weight, and in particular 1% by weight.
  • the upper limit of the carbide content is preferably 30% by weight, and in particular 15% by weight.
  • the starting mixture (powder body) for the process according to the invention can also contain customary additives or melting phases for such processes for the production of silicon nitride moldings, such as, for. B. usual sintering aids (sintering additives).
  • sintering additives Y 2 O 3 , Al 2 O 3 and AlN, and in particular powder mixtures thereof, are preferably used as sintering aids, or Y 3 Al 5 O 12 .
  • the proportion of sinter additives preferably increases with increasing carbide content. In particular, the proportion of sintering additives is 5 to 15% by weight (based on the starting mixture), the lower limit of 5% by weight preferably being used for the lower limit of the carbide content, and the upper limit of 15% by weight.
  • the ratio of the sintering additive powder is preferably within the limits: Y 2 O 3 80 to 40% by weight; Al 2 O 3 10 to 30% by weight and AlN 10 to 30% by weight.
  • the method according to the invention is combined for hot isostatic pressing (HIPen) with a previous pressure-free presintering in a nitrogen atmosphere, preferably until a closed porosity (greater than 95%) is reached.
  • the pre-sintering can be done on known and. take place in the usual way and using additives customary for this, such as sintering aids (sintering additives).
  • sintering additives sintering additives
  • sintering additives sintering additives
  • sintering additives sintering additives
  • sintering additives are used as sintering aids, and in particular powder mixtures of Y 2 O 3 , Al 2 O 3 and AlN, or Y 3 Al 5 O 12 .
  • the preferred proportion of sintering additives also corresponds to the preferred proportion ranges mentioned above.
  • Sintering additives greatly reduce the mechanical properties of the ceramic, especially at high temperatures.
  • fewer additives are required in order to achieve a maximum density of a ceramic body.
  • Another advantage of the method according to the invention is that with low nitrogen partial pressure but high total gas pressure, maximum compression can be achieved even at relatively low temperatures.
  • a powder mixture consisting of 85 to 70% by weight of Si 3 N 4 , 0 to 15% by weight of ⁇ -SiC whisker, and 9.8% by weight of Y 2 O 3 , 1.7% by weight Al 2 O 3 and 3.5% by weight of AlN are mixed homogeneously by attrition in an organic liquid.
  • the whisker-containing powder suspension is then dried in a rotary evaporator and cold isostatically pressed into test specimens.
  • the green density is 2 - 2.1 g / cm 3 (60 - 63% th.D.).
  • the composite ceramic is pre-sintered at 1850 ° C under an N 2 pressure of 1 bar (0.1 MPa) to the closed porosity for 30 minutes.
  • the density after presintering reaches 3.3 to 3.15 g / cm 3 for whisker contents from 0 to 15% by weight (99 to 95% th.D.).
  • the presintered specimen is then hot-isostatically compressed in a gas mixture of 1% by volume of N 2 and 99% by volume of Ar without capsules at a temperature of 1900 ° C. for 10 minutes (HIP method).
  • the total isostatic pressure is 1000 bar (100 MPa), the N 2 partial pressure reaching 10 bar (1 MPa).
  • the density also increases in the samples with up to 15% by weight SiC whisker content up to over 3.3 g / cm 3 (99% th.D.), without the SiC whiskers being destroyed in the test specimen .
  • FIG. 2 graphically shows the absolute density and relative density (fractional density; in%) in relation to the part of the whisker.
  • Figure 3 shows the K Ic values in relation to the Whiskerantexl. Maximum values of the K Ic of over 8.5 MPa m 1/2 are achieved with a ⁇ -SiC whisker content of 10% by weight.

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Abstract

Un procédé d'emboutissage isostatique à chaud (EIC) de corps en nitrure de silicium renforcés par des fibres et des barbes de carbure est appliqué sur des moules préfrittés sans pression non-scellés à des températures comprises entre 1000 et 3000°C dans une atmosphère contrôlée d'azote sous une pression partielle d'azote représentée par l'équation (I), dans laquelle PN2 représente la pression partielle de N2 et Ts la température en °K. La limite inférieure de la pression partielle est donnée par les valeurs a = 872 213, b = 405,6 et c = -16,6, et la limite supérieure de la pression partielle, selon le carbure utilisé, est donnée par les valeurs suivantes: (II). Selon ce procédé, on peut atteindre avec une faible pression partielle d'azote mais avec une haute pression globale de gaz une condensation maximale à des températures encore relativement basses, sans détruire les fibres et les barbes de carbure.
EP88902464A 1987-03-17 1988-03-15 Procede d'emboutissage isostatique a chaud de corps en nitrure de silicium renforces par des fibres et des barbes de carbure Ceased EP0417081A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873708689 DE3708689A1 (de) 1987-03-17 1987-03-17 Verfahren zum heissisostatischen pressen von carbidfaser- und carbidwhisker verstaerkten siliziumnitridkoerpern
DE3708689 1987-03-17

Publications (1)

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EP0417081A1 true EP0417081A1 (fr) 1991-03-20

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EP88902464A Ceased EP0417081A1 (fr) 1987-03-17 1988-03-15 Procede d'emboutissage isostatique a chaud de corps en nitrure de silicium renforces par des fibres et des barbes de carbure

Country Status (5)

Country Link
US (1) US5106793A (fr)
EP (1) EP0417081A1 (fr)
JP (1) JPH02501382A (fr)
DE (1) DE3708689A1 (fr)
WO (1) WO1988007029A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3805641A1 (de) * 1988-02-24 1989-09-07 Hoechst Ag Verbundwerkstoff und verfahren zu seiner herstellung
JP2730245B2 (ja) * 1990-01-29 1998-03-25 日産自動車株式会社 炭化珪素・窒化珪素質複合焼結体の製造方法
KR960012714B1 (ko) * 1994-06-29 1996-09-24 한국과학기술연구원 SiC 휘스커 강화 세라믹스 복합 재료의 제조 방법

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DE3141590C2 (de) * 1980-10-20 1985-01-03 Kobe Steel, Ltd., Kobe, Hyogo Verfahren zur Herstellung von hochdichtem gesintertem Siliziumnitrid
JPS57209884A (en) * 1981-06-17 1982-12-23 Kobe Steel Ltd Manufacture of high strength silicon carbide sintered body
DE3129633A1 (de) * 1981-07-28 1983-02-17 Elektroschmelzwerk Kempten GmbH, 8000 München "praktisch porenfreie formkoerper aus polykristallinem siliciumcarbid, die durch isostatisches heisspressen hergestellt worden sind"
DE3142058A1 (de) * 1981-10-23 1983-05-05 Elektroschmelzwerk Kempten GmbH, 8000 München Praktisch porenfreie formkoerper aus polykristallinem siliciumnitrid und siliciumcarbid und verfahren zu ihrer herstellung durch isostatisches heisspressen
DE3201563A1 (de) * 1982-01-20 1983-07-28 Elektroschmelzwerk Kempten GmbH, 8000 München Dichte formkoerper aus polykristallinem, hexagonalem bornitrid und verfahren zu ihrer herstellung durch isostatisches heisspressen
US4552711A (en) * 1983-06-21 1985-11-12 Cornell Research Foundation, Inc. Use of free silicon in liquid phase sintering of silicon nitrides and sialons
DE3403917C1 (de) * 1984-02-04 1985-11-28 Deutsche Forschungs- und Versuchsanstalt für Luft- und Raumfahrt e.V., 5000 Köln Verfahren zum Verdichten poroeser keramischer Bauteile fuer das heissisostatische Pressen
US4603116A (en) * 1984-04-09 1986-07-29 Gte Laboratories Incorporated Silicon nitride based ceramics and method
DE3445766A1 (de) * 1984-12-14 1986-06-19 Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V., 3400 Göttingen Verfahren zur herstellung von kurzfaserverstaerkten keramikformkoerpern
AU5868386A (en) * 1985-03-14 1986-10-13 Atlantic Richfield Company High density reinforced ceramic bodies and method of making same
JPS6274003A (ja) * 1985-09-26 1987-04-04 Nippon Kokan Kk <Nkk> 圧粉体の焼結方法
SE456563B (sv) * 1986-05-13 1988-10-17 Asea Cerama Ab Sett vid isostatisk pressning av pulver till foremal i en omslutning av glas
JPS63123868A (ja) * 1986-11-10 1988-05-27 日産自動車株式会社 窒化珪素質焼結体の製造方法
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Also Published As

Publication number Publication date
JPH02501382A (ja) 1990-05-17
JPH0577633B2 (fr) 1993-10-27
DE3708689C2 (fr) 1989-01-19
WO1988007029A1 (fr) 1988-09-22
US5106793A (en) 1992-04-21
DE3708689A1 (de) 1988-10-20

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