Ceramic composite and process for the production thereof

BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a ceramic composite comprising particles of an inorganic compound and particles and whiskers of silicon nitride, silicon oxynitride and silicon oxide, and to a process for producing the ceramic composite. Further, this invention relates to an electric conductor, heater and sliding material comprising the ceramic composite.
2. Description of Related Art
Ceramics to be used as a conducting material, structural material or etc. has recently been required to have a high high-temperature strength, high toughness, high thermal shock resistance and high accuracy of dimension. As such ceramics are known inorganic compounds such as carbides, nitrides, oxides, borides, silicides and oxynitrides, for example, silicon nitride, silicon carbide, alumina and zirconia. These ceramic materials each is hardly used by itself to have so excellent properties as mentioned above. Therefore, many proposals have been made to achieve such properties by selecting the combinations of the ceramic materials and changing the design of structure.
As a heater there has hitherto been used a metal heater or ceramic heater. The metal heater includes nichrome or tantalumn. This heater has such a problem that it is poor in heat resistance and degraded at a temperature of 1,000.degree. C. or higher.
As a ceramic heater practically used there are silicon carbide, stabilized zirconia, lanthanchromite, molybdenum silicide and the like. These ceramic materials have a relatively high electric resistance, and thermo-runaway easily occurs and temperature-controlling is very hard in such heater since such ceramic materials have a negative resistance-temperature coefficient. Furthermore, these ceramic materials have such defects that they are poor in mechanical strength and thermal shock resistance. Therefore, new electrically conductive ceramics as substitutions for the above-mentioned ceramic materials have been demanded and various trials have been made.
As described in, for example, Japanese Patent KOKAI (Laid-Open) No. 50-84936, SiC or Si.sub.3 N.sub.4 is mixed with an electrically conductive compound and subjected to hot press sintering to eliminate the problem or defects as mentioned above. However, the hot press sintering method makes it possible to densify sintered bodies but the method has such a problem that cost for production is high since a great amount of energy is required for production.
As described in Japanese Patent KOKAI (Laid-Open) No. 60-44990, an electrically conductive ceramic enveloped with an electrically insulating ceramic is sintered by hot pressing, which requires a great amount of energy. Further, the hot pressing makes it impossible to mold and sinter products having a complicated shape. Generally, to integrate and sinter two or more ceramics having electric resistances different from each other, their coefficients of thermal expansion must be adjusted, but the hot pressing is carried out at so high temperatures that a small difference in coefficient of thermal expansion makes it easy for cracks to form.
Furthermore, Japanese Patent KOKAI (Laid-Open) No. 60-60983 discloses a process in which an electrically conductive material is mixed with Si.sub.3 N.sub.4 particles and the mixture is sintered by pressureless sintering. In this process, a sintering aid is used and hence softening or deformation takes place inconveniently at high temperatures, and further a volume shrinkage of about 40 to 60% is brought about on sintering to induce deformation of sintered bodies. On the other hand, the sintering of the conductive material and Si.sub.3 N.sub.4 particles in the absence of any sintering aid do not improve the density of the sintered bodies and, therefore, the specific resistance of the bodies is inconveniently high. Thus, the electrically conductive product according to this Patent KOKAI has unsatisfactory performance.
The Japanese Patent KOKAI references above do not take any account of shrinkage of molded bodies on sintering. Therefore, in these references shrinkage is brought about.
Generally, SiC, Si.sub.3 N.sub.4 or the like is known as an engineering ceramic suitable for a structural material for engines or turbines. These ceramics are excellent in heat resistance and they are sintered by pressureless sintering, pressure sintering or reaction sintering. With the pressureless sintering and pressure sintering, a rate of dimensional change before and after sintering is 15 to 20%. Thus, these sintering techniques provide deformation and poor accuracy of dimension. On the other hand, it is known that the reaction sintering technique provides a lower rate of dimensional change than that of the other sintering techniques, but nevertheless, the rate is as high as about 1 to 1.5%, as shown in Japanese Patent KOKAI (Laid-Open) No. 58-140375.
As a material having a low rate of dimensional change, there is known a bonded Si.sub.3 N.sub.4 product which has been used as a refractory material. Such material has a mechanical strength of only about 50 MN/m.sup.2, as shown in Japanese Patent KOKAI (Laid-Open) No. 58-88169, and is not suitable as a structural material.
Furthermore, Japanese Patent KOKAI (Laid-Open) No. 61-201662 which has filed by the present applicant, discloses that a fully satisfactory rate of dimensional change on sintering is obtained but a body having a complicated shape is hardly obtained due to poor flowability of a starting mixture, and further the resultant sintered body has an insufficient mechanical strength.
Some of the reasons for hardly popularizing the engineering ceramics are that the rate of dimensional change on sintering is high and sintered bodies are hardly workable due to the high hardness and brittleness thereof. It is not too much to say that there have never been any practical process for producing a ceramic material having a high strength, low rate of dimensional change and high accuracy of dimension.
On the other hand, the ceramic material has been used as a sliding material for sealing having an excellent resistance to thermal shock.
Generally, working of a machine is always accompanied with sliding. Reduction of friction and wear will induce saving of energy and long life of a sliding material. For example, a floating seal comprising O-ring 4 and sealing elements 5 and 6 as shown in FIG. 17, has been used as a sealing means for cars or construction machines. In this means, one of these sealing elements is fixed, and the other is rotated in contact with the fixed element at the sliding surface 7 thereof and set through a lubricant 8 in a floating state with respect to an axis 9, thereby keeping the sealing property of the means. Therefore, this means is most suitable for sealing or protecting from earth and sand and has widely been used. However, this floating seal has such a defect that it is poor in heat resistance and wear resistance since it is made of a cast iron material. Another sealing means is known in which one of sealing elements 10 is made of Cr cast iron and the other 11 is made by injection molding. This sealing means has also the same defect as mentioned above.
On the other hand, a ceramic-made sliding means has recently been provided. A typical example of the ceramics for the sliding means includes SiC, Si.sub.3 N.sub.4, Al.sub.2 O.sub.3 or ZrO.sub.2, but it is practically required to have the following properties as the sliding material (see "Kogyo Zairyo", Vol. 31, No. 12, pp. 139-146, particularly 140):
(1) a high hardness and an excellent resistance to wearness and seizing;
(2) a good affinity to a sliding partner (a low coefficient of friction and a small amount of the partner worn);
(3) a good corrosion resistance;
(4) a high strength, toughness and resistance to thermal shock;
(5) a small amount of deformation by stress and/or heat at sliding surfaces to keep a good lubrication state on the sliding surfaces (i.e., a high Young's modulus and a small coefficient of thermal expansion);
(6) a high thermal conductivity (The increase of the coefficient of friction and thermal deformation on the sliding surfaces are prevented by increasing the resistance to thermal shock and inhibiting the accumulation of frictional heat.); and
(7) a low specific gravity (centrifugal stress is reduced).
These required properties all are not satisfied by known materials. For example, a metallic material is questionable in the resistance to seizing. Al.sub.2 O.sub.3 itself has a low resistance to thermal shock, and since it has a high coefficient of thermal expansion, it is easily deformed by heat on the sliding surfaces thereof. ZrO.sub.2 itself also has a low resistance to thermal shock and a high coefficient of thermal expansion. Si.sub.3 N.sub.4 itself has a low thermal conductivity. SiC alone has a high hardness and high thermal conductivity but has a poor resistance to thermal shock. A sliding material having both excellent wear resistance and corrosion resistance and conspicuously improved resistance to thermal shock has been demanded.
Among these sliding materials SiC is widely used in a sintered form. For example, Japanese Patent KOKAI (Laid-Open) No. 61-163174 discloses "a sliding material comprising an SiC sintered porous body having an excellent sliding property under wet conditions" and Japanese Patent KOKAI (Laid-Open) No. 55-100421 discloses "a sliding means comprising a fixed part and rotating part, any one of the parts being made of Si.sub.3 N.sub.4 and the other made of SiC".
However, these Japanese Patent KOKAI references all do not draw any attention to resistance to thermal shock and one-side contact.
Thus, the prior art materials have no combination of good wear resistance and thermal shock resistance and further have such drawbacks that cracks are generated due to a rapid change of temperatures and they allow their partners to be worn.
SUMMARY OF THE INVENTION
The objects of the present invention are to eliminate the defects or drawbacks as described above.
The present invention has the following three aspects:
FIRST ASPECT
One object of the present invention is to provide a ceramic composite containing two or more layers having different electric resistances formed by near net shaping.
Another object of the present invention is to provide the ceramic composite further having a very small rate of dimensional change on sintering molded bodies.
A still further object of the present invention is to provide a current collector ring for revolving electric machines, made from the ceramic composite.
SECOND ASPECT
An object of the present invention is to provide an engineering ceramic composition suitable for near net shaping with a high accuracy of dimension and giving a ceramic sintered body which does not require any machining and has a small rate of dimensional change on sintering, high high-temperature strength and good resistance to thermal shock, the composition further having a good flowability in molding.
THIRD ASPECT
An object of the present invention is to a sliding and sealing means having a good wear resistance, corrosion resistance and thermal shock resistance and a reduced worn amount of a sliding partner.

BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1(A) and 1(B) are schematical cross-sectional views of one embodiment according to the FIRST ASPECT of the present invention.
FIG. 2 is a micrograph of crystal grains of the sintered body comprising a conductive portion and an insulating portion of a ceramic composite according to the FIRST ASPECT of the present invention.
FIGS. 3(A) and 3(B) are schematical cross-sectional views of another embodiment according to the FIRST ASPECT of the present invention.
FIG. 4 is a graph which shows the relation between contents of TiN and Al.sub.2 O.sub.3 and dimensional change on sintering in the FIRST ASPECT of the present invention.
FIG. 5 is a graph which shows the relation between bending strength and temperature in the FIRST ASPECT of the present invention.
FIG. 6 is a graph which shows the relation between particle size of metallic Si and bending strength in the FIRST ASPECT of the present invention.
FIGS. 7(A) and 7(B) are schematical cross-sectional views of a further embodiment according to the FIRST ASPECT of the present invention.
FIG. 8 is a graph which shows the relation between rate of dimensional change on sintering and mixing ratios of raw materials in the SECOND ASPECT of the present invention.
FIG. 9 is a graph which shows the relation among mixing ratios of raw materials [Si/(Si+inorganic compound)], rate of dimensional change on sintering and bending strength in the SECOND ASPECT of the present invention.
FIG. 10 is a graph which shows the relation between amount of binder resin and bending strength in the SECOND ASPECT of the present invention.
FIGS. 11 and 12 are graphs which show the relation between volumetric particle packing rate of molded bodies and bending strength in the SECOND ASPECT of the present invention.
FIG. 13 is a graph which shows the relation between specific surface area of raw material powder and amount of molding binder in the SECOND ASPECT of the present invention.
FIG. 14 is a graph which shows the relation between apparent viscosity of raw material composition measured by flow tester and volumetric particle packing rate in the SECOND ASPECT of the present invention.
FIG. 15 is a micrograph of ceramic composition of a sliding surface in an example of the THIRD ASPECT of the present invention.
FIG. 16 is a graph which shows the relation between surface pressure and coefficient of friction in the THIRD ASPECT of the present invention.
FIG. 17 is a cross-sectional view of an example of a conventional floating seal.
FIG. 18 is also a cross-sectional view of another example of a floating seal.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
FIRST ASPECT
The ceramic composite of the present invention is one prepared by integral molding and integral sintering ceramics different in electric resistivity to bond them with particles or whiskers of at least one of Si.sub.3 N.sub.4, Si.sub.2 N.sub.2 O and SiO.sub.2 produced from metallic Si or ferro-Si.
In the ceramic composite of the present invention, ceramics contiguous to each other and different in electrical resistivity and electrically conductive compounds for changing the resistivity are non-oxide type conductive materials which are nitrides, carbides, borides and silicides of substances of Groups IIIa, IVa, Va, VIa and VIII of the periodic table and preferred are TiN, TiC, TiB.sub.2, TiSi.sub.2, ZrN, ZrC, ZrB.sub.2, ZrSi.sub.2, HfN, HfC, TaN, TaC, TaB.sub.2, TaSi.sub.2, Mo.sub.2 N, Mo.sub.2 C, MoB, Cr.sub.2 N, Cr.sub.3 C.sub.2, CrB, CrSi.sub.2, NbN, NbC, NbSi.sub.2, VN, VC, WC and WSi.sub.2. Especially, TiN, TiC, ZrN, ZrC, Cr.sub.2 N and Cr.sub.3 C.sub.2 are excellent in oxidation resistance and are suitable.
Content of electrically conductive particles in sintered body which are for decreasing electrical resistivity in the present invention is preferably 80 vol % or less. If the content is more than 80 vol %, characteristics of ceramics such as mechanical strength, thermal shock resistance and oxidation resistance decrease.
In the present invention, electrical resistivity of sintered bodies can be optionally changed by changing content of conductive particles in the sintered bodies in the range of 5-80 vol %. Furthermore, the resistivity in the range of 10.sup.14 .OMEGA. cm-10.sup.-5 .OMEGA. cm can be optionally obtained by containing electrically insulating particles in sintered body.
In the ceramic composite of the present invention, conductive particles or insulating particles are bonded with at least one of Si.sub.3 N.sub.4, Si.sub.2 N.sub.2 O and SiO.sub.2 produced from metallic Si or ferro-Si and volume change on sintering is small and there occur no deformation. Further, two layers different in electrical resistivity are bonded with Si.sub.3 N.sub.4, Si.sub.2 N.sub.2 O or SiO.sub.2 produced from metallic Si or ferro-Si and the bonded interface is also superior in heat resistance and thermal shock resistance like the body.
The sintered bodies of the present invention preferably have a void content of 5-40%. When void content exceeds 40%, mechanical strength decreases and besides it is difficult to lower the resistivity. When it is less than 5%, permeation resistance of nitriding gas or oxidizing gas with which metallic Si or ferro-Si reacts is increased to make it difficult to obtain good sintered bodies. This is because in order that conductive compound or insulating compound, metallic Si or ferro-Si react with nitriding gas or oxidizing gas to form Si.sub.3 N.sub.4, SiO.sub.2 or Si.sub.2 N.sub.2 O phase to bond the insulating compound or conductive compound, there are needed voids for permeation of said gas through molded body.
Presence of 5-40% of voids in sintered body causes relaxation of strain produced due to difference in thermal expansion coefficient of the layers different in electrical resistivity and thus formation of cracks can be prevented.
It is preferred that metallic Si or ferro-Si has an average particle size of 5 .mu.m or less. When this is greater than 5 .mu.m, nitriding requires much time and besides remaining Si is present.
In the present invention, as molding binders, there may be used, for example, thermoplastic resins such as polyvinyl butyral and polyethylene and organosilicone high molecular compounds such as silicone imide compounds and polysilane compounds. These binders are preferably added in an amount of 2-20 parts by weight to adjust the relative density of molded body to 60% or higher.
In the present invention, molded body is heated to 1350.degree. C. or higher in a nitriding gas, oxidizing gas or oxidizing and nitriding gas atmosphere such as nitrogen, ammonia and oxygen (if necessary, gases such as hydrogen, argon, helium and carbon monoxide may be contained).
As the metallic Si, ferro-Si, insulating compounds and conductive compounds, commercially available ones may be used as such. More preferably, they are pulverized by a mill to round particles.
In case whiskers are previously mixed with and dispersed in raw materials, all whiskers are not bonded to particles and massive whiskers or singly existing whiskers remain between particles of sintered body. On the other hand, in the present invention, particles and whiskers are bonded by a lot of needle-like whiskers produced from particles in molded body crossing nearly straightly in the spaces between particles and this greatly takes part in the high thermal shock resistance and strength.
According to the present invention, spaces between particles and/or whiskers of the insulating compound and conductive compound are bonded three-dimensionally with many whiskers produced from Si particles in the molded body and there are substantially no whiskers not in bonded state and thus sintered bodies of high toughness and high-temperature strength can be obtained.
Average particle size of the insulating compound and the conductive compound is preferably 100 .mu.m or less. When it is more than 100 .mu.m, strength of sintered body is reduced. When previously produced whiskers of the insulating compound or the conductive compound are used, they preferably have an average aspect ratio of 2-50 and length of 0.2-100 .mu.m. When the aspect ratio is less than 2 and length is less than 0.2 .mu.m, they have no effects as whiskers and when the aspect ratio is more than 50 and the length is more than 100 .mu.m, mixing of raw materials becomes difficult and dispersibility is inferior.
In the present invention, the ceramic composite contains whiskers in an amount of 1-70 vol % (preferably 10-30 vol %) per particles and whiskers produced in sintered body because outside this range, effects of the present invention cannot be obtained.
Molding method is selected from injection molding, casting, rubber press molding, extrusion molding, metal mold molding and the like depending on shape and required characteristics.
After removal of molding aid and the like, the molded body is subjected to heat treatment for formation of whiskers.
Particles or whiskers produced from metallic Si or ferro-Si are most preferably of Si.sub.3 N.sub.4.
Among the conductive compounds used in the present invention, silicides and borides react with nitrogen in nitriding gas, resulting in cracks in sintered body if sintering time is not proper. Therefore, nitrides and carbides are most preferred.
Whiskers of Si.sub.3 N.sub.4, SiC or the like may be blended as raw materials in addition to the whiskers produced from Si particles. However, use of the former whiskers in a large amount causes ununiformity and is not preferred. Further, whiskers may be used as insulating compound and conductive compound.
In order to obtain a void content of less than 5%, it is possible to re-sinter the sintered body. The re-sintering can be effected by hot pressing, hot isotactic pressing or under normal pressure using a sintering aid. Thus, whiskers are present three-dimensionally in the sintered body and so a ceramic composite of high heat resistance can be obtained. However, unless the difference in thermal expansion coefficient is made as small as possible, cracks can occur.
Further, since the sintered body of the present invention has voids, lubricants can be contained in the voids.
In the ceramic composite of the present invention, since the electrically conductive compound and the insulating compound are firmly bonded with particles or whiskers of Si.sub.3 N.sub.4, Si.sub.2 N.sub.2 O or SiO.sub.2 produced from metallic Si or ferro-Si, volume change on sintering is small and the composite is excellent in heat resistance. Further, it has voids and can absorb thermal shock.
According to the present invention, there can be easily obtained ceramic composite small in volume change on sintering and having optional resistivity within the range of 10.sup.14 -10.sup.-5 .OMEGA.cm by adjusting amount of conductive compound and insulating compound.
Thus, the composite can be used for various heaters, current collector of generators, brushes for motors, commutators for starter motors, commutators for alternators, etc.
According to the present invention, the sintered body obtained by molding and sintering by near net shaping has markedly small dimensional changes and ceramic composites comprising conductive portion and insulating portion of optional resistivities can be easily obtained.
By using these ceramic composites, ceramic heaters, current collector rings for revolving electrical machinery, brushes for motors and commutators for starters and alternators can be provided.
SECOND ASPECT
The present invention relates to a method for making ceramics of high strength and high dimensional accuracy which comprises adding a thermoplastic resin as a binder to metallic Si powders or inorganic compound powders containing at least 45 vol % of metallic Si powders, heating and kneading the mixture, subjecting the kneader product to warm pressure molding to form a molded body of at least 70 vol % in volumetric packing of powders (ratio of volume occupied by powders in the molded body), removing the binder in the molded body by heating and then heating and sintering the molded body in a nitriding gas atmosphere to bond particles of Si.sub.3 N.sub.4 and the inorganic compound with Si.sub.3 N.sub.4 particles and whiskers produced from said Si.
Furthermore, the present invention relates to a composition for ceramics of high dimensional accuracy which contains metallic Si powders or inorganic compound powders containing at least 45 vol % of metallic Si powders and a binder of thermoplastic resin and has an apparent viscosity at 150.degree. C. of (3-90).times.10.sup.4 N.multidot.s/m.sup.2.
When amount of Si powders is less than 45 vol %, dimensional change on sintering cannot be made small and besides, ceramic sintered body of enough strength cannot be obtained. In the present invention, the dimensional change on sintering can be made less than 0.2% by adjusting the content of Si powders to at least 45 vol %. Of course, Si content may be 100%.
When volumetric packing of particles in the molded body is less than 70 vol %, ceramic sintered body of sufficient strength cannot be obtained. By increasing it to at least 70 vol %, sintered body having a bending strength of about 300 MN/m.sup.2 or more can be obtained. This is the most effective means especially for improvement of strength.
Said inorganic compound is at least one compound selected from oxides, carbides, nitrides, oxy-nitrides, silicides and borides and the inorganic compound desirably has a melting point or sublimation temperature of 1400.degree. C. or higher.
As the inorganic compound, mention may be made of, for example, TiN, Si.sub.3 N.sub.4, Si.sub.2 N.sub.2 O, TiC, TiO.sub.2, AlN, Al.sub.2 O.sub.3, SiO.sub.2, ZrN, ZrO.sub.2, ZrC, TiB.sub.2, ZrB.sub.2, Cr.sub.3 C.sub.2, Cr.sub.7 C.sub.2, CrB, Cr.sub.2 N, WC, W.sub.2 C, WSi.sub.2, TiSi.sub.2, ZrSi.sub.2, Fe.sub.3 C, VC, VN, CeC.sub.2, MgO, Mo.sub.2 N, Mo.sub.2 C, MoB, ThC, HfN, HfC, TaN, TaC, TaB.sub.2, NbN, BeO, WN, CaO, TaSi.sub.2 and CrSi.sub.2.
Among these inorganic compounds, silicides and borides react with nitrogen during sintering in a nitriding gas and hence cracks might occur in the sintered body if sintering conditions are not proper. Therefore, carbides, nitrides and oxy-nitrides are preferred.
As the metallic Si powders, ferro-Si containing Fe may be used. However, there is the possibility of Fe remaining in the sintered body to cause reduction of high-temperature strength.
Desirably, particle size of said Si powders is 10 .mu.m or less, preferably 1 .mu.m or less and that of the inorganic compound is 100 .mu.m or less, preferably 20 .mu.m or less. As these powders, there may be used commercially available ones as they are, but preferably they are pulverized by a mill to round particles.
A part of said inorganic compound powders may be replaced with whiskers. In this case, amount of whiskers is desirably 55 vol % or less in the sintered body. When the amount is more than 55 vol %, sometimes uniform blend of raw materials cannot be obtained. The whiskers added preferably have an average aspect ratio of 200 or less and an average length of 200 .mu.m or less.
As the binder resins, there may be used thermoplastic resins used for preparation of pre-molded body for obtaining sintered ceramics. Examples thereof are polyvinyl butyral, polyethylene, polysilicone, synthetic waxes.
In the present invention, the binder has an important role and addition amount thereof has a great function for attaining a packing of particles of at least 70 vol % in molded body.
The inventors have made various studies on this point and have found that there is a very close correlation between specific surface area of raw material powders and addition amount of the binder per 100 parts by weight of said raw material powders. The present invention is based on this finding.
Firstly, the specific surface area S (cm.sup.2 /g) of raw material powders can be obtained by the following formula. ##EQU1## wherein .rho. is a density and d is an average particle size (.mu.m).
Relation between said specific surface area and amount B of the binder (part by weight per 100 parts by weight of raw material powder composition) necessary for obtaining a particle packing of molded body of at least 70 vol % is shown by the following formula.
B=[(7S/20,000)+3].+-.2.5
By adding the binder in an amount within the range given by the above formula, particle packing of the molded body can be made at least 70 vol % and a sintered body having a bending strength of about 300 MN/m.sup.2 or more can be provided.
Raw material composition containing the binder in an amount of the above range has an apparent viscosity of (3-90).times.10.sup.4 N.multidot.s/m.sup.2 as explained hereinafter and by selection of this viscosity range, fluidity at molding can be estimated and besides a molded body of at least 70 vol % in packing can be obtained. Thus, composition suitable for near net shaping can be provided.
From the point of fluidity of raw material composition, it is preferred to use Si powders of 1 .mu.m or less in particle size and to use as a binder a blend comprising 15-60% by weight of polyethylene, 30-70% by weight of wax and 5-25% by weight of stearic acid.
The raw material composition to which the binder is added is well kneaded and then molded. Molding method is selected from injection molding, press molding, rubber press molding, extrusion molding, powder molding and the like depending on shape and required characteristics and warm molding is carried out at higher than softening point of binder resin. For example, when mechanical press is used, molding pressure may be about 1000 kgf/cm.sup.2.
The resulting molded body is degreased (removal of binder) before sintering. Degreasing is carried out by gradually heating the molded body from room temperature to about 500.degree. C. at about 2.degree. C./h.
This molded body is preferably heated to lower than the melting point of metallic Si (lower than 1410.degree. C.), especially 1100.degree.-1350.degree. C. in a nitriding gas atmosphere comprising nitrogen and/or ammonia, and if necessary, further comprising hydrogen, argon, helium or the like. Heating rate until sintering temperature is suitably 4.degree. C./h and the molded body can be easily sintered by such heating. If necessary, hot pressing may be applied.
Preferably, the sintered body has a void content of 30% or less. When the void content exceeds 30%, strength decreases. The void content of 30% or less can be obtained by adjusting the volumetric packing of particles in the molded body to at least 70 vol %.
Si.sub.3 N.sub.4 whiskers are produced in the sintered body during sintering and such whiskers are preferably contained in an amount of 1-70 vol %, especially 10-30 vol % for the reaction-produced phase.
The reasons why according to the present invention, there is obtained ceramics small in dimensional change (less than about 0.15%) on sintering and having a bending strength of 300 MN/m.sup.2 or higher are considered as follows.
First, Si.sub.3 N.sub.4 whiskers produced by sintering in nitriding atmosphere greatly take part in dimensional change on sintering. This is clear from accompanying FIGS. 8 and 9.
FIGS. 8 and 9 show relation between blending ratio of raw materials [Si/(Si+inorganic compound)] and dimensional change on sintering or bending strength when sintered bodies were produced by adding 9 parts by weight of a thermoplastic resin to a mixture of Si and inorganic compound, heating and kneading the mixture, subjecting it to warm pressure molding, then removing the binder and sintering the molded body in nitrogen gas. With increase in the amount of Si, amount of whiskers of produced Si.sub.3 N.sub.4 increases and strength increases. Dimensional change on sintering increases, but this increase can be practically ignored.
It is considered that this is because the whiskers produced by sintering closely connect the particles of sintered body. That a sintered body having a bending strength of 300 MN/m.sup.2 is obtained especially when Si is more than 45 vol % is considered due to the increase of such connecting chains.
Next, relation between amount of binder resin and bending strength with amount of Si being 60 vol % is shown in FIGS. 10 and 11, from which it can be seen that amount of binder resin has a great effect on bending strength. This is influenced by volumetric packing of molded body.
The raw material powder per se are fragile solid fine powder particles and are difficult to pack by pressing them as such. Therefore, it is necessary to add binder thereto to accelerate fluidity of powders and besides to increase strength of molded body. Strength of sintered body changes depending on addition amount of binder and as mentioned hereinbefore, this has a relation with volumetric packing of powders of molded body (density). With increase of amount of binder, fluidity of mixture under heating increases and pressure molding becomes easy. As a result, volumetric packing of particles of molded body is improved. However, if binder is added in an amount more than the vacancy when raw material powders are in ideal dense packing, the raw material powders are isolated in the binder and fluidity is increased, but solid ratio in the molded body is decreased, resulting in decrease of volumetric packing of particles of the molded body. Thus, void content of sintered body increases and this causes reduction of strength of sintered body.
As mentioned before, when the molded body is sintered in nitriding atmosphere, whiskers produced from Si powders connect particles and besides fill the vacancy between the particles and grow three-dimensionally in sintered body. Thus, ceramics of high toughness can be obtained.
In the ceramics of the present invention, particles in the molded body of at least 70 vol % in volumetric packing of particles are connected by nitride produced from metallic Si powders and hence, dimensional change on sintering is small and no deformation occurs.
In the present invention, particles and whiskers produced from metallic Si are preferably nitride. Oxy-nitride and oxide tend to decrease high-temperature strength.
According to the present invention, ceramics of less than 0.2% in dimensional change on sintering and having a bending strength of about 300 MN/m.sup.2 or more can be obtained by near net shaping. Such ceramics require substantially no mechanical working after sintering and can be applied to various fields of structural parts such as engines and turbines.
THIRD ASPECT
The present invention relates to a sliding member for sealing wherein one surface of sliding surfaces comprises ceramics composed of SiC and Si.sub.3 N.sub.4 as a composite material and this composite material, Si.sub.3 N.sub.4 contains at least one of particles and whiskers and said ceramics have void and besides, another surface of the sliding surfaces has a hardness smaller than that of the composite material of said surface.
In the present invention, Si.sub.3 N.sub.4 particles or whiskers for bonding SiC are preferably those produced by heat treatment of metallic Si. They bond particles and reduce vacancy between the particles. Thus, sintered body having open voids of 2-30% in void content and 100 .mu.m or less in diameter can be obtained.
In the present invention, it is preferred that average particle size of SiC particles is 100 .mu.m or less, average aspect ratio of SiC whiskers is 200 or less and average length of SiC whiskers is 200 .mu.m or less. Outside these ranges, mixing of raw materials is difficult and dispersion is not uniform, resulting in reduction of mechanical strength.
The reason why one surface of seal sliding member is made of a composite material of SiC and Si.sub.3 N.sub.4 in the present invention is that a sliding material having the characteristics of both the SiC and Si.sub.3 N.sub.4 can be obtained and unexpectedly excellent thermal shock resistance can be obtained by bonding SiC superior in wear resistance, hardness and thermal conductivity with Si.sub.3 N.sub.4 low in thermal expansion coefficient. The reason why another surface is made of a composition having a hardness lower than that of SiC particles and Si.sub.3 N.sub.4 particles of the other sliding surface is that if it is harder than the sliding surface comprising SiC and Si.sub.3 N.sub.4 and voids, SiC and Si.sub.3 N.sub.4 are worn by the harder particles of another surface and fall off between the sliding surfaces to cause wear due to scratch. When materials of compositions having particles of same hardness are combined and slidden, marks are apt to be formed on the sliding surface. This is because even if the sliding surface is mirror-polished, the contact is microscopically point or line contact and the surfaces are in the state of one-side contacting and this naturally forms sliding marks. On the other hand, according to the present invention, another surface is made of a material having a hardness lower than that of SiC and Si.sub.3 N.sub.4 particles and thus, substantially no wear is caused on one surface and a sliding material superior in wear resistance can be obtained. By employing a material for one sliding surface which is softer than another sliding surface, even if one-side contact occurs, one surface of lower hardness is mirror-polished with the harder surface by sliding and so the period of the state of one-side contact is short and a sliding material superior in sealing property can be obtained.
The reason why one surface of seal sliding surfaces is made of a ceramic sintered body having open voids of 2-30% in void content is that said open voids relax thermal shock strain to provide a sliding material of unexpectedly superior thermal shock resistance. When diameter of voids is more than 100 .mu.m and void content is more than 30%, mechanical strength decreases and besides bonding strength between SiC and produced Si.sub.3 N.sub.4 phase decreases, resulting in considerable falling-off of SiC and Si.sub.3 N.sub.4 particles during sliding. Further, breakage of lubricant oil film does not occur due to these open voids and so cohesion and scorch are not caused. This is because lubricant oil penetrates into the open voids and oozes out on the sliding surface to give the above effects. Therefore, as far as one surface is made of the ceramics of the present invention, another surface may be of metals, ceramics, carbon or synthetic resins lower in hardness than the particles of said one surface. It has been confirmed by experiments that especially, when oxide ceramics are used as the partner material (another material), sliding characteristics are improved. This is because SiC and Si.sub.3 N.sub.4 are high in covalent bonding and when amount of adsorbates on the surface decreases, cohesion is apt to occur. However, if the partner surface is made of oxide, oxygen ion is produced on the sliding surface to produce surface adsorbates which prevent the cohesion.
In the present invention, in case SiC contained in ceramics composed of SiC, Si.sub.3 N.sub.4 and voids is greater than the particles of whiskers of Si.sub.3 N.sub.4 or the like produced from metallic Si powders, the material is better in wear resistance and thermal shock resistance. Especially, because of composite ceramics, thermal shock resistance is superior to that of other ceramics having the same void content.
The characteristics are further improved when a solid lubricant or resin such as furan resin is contained in the void of sintered body.
According to the present invention, one surface of sliding surfaces of sliding member for sealing is made of ceramics composed of at least one of particles and whiskers of SiC and Si.sub.3 N.sub.4 and voids and another surface (partner surface) is made of a material having a hardness lower than that of particles or whiskers of Si.sub.3 N.sub.4 of said one surface, whereby excellent wear resistance, corrosion resistance and thermal shock resistance can be obtained and wear of a partner material can be reduced and hence, performance of various seals can be markedly improved.
As explained hereinabove, according to the present invention, the sliding members have extremely excellent sliding properties such as wear resistance and thermal shock resistance and so, endurance and reliability of seal can be remarkably improved. This is effective for various sliding mechanisms such as mechanical seal, floating seal, plain bearing and the like.
EXAMPLE 1
To 100 parts by weight of a raw material comprising 22.7 wt. % of metallic Si powder of 0.9 .mu.m in average particle size and 77.3 wt. % of TiN powder of 1.2 .mu.m in average particle size was added 9 parts by weight of binder comprising polyethylene based thermoplastic resin and stearic acid and the mixture was kneaded at 160.degree. C. for 12 hours by a pressure kneader. The kneaded product was pulverized to 10 meshes or less to obtain a raw material for electrical conductor ceramics A.
To 100 parts by weight of raw material comprising 38 wt. % of metallic Si powder of 0.9 .mu.m in average particle size and 62 wt. % of Al.sub.2 O.sub.3 of 2 .mu.m in average particle size was added 9 parts by weight of a binder comprising a low-density polyethylene, a synthetic wax and stearic acid and the mixture was kneaded at 160.degree. C. for 12 hours by a pressure kneader. The kneaded product was pulverized to 10 meshes or less to obtain a raw material for insulant ceramics B.
Then, the raw materials for ceramics A and B were filled in succession in a mold at 160.degree. C. and under 1000 kg/cm.sup.2 to obtain a layered ring as shown in FIG. 1(A) and FIG. 1(B). FIG. 1(B) is a cross-sectional view of FIG. 1(A) at Z--Z. This molded ring was heated to 500.degree. C. at 3.degree. C./h to remove the binder therein and then, was heated to 1100.degree. C. at 5.degree. C./min in a nitrogen atmosphere and then, from 1100.degree. C. to 1350.degree. C. at 4.degree. C./h to obtain a sintered body having whisker/particle of Si.sub.3 N.sub.4 of 1/9.
The ratio of whisker/particle can be adjusted by changing the rate of heating of from 1100.degree. C.-1400.degree. C. and retaining stepwise the temperature during the heating. The ratio of whisker/particle can be obtained by observation of the sintered body under scanning electron microscope and transmission electron microscope. The characteristics of the obtained sintered body are shown in Table 1. Rate of dimensional change when molded product was sintered was small, namely, .+-.0.2 and no cracks occurred. Resistivity of the portion of ceramics A was 9 .times.10.sup.-4 .OMEGA. cm and that of the portion of ceramics B was 7 .times.10.sup.13 .OMEGA. cm. FIG. 2 shows an electron micrograph of around the boundary between the conductive portion and the insulating portion. It can be seen that the conductive portion and the insulating portion were firmly bonded. This bonding is due to Si.sub.3 N.sub.4 produced from metallic Si.
TABLE 1______________________________________ Composition ofEx- sintered body Resis- Bendingam- Cer- (vol %) Void tivity strengthple amics Si.sub.3 N.sub.4 TiN Al.sub.2 O.sub.3 (%) (.OMEGA. cm) (MPa)______________________________________1 A 40 60 -- 22 9 .times. 10.sup.-4 280 B 50 -- 50 18 7 .times. 10.sup.13 270______________________________________
The coefficient of thermal expansion of the conductive portion was 5.2.times.10.sup.-6 .degree. C..sup.-1 and that of the insulating portion was 5.1.times.10.sup.-6 .degree. C..sup.-1 and these were nearly the same. This also indicates superior thermal shock resistance of the sintered body.
EXAMPLES 2-36
Sintered bodies were prepared in the same manner as in Example 1 except that the conductive particles were used in place of TiN particle. The results are shown in Table 2. Composition of the sintered bodies was not shown in Table 2 because composition of insulating portion B of the sintered body was Si.sub.3 N.sub.4 Al.sub.2 O.sub.3 =50 : 50 (vol %) as in Example 1.
Rate of dimensional change of from molded product to sintered body was small, namely, less than +0.2% and no cracks occurred. Conductive portion A and insulating portion B were firmly bonded at their boundary as in Example 1.
Furthermore, integral molding and sintering with optional combination of resistivity of from 10.sup.14 .OMEGA. cm to 10.sup.-5 .OMEGA. cm are possible by allowing a conductive compound and an insulating compound to be present together.
TABLE 2______________________________________ Raw materialEx- ratio (wt. %) Voidam- Electro- con- Resis- Bendingple conductive tent tivity strength Appear-No. Si particles (%) (.OMEGA. cm) (MPa) ance______________________________________ 2 20 TiC80 28 5 .times. 10.sup.-3 161 No cracks3 20 TiB.sub.2 80 29 2 .times. 10.sup.-3 145 "4 20 ZrN80 27 1 .times. 10.sup.-3 155 "5 5 ZrC95 30 2 .times. 10.sup.-5 101 "6 20 ZrB.sub.2 80 28 5 .times. 10.sup.-3 138 "7 20 Cr.sub.2 N80 20 7 .times. 10.sup.-3 167 "8 20 Cr.sub.3 C.sub.2 80 21 5 .times. 10.sup.-3 161 "9 20 CrB80 21 6 .times. 10.sup.-3 147 "10 20 HfN80 23 8 .times. 10.sup.-3 161 "11 90 HfC10 12 3 .times. 10.sup.2 355 "12 20 TaN80 26 6 .times. 10.sup.-3 151 "13 20 TaC80 23 4 .times. 10.sup.-5 162 "14 20 TaB.sub.2 80 27 4 .times. 10.sup.-3 155 "15 20 Mo.sub.2 N80 22 8 .times. 10.sup.-3 171 "16 20 Mo.sub.2 C80 22 7 .times. 10.sup.-4 162 "17 20 MoB80 27 6 .times. 10.sup.-3 143 "18 20 NbN80 23 6 .times. 10.sup.-3 153 "19 25 NbC75 27 6 .times. 10.sup.-3 195 "20 25 NbB.sub.2 75 26 5 .times. 10.sup.-3 191 "21 5 WC95 30 3 .times. 10.sup.-5 108 "22 22 W.sub.2 C78 28 3 .times. 10.sup.-3 178 "23 25 TiB75 24 4 .times. 10.sup.-3 185 "24 20 VN80 22 6 .times. 10.sup.-3 182 "25 30 WSi.sub.2 70 22 8 .times. 10.sup.-4 225 "26 90 TiSi.sub.2 10 13 3 .times. 10.sup.3 345 "27 90 ZrSi.sub.2 10 13 8 .times. 10.sup.3 365 "28 90 NbSi.sub.2 10 13 6 .times. 10.sup.3 350 "29 90 TaSi.sub.2 10 13 6 .times. 10.sup.3 351 "30 90 CrSi.sub.2 10 12 1 .times. 10.sup.4 365 "31 90 MoSi.sub.2 10 14 5 .times. 10.sup.3 362 "32 80 VC20 14 2 .times. 10.sup.1 360 "33 75 Fe.sub.3 C15 13 8 .times. 10.sup.1 358 "34 90 ThC10 13 3 .times. 10.sup.2 358 "35 90 CeC.sub.2 10 13 5 .times. 10.sup.2 362 "36 95 Cr.sub.7 C.sub.2 5 13 4 .times. 10.sup.3 360 "______________________________________
COMPARATIVE EXAMPLES 1-2
For comparison, a molded product was produced in the same manner as in Example 1 except that Si.sub.3 N.sub.4 powder of 0.8 .mu.m in average particle size was used in place of metallic Si powder and this was sintered by a hot press under 150 kg/cm.sup.2 at 1800.degree. C. for 4 hours under vacuum to obtain a sintered body. Separately, a molded product was produced in the same manner as in Example 1 with addition of 3 vol % of Y.sub.2 O.sub.3 and 3 vol % of AlN as sintering aids and this was sintered at 1800.degree. C. for 4 hours under low-pressure in nitrogen atmosphere. Characteristics of the resulting sintered bodies are shown in Table 3.
TABLE 3__________________________________________________________________________ Composition of sintered body State of Void BendingComparative (vol %) sintered content Resistivity strengthExamples Ceramics Si.sub.3 N.sub.4 TiN Al.sub.2 O.sub.3 body (%) (.OMEGA. cm) (MPa)__________________________________________________________________________1 Hot A 40 60 -- Cracks 4 7 .times. 10.sup.-4 Unmeas- press- urable ing B 50 -- 50 Good 4 8 .times. 10.sup.10 3302 Pressure- A 37.6 56.4 -- Cracks and 2 8 .times. 10.sup.-4 Unmeas- less deforma- urable sinter- tion ing B 48 -- 48 Deforma- 2 8 .times. 10.sup.10 380 tion__________________________________________________________________________
Both the hot press sintered body and pressureless sintered body cracks and good ceramic composites were not able to be obtained. It is considered that cracks or deformation do not occur in the products of the present invention because sintering temperature is low and there are open voids and thus stress caused by difference in coefficient of thermal expansion is relaxed.
EXAMPLES 37-43
To 100 parts by weight of raw materials comprising a mixture of metallic Si powder of 0.9 .mu.m in average particle size and TiN powder of 1.2 .mu.m in average particle size at the ratio as shown in Table 4 was added 9 parts by weight of a binder comprising a polyethylene based thermoplastic resin and stearic acid and the mixture was kneaded at 160.degree. C. for 12 hours by a pressure kneader. The kneaded product was pulverized to 10 meshes or less and this was used as a raw material for conductor ceramics A. Separately, to 100 parts by weight of a raw material comprising a mixture of metallic Si powder of 0.9 .mu.m in average particle size and Al.sub.2 O.sub.3 powder of 2 .mu.m in average particle size at the ratio as shown in Table 4 was added 9 parts by weight of a binder comprising a polyethylene based thermoplastic resin and stearic acid and the mixture was kneaded by a pressure kneader at 160.degree. C. for 12 hours. The kneaded product was pulverized to 10 meshes or less and this was used as a raw material for insulant ceramics B.
Then, the raw materials for A and B were filled in succession in a mold to produce a layered ring as shown in FIG. 3(A) and FIG. 3(B). FIG. 3(B) is cross-sectional view of FIG. 3(A) at Z--Z. After removal of the binder, the molded product was heated to 1100.degree. C. at 5.degree. C./min in nitrogen atmosphere and then heated from 1100.degree. C. to 1350.degree. C. at a rate of 3.degree. C./h over a long period of time to obtain a sintered body of whisker/particle of Si.sub.3 N.sub.4 =2/9. Characteristics of the thus obtained sintered body are shown in Table 4.
TABLE 4__________________________________________________________________________ Composition of sintered body Void Bending (vol %) content Resistivity strengthExample No. Ceramics Si.sub.3 N.sub.4 TiN Al.sub.2 O.sub.3 (%) (.OMEGA. cm) (MPa)__________________________________________________________________________ 37 A 95 5 -- 8 4 .times. 10.sup.5 420 B 90 -- 10 13 8 .times. 10.sup.13 40038 A 90 10 -- 13 2 .times. 10.sup.3 403 B 90 -- 10 12 8 .times. 10.sup.13 40039 A 80 20 -- 14 9.7 .times. 10.sup.0 395 B 80 -- 20 14 6 .times. 10.sup.12 39040 A 60 40 -- 16 3.1 .times. 10.sup.-3 380 B 60 -- 40 16 8 .times. 10.sup.13 38041 A 40 60 -- 20 9 .times. 10.sup.-4 280 B 40 -- 60 18 7 .times. 10.sup.12 25042 A 20 80 -- 23 2.1 .times. 10.sup.-4 180 B 30 -- 80 21 8 .times. 10.sup.13 20643 A 5 95 -- 30 8 .times. 10.sup.-5 103 B 20 -- 80 26 7 .times. 10.sup.13 158__________________________________________________________________________
Thus, according to the present invention, integrally molded and sintered ceramics comprising layers different in resistivity can be obtained by changing addition amount of the electrically conductive compound.
FIG. 4 is a graph which shows relation between content of TiN and volume change on sintering and relation between content of Al.sub.2 O.sub.3 and volume change on sintering.
As comparative example, molding and sintering were effected in the same manner as in Comparative Example 2 except that the composition of sintered body was as in Examples 37-43 and volume change on sintering is also shown in FIG. 4.
According to FIG. 4, the products of the present invention are superior sintered bodies which are extremely smaller in dimensional change than the pressureless sintered products and free from cracks.
FIG. 5 shows relation between bending strength and test temperature.
According to FIG. 5, the products of the present invention showed no reduction in strength even at high temperatures. On the other hand, since the comparative products contained sintering aids, there exists a glass phase, which is softened at high temperature, resulting in reduction in strength at high temperatures.
EXAMPLE 44
To 100 parts by weight of a raw material comprising a mixture of 50 vol % (in terms of Si.sub.3 N.sub.4) of ferro-Si powder (average particle size 2 .mu.m) and 50 vol of ZrN powder (average particle size 2 .mu.m) was added 10 parts by weight of a polysilane compound as a binder. From this mixed powder, ceramics A was prepared in the same manner as in Example 1. Ceramics B was prepared in the same manner as in Example 1 except that 10 parts by weight of a polysilane compound was used as a binder. These powders were molded in the same manner as in Example 1 and the molded product was heated to as high as 1450.degree. C. with stepwise retention of time in nitrogen atmosphere to obtain a sintered body.
Characteristics of the resulting ceramics composite were relative density: 93%; resistivity: 4.times.10.sup.-3 .OMEGA. cm; bending strength: 420 MPa and dimensional change on sintering: +3.8%.
EXAMPLE 45
Sintered bodies were produced in the same manner as in Example 44 with changing the particle size of the raw material ferro-Si powder and relation between the particle size and bending strength was examined.
The results are shown in FIG. 6. Si particle size of 5 .mu.m or less is preferred.
It is considered that when the particle size exceeds 5 .mu.m, unnitrided Si remains in sintered body and this is evaporated by heating, resulting in reduction of strength.
EXAMPLES 46-50 AND COMPARATIVE EXAMPLES 3 AND 4
Molded products were prepared in the same manner as in Example 1. They were sintered with changing heating rate and changing stepwise heating time from 1100.degree. C. to 1400.degree. C., thereby to obtain sintered bodies adjusted in amount of Si.sub.3 N.sub.4 whisker produced. Characteristics of the resulting sintered body are shown in Table 5.
TABLE 5__________________________________________________________________________ Composition of sintered Void Thermal body (vol %) con- Resis- Bending shock Ceram- Si.sub.3 N.sub.4 tent tivity strength resistanceNo. ics Si.sub.3 N.sub.4 Whisker TiN Al.sub.2 O.sub.3 (%) (.OMEGA. cm) (MPa) (times)__________________________________________________________________________Exam- 46 A 39.6 0.4 60 -- 21 9 .times. 10.sup.-4 280 45ples B 49.5 0.5 -- 50 20 7 .times. 10.sup.13 272 45 47 A 32 8 60 -- 21 9 .times. 10.sup.-4 281 47 B 40 10 -- 50 19 7 .times. 10.sup.13 273 47 48 A 24 16 60 -- 21 9 .times. 10.sup.-4 280 50 B 30 20 -- 50 19 7 .times. 10.sup.13 270 50 49 A 16 24 60 -- 22 9 .times. 10.sup.-4 270 52 B 20 30 -- 50 20 7 .times. 10.sup.13 270 52 50 A 12 28 60 -- 22 9 .times. 10.sup.-4 265 48 B 15 35 -- 50 22 7 .times. 10.sup.13 245 48Compar- 3 A 39.76 0.24 60 -- 22 9 .times. 10.sup.-4 280 38ative B 49.7 0.3 -- 50 23 7 .times. 10.sup.13 275 38Exam- 4 A 8 32 60 -- 23 9 .times. 10.sup.-4 221 33ples B 10 40 -- 50 23 7 .times. 10.sup.13 220 33__________________________________________________________________________
From the above, it can be seen that the products of the present invention where Si.sub.3 N.sub.4 whisker was present in an amount of 1-70 vol % of Si.sub.3 N.sub.4 phase produced from Si were superior in thermal shock resistance.
The thermal shock resistance was evaluated as follows: A sintered body was kept at 1200.degree. C. for 30 minutes and then introduced it into water to quench. This was repeated until cracks occurred and the number of the repetition was taken as thermal shock resistance value.
EXAMPLES 51-57
Molded products were prepared in the same manner as in Example 1 and sintered bodies were obtained therefrom wherein amounts of Si.sub.3 N.sub.4, Si.sub.2 N.sub.2 O and SiO.sub.2 in the phase produced from Si by changing oxygen partial pressure in nitriding gas. Characteristics of the sintered bodies are shown in Table 6.
TABLE 6__________________________________________________________________________ Thermal Composition of sintered body Resis- Bending shock Ceram- (vol %) tivity strength resistanceExample No. ics Si.sub.3 N.sub.4 Si.sub.2 N.sub.2 O SiO.sub.2 TiN Al.sub.2 O.sub.3 (.OMEGA. cm) (MPa) (times)__________________________________________________________________________ 51 A 40 0 0 60 -- 9 .times. 10.sup.-4 280 45 B 50 0 0 -- 50 7 .times. 10.sup.13 270 4552 A 36 4 0 60 -- 9 .times. 10.sup.-4 280 45 B 45 5 0 -- 50 7 .times. 10.sup.13 270 4553 A 24 16 0 60 -- 9 .times. 10.sup.-4 280 47 B 30 20 0 -- 50 7 .times. 10.sup.13 272 4754 A 20 16 4 60 -- 3 .times. 10.sup.-3 260 40 B 25 20 5 -- 50 5 .times. 10.sup.14 260 4055 A 0 32 8 60 -- 8 .times. 10.sup.-3 251 28 B 0 40 10 -- 50 8 .times. 10.sup.14 253 2856 A 0 4 36 60 -- 2 .times. 10.sup.-2 205 20 B 0 5 45 -- 50 8 .times. 10.sup.14 210 2057 A 0 0 40 60 -- 4 .times. 10.sup.-2 191 15 B 0 0 50 -- 50 9 .times. 10.sup.14 198 15__________________________________________________________________________
From the above, it is seen that when amounts of Si.sub.2 N.sub.2 O and SiO.sub.2 are larger than that of Si.sub.3 N.sub.4 in the phase produced from Si, resistivity and thermal shock resistance tend to decrease.
EXAMPLES 58-61
Sintered bodies were prepared in the same manner as in Example 1 except that the raw materials as shown in Table 7 were used in place of TiN and Al.sub.2 O.sub.3 particles. The results are shown in Table 7.
According to the present invention, integral molding and sintering with optional combination of resistivities within the range of 10.sup.14 .OMEGA. cm to 10.sup.-5 .OMEGA. cm are possible by compositely combining conductive compound and insulating compound.
TABLE 7__________________________________________________________________________ Bending Raw material ratio Resistivity strengthExample No. Ceramics (wt. %) (.OMEGA. cm) (MPa)__________________________________________________________________________ 58 A Si(25), TiC(10), ZrN(65) 5 .times. 10.sup.-3 182 B Bi(30), TiN(30), SiC(40) 1 .times. 10.sup.-1 20559 A Si(50), ZrO.sub.2 (10), Cr.sub.2 N(40) 2 .times. 10.sup.-2 275 B Si(30), Al.sub.2 O.sub.3 (50), Si.sub.3 N.sub.4 (20) 4 .times. 10.sup.13 23260 A Si(30), B.sub.4 C(10), TiC(60) 8 .times. 10.sup.-3 205 B Si(30), Si.sub.2 N.sub.2 O(10), ZrO.sub.2 (60) 3 .times. 10.sup.13 21361 A Si(30), TiSi.sub.2 (5), WC(65) 4 .times. 10.sup.-4 189 B Si(30), CrB(5), Al.sub.2 O.sub.3 (65) 2 .times. 10.sup.2 193__________________________________________________________________________
EXAMPLE 62
Si.sub.3 N.sub.4 /TiN conductive ceramics and Si.sub.3 N.sub.4 /Al.sub.2 O.sub.3 insulating ceramics obtained in Example 1 were integrally molded and sintered as shown in FIG. 3(A) and FIG. 3(B) as current collector for alternator of automobiles. Current collecting characteristics thereof were examined. The results are shown in Table 8. From the results, it can be seen that the product of the present invention is superior to the conventional copper/heat resisting resin in heat resistance and wear resistance.
TABLE 8______________________________________ Comparative Example 62 Example 5______________________________________Current Conductive Si.sub.3 N.sub.4 /TiN CopperCollect- portioning ring Insulating Si.sub.3 N.sub.4 /Al.sub.2 O.sub.3 Heat resist- portion ing resinCurrent collector Carbon CarbonState of Current Gloss Blackishsliding collecting brownsurface ring Current Gloss Scratch collectorDamage Current 1-3 .mu.m 10-20 .mu.m Collecting ring Current .apprxeq.0 0.82 collectorSpark No NoState after test No change Scorching mark in the insulating portion Blackening of copper portion______________________________________ Condition: 30,000 rpm Current density of current collector 70 A/cm.sup.2
Example 63
Si.sub.3 N.sub.4 /TiN conductive ceramics and Si.sub.3 N.sub.4 /Al.sub.2 O.sub.3 ceramics obtained in Example 1 were integrally molded and sintered as shown in FIG. 7(A) and FIG. 7(B) as a commutator for starter motor of automobiles. Current collecting characteristics were examined. As in Example 63, it has been confirmed that the product of the present invention is superior to the conventional copper/heat resisting resin in heat resistance and wear resistance and production of non-combustible motor is possible.
EXAMPLE 64
To 100 parts by weight of raw material comprising a mixture of 22.7 wt. % of metallic Si powder of 0.5 .mu.m in average particle size and 77.3 wt. % of TiN whisker of 50 in aspect ratio and 50 .mu.m in length was added 9 parts by weight of binder comprising a low-density polyethylene, a synthetic wax and stearic acid and the mixture was kneaded by a pressure kneader at 160.degree. C. for 12 hours. The kneaded product was pulverized to 10 meshes or less and this was used as a conductor ceramics A.
Separately, to 100 parts by weight of raw material comprising a mixture of 38 wt. % of metallic Si powder of 0.9 .mu.m in average particle size and 62 wt. % of Al.sub.2 O.sub.3 of 35 .mu.m in average particle size was added 9 parts by weight of the above binder. The mixture was kneaded and pulverized in the same manner as above and this was used as a raw material for insulant ceramics B. In the same manner as in Example 1, a composite sintered body was prepared using these ceramics A and B.
Dimensional change of this sintered body was .+-.0.2. The portion A had a resistivity of 7.times.10.sup.-4 .OMEGA. cm, a void of 18%, a bending strength of 291 MPa and a coefficient of thermal expansion of 5.2.times.10.sup.-6. The portion B had a resistivity of 5.times.10.sup.13 .OMEGA. cm, a void of 20%, a bending strength of 250 MPa and a coefficient of thermal expansion of 5.1.times.10.sup.-6.
EXAMPLES 65-70
To 500 g of a mixed powder comprising SiC particle of 16 .mu.m in average particle size and metallic Si of 0.9 .mu.m in average particle size at the ratio as shown in Table 8 was added 8-12 parts by weight of a molding binder comprising 21% of polyethylene (melt index 1.5), 43% of polyethylene wax (PE-520 manufactured by Hoecht, Japan) 21% of blend wax (D-556 manufactured by Chukyo Yushi Co.) and 15% of stearic acid and the mixture was kneaded in a pressure kneader at 160.degree. C. for 5 hours. The kneaded product was crushed to obtain a raw material under test. This raw material was molded into a molded body of 50 mm in diameter and 20 mm thick by a mechanical press at 160.degree. C. under a molding pressure of 1000 kgf/cm.sup.2. Volumetric packing of particle of the resulting molded body was at least 70 vol %. This molded body from which the molding binder had been removed was heated from 1100.degree. C. to 1350.degree. C. at a rate of 4.degree. C./h in a nitrogen atmosphere, whereby a sintered body with whisker/particle of Si.sub.3 N.sub.4 of 1/9 was obtained. The blending ratio of whisker/particle can be adjusted by changing heating rate and retention time. The ratio of whisker/particle can be obtained by observation of the sintered body under scanning electron microscope and transmission electron microscope.
Characteristics of the thus obtained sintered body are shown in Table 8. The breaking toughness was measured by notched beam method using a test piece of 3.times.4.times.40 mm having a notch of 0.5 mm made by a diamond wheel. For the thermal shock, the sintered body was kept at 1250.degree. C. for 30 minutes and then introduced it into water to quench it. This was repeated until cracks occurred and the thermal shock was evaluated by the number of the repetition.
Next, mixed powder of the compositions as shown in Comparative Examples 65-70 of Table 9 was prepared. This mixed powder contained Y.sub.2 O.sub.3 as a sintering aid. This was molded in the same manner as above and sintered at 1700.degree. C. for 5 hours to obtain a sintered body. Characteristics of the obtained sintered body are shown in Table 9.
FIG. 8 shows the relation between the content of SiC and the rate of dimensional change on sintering. The product (A) of the present invention is a markedly superior sintered body with very small rate of dimensional change as compared with the product (B) comprising Si.sub.3 N.sub.4 powder, SiC powder to which sintering aid Y.sub.2 O.sub.3 was added.
TABLE 8__________________________________________________________________________ Volumetric Dimen- Bending packing of Composition sional strength ThermalRaw- particles of sintered change (MN/m.sup.2) shockmaterial in molded body on sin- Room Breaking resis-(vol %) product (vol %) tering temper- toughness tanceExample Si SiC (%) Si.sub.3 N.sub.4 SiC (%) ature 1200.degree. C. (MN/m.sup.3/2) (Times)__________________________________________________________________________65 100 0 72 100 0 0.13 584 582 5 4366 90 10 75 90 10 0.12 512 510 6 4567 80 20 74 80 20 0.12 490 489 7 5068 70 30 73 70 30 0.12 430 430 7 5069 60 40 75 60 40 0.12 390 390 7 5070 45 55 74 45 55 0.12 310 310 6 49__________________________________________________________________________
TABLE 9__________________________________________________________________________ Bending strength Thermal Composition of (MN/m.sup.2) shock sintered body Room Breaking resist-Comparative (vol %) temper- toughness anceExamples Si.sub.3 N.sub.4 Y.sub.2 O.sub.3 SiC ature 1200.degree. C. (MN/m.sup.3/2) (times)__________________________________________________________________________5 93 7 0 753 352 5 216 84 6 10 518 321 3 217 75 5 20 462 255 3 188 66 4 30 391 211 3 179 57 3 40 358 208 3 1510 42 3 55 211 127 2 15__________________________________________________________________________
EXAMPLES 71-113
Sintered bodies were prepared in the same manner as in Example 69 except that the inorganic compounds shown in Table 10 were used in place of SiC powder. Characteristics of the resulting sintered bodies are shown in Table 10.
It can be seen from Table 10 that the products of the present invention were superior in high-temperature strength, breaking toughness and thermal shock resistance. The rate of dimensional change on sintering was nearly the same as shown by curve (A) in FIG. 8.
TABLE 10______________________________________Rawmaterialcom-pound Ther-in Bending strength malsintered (MN/m.sup.2) Void shockEx- body Room con- Breaking resis-am- (40 vol temper- tent toughtness tanceples %) ature 1200.degree. C. (%) (MN/m.sup.3/2) (times)______________________________________71 TiN 358 351 12 7 4872 Si.sub.3 N.sub.4 362 354 12 5 4573 Si.sub.2 N.sub.2 O 341 330 13 6 4874 TiC 367 358 12 7 4875 TiO.sub.2 357 352 12 7 4776 AlN 365 360 11 7 5077 Al.sub.2 O.sub.3 351 343 12 7 4878 SiO.sub.2 342 336 13 6 4579 ZrN 361 356 11 7 5180 ZrO.sub.2 356 345 12 7 4981 ZrC 356 354 12 7 5282 TiB.sub.2 332 330 13 6 4883 ZrB.sub.2 341 335 13 6 4884 Cr.sub.3 C.sub.2 356 352 12 7 5185 CrB 332 329 13 6 4786 Cr.sub.2 N 365 359 11 7 5387 Cr.sub.7 C.sub.2 355 353 12 7 5188 WC 345 341 12 7 4789 W.sub.2 C 346 343 12 7 4790 WSi.sub.2 331 330 13 6 4591 TiSi.sub.2 333 328 13 6 4592 ZrSi.sub.2 338 335 13 6 4593 Fe.sub.3 C 362 359 11 8 5294 VC 356 346 12 7 4995 VN 367 364 11 7 5196 CeC.sub.2 367 366 11 7 5097 MgO 336 328 13 6 4598 Mo.sub.2 N 349 346 12 7 4999 Mo.sub.2 C 365 346 12 7 50100 MoB 336 324 13 6 45101 ThC 368 358 12 7 50102 HfN 359 355 12 7 52104 HfC 357 354 12 7 52105 TaN 349 347 12 7 49106 TaC 347 346 12 7 51107 TaB.sub.2 341 332 13 7 46108 NbN 338 331 13 7 47109 BeO 359 358 12 7 50110 WN 356 352 12 7 52111 CaO 352 347 12 7 50112 TaSi.sub.2 335 331 13 7 48113 CrSi.sub.2 332 328 13 7 47______________________________________
EXAMPLES 114-117
Sintered bodies were prepared in the same manner as in Example 69 except that the SiC whiskers as shown in Table 11 were used in place of SiC powder. Characteristics of the resulting sintered bodies are shown in Table 11. The rate of dimensional change on sintering was less than 0.13% for all of them. From the results, it will be seen that preferable average aspect ratio of raw material whisker is 200 or less and preferable average length is 200 .mu.m or less.
TABLE 11______________________________________Raw materialwhisker insintered body Ther- Aver- Aver- Bending mal age age strength Breaking resist-Exam- aspect length room toughness anceples ratio (.mu.m) temp. 1200.degree. C. (MN/m.sup.3/2) (times)______________________________________114 180 50 364 356 8 55115 50 150 374 375 8 55116 230 100 310 305 6 50117 50 220 312 310 6 50______________________________________
EXAMPLE 118-124
Molded products were prepared in the same manner as in Examples 65-70 and then they were sintered with changing stepwise the heating time until 1400.degree. C. in a nitrogen atmosphere thereby to adjust the amount of Si.sub.3 N.sub.4 whisker produced. Test results of the resulting sintered bodies are shown in Table 12. From the results, it can be seen that the products of the present invention where 1-70 vol % of Si.sub.3 N.sub.4 whisker was present for 100 vol % of the produced Si.sub.3 N.sub.4 phase were especially excellent in toughness.
TABLE 12__________________________________________________________________________Composition ofsintered body Bending strength Thermal(vol %) (MN/m.sup.2) Breaking shock Si.sub.3 N.sub.4 Room troughness resistanceExamples Si.sub.3 N.sub.4 whisker SiC temp. 1200.degree. C. (MN/m.sup.3/2) (times)__________________________________________________________________________118 49.5 0.5 50 330 334 6 50119 40 10 50 332 332 7 50120 30 20 50 334 331 7 50121 20 30 50 332 331 7 50122 15 35 50 335 332 6 50123 49.7 0.3 50 331 332 4 50124 10 40 50 334 332 4 50__________________________________________________________________________
EXAMPLES 125-129
Table 13 shows characteristics of sintered bodies made in accordance with Example 65 using 55 vol % of Si and 45 vol % of SiC and molding binder in the amounts changed within the range of 5-13 parts by weight whereby volumetric particle packing rate of molding products was changed. Relation between the volumetric particle packing rate of molded products and bending strength is shown in FIG. 12. From these results, it can be seen that it is preferred that the molded products have a volumetric particle packing rate of at least 70 vol %.
TABLE 13______________________________________Volumetricpacking of Thermalparticles Bending strength shockin molded (MN/m.sup.2) Breaking resist-Exam- product Room toughness anceples (%) temp. 1200.degree. C. (MN/m.sup.3/2) (times)______________________________________125 65 154 154 3 42126 69 257 254 3 48127 70 310 310 5 48128 73 359 358 6 50129 75 390 390 7 50______________________________________
EXAMPLES 130-144
Table 14 shows volumetric particle packing rate of molded bodies made in the same manner as in Example 65 with changing blending ratio of raw materials and amount of molding binder.
FIG. 13 shows relation between specific surface area of the raw materials and suitable amount of binder. When the relation is within the hatched area, volumetric particle packing rate of molded bodies can be at least 70 vol %.
TABLE 14______________________________________ Specific Volumetric surface Amount of packing ofRaw material area of molding particles(parts by raw binder in moldedweight) material (part by productExamples Si SiC (cm.sup.2 /g) weight) (vol %)______________________________________130 60 40 17100 5.0 65131 60 40 17100 6.5 70132 60 40 17100 9.0 76133 60 40 17100 11.5 70134 60 40 17100 12.5 64135 90 10 25100 6.5 64136 90 10 25100 9.3 70137 90 10 25100 11.8 75138 90 10 25100 14.3 70139 90 10 25100 16.3 63140 50 50 14500 4.1 63141 50 50 14500 5.6 70142 50 50 14500 8.1 76143 50 50 14500 10.5 70144 50 50 14500 12.4 62______________________________________
EXAMPLE 145
Apparent viscosity of the kneaded products of the raw materials and the molding binder in Examples 130-144 was measured by flow tester.
Relation between the apparent viscosity and volumetric particle packing rate of the molded bodies is shown in FIG. 14. The smaller value of the apparent viscosity indicates better flowability, namely, superior moldability.
The apparent viscosity was measured by a flow tester having a nozzle of 6 mm diameter and 6.8 mm length at 150.degree. C. and under a pressure of 39 MN/m.sup.2.
FIG. 14 shows that the molded products can have a volumetric particle packing rate of at least 70 vol % by using a composition having an apparent viscosity within the range of (3-90).times.10.sup.4 N.multidot.s/m.sup.2. The apparent viscosity of this range is relatively low and thus molded products of complicated shape can be easily produced.
EXAMPLE 146
60 Parts by weight of metallic Si powder of 0.9 .mu.m in average particle size and 40 parts by weight of .alpha.-SiC powder of 16 .mu.m in average particle size were mixed together with methanol in a pot mill and dried. Then, thereto was added 9 parts by weight of a polyethylene wax and the mixture was kneaded by a pressure kneader at 150.degree. C. for 5 hours. Then, the mixture was pulverized and molded at 150.degree. C. and under 1000 kg/cm.sup.2 to a ring of 60 mm in outer diameter and 40 mm in inner diameter. After removal of the wax, the molded body was subjected to stepwise heat treatment to 1380.degree. C. over a long period of time in nitrogen atmosphere to obtain a sintered body. Dimensional change between the molded body and the sintered body was small, namely, 0.15% and the sintered body was superior in dimensional accuracy. Void content of the sintered body was 15% and diameter of void was 20 .mu.m or less.
Sliding surface was produced by polishing and subjected to sliding test using Al.sub.2 O.sub.3 (relative density: 98%) as a partner material. The results are shown in Table 15. As a comparative example, results of test between FC-20 cast-iron products are also shown in Table 15.
FIG. 15 shows a micrograph of the sliding surface of the sintered body obtained in this Example. In FIG. 15, 1 indicates a matrix phase, 2 indicates Si.sub.3 N.sub.4 particles and 3 indicates voids.
From Table 1, it can be seen that the product of the present invention is small in friction coefficient and superior in wear resistance.
Relation between surface pressure and friction coefficient when surface pressure was changed with keeping sliding speed at constant 3 m/sec is shown by curve A in FIG. 16. The result on Comparative Example 11 is also shown by curve B in FIG. 16. It can be recognized that the product of the present invention is superior in sliding characteristics.
TABLE 15______________________________________ Total abrasion Sliding Friction wear material coeffi- (mg/cm/ State of (I) (II) cient 100 h) sliding______________________________________Example 146 SiC/ Al.sub.2 O.sub.3 0.008 0.06 Good Si.sub.3 N.sub.4Compar- 11 FC-20 FC-20 0.12 72 BraggingativeExample______________________________________ Sliding conditions: In machine oil at surface pressure of 10 kgf/cm.sup.2 and sliding speed of 3 m/sec.
EXAMPLES 147-204
The sliding test was conducted in the same manner as in Example 146 except that Al.sub.2 O.sub.3 as the partner material was replaced by other materials. The results are shown in Table 16. Results of comparative examples are shown in Table 17. Sliding conditions were surface pressure: 2 kgf/cm.sup.2 and sliding speed: 2 m/sec.
From the results, it can be seen that the products of the present invention are small in friction coefficient and superior in thermal shock resistance. This is because the products of the present invention have open voids and comprise composite material. When test was conducted using SiC, Si.sub.3 N.sub.4 having the same particle hardness as the partner material, particles of the products of the present invention were fallen off, leaving great sliding marks. The thermal shock resistance was evaluated as follows: A sintered body was kept at 1200.degree. C. for 30 minutes and then quenched in water. This was repeated until cracks occurred and the number of the repetition was taken for evaluation.
TABLE 16__________________________________________________________________________ Abrasion SiC/Si.sub.3 N.sub.4 wear of Abrasion partner Thermal shock Friction wear material resistance of Partner material coeffi- (mg/cm.sup.2 / (mg/cm.sup.2 / SiC/Si.sub.3 N.sub.4No. for sliding test cient 100 h) 100 h) (times)__________________________________________________________________________Exam- 147 AlN 0.014 0.03 0.08 51ples 148 SiO.sub.2 glass 0.008 0.02 0.04 51 149 SiO.sub.2 0.007 0.03 0.03 51 150 TiN 0.013 0.04 0.08 51 151 TiO.sub.2 0.008 0.03 0.04 51 152 ZrN 0.012 0.03 0.09 51 153 ZrO.sub.2 0.007 0.03 0.04 51 154 carbon 0.010 0.01 0.20 51 155 MgO 0.010 0.02 0.03 51 156 apatite 0.012 0.02 0.04 51 157 ZnO 0.009 0.01 0.04 51Exam- 158 ferite 0.008 0.03 0.05 51ples 159 UO.sub.2 0.010 0.03 0.05 51 160 BaTiO.sub.2 0.009 0.02 0.07 51 161 PZT 0.009 0.01 0.04 51 162 B.sub.4 C 0.007 0.03 0.08 51 163 ZrB.sub.2 0.012 0.03 0.12 51 164 TiB.sub.2 0.012 0.03 0.11 51 165 TiO 0.009 0.03 0.04 51 166 BeO 0.009 0.03 0.05 51 167 (ZrO)P.sub.2 O.sub.7 0.010 0.04 0.06 51 168 beryl 0.010 0.03 0.05 51Exam- 169 TiO.sub.2 --Al.sub.2 O.sub.3 0.008 0.04 0.03 51ples 170 cordierite 0.009 0.03 0.02 51 171 .beta.-spodumene 0.011 0.03 0.04 51 172 ZrC 0.010 0.03 0.11 51 173 NgAl.sub.2 O.sub.4 0.012 0.02 0.04 51 174 BeAl.sub.2 O.sub.4 0.010 0.04 0.06 51 175 Be.sub.2 SiO.sub.4 0.011 0.03 0.05 51 176 ZrSiO.sub.4 0.011 0.04 0.05 51 177 celsian 0.012 0.04 0.04 51 178 willemite 0.012 0.04 0.05 51 179 3Al.sub.2 O.sub.3.2SiO.sub.2 0.009 0.04 0.04 51Exam- 180 2BaO.3SiO.sub.2 0.009 0.02 0.04 51ples 181 MgO--SiO.sub.2 0.009 0.03 0.04 51 182 MgO 0.009 0.04 0.03 51 183 B.sub.2 O.sub.3 0.009 0.03 0.04 51 184 MoC 0.010 0.05 0.11 51 185 Al.sub.2 O.sub.3 --ZrO.sub.2 0.008 0.03 0.04 51 186 Al.sub.2 O.sub.3 --TiN 0.008 0.04 0.08 51 187 SiO.sub.2 --Al.sub.2 O.sub.3 0.008 0.03 0.07 51 188 TiC 0.009 0.07 0.15 51 189 Al.sub.2 O.sub.3 --TiC 0.008 0.05 0.09 51Exam- 190 CaO 0.010 0.02 0.05 51ples 191 TaC 0.011 0.04 0.13 51 192 SUS304 0.009 0.01 0.03 51 193 Cr cast iron 0.009 0.01 0.02 51 194 Super hard alloy 0.009 0.01 0.02 51 195 FC20 0.009 0.01 0.03 51 196 Ni-Resist 0.009 0.01 0.02 51 197 Steatite 0.009 0.01 0.02 51 198 Ni-cast iron 0.009 0.01 0.02 51 199 Al bronze 0.010 0.01 0.04 51 200 P bronze 0.010 0.01 0.04 51 201 MoS.sub.2 --C 0.007 0.01 0.02 51Exam- 202 Teflon 0.007 0.01 0.02 51ples 203 Fluorine contain- 0.007 0.01 0.02 51 ing resin 204 Glass-nylon 0.008 0.01 0.02 51__________________________________________________________________________ Sliding conditions: In machine oil at surface pressure of 2 kg/cm.sup.2 and sliding speed of 2 m/sec.
TABLE 17__________________________________________________________________________ (I) (II) Thermal Abrasion Abrasion shock Condition of Friction wear wear resistance sliding materials coeffi- (mg/cm.sup.2 / (mg/cm.sup.2 / (times)No. (I) (II) cient 100 h) 100 h) (I) (II)__________________________________________________________________________Compara- 12 SiC SiC 0.12 0.24 0.24 31 31tive 13 SiC Si.sub.3 N.sub.4 0.15 0.22 0.31 31 37Examples 14 SiC Al.sub.2 O.sub.3 0.18 0.18 0.41 31 12 15 SiC TiC 0.12 0.19 0.22 31 30 16 SiC SiO.sub.2 0.17 0.12 0.75 31 19 17 SiC TiO.sub.2 0.15 0.19 0.42 31 24 18 SiC Carbon 0.12 0.09 0.96 31 -- 19 SiC ZrO.sub.2 0.14 0.18 0.22 31 16 20 SiC ZrN 0.16 0.17 0.23 31 30 21 SiC AlN 0.11 0.14 0.31 31 28 22 SiC MgO 0.22 0.16 0.56 31 10Compara- 23 SiC B.sub.4 C 0.14 0.21 0.26 31 20tive 24 SiC UO.sub.2 0.15 0.19 0.18 31 19Examples 25 Si.sub.3 N.sub.4 Si.sub.3 N.sub.4 0.14 0.24 0.24 37 37 26 Si.sub.3 N.sub.4 Al.sub.2 O.sub.3 0.23 0.18 0.42 37 12 27 Si.sub.3 N.sub.4 TiC 0.18 0.34 0.22 37 30 28 Si.sub.3 N.sub.4 SiO.sub.2 0.19 0.19 0.56 37 19 29 Si.sub.3 N.sub.4 TiO.sub.2 0.18 0.20 0.22 37 24 30 Si.sub.3 N.sub.4 Carbon 0.12 0.09 0.89 37 -- 31 Si.sub.3 N.sub.4 ZrO.sub.2 0.17 0.18 0.23 37 16Compara- 32 Si.sub.3 N.sub.4 ZrN 0.20 0.22 0.23 37 30tive 33 Si.sub.3 N.sub.4 AlN 0.24 0.21 0.31 37 28Examples 34 Si.sub.3 N.sub.4 MgO 0.22 0.16 0.48 37 10 35 Si.sub.3 N.sub.4 B.sub.4 C 0.18 0.31 0.28 37 20 36 Si.sub.3 N.sub.4 UO.sub.2 0.17 0.21 0.18 37 19 37 Al.sub.2 O.sub.3 Al.sub.2 O.sub.3 0.38 0.24 0.24 12 12 38 Al.sub.2 O.sub.3 TiC 0.24 0.24 0.25 12 30 39 Al.sub.2 O.sub.3 SiO.sub.2 0.23 0.19 0.48 12 19 40 Al.sub.2 O.sub.3 TiO.sub.2 0.24 0.21 0.21 12 24Compara- 41 Al.sub.2 O.sub.3 Carbon 0.10 0.09 1.17 12 --tive 42 Al.sub.2 O.sub.3 ZrO.sub.2 0.28 0.17 0.18 12 16Examples 43 Al.sub.2 O.sub.3 ZrN 0.26 0.21 0.16 12 30 44 Al.sub.2 O.sub.3 AlN 0.21 0.31 0.34 12 28 45 Al.sub.2 O.sub.3 FC-20 0.28 0.24 1.21 12 -- 46 Al.sub.2 O.sub.3 Carbon iron 0.28 0.23 1.02 12 -- 47 Al.sub.2 O.sub.3 PTFE 0.17 0.14 0.56 12 -- 48 ZrO.sub.3 Carbon iron 0.27 0.21 0.98 16 -- 49 Product of Product of 0.27 1.71 1.71 51 51 the present the present invention inventionCompara- 50 Product of SiC 0.24 2.95 0.45 51 31tive the presentExamples invention 51 Product of Si.sub.3 N.sub.4 0.28 2.24 0.53 51 37 the present invention__________________________________________________________________________ Sliding conditions: In machine oil at surface pressure of 2 kg/cm.sup.2 and sliding speed of 2 m/sec.
EXAMPLES 205-210
The same test as in Example 146 was conducted on sintered bodies different in void content and diameter obtained in the same manner as in Example 146 with changing amount of binder. The results are shown in Table 18.
Sliding conditions were surface pressure: 10 kgf/cm.sup.2 and sliding speed: 1 m/sec.
From the results, it can be seen that when void content exceeds 30%, abrasion were abruptly increases and when diameter of void is more than 100 .mu.m, abrasion wear also increases and the products of the present invention are superior in sliding properties.
TABLE 18__________________________________________________________________________ SiC/Si.sub.3 N.sub.4 Total SiC/Si.sub.3 N.sub.4 Maximum abrasion Void void Friction wear Sliding materials content diameter coeffi- (mg/cm.sup.2 /No. (I) (II) (%) (.mu.m) cient 100 h)__________________________________________________________________________Examples 205 SiC/Si.sub.3 N.sub.4 Al.sub.2 O.sub.3 5 5 0.007 0.07 206 SiC/Si.sub.3 N.sub.4 Al.sub.2 O.sub.3 10 8 0.007 0.08 207 SiC/Si.sub.3 N.sub.4 Al.sub.2 O.sub.3 15 15 0.007 0.08 208 SiC/Si.sub.3 N.sub.4 Al.sub.2 O.sub.3 20 15 0.007 0.08 209 SiC/Si.sub.3 N.sub.4 Al.sub.2 O.sub.3 25 30 0.007 0.11 210 SiC/Si.sub.3 N.sub.4 Al.sub.2 O.sub.3 30 100 0.007 0.89Examples 52 SiC/Si.sub.3 N.sub.4 Al.sub.2 O.sub.3 35 40 0.007 1.57(Compar- 53 SiC/Si.sub.3 N.sub.4 Al.sub.2 O.sub.3 40 50 0.007 2.96ative) 54 SiC/Si.sub.3 N.sub.4 Al.sub.2 O.sub.3 50 80 0.007 3.24 55 SiC/Si.sub. 3 N.sub.4 Al.sub.2 O.sub.3 30 110 0.007 1.54Examples 56 SiC/Si.sub.3 N.sub.4 Al.sub.2 O.sub.3 30 150 0.007 3.21(Compar- 57 SiC/Si.sub.3 N.sub.4 Al.sub.2 O.sub.3 30 210 0.007 Draggingative) for 70 h__________________________________________________________________________ Sliding conditions: In machine oil at surface pressure of 10 kgf/cm.sup.2 and sliding speed of 2 m/sec.
EXAMPLES 211-217
Sintered bodies were prepared in the same manner as in Example 146 with changing average particle size of SiC powder and the sliding test was conducted using Al.sub.2 O.sub.3 as the partner material. The results are shown in Table 19. When SiC particle is great, dragging occurs due to the SiC particles fallen off. The products of the present invention are superior in wear resistance. Excellent sliding properties were exhibited also when two or more SiC particles different in average particle size were mixed.
TABLE 19__________________________________________________________________________ SiC/Si.sub.3 N.sub.4 Al.sub.2 O.sub.3 Average particle Abrasion Abrasion SiC/Si.sub.3 N.sub.4 size of SiC in Friction wear wear Thermal shock SiC/Si.sub.3 N.sub.4 coeffi- (mg/cm.sup.2 / (mg/cm.sup.2 / resistanceNo. (.mu.m) cient 100 h) 100 h) (times)__________________________________________________________________________Examples 211 0.5 0.08 0.02 0.03 50 212 2 0.08 0.03 0.03 51 213 10 0.07 0.03 0.04 51 214 50 0.07 0.04 0.07 51 215 72 0.07 0.07 0.12 52 216 85 0.07 0.09 0.17 52 217 100 0.07 0.10 0.22 51Examples 58 120 0.07 0.22 1.08 51(Compar- 59 240 0.07 0.44 1.54 51ative) 60 400 0.07 0.81 2.12 51 61 800 0.07 1.23 5.23 51__________________________________________________________________________ Sliding conditions: Surface pressure 10 kgf/cm.sup.2 and sliding speed 5 m/sec. in SUNISO 4GS oil (made by Nippon Sun Sekyu K.K.)
EXAMPLES 218-220
60 parts by weight of metallic Si powder of 1 .mu.m in average particle size and 40 parts by weight of .beta.-SiC powder of 8 .mu.m in average particle size were mixed together with an organosilicone high polymer and xylene as a binder in a pot mill and dried. The mixture was solded to a ring of 150 mm outer diameter, 100 mm inner diameter and 20 mm thick at 100.degree. C. and under 2000 kgf/cm.sup.2. The molded body was heated stepwise to 1400.degree. C. over a long period of time in nitrogen and ammonia mixed atmosphere. Void content of the sintered bodies was 10% and void diameter was 10 .mu.m or less. Sliding test was conducted in the same manner as in Example 146 and the results are shown in Table 20. From the results, it can be seen that the products of the present invention are superior in sliding properties.
TABLE 20__________________________________________________________________________ Abrasion SiC/Si.sub.3 N.sub.4 wear of Abrasion partner Organo Si high wear material polymer compound Partner Friction (mg/cm.sup.2 / (mg/cm.sup.2 /No. (part by weight) material coefficient 100 h) 100 h)__________________________________________________________________________Examples 218 Siliconimide Al.sub.2 O.sub.3 0.007 0.02 0.03 MW: 1500 (15) 219 Polysilane Al.sub.2 O.sub.3 0.007 0.02 0.03 MW: 500 (10) 220 Polysil Al.sub.2 O.sub.3 0.007 0.02 0.03 MW: 800 (12)__________________________________________________________________________ Sliding conditions: Surface pressure 10 kgf/cm.sup.2 and sliding speed 5 m/sec. in SUNISO 4GS oil.
EXAMPLES 221-229
Sintered bodies were prepared in the same manner as in Example 146 with changing the raw material ratio of metallic Si and SiC to change the ratio of Si.sub.3 N.sub.4 phase and SiC phase in the sintered bodies. Results of sliding test on these sintered bodies are shown in Table 21. The sliding conditions were same as in Example 210.
From the results, it can be seen that with increase in the amount of SiC particle the mechanical strength decreases, resulting in increase in abrasion wear. Therefore, it is preferred that amount of SiC particle is 70 vol % or less. Considering thermal shock resistance, SiC particle is preferably contained in an amount of at least 20 vol %.
Therefore, it is seen that reaction-bonded material of the present invention where SiC particles are bonded with Si.sub.3 N.sub.4 is superior to the material comprising only Si.sub.3 N.sub.4 or SiC in thermal shock resistance.
As comparative examples, the same tests were conducted on porous reaction-sintered Si.sub.3 N.sub.4 body and SiC body and the results are also shown in Table 21.
TABLE 21__________________________________________________________________________ Abrasion Si.sub.3 N.sub.4 /SiC wear of Abrasion partner Si.sub.3 N.sub.4 /SiC Composition of Friction wear material Thermal shock sintered body Partner coeffi- (mg/cm.sup.2 / (mg/cm.sup.2 / resistanceNo. Si.sub.3 N.sub.4 SiC material cient 100 h) 100 h) (times)__________________________________________________________________________Examples 221 95 5 Al.sub.2 O.sub.3 0.022 0.38 0.24 37 222 90 10 Al.sub.2 O.sub.3 0.019 0.18 0.09 42 223 80 20 Al.sub.2 O.sub.3 0.008 0.04 0.04 50 224 70 30 Al.sub.2 O.sub.3 0.007 0.04 0.03 51 225 50 50 Al.sub.2 O.sub.3 0.007 0.04 0.03 52 226 40 60 Al.sub.2 O.sub.3 0.008 0.05 0.05 52 227 30 70 Al.sub.2 O.sub.3 0.009 0.09 0.15 51 228 20 80 Al.sub.2 O.sub.3 0.012 0.15 0.48 43 229 10 90 Al.sub.2 O.sub.3 0.057 0.34 0.89 40Compara- 62 100 -- Al.sub.2 O.sub.3 0.101 Reaction 1.24 20tive sinteringExamples 2.10 63 -- 100 Al.sub.2 O.sub.3 0.120 Reaction 3.24 34 sintering 1.54__________________________________________________________________________ Sliding conditions: Surface pressure of 12 kgf/cm.sup.2 and sliding speed of 5 m/sec. in SUNISO 4GS oil.
EXAMPLE 230
13 Parts by weight of a mixture of polyethylene, stearic acid and a synthetic wax was added to 60 parts by weight of metallic Si powder of 0.5 .mu.m in average particle size and 40 parts by weight of SiC powder of 10 .mu.m in average particle size and the mixture was kneaded. This raw material was injection molded into a floating seal as shown by reference number 7 in FIG. 18. After removal of the wax in the molded body, this was heated from 1100.degree. C.-1400.degree. C. at 6.degree. C./h in nitrogen atmosphere. The dimensional change of the floating seal on sintering was small, namely, 0.13% and this was able to be used only by finishing a sliding surface. Therefore, it is considered that variability in dimension of bodies can be inhibited and working cost can be reduced to half. Thus, the bodies are suitable for mass production. Results of sliding tests are shown in Table 22.
TABLE 22______________________________________ Total Combination Fric- abrasion Abrasion of sliding tion wear wear material coeffi- (mg/cm.sup.2 / (mg/cm.sup.2 /No. (I) (II) cient 100 h) 100 h)______________________________________Ex- 230 Si.sub.3 N.sub.4 / Cr cast 0.007 0.02 0.22ample SiC iron______________________________________ Sliding conditions: Surface pressure of 8 kgf/cm.sup.2 and sliding speed m/sec. in SUNISO 4GS oil.
EXAMPLE 231
The sintered body obtained in Example 146 was subjected to HIP treatment at 2000.degree. C. for 4 hours under 80 atm in nitrogen atmosphere. Test results on the resulting sintered body are shown in Table 23.
TABLE 23__________________________________________________________________________ Sintered body after HIP treatment (I) (II) (I) Abrasion Abrasion Void Thermal shock Partner Friction wear wear content resistance material coeffi- (mg/cm.sup.2 / (mg/cm.sup.2 /No. (%) (times) (II) cient 100 h) 100 h)__________________________________________________________________________Example 231 2 53 Al.sub.2 O.sub.3 0.007 0.01 0.02__________________________________________________________________________ Sliding conditions: Surface pressure of 10 kgf/cm.sup.2 and sliding speed 7 m/sec. in SUNISO 4GS oil.
EXAMPLE 232
A furan resin was impregnated into the voids of the sintered body obtained in Example 146 by autoclave to reduce open void content. Test results on the resulting sintered body are shown in Table 24.
TABLE 24__________________________________________________________________________ Furan resin (I) (II) impregnated Abrasion Abrasion product Partner Friction wear wear (I) material coeffi- (mg/cm.sup.2 / (mg/cm.sup.2 /No. Void content (II) cient 100 h) 100 h)__________________________________________________________________________Example 232 7 Al.sub.2 O.sub.3 0.005 0.001 0.002__________________________________________________________________________ Sliding conditions: Surface pressure of 10 kgf/cm.sup.2 and sliding speed 7 m/sec. in SUNISO 4GS oil.
EXAMPLES 233-240
Sintered bodies were made in the same manner as in Example 146 except that SiC whisker as shown in Table 25 was used in place of .alpha.-SiC particle. Sliding test results on the resulting sintered bodies are shown in Table 25, wherein average aspect ratio of whisker is indicated by A and average length by L.
TABLE 25______________________________________ (I) (II) Abra- Abra- Fric- sion sion tion wear wear SiC Partner co- (mg/ (mg/ Whisker material effi- cm.sup.2 / cm.sup.2 /No. (I) (II) cient 100 h) 100 h)______________________________________Ex- 233 A = 50 Al.sub.2 O.sub.3 0.007 0.01 0.02amples L = 10 .mu.m 234 A = 100 Al.sub.2 O.sub.3 0.007 0.01 0.02 L = 50 .mu.m 235 A = 200 Al.sub.2 O.sub.3 0.007 0.03 0.05 L = 35 .mu.m 236 A = 100 Al.sub.2 O.sub.3 0.007 0.03 0.04 L = 100 .mu.m 237 A = 60 Al.sub.2 O.sub.3 0.007 0.09 0.11 L = 200 .mu.m 238 A = 50 Al.sub.2 O.sub.3 0.007 0.10 0.23 L = 250 .mu.m 239 A = 210 Al.sub.2 O.sub. 3 0.007 0.15 0.26 L = 100 .mu.m 240 A = 220 Al.sub.2 O.sub.3 0.007 0.25 0.56 L = 350 .mu.m______________________________________ Sliding conditions: Surface pressure of 10 kgf/cm.sup.2 and sliding speed 7 m/sec. in SUNISO 4GS oil.
EXAMPLE 241
The raw material obtained in Example 146 was injection molded into a floating seal as shown in FIG. 18 and this molded body was impregnated with a furan resin using an autoclave in the same manner as in Example 232. As a partner material, a floating seal as shown in FIG. 18 was made by injection molding of Al.sub.2 O.sub.3 (relative density 98%). They were incorporated into rolling wheel of caterpiller rotating axis of a construction machine and actual working test was conducted. After 500 hours test, overhaul thereof was carried out to find no hydraulic leakage and sliding marks.

Number	Date	Country
62-86871	Apr 1987	JPX
62-110556	May 1987	JPX
62-206698	Aug 1987	JPX

Number	Name	Date
3875476	Crandall et al.	Apr 1975
4341965	Okuo et al.	Jul 1982
4579699	Verzemnieks	Apr 1986
4719151	Chyung et al.	Jan 1988

Number	Date	Country
0107349	Sep 1983	EPX
0181208	Nov 1985	EPX
0209320	Jul 1986	EPX
2084703	Dec 1971	FRX

Ceramic composite and process for the production thereof

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