Low frictional ceramic material for sliding member

Abstract: A low frictional ceramic material for sliding member, consists essentially of oxide of aluminum (Al) and oxide of zirconium (Zr) and contains oxide of cerium (Ce). Aluminum (Al) content is 50 to 75 wt.% in terms of alumina (Al 2 O 3 ), zirconium (Zr) content is 20 to 45 wt.% in terms of zirconia (ZrO 2 ), and cerium (Ce) content is 3 to 20 wt.% in terms of ceria (CeO 2 ) in said low frictional ceramic material for sliding member. Instead of oxide of aluminum (Al) and oxide of zirconium (Zr), it is capable to use α-sialon.

Description: The present invention relates to a low frictional ceramic material for sliding member which is high in mechanical strength, small in coefficient of friction and excellent in abrasion resistance. Generally, an iron based material is used for a sliding member, ceramics such as alumina (Al 2 O 3 ) is used for a sliding member for which abrasion resistance is required, and silicon nitride (Si 3 N 4 ) and zirconia (ZrO 2 ) which is higher in price than alumina are used for a construction member for which mechanical strength and toughness are required, as disclosed in Japanese Patent Laid-Open No. 63-265,860 Publication. The iron based material undergoes cohesion and transition under the severe sliding conditions and becomes worn. Alumina is excellent in abrasion resistance but cannot expect a low frictional property because it is hard to adsorb lubricating oil. Further, alumina is inferior in toughness compared to silicon nitride and zirconia. JP 06 234 569 discloses a sliding part formed with a ceramic-sintered compact consisting of 5-20 mol% cerium oxide, 10-60 mol% aluminium oxide and the balance zirconium oxide. An alumina sintered body containing 10 to 60 vol.% of needle-like La based β-alumina (see Japanese Patent Laid-Open No. 63-134551 Publication) is excellent in mechanical properties such as toughness but is large in coefficient of friction because it is hard to adsorb lubricating oil. When it contains 30 vol.% or more of needle-like crystal material, the number of pores increases and the strength materially lowers. An alumina sintered body using needle-like boric acid aluminum as a precursor is also large in coefficient of friction because it is hard to adsorb lubricating oil. Further, since raw material is needle-like, it is difficult to be mixed evenly. Accordingly, a better sintered body cannot be obtained unless a sintering method utilizing high pressure such as HIP (Hot Hydrostatic Press), HP (Hot Press) and the like is used. In view of the aforementioned problem, it is an object of the present invention to provide a low frictional ceramic material for sliding member which is well conformed to lubricating oil, small in coefficient of friction, and excellent in mechanical strength, heat resistance and abrasion resistance. In a view of the structure of tissue, the low frictional ceramic material for sliding member according to the present invention comprises alumina as a matrix, and needle-like crystal substance such as 5 to 30 wt.% of CaAl 12 O 19 contained in the matrix and 3 to 20 wt.% of ceria contained in the matrix. Since ceria as a dispersive phase tends to adsorb lubricating oil, the low frictional ceramic material for sliding member according to the present invention is smaller in coefficient of friction than conventional alumina and conventional alumina containing a needle-like crystal substance. Further, since the needle-like crystal substance such as CaAl 12 O 19 as a dispersive phase and ceria impedes cracks due to the external force and deflects or goes round a direction of the crack, the low frictional ceramic material for sliding member according to the present invention is high in toughness as compared with conventional alumina and conventional alumina containing a needle-like crystal substance. These and other aims and features of the invention will become more apparent upon a perusal of the following description taken in conjunction with the accompanying drawings. Fig. 1 is a schematic view showing a tissue section of low frictional ceramic material for sliding member according to the present invention. Fig. 2 is a diagram showing the frictional characteristic of the low frictional ceramic material for sliding member. Fig. 3 is a diagram showing the relationship between the addition of ceria and coefficient of friction of the low frictional ceramic material for sliding member. Fig. 4 is an illustrated view showing the mechanical strength of the low frictional ceramic material for sliding member according to the present invention and the conventional low frictional ceramic material for sliding member. As shown in Fig. 1, a low frictional ceramic material for sliding member "M" according to the present invention is characterized in that β -alumina 3 in the form of a needle-like crystal and a spherical particle 4 of ceria (CeO 2 ) of which particle diameter or grain size is 10 µ m or less are mixed in a matrix 2 comprising fine particulate of α -alumina (Al 2 O 3 ). More specifically, 5 to 30 parts of β -alumina and 3 to 20 parts of ceria are mixed in a matrix 2 comprising 50 to 92 parts of α - alumina (parts termed herein represent weight ratio). For β - alumina, at least one is selected out of CaAl 12 O 19 , SrAl 12 O 19 , BaAl 12 O 19 and LaAl 11 O 18 . EXAMPLE 1 For obtaining the low frictional ceramic material for sliding member of this invention, α -alumina powder, ceria powder and a precursor of CaAl 12 O 19 powder were prepared and mixed while crushing them for 24 hours in a ball mill. A molded body was pressed and molded from the obtained powder, and then it was sintered for about three hours in air at a temperature of approximately 1,600' C. With respect to the obtained the low frictional ceramic material for sliding member, the tissue thereof was examined. As a result, it has been found that CaAl 12 O 19 needle-like clystal substances of which aspect ratio (elongation ratio) is 3 to 10 and length is 5 to 20 µ m were dispersed, and substantially spherical ceria particles of which particle diameter or grain size is 5 µ m or less were evenly dispersed. The weight ratios (obtained from volume ratio and specific gravity; the same is true hereinafter) between α -alumina, ceria and CaAl 12 O 19 contained in the low frictional ceramic material for sliding member of this invention were 75 wt.% for α -alumina, 10 wt.% for ceria and 15 wt.% for CaAl 12 O 19 . A rectangular plate for sliding test having a dimension 65 x 15 x 10 mm was cut out from the low frictional ceramic material for sliding member of this invention, and the surface roughness Rz of the sliding surface was processed to 0.4 µ m or less. As a comparative material, a similar plate for sliding test was prepared from alumina added no ceria thereto and cast iron, respectively. On the other hand, As a mating material, a pin for sliding test having 8 mm of outside diameter and 23 mm of length was prepared from spheroidal graphite cast iron, and one end of the pin for sliding test was processed to a hemispherical shape (SR18). The pin for sliding test was vertically pressed against the plate for sliding test and relatively slidably moved to measure the coefficient of friction, using a reciprocating type sliding tester. The sliding conditions were that a mean sliding speed was 0.2 m/sec, a pressing load of the pin for sliding test was 0.2 to 15 kgf, and a temperature was 100'C. For lubricating sliding portions, lubricating oil for Diesel engine (lubricating oil "A" described above) was used. It is understood from Stribeck curve according to the result of aforementioned sliding test, shown in Fig. 2, that the low frictional ceramic material for sliding member of this invention is excellent in frictional characteristic as compared with the comparative material. A beam-like strength test piece having a dimension 4 x 3 x 40 mm prepared from the low frictional ceramic material for sliding member of this invention was used to measure 4-point bending strength and fracture toughness value. It is understood that according the test result, as shown in Fig. 4, the low frictional ceramic material for sliding member (sample D13 in Table 3) of this invention substantially equal in the 4-point bending strength to that of conventional alumina (sample E20 in Table 3), and is higher in the fracture toughness than that of conventional alumina. sample compound ratio (wt.%) α-Al 2 O 3 CaAl 12 O 19 SrAl 12 O 19 BaAl 12 O 19 LaAl 11 O 18 CeO 2 MgO D11 95 0 0 0 0 5 0 D12 92 5 0 0 0 3 0 D13 75 15 0 0 0 10 0 D14 60 30 0 0 0 10 0 D15 50 40 0 0 0 10 0 D16 40 40 0 0 0 20 0 D17 75 0 15 0 0 10 0 D18 75 0 0 15 0 10 0 D19 75 0 0 0 15 10 0 *E20 98 0 0 0 0 0 2 EXAMPLE 2 Similar to the case of Example 1, α -alumina powder, ceria powder and a precursor of various β -alumina (CaAl 12 O 19 , SrAl 12 O 19 , BaAl 12 O 19 , etc.) powder were prepared at a weight ratio shown in Table 3 and mixed while crushing them for 24 hours in a ball mill. A molded body was pressed and molded from the obtained powder, and then it was sintered for about three hours in air at a temperature of approximately 1,600'C to obtain low frictional ceramic material for sliding member. A plate for sliding test and a strength test piece similar to those of Example 1 were prepared from the obtained low frictional ceramic material for sliding member. The above-described plate for sliding test was used and the coefficient of friction thereof was measured by the reciprocating type sliding tester under the sliding conditions similar to those of Example 1. According to the result of the sliding test, as shown in Fig. 3, it is understood that the low frictional ceramic material for sliding member of this invention is small in coefficient of friction when the addition of ceria with respect to the sum total of raw material exceeds 3 wt.%, and is large in coefficient of friction when the addition of ceria with respect to the sum total of raw material exceeds 20 wt.%. It is considered that the coefficient of friction is small when ceria is added because the adsorbing property of lubricating oil to the low frictional ceramic material for sliding member is enhanced. It is considered that the coefficient of friction is large when the addition of ceria exceeds 20 wt.% because pores increase in the sintered body, and irregularities occur in the surface (sliding surface) of the low frictional ceramic material for sliding member due to the presence of the pores. A beam-like strength test piece having a dimension 4 x 3 x 40 mm prepared from the low frictional ceramic material for sliding member of this invention was used to measure 4-point bending strength and fracture toughness value, similar to the case of Example 1. According to the aforementioned test result, as shown in Fig. 4, it has been found that when the weight ratio of CaAl 12 O 19 with respect to the sum total of raw material is 5 to 30 wt.%, the 4-point bending strength and fracture toughness value were enhanced. The reason is that when the weight ratio of CaAl 12 O 19 is less than 5 wt.%, the suppression effect of cracks cannot be obtained, and when the weight ratio of CaAl 12 O 19 exceeds 30 wt.%, the pores of the sintered body increase. It has been found from the above-described test result that when the composition weight ratio of the low frictional ceramic material for sliding member of this invention is 50 to 92 parts for α -alumina, 5 to 30 parts for β -alumina and 3 to 20 parts for ceria, the excellent frictional characteristic and mechanical characteristic are obtained. As described above, the low frictional ceramic material for sliding member of this invention, contains β -alumina and 5 to 20 wt.% of ceria in a matrix comprising α -alumina, the particle diameter or grain size of ceria being under 10 µ m. The adsorptive property (conformability) of lubricating oil is improved by the addition of ceria and the low frictional ceramic material for sliding member is high in mechanical strength and toughness, small in coefficient of friction, thus causes less frictional force and amount of abrasion in a sliding portion. Obviously, many modifications and variations of the present invention are possible in right of the above teachings. It is to be understood, therefore, that the invention can be practiced otherwise than as specifically described.

Claims: A low frictional ceramic material comprising: a matrix containing 50 to 92wt.% α-alumina; needle-shaped crystals dispersed through the matrix, said needle-shaped crystals containing 5 to 30wt.% of β-alumina; and 5 to 20wt.% of spherical ceria particles having a diameter of less than 10µm. The low frictional ceramic material according to claim 1, wherein said β-alumina is at least one of CaAl 12 O 19 , SrAl 12 O 19 and BaAl 12 O 19 , LaAl 11 O 18 .

Inventors: YASUAKI UNNO, YASUAKI, UNNO
Applicants: ISUZU CERAMICS RES INST, ISUZU CERAMICS RESEARCH INSTITUTE CO., LTD.
Application year: 1997
Main classification: C04B35
IPC codes: C04B35, F16C33