Silicon nitride sintered product excellent in wear resistance

Abstract: A silicon nitride sintered product for use in cutting tools and the like which has silicon nitride as a predominant phase, and comprises 0.1 to 1% by weight of Al as calculated on the basis of Al₂O₃, the total amount of sintering aid constituents other than Al being 6% by weight or less on the oxide basis, the content of the grain boundary glassy phase being 8% by volume or less. The silicon nitride sintered product preferably has a relative density of 99% or more.

Description: FIELD OF THE INVENTION The present invention relates to a silicon nitride sintered product suitable for use in a cutting tool, a wear-resistant tool, a wear-resistant component and a reciprocating component. The term, silicon nitride used herein means Si 3 N 4 , β'-sialon represented by Si 6-z Al z O z N 8-z (Z is 0 to 4.2) and the like. BACKGROUND OF THE INVENTION Silicon nitride sintered products are ceramics which are extremely hard and exhibit excellent wear resistance as well as strength and toughness. Therefore, silicon nitride sintered products have been used in cutting tools and wear-resistant components. In JP-A-1-157466 (1989) (the term "JP-A" as used herein means an "unexamined published Japanese patent application") which corresponds to US-A-4,880,756 a silicon nitride sintered product in which Mg, Zr, Al or the like is used as a sintering aid is proposed as a product having excellent wear resistance. This prior art teaching as well as the teaching disclosed in EP-A-0 356 244 is based on the finding that Al and the like contribute to product densification by forming, together with Si, N and O, a liquid phase in the interstices between Si 3 N 4 grains during firing, and also bond Si 3 N 4 grains by glassification during cooling to avoid debonding of Si 3 N 4 grains during abrasion, thereby enhancing toughness. In some cases, a wear-resistant film may be formed on the surface of the base material of a cutting tool, giving it excellent strength and toughness so that the wear resistance is improved. However, in these cutting tools, despite the wear-resistant components and the reciprocating components, still further alleviation of wear is required to prolong tool life, since the techniques described in JP-A-1-157466 do not satisfy such requirements. Although it was possible to obtain the sintered products which exhibit excellent defect resistance by improving the strength and toughness, there was previously no specific means for improving the wear resistance, since the relationship between wear resistance and mechanical properties was not known. SUMMARY OF THE INVENTION The present inventors have found, after thorough studies, that reducing the amount of the grain boundary glassy phase is unexpectedly effective in improving wear resistance. The present invention has been made based on such knowledge. The object of the present invention is to provide a silicon nitride sintered product which exhibits excellent wear resistance. According to the present invention, a silicon nitride sintered product is provided which exhibits excellent wear resistance. Said product is defined by the features of claim 1. DETAILED DESCRIPTION OF THE INVENTION The operation of the present invention is described below. Our studies regarding the wear resistance of the cutting tools have revealed the following facts: It is said that generally the temperature of the edge of the blade of cutting tool during cutting reaches as high as 800°C or more, although this depends on the workpiece and the cutting conditions. Therefore, in order to improve the wear resistance of cutting tools, it is important that the cutting tools have good heat resistance and chemical stability. The grain boundary phase in the silicon nitride sintered product is present as a crystal phase or an amorphous glassy phase comprising the sintering aid constituents such as Al, Mg, Zr, Ce, Yb, Er, Pr, or oxides thereof, as well as Si, N and O. The amorphous glassy phase has poor heat resistance and poor corrosion resistance as compared with silicon nitride. Therefore, the amount and composition of the grain boundary glassy phase greatly affect the heat resistance and chemical stability of the sintered product. In view of the above, if the amount of a sintering aid to be used can be reduced by the use of a sintering aid system having such an excellent sintering capability as to enable the product densification even with a small amount thereof, sufficient product densification and improved wear resistance of the product can be attained even though the amount of the grain boundary glassy phase is small. The present inventors have found that an Al constituent satisfies these requirements. Further, the addition of a very small amount of an Al compound, especially Al 2 O 3 , as a sintering aid results in the improvement of sinterability of the green body for the product, and thus the reduction of the contents of the other sintering aid constituents, whereby the reduction of the amount of the grain boundary glassy phase can be attained. The addition of a very small amount of the above Al compound also results in resistance of the grain growth of the silicon nitride grains in the sintered product, and thus provides a finer structure, whereby wear resistance can be improved. If Al 2 O 3 is added as a sintering aid, Al and O atoms in Al 2 O 3 are substituted with a part of Si and N atoms in Si 3 N 4 , respectively to form β'-sialon. In order to impart good wear resistance to the wear-resistant components and the reciprocating components in addition to the cutting tools, it is important to improve the abrasive wear resistance of the material. It has been found through various studies that a reduction in the amount of the grain boundary phase in the silicon nitride sintered product and the reduced grain size of the silicon nitride grains contribute to the improvement of the abrasive wear resistance. Also, it has been found that the addition of Al 2 O 3 as a sintering aid results in finer silicon nitride grains in the sintered product. In the present invention, in order to obtain a silicon nitride sintered product which has improved heat resistance, chemical stability and abrasive wear resistance and which exhibits excellent wear resistance, it is essential to make the content of the grain boundary glassy phase 8% by volume or less and to include 0.1 to 1% by weight of Al as calculated on the basis of Al 2 O 3 . If the content of the grain boundary glassy phase exceeds 8% by volume, the wear resistance deteriorates. When the sintered product is used in the cutting tools, it is especially preferred that the content of the grain boundary glassy phase is 6% by volume or less. However, if the content is less than 3% by volume, the toughness deteriorates, which may result in the deterioration of the defect resistance of the sintered product. An amount of Al is preferably 0.1 to 1% by weight, the most preferably 0.3 to 0.7% by weight as calculated on the basis of Al 2 O 3 . If the content of Al is less than 0.1% by weight, the results that the sintering aid is intended to accomplish cannot be attained, nor can the finer structure of the sintered product be obtained. If the content of Al exceeds 1% by weight, the thermal conductivity of the sintered product is reduced, and thus the temperature of the edge of the cutting tool blade increases to a greater degree during cutting when the sintered product is used for the cutting tool, whereby the wear loss is increased. As the density of the silicon nitride sintered product increases, the wear resistance increases as well. Thus, the relative density of the sintered product is 99% or more. If the relative density is less than 99%, a pore of 1% or more remains in the sintered product, which causes not only the deterioration of the chipping resistance but also the deterioration of wear resistance of the cutting tool made from the sintered product. The sintering aids in addition to Al 2 O 3 must be those which have a high sintering capability, so as to effect the sintering even with a small amount thereof. Examples of such sintering aids include, preferably, Mg, Zr and Ce. As these constituents, there are used oxides, or the materials which can be converted to oxides during a firing process. In order to achieve a relative density of 99% or more in the sintering process, sintering under a pressurized atmosphere is carried out as a secondary sintering step after an atmospheric sintering step is carried out. The firing temperature used in both the atmospheric sintering and the sintering under a pressurized atmosphere ranges from 1600°C to 1900°C, preferably from 1650°C to 1850°C, and most preferably from 1700°C to 1800°C. The secondary sintering is carried out under a pressurized atmosphere having a partial nitrogen pressure of 10 atm or more. Examples of the sintering under a pressurized atmosphere which can be used in the present invention include sintering under hot isostatic press (HIP) and gas pressure sintering (GPS). The present invention is hereinafter described in greater detail with reference to examples, which are not to be construed as limiting the scope thereof. EXAMPLES Si 3 N 4 powder having an average particle diameter of 0.7 µm, an α rate of 98% and a specific surface area of 10 m 2 /g; and as sintering aids, Al 2 O 3 powder having a specific surface area of 10 m 2 /g, MgO powder having a specific surface area of 4 m 2 /g, ZrO 2 powder having a specific surface area of 14 m 2 /g and CeO 2 powder having a specific surface area of 8 m 2 /g, and optionally Yb 2 O 3 powder having a specific surface area of 9 m 2 /g, Er 2 O 3 powder having a specific surface area of 9 m 2 /g or Pr 6 O 11 powder having a specific surface area of 8 m 2 /g were added at proportions shown in Table 1, and dried. Then, the resulting powder mixtures were pressed in molds under a pressure of 2 ton/cm 2 , and subjected to a primary firing process at 1600 to 1750°C (held under an atmospheric pressure of N 2 for 2 hours) followed by a secondary firing process under N 2 atmosphere of 100 atm, to give silicon nitride sintered products. Sample No. Composition (% by weight) Remarks Si 3 N 4 Sintering aid constituents Al 2 O 3 MgO ZrO 2 CeO 2 Others 1 98.8 0.3 0.3 0.3 0.3 - - Within the scope of the present invention 2 98.3 0.5 0.5 0.2 0.5 - - 3 96.9 0.1 1.0 1.0 1.0 - - 4 97.0 0.9 1.0 0.6 0.5 - - 5 93.5 0.5 2.0 2.0 2.0 - - 6 96.9 0.5 1.0 0.6 - Yb 2 O 3 1.0 7 96.0 0.7 0.8 1.0 - Pr 6 O 11 1.5 8 97.3 0.3 0.6 0.8 - Er 2 O 3 1.0 9 98.8 - 0.5 0.2 0.5 - - Comparative Examples 10 90.5 0.5 3.0 3.0 3.0 - - 11 87.5 0.5 4.0 4.0 4.0 - - 12 84.5 0.5 5.0 5.0 5.0 - - 13 89.8 0.2 5.0 5.0 - - - 14 96.3 2.5 0.5 0.2 0.5 - - The amount of the grain boundary glassy phase, the relative density, and the wear resistance when used as a cutting tool were determined on the obtained silicon nitride sintered products. The results of the determinations are shown in Table 2. The sintering conditions and the methods for the measurement of the respective properties are discussed below. Sintering Conditions The primary firing: N 2 1 atm, 1600 to 1750°C, 2 hours The secondary firing: N 2 100 atm, 1800°C, 2 hours Methods for Measurements (1) Amount of the Grain Boundary Glassy Phase A particular sintered product was subjected to mirror polishing. Then, the proportion of the area occupied by the grain boundary phase in the product was measured by observation using a SEM (scanning electron microscope). The results of the measurement were designated as the amount of the grain boundary glassy phase. (2) Relative Density The density of each particular sintered product was measured by the Archimedean Method. The relative density of the product was determined by means of the equation as set forth below. In determining the relative density, completely densified products were prepared by the process comprising charging approximately 10 g of composition powder having the same compositions as those of the respective sintered products into a hollow cylinder made of carbon having 20 mmH x 20 mmD, hot-pressing thereof under 200 Kgf/cm 2 pressure, and sintered at 1800°C for 1 hour.. The sintered products, and completely densified products, thus formed, were selected, in which no pores were found by observation at 200 magnification using a metallurgical microscope after the products were subjected to mirror polishing and in which no fine pores on the order of microns were found by observation at 2000 to 5000 magnifications using a SEM. Relative Density (%) = (Density of Sintered Product/Density of Completely Densified Product Having Same Composition) × 100 (3) Wear Resistance Flank wear width V B was shown as a maximum abrasion loss, which was measured by using a test piece formed by processing a particular sintered product into chips specified as SNGN432 to machine a cutting material (JIS FC23), and cutting conditions such as a cutting speed of 100 m/min, a feed rate of 0.1 mm/rev, a depth of cut of 1.0 mm and a cutting time of 30 minutes in dry cutting. Sample No. Results Remarks Relative Density (%) Amount of Grain Boundary Glassy Phase (vol%) Wear Resistance V B (mm) 1 99.5 3.6 0.21 Within the scope of the present invention 2 100 3.8 0.22 3 100 5.0 0.26 4 100 5.1 0.27 5 100 7.1 0.36 6 100 4.8 0.24 7 100 5.5 0.31 8 100 4.2 0.28 9 92.0 4.1 0.61 Comparative Examples 10 100 8.7 0.48 11 100 10.4 0.63 12 100 12.5 0.70 13 100 9.3 0.52 14 99.2 4.8 0.56 As can be seen from Table 2, the sintered products according to the present invention have excellent cutting properties such as V B values of 0.4 mm or less for wear resistance. In contrast, Sample No. 9 does not contain Al 2 O 3 and has poor sinterability, resulting in the attainment of a relative density of as low as 99% or less and poor wear resistance. Sample Nos. 10 to 13 have an amount of the grain boundary glassy phase of more than 8% by volume. Consequently, they have poor wear resistance in spite of their sufficient densification, as is shown by their having a relative density of 100%. Further, sufficient wear resistance is not attained in Sample No. 14, which has an excessive content of Al 2 O 3 . In the silicon nitride sintered products according to the present invention, wherein the amount of the grain boundary glassy phase is 8% by volume or less and wherein Al is contained in an amount of 0.1 to 1% by weight as calculated on the basis of Al 2 O 3 , excellent wear resistance can be attained as is illustrated by the above-described examples.

Claims: A silicon nitride sintered product having a grain boundary glassy phase content of 8% by volume or less and a relative density of 99% or more, and comprising: (i) silicon nitride as the predominant phase, (ii) 0.1 to 1% by weight of Al as calculated on the basis of Al 2 O 3 , (iii) sintering aid constituents Mg, Zr, and at least one of the rare earth elements selected from Ce, Yb, Er, and Pr, or oxides thereof present in an amount of more than 0% to 6% by weight on oxide basis. The silicon nitride sintered product according to claim 1, wherein said grain boundary glassy phase content is 3% to 6% by volume.

Inventors: MIZUNO KEN-ICHI, TAJIMA YO, MIZUNO, KEN-ICHI, TAJIMA, YO, Mizuno, Ken-ichi, c/o NGK Spark Plug Co., Ltd., Tajima, Yo, c/o NGK Spark Plug Co., Ltd.
Applicants: NGK SPARK PLUG CO, NGK SPARK PLUG CO., LTD
Application year: 1992
Main classification: C04B35
IPC codes: C04B35, B23P15