COMPOSITE CERAMIC MATERIAL

Abstract: This invention relates to sintered ceramic materials in which the densification during sintering takes place with a liquid phase preferably based on silicon nitride. During sintering such materials are often embedded in a powder of inert material such as BN etc. The invention resides in the fact that by embedding the material to be sintered in a protective powder with a composition similar to that of the intergranular phase a surface zone with a composition and/or structure different from that of the core can be obtained.

Description: This invention relates to a compound ceramic material, preferably based on silicon nitride, useful for cutting tools and structural components where the wear resistance and toughness behaviour is important. Silicon nitride ceramics have many interesting features which have made them extremely suitable for certain wear part applications and as cutting tools. Intrinsic properties such as low thermal expansion, relatively high thermal conductivity and high elastic modulus give the material excellent resistance against thermal shocks and, thus, good toughness behaviour. However, it is difficult to sinter silicon nitride ceramics to full density without using sintering aids. Such sintering aids include magnesia, alumina, beryllia, zirconia and the rare earth oxides including yttria. Also the related nitrides, oxynitrides or silicates may be used as sintering aids. By applying standard sintering techniques, Si-Al-O-N ceramics may be formed in which Al and O have been substituted for some Si and N atoms in the crystal lattice. The chemical formula for this material may be written Si 6-z Al z O z N 8-z (where 0<z<4.2). This beta-sialon pha the same crystal structure as beta - Si₃N₄. Another sialon phase, for instance, alpha sialon stabilized by yttria, is M x (Si,Al)₁₂(O,N)₁₆, where M = yttrium or other atoms with a suitable atom radius and x is typically between 0 and 2. By using hot pressing, HIP sintering or similar sintering methods, dense Si-Al-O-N ceramics will be formed in which the silicon nitride is essentially alumina free (or with very low alumina substitution). The added sintering aids form an intergranular phase during the sintering. The amount is typically 5 - 20 vol-%. This phase can be amorphous or partly or fully crystalline depending on sintering conditions, composition, e t c. During sintering, the ceramic material is often embedded in a protective powder bed with inert material such as BN or Si₃N₄ or mixtures of these materials with SiO₂ or other metal oxides. It is important to avoid excessive degradation of the ceramic material by formation of gaseous compounds such as SiO and N₂. The powder provides a protective embedment and a local atmosphere with sufficiently high counterpressure of SiO and N₂. This could be done on the microscale (powder surrounding each compact) or on macroscale (the powder or the powder compacts are used as a gas generator to produce the necessary counterpressure for the whole sintering system). Essentially no solid state reactions take place between the ceramic compacts and the protective powder, only gas reactions. EP-A-0 082 371 discloses a sintered silicon nitride-based ceramic article comprising a core and a surface zone with a gradual transition of the composition between said core and said surface zone. The ceramic composite article is produced by sintering a pre-formed compact in a setter bed which has a composition similar to that of the compact. However, it has surprisingly been found that if the protective powder has a similar composition as the intergranular phase of the sintered compacts, rapid, probably diffusion controlled, reactions take place in the surface zone of the ceramic bodies during the sintering. This makes it possible to obtain dense ceramic materials with one composition in the outer part and another composition in the core and with a gradual change in composition and/or structure because the densification is favoured by a rapid liquid phase sintering. The thickness of the surface transition zone is generally more than 50 µm, preferably more than 100 µm. In addition, the obtained ceramic materials comprise a gradual change in composition and thus in properties from the transition zone towards the core. The thickness of the surface zone is generally more than 100 µm, preferably more than 500 µm and most preferably 0.8 - 2 mm. The density of the ceramic body is generally more than 98 %, preferably more than 99 %, of the theoretical density. The grain size is in most cases below 15 µm. If too high sintering temperatures are used, the surface zone will be too wide and almost no difference in composition and structure between core and surface zone will be obtained. By using the method of the invention, ceramic materials can be made in which, for instance, the surface zone can comprise beta-sialon ceramic material having high toughness but moderate hot hardness, while the core comprises ceramics containing mixtures of alpha and beta sialon phases which exhibit much improved hot hardness but somewhat lower toughness behaviour. Such materials will be obtained by using a protective powder with an active part comprising more than 40 % Si₃N₄, more than 10 % SiO₂ and more than 10 % Al₂O₃ which has a relatively high SiO₂ activity. By using a more nitrogen rich surrounding during sintering or post treatment e.g. by using AlN, YN or similar nitrides, alpha - beta sialon structures can be formed in the surface zone of the ceramic material while the overall composition is such that a beta sialon structure is formed in the centre. In order to be effective more than 10 % AlN and/or YN is preferred to be used in the active part of the protective powder. Also other phases such as the Si-Al-O-N polytypes may be formed as well as other phases in the Si₃N₄-AlN-Al₂O₃-SiO₂+MeO (Me=metal) system. In addition, the sintering can be performed at higher nitrogen pressures than 0,1 MPa (1 atm) e.g. at 1,5-3,0 MPa (15 - 30 atm), or very high pressures, 1000 - 2000 atm or more. Using elevated nitrogen pressures, it is possible to use smaller additions of sintering aids and still obtain dense ceramic materials according to the invention with densities of 98 % of the theoretical or more. It is also possible to use other gases than nitrogen, e.g., argon or other inert gases or hydrogen or hydrocarbons. However, nitrogen or gas mixtures containing nitrogen are preferred. The intergranular phase is generally more than 0.5 vol-%, preferably more than 1 vol-%. It is also possible to obtain Si₃N₄-materials with different compositions in core and surface zone by applying, before the sintering, one or more layers with different compositions on the green body. Such layers could be applied by spraying or painting techniques as well as other established techniques such as CVD, PVD etc. This new technique opens up the possibility of producing compound materials with different properties in the core and outer parts also for other systems. The essential thing is that the densification takes place with the help of a liquid phase and that it is possible to change the properties of the material by changing the composition of the liquid phase. By using the sintering technique or post heat treatment according to the invention, ceramic materials can be tailored to meet different specific demands. The invention can be applied to many ceramic systems such as sialon, Si₃N₄ or AlN with minor or larger amounts of sintering aids, with or without refractory compounds such as TiN, WC or similar compounds. The invention can also be applied to alumina based ceramic systems. It can also be used to fiber- or whisker-reinforced ceramics in which the diameter of the whiskers is less than 5 µm and the aspect ratio (length/diameter ratio) >10 or in systems in which a metallic binder is used, systems such as a metal-ceramics or metal-glass-ceramics, etc. Another important advantage of the invention resides in the fact that ceramic materials with different coefficients of thermal expansion can be formed in which the resulting stress system is such that the toughness behaviour is increased. In addition, by using ceramic materials according to the invention, excellent substrate materials can be made for CVD or PVD coatings due to the possibility of gradual change of the expansion behaviour from that of the substrate to that of the coating. It is also very beneficial to use the invention with transformation toughened ceramic systems and, e.g., in systems where the outer part has such a composition that a phase transformation can take place with a subsequent change in volume and development of compressive forces. This would be very favourable for most ceramic materials, especially to those inclined to slow crack growth. Example 1 (Comparative) An alpha-beta sialon ceramic material was made by mixing 81.8 g Si₃N₄, 2.5 g Al₂O₃, 6.1 g Y₂O₃ and 9.6 g AlN in 1 000 ml propanol together with a lubricant and milling for 20 hours with alumina milling media. After drying and granulation, the material was sintered between 1780-1800°C for 2 hrs according to standard procedures, embedded in BN. A sialon material was obtained which had the same structure in the core and in the outer parts. The so obtained reference material (Ref 1) had the following crystalline phase composition (the amount of the crystalline phases is taken as the relative peak height of the X-ray diagram for the respective phase): beta-sialon, (z=0.75) 59 % alpha-sialon 30 % b-phase 9 % 12H(polytype) 1 % Hardness = 1550 HV10 Hot hardness, 1000 °C= 1050 HV Toughness (K-idt) = 4.2 MN m -1.5 Example 2 (Comparative) Another sialon ceramic material was made by adding 88.2 g Si₃N₄, 6.0 g Al₂O₃ and 5.8 g Y₂O₃ and following the same manufacturing procedure as described above. The obtained beta-sialon material had the following crystalline phase composition: beta-sialon (z=0.24) 100 % Hardness = 1350 HV 10 Hot hardness, 1000°C= 550 HV Toughness (K-idt) = 5.6 MN m -1.5 This is reference material 2 (Ref 2). Example 3 The material of Example 1 was sintered in a powder bed comprising a mixture of 14 g SiO₂, 17 g Al₂O₃, 45 g Si₃N₄, 27 g Y₂O₃ and 30 g BN. A sialon material was obtained which comprises a core with a composition according to Ref 1 but with an about 1 mm thick surface zone close in composition to Ref 2. In a cutting operation inserts made from this compound material were tested with the following conditions: Workpiece material: Inconel 718 Insert style: RCGX, 120800 E Speed: 200 m/min Feed: 0.20 mm/rev D.O.C. (depth of cut): 2.0 mm Result: Tool life (any of flank wear > 0.5 mm, D.O.°C. notch wear >2 mm or fracture) in minutes: Material A(this Example) 2.8 Ref 1.8 Ref 2 2.0 Example 4 An alpha-beta sialon material was made according to Example 1, but with reduced amount of AlN (3.5 g instead of 9.6 g). When this material was sintered in the same powder mixture as in Example 3 in N₂/H₂ (4:1) for 2 hours, a compound material with the following properties was obtained: The material was tested in a cutting operation with the following conditions: Workpiece material: Inconel 718 Insert style: SNGN 120416 E Speed: 180 m/min Feed: 0.15 mm/rev D.O.C.: 1.5 mm Result Tool life (criteria as Example 3), minutes Material B(this Example) 3.6 Ref 1 2.7 Ref 2 2.0 In another cutting test, the following conditions were used: Workpiece material: Incoloy 901 Insert style: SNGN 120416 E Speed: 280 m/min Feed: 0.15 mm/rev D.O.C.: 2.0 mm Result: Tool life (criteria as Example 3), minutes Material B(this Example) 3.3 Ref 1 3.1 Ref 2 0.2 Example 5 A powder was prepared by mixing 99 g Si₃N₄ and 1 g Y₂O₃ with a lubricant and milling 12 h in a vibromill with alumina milling media. After compaction of blanks (by die-pressing) and dewaxing the samples were hot pressed (encapsulated HIP) at 1740°C and 150 MPa for 1 h. By having the samples coated by a mixture of 80 % Si₃N₄, 10 % SiO₂ and 10 % Al₂O₃ and with minor amounts of silicon and BN (1:1) during the hot pressing, Si₂N₂O was formed in the surface of the samples. A material with the following properties was formed: In a cutting operation in grey cast iron with sand inclusions from the casting, the following conditions were used: Speed = 700 m/min Feed = 0.2 mm/rev D.O.C. = 2.0 mm Tool life (flank wear > 1 mm or fracture) in minutes Cutting 1 is a longitudinal cutting operation and cutting 2 is an intermittent facing operation (holes and slits were machined in the workpiece). Material CC was a hot pressed material with the same phase composition as in the core of material C (prior art). Example 6 A powder was prepared by mixing 82 g Si₃N₄, 2.1 g Al₂O₃, 6.0 g Y₂O₃ and 6.7 g AlN. After milling, drying, granulation, compaction, dewaxing and sintering, sialon pieces were obtained. The sintering was performed in a powder bed comprising a mixture of 11 g SiO₂, 15 g Al₂O₃, 50 g Si₃N₄, 24 g Y₂O₃ and 30 g BN. A material with the following crystalline phase composition was obtained: In a turning operation in grey cast iron, with inserts SNGN 120816T, the following conditions were used: Speed = 500 m/min Feed = 0.35 mm/rev D.O.C. = 2.0 mm Result Tool life (flank wear > 2 mm) in minutes: Material D(this Example) 10.8 Ref. 2 6.2 Example 7 A material was made as in Example 5, but with the addition of 30 g SiC-whiskers to the Si₃N₄-Y₂O₃ powder. The powder was hot pressed and treated in the same manner as in Example 5. A material with the following properties was obtained (the peaks from SiC have been excluded): In a cutting operation in Meehanite cast iron the following conditions were used: Speed = 700 m/min Feed = 0.25 mm D.O.C. = 2.0 mm Result Tool life (flank wear > 1 mm or fracture) in minutes: Material E(this Example) 17.2 Material EE(prior art) 15.2 Material CC(prior art) 7.1 Material EE is a hot pressed material according to prior art with the same structure as the core of material E. Example 8 In a blasting experiment using alumina sand (Alodur) the following removal rates, in mm³/hour, were obtained. The impact velocity was about 150 m/s.

Claims: Sintered ceramic material based on silicon nitride, silicon oxide, aluminium nitride, aluminium oxide or mixtures thereof, in which the densification during sintering takes place with an intergranular liquid phase, said material comprising a core and a surface zone with a gradual transition in at least one of composition and crystal structure between said core and said surface zone characterized in that the material includes more than two different phases, the relative amount of phases present being different between the surface zone and core, whereby a certain phase may be present only in the core or only in the surface zone. Sintered material according to claim 1, in which the surface zone is more than 100 µm thick and with a density of more than 98 % of theoretical density. Method of producing a sintered material according to any of the preceeding claims comprising the step of sintering the ceramic material in a protective powder with a composition similar to that of the intergranular phase.

Inventors: INGELSTROEM, NILS ANDERS, Ingelström, Nils Anders
Applicants: SANDVIK AKTIEBOLAG
Application year: 1988
Main classification: C04B35
IPC codes: C04B35