CERAMIC CUTTING TOOL COMPOSITION, METHOD OF ITS MANUFACTURE AND ITS USE IN MACHINING CAST IRON

Abstract: A ceramic material suitable for use in cutting tools comprises a hot pressed composition containing Si₃N₄ and at least one of the oxides Y₂ O₃, ZrO₂ and MgO. Ternary systems based on Si₃N₄, SiO₂ and 4 to 12 wt% Y₂ O₃ are preferred in which Y₂ O₃: SiO₂ is from 1.2 to 3.0 Hot pressing at 1700 to 1750°C and 5000 to 6,500 psi for 3 to 8.5 hours produces a material with a thermal shock parameter of at least 26 x 10⁴ BUT - lbs/hr (in³) at 1200°C which can be used for making cast iron.

Description: TITLE CERAMIC COMPOSITION USEFUL FOR MACHINING CA#T IRON, AND ITS METHOD OF MANUFACTURE. DSSCRIPT}ON This invention relates to ceramic compositions and articles made therefrom. Ceramic compositions composed principally of silicon nitride tsi 4) have found significant use as ceramic components for machines or as vessel coatings. This material is known to have many good characteristics such as high oxidation resistance at high temperatures (1400 C), good mechanical strength at high temperatures, and good hardness at high temperature. The strength of this material is related to its density and it has been found that the densification property of silicon nitride, sintered under atmospheric pressure, is very inferior. Therefore, it has been considered important to employ high pressure when a product of good strength is desired. This is commonly referred to as "hot pressing" of silicon nitride. However, in spite of the use of hot pressing, the bend strength of simple Ski#;4 has not been as high as desired at high temperatures. Accordingly, other avenues of strength improvement have been sought such as through the use of additives which operate as a low temperature liquid phase to facilitate densification and not significantly imparing the creep resistance of the ceramic body at high temperatures. These added materials have included relatively large amounts of chromium oxide, zinc oxide, nickel oxide, titanium oxide, cerium oxide, magnesium oxide, yttrium oxide and others, ranging in excess of 2OWb (wt.) of the matrix material. Silicon nitride with these particular additives tends to form a structure having a strength level which does not usually exceed 50 KSI at high temperatures. In one instance (U.S. Patent 3,830,652 to Gala) did the prior art obtain strength levels in excess of 50 KSI. In this instance, the concern was for physical characteristics useful for turbine elements: hardness, oxidation resistance (inertness) and transverse rupture strength. Gaza explored metal oxide additives to a Ski?4 system which ranged in amounts related solely to machine element usage. The additions were added in amounts up to 20, < . However, commercial cutting tools today exhibit the same or better physical properties that were the focus of Gaza's work. For example, commercial A1203 or TiC tools have excellent hardness at high temperature, high resistance to oxidation and transverse rupture strengths at high temperatures which range up to 100,000 psi. Strength is considered the most important feature because of the necessity to withstand forces imposed on the tool material by the tool fixture and by the resistance of the stock material, particularly at heavy depths of cutting. These forces become unusually exaggerated when cutting ferrous material such as cast iron at high speeds and feeds. Without increased strength, it is believed by those skilled in the art that further improvements in tool life cannot be achieved. Since the strength level of Si 4 is equal to or lower than commercial materials now available, it has been rejected as a tool material with little hope in improving tool life. In only one known instance has the art attempted to employ 8isiqr directly as a cutting tool material and this was for use only on hypereutectic aluminim alloys. This attempt is reported in a Japanese Patent 49-113803 (dated 30th October 1974) by Kazutaka Ohgo, a summary of which appears in Chemical Abstracts, Volume 84, 1976, page 286 (84:21440t). In this work, silicon nitride was sintered (as opposed to hot pressing) and metal oxide spinels were employed in solid solution in the silicon nitride matrix. The spinels were formed by a mixture of divalent and trivalent metal oxides (including magnesium oxide and I2 3) However, the molar percentage of the spinel metal oxide in the material was taught to be 10-40p < . The author experienced difficulty in obtaining good sintering density when the molar percentage fell below 10. The highest density achieved was 3.i8Wcm3. A two step method was used by this author requiring first a heating of the metal oxide powders to 1300-1 6000c for 3-10 hours to form the spinel. The spinel was pulverized and mixed with a silicon nitride powder, which in turn, was sintered to form citing tools. Only a quarternary system was employed involving So 4, SiO2, MgO, and Y203. This produced many secondary phases which weakened the physical characteristics, particularly strength, thermal conductivity, ana increased the thermal coef icient of expansion A loss of these physical characteristics make it most difficult to obtain even equivalent performance to commercially available tools when applied to a rigorous cutting enyironment such as interrupted cutting on cast iron. The cutting operation was of very short duration (2 minutes) of continuous machining and at low metal removal rates (cutting speeds of 1000 sfm, 0.012 inches per rev. of feed and 0.060 inches of depth of cut and metal removal of 8.64 in.3/min.). This type of test information, of course, did not investigate cutting applications where large forces are applied to the tool, did not investigate the elimination of spinel additives, did not investigate heavy cutting against rough surfaces such as cast iron, nor continuous cutting for periods of several hours or greater, nor did it explore intermittent, interrupted high speed cutting at speeds of 4000-5000 sfm at heavy feeds and depths of cutting. The demonstrated wear of 0.006-0.008 inches, in Ohgo's work, for 2 minutes of cutting time is highly excessive when compared to the goals of the present invention. Therefore, this work did not demonstrate that possessed sufficient characteristics to be used as a tool material on ferrous materials which apply large bend forces to the tool. moreover, the art has been possessed of sufficient knowledge in the making of Si3N4 with additives for many years; during this long term no effort was made to apply this material as a cutting tool against cast iron. This tends to support the contention of this invention that if tool life is dramatically increased for certain Si3N4 composites when used for machining cast iron, there must be same unobvious characteristics independent of strength that layed undiscovered to promote this new use. The present invention provides a material suitable for machining cast iron which comprises a hot-pressed ceramic composition composed of silicon nitride and at least one metal oxide selected from Y203 ZrO2 flnd XgO, yttria being the preferred metal oxide. The invention also includes a method of machining cast iron characterised by the use of a cutting tool composed of a ceramic composition according to the invention. Preferably, the composition is a ternary system containing silicon nitride, silica and the metal oxide. The metal oxide is desirably employed in an amount such as to be contained in the grain boundaries of the silicon nitride in non-spinel form. This can be achieved in compositions containing, by weight, 1 to ffi MgO For 4 to 1# Y203 or 4 to 12% Zero2. The preferred systems of the invention are (Si?4. SiO2. Y203) systems having a Y203 to 8i02 ratio of between 1.2 and 3.0. We have also found that a correlation exists between a thermal shock parameter and promotion of prolonged life in Silt, materials when used as a cutting tool on cast iron. This para EMI5.1 thermal expansion, and E is Young modulus. E can be eliminated from the parameter since it remains substantially constant for the contemplated variation in ceramic chemistry which controls this parameter. In order to obtain the most significant improre- ments in tool life, this parameter must exceed 26 lbs/in.2. In the preferred compostions of invention, which are simple ternary ceramic systems (Si?4. SiO2. low temp. liquid phase), the 8i02 is present, not as an additive, but as an inherent reaction product of heating Ski 4 which provides the proper mechanism for achieving the required thermal shock parameter. The low temperature liquid phase must be one which produces a small amount of a highly refractory silicate which will reside totally in the grain boundary of the matrix. There are mass other physical characteristics beyond its thermal shock parameter that should be improved in silicon nitride if it is to be successful as a tool material for cutting cast iron. As indicated earlier, the densification of the material has been a point of concern and has been alleviated by use of hot pressing techniques and oxide additives. This has permitted the density to be elevated close to theoretical density, but improving density by itself through increasing amounts of oxide leads to a decrease in several other physical properties. Investigators have failed to perceive this interplay of physical ck, racteristics. More importantly, known silicon nitride compositions, when used as a cutting tool against relatively rough surfaces such as cast iron, exhibit a failure mode under such circumstances is typically due to thermal shock as opposed to the more desirable mode by wear. Further the attainable hardness level and general rigidity of the known silicon nitride composites have yet to be comparable to commercial cutting tools. Desirably the composition has a density of at least 95% of the theoretical density, which is usally at least 3.25 gficm3. Preferably the transverse rupture strength of the ceramic material is at least 67,000 psi at 12000C and its hardness is at least 86 Rockwell 45-N. The modulus of elasticity of the composition is preferably no greater than 56 x 106 psi. The thermal conductivity of the composition is preferably at least 3.0 STU/hr.in. F, and its coefficient of expansion is preferably no greater than 1.9 x 10-6 ixVin.#. EMI6.1 Rockwell 45-N. The bend strength of the compostion is preferably 70,000 psi at 12000C and its density is preferably at least 3.398 vem3. The thermal conductivity of the composition is preferably at least 3.2 BTU J r.in. F and its coefficient of thermal expansion is preferably no greater than 1.87 x 10 6 i i in. F. The modulus of elasticity is preferably no greater than 53 x 106 psi. The ceramic compositions of the invention are preferably formed by heating a mixture of silicon nitride, which is preferably completely in the alpha phase, and one or more of the metal oxides yttria, magnesium oxide or zirconium oxide to a temperature of from 1700 to 17500C for a period of from 3 to 8.5 hours (preferably less than 8 hours) at a pressure of from 5000 to 6,500 psi (preferably 5 - 6000 psi) and allowing the material to cool. Preferably the material is allowed to cool slowly without application of pressure at a rate of at least 100 C/ hour. The preferred method of the invention results in a (Si#T4. SiO2.metal oxide) ceramic system whi EMI7.1 shock parameter -at 1200 C which is at least EMI7.2 and a thermal shock parameter at room temperature which is at least EMI7.3 The ceramic system should be regulated to avoid the presence of a spinel oxide and to insure formation of a low temperature liquid phase effective to form a highly refractory silicate residing only in the grain boundaries of the Si3N5 matrix. AdditionaSyboth the processing of the ceramic system and the formulation of the system should be regulated to provide a combination of specific physical characteristics in the material including; physical strength (as measured in a 4-point bend test) which is at least 70,000 psi at 7000C, a hardness level which is at least 86 using the Rockwell 45-N standard, a density of at least 3.25g/cm3, a coefficient of thermal expansion which is no greater than 1.88 z 10-6 intin OF at 12000C, a thermal conductivity level of at least 0.727 BTU/HR in s at 12000C, and a modulus of elasticity no greater than 55.3 x 106 psi. Preferred embodiments of the invention will now be described by way of example only, with reference to the dranngs, in which: Figure 1 is a perspective view of the work stock employed in a first set of laboratory cutting operations requiring continuous cutting simulation. Figure 2 is an end view of a work stock similar to Figure 1 illustrating the modae to simulate interrupted cutting. Figure 3 is central sectional view of a stator support casting used the stock material for production machining examples. Figures 4 and 5 are before machining and after machining photographs of the actual casting of Figure 3. Figure 4 depicts the front face side and Figure 5 depicts the rear spindle side. Figure 6 is a graphical illustration of wear life to failure vs. thermal shock parameter employing the invention. Figure 7 is a graphical illustration of wear life to failure vs. YOJSIO, ratio. The tendency toward higher speeds and feeds to achieve lower production costs and higher productivity imposes an ever increasing demand for greater wear life on cutting tools. The temperature rise at the tool tips at these speeds and feeds is very high. Tool materials have to be inert at such working temperatures and their dynamic properties have to be superior than those of existing tool materials. In accordance with this invention, it has been discovered that Si when combined with critically controlled amounts of certain metal oxides in a narrow volume fraction range, then hot pressed under controlled temperature, pressure and time conditions, will produce a cutting tool composition for a simple ternary system (Si#4. SiO2.Y2o3) that can be utilized at high speeds and heavy feeds on cast iron and will exhibit high wear resistance and will fail by a mode of gradual wear rather than thermal fatigue or catashopic failure. The cutting tool formulation meets the needs of a specific set of cutting conditions created by working on cast iron. The tip temperature of the tool will experience a temperature typically in the range of 600-8800C. This temperature factor is important since it is high enough to create thermal shock sites in portions of the tool, but not high enough to create a serious oxidation erosion problem. When machining cast iron, the chip easily fragments keeping sny hot chip normally away from the tool tip. Due to the resistance of cast iron to cutting, large fixture forces must be applied to the tool to move it through the stock material. Moreover, the mass removal rates required in many cutting operations on cast iron is considerably greater than used with other stock materials. This necessitates a strong tool material with respect to transverse rupture strength. All tool designers consider this latter aspect the most important consideration with respect to evaluating the success of a new tool material. The three virtues normally recognized of So 4would not suggest to one skilled in the art that it would be a successful candi.date for machining cast iron, its transverse rupture strength at high temperature rarely exceeded 50,000 psi (while commercial tools regularly experienced strength levels of 100,000200,000 psi); its high oxidation resistance was not critically needed; and its good hardness at high temperature was easily exceeded by the hardness of commercially available silicon carbide tools. The present invention recognized for the first time the role played by thermal shock resistance factors, namely, the coefficient of thermal expansion (o# and thermal conductivity (K) related to the modulus of rupture (S). This is defined herein by the expressiono# where E is Young's modulus and can be eliminated because it remains substantially constant under varying cutting conditions and material variations. By maintaining this thermal shock parameter above EMI9.1 it has been determined that a significant increase in wear life can be achieved on cast iron. It is difficult to theorize why this phenomenon takes place, but it may be due to the greater structural stability that is achieved by the ceramic at 7000C when generated heat is quickly conducted away preventing a large temperature gradient in the tool which leads to cracking if the material has an undesirable coefficient of thermal expansion; this may more readily be experienced when the tool tip is slightly cooled by intermittent or interrupted cutting. A preferred method for making such a cutting tool is as follows: (i) A first powder of substantially alpha phase silicon nitride is prepared having less than 1.0 cation impurities (excluding free silicon), about 1, free silicon, and about .7;. by weight oxygen. (2) A second powder of one or more selected metal oxides is prepared. The metal oxides are selected from a group consisting of Y203, MgO, and ZrO2. These metal oxides are characterized by their small atom size and their affinity to form a low temperature liquid phase which solidifies as a highly refractory silicate residing solely within the grain boundaries of the matrix. The oxides must be simple; it is important to avoid the formation of spinels which will produce weaker secondary phases. (3) The first and second powders are blended and mixed in a prescribed proportion. The second powder should have a weight percent of 1 - 15;. However, the ingredients of the second powder must fall within the following ranges: 0.75-5; LgO, 4-12 Y203, and 1-13- ZrO2. (4) The powder mixture is heated to a temperature level of 1700-1 7500C for a period of 3.-5. > hours under a pressure of 5,000-6,500 psi, and allowed to cool at an average rate of 1000C/hr. The hot pressed compact will exhibit substantially complete Beta phase silicon nitride. The resulting product must exhibit the following combination of physical characteristics: (a) 100% theoretical density (Zero porosity); (b) a thermal shock parameter of at least 26 x 109 EMI10.1 (c) a transverse rupture strength at 1200 C (in 4 point bending) of at least 67,000 psi; (d) a hardness level of at least 86 Rockwell 45-N; (e) a measured density of at least 3.25 g/cm3; (f) a wear life characterized by measured wear of no greater than .010" after one hour of continuous cutting of cast iron at a mass removal rate of at least 25 in3/min or mechanical failure under cutting conditions prescribes by at least 2000 feet per minute with a depth of cut of at least .06 in ches and a rate of feed of at least .012 inches per IPR; ; (g) the absence of tool failure by fracture or chipping. The following examples illustrate the invention: EXAMPLE 1 A sample canting tool material (identified as Sample 1) was prepared employing hot pressed silicon nitride with 7.47 weight percent Y203 ($ Y203 was added as a powder to a powder having 85 alpha phase Ski 4); the powder mixture was hot pressed at a temperature 1740 C under 6500 psi (9.55 x 106 kilogram/cm2) for a period of 6 - 1/2 hours. The pieces of hot pressed material were ground to a tool geometry of of 434 and the edges were prepared with 0.006" x 30-K land (chamfer). Each of the cutting tool prepared from this material were subjected to a cutting sequence on a simple cylindrical cast iron casting which varied between continuous, intermittent, or interrupted. As shown in Figure 1, the continuous cutting consisted of generating cylindrical surface 10 at a prescribed speed, feed and depth of cut. Due to the expanded length of the blinder II, the tool tip experiences a relatively constant high temperature for the duration of the pass. Intermittent cutting consisted of wfthdravting the tool intermittently along a longitudinal pass. Interrupted cutting consisted of passing the tool circumferentially about the cylinder along a path 12 (as shown in Figure 2) which path encounters the previously cut longitudinal grooves. The latter provides repeated impacts for the tool. Each type of cutting style imposes a different thermal condition on the tool which affects tool life in different ways. Other tool material samples were similarly prepared with different chemistries, as shown in Table 1, along with their resultant physical properties. The cutting operation for all these samples was carried out in a 3oratory environment at a variety of speeds and varying feed rates at a constant depth of cut; the tool geometry was varied only in the corner configuration as indicated. The wear in inches was measured for specific period of time. The results of such cutting are shown in Table II. None of the tools were used to full life; the cutting time was terminated when a significant increase in tool life was perccived. Five minutes, under high cutting speeds (3,000 -4,000 sfm) was deemed an unusually high increase in life when compared to commercial tools which typically fail after one minute. It is believed that optimization of the thermal shock parameter of Si3N4 under extreme temperature conditions has led to this increase in tool life. The ability to have a stable structure at 600 - 800 C temperature while under severe stress along with the ability to effectively conduct away heat preventing a loss in high temperature strength provides the basis for this life improvement. These physical characteristics are critically affected by the compositional phase of the Si3N4 composite. It is most important that the selected additives form a highly stable refractory silicate which resides totally in the grain boundary of the matrix. EXA#':#I# 11 Substantially the same cutting tool materials, prepared as indicated from Example 1, were prepared for cutting use in a production environment with actual production machines at Ford Motor Company's machining plants. The casting to be machined was a difficult production vehicle casting (stator support) in some cases and an engine block in others; the stator support is shown in Figures 3, 4 and 5. For the stator support, continuous cutting was experienced at surfaces B and D, intermittent cutting at surface A, and interrupted cutting at surfaces C and F (see Figure 4). These sample materials were run under a variety of cutting conditions as set forth in Table III. All tool materials were run to failure which is measured by the number of pieces produced up to that failure event. Failure herein is defined (as regularly as accepted in the industry) to mean loss of workpiece tolerance or failure by fracture or chipping. From the data in Tables II and III, we have discovered that controlled processing of Si?4 with Y203, MgO, or ZrO provides the kind of thermal shock parameter that leads to longer tool life when machining cast iron at large mass removal rates or high speed. These metal oxides operate upon the controlled free silica to form a highly stable refractory silicate which resides totally in the grain boundary of the Si?4 matrix. Table III proceeds from lower cutting speeds to higher speeds with comparative materials grouped adjacent each other. For each comparison the inventive samples render significant increases in tool life. The inventive materials perform 3 - 8 times better than the current commercial tools. In finish machining of the front end of an engine block, the number of blocks milled were 2100 pieces per corner with a depth of cut of .065 inch. Whereas using commercially available ceramics with half of that feed rate, the number is 600 pieces. The inventive material will prbvide (a) increased production at current cutting conditions, (b) increased production capacity at hither cutting speeds and feeds, (c) savings in tool material cost, (d) reduction in tool change downtime, and (e) increased production capacity leading to free machine time for preventive maintenance. To obtain at least a four-fold increase in tool life over commercially available tool materials the soSi?4. SiO2. Y203 ternary system must be employed with Y203 controlled to a limit of 7- In this manner the thermal shock parameters can be optimized at either cont#nuous or interrupted cutting conditions. Figure 6 and Table lV portrays the role played by the thermal shock parameter. Additionally, Y20 gSiO2 ratio must exceed 1.60. The influence of the Y203/SiO2 ratio is portrayed in Figure 7 and Table V. TABLE I EMI14.1 <tb> <SEP> Material <SEP> <SEP> Sample <SEP> S, <SEP> Transverse <SEP> Hardness. <SEP> Density <SEP> Coefficient <SEP> of <tb> <SEP> Rupture <SEP> Strength <SEP> Room <SEP> Temp <SEP> gm/cm3 <SEP> <SEP> Thermal <SEP> Expans <tb> <SEP> (4-Point <SEP> Bending), <SEP> <tb> <SEP> KSI <SEP> Rockwell <tb> <SEP> Room <SEP> Temp. <SEP> 12000C <SEP> 45-N <SEP> Room <SEP> Temp. <SEP> 1200 C <SEP> <tb> Sample <SEP> No. <SEP> 1 <SEP> I <tb> <SEP> Si3N4+8%Y2O3 <SEP> 103.6 <SEP> 105.7 <SEP> 87.6 <SEP> 3.4 <SEP> 0.87 <SEP> 1.87 <SEP> <tb> Sample <SEP> No. <SEP> 2 <tb> 5i3N4+11-12% <SEP> <tb> <SEP> Y2O3 <SEP> 115 <SEP> 70 <SEP> 87.0 <SEP> 3.398 <SEP> 1.5 <SEP> 2.7 <SEP> <tb> Sample <SEP> No. <SEP> 3 <tb> <SEP> Si3N445% <SEP> <SEP> high <SEP> <SEP> 85 <SEP> 67 <SEP> 86.3 <SEP> 3.272 <SEP> 84 <SEP> 1.84 <tb> Sample <SEP> No. <SEP> 4 <tb> Si3N4+ <SEP> 1% <SEP> <SEP> MgO <SEP> 129 <SEP> 87.4 <SEP> 89.2 <SEP> 3.25 <SEP> <SEP> .74 <SEP> 1.74 <tb> Sample <SEP> No. <SEP> 5 <tb> Si3N4+15% <SEP> <SEP> (88% <SEP> <tb> ZrO+ <SEP> <SEP> 12% <SEP> Y2O3 <tb> known <SEP> as <SEP> Zytrite) <SEP> Substantially <SEP> equivalent <SEP> properties <SEP> to <SEP> Sample <SEP> 2. <tb> Sample <SEP> No. <SEP> 6 <tb> Si3N4+15(88% <SEP> ZrO <SEP> <tb> +12% <SEP> Y2O3 <SEP> + <SEP> 1.5 <tb> Fe <SEP> impurities <tb> known <SEP> as <SEP> modified <tb> Zytrite) <SEP> Substantially <SEP> equivalent <SEP> properties <SEP> to <SEP> Sample <SEP> 2. <tb> Sample <SEP> No. <SEP> 7 <tb> SiC. <SEP> (Prior <SEP> Art) <SEP> 93 <SEP> 91.5 <SEP> <SEP> 3.29 <SEP> 1.53 <SEP> 2.57 <tb> Sample <SEP> No. <SEP> 8 <tb> Al2O3 <SEP> <SEP> (Prior <SEP> Art) <SEP> 75 <SEP> 30 <SEP> 90.14 <SEP> <SEP> 4.252 <SEP> <SEP> 4.4 <SEP> 5¯7 <SEP> <tb> TABLE I (Contd) EMI15.1 <tb> Material <SEP> K, <SEP> Thermal <SEP> Con-BTU-lbsMaterial <SEP> E(Young's <SEP> Modulus <SEP> <tb> <SEP> Sample <SEP> ductivity, <SEP> Rr <SEP> <SEP> (in <SEP> 3) <SEP> 106 <tb> <SEP> BTU/Hr <SEP> in <SEP> OF <SEP> KS, <SEP> Thermal <SEP> 106 <SEP> psi <SEP> <tb> <SEP> C' <SEP> <tb> <SEP> Room <SEP> Temp. <SEP> 1200 <SEP> C <SEP> <SEP> Shock <SEP> Factor <SEP> <SEP> 12000C <SEP> <tb> <SEP> Room <SEP> Temp. <tb> Sample <SEP> No.1 <SEP> 3.23 <SEP> 3.23 <SEP> 179 <SEP> 182 <SEP> 53 <tb> Sample <SEP> No.2 <SEP> 4.4 <SEP> 4.4 <SEP> 337 <SEP> 114 <SEP> 51 <tb> Sample <SEP> No.3 <SEP> 1.917 <SEP> .727 <SEP> 194 <SEP> 26 <SEP> 55.3 <tb> Sample <SEP> No.4 <SEP> 1.917 <SEP> .727 <SEP> 334 <SEP> 36 <SEP> 54.7 <tb> Sample <SEP> No.5 <SEP> Substantially <SEP> equivalent <SEP> properties <SEP> to <SEP> Sample <SEP> 2. <tb> Sample <SEP> No.6 <SEP> Substantially <SEP> equivalent <SEP> propertiesto <SEP> Sample <SEP> 2. <tb> Sample <SEP> No.7 <SEP> 4.09 <SEP> 1.72 <tb> Sample <SEP> No.8 <SEP> 1.9 <SEP> 3 <SEP> 324 <SEP> 16 <SEP> 67 <tb> TABLE II EMI16.1 <tb> <SEP> Sample <SEP> Corner <SEP> Cutting <SEP> Condition <SEP> Mass <SEP> of <tb> <SEP> No. <SEP> - <SEP> <SEP> Configuration <SEP> Speed <SEP> Feed <SEP> Depth <SEP> Naterial <SEP> <SEP> Removed <tb> <SEP> Number <SEP> of <tb> <SEP> cut <tb> <SEP> (sfm) <SEP> <SEP> (ipr) <SEP> (in,) <SEP> <SEP> in3 <SEP> /min <tb> <SEP> Continuous <SEP> Cutting. <tb> <SEP> 1A <SEP> <SEP> 1 <SEP> 4000 <SEP> .010 <SEP> .100 <SEP> 48 <tb> <SEP> 1B <SEP> <SEP> 3 <SEP> 3000 <SEP> .020 <SEP> .100 <SEP> 72 <tb> <SEP> 1C <SEP> <SEP> 1 <SEP> 3000 <SEP> .010 <SEP> .100 <SEP> 36 <tb> <SEP> 1D <SEP> <SEP> 1 <SEP> 2000 <SEP> .0111 <SEP> .100 <SEP> 26.4 <tb> <SEP> Is <SEP> <SEP> 3 <SEP> 1000 <SEP> .0222 <SEP> .100 <SEP> 26.4 <tb> <SEP> 1F <SEP> <SEP> 2 <SEP> 750 <SEP> .029 <SEP> .100 <SEP> 26.4 <tb> <SEP> 1G <SEP> <SEP> 1 <SEP> 500 <SEP> .044 <SEP> .100 <SEP> 26.4 <tb> <SEP> 111 <SEP> <SEP> 2 <SEP> 333 <SEP> .066 <SEP> .100 <SEP> 26.4 <tb> <SEP> II <SEP> 3 <SEP> 2000 <SEP> .011 <SEP> .100 <tb> Intermittent <SEP> cutting. <tb> <SEP> IK <SEP> 2 <SEP> 1000 <SEP> .011 <SEP> .100 <SEP> 13.2 <tb> <SEP> IL <SEP> 5 <SEP> 750 <SEP> <SEP> .029 <SEP> .100 <SEP> 26.4 <tb> <SEP> 6 <SEP> <SEP> 6 <SEP> 750 <SEP> .044 <SEP> .100 <SEP> 39.6 <tb> <SEP> IN <SEP> 7 <SEP> 500 <SEP> .011 <SEP> .100 <SEP> 6.6 <tb> <SEP> IO <SEP> 4 <SEP> 2000 <SEP> .011 <SEP> .100 <SEP> 26.4 <tb> <SEP> IP <SEP> a <SEP> <SEP> 1000 <SEP> .022 <SEP> .100 <SEP> 26.4 <tb> Interrupted <SEP> cutting. <tb> <SEP> IQ <SEP> 6 <SEP> 1000 <SEP> .0111 <SEP> .100 <SEP> 13.2 <tb> <SEP> IR <SEP> 8 <SEP> 1000 <SEP> .0222 <SEP> .100 <SEP> <SEP> 26.4 <tb> <SEP> IS <SEP> 7 <SEP> 2000 <SEP> .0111 <SEP> .100 <SEP> 26.4 <tb> Continuous <SEP> Cutting. <tb> <SEP> 3A <SEP> 1 <SEP> (Trial <SEP> 1) <SEP> 2000 <SEP> .0111 <SEP> .100 <SEP> 26.4 <tb> <SEP> 3B <SEP> <SEP> 3 <SEP> (Trial <SEP> 2) <SEP> 2000 <SEP> .0111 <SEP> .100 <SEP> 26.4 <tb> <SEP> 30 <SEP> 4 <SEP> 1000 <SEP> .0222 <SEP> .100 <SEP> 26.4 <tb> Interrupted <SEP> end <SEP> Cutting <tb> <SEP> 3D <SEP> 4 <SEP> 1000 <SEP> .0222 <SEP> .100 <SEP> 26.4 <tb> Continuous <SEP> Cutti <SEP> <tb> <SEP> 4A <SEP> 1 <SEP> 2000 <SEP> .0111 <SEP> .100 <SEP> 26.4 <tb> <SEP> 4B <SEP> <SEP> 2 <SEP> 1000 <SEP> .0222 <SEP> .100 <SEP> 26.4 <tb> <SEP> 5A <SEP> 2 <SEP> (Trial <SEP> 1) <SEP> 2000 <SEP> .0111 <SEP> .100 <SEP> 26.4 <tb> <SEP> 5B <SEP> <SEP> 3 <SEP> (Trial <SEP> 2) <SEP> 2000 <SEP> .0111 <SEP> .100 <SEP> 26.4 <tb> <SEP> 50 <SEP> 1 <SEP> 1000 <SEP> .0222 <SEP> .100 <SEP> 26.4 <tb> <SEP> 6A <SEP> (Trial <SEP> 1) <SEP> 2000 <SEP> .011 <SEP> .100 <SEP> 26.4 <tb> <SEP> 6B <SEP> <SEP> (Trial <SEP> 2) <SEP> 2000 <SEP> .011 <SEP> .100 <SEP> 26.4 <tb> <SEP> 60 <SEP> 1000 <SEP> .022 <SEP> .100 <SEP> 26.4 <tb> Continuous <SEP> <SEP> Cutting, <SEP> <tb> <SEP> 7A <SEP> 2000 <SEP> .0111 <SEP> .10 <SEP> 26.4 <tb> <SEP> 7B <SEP> <SEP> 1000 <SEP> .0222 <SEP> .10 <SEP> 26.4 <tb> <SEP> 70 <SEP> 1000 <SEP> .0111 <SEP> .100 <SEP> 13.2 <tb> II TABLE II (Cont..) EMI17.1 <tb> Sample <SEP> Time <SEP> Tool <SEP> Wear <SEP> Thermal <SEP> and <tb> <SEP> No, <SEP> <SEP> (MIN) <SEP> (inches) <SEP> Mechanical <SEP> <tb> <SEP> or <SEP> Cracks. <tb> <SEP> (min-sec.) <SEP> Flank <SEP> Crater <tb> <SEP> Continuou# <SEP> Cutting <tb> <SEP> 1A <SEP> 5.2 <SEP> None <SEP> None <SEP> NIL <tb> <SEP> 1B <SEP> 5.7 <SEP> none <SEP> none <SEP> NIL <tb> <SEP> 1C <SEP> 17.5 <SEP> none <SEP> none <SEP> NIL <tb> <SEP> 1D <SEP> 43.7 <SEP> none <SEP> none <SEP> NIL <tb> <SEP> 1E <SEP> 26.8 <SEP> none <SEP> none <SEP> NIL <tb> <SEP> 1F <SEP> <SEP> 11.7 <SEP> none <SEP> none <SEP> NIL <tb> <SEP> 1G <SEP> 10.5 <SEP> none <SEP> none <SEP> NIL <tb> <SEP> 1H <SEP> <SEP> 1.9 <SEP> none <SEP> none <SEP> Mechanical <tb> <SEP> Fracture <tb> <SEP> 1I <SEP> <SEP> 21.0 <SEP> .015 <SEP> none <SEP> NIL <tb> Intermittent <SEP> cutting. <SEP> <tb> <SEP> 1K <SEP> 2.3 <SEP> none <SEP> none <SEP> NIL <tb> <SEP> 1L <SEP> 1.1 <SEP> none <SEP> none <SEP> NIL <tb> <SEP> 1M <SEP> 0.6 <SEP> none <SEP> none <SEP> NIL <tb> <SEP> 1N <SEP> 4.1 <SEP> none <SEP> none <SEP> NIL <tb> <SEP> 10 <SEP> 8.8 <SEP> none <SEP> none <SEP> NIL <tb> <SEP> 1P <SEP> 7.7 <SEP> none <SEP> none <SEP> NIL <tb> Interrupted <SEP> cutting. <tb> <SEP> 1Q <SEP> 3.7 <SEP> .0116 <SEP> NIL <SEP> NIL <tb> <SEP> 1R <SEP> 10.0 <SEP> .0013 <SEP> NIL <SEP> NIL <tb> <SEP> iS <SEP> 10.5 <SEP> .0021 <SEP> NIL <SEP> NIL <tb> Continuous <SEP> Cutting. <SEP> <tb> <SEP> 3A <SEP> 2.05 <SEP> .0055 <SEP> - <SEP> NIL <SEP> <tb> <SEP> 3B <SEP> 9.95 <SEP> .0015 <SEP> - <SEP> - <SEP> <SEP> NIL <tb> <SEP> 3C <SEP> 9.92 <SEP> .0018 <SEP> - <SEP> - <SEP> <SEP> NIL <tb> Interrupted <SEP> Cutting. <SEP> <tb> <SEP> 3D <SEP> 10.00 <SEP> - <SEP> - <SEP> <SEP> NIL <tb> continuous <SEP> Cutting. <SEP> <tb> <SEP> 4A <SEP> 9.65 <SEP> .002 <SEP> - <SEP> - <SEP> <SEP> NIL <tb> <SEP> 4B <SEP> 10.5 <SEP> .001 <SEP> - <SEP> - <SEP> <SEP> NIL <tb> <SEP> 5A <SEP> 9.82 <SEP> .0016 <SEP> - <SEP> - <SEP> <SEP> NIL <tb> <SEP> 5B <SEP> 10.00 <SEP> .002 <SEP> - <SEP> - <SEP> <SEP> NIL <tb> <SEP> SC <SEP> <SEP> 9.88 <SEP> .0019 <SEP> I <SEP> <SEP> NIL <tb> <SEP> 6A <SEP> 10.00 <SEP> .005 <SEP> - <SEP> - <SEP> <SEP> NIL <tb> <SEP> 6B <SEP> 5.15 <SEP> .002 <SEP> -- <SEP> NIL <tb> <SEP> 6C <SEP> 10.10 <SEP> .002 <SEP> - <SEP> - <SEP> NIL <tb> <SEP> 7A <SEP> 0'02" <SEP> Fraction <SEP> by <SEP> Fracture <SEP> Mechanical <SEP> Fracture <tb> <SEP> 7B <SEP> 0'15" <SEP> Fraction <SEP> by <SEP> Fracture <SEP> Mechanical <SEP> Fracture <tb> <SEP> 7C <SEP> 0'11" <SEP> Fraction <SEP> b <SEP> <SEP> Fracture <SEP> Mechanical <SEP> Fracture <tb> TABLE III EMI18.1 <tb> Sample <SEP> Material <SEP> Cutting <SEP> Tool <SEP> Cutting <SEP> Conditions <SEP> Work <SEP> Pieces <tb> No <SEP> Operation <SEP> Oeoifletry <SEP> Speed <SEP> Feed <SEP> Depth <SEP> Produced <tb> <SEP> (sfm) <SEP> (ipr) <SEP> of <SEP> cut <SEP> Ibefore <tb> <SEP> inch <SEP> Failure. <tb> <SEP> 1Hot <SEP> Pressed <SEP> % <SEP> Broaching <tb> <SEP> of <SEP> rr+8#0or <SEP> Enginea <SEP> 636 <SEP> 150 <SEP> .02 <SEP> 191o <tb> <SEP> 3 <SEP> 4,203 <SEP> block <tb> <SEP> 1, <SEP> surface <tb> 1 <SEP> Hot <SEP> Pressed <SEP> Rough <tb> <SEP> Si <SEP> N <SEP> +8% <SEP> facing <SEP> of <SEP> NG <SEP> 434 <SEP> 496 <SEP> .016 <SEP> .125 <SEP> -or250 <tb> <SEP> 3 <SEP> (inter;ni <tb> <SEP> ttent <tb> <SEP> cutting <tb> <SEP> Hot <SEP> Pressed <tb> <SEP> si3}X4+ <SEP> 1 <SEP> & fi'.. <SEP> .. <SEP> w. <SEP> 800 <tb> <SEP> Hot <SEP> Pressed <tb> <SEP> Si <SEP> N <SEP> + <SEP> S#aso <tb> <SEP> &num; <SEP> n <SEP> 740 <tb> <SEP> Tool) <SEP> SiC <SEP> .. <SEP> .. <SEP> . <SEP> , <SEP> n <SEP> 150 <tb> <SEP> (Prior <SEP> Art <tb> <SEP> Tool) <SEP> SC <SEP> n <SEP> 150 <tb> <SEP> Lase <SEP> tool <tb> <SEP> coated <SEP> trith <SEP> I <tb> <SEP> A120, <tb> <SEP> 1 <SEP> Hot <SEP> Pressed <SEP> Semi <SEP> finish <SEP> #PG <SEP> 322 <SEP> 516 <SEP> .012 <SEP> .025 <SEP> 1000 <tb> <SEP> Si <SEP> N <SEP> + <SEP> 8% <SEP> i <SEP> and <SEP> finish <SEP> -.006 <tb> <SEP> 3 <SEP> #y <SEP> O <SEP> i <SEP> bore <SEP> surface <tb> <SEP> 23 <SEP> i <SEP> E(contirr <tb> <SEP> UOUS <tb> <SEP> cut-ting) <SEP> . <tb> <SEP> Prior <SEP> Art <tb> 1 <SEP> Hot <SEP> Pressed <SEP> Semi-finish <SEP> TPG <SEP> 322 <SEP> 516 <SEP> .ole5 <SEP> .025 <SEP> 320 <tb> <SEP> Si <SEP> N <SEP> + <SEP> and <SEP> finish <SEP> -.006 <tb> <SEP> 3 <SEP> bore <tb> <SEP> 203 <SEP> bore <SEP> surface <tb> <SEP> F <SEP> (spline <tb> <SEP> hole) <SEP> Inter <tb> <SEP> rupted <SEP> I <tb> <SEP> cutting) <tb> <SEP> I <tb> <SEP> 1 <SEP> Hot <SEP> Pressed <SEP> Rou#h <SEP> fa#e <SEP> TNC <SEP> 434 <SEP> 965 <SEP> - <SEP> ¯012 <SEP> .093 <SEP> 4X, <tb> <SEP> 2 <SEP> 3 <SEP> rutted <tb> <SEP> cutting). <tb> TABLE III (Contd) EMI19.1 <tb> <SEP> Sample <SEP> #aterial <SEP> Cutting <SEP> Tool <SEP> Cutting <SEP> Conditions <SEP> Work <SEP> Pieces <tb> <SEP> Operation <SEP> Geometry <SEP> Speed <SEP> Feed <SEP> Depth <SEP> Produced <tb> <SEP> (sfm) <SEP> ipr) <SEP> of <SEP> cut <SEP> before <tb> (inch <SEP> Failure. <tb> <SEP> I <tb> <SEP> I <SEP> I <tb> <SEP> Hot <SEP> Presset <SEP> Rough <SEP> face <SEP> / <SEP> mJG <SEP> 434 <SEP> 965- <SEP> .012 <SEP> ¯093 <SEP> 14# <tb> <SEP> of <SEP> Surface <SEP> 49# <tb> <SEP> #O <SEP> G <SEP> (irt$er- <SEP> i <SEP> I <tb> <SEP> ru#.te#. <SEP> i <SEP> i <tb> <SEP> base <SEP> tool <tb> <SEP> coated <tb> <SEP> with <SEP> A1203 <tb> <SEP> I <SEP> 1 <tb> <SEP> Hot <SEP> Pressed <SEP> Rough <SEP> TNG <SEP> 434 <SEP> 998 <SEP> .014 <SEP> .0625 <SEP> 420 <tb> <SEP> 1 <SEP> N <SEP> +8 <SEP> turning <SEP> of <tb> <SEP> 3 <SEP> 3 <SEP> outside <tb> <SEP> diameter <SEP> on <tb> <SEP> surface <SEP> B <tb> <SEP> (continuous <tb> <SEP> cutting) <tb> <SEP> I <tb> <SEP> (Prior <SEP> Art <SEP> Rough <SEP> turn <SEP> TNG <SEP> 434 <SEP> i998 <SEP> .014 <SEP> .0625 <SEP> 50 <tb> <SEP> Tool) <SEP> SiC <SEP> ing <SEP> of <SEP> out <tb> <SEP> base <SEP> tool <SEP> side <SEP> dia <tb> <SEP> coated <SEP> with <SEP> meter <SEP> on <tb> <SEP> At203 <SEP> surface <SEP> B <tb> <SEP> (con <tb> <SEP> tinuous <tb> <SEP> cutting) <tb> <SEP> 1 <SEP> Hot <SEP> Pressed <SEP> Rough <SEP> boring <SEP> TNG <SEP> 434 <SEP> 1026 <SEP> .0189 <SEP> .0625 <SEP> 157 <tb> <SEP> Si <SEP> N <SEP> + <SEP> 8h <SEP> of <SEP> inside <SEP> 674 <SEP> to <tb> <SEP> 34 <tb> <SEP> Y <SEP> O <SEP> diameter <SEP> on <SEP> .0039 <tb> <SEP> surface <SEP> D <tb> <SEP> (continuous <tb> <SEP> cutti <tb> <SEP> (Prior <SEP> Art <tb> <SEP> Tool) <SEP> SiC <SEP> tr <SEP> n <SEP> 50 <tb> <SEP> base <SEP> tool <SEP> fl <SEP> 50 <tb> <SEP> coated <SEP> with <tb> <SEP> A1203 <tb> ¯ <SEP> . <SEP> . <SEP> - <SEP> F <tb> <SEP> 1 <SEP> Hot <SEP> Pressed <SEP> Finish <SEP> mill <SEP> .0043 <SEP> .065 <SEP> 2100 <tb> <SEP> 3 <SEP> N <SEP> + <SEP> end <SEP> of <SEP> block <SEP> (ipt) <tb> <SEP> 34 <SEP> (intermitt <tb> <SEP> 2 <SEP> 3 <SEP> ent <SEP> cutting <tb> <SEP> I <tb> <SEP> A1203 <SEP> base <tb> <SEP> + <SEP> 5% <SEP> TiN <SEP> n <SEP> s <SEP> n <SEP> It <SEP> 400 <tb> TABLE IV EMI20.1 <tb> Thermal <SEP> KS <SEP> Parts <SEP> Produced <tb> Sample <tb> <SEP> 0. <SEP> i <SEP> Shock <SEP> Parameter <SEP> ¯x <SEP> (Continuous <SEP> Interrupted <tb> <SEP> I <SEP> Room <SEP> Temp. <SEP> Iligh <SEP> Temp. <SEP> Cutting) <SEP> Cutting <tb> <SEP> (1200so) <SEP> End <SEP> Facing <SEP> Flange <SEP> <tb> <SEP> (A) <SEP> Machine <tb> <SEP> : <SEP> (B) <tb> i <SEP> 3N4+ <SEP> 8% <SEP> | <SEP> 179 <SEP> 182 <SEP> 1200 <SEP> 420 <tb> <SEP> 203 <SEP> I <SEP> I <tb> SiN4+ <SEP> 1% <SEP> 334 <SEP> 36 <SEP> 800 <SEP> 140 <tb> kgd <SEP> I <SEP> 1 <SEP> 800 <SEP> i <SEP> 140 <tb> Si3N4 <SEP> + <SEP> 5% <SEP> 220 <SEP> 26 <SEP> 740 <SEP> - <tb> p90 <tb> Y203 <SEP> 114 <SEP> 600 <SEP> 210 <tb> 210 <tb> yo <tb> j23 <SEP> tF#rnil5a#Y <tb> <SEP> 0 <SEP> 16 <SEP> 200 <SEP> cra#dng <tb> r <tb> 23 <tb> <SEP> at <SEP> outset <SEP> ¯ <tb> K = Thermal Conductivity, BTU/Hr in F. S = Modulus of Rupture, KSI, (4-point bending). &alpha; = Coefficient of Thermal Expansion, X10 -6 in/in F. TABLE V EMI21.1 <tb> <SEP> Cutting <SEP> Condition <SEP> I <tb> <SEP> Material <SEP> Speed <SEP> Feed <SEP> Depth <SEP> of <SEP> Cut <SEP> No. <SEP> of <SEP> Work <tb> <SEP> (sfm) <SEP> (irk) <SEP> (in) <SEP> Piecere <SEP> Aodaoc# <tb> <SEP> I <tb> Hot <SEP> Pressed <tb> tSi3N <SEP> with <SEP> 8E <tb> 1 <SEP> 4 <SEP> 496 <SEP> * <SEP> | <SEP> .016 <SEP> .125 <SEP> to <SEP> 1200 <tb> <SEP> .250# <tb> <SEP> SiO2 <SEP> I <tb> <SEP> 2.30 <tb> <SEP> Same; <tb> <SEP> 1.7 <SEP> '1 <SEP> 1112 <tb> 1Si02 <tb> <SEP> . <SEP> &verbar; <SEP> . <SEP> , <tb> Same <tb> 0 <tb> 23 <SEP> 1 <tb> 620 <SEP> i <tb> 1S <SEP> 102 <tb> <SEP> same; <tb> <SEP> I.ls <SEP> C <SEP> 200 <tb> S1Oz <SEP> . <tb> <SEP> I <SEP> I <tb> <SEP> Hot <SEP> Presse# <tb> <SEP> ;i,N, <SEP> with <tb> <SEP> II <SEP> ft <tb> 45 <SEP> i <SEP> i <tb>

Claims: 1. A method of machining cast iron characterised in that the cast iron is machined with a cutting tool composed of a hotpressed silicon nitride ceramic compost ion containing at least one metal oxide selected from Y203, ZrO2 and MgO. 2. A method according to claim 1 wherein the ceramic composition comprises a ternary system containing silicon nitride, silica and the said metal oxide. 3. A method according to claim 1 or claim 2 wherein the said metal oxide is employed in an amount such as to be contained in the grain boundaries of the silicon nitride in non-spinel form. 4. A method according to claim 2 or claim 3 wherein the ceramic composition containsfrom 1 to 5g by weight of MgO, and/or from 4 to 1$ by weight of Y203 and/or from 4 to 12 % by weight of ZrO2. 5. A method according to any one of claims 1 to 4 wherein the ceramic composition was a thermal shock parameter of at least EMI22.1 6. A method according to any one of claims 1 to 5 wherein the ceramic composition has a density of at least 95 of the theoretical density, a thermal shock parameter at 12000C of at least EMI22.2 a transverse rupture strength of at least 67,000 psi at 1200 C, and a hardness of at least 86 Rockwell 45-N. 7. A method according to any one of claims 1 to 6 wherein the ceramic composition has a density of at least 3.25 g/cm . 8. A method according to any one of claims 1 to 4 wherein the ceramic composition was a modulus of elasticity which is no greater than 56 x 106 psi. 9. A method according to any one of claims I to 5 wherein the ceramic composition has a thermal conductivity of at least 3.0 BTU r. in. OT, and a coefficient of thermal expansion no greater than 1.9 x1.9 10-6 in/in. F. 10. A method according to any Qne of the preceding claims wherein the ceramic composition contains from 4 to 1g% by weight of Y203 and SiO2 in an amount such that the ratio of Y203 to Si02 is from 1.2 to 3.0. 11. A method according to claim 10 wherein the ceramic composition has a density of at least 95% of the theoretical density, a thermal shock parameter at 12000C of least 110x EMI23.1 and a hardness of at least 87 Rockwell 45-N. 12. A method according to claim 10 or claim 11 wherein the ceramic composition has a bend strength of at least 70,000 psi at 1200 C and a density of at least 3.398 13. A method according to any one of claims 10 to 12 wherein the ceramic composition.has a thermal conductivity of at least 3.2 STU/Hr. in.QP, and a coefficent of thermal expansion no greater than 1.87 x 10 i iin. 14. A method according to any one of claims 10 to 13 wherein the ceramic composition has a modulus of elasticity no greater than 53 x 106 psi. 15. A cutting tool for machining cast iron formed from a ceramic composition as defined in any one of the preceding claims. 16. A ceramic composition suitable for manufacturing cutting tools for cast iron and as defined in any one of claims 1 to 14. 17. A method of manufacturing a ceramic composition suitable for manufacturing cutting tools for cast iron comprising the steps of preparing a mixture of silicon nitride which is substantially completely in the alpha phase, and a metal oxide selected from yttria, magnesium oxide and zirconium oxide, the mixture being substantially free from spinel oxides, heating the mixture to a temperature of from 1700 to 17500C for a period of from 3 to 8.5 hours at a pressure of from 5,000 to 6,500 psi and thereafter allowing the material to cool. 18. A method according to claim 17 wherein the metal oxide is yttrium oxide. 19. A method according to claim 17 or claim 18 wherein the total amount of metal oxide in the mixture is from 1 to 1 ssby weight of the silicon nitride. 20. A method according to claim 18 or claim 19 wherein the resulting composition is as defined in any one of claims 2 to 14.

Inventors: EZIS, ANDRE, MOSKOWITZ, DAVID, SAMATA, SHYAM KINKAR, SUBRAMANIAN, KRISHNAMOORTHY
Applicants: FORD FRANCE SOCIETE ANONYME, FORD MOTOR COMPANY, FORD MOTOR COMPANY LIMITED, FORD-WERKE AKTIENGESELLSCHAFT
Application year: 1979
Main classification: C04B35
IPC codes: C04B35, B23B27