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(11) | EP 1 500 713 A1 |
| (12) | EUROPEAN PATENT APPLICATION |
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| (54) | Method of making a fine grained cemented carbide |
| (57) According to the present invention there is a provided a method of making a finegrained
tungsten carbide - cobalt cemented carbide comprising mixing, milling according to
standard practice followed by sintering. By introducing nitrogen at a pressure of
more than 0.5 atm into the sintering atmosphere after dewaxing but before pore closure
a grain refinement including reduced grain size and less abnormal grains can be obtained. |
[0001] The present invention relates to a method of making a fine grained cemented carbide. By performing the sintering at least partly in a nitrogen-containing atmosphere, a grain refined cemented carbide structure has been obtained.
[0002] Cemented carbide inserts with a grain refined structure are today used to a great extent for machining of steel, stainless steels and heat resistant alloys in applications with high demands on both toughness and wear resistance. Another important application is in microdrills for the machining of printed circuit board so called PCB-drills.
[0003] Common grain growth inhibitors include vanadium, chromium, tantalum, niobium and/or titanium or compounds involving these. When added, generally as carbides, they limit grain growth during sintering, but they also have undesirable side effects such as unfavorably affecting the toughness behaviour. Additions of vanadium or chromium are particularly detrimental and have to be kept on a very low level in order to limit their negative influence on the sintering behaviour. Both vanadium and chromium reduce the sintering activity often resulting in an uneven binder phase distribution and toughness reducing defects in the sintered structure. Large additions are also known to result in precipitation of embrittling phases in the WC/Co grain boundaries. According to WO 99/13120, the amount of grain growth inhibitors can be reduced if a carbon content of the cemented carbide close to eta-phase formation is chosen.
[0004] In order to maintain a fine grain size sintering is generally performed at a relatively low temperature of 1360 °C followed by sinterHIP in order to obtain a dense structure. Such production route, of course, increases the production cost.
[0005] It is known that tungsten carbonitride can be produced by high pressure nitrogen treatment of a mixture of tungsten and graphite powder. The process is described in JP-A-03-208811 and JP-A-11-35327 and it is claimed that the resulting tungsten carbonitride powder can be used as a raw material for manufacturing of super hard alloys. JP-A-11-152535 discloses a process to manufacture fine grained tungsten carbonitride - cobalt hard alloys using tungsten carbonitride as a raw material.
[0006] JP-A-10-324942 and JP-A-10-324943 disclose methods to produce ultra-fine grained cemented carbide by adding the grain growth inhibitors as nitrides. In order to avoid pore formation by denitrification of the nitrides sintering is performed in a nitrogen atmosphere.
[0007] It is an object of the present invention to avoid or alleviate the problems of the prior art. It is further an object of the present invention to provide a cemented carbide insert with a combination of high toughness and high deformation resistance along with a method for making the same.
[0008] It has now surprisingly been found that a pronounced grain refining effect in combination with an improved binder phase distribution can be obtained by introduction of nitrogen as a process gas in sintering furnace prior to pore closure.
[0009] Fig. 1 shows in about 1500X a typical example of the structure of a "pure" WC-Co grade, alloyed with nitrogen by sintering according to the invention.
[0010] Fig. 2 shows in about 1500X a typical example of the structure of the same grade sintered according to prior art.
[0011] Fig. 3 shows in about 1500X a typical example of the structure of the same grade, alloyed with nitrogen by sintering according to the invention, after sintering at reduced temperature.
[0012] Fig. 4 shows in about 1500X a typical example of the structure after conventional sintering at reduced temperature.
[0013] Fig. 5 shows in about 1200X a typical example of the structure of a Cr3C2 containing WC-Co grade, alloyed with nitrogen by sintering according to the invention, after sintering at reduced temperature.
[0014] Fig. 6 shows in about 1200X a typical example of the structure of the same grade after conventional sintering at reduced temperature.
[0015] Fig. 7 shows in about 1200X a typical example of the structure of a "pure" submicron (0.25 µm) WC-Co grade, alloyed with nitrogen by sintering according to the invention.
[0016] Fig. 8 shows in about 1200X a typical example of the structure of the same grade sintered according to prior art.
[0017] Fig. 9 shows in about 1200X a typical example of the structure of a Cr3C2 containing submicron 0.25 µm WC-Co grade, alloyed with nitrogen by sintering according to the invention.
[0018] Fig. 10 shows in about 1200X a typical example of the structure of the same grade after conventional sintering.
[0019] Fig. 11 shows in about 1200X a typical example of the structure of a Cr3C2 containing submicron 0.6 µm WC-Co grade, alloyed with nitrogen by sintering according to the invention.
[0020] Fig. 12 shows in about 1200X a typical example of the structure of the same grade after conventional sintering.
[0021] The method according to the present invention comprises mixing, milling and pressing of tungsten carbide - cobalt bodies according to conventional powder metallurgical methods, followed by sintering in a process characterised by introduction of nitrogen at a pressure of more than 0.5 atm, preferably more than 0.75 atm, into the sintering atmosphere after dewaxing but before pore closure, preferably before 1000 °C.
[0023] In an alternative embodiment, the nitrogen is after pore closure replaced by a protective atmosphere of e.g. argon or vacuum.
[0024] The resulting sintered body is characterised by a grain refined structure, reduced grain size and less abnormal grains, in combination with an improved binder phase distribution compared to sintering according to normal practices with a nitrogen content of more than 0.03 weight-%, preferably more than 0.05 weight-%.
[0025] The cobalt content for these alloys should be in the range 4 to 15 weight-%, preferably 5 to 12 weight-%.
[0026] The average number of abnormal grains can be determined using inserts etched for 2 minutes at room temperature in Murakamis regent, examining the etched surface with optical microscope at 1500X, counting the number of abnormal grains on ten micrographs, taken randomly from the surface, and calculating the average number of abnormal grains per micrograph. Each micrograph corresponds to a surface area of 8360 µm2.
[0027] Using the process of the invention with a pure WC-Co alloy, the average number of abnormal grains per micrograph, having a maximum length in any direction >15 µm, is <1.0, preferably <0.7. The average number of abnormal grains per micrograph, having a maximum length in any direction >20 µm, is <0.5. The average number of abnormal grains per micrograph, having a maximum length in any direction >25 µm, is <0.1.
[0028] Using the process of the invention with a WC-Co alloy containing grain growth inhibitors, the average number of abnormal grains per micrograph, having a maximum length in any direction >5 µm, is <0.15.
[0029] For a WC grain size below 0.5 µm the beneficial effect of nitrogen alloying has to be combined with an addition of conventional grain growth inhibitors from groups IVb, Vb and/or VIb of the periodic table, preferably Cr, V and/or Ta, most preferably Cr and/or Ta, either as pure metals or compounds thereof except the nitrides thereof, preferably compounds free of nitrogen, most preferably carbides.
[0030] The process of the invention works on pure WC-Co alloys as well as on WC-Co alloys containing grain growth inhibitors. But the most significant improvement regarding grain growth control has been seen for straight WC-Co alloys with a sintered average grain size of <1.5 µm, preferably <1 µm but larger than 0.5 µm where no further grain growth inhibitors are necessary.
[0031] It has thus been found that the introduction of nitrogen into the sintering furnace after dewaxing but before pore closure results in a significant nitrogen pickup even for nominally pure WC-Co alloys. It has further surprisingly been found that the introduced nitrogen acts as a grain growth inhibitor at the same time as it improves the sintering activity and thus the resulting binder phase distribution. It has also been found that the nitrogen content achieved before pore closure becomes entrapped as soon as the temperature becomes high enough for pore closure. Extended sintering time in vacuum after pore closure has been found to have only a minor effect on the resulting nitrogen content in the as sintered samples.
Example 1
[0032] From a powder mixture consisting of 6.0 weight-% Co, and balance WC with an average grain size of about 1 µm with 0.01 weight-% overstoichiometric carbon content, turning inserts CNMG120408 were pressed. The inserts were sintered in H2 up to 450 °C for dewaxing. At 450 °C, the furnace was evacuated and refilled with nitrogen up to a pressure of 0.8 atm. The temperature was kept constant at 450 °C during the nitrogen filling procedure. After completed filling the temperature was increased to 1370 °C with a speed of 15 °C/min, keeping the nitrogen pressure constant. At 1370 °C, the furnace was evacuated and refilled with a protective atmosphere of 10 mbar Argon and kept at 1370 °C for 30 minutes followed by increased Ar pressure 40 mbar and a temperature increase up to the final sintering temperature 1410 °C where the temperature was kept for an additional hour before cooling and opening of the furnace.
[0033] The structure in the cutting inserts consisted of comparably fine and uniform tungsten carbide grain size in combination with a good binder phase distribution, Fig. 1.
Example 2 (reference example to Example 1)
[0034] Pressed inserts from Example 1 were sintered in H2 up to 450 °C for dewaxing, further in vacuum to 1370 °C, then filled with a protective gas of 10 mbar of Ar and kept at 1370 °C for 30 minutes followed by an increased Ar pressure of 40 mbar and a temperature increase up to the final sintering temperature 1410 °C where the temperature was kept for an additional hour before cooling and opening of the furnace.
[0035] The structure in the cutting inserts consisted of a comparably less fine and uniform tungsten carbide grain size in combination with a acceptable binder phase distribution, Fig. 2.
Example 3
[0036] Pressed inserts from Example 1 were sintered in H2 up to 450°C for dewaxing. At 450 °C, the furnace was evacuated and refilled with nitrogen up to a pressure of 0.8 atm. The temperature was kept constant at 450 °C during the nitrogen filling procedure. After completed filling, the temperature was increased to 1370 °C with a speed of 15 °C/min, keeping the nitrogen pressure constant. At 1370 °C the furnace was evacuated and refilled with a protective atmosphere of 10 mbar Argon. The actual sintering was limited to a 30 min hold at 1370 °C followed by cooling and opening of the furnace.
[0037] The structure in the cutting inserts consisted of comparably fine and uniform tungsten carbide grain size in combination with an acceptable binder phase distribution, Fig. 3.
Example 4 (reference example to Example 3)
[0038] Pressed inserts from Example 1 were sintered in H2 up to 450°C for dewaxing, further in vacuum to 1370 °C. At 1370 °C, the furnace was filled with a protective atmosphere of 10 mbar Argon. The actual sintering was limited to a 30 min hold at 1370 °C followed by cooling and opening of the furnace.
[0039] The structure in the cutting inserts consisted of a comparably less fine and uniform tungsten carbide grain size in combination with an unacceptable binder phase distribution, Fig. 4.
Example 5
[0040] From a powder mixture consisting of 5.2 weight-% Co, 0.6 weight-% Cr3C2 and balance WC with an average grain size of about 1 µm with 0.05 weight-% overstoichiometric carbon content, turning inserts CNMG120408 were pressed. The inserts were sintered in H2 up to 450 °C for dewaxing. At 450 °C, the furnace was evacuated and refilled with nitrogen up to a pressure of 0.8 atm. The temperature was kept constant at 450 °C during the nitrogen filling procedure. After completed filling, the temperature was increased to 1370 °C with a speed of 15 °C/min, keeping the nitrogen pressure constant. At 1370 °C the furnace was evacuated and refilled with a protective atmosphere of 10 mbar Argon. The actual sintering was limited to a 30 min hold at 1370 °C followed by cooling and opening of the furnace.
[0041] The structure in the cutting inserts consisted of comparably fine and uniform tungsten carbide grain size in combination with a good binder phase distribution, Fig. 5.
Example 6 (reference example to Example 5)
[0042] Pressed inserts from Example 5 were sintered in H2 up to 450°C for dewaxing, further in vacuum to 1370 °C. At 1370 the furnace was filled with a protective atmosphere of 10 mbar Argon. The actual sintering was limited to a 30 min hold at 1370 °C followed by cooling and opening of the furnace.
[0043] The structure in the cutting inserts consisted of a comparably less fine and uniform tungsten carbide grain size in combination with an unacceptable binder phase distribution, Fig. 6.
Example 7
[0044] From a powder mixture consisting of 10.0 weight-% Co, and balance WC with an average grain size of about 0.25 µm with 0.01 weight-% overstoichiometric carbon content, turning inserts CNMG120408 were pressed. The inserts were sintered in H2 up to 450 °C for dewaxing. At 450 °C, the furnace was evacuated and refilled with nitrogen up to a pressure of 0.8 atm. The temperature was kept constant at 450 °C during the nitrogen filling procedure. After completed filling the temperature was increased to 1370 °C with a speed of 15 °C/min, keeping the nitrogen pressure constant. At 1370 °C, the furnace was evacuated and refilled with a protective atmosphere of 10 mbar Argon and kept at 1370 °C for 30 minutes followed by an increased Ar pressure of 40 mbar and a temperature increase up to the final sintering temperature 1410 °C where the temperature was kept for an additional hour before cooling and opening of the furnace.
[0045] The structure in the cutting inserts consisted of compared to the reference in example 8 finer large tungsten carbide grains in combination with a good binder phase distribution, Fig. 7.
Example 8 (reference example to Example 7)
[0046] Pressed inserts from Example 7 were sintered in H2 up to 450°C for dewaxing, further in vacuum to 1370 °C, then filled with an protective gas of 10 mbar of Ar and kept at 1370 °C for 30 minutes followed by an increased Ar pressure of 40 mbar and a temperature increase up to the final sintering temperature 1410 °C where the temperature was kept for an additional hour before cooling and opening of the furnace.
[0047] The structure in the cutting inserts consisted of large grains and a non-uniform tungsten carbide grain size in combination with an acceptable binder phase distribution, Fig. 8.
Example 9
[0048] Inserts from Example 7 and 8 were etched for 2 minutes at room temperature in Murakamis regent and examined under optical microscope at 1500X. Ten micrographs were taken. In all ten micrographs, WC grains having a length in any direction >15 µm were detected and the maximum length for each such grain was measured. An average number of abnormal grains per micrograph, corresponding to a surface area of 8360 µm2, was calculated by dividing the number of grains by 10.
| Result: | |||
| Average number of grains with max. length | |||
| >15 µm | >20 µm | >25 µm | |
| Example 7 (invention) | 0.33 | 0 | 0 |
| Example 8 (reference) | 1.4 | 0.6 | 0.2 |
Example 10
[0049] From a powder mixture consisting of 10.0 weight-% Co, 0.5 weight-% Cr3C2 and balance WC with an average grain size of about 0.25 µm with 0.05 weight-% overstoichiometric carbon content, turning inserts SNUN were pressed. The inserts were sintered in H2 up to 450 °C for dewaxing. At 450 °C the furnace was evacuated and refilled with nitrogen up to a pressure of 0.8 atm. The temperature was kept constant at 450 °C during the nitrogen filling procedure. After completed filling the temperature was increased to 1370 °C with a speed of 15 °C/min, keeping the nitrogen pressure constant. At 1370 °C, the furnace was evacuated and refilled with a protective atmosphere of 10 mbar Argon and kept at 1370 °C for 30 minutes followed by an increased Ar pressure of 40 mbar and a temperature increase up to the final sintering temperature of 1410 °C where the temperature was kept for an additional hour before cooling and opening of the furnace.
[0050] The structure in the cutting inserts consisted of a uniform submicron tungsten carbide grain size and in combination with an almost absence of large grains and a uniform Co distribution, Fig. 9.
Example 11 (reference example to Example 10)
[0051] Pressed inserts from Example 10 were sintered in H2 up to 450°C for dewaxing, further in vacuum to 1370 °C, then filled with a protective gas of 10 mbar of Ar and kept at 1370 °C for 30 minutes followed by an increased Ar pressure of 40 mbar and a temperature increase up to the final sintering temperature 1410 °C where the temperature was kept for an additional hour before cooling and opening of the furnace.
[0052] The structure in the cutting inserts consisted of a less uniform submicron tungsten carbide grain size and in combination with some large WC grains, Fig. 10.
Example 12
[0053] Inserts from Example 10 and 11 were etched for 2 minutes at room temperature in Murakamis regent and examined under optical microscope at 1500X. Ten micrographs were taken. In all ten micrographs, WC grains having a length in any direction >5 µm were detected and the maximum length for each such grain was measured. An average number of abnormal grains per micrograph, corresponding to a surface area of 8360 µm2, was calculated by dividing the number of grains by 10.
| Result: | |
| Average number of grains with max. length >5 µm | |
| Example 10 (invention) | 0-0.1 |
| Example 11 (reference) | 0.25-0.4 |
Example 13
[0054] From a powder mixture consisting of 10.0 weight-% Co, 0.5 weight-% Cr3C2 and balance WC with an average grain size of about 0.6 µm with 0.05 weight-% overstoichiometric carbon content, turning inserts SNUN were pressed. The inserts were sintered in H2 up to 450 °C for dewaxing. At 450 °C, the furnace was evacuated and refilled with nitrogen up to a pressure of 0.8 atm. The temperature was kept constant at 450 °C during the nitrogen filling procedure. After completed filling, the temperature was increased to 1370 °C with a speed of 15 °C/min, keeping the nitrogen pressure constant. At 1370 °C, the furnace was evacuated and refilled with a protective atmosphere of 10 mbar Argon and kept at 1370 °C for 30 minutes followed by an increased Ar pressure of 40 mbar and a temperature increase up to the final sintering temperature of 1410 °C where the temperature was kept for an additional hour before cooling and opening of the furnace.
[0055] The structure in the cutting inserts consisted of a uniform submicron tungsten carbide grain size and in combination with an almost absence of large grains and a uniform Co distribution, Fig. 11.
Example 14 (reference example to Example 13)
[0056] Pressed inserts from Example 13 were sintered in H2 up to 450 °C for dewaxing, further in vacuum to 1370 °C, then filled with a protective gas of 10 mbar of Ar and kept at 1370 °C for 30 minutes followed by an increased Ar pressure of 40 mbar and a temperature increase up to the final sintering temperature 1410 °C where the temperature was kept for an additional hour before cooling and opening of the furnace.
[0057] The structure in the cutting inserts consisted of a less uniform submicron tungsten carbide grain size and in combination with some large WC grains, Fig. 12.
Example 15
[0058] Inserts from Example 13 and 14 were etched for 2 minutes at room temperature in Murakamis regent and examined under optical microscope at 1500X. Ten micrographs were taken. In all ten micrographs, WC grains having a length in any direction >5 µm were detected and the maximum length for each such grain was measured. An average per micrograph was calculated by dividing the number of grains by 10. An average number of abnormal grains per micrograph, corresponding to a surface area of 8360 µm2, was calculated by dividing the number of grains by 10.
| Result: | |
| Average number of grains with max. length >5 µm | |
| Example 13 (invention) | 0-0.1 |
| Example 14 (reference) | 0.2-0.4 |
1. Method of making a finegrained tungsten carbide - cobalt cemented carbide comprising
mixing, milling according to conventional powder metallurgical methods, followed by
sintering in a process characterised in introducing nitrogen at a pressure of more than 0.5 atm, preferably more than 0.75
atm, into the sintering atmosphere after dewaxing but before pore closure, preferably
before 1000 °C.
2. Method according to claim 1 characterised in that the whole sintering process is performed in nitrogen.
3. Method according to claim 1 characterised in that the nitrogen after pore closure is replaced by a protective atmosphere of e.g. argon
or vacuum.
4. Method according to any of the preceding claims characterised in adding conventional grain growth inhibitors of metals from groups IVb, Vb and/or
VIb of the periodic table or compounds thereof except nitrides preferably Cr, V and/or
Ta, most preferably Cr and/or Ta.
5. Method according to claim 4 characterised in that said compounds are free of nitrogen.
6. Method according to claim 4 characterised in that said compounds are carbides.