WO2019128965A1 - 一种TiCN基金属陶瓷 - Google Patents

一种TiCN基金属陶瓷 Download PDF

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WO2019128965A1
WO2019128965A1 PCT/CN2018/123382 CN2018123382W WO2019128965A1 WO 2019128965 A1 WO2019128965 A1 WO 2019128965A1 CN 2018123382 W CN2018123382 W CN 2018123382W WO 2019128965 A1 WO2019128965 A1 WO 2019128965A1
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peak
hard phase
ticn
diffraction peak
diffraction
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PCT/CN2018/123382
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English (en)
French (fr)
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鲁攀
许荣杰
聂洪波
项忠楠
郭新营
江嘉鹭
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厦门钨业股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23B—TURNING; BORING
    • B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
    • B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/04—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbonitrides

Definitions

  • the invention belongs to a cermet material, in particular to a TiCN-based cermet.
  • TiCN-based cermets have attracted widespread attention at home and abroad due to their good red hardness, high wear resistance, small thermal expansion coefficient, excellent chemical stability, extremely low friction coefficient, abundant raw material resources and low cost. A material with great potential. TiCN-based cermets have higher high-temperature hardness than WC-Co cemented carbides, and have better toughness than ceramic tools such as Al2O3. In recent years, with the development of high performance of cutting devices, higher requirements have been placed on the materials for manufacturing cutting tools. TiCN-based cermets can improve cutting performance by means of surface coating treatment or gradient functional materials, but as a matrix.
  • the TiCN-based cermet inherits the fragility of ceramic materials, that is, the material toughness is poor, in the face of large processing volume (medium heavy cutting), the material to be processed is hard (hardened die steel, etc.), difficult to process materials ( Stainless steel work hardening, complex composition of composite materials) or intermittent processing, prone to sudden avalanche loss at the blade edge, groove wear failure at the intersection of the blade and the workpiece surface, etc., both in the scope of use and processing Larger limit.
  • the improvement of cermet toughness is mainly through: 1) adjusting the formulation, adding carbide or TiCN solid solution; 2) adding nano-hard phase to control powder particle size; 3) adjusting process parameters.
  • simply increasing the toughness of the TiCN-based cermet tends to reduce the hardness of the material, that is, the reduction of wear resistance, that is, the loss of the maximum advantage of the cermet material itself; on the other hand, the above method does not start with the real core microstructure, adding
  • the selection of materials, the adjustment of formula and the formulation of process parameters have no clear direction guidance, and there are certain randomness, repeated trials, large workload, poor effect, and it is difficult to effectively guarantee the overall performance improvement of the product. Therefore, in order to solve the problem of material application, it is necessary to combine the microstructure of the material to improve the toughness and fracture resistance of the material under the premise of ensuring sufficient hardness, that is, to improve the toughness of the material.
  • the present invention provides a special structure of TiCN-based cermet, which can significantly improve the toughness and fracture resistance of the cermet and prolong its service life as a cutting tool under the premise of ensuring hardness.
  • the present invention adopts the following technical solutions:
  • a TiCN-based cermet comprising a hard phase having a TiCN-based composition as a main phase, and an X-ray diffraction pattern (XRD pattern) of the TiCN-based cermet with a Co target as a radiation source, at a Bragg angle of 2 ⁇ of 47
  • the diffraction peak A appears at ⁇ 49.7° and the diffraction peak B appears at a Bragg angle 2 ⁇ of 132.1°-139.7°; the peak width WA of the diffraction peak A is 0.92°-1.48°, and the peak width of the diffraction peak B is wide.
  • WB is 0.84°-2.0°; the diffraction peak A is subjected to peak shape fitting to obtain a fitting map A, and the number of peaks of the diffraction peak A in the fitting spectrum is 1 to 3, and the diffraction peak A
  • the peak area of the strongest peak in the partial peak accounts for 80.3% to 91.6% of the sum of the peak areas of the respective peaks of the diffraction peak A.
  • the composition of TiCN-based cermet is extremely complicated, and its structure is composed of binder phase and hard phase (core phase, inner ring phase and outer ring phase).
  • the composition has a large number of complex interfaces between the inner ring phase, the outer ring phase and the core phase. Due to differences in composition and physical properties, complex interfacial stresses are created at these complex interfaces after sintering. Thus the phase composition and its distribution significantly affect the properties of the TiCN-based cermet material.
  • the solid solution phase formed by solid solution of Ti with W, Mo, etc., and the wettability between the binder phase and the binder phase are much higher than the wettability between the TiCN main phase and the binder phase, so the crystal structure is intact and a sufficient amount of solid solution
  • the phase can significantly improve the bonding strength between the hard phase and the binder phase, thereby suppressing the crack generation and expansion of the material due to stress during use.
  • too much solid solution phase will lower the hardness of the material, so that the wear resistance and the like of the material are lowered. Therefore, the degree of crystallization of the solid solution, the content ratio, and the like should be limited to a suitable range.
  • the position of the diffraction peak and the width of the peak edge in the TiCN-based cermet structure with TiCN as the main phase are first defined.
  • the peak width refers to the XRD spectrum (the X-axis is the 2 ⁇ angle and the Y-axis is the intensity).
  • the highest peak position corresponds to the 2 ⁇ angle to the left bottom and the bottom horizontal position is closest to the peak intensity.
  • the width value on the X-axis of the point at the highest position After long-term research, the inventor realized for the first time that by defining and quantifying the peak width, it can reflect the crystallinity of the hard phase.
  • the hard phase Due to the complex composition of the cermet, the hard phase is generally not a single pure substance.
  • the phase composition is relatively simple, the peak width is lower than the limit value, and the toughness may be difficult to be effectively improved. If the added hard phase components are different, that is, the problem of composition addition or process formulation in the preparation process of the cermet occurs. Other miscellaneous phases, the peak shape is abnormally widened, will significantly affect the material toughness.
  • TiCN is mainly used, and various additives are used as the hard phase, and the peak width is generally high.
  • the present invention selectively uses 0.92° ⁇ WA ⁇ 1.48° and 0.84° ⁇ WB ⁇ 2.0°.
  • the present invention defines the peak shape of the diffraction peak A. Due to the similarity between TiCN particles and other additive particles in TiCN cermet, the peak shape will be superimposed on each other in a suitable composition ratio range, but a single peak state, but the state of this single peak and pure substance There is a significant difference between the single peaks. By fitting the XRD original spectrum to the peak shape, the diffraction peak will be peaked. The software can use Jade, origin or Maud. Therefore, it is difficult to ensure that the cermet hard phase composition and the solid solution shell composition meet the requirements by simply defining the peak width.
  • the TiCN-based cermet has a complex composition, and the definition of the peak shape can also enhance the toughness of the cermet while effectively ensuring the hardness of the cermet. If there are more than three peaks of the diffraction peak A in the fitted spectrum, there are many compositions in the hard phase, that is, there are many hetero phases, which also significantly reduces the toughness of the alloy. In addition, when the number of peaks of the diffraction peak A is more than three, the peak shape of the XRD pattern tends to exhibit a saddle-like bimodal structure.
  • the present invention also defines the ratio of the peak area of the strongest peak in the peak of the diffraction peak A after fitting.
  • the peak area ratio is defined by the peak shape to ensure that a certain amount of TiCN particles or TiCN particles are contained in the cermet, and a sufficient amount of solid solution shell formed with the added hard phase is provided, thereby ensuring improvement of the core phase and adhesion.
  • the doped TiCN particles in the present invention are not particularly limited, however, from the viewpoint of efficiently preparing the TiCN-based cermet, the doped TiCN particles are TiCN composite particles containing a metal such as Fe, and the TiCN content is 99 wt% or more.
  • the metal content of Fe or the like is 1% by weight or less, and unavoidable impurities.
  • the present invention can obtain a TiCN-based cermet with a markedly improved toughness while maintaining the hardness by controlling the above-mentioned set index/parameter.
  • the cutting effect is excellent after the tool is formed, and the service life is long.
  • a cutting tool using the TiCN-based cermet described above as a substrate is provided.
  • the toughness mentioned in the present invention is hardness and toughness.
  • the wt% mentioned in the present invention is a weight percentage.
  • FIG. 1 is an XRD pattern of a TiCN-based cermet in Example 5 of the present invention.
  • Fig. 2 is a partial XRD pattern of a TiCN-based cermet in Example 5 of the present invention illustrating WA.
  • Fig. 3 is a partial XRD pattern of a TiCN-based cermet in Example 5 of the invention of WB.
  • Fig. 4 is a view showing a peak-fitting peak of a diffraction peak A in Example 5 of the present invention.
  • Hardness test refers to GB/T 7997-2014 "hard alloy Vickers hardness test method”.
  • the toughness test refers to GB/T 33819-2017 "Carbide Toughness Test”.
  • Tool cutting test Perform the cutting comparison experiment of Table 1.
  • the cutting length of the cutting test is more than 25m, and the wear of the flank is not more than 110 ⁇ m, which means that the tool is qualified, that is, the toughness of the cermet meets the need;
  • the chipping refers to the notch of the tool edge which is less than 110 ⁇ m, which is also a tool failure, but not It will have a great impact on the workpiece;
  • the broken knife means that the tool is broken, or the blade of a larger size is missing, which will have a significant impact on the workpiece. In severe cases, it may also affect the equipment, which is a serious unacceptable phenomenon.
  • the hard phase comprises a first hard phase, a second hard phase and a third hard phase, the first hard phase being TiCN particles or doped TiCN particles, the first The second hard phase is composed of WC particles and Mo 2 C particles, and the third hard phase is selected from carbide particles, nitride particles or carbon of a Group 4, Group 5 or Group 6 metal element of the periodic table. At least one of the nitride particles.
  • the first hard phase is the source of material hardness; the second hard phase and the third hard phase affect the peak shape, improve the material properties, and the second hard phase is an objective condition for toughness improvement; when the third hard phase is in the third hard phase
  • the addition of carbides can increase the W A value of the cermet, significantly increase the hardness, and significantly improve the high temperature performance, but the toughness may slightly decrease.
  • the peak shape fit uses the P-VII (Pearson-VII) method.
  • the original spectrum peak shape fitting method includes Gauss, Lorentz, Pearson-IV, Pearson-VII, etc., and is set according to the XRD index, preferably P-VII.
  • the diffraction peak A is located in a region where the Bragg angle 2 ⁇ is 48.1°-49.7°, and the diffraction peak B is located in a region where the Bragg angle 2 ⁇ is 132.1°-138.5°.
  • the diffraction peak A and the diffraction peak B appearing in the above preferred Bragg angle 2 ⁇ range are more favorable for the definition of the additive hard phase.
  • the proportion of hard phase components contains more heavy metal elements (such as W, Ta, etc.)
  • the proportion of TiCN phase decreases, the peak shape of the diffraction peak will show an overall leftward shift, and the hardness of the material may show significant attenuation.
  • the increase in toughness may not be apparent, resulting in a decrease in cutting performance.
  • the maximum peak half-height width of the diffraction peak A is 0.3°-0.447°
  • the diffraction peak B is fitted by peak shape fitting.
  • the number of peaks of the diffraction peak B in the fitting spectrum B is from 1 to 3
  • the maximum peak width in the diffraction peak B is 0.86°-1.2°.
  • the FWHM is a standard method for reflecting the crystallinity of materials. Since TiCN-based cermets usually have a special shell structure, the crystallinity and composition ratio of solid solution shells can significantly affect the homogenization of the material during sintering. And densification, FWHM can ensure that the solid solution shell in the hard phase has sufficient time and conditions to obtain sufficient crystallization, so that the TiCN-based cermet has better toughness.
  • the number of peaks of the diffraction peak A in the partial peak spectrum is two.
  • the number of peaks of the diffraction peak A in the partial peak spectrum is three.
  • the hard phase accounts for 72% by weight or more of the TiCN-based cermet
  • the first hard phase accounts for 50% by weight or more of the hard phase
  • the second hard phase occupies 20.05 wt% - 40 wt% of the hard phase
  • the third hard phase accounts for 3.41 wt% - 25 wt% of the hard phase; in the hard phase, the C content is 7.8 wt% - 12.0 wt
  • the %, N content is from 3.5 wt% to 8.7 wt%.
  • the proportion of the first hard phase mass affects the hardness of the material.
  • the F A and F B in the cermet increase, the toughness of the cermet increases, but the toughness after excess The increase is not obvious, but the hardness of the cermet decreases.
  • the C content in the hard phase is low, the cermet W A and W B increase, the number of peaks of the diffraction peak A may exceed 3, and the toughness of the cermet decreases remarkably;
  • the content of N in the phase is high, the cermet W A and W B increase, the peak area ratio of the strongest peak after fitting decreases, and the toughness of the cermet decreases.
  • the peak shape of the diffraction peak in the original spectrum is saddle-shaped. Double peak structure.
  • the content range of the hard phase of 72% by weight or more is a conventional choice in the industry, and therefore, in the examples, the range of the hard phase content was not tested and verified.
  • the content of the hard phase ranges from 72% by weight to 88% by weight of the TiCN-based cermet, but it does not constitute a limitation on the scope of protection.
  • the TiCN-based cermet further comprises a binder phase and the binder phase is a metal.
  • the method for producing the TiCN-based cermet in the present invention is not particularly limited, however, from the viewpoint of efficiently preparing the cutting tool and having a TiCN-based cermet having excellent toughness, the method preferably follows the following process. It includes powder formulation, wet milling, pressing and sintering.
  • the particle diameter of the hard phase powder and the particle diameter of the binder phase powder are not particularly limited, however, from the viewpoint of efficiently preparing the TiCN-based cermet, the average particle diameter of the hard phase is preferably 0.5 ⁇ m to 2 ⁇ m.
  • the binder phase has an average particle diameter of 1 ⁇ m to 2 ⁇ m.
  • the mixing in the preparation of the TiCN-based cermet is not particularly limited. However, from the viewpoint of effectively obtaining uniform distribution and stable phase composition, it is preferred to carry out mixing by wet ball milling and a suitable solvent for wet ball milling. There are no special restrictions on the molding agent.
  • an ethanol solvent and a paraffin forming agent are used, wherein the paraffin is added in an amount of 2% to 5% of the total weight of the material, and is sufficiently mixed for 50 to 70 hours, but it does not constitute a limitation on the protection range.
  • the manner of pressing in the preparation process of the TiCN-based cermet is not particularly limited, and may be appropriately selected according to the purpose of those skilled in the art.
  • dry press forming may be used for pressing, cold isostatic pressing for pressing, or injection molding for pressing.
  • the pressure for pressing is also not particularly limited, and is preferably 100 MPa.
  • sintering in the preparation process of the TiCN-based cermet is not particularly limited, and may be appropriately selected according to the purpose of those skilled in the art.
  • a dewaxing, vacuum sintering and atmosphere sintering step of 250 ° C - 300 ° C is used, wherein the atmosphere is preferably an inert gas such as nitrogen or argon, and the sintering temperature is preferably 1470 ° C to 1500 ° C, and the holding time is preferably It is 1h-5h, but it does not constitute a limitation on the scope of protection.
  • the binder phase employed for the TiCN-based cermet is not particularly limited, and may be appropriately selected according to the purpose of those skilled in the art.
  • the binder phase is Co and Ni metal, but it does not constitute a limitation on the scope of protection.
  • the TiCN-based cermets of Examples 1-5 and Comparative Examples 1-2 are composed of a hard phase and a binder phase, wherein the hard phase is composed of a first hard phase, a second hard phase, and a third hard phase, Formulated in mass percent wt%.
  • the average particle diameter of each component of the hard phase was 1 ⁇ m
  • the binder phase was selected to have an average particle diameter of 1.5 ⁇ m, a ratio of 50 wt% of Co, and 50 wt% of Ni.
  • Table 2 The distribution of each embodiment and each comparative example is shown in Table 2.
  • the first hard phase accounts for 54.55 wt% to 65.09 wt% of the hard phase
  • the second hard phase accounts for 20.05 wt% to 38.55 wt% of the hard phase
  • the third hard The mass phase accounts for 3.61 wt% to 25 wt% of the hard phase
  • the C content in the hard phase is 7.80 wt% to 12.00 wt%
  • the N content in the hard phase is 3.82 wt% to 8.49 wt%.
  • the first hard phase accounts for 68.60% by weight of the hard phase
  • the second hard phase accounts for 26.74% by weight of the hard phase
  • the third hard phase accounts for 4.65 wt% of the hard phase
  • the hard phase The content of C in the medium was 8.18 wt%
  • the content of N in the hard phase was 4.80 wt%.
  • the first hard phase accounts for 50.59 wt% of the hard phase
  • the second hard phase accounts for 37.6 wt% of the hard phase
  • the third hard phase accounts for 11.76 wt% of the hard phase
  • the hard phase The content of C in the medium is 10.91% by weight, and the content of N in the hard phase is 6.60% by weight.
  • the above powder was wet-milled in an ethanol solvent and a paraffin forming agent, wherein the paraffin was added in an amount of 2.5% of the total weight of the material, thoroughly mixed for 50 hours, and dried to obtain RTP pellets.
  • the RTP pellet of step 1 was pressed at 100 MPa to obtain a standard D6 mm*50 mm round bar.
  • the round rod of step 2 is dewaxed at 250 ° C, vacuum sintered and atmospheric sintering step, and kept at a temperature of 1470 ° C for 5 h, and the cermet material can be obtained after cooling.
  • the X-ray measurement and performance test of the TiCN-based cermets prepared in each of the examples and the comparative examples were carried out, and the samples were made into D6 mm*50 mm four-blade flat-end milling cutters for cutting performance test.
  • the parameters measured by the respective examples and the respective comparative examples XRD are shown in Table 3.
  • the evaluation results of the respective examples and the respective comparative examples are shown in Tables 4 and 5.
  • the diffraction peak A of Example 1-5 appears at a Bragg angle 2 ⁇ of 47°-49.7°
  • the diffraction peak B appears at a Bragg angle 2 ⁇ of 132.1°-139.7°.
  • the peak width of the diffraction peak A, the peak width of the diffraction peak B, the number of peaks of the diffraction peak A in the fitted spectrum, and the area of the strongest peak peak occupy the above-defined range
  • the cutting length of the obtained tool Both are above 25m, the flank wear does not exceed 110 ⁇ m, and the tool is qualified, that is, the toughness of the cermet meets the needs.
  • a TiCN-based cermet exhibiting a diffraction peak A at a Bragg angle of 2 ⁇ of 47°-49.7° and a diffraction peak B at a Bragg angle 2 ⁇ of 132.1°-139.7° the toughness and the cutting performance are improved, and
  • the TiCN-based cermet exhibiting a diffraction peak B at a Bragg angle 2 ⁇ of 132.1°-138.5° is more remarkable in toughness and cutting performance.
  • the TiCN-based cermets of Examples 6-8 and Comparative Examples 3-5 consist of a hard phase and a binder phase, wherein the hard phase is composed of a first hard phase, a second hard phase, and a third hard phase, Formulated in mass percent wt%.
  • the average particle diameter of each component of the hard phase was 1.2 ⁇ m
  • the binder phase was selected to have an average particle diameter of 1.8 ⁇ m, a ratio of 55 wt% of Co, and 45 wt% of Ni.
  • Table 6 The distribution of each embodiment and each comparative example is shown in Table 6.
  • the first hard phase accounts for 57.83 wt% to 66.67 wt% of the hard phase
  • the second hard phase accounts for 27.78 wt% to 38.55 wt% of the hard phase
  • the third hard The mass phase accounts for 3.41 wt% to 25 wt% of the hard phase
  • the C content in the hard phase is 8.06 wt% to 11.64 wt%
  • the N content in the hard phase is 4.05 wt% to 8.16 wt%.
  • the first hard phase accounts for 54.65 wt% of the hard phase
  • the second hard phase accounts for 27.91 wt% of the hard phase
  • the third hard phase accounts for 17.44 wt% of the hard phase
  • the hard phase The content of C in the medium was 8.25 wt%
  • the content of N in the hard phase was 3.83 wt%.
  • the first hard phase accounts for 54.12% by weight of the hard phase
  • the second hard phase accounts for 29.41% by weight of the hard phase
  • the third hard phase accounts for 16.47% by weight of the hard phase
  • the hard phase The content of C in the medium is 11.50% by weight, and the content of N in the hard phase is 7.06% by weight.
  • the first hard phase accounts for 65.52 wt% of the hard phase
  • the second hard phase accounts for 27.59 wt% of the hard phase
  • the third hard phase accounts for 6.90 wt% of the hard phase
  • the hard phase The content of C in the medium was 8.25 wt%
  • the content of N in the hard phase was 4.59 wt%.
  • the above powder was wet-milled in an ethanol solvent and a paraffin forming agent to prepare a slurry in which the paraffin wax was added in an amount of 4% by weight based on the total weight of the material, and thoroughly mixed for 52 hours to obtain an RTP pellet.
  • the RTP pellet of step 1 was pressed at 110 MPa to obtain a standard D6 mm*50 mm round bar.
  • the round bar of step 2 is dewaxed, vacuum sintered and sintered at 255 ° C, and is kept at a temperature of 1485 ° C for 2.5 h, and the cermet material can be obtained after cooling.
  • the peak width W A of Example 6-8 was 0.92 ° - 1.48 °
  • the peak width W B was 0.84 ° - 2.0 °
  • the position of the diffraction peak A was obtained.
  • the cutting length of the obtained tool is more than 25 m
  • the flank wear is both Not exceeding 110 ⁇ m
  • the tool is qualified, that is, the toughness of the cermet meets the needs.
  • the TiCN-based cermets of Examples 9-11 and Comparative Examples 6-7 are composed of a hard phase and a binder phase, wherein the hard phase is composed of a first hard phase, a second hard phase, and a third hard phase, Formulated in mass percent wt%.
  • the average particle diameter of each component of the hard phase was 0.8 ⁇ m
  • the binder phase was selected to have an average particle diameter of 1.2 ⁇ m, a ratio of 60 wt% of Co, and 40 wt% of Ni.
  • the distribution of each embodiment and each comparative example is shown in Table 10.
  • Examples 9-11 the first hard phase accounts for 52.94 wt% to 66.67 wt% of the hard phase, and the second hard phase accounts for 29.82 wt% to 40.00 wt% of the hard phase, the third hard The mass phase accounts for 3.41 wt% to 7.06 wt% of the hard phase, the C content in the hard phase is 8.10 wt% to 11.86 wt%, and the N content in the hard phase is 4.38 wt% to 8.70 wt%.
  • the first hard phase accounts for 64.71 wt% of the hard phase
  • the second hard phase accounts for 35.29 wt% of the hard phase
  • the third hard phase accounts for 0 wt% of the hard phase, in the hard phase.
  • the C content was 7.93 wt%
  • the N content in the hard phase was 4.53 wt%.
  • the first hard phase accounts for 64.10% by weight of the hard phase
  • the second hard phase accounts for 16.67% by weight of the hard phase
  • the third hard phase accounts for 19.23% by weight of the hard phase
  • the hard phase The content of C in the medium was 12.26% by weight, and the content of N in the hard phase was 8.37% by weight.
  • the above powder was wet-milled in an ethanol solvent and a paraffin forming agent, wherein the paraffin was added in an amount of 2% by weight of the total material, mixed thoroughly for 55 hours, and dried to obtain RTP pellets.
  • the RTP pellet of step 1 was pressed at a pressure of 105 MPa to obtain a standard D6 mm*50 mm round bar.
  • the round rod of step 2 is dewaxed, vacuum sintered and sintered at 300 ° C, and kept at a temperature of 1500 ° C for 1 h, and the cermet material can be obtained after cooling.
  • the peak area ratio of S1 in the peak of the diffraction peak A of Example 9-11 was 80.3% to 91.6%, and the peak width and position of the diffraction peak A, the diffraction peak B
  • the cutting length of the obtained tool is more than 25 m, and the flank wear does not exceed 110 ⁇ m.
  • the toughness of cermet meets the needs.
  • the TiCN-based cermets of Examples 12-14 and Comparative Example 8 are composed of a hard phase and a binder phase, wherein the hard phase is composed of a first hard phase, a second hard phase and a third hard phase, with mass Percentage wt% formulation.
  • the first hard phase has an average particle diameter of 1.0 ⁇ m
  • the second hard phase and the third hard phase have an average particle diameter of 1.5 ⁇ m
  • the binder phase has a Co-average particle diameter of 1.5 ⁇ m and a ratio of 65 wt% of Co.
  • 35 wt% of Ni The distribution of the respective examples and comparative examples is shown in Table 14.
  • the above powder was wet-milled in an ethanol solvent and a paraffin forming agent to prepare a slurry in which the amount of paraffin added was 3% of the total weight of the material, and the mixture was thoroughly mixed for 60 hours, and dried to obtain RTP pellets.
  • step 1 The RTP pellets of step 1 were pressed at 95 MPa to obtain a standard D6 mm*50 mm round bar.
  • the round bar of step 2 is dewaxed at 280 ° C, vacuum sintered and atmospheric sintering step, and kept at a temperature of 1480 ° C for 3 h, and the cermet material can be obtained after cooling.
  • Examples 12-14 the first hard phase accounts for 50 wt%, 52.33%, and 55.81 wt%, respectively, and the second hard phase accounts for 37.21 wt% and 34.88 wt%, respectively. 31.39wt%, the third hard phase accounts for 12.79wt%, 12.79wt%, 12.79wt%, and the C content in the hard phase is 7.90wt%-10.95wt%, and the N content in the hard phase is 3.50 wt% - 6.83 wt%.
  • the first hard phase accounts for 48.19 wt% of the hard phase
  • the second hard phase accounts for 38.55 wt% of the hard phase
  • the third hard phase accounts for 13.25 wt% of the hard phase
  • the hard phase The medium C content was 7.81% by weight, and the N content in the hard phase was 3.26% by weight.
  • the first hard phase of Comparative Example 8 accounts for less than 50% by weight of the hard phase, exhibiting insufficient hardness, which is reflected in the cutting performance, that is, the cutting length is short, and the flank wear is fast.
  • the toughness is insufficient and the cutting performance is difficult to meet the requirements.
  • the TiCN-based cermet of Examples 15-18 consists of a hard phase composed of a first hard phase, a second hard phase and a third hard phase, and a binder phase, which is formulated in mass% wt%. .
  • the average hardness of the first hard phase is 0.5 ⁇ m
  • the average particle diameter of the second hard phase is 1.5 ⁇ m
  • the average particle diameter of the third hard phase is 1.0 ⁇ m
  • the average particle diameter of the binder phase is 2 ⁇ m.
  • the ratio is 45 wt% Co and 55 wt% Ni.
  • Table 18 The distribution of the respective examples and comparative examples is shown in Table 18.
  • the above powder was wet-milled in an ethanol solvent and a paraffin forming agent to prepare a slurry in which the amount of paraffin added was 5% of the total weight of the material, and the mixture was thoroughly mixed for 70 hours, and dried to obtain RTP pellets.
  • the RTP pellet of step 1 was pressed at 100 MPa to obtain a standard D6 mm*50 mm round bar.
  • the round rod of step 2 is dewaxed, vacuum sintered and sintered at 300 ° C, and kept at a temperature of 1500 ° C for 1 h, and the cermet material can be obtained after cooling.
  • the first hard phase accounts for 60.47 wt%, 57.83%, 60.24 wt%, 65.88 wt%, and 67.44 wt%, respectively
  • the second hard phase accounts for the hard phase.
  • the third hard phase accounts for 6.98 wt%, 3.61 wt%, 18.07 wt%, 3.53 wt%, 5.81, respectively.
  • the wt%, the C content in the hard phase is 8.14 wt% to 11.91 wt%
  • the N content in the hard phase is 4.22 wt% - 8.60 wt%.

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Abstract

一种TiCN基金属陶瓷及使用该金属陶瓷为基材的切削工具，该TiCN基金属陶瓷包括以TiCN为主相的硬质相，通过对TiCN基金属陶瓷进行X射线衍射测量得到原始谱图，原始谱图包括在布拉格角2θ为47°-49.7°出现的衍射峰A和在布拉格角2θ为132.1°-139.7°出现的衍射峰B；衍射峰A的峰边宽0.92°-1.48°，衍射峰B的峰边宽0.84°-2.0°；衍射峰A峰形拟合后得到拟合图谱，拟合图谱中衍射峰A分峰数量为1-3个，衍射峰A分峰中最强峰的峰面积占衍射峰A各分峰峰面积之和的80.3％-91.6％，定量化控制并优化微观结构，从而在保证硬度的前提下显著提升TiCN基金属陶瓷韧性和抗崩损能力，延长其作为切削工具的使用寿命。

Description

一种TiCN基金属陶瓷 技术领域
本发明属于金属陶瓷材料，具体涉及一种TiCN基金属陶瓷。
背景技术
TiCN基金属陶瓷因具有红硬性好、耐磨性高、热膨胀系数小、优良的化学稳定性、极低的摩擦系数以及原料资源丰富、成本低等优点而受到国内外的普遍关注，成为一类极具潜力的材料。TiCN基金属陶瓷与WC-Co硬质合金相比，高温硬度较高，而相比于Al2O3等陶瓷刀具材料其韧性更好，综合两者优势，应用前景巨大。近年来随着切削装置的高性能发展，对制造切削刀具的材料提出了更高的要求，TiCN基金属陶瓷虽可借助表面涂层处理或梯度功能材料等方式短时提升切削性能，但作为基体的TiCN基金属陶瓷继承陶瓷材料的易崩损性，即材料韧性较差，在面对较大加工量(中重切削)、被加工材质较硬(淬硬模具钢等)、难加工材料(不锈钢的加工硬化、复合材料的复杂组成)或断续加工时，易发生刀刃处的突然崩损失效、刀刃与工件表面交接处的沟槽磨损失效等问题，在使用范围及加工领域均受到了较大限制。
目前文献及报道中，普遍认为造成TiCN基金属陶瓷韧性较低的主要原因为合金的主要组成TiCN与合金粘结相之间较差的润湿性，即两者无法形成较强力的化学结合或其他结合方式，应力易在晶界处集中，并沿着结合力较差的TiCN/粘结相界面处释放，易形成裂纹并迅速扩展，从而产生失效。
而改善金属陶瓷韧性主要是通过：1)调整配方，添加碳化物或TiCN固溶体；2)添加纳米硬质相，控制粉末粒度；3)工艺参数的调整。但单纯提高TiCN基金属陶瓷韧性，往往会降低材料的硬度，也就是耐磨性的降低，即失去金属陶瓷材料本身的最大优势；另一方面，上述方法未从真正核心的微观组织入手，添加物的选取、配方的调整和工艺参数的制定无明确方向性指导，有一定随意性，反复试验，工作量大，效果不佳，产品整体性能提升难以得到有效保障。因此，如要解决材料应用上的问题，必须结合材料的微观结构，在保证足够硬度的前提下，提高材料的韧性和抗崩损能力，即提高材料的强韧性。
目前未见通过X射线衍射测量(XRD)方式测定并优化相组成来实现TiCN基金属陶瓷 强韧性提升的报道。
发明内容
鉴于上述情况，本发明提供了一种特殊结构的TiCN基金属陶瓷，在保证硬度的前提下高效显著提升金属陶瓷韧性和抗崩损能力，延长其作为切削工具的使用寿命。
为实现上述目的，本发明采用以下技术方案：
一种TiCN基金属陶瓷，包括以TiCN系组成为主相的硬质相，在所述TiCN基金属陶瓷以Co靶作为射线源的X射线衍射图谱(XRD图谱)中，在布拉格角2θ为47°-49.7°出现衍射峰A和在布拉格角2θ为132.1°-139.7°出现衍射峰B；所述衍射峰A的峰边宽WA为0.92°-1.48°，所述衍射峰B的峰边宽WB为0.84°-2.0°；所述衍射峰A进行峰形拟合得到拟合图谱A，所述拟合图谱中所述衍射峰A分峰数量为1个-3个，所述衍射峰A分峰中最强峰的峰面积占所述衍射峰A各分峰峰面积之和的80.3％-91.6％。
与WC-Co硬质合金由两种成分构成的两相结构不同，TiCN基金属陶瓷的成分极为复杂，其组织结构由粘结相、硬质相(芯相、内环相和外环相)构成，在内环相、外环相及芯相间又存在大量的复杂界面。由于成分及物性参数的差异，在烧结后，这些复杂界面上产生复杂的界面应力。因而相组成及其分布显著影响TiCN基金属陶瓷材料的性能。
由Ti与W、Mo等固溶形成的固溶体相，其与粘结相之间的润湿性远高于TiCN主相与粘结相间的润湿性，因此结晶结构完整，且足够量的固溶体相能够显著的改善硬质相与粘结相之间的结合强度，从而抑制材料在使用过程中因应力而造成的裂纹产生及扩展。但同时过多的固溶体相也会降低材料的硬度，从而使得材料的耐磨性等性能出现降低，因此固溶体的结晶程度、含量比例等应限制在合适的区间范围。
本发明通过XRD相成分分析，首先对以TiCN为主相的TiCN基金属陶瓷组织中衍射峰位置及峰边宽进行限定。峰边宽是指XRD图谱(以X轴为2θ角，Y轴为强度)中，对于指定可见峰形，其峰强度最高位置所对应2θ角至左侧背底水平位置段最靠近上述峰强度最高位置的点的X轴上宽度值。发明人经过长期研究，首次认识到通过定义并且量化峰边宽，可反映硬质相的结晶度，由于金属陶瓷存在复杂的成分组成，硬质相一般不为单一的纯物质，若添加的硬质相成分较为单一，峰边宽低于限定值，韧性可能难以得到有效提升，而若添加 的硬质相成分差异较大，即在金属陶瓷制备过程中因成分添加或工艺制定的问题产生了其他杂相，峰形异常宽化，将显著影响材料强韧性。本发明以TiCN为主体，采用多种添加物作为硬质相，其峰边宽通常较高，本发明有选择的采用0.92°≤WA≤1.48°和0.84°≤WB≤2.0°。
为进一步优化组织结构，本发明对衍射峰A的峰形进行限定。由于TiCN金属陶瓷中TiCN颗粒与其他添加物颗粒存在一定的相似性，在合适的组成比例范围内，其峰形会相互叠加，而呈现类似单峰的状态，但此单峰的状态与纯物质的单峰存在明显的不同，通过对XRD原始谱图进行峰形拟合，该衍射峰会分峰，软件可采用Jade、origin或Maud等。因此单纯限定峰边宽难以保证金属陶瓷硬质相成分和固溶体壳层组成达到要求。TiCN基金属陶瓷存在复杂的成分组成，通过峰形的限定还可在有效保证金属陶瓷硬度的同时，增强材料韧性。若在拟合图谱中，衍射峰A的分峰数量多于3个，硬质相存在多种组成，也即是存在较多杂相，这也会显著地降低合金的韧性。另外，在衍射峰A的分峰数量多于3个时，XRD图谱峰形会趋于呈现马鞍状双峰结构。
本发明还对拟合后衍射峰A分峰中最强峰的峰面积占比进行限定。峰面积占比配合峰形限定，以保证金属陶瓷中具备一定量的TiCN颗粒或掺杂TiCN颗粒，同时具备足够量的与所添加硬质相形成的固溶体壳层，从而确保改善芯相与粘结相的润湿性。两者缺一不可，比例的失调均会造成强韧性的降低。
本发明中的掺杂TiCN颗粒没有特别地限制，然而，从有效地制备所述TiCN基金属陶瓷的观点出发，掺杂TiCN颗粒为含Fe等金属的TiCN复合颗粒，其中TiCN含量为99wt％以上，Fe等金属含量为1wt％以下，以及不可避免的杂质。
综上所述，本发明通过对以上设定指标/参数的控制，可以在兼顾硬度的同时，获得强韧性显著提升的TiCN基金属陶瓷，制成工具后切削效果优异，使用寿命长。
本发明的又一目的在于提供一种切削工具。
一种切削工具，使用上述的TiCN基金属陶瓷作为基材。
需要说明的是，本发明中公布的所有数字范围包括这个范围内的所有点值。
本发明中提及的强韧性为硬度和韧性。
本发明中提及的wt％为重量百分比。
附图说明
图1是本发明实施例5中TiCN基金属陶瓷的XRD图谱。
图2是示意WA的本发明实施例5中TiCN基金属陶瓷的XRD局部图谱。
图3是示意WB的本发明实施例5中TiCN基金属陶瓷的XRD局部图谱。
图4是本发明实施例5中衍射峰A拟合分峰图谱。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合具体实施方式对本发明做进一步详细的说明，但本发明的保护范围不限于下述的实施例，下列实施例中未注明具体条件的实验方法，通常按照常规条件。
XRD测量：
1)对样品进行XRD扫描，采用Co靶作为射线源，连续式扫描方式，步长0.033°，扫描速度1°/min，扫描范围25°-150°，得到原始的X射线衍射图谱；
2)对X射线衍射图谱使用最小二乘法对衍射峰进行寻峰，初步获得分峰数量，记录肉眼可见的峰形；将X射线衍射图谱数据导入峰形拟合软件，扣除基线，采用P-VII(Pearson-VII)法对衍射峰进行峰形拟合，确定分峰数量；
3)观察X射线衍射图谱，记录在布拉格角2θ为47°～50°和在布拉格角2θ为132°～140°出现的衍射峰的峰位，分别定义为衍射峰A和衍射峰B，并记录衍射峰A和衍射峰B的峰边宽；衍射峰A进行峰形拟合后，记录衍射峰A分峰数量，定义衍射峰A分峰中最强峰为S1，计算S1峰面积占衍射峰A各分峰峰面积之和的比例，定义衍射峰A分峰中最强峰S1的半高宽值为FA，衍射峰B进行峰形拟合后，定义衍射峰B分峰中最强峰的半高宽值为FB，测得FA和FB的值。
性能测试：
1、硬度测试参照GB/T 7997-2014《硬质合金维氏硬度试验方法》。
2、韧性测试参照GB/T 33819-2017《硬质合金巴氏韧性试验》。
3、刀具切削试验：进行表1的切削对比实验。通常刀具切削试验切削长度25m以上， 并且后刀面磨损未超过110μm视为刀具合格，即金属陶瓷强韧性满足需要；崩刃是指刀具刃口出现小于110μm的缺口，也属刀具失效，但不会对工件产生较大影响；断刀是指刀具出现折断，或较大尺寸的刀刃缺失，会对工件产生明显影响，严重时可能对设备也产生影响，属严重不可接受现象。
表1 切削实验参数
Figure PCTCN2018123382-appb-000001
在推荐的实施方式中，所述硬质相包括第一硬质相、第二硬质相和第三硬质相，所述第一硬质相为TiCN颗粒或掺杂TiCN颗粒，所述第二硬质相由WC颗粒和Mo 2C颗粒组成，所述第三硬质相选自元素周期表中第四族、第五族或第六族金属元素的碳化物颗粒、氮化物颗粒或碳氮化物颗粒中的至少一种。第一硬质相是材料硬度的来源；第二硬质相和第三硬质相则影响峰形，改进材料性能，第二硬质相是韧性提升的客观条件；当第三硬质相中加入碳化物，可使金属陶瓷W A值增大，硬度显著提升，高温性能明显改善，但韧性可能略微下降。
在推荐的实施方式中，所述峰形拟合采用P-VII(Pearson-VII)法。原始谱图峰形拟合法包括Gauss、Lorentz、Pearson-IV和Pearson-VII等，根据XRD指标设定，优选P-VII。
在推荐的实施方式中，所述衍射峰A位于布拉格角2θ为48.1°-49.7°的区域，所述衍射峰B位于布拉格角2θ为132.1°-138.5°的区域。在上述优选的布拉格角2θ范围内出现的衍射峰A和衍射峰B更利于添加物硬质相的限定。当硬质相成分占比中包含较多的重金属元素时(如W、Ta等)，TiCN相占比下降，衍射峰峰形将呈现整体的向左偏移，材料硬度可能出现显著衰减，而韧性提升可能不明显，从而导致切削使用性能的下降。
在推荐的实施方式中，所述拟合图谱A中，所述衍射峰A分峰中最强峰半高宽值为0.3°-0.447°，所述衍射峰B进行峰形拟合得到拟合图谱B，所述拟合图谱B中所述衍射峰B分峰数量为1个-3个，所述衍射峰B中最强峰半高宽值为0.86°-1.2°。半高宽值(FWHM)是反映材料结晶度标准方法，由于TiCN基金属陶瓷通常具有特殊的壳层结构，固溶体壳层的结晶度、成分组成比例等都会显著影响到材料烧结过程中的均匀化和致密化，FWHM可以保证硬质相中固溶体壳层有足够的时间和条件获得充分的结晶，使TiCN基金属陶瓷具有更佳的强韧性。
需要说明的是，拟合图谱B中衍射峰B的分峰数量是本行业的常规选择，因此，在实施例中，没有对拟合图谱B中衍射峰B的分峰数量加以试验和验证。
在推荐的实施方式中，所述分峰图谱中所述衍射峰A分峰数量为2个。
在推荐的实施方式中，所述分峰图谱中所述衍射峰A分峰数量为3个。
在推荐的实施方式中，所述硬质相占所述TiCN基金属陶瓷的72wt％以上，所述第一硬质相占所述硬质相的50wt％以上，所述第二硬质相占所述硬质相的20.05wt％-40wt％，所述第三硬质相占所述硬质相的3.41wt％-25wt％；所述硬质相中，C含量为7.8wt％-12.0wt％，N含量为3.5wt％-8.7wt％。
第一硬质相质量占比影响材料硬度，随着成分中如WC、Mo 2C、NbC等添加量增多，金属陶瓷中F A和F B增大，金属陶瓷韧性升高，但过量后韧性提升不明显，反而导致金属陶瓷硬度下降；硬质相中C含量较低时，金属陶瓷W A及W B增大，衍射峰A分峰数量可能超过3个，金属陶瓷韧性显著降低；硬质相中N含量较高时，金属陶瓷W A及W B增大，拟合后最强峰的峰面积占比值下降，金属陶瓷韧性降低，严重时原始谱图中衍射峰峰形呈明显马鞍状双峰结构。
需要说明的是，硬质相占72wt％以上的含量范围是本行业的常规选择，因此，在实施例中，没有对硬质相含量范围加以试验和验证。本发明的实施例中，所述硬质相的含量范围为所述TiCN基金属陶瓷的72wt％-88wt％，但其不构成对保护范围的限制。
在推荐的实施方式中，TiCN基金属陶瓷还包括粘结相，粘结相为金属。
需要说明的是，本发明中对TiCN基金属陶瓷的制备方法没有特别地限制，然而，从有效地制备所述切削工具并且具有优异强韧性的TiCN基金属陶瓷的观点出发，该方法优选以下工艺，其包括粉末配制、湿磨、压制和烧结。
本发明中，对于硬质相粉末粒径和粘结相粉末粒径没有特别地限制，然而，从有效地制备所述TiCN基金属陶瓷的观点出发，优选硬质相平均粒径0.5μm-2μm，粘结相平均粒径1μm-2μm。
本发明中，对TiCN基金属陶瓷制备过程中的混合没有特别地限制，然而，从有效获得分布均匀、相成分稳定的观点出发，优选用湿式球磨法进行混合，并对湿式球磨法适合的溶 剂和成型剂没有特殊限制。在本发明的实施例中，包括采用乙醇溶剂及石蜡成型剂，其中石蜡的添加量为物料总重的2％-5％，并充分混合50h-70h，但其不构成对保护范围的限制。
本发明中，对于TiCN基金属陶瓷制备过程中的压制方式没有特别地限制，并且可以根据本领域技术人员的目的而适当选择。例如，可以选用干式加压成形进行压制，以及冷等静压成形进行压制，或者注射成形进行压制。对压制的压力也没有特别地限制，优选为100MPa。
本发明中，对于TiCN基金属陶瓷制备过程中的烧结没有特别地限制，并且可以根据本领域技术人员的目的而适当选择。在本发明的实施例中，采用250℃-300℃脱蜡、真空烧结和气氛烧结步骤，其中气氛优选为氮气或氩气之类的惰性气体，烧结温度优选1470℃～1500℃，保温时间优选为1h-5h，但其不构成对保护范围的限制。
本发明中，对于TiCN基金属陶瓷所采用的粘结相没有特别地限制，并且可以根据本领域技术人员的目的而适当选择。在本发明的实施例中，粘结相为Co和Ni金属，但其不构成对保护范围的限制。
实施例Ⅰ
实施例1-5和对比例1-2的TiCN基金属陶瓷由硬质相和粘结相构成，其中硬质相由第一硬质相、第二硬质相和第三硬质相构成，以质量百分比wt％配制。硬质相各成分的平均粒径均为1μm，粘结相选用平均粒径为1.5μm、配比为50wt％的Co和50wt％的Ni。各实施例和各对比例的成分配比如表2所示。
表2 各实施例和各对比例成分配比(wt％)
Figure PCTCN2018123382-appb-000002
通过计算可以得知实施例1-5：第一硬质相占硬质相的54.55wt％-65.09wt％，第二硬质相占硬质相的20.05wt％-38.55wt％，第三硬质相占硬质相的3.61wt％-25wt％，硬质相中C含量 为7.80wt％-12.00wt％，硬质相中N含量为3.82wt％-8.49wt％。
对比例1中，第一硬质相占硬质相的68.60wt％，第二硬质相占硬质相的26.74wt％，第三硬质相占硬质相的4.65wt％，硬质相中C含量为8.18wt％，硬质相中N含量为4.80wt％。
对比例2中，第一硬质相占硬质相的50.59wt％，第二硬质相占硬质相的37.6wt％，第三硬质相占硬质相的11.76wt％，硬质相中C含量为10.91wt％，硬质相中N含量为6.60wt％。
详细工艺如下所示：
步骤1：湿磨
将上述粉末在乙醇溶剂及石蜡成型剂中湿磨制成料浆，其中石蜡的添加量为物料总重的2.5％，充分混合50h，经干燥获得RTP料粒。
步骤2：压制
将步骤1的RTP料粒经100MPa压力压制获得标准的D6mm*50mm的圆棒。
步骤3：烧结
将步骤2的圆棒经250℃脱蜡、真空烧结和气氛烧结步骤，并于1470℃温度段保温5h，经降温后即可获得金属陶瓷材料。
各实施例和各对比例制成的TiCN基金属陶瓷进行XRD测量及性能测试，将样品制成D6mm*50mm四刃平头铣刀进行切削性能测试。各实施例和各对比例XRD测得的参数如表3所示，各实施例和各对比例性能评价结果如表4和表5所示。
表3 各实施例和各对比例XRD测得参数
Figure PCTCN2018123382-appb-000003
表4 实施例和对比例硬度和韧性评价情况
Figure PCTCN2018123382-appb-000004
表5 各实施例和各对比例切削性能评价情况
Figure PCTCN2018123382-appb-000005
从表3结合表4和表5可以看出，实施例1-5的衍射峰A出现在布拉格角2θ为47°-49.7°处，并且衍射峰B出现在布拉格角2θ为132.1°-139.7°处，且衍射峰A的峰边宽、衍射峰B的峰边宽、拟合图谱中衍射峰A分峰数量和最强峰峰面积占比上述限定范围内时，所制得的刀具切削长度均在25m以上，后刀面磨损均未超过110μm，刀具合格，即金属陶瓷强韧性满足需要。
对比例1中，衍射峰A和衍射峰B的峰位略微左移，金属陶瓷硬度提高，但韧性显著下降，所制得的刀具出现断刀现象，表现出切削寿命不稳定，无法达到要求。
对比例2中，衍射峰A和衍射峰B的峰位略微右移，但金属陶瓷硬度显著降低，所制得的刀具切削长度少于25m，后刀面磨损严重，刀具寿命较短，不合格。
作为结论我们可以得出：
对于在布拉格角2θ低于47°出现衍射峰A和在布拉格角2θ低于132.1°出现衍射峰B的TiCN基金属陶瓷来说，韧度不足，切削寿命不稳定，无法达到要求。
对于在布拉格角2θ为47°-49.7°出现衍射峰A，且在布拉格角2θ为132.1°-139.7°出现衍 射峰B的TiCN基金属陶瓷来说，强韧性和切削性能有所改善，而对于在布拉格角2θ为48.1°-49.7°出现衍射峰A，且在布拉格角2θ为132.1°-138.5°出现衍射峰B的TiCN基金属陶瓷来说，强韧性和切削性能提升更为显著。
对于在布拉格角2θ高于49.7°出现衍射峰A和在布拉格角2θ高于139.7°出现衍射峰B的TiCN基金属陶瓷来说，硬度不足，切削寿命难以达到要求。
实施例Ⅱ
实施例6-8和对比例3-5的TiCN基金属陶瓷由硬质相和粘结相构成，其中硬质相由第一硬质相、第二硬质相和第三硬质相构成，以质量百分比wt％配制。硬质相各成分的平均粒径均为1.2μm，粘结相选用平均粒径为1.8μm、配比为55wt％的Co和45wt％的Ni。各实施例和各对比例的成分配比如表6所示。
表6 各实施例和各对比例成分配比(wt％)
Figure PCTCN2018123382-appb-000006
通过计算可以得知实施例6-8：第一硬质相占硬质相的57.83wt％-66.67wt％，第二硬质相占硬质相的27.78wt％-38.55wt％，第三硬质相占硬质相的3.41wt％-25wt％，硬质相中C含量为8.06wt％-11.64wt％，硬质相中N含量为4.05wt％-8.16wt％。
对比例3中，第一硬质相占硬质相的54.65wt％，第二硬质相占硬质相的27.91wt％，第三硬质相占硬质相的17.44wt％，硬质相中C含量为8.25wt％，硬质相中N含量为3.83wt％。
对比例4中，第一硬质相占硬质相的54.12wt％，第二硬质相占硬质相的29.41wt％，第三硬质相占硬质相的16.47wt％，硬质相中C含量为11.50wt％，硬质相中N含量为7.06wt％。
对比例5中，第一硬质相占硬质相的65.52wt％，第二硬质相占硬质相的27.59wt％，第三硬质相占硬质相的6.90wt％，硬质相中C含量为8.25wt％，硬质相中N含量为4.59wt％。
详细工艺如下所示：
步骤1：湿磨
将上述粉末在乙醇溶剂及石蜡成型剂中湿磨制成料浆，其中石蜡的添加量为物料总重的4％，充分混合52h，经干燥获得RTP料粒。
步骤2：压制
将步骤1的RTP料粒经110MPa压力压制获得标准的D6mm*50mm的圆棒。
步骤3：烧结
将步骤2的圆棒经255℃脱蜡、真空烧结和气氛烧结步骤，并于1485℃温度段保温2.5h，经降温后即可获得金属陶瓷材料。
各实施例和各对比例制成的TiCN基金属陶瓷进行XRD测量及性能测试，将样品制成D6mm*50mm四刃平头铣刀进行切削性能测试。各实施例和各对比例XRD测得的参数如表7所示，各实施例和各对比例性能评价结果如表8和表9所示。
表7 各实施例和各对比例XRD测得参数
Figure PCTCN2018123382-appb-000007
表8 各实施例和各对比例硬度和韧性评价情况
Figure PCTCN2018123382-appb-000008
表9 各实施例和各对比例切削性能评价情况
Figure PCTCN2018123382-appb-000009
从表7结合表8和表9可以看出，实施例6-8的峰边宽W A为0.92°-1.48°，峰边宽W B为0.84°-2.0°时，且衍射峰A的位置、衍射峰B的位置、拟合图谱中衍射峰A分峰数量和最强峰峰面积占比均在上述限定范围内时，所制得的刀具切削长度均在25m以上，后刀面磨损均未超过110μm，刀具合格，即金属陶瓷强韧性满足需要。
对比例3中，XRD中峰边宽W A略小，金属陶瓷硬度较低，所制得的金属陶瓷刀具在切削过程中后刀面磨损较快，切削长度短，寿命低。
对比例4中，XRD中峰边宽W B略小，金属陶瓷硬度较低，所制得的金属陶瓷刀具在切削过程中后刀面磨损较快，切削长度短，寿命低。
对比例5中，XRD中峰边宽W A和W B偏大，金属陶瓷韧性显著降低，所制得的刀具在切削性能上不稳定，易断刀，不合格。
作为结论我们可以得出：
对于峰边宽W A为0.92°-1.48°和峰边宽W B为0.84°-2.0°的TiCN基金属陶瓷来说，强韧性和切削性能提升更为显著。
实施例Ⅲ
实施例9-11和对比例6-7的TiCN基金属陶瓷由硬质相和粘结相构成，其中硬质相由第一硬质相、第二硬质相和第三硬质相构成，以质量百分比wt％配制。硬质相各成分的平均粒径均为0.8μm，粘结相选用平均粒径为1.2μm、配比为60wt％的Co和40wt％的Ni。各实施例和各对比例的成分配比如表10所示。
表10 各实施例和各对比例成分配比(wt％)
Figure PCTCN2018123382-appb-000010
通过计算可以得知实施例9-11：第一硬质相占硬质相的52.94wt％-66.67wt％，第二硬质相占硬质相的29.82wt％-40.00wt％，第三硬质相占硬质相的3.41wt％-7.06wt％，硬质相中C含量为8.10wt％-11.86wt％，硬质相中N含量为4.38wt％-8.70wt％。
对比例6中，第一硬质相占硬质相的64.71wt％，第二硬质相占硬质相的35.29wt％，第三硬质相占硬质相的0wt％，硬质相中C含量为7.93wt％，硬质相中N含量为4.53wt％。
对比例7中，第一硬质相占硬质相的64.10wt％，第二硬质相占硬质相的16.67wt％，第三硬质相占硬质相的19.23wt％，硬质相中C含量为12.26wt％，硬质相中N含量为8.37wt％。
详细工艺如下所示：
步骤1：湿磨
将上述粉末在乙醇溶剂及石蜡成型剂中湿磨制成料浆，其中石蜡的添加量为物料总重的2％，充分混合55h，经干燥获得RTP料粒。
步骤2：压制
将步骤1的RTP料粒经105MPa压力压制获得标准的D6mm*50mm的圆棒。
步骤3：烧结
将步骤2的圆棒经300℃脱蜡、真空烧结和气氛烧结步骤，并于1500℃温度段保温1h，经降温后即可获得金属陶瓷材料。
各实施例和各对比例制成的TiCN基金属陶瓷进行XRD测量及性能测试，将样品制成D6mm*50mm四刃平头铣刀进行切削性能测试。各实施例和各对比例XRD测得的参数如表11所示，各实施例和各对比例性能评价结果如表12和表13所示。
表11 各实施例和各对比例XRD测得参数
Figure PCTCN2018123382-appb-000011
表12 各实施例和各对比例硬度和韧性评价情况
Figure PCTCN2018123382-appb-000012
表13 各实施例和各对比例切削性能评价情况
Figure PCTCN2018123382-appb-000013
从表11结合表12和表13可以看出，实施例9-11衍射峰A分峰中S1的峰面积比为80.3％-91.6％，且衍射峰A的峰边宽和位置、衍射峰B的峰边宽和位置、拟合图谱中衍射峰A分峰数量均在上述限定范围内时，所制得的刀具切削长度均在25m以上，后刀面磨损均未超过110μm，刀具合格，即金属陶瓷强韧性满足需要。
对比例6，衍射峰A分峰中S1的峰面积比高于91.6％，反映在切削性能上即是切削长度短，存在断刀现象，切削寿命差。
对比例7，衍射峰A分峰中S1的峰面积比低于80.3％，表现出韧性不足，反映在切削性能上即是切削长度短，易崩刃断刀。
作为结论我们可以得出：
对于S1峰面积比低于80.3％的TiCN基金属陶瓷来说，韧性不足，切削性能难以达到要 求。
对于S1峰面积比80.3％以上、91.6％以下的TiCN基金属陶瓷来说，强韧性和切削性能提升更为显著。
对于S1峰面积比高于91.6％的TiCN基金属陶瓷来说，切削长度短，切削寿命差。
实施例Ⅳ
实施例12-14和对比例8的TiCN基金属陶瓷由硬质相和粘结相构成，其中硬质相由第一硬质相、第二硬质相和第三硬质相构成，以质量百分比wt％配制。第一硬质相的平均粒径为1.0μm、第二硬质相和第三硬质相的平均粒径为1.5μm，粘结相选用平均粒径为1.5μm、配比为65wt％的Co和35wt％的Ni。各实施例和对比例的成分配比如表14所示。
表14 各实施例和对比例成分配比(wt％)
Figure PCTCN2018123382-appb-000014
详细工艺如下所示：
步骤1：湿磨
将上述粉末在乙醇溶剂及石蜡成型剂中湿磨制成料浆，其中石蜡的添加量为物料总重的3％，充分混合60h，经干燥获得RTP料粒。
步骤2：压制
将步骤1的RTP料粒经95MPa压力压制获得标准的D6mm*50mm的圆棒。
步骤3：烧结
将步骤2的圆棒经280℃脱蜡、真空烧结和气氛烧结步骤，并于1480℃温度段保温3h，经降温后即可获得金属陶瓷材料。
各实施例和对比例制成的TiCN基金属陶瓷进行XRD测量及性能测试，将样品制成D6mm*50mm四刃平头铣刀进行切削性能测试。各实施例和对比例XRD测得的参数如表15所示，各实施例和对比例性能评价结果如表16和表17所示。
表15 各实施例和对比例XRD测得参数
Figure PCTCN2018123382-appb-000015
表16 各实施例和对比例硬度和韧性评价情况
Figure PCTCN2018123382-appb-000016
表17 各实施例和对比例切削性能评价情况
Figure PCTCN2018123382-appb-000017
通过计算可以得知实施例12-14：第一硬质相占硬质相分别为50wt％、52.33％、55.81wt％，第二硬质相占硬质相分别为37.21wt％、34.88wt％、31.39wt％，第三硬质相占硬质相分别为12.79wt％、12.79wt％、12.79wt％，硬质相中C含量为7.90wt％-10.95wt％，硬质相中N含量为3.50wt％-6.83wt％。
对比例8中，第一硬质相占硬质相的48.19wt％，第二硬质相占硬质相的38.55wt％，第三硬质相占硬质相的13.25wt％，硬质相中C含量为7.81wt％，硬质相中N含量为3.26wt％。
从表16和表17可以看出，对比例8的第一硬质相占硬质相不足50wt％，表现出硬度不足，反映在切削性能上即是切削长度短，后刀面磨损较快。
作为结论我们可以得出：
对于第一硬质相占硬质相低于50wt％的TiCN基金属陶瓷来说，强韧性不足，切削性能难以达到要求。
实施例Ⅴ
实施例15-18的TiCN基金属陶瓷由硬质相和粘结相构成，其中硬质相由第一硬质相、第二硬质相和第三硬质相构成，以质量百分比wt％配制。第一硬质相的平均粒径为0.5μm、第二硬质相的平均粒径为1.5μm、第三硬质相的平均粒径为1.0μm，粘结相选用平均粒径为2μm、配比为45wt％的Co和55wt％的Ni。各实施例和对比例的成分配比如表18所示。
表18 各实施例成分配比(wt％)
Figure PCTCN2018123382-appb-000018
详细工艺如下所示：
步骤1：湿磨
将上述粉末在乙醇溶剂及石蜡成型剂中湿磨制成料浆，其中石蜡的添加量为物料总重的5％，充分混合70h，经干燥获得RTP料粒。
步骤2：压制
将步骤1的RTP料粒经100MPa压力压制获得标准的D6mm*50mm的圆棒。
步骤3：烧结
将步骤2的圆棒经300℃脱蜡、真空烧结和气氛烧结步骤，并于1500℃温度段保温1h，经降温后即可获得金属陶瓷材料。
各实施例和对比例制成的TiCN基金属陶瓷进行XRD测量及性能测试，将样品制成D6mm*50mm四刃平头铣刀进行切削性能测试。各实施例和对比例XRD测得的参数如表19所示，各实施例和对比例性能评价结果如表20和表21所示。
表19 各实施例XRD测得参数
Figure PCTCN2018123382-appb-000019
表20 各实施例硬度和韧性评价情况
Figure PCTCN2018123382-appb-000020
表21 各实施例切削性能评价情况
Figure PCTCN2018123382-appb-000021
通过计算可以得知实施例15-19：第一硬质相占硬质相分别为60.47wt％、57.83％、60.24wt％、65.88wt％、67.44wt％，第二硬质相占硬质相分别为32.56wt％、38.55wt％、21.69wt％、30.59wt％、26.74wt％，第三硬质相占硬质相分别为6.98wt％、3.61wt％、18.07wt％、3.53wt％、5.81wt％，硬质相中C含量为8.14wt％-11.91wt％，硬质相中N含量为4.22wt％-8.60wt％。
从表20和表21可以看出，对于F A为0.3°-0.447°且F B为0.86°-1.2°的TiCN基金属陶瓷来说，强韧性和切削性能更佳。
上述实施例仅用于对本发明所提供的技术方案进行解释，并不能对本发明进行限制，凡是依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰，均落入本发明技术方案的保护范围内。

Claims (9)

  1. 一种TiCN基金属陶瓷，包括以TiCN系组成为主相的硬质相，其特征在于：在所述TiCN基金属陶瓷的以Co靶作为射线源的X射线衍射图谱中，在布拉格角2θ为47°-49.7°出现衍射峰A和在布拉格角2θ为132.1°-139.7°出现衍射峰B；所述衍射峰A的峰边宽WA为0.92°-1.48°，所述衍射峰B的峰边宽WB为0.84°-2.0°；所述衍射峰A进行峰形拟合得到拟合图谱A，所述拟合图谱A中所述衍射峰A分峰数量为1个-3个，所述衍射峰A分峰中最强峰的峰面积占所述衍射峰A各分峰峰面积之和的80.3％-91.6％。
  2. 根据权利要求1所述的一种TiCN基金属陶瓷，其特征在于：所述硬质相包括第一硬质相、第二硬质相和第三硬质相，所述第一硬质相为TiCN颗粒或掺杂TiCN颗粒，所述第二硬质相由WC颗粒和Mo2C颗粒组成，所述第三硬质相选自元素周期表中第四族、第五族或第六族金属元素的碳化物颗粒、氮化物颗粒或碳氮化物颗粒中的至少一种。
  3. 根据权利要求1所述的一种TiCN基金属陶瓷，其特征在于：所述峰形拟合采用P-VII法。
  4. 根据权利要求1所述的一种TiCN基金属陶瓷，其特征在于：所述衍射峰A位于布拉格角2θ为48.1°-49.7°的区域，所述衍射峰B位于布拉格角2θ为132.1°-138.5°的区域。
  5. 根据权利要求3所述的一种TiCN基金属陶瓷，其特征在于：所述拟合图谱A中，所述衍射峰A分峰中最强峰半高宽值为0.3°-0.447°，所述衍射峰B进行峰形拟合得到拟合图谱B，所述拟合图谱B中所述衍射峰B分峰数量为1个-3个，所述衍射峰B中最强峰半高宽值为0.86°-1.2°。
  6. 根据权利要求2所述的一种TiCN基金属陶瓷，其特征在于：所述硬质相占所述TiCN基金属陶瓷的72wt％以上，所述第一硬质相占所述硬质相的50wt％以上，所述第二硬质相占所述硬质相的20.05wt％-40wt％，所述第三硬质相占所述硬质相的3.41wt％-25wt％；所述硬质相中，C含量为7.8wt％-12.0wt％，N含量为3.5wt％-8.7wt％。
  7. 根据权利要求6所述的一种TiCN基金属陶瓷，其特征在于：所述硬质相占所述TiCN基金属陶瓷的72wt％-88wt％。
  8. 根据权利要求2所述的一种TiCN基金属陶瓷，其特征在于：所述TiCN基金属陶瓷还包括粘结相，所述粘结相为金属。
  9. 一种切削工具，其特征在于：使用权利要求1至权利要求8中任一项所述的TiCN基金属 陶瓷作为基材。
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