CN104099580A - Cutter coating layer having nanometer columnar crystal for enhancing wear resistance and toughness - Google Patents
Cutter coating layer having nanometer columnar crystal for enhancing wear resistance and toughness Download PDFInfo
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- CN104099580A CN104099580A CN201410232242.3A CN201410232242A CN104099580A CN 104099580 A CN104099580 A CN 104099580A CN 201410232242 A CN201410232242 A CN 201410232242A CN 104099580 A CN104099580 A CN 104099580A
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Abstract
The invention discloses a cutter coating layer having a nanometer columnar crystal for enhancing wear resistance and toughness; and the wear resistance and the impact resistance are prominently improved through optimizing the grain size and the microstructure. The improved coating layer comprises the nanometer columnar crystal; and the control to the grain size and shape is guaranteed through adopting CH4, C2H6, C2H4, C2H2, N2 and CH3CN to serve as the composition of carbon and nitrogen sources. The composition ratio of all gases is necessarily and carefully controlled so as to maintain the structure of the nanometer columnar crystal. Preferably, the grain size of the columnar crystal is 50-150 nm, and the length-width ratio is greater than 10. The cutter coating layer overcomes the defects of weak wear resistance and impact resistance when grains of the columnar crystal of an MT-TiCN coating layer are thick, and overcomes the defect that a fine MT-TiCN coating layer is easy to form an isometric crystal to result in reduced wear resistance. The cutter coating layer has excellent toughness and good wear resistance, and has excellent cutting performance in the cutting of such materials as steel, cast iron and stainless steel.
Description
Technical field
The present invention relates to comprise the cutting tool that is coated with MT-TiCN nanometer column crystal coating main body, particularly relate to a kind of cutter coat with the nanometer column crystal that strengthens wear resistance and toughness.
Background technology
It is one of important channel of improving cutting tool performance in cutting tool surface-coated coating, the features such as coated cutting tool has that surface hardness is high, wear resistance good, stable chemical performance, heat-resistant oxidized, frictional coefficient is little and thermal conductivity is low, when cutting, comparable non-coated tool improves the life-span more than 5～10 times.The high-quality process for modifying surface that the top coat technology of cutting tool grows up as the market requirement, because can making cutting tool, this technology obtains good comprehensive mechanical performance, not only can effectively improve cutting tool work-ing life, and can also improve significantly mechanical workout efficiency, therefore this technology becomes one of gordian technique of cutting tool manufacture.
MT-TiCN coating is as one of critical function layer of CVD coating, and the columnar grain that normally approaches coat-thickness by its crystal grain length forms.This coating is in single TiC lattice, and N atom occupies the position of original C atom in dot matrix and the complex compound that forms.Because MT-TiCN coating has the over-all properties of TiC and TiN, can in coating procedure, can, by changing the Composition Control MT-TiCN coating performance of C, N, be therefore a kind of comparatively ideal cutting tool coating material simultaneously.But adopt traditional technology TiCl
4-CH
3cN-N
2-H
2system deposits the MT-TiCN coating making and has large columnar grain, and the wear resistance of cutter and shock resistance have been subject to certain impact.
Thin crystal fiber shape structure MT-TiCN coating crack is few, reduces the internal stress of coating, improves coating toughness, stops the expansion of crackle, reduces blade tipping.Because crystal grain is thinner, wear resisting property is more excellent simultaneously.Even be subject to mechanical shock and thermal shocking repeatedly in when cutting, coating is also not easy to produce and peels off or destroy, thereby has improved the anti-tipping blade performance of cutter under continuous cutting condition, and this is to processing stainless steel, steel alloy, and spheroidal graphite cast iron etc. are very favourable.
As everyone knows, the hardness of polycrystalline material is conventionally in accordance with Hall-Petch formula:
the hardness that wherein H is polycrystalline material, the H ° of hardness that is monocrystalline, C is material constant (C>0), and d is grain-size.Find out from this formula, can improve by reducing grain-size the hardness of material.
According to materialogy principle, crystal grain is more tiny, and comprehensive mechanical property is better.Fine grain structure is more even, and crystal boundary is many, plays the effect of refined crystalline strengthening, so intensity, hardness ratio are higher, and in the time of viscous deformation, more even owing to organizing, can not produce excessive deformation and destroy structure in part, show good plasticity and toughness.So can develop evenly tiny MT-TiCN column crystal coating plays an important role in cutter chemical coating process exploitation.
In US20020012818, disclose employing CO and adulterated to realize nanocrystal MT-TiCN coating.A kind of MT-TiCN coating that adopts CO (preferably approximately the is 7-9%) doping of high flow to realize wear-resisting crystal grain is disclosed in US6472060.But the nanocrystal MT-TiCN coating of CO doping is equiax crystal, toughness improves, and wear resistance declines.The people such as Ruppi have confirmed at Thin Solid Film402 (2002) 203, will reduce the wear resistance in crescent moon low-lying area the crystal grain of coating being reduced to (20-50nm) below nanocrystal region.These nanocrystal coatings are harder, but have intercrystalline slip, thereby cause occurring viscous deformation under higher temperature.In CN200410036997.2, disclose a kind of by adopting CO, CO
2, ZrCl
4and AlCl
3or these combinations are adulterated and are obtained MT-TiCN nanometer column crystal coating.
As can be seen from the above, a kind of comparatively ideal cutting tool coating material of MT-TiCN column crystal coating, but the coated grains that traditional technology makes is thicker.Disclosed ultra-fine MT-TiCN column crystal coating mostly obtains by the doping of different elements at present, and tiny MT-TiCN coating easily forms equiax crystal.
Summary of the invention
The object of the invention is to overcome the deficiency of prior art, a kind of cutter coat with the nanometer column crystal that strengthens wear resistance and toughness is provided, by the process modification to MT-TiCN coating, both overcome the drawback of its wear resistance and shock resistance deficiency when MT-TiCN coating columnar grain is thicker, and overcome again tiny MT-TiCN coating and easily formed the drawback that equiax crystal causes wear resistance to decline.
The technical solution adopted for the present invention to solve the technical problems is: a kind of have a nanometer column crystal cutter coat that strengthens wear resistance and toughness, comprises and adopts chemical vapour deposition mode to be deposited on one or more layers the coating on blade base; In described coating, at least contain one deck MT-TiCN layer; Described MT-TiCN layer has the columnar grain of uniform superfine crystalline grain, columnar grain diameter dimension is 50～200nm, long-width ratio is greater than 10, preferably be greater than 20, the gauge of MT-TiCN layer is 1～20 μ m, and this MT-TiCN layer is in reaction chamber, to pass into the mixed gas deposition that contains carbon nitrogen source gas to form, and described carbon nitrogen source gas is CH
4, C
2h
6, C
2h
4, C
2h
2, N
2, CH
3a kind of gas in CN or multiple gases combination.
Described columnar grain diameter dimension is preferably 80～150nm.
The gauge of described MT-TiCN layer is preferably 3～10 μ m.
Described carbon nitrogen source gas is CH
4, C
2h
6, C
2h
4, C
2h
2, N
2, CH
3two or more combination of gases in CN; Preferably more than three kinds or three kinds combination of gases.
Described carbon nitrogen source gas is to account for the N of the volume 1%～20% of mixed gas
2, account for the CH of the volume 0.2%～5% of mixed gas
3cN, account for the C of the volume 0%～6% of mixed gas
2h
4, account for the CH of the volume 0%～10% of mixed gas
4, account for the C of the volume 0%～6% of mixed gas
2h
6.
Described MT-TiCN layer is in reaction chamber, to pass into the mixed gas that contains carbon nitrogen source gas, and is 800～950 DEG C in temperature, and under the condition that pressure is 50～500mbar, deposition forms.
Described MT-TiCN layer is in reaction chamber, to pass into the mixed gas that contains carbon nitrogen source gas, and is preferably 850～930 DEG C in temperature, and pressure is preferably under the condition of 60～150mbar and deposits and form.
Described MT-TiCN layer is to grow above TiN layer, can provide good nucleating condition for MT-TiCN layer by effective control of the TiN processing parameter to TiN layer and thickness; The thickness of this TiN layer is 0.5 μ m～2 μ m, and depositing temperature is 850～950 DEG C.
The thickness of described TiN layer is preferably 0.5 μ m～1 μ m, and depositing temperature is preferably 890-915 DEG C.
In described coating, be also included in the Al that described MT-TiCN layer applies above
2o
3, HT-TiCN, TiN, the simple layer of TiO, ZrCN or the composite bed of multiple layer combination, the total coating thickness increasing is 1～20 μ m.
A kind of cutter coat with the nanometer column crystal that strengthens wear resistance and toughness of the present invention, significantly improves wear resistance and the shock resistance of the MT-TiCN coating of prior art by optimizing grain-size and microtexture.This improved coating is made up of nanometer column crystal.Can be by adopting CH
4, C
2h
6, C
2h
4, C
2h
2, N
2, CH
3cN guarantees the control to grain-size and shape as the combination of carbon nitrogen source.Must carefully control the portfolio ratio of each gas, to keep nanometer columnar crystal structure.Preferred columnar grain size should be in the region that its crystal grain width is 50～150nm, and long-width ratio should be greater than 10, is preferably greater than 20.Cutting tool coating toughness of the present invention is outstanding, wear resistance good, in the machining of the materials such as steel, cast iron, stainless steel, has excellent cutting ability.
Compared with prior art, the invention has the beneficial effects as follows:
The present invention does not pass through other element combinations doping (CO, CO by employing as prior art
2, ZrCl
4and AlCl
3) obtain MT-TiCN nanometer column crystal coating, but by regulating carbon nitrogen source ratio and the combination (CH in MT-TiCN coating
4, C
2h
6, C
2h
4, C
2h
2, N2, CH
3cN), control the impact of MT-TiCN coating on grain-size, shape and constitutive property, this has not only further improved homogeneity, hardness, abrasion resistance properties and the toughness of MT-TiCN coating, and avoid a kind of reverse Hall-Petch phenomenon, the hardness causing and the decline of abrasion resistance properties because of the too small appearance of grain-size.
MT-TiCN coating of the present invention is at TiN coatings growth, by the effective control to bottom TiN processing parameter and thickness, for MT-TiCN coating provides good nucleating condition, avoid the thick and abnormal growth of MT-TiCN coated grains, thereby obtain tiny uniform MT-TiCN coating.
Coating of the present invention is one of major function layer of cutting tool, and designed have a ultra-fine column crystal MT-TiCN coating, and MT-TiCN coating forms by having even compact grained columnar grain, and crystal grain diameter is 50～200nm, is preferably 80～150nm; MT-TiCN coat-thickness is 1～15 μ m, preferably 3～10 μ m; Match with other coating by the ultra-fine column crystal MT-TiCN coating after improving, this makes cutting tool of the present invention have very excellent wear resisting property and shock resistance.
Below in conjunction with drawings and Examples, the present invention is described in further detail; But a kind of cutter coat with the nanometer column crystal that strengthens wear resistance and toughness of the present invention is not limited to embodiment.
Brief description of the drawings
Fig. 1 is the surperficial electromicroscopic photograph of the ultra-fine column crystal MT-TiCN of the present invention coating;
Fig. 2 is the coating a section electromicroscopic photograph that contains the ultra-fine column crystal MT-TiCN of the present invention;
Fig. 3 is the surperficial electromicroscopic photograph of prior art MT-TiCN coating;
Fig. 4 is the coating b section electromicroscopic photograph that contains prior art MT-TiCN.
Embodiment
Embodiment
A kind of nanometer column crystal cutter coat that strengthens wear resistance and toughness that has of the present invention, comprises and adopts chemical vapour deposition mode to be deposited on one or more layers the coating on blade base; In described coating, at least contain one deck MT-TiCN layer; Described MT-TiCN layer has the columnar grain of uniform superfine crystalline grain, columnar grain diameter dimension is 50～200nm, long-width ratio is greater than 10, preferably be greater than 20, the gauge of MT-TiCN layer is 1～20 μ m, and this MT-TiCN layer is in reaction chamber, to pass into the mixed gas deposition that contains carbon nitrogen source gas to form, and described carbon nitrogen source gas is CH
4, C
2h
6, C
2h
4, C
2h
2, N
2, CH
3a kind of gas in CN or multiple gases combination.
Described columnar grain diameter dimension is preferably 80～150nm.
The gauge of described MT-TiCN layer is preferably 3～10 μ m.
Described carbon nitrogen source gas is CH
4, C
2h
6, C
2h
4, C
2h
2, N
2, CH
3two or more combination of gases in CN; Preferably more than three kinds or three kinds combination of gases.
Described carbon nitrogen source gas is to account for the N of the volume 1%～20% of mixed gas
2, account for the CH of the volume 0.2%～5% of mixed gas
3cN, account for the C of the volume 0%～6% of mixed gas
2h
4, account for the CH of the volume 0%～10% of mixed gas
4, account for the C of the volume 0%～6% of mixed gas
2h
6.
Described MT-TiCN layer is in reaction chamber, to pass into the mixed gas that contains carbon nitrogen source gas, and is 800～950 DEG C in temperature, and under the condition that pressure is 50～500mbar, deposition forms.
Described MT-TiCN layer is in reaction chamber, to pass into the mixed gas that contains carbon nitrogen source gas, and is preferably 850～930 DEG C in temperature, and pressure is preferably under the condition of 60～150mbar and deposits and form.
Described MT-TiCN layer is to grow above TiN layer, can provide good nucleating condition for MT-TiCN layer by effective control of the TiN processing parameter to TiN layer and thickness; The thickness of this TiN layer is 0.5 μ m～2 μ m, and depositing temperature is 850～950 DEG C.
The thickness of described TiN layer is preferably 0.5 μ m～1 μ m, and depositing temperature is preferably 890-915 DEG C.
In described coating, be also included in the Al that described MT-TiCN layer applies above
2o
3, HT-TiCN, TiN, the simple layer of TiO, ZrCN or the composite bed of multiple layer combination, the total coating thickness increasing is 1～20 μ m.
Below compare by concrete example and experiment, shock resistance of the present invention and wear resistance are described.
In keeping columnar crystal structure, reduce MT-TiCN coated grains size, in steel and cast iron, be significantly improved aspect wear resistance and in toughness than prior art MT-TiCN coating.According to coating of the present invention and TiN, Al
2o
3coating is in conjunction with the cutter coat that can customize various different purposes.Adopt modern CVD reactor to carry out in a controlled manner this technique at 800-920 DEG C.
Specific examples: component is 6% (mass percent) Co, the carbide cutting blade that surplus is WC, its surface-coated has TiN layer, MT-TiCN layer, α-Al
2o
3layer, the thickness of each layer is respectively 0.5～1 μ m, 7～9 μ m, 6～8 μ m.Detailed MT-TiCN layer is that a layer process parameter is as shown in table 1.
Table 1
| Step | ? | TiCl 4 | N 2 | CH 3CN | CH 4 | C 2H 4 | C 2H 6 | H 2 | Pressure mbar | Temperature DEG C | Time min |
| 1 | TiN | 1.7 | 38 | ? | ? | ? | ? | Surplus | 160 | 900 | 80 |
| 2 | TiCN | 3 | 20 | 0.6 | 0～5 | 0～5 | 0～5 | Surplus | 80 | 880 | 250 |
Reference example, as a reference, according to prior art MT-TiCN coating, deposited coatings b, and the employing blade base same with coating a, same coating structure and same blade model, concrete technology parameter is as shown in table 2.
Table 2
| Step | ? | TiCl 4 | N 2 | CH 3CN | H 2 | Pressure mbar | Temperature DEG C | Time min |
| 1 | TiN | 1.7 | 38 | ? | Surplus | 160 | 900 | 80 |
| 2 | TiCN | 2.7 | 20 | 0.8 | Surplus | 80 | 880 | 300 |
Utilize scanning electron microscope to analyze MT-TiCN coating section, as shown in Figure 1, Figure 2, Figure 3, Figure 4.Determine the MT-TiCN coated grains pattern of coating a and coating b, as shown in table 3.
Table 3
Experiment one, carries out shock resistance experiment relatively to coating a and coating b, and experimental result is as shown in table 4.
Workpiece: the cylindrical rod material with 4 fault troughs: 45# steel blade model: WNMG080412;
Cutting parameter: V=150r/min, ap=2mm, F=0.20mm/r;
Table 4
| Sequence number | The trade mark | Time (min) | Number of shocks (inferior) | Remarks |
| 1 | Coating a (the present invention) | 10 | 6000 | Point of a knife is intact |
| 2 | Coating a (the present invention) | 10 | 6000 | Point of a knife is intact |
| 3 | Coating a (the present invention) | 10 | 6000 | Point of a knife is intact |
| 4 | Coating b prior art | 3 | 1800 | Collapse |
| 5 | Coating b prior art | 4.2 | 2520 | Collapse |
| 6 | Coating b prior art | 5 | 3000 | Collapse |
As can be seen from Table 4, the Toughness Ratio prior art coating b of coating a of the present invention is good.
Experiment two, is used the mode of water-cooled to carry out cutting experiment to QT500 spheroidal graphite cast iron, thus checking coating a and coating b wear resisting property, and experimental result is as shown in table 5.
Workpiece: cylindrical rod material: QT500 cast iron blade model: WNMG080412
Cutting parameter: V=300m/min, ap=3mm, F=0.20mm/r
Cutter life standard: corner wear amount exceedes 0.3mm.
Table 5
As can be seen from Table 5, the wear resisting property of coating a of the present invention is better than prior art coating b.
Can find out that from above-mentioned specific examples MT-TiCN nanometer column crystal coating of the present invention has better toughness and wear resisting property than existing technology.
The present invention does not pass through other element combinations doping (CO, CO by employing as prior art
2, ZrCl
4and AlCl
3) obtain MT-TiCN nanometer column crystal coating, but by regulating carbon nitrogen source ratio and the combination (CH in MT-TiCN coating
4, C
2h
6, C
2h
4, C
2h
2, N2, CH
3cN), control the impact of MT-TiCN coating on grain-size, shape and constitutive property, this has not only further improved homogeneity, hardness, abrasion resistance properties and the toughness of MT-TiCN coating, and avoid a kind of reverse Hall-Petch phenomenon, the hardness causing and the decline of abrasion resistance properties because of the too small appearance of grain-size.
MT-TiCN coating of the present invention is at TiN coatings growth, by the effective control to bottom TiN processing parameter and thickness, for MT-TiCN coating provides good nucleating condition, thereby avoid coarsening and the abnormal growth of MT-TiCN coated grains, thereby obtain tiny uniform MT-TiCN coating.
Coating of the present invention is one of major function layer of cutting tool, and designed have a ultra-fine column crystal MT-TiCN coating, and MT-TiCN coating forms by having even compact grained columnar grain, and crystal grain diameter is 50～200nm, is preferably 80～150nm; MT-TiCN coat-thickness is 1～15 μ m, preferably 3～10 μ m; Match with other coating by the ultra-fine column crystal MT-TiCN coating after improving, this makes cutting tool of the present invention have very excellent wear resisting property and shock resistance.
A kind of cutter coat with the nanometer column crystal that strengthens wear resistance and toughness of the present invention, significantly improves wear resistance and the shock resistance of the MT-TiCN coating of prior art by optimizing grain-size and microtexture.This improved coating is made up of nanometer column crystal.Can be by adopting CH
4, C
2h
6, C
2h
4, C
2h
2, N
2, CH
3cN guarantees the control to grain-size and shape as the combination of carbon nitrogen source.Must carefully control the portfolio ratio of each gas, to keep nanometer columnar crystal structure.Preferred columnar grain size should be in the region that its crystal grain width is 50～150nm, and long-width ratio should be greater than 10, is preferably greater than 20.Cutting tool coating toughness of the present invention is outstanding, wear resistance good, in the machining of the materials such as steel, cast iron, stainless steel, has excellent cutting ability.
Above-described embodiment is only used for further illustrating a kind of cutter coat with the nanometer column crystal that strengthens wear resistance and toughness of the present invention; but the present invention is not limited to embodiment; any simple modification, equivalent variations and modification that every foundation technical spirit of the present invention is done above embodiment, all fall in the protection domain of technical solution of the present invention.
Claims (10)
1. there is a nanometer column crystal cutter coat that strengthens wear resistance and toughness, comprise and adopt chemical vapour deposition mode to be deposited on one or more layers the coating on blade base; In described coating, at least contain one deck MT-TiCN layer; It is characterized in that: described MT-TiCN layer has the columnar grain of uniform superfine crystalline grain, columnar grain diameter dimension is 50～200nm, long-width ratio is greater than 10, the gauge of MT-TiCN layer is 1～20 μ m, and this MT-TiCN layer is in reaction chamber, to pass into the mixed gas deposition that contains carbon nitrogen source gas to form, and described carbon nitrogen source gas is CH
4, C
2h
6, C
2h
4, C
2h
2, N
2, CH
3a kind of gas in CN or multiple gases combination.
2. nanometer column crystal cutter coat according to claim 1, is characterized in that: described columnar grain diameter dimension is 80～150nm.
3. nanometer column crystal cutter coat according to claim 1, is characterized in that: the gauge of described MT-TiCN layer is 3～10 μ m.
4. nanometer column crystal cutter coat according to claim 1, is characterized in that: described carbon nitrogen source gas is CH
4, C
2h
6, C
2h
4, C
2h
2, N
2, CH
3two or more combination of gases in CN.
5. nanometer column crystal cutter coat according to claim 4, is characterized in that: described carbon nitrogen source gas is to account for the N of the volume 1%～20% of mixed gas
2, account for the CH of the volume 0.2%～5% of mixed gas
3cN, account for the C of the volume 0%～6% of mixed gas
2h
4, account for the CH of the volume 0%～10% of mixed gas
4, account for the C of the volume 0%～6% of mixed gas
2h
6.
6. nanometer column crystal cutter coat according to claim 1, it is characterized in that: described MT-TiCN layer is in reaction chamber, to pass into the mixed gas that contains carbon nitrogen source gas, and be 800～950 DEG C in temperature, under the condition that pressure is 50～500mbar, deposition forms.
7. nanometer column crystal cutter coat according to claim 6, it is characterized in that: described MT-TiCN layer is in reaction chamber, to pass into the mixed gas that contains carbon nitrogen source gas, and be 850～930 DEG C in temperature, under the condition that pressure is 60～150mbar, deposition forms.
8. nanometer column crystal cutter coat according to claim 1, is characterized in that: described MT-TiCN layer is to grow above TiN layer, can provide good nucleating condition for MT-TiCN layer by effective control of the TiN processing parameter to TiN layer and thickness; The thickness of this TiN layer is 0.5 μ m～2 μ m, and depositing temperature is 850～950 DEG C.
9. nanometer column crystal cutter coat according to claim 8, is characterized in that: the thickness of described TiN layer is 0.5 μ m～1 μ m, and depositing temperature is 890-915 DEG C.
10. nanometer column crystal cutter coat according to claim 1, is characterized in that: in described coating, be also included in the Al that described MT-TiCN layer applies above
2o
3, HT-TiCN, TiN, the simple layer of TiO, ZrCN or the composite bed of multiple layer combination, the total coating thickness increasing is 1～20 μ m.
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