CN104060143A - Method for preparing nitrogen-enriched functional gradient metal ceramic by low pressure nitriding method - Google Patents
Method for preparing nitrogen-enriched functional gradient metal ceramic by low pressure nitriding method Download PDFInfo
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Abstract
The invention discloses a method for preparing nitrogen-enriched functional gradient metal ceramic by a low pressure nitriding method. The metal ceramic prepared by the method is Ti(C, N)-based metal ceramic which takes Ti(C, N) and/or TiC and TiN as a main hard phase and metals in the iron group such as Co and/or Ni and the like as a bonding phase. The method disclosed by the invention comprises the steps of filling a metal ceramic sintering body in a vacuum integrated furnace; in a vacuum sintering state, heating to a predetermined nitriding temperature at a heating speed being 3-7 DEG C/min, wherein the predetermined nitriding temperature is 1200-1400 DEG C; when the furnace temperature reaches the predetermined nitriding temperature, nitriding by adopting a nitrogen partial pressure sintering process, controlling the partial pressure at 2000-6000Pa, preserving the heat for 2-6 hours, and cooling in a nitrogen atmosphere to obtain the surface nitrogen-enriched functional gradient metal ceramic. The method disclosed by the invention has the characteristics of less investment, low production cost and high efficiency, and is easy to realize industrialized conversion.
Description
Technical field
The present invention relates to ceramic-metallic preparing technical field, particularly relate to a kind of method that low pressure nitriding process is prepared rich nitrogen functionally graded metal pottery.
Background technology
Ti (C, N) based ceramic metal has higher hardness, wear resistance, and red hardness possesses excellent high-temperature behavior and chemical stability simultaneously.As cutter base material, sintering metal is widely used in the precision work of the materials such as steel class because of its good processing characteristics, contrast traditional inserted tool, the hardness that it is higher and chemical stability can realize High-speed machining, improve working (machining) efficiency, and workpiece to be machined has good surface smoothness.But, be worth pointing out to such an extent that be, the relatively low fracture toughness property of sintering metal has greatly limited its application.
Coating technology is undoubtedly a kind of better means that improve sintering metal use properties.But due to the difference of tool matrix and coating thermal expansivity, make coating in process of cooling, easily occur crackle and make crack propagation in matrix, thereby affect cutter life.Adding coating need increase coating furnace and corresponding pre-process and post-process equipment, has also increased the Production Flow Chart of cutter, has improved production cost.
For the defect of avoiding coating to bring, the sintering metal tissue that a kind of surface has rich nitrogen gradient layer is developed, because rich nitrogen gradient is to generate on matrix, moiety from outward appearance to inner essence changes in gradient, there is no sharp interface, the problem of Presence of an interface bonding strength and disbonding not, such alloy has shown good use properties.
But, so far, the method for the preparation of rich surface nitrogen functionally graded metal pottery of bibliographical information is High Temperature High Pressure nitriding process, and nitriding time long (>=10h), using low pressure furnace or hot isostatic pressing stove as nitriding equipment, and facility investment is large, has certain potential safety hazard, production efficiency is low, has suppressed the industrial application of rich surface nitrogen functionally graded metal stupalith.
Patent CN1603280A has proposed the method for High Temperature High Pressure short period of time a kind of and has prepared case-hardened functionally graded metal pottery, although nitriding time has been foreshortened to 1～2h, but its nitriding pressure is up to 90～130MPa, must adopt hot isostatic pressing stove, not only increase equipment cost, and brought high top pressure operation risk.In patent CN1772701A, propose under the lower nitriding pressure of 0.08MPa, to realize the preparation of gradient metal ceramic, but according to its patent specification, nitriding time reaches 24h, production efficiency is low.In addition, also there is patent to propose, the method that can fill out paving by layering realizes the preparation (CN101838766A) of gradient metal ceramic, but first its preparation process needs to prepare respectively the compound of various moietys, secondly in pressing process, needing that compound is carried out to meticulous layering fills out paving, cause preparation process technique loaded down with trivial details, be difficult to be applied to batch production.
Summary of the invention
The object of the invention is to overcome the deficiency of prior art, provide a kind of low pressure nitriding process to prepare the method for rich nitrogen functionally graded metal pottery, in vacuum all-in-one oven, adopt low pressure nitridation process, controlling under suitable nitriding temperature, can be in relatively short nitriding time, realize the preparation of rich surface nitrogen gradient metal ceramic, it is little that the inventive method has facility investment, and the feature that production cost is low is easy to realize the suitability for industrialized production of rich surface nitrogen functionally graded metal stupalith.
The technical solution adopted for the present invention to solve the technical problems is: a kind of low pressure nitriding process is prepared the method for rich nitrogen functionally graded metal pottery, that sintered cermet is packed in vacuum all-in-one oven, under vacuum sintering state, with the heat-up rate of 3～7 ℃/min, rise to preset nitriding temperature; When furnace body temperature reaches preset nitriding temperature, adopt nitrogen partial pressure sintering process to carry out nitriding, controlling a minute pressure pressure is 2000～6000Pa, after insulation 2～6h, cooling under nitrogen atmosphere, obtains rich surface nitrogen functionally graded metal pottery.
Described preset nitriding temperature is 1200～1400 ℃.
Further, be under vacuum sintering state, with the heat-up rate of 5 ℃/min, rise to preset nitriding temperature.
The rich nitrogen functionally graded metal pottery of described preparation, has component gradient from outward appearance to inner essence, rich surface N, and the Binder Phases such as poor Co and/or Ni, alloy bending strength reaches 2200～2500MPa simultaneously, and surface graded layer thickness is 5～15 μ m.
A kind of low pressure nitriding process of the present invention is prepared the method for rich nitrogen functionally graded metal pottery, sintering metal is Ti (C, N) based ceramic metal, with Ti (C, N) and/or TiC, TiN is main hard phase, take the iron family metals such as Co and/or Ni is Binder Phase, contain simultaneously a certain amount of other two classes carbide (containing WC, NbC, TaC, Mo
2c, Cr
3c
2, VC etc. one or more).First the inventive method obtains sintering metal dense sintering body through batching-wet-milling batch mixing-compression moulding-degreasing-vacuum (or dividing potential drop) sintering, and then obtained sintered compact is placed in to nitrogen atmosphere carries out low pressure nitriding treatment, thereby obtain rich surface nitrogen functionally graded metal stupalith.
Compared with prior art, the invention has the beneficial effects as follows:
The method that is applied in the world at present to prepare rich surface nitrogen gradient metal ceramic is high pressure-temperature nitriding process, and equipment used is low pressure furnace or hot isostatic pressing stove, and equipment cost is high, and the production time is long, cannot be applied to suitability for industrialized production; The present invention is on to the basis of sintering metal property research, creativeness has proposed low pressure nitriding process, utilize vacuum all-in-one oven, under nitrogen partial pressure sintering condition, (a minute pressure pressure is set to 2000～6000Pa), keeps suitable nitriding temperature (being generally 1200～1400 ℃) and the time (2～6h), can realize the preparation of rich surface nitrogen gradient metal ceramic alloy, it is little that the inventive method has investment, production cost is low, and the feature that efficiency is high is easy to realize industrialization and transforms.
The gradient metal ceramic that adopts the inventive method to prepare, surface graded layer thickness can reach 5～15 μ m, and can realize the controllable adjustment of Thickness of Gradient Layer; With matrix phase ratio, surface graded layer has relatively high hardness.It is worthy of note, above-mentioned gradient treatment process, little on material surface smooth finish impact, so this processing method can be directly used in the processing to fine work ceramic tip, the gradient metal ceramic blade of acquisition, without any aftertreatment, can directly be used.
Below in conjunction with drawings and Examples, the present invention is described in further detail; But the method that a kind of low pressure nitriding process of the present invention is prepared rich nitrogen functionally graded metal pottery is not limited to embodiment.
Accompanying drawing explanation
Fig. 1 is the photo of sintering metal textura epidermoidea structure after nitriding;
Fig. 2 is the photo of sintering metal textura epidermoidea structure before nitriding;
Fig. 3 is the EPMA analysis chart of gradient metal ceramic.
Embodiment
Embodiment
A kind of low pressure nitriding process of the present invention is prepared the method for rich nitrogen functionally graded metal pottery, is sintered cermet is packed in vacuum all-in-one oven, under vacuum sintering state, with certain heat-up rate, rises to preset nitriding temperature; When furnace body temperature reaches preset nitriding temperature, adopt nitrogen partial pressure sintering process to carry out nitriding, by controls, divide pressure pressure and soaking time, then, cooling under nitrogen atmosphere, acquisition rich surface nitrogen functionally graded metal is ceramic.
The rich nitrogen functionally graded metal pottery of described preparation, has component gradient from outward appearance to inner essence, rich surface N, and the Binder Phases such as poor Co and/or Ni, alloy bending strength reaches 2200～2500MPa, and surface graded layer thickness is 5～15 μ m.
A kind of low pressure nitriding process of the present invention is prepared the method for rich nitrogen functionally graded metal pottery, sintering metal is Ti (C, N) based ceramic metal, with Ti (C, N) and/or TiC, TiN is main hard phase, take the iron family metals such as Co and/or Ni is Binder Phase, contain simultaneously a certain amount of other two classes carbide (containing WC, NbC, TaC, Mo
2c, Cr
3c
2, VC etc. one or more).First the inventive method obtains sintering metal dense sintering body through batching-wet-milling batch mixing-compression moulding-degreasing-vacuum (or dividing potential drop) sintering, and then obtained sintered compact is placed in to nitrogen atmosphere carries out low pressure nitriding treatment, thereby obtain rich surface nitrogen functionally graded metal stupalith.
Table 1 is the present invention's two kinds of ceramic-metallic component prescriptions used, and unit is wt%.
Table 1
| Ti(C 0.5N 0.5) | WC | NbC | Mo 2C | TaC | Co | Ni | |
| 1# | 55 | 15 | 7 | 9 | 0 | 7 | 7 |
| 2# | 57 | 20 | 3 | 3 | 3 | 8 | 6 |
Embodiment mono-
(1) batching+wet-milling: according to 1# formula in table 1, selecting mean particle size is Ti (CN) powder of 1～1.5um, with the powder of about other mean particle sizes 1um be raw material, batching, take alcohol as grinding medium, using paraffin as forming agent, paraffin addition accounts for total weight of material 4%, grind ratio of grinding media to material 7:1, milling time 72 hours.
(2) spraying is dry: the slip spraying of step (1) gained is dry, and the RTP compound of acquisition mean particle size 100um left and right.
(3) moulding+sintering: the compound of step (2) gained is suppressed, and pressing pressure 150Mpa, then enters vacuum oven and carry out sintering, 1400～1500 ℃ of sintering temperatures, obtain densified sintering product body alloy.
(4) gradient is processed: step (3) gained cermet is packed in vacuum all-in-one oven, sintering temperature with 5 ℃/min, under vacuum condition, be warming up to 1200 ℃, then go to dividing potential drop sintering, a minute pressure pressure is 6000Pa, and sintering atmosphere is nitrogen atmosphere, nitrogen gas purity is more than 99%, soaking time is 2h, can obtain rich surface nitrogen functionally graded metal ceramal, and wherein surface graded layer thickness is 5 μ m left and right.
Under above-mentioned technique, respectively as shown in Table 2 and Figure 1, Fig. 2 is sintering metal textura epidermoidea structure iron before nitriding for the performance of the gradient metal ceramic of preparation and tissue.
Table 2
Embodiment bis-
The cermet composition that the present embodiment adopts is with embodiment mono-, and its gradient treatment process is as follows:
Cermet is packed in vacuum all-in-one oven, sintering temperature with 5 ℃/min, under vacuum condition, be warming up to 1300 ℃, then go to dividing potential drop sintering, a minute pressure pressure is 6000Pa, and sintering atmosphere is nitrogen atmosphere, nitrogen gas purity is more than 99%, soaking time is 6h, can obtain rich surface nitrogen functionally graded metal ceramal, and wherein surface graded layer thickness is 15 μ m left and right.
The surface graded cermet that adopts above technique to prepare, its performance is as shown in table 3.
Table 3
Surface graded layer is carried out to EDS analysis with matrix, and its component difference is as shown in table 4.
Table 4
| C | N | Nb | Mo | Ti | Co | Ni | W | |
| Gradient layer | 11.6 | 7.1 | 8 | 6.5 | 50 | 5 | 4.5 | 7.3 |
| Matrix | 10 | 4 | 3.5 | 8.5 | 35 | 13 | 12.5 | 13.5 |
Embodiment tri-
(1) batching+wet-milling: according to 2# formula in table 1, selecting mean particle size is Ti (CN) powder of 1～1.5um, powder with other mean particle sizes 1um left and right, batching, take alcohol as grinding medium, using paraffin as forming agent, paraffin addition accounts for total weight of material 4%, grind ratio of grinding media to material 7:1, milling time 72 hours.
(2) spraying is dry: the slip spraying of step (1) gained is dry, and the RTP compound of acquisition mean particle size 100um left and right.
(3) moulding+sintering: the compound of step (2) gained is suppressed, and pressing pressure 150Mpa, then enters vacuum oven vacuum sintering, 1400～1500 ℃ of sintering temperatures, obtain densified sintering product body alloy.
(4) gradient is processed: step (3) gained cermet is packed in vacuum all-in-one oven, sintering temperature with 5 ℃/min, under vacuum condition, be warming up to 1300 ℃, then go to dividing potential drop sintering, a minute pressure pressure is 6000Pa, and sintering atmosphere is nitrogen atmosphere, nitrogen gas purity is more than 99%, soaking time is 6h, can obtain rich surface nitrogen functionally graded metal ceramal, and wherein surface graded layer thickness is 5 μ m left and right.
The surface graded cermet that adopts above technique to prepare, its performance is as shown in table 5.
Table 5
Surface graded sintering metal prepared by above technique carries out EPMA analysis, and its result as shown in Figure 3.
The present invention is on to the basis of sintering metal property research, creativeness has proposed low pressure nitriding process, utilize vacuum all-in-one oven, under nitrogen partial pressure sintering condition, (a minute pressure pressure is set to 2000～6000Pa), keeps suitable nitriding temperature (being generally 1200～1400 ℃) and the time (2～6h), can realize the preparation of rich surface nitrogen gradient metal ceramic alloy, it is little that the inventive method has investment, production cost is low, and the feature that efficiency is high is easy to realize industrialization and transforms.
Above-mentioned is preferred embodiment of the present invention, not the present invention is done to any pro forma restriction.Although the present invention discloses as above with preferred embodiment, yet not in order to limit the present invention.Any those of ordinary skill in the art, in the situation that not departing from technical solution of the present invention scope, can utilize the technology contents of above-mentioned announcement to make many possible changes and modification to technical solution of the present invention, or the equivalent embodiment of assimilation such as are revised as.Therefore, every content that does not depart from technical solution of the present invention,, all should drop in the scope of technical solution of the present invention protection any simple modification made for any of the above embodiments, equivalent variations and modification according to the technology of the present invention essence.
Claims (5)
1. low pressure nitriding process is prepared a method for rich nitrogen functionally graded metal pottery, it is characterized in that: be that sintered cermet is packed in vacuum all-in-one oven, under vacuum sintering state, with the heat-up rate of 3～7 ℃/min, rise to preset nitriding temperature; When furnace body temperature reaches preset nitriding temperature, adopt nitrogen partial pressure sintering process to carry out nitriding, controlling a minute pressure pressure is 2000～6000Pa, after insulation 2～6h, cooling under nitrogen atmosphere, obtains rich surface nitrogen functionally graded metal pottery.
2. low pressure nitriding process according to claim 1 is prepared the method for rich nitrogen functionally graded metal pottery, it is characterized in that: described preset nitriding temperature is 1200～1400 ℃.
3. low pressure nitriding process according to claim 1 and 2 is prepared the method for rich nitrogen functionally graded metal pottery, it is characterized in that: further, be under vacuum sintering state, with the heat-up rate of 5 ℃/min, rise to preset nitriding temperature.
4. low pressure nitriding process according to claim 1 and 2 is prepared the method for rich nitrogen functionally graded metal pottery, it is characterized in that: the rich nitrogen functionally graded metal pottery of described preparation, there is component gradient from outward appearance to inner essence, rich surface N, poor Co and/or Ni Binder Phase, alloy bending strength reaches 2200～2500MPa, and surface graded layer thickness is 5～15 μ m.
5. low pressure nitriding process according to claim 3 is prepared the method for rich nitrogen functionally graded metal pottery, it is characterized in that: the rich nitrogen functionally graded metal pottery of described preparation, there is component gradient from outward appearance to inner essence, rich surface N, poor Co and/or Ni Binder Phase, alloy bending strength reaches 2200～2500MPa, and surface graded layer thickness is 5～15 μ m.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106083203A (en) * | 2016-06-03 | 2016-11-09 | 哈尔滨东安发动机（集团）有限公司 | A kind of method for nitridizing surfaces of ternary layered ceramic |
| CN110343993A (en) * | 2019-08-07 | 2019-10-18 | 广东工业大学 | A kind of carbide surface processing method and application |
| CN110387544A (en) * | 2019-07-17 | 2019-10-29 | 吉林大学 | A kind of TiCN cermet composite coating preparation method based on electric spark deposition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102011041A (en) * | 2010-12-24 | 2011-04-13 | 重庆市科学技术研究院 | Nitriding sintering technology for YT15 hard alloy |
| CN102134660A (en) * | 2011-03-04 | 2011-07-27 | 重庆文理学院 | Functionally gradient hard alloy with cubic phase-rich surface and preparation method thereof |
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2014
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102011041A (en) * | 2010-12-24 | 2011-04-13 | 重庆市科学技术研究院 | Nitriding sintering technology for YT15 hard alloy |
| CN102134660A (en) * | 2011-03-04 | 2011-07-27 | 重庆文理学院 | Functionally gradient hard alloy with cubic phase-rich surface and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106083203A (en) * | 2016-06-03 | 2016-11-09 | 哈尔滨东安发动机（集团）有限公司 | A kind of method for nitridizing surfaces of ternary layered ceramic |
| CN106083203B (en) * | 2016-06-03 | 2021-09-10 | 哈尔滨东安发动机（集团）有限公司 | Surface nitriding method of ternary layered ceramic |
| CN110387544A (en) * | 2019-07-17 | 2019-10-29 | 吉林大学 | A kind of TiCN cermet composite coating preparation method based on electric spark deposition |
| CN110387544B (en) * | 2019-07-17 | 2021-06-18 | 吉林大学 | Preparation method of titanium carbonitride metal ceramic composite coating based on electric spark deposition |
| CN110343993A (en) * | 2019-08-07 | 2019-10-18 | 广东工业大学 | A kind of carbide surface processing method and application |
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