CN104131192A - Ti(C,N)-based metal ceramic with gradient structure and plasma-nitriding preparation method thereof - Google Patents
Ti(C,N)-based metal ceramic with gradient structure and plasma-nitriding preparation method thereof Download PDFInfo
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Abstract
The invention discloses a Ti(C,N)-based metal ceramic with a gradient structure and a plasma-nitriding preparation method thereof. The metal ceramic comprises the following components by mass: 6.5 to 7.5 parts of C, 1.5 to 2.5 parts of N, 36 to 45 parts of Ti, 25 to 32 parts of Ni, 13 to 18 parts of Mo and 6 to 10 parts of W. The preparation method for the metal ceramic comprises the following steps: (1) preparing a mixture; (2) successively carrying out mixing, addition of a forming agent, compression molding, vacuum degreasing and vacuum sintering so as to prepare a compact metal ceramic sintered body; and (3) subjecting the sintered body prepared in the step (2) to plasma nitriding in a plasma nitriding furnace equipped with a high temperature auxiliary heating device, carrying out vacuum pumping on an operating chamber until the operating chamber has a pressure of less than 10 Pa and introducing mixed gas of Ar and N2, wherein total air pressure is 120 to 180 Pa, a flow ratio of Ar to N2 (PAr/PN2) is 1/2, workpiece voltage is 500 to 700 V, treating temperature is 1140 to 1200 DEG C and treating time is 3 to 5 h. The prepared metal ceramic has high bending strength and high surface hardness, wherein sigma b is no less than 1750 MPa and surface hardness is no less than 1700 HV.
Description
Technical field
The present invention relates to a kind of gradient-structure Ti (C, N) based ceramic metal, the invention still further relates to and adopt the plasma nitrided method of preparing gradient-structure Ti (C, N) based ceramic metal, belong to stupalith and preparation method thereof technical field.
Background technology
Ti (C, N) based ceramic metal not only has higher hardness, wear resistance, red hardness, good chemical stability, the frictional coefficient low with metal compole, and also has certain toughness and intensity.Compare with cutting tool coated with hard alloy material with most popular Wimet in current manufacture manufacture field, it has obvious advantage in the following aspects: it can allow higher cutting speed, there is the larger depth of cut, better wear resisting property, work piece has good surface property; In addition, this material does not contain or less containing strategic substance C o and valuable compound WC, the raw materials overwhelming majority is conventional, the easy element obtaining, and manufacturing process is similar to Wimet, thereby its total cost is cheaply many.Tool Industry in Japan, Sweden is used in a large number.The main trade mark of Japanese market is in table 1.US and European is about Ti (C in recent years, N) research of based ceramic metal and application also sharply increase, also the have high input amount of measuring one's own ability developed the Ti (C of some trades mark of relevant department of China, N) based ceramic metal, its product can partly replace the inserted tool such as YG8, YT15 in cutting field.Ti (C, N) based ceramic metal has shown its great potential as the upgrading equivalent material of traditional WC-Co Wimet.
But the problem reflecting is at present still obdurability deficiency, as unstable in the product performance of China's development, particularly in keeping higher hardness, obdurability is poor, market consumption is few, thereby the superiority that this kind of material should be had in theory do not give full play to, and limit its use range.
The ceramic-metallic trade mark and the performance on table 1 Japanese market, commonly used
Prepare high performance homogeneous sintering metal is the emphasis of material supplier author's research always.The main method adopting is to optimize composition and the preparation technology of material; Test new forming technique and sintering technology; Improve the control accuracy of producing apparatus.Particularly in recent years, the research aspect of exploitation Investigation for Super-fine Cermets has obtained the progress attracting people's attention.But the same with traditional Wimet, ceramic-metallic wear resistance and obdurability always exist contradiction: wear resistance is higher, obdurability is lower, and vice versa.The material of heterogeneous texture shows obvious performance advantage.Therefore, further improve ceramic-metallic performance and expand its range of application, development composition and microstructure distribution gradient, rich surface is containing wear-resisting hard phase and the inner sintering metal that is rich in the Binder Phase of toughness seems particularly necessary.
The usual practice that solves above-mentioned contradiction is in the preferably coating of metal ceramic surface coating high rigidity of obdurability by the method for PVD and CVD.But, between the upper layer of resulting materials and matrix, all exist obvious interface at the aspect such as composition and microtexture like this, in the time carrying out high speed cutting, cementation zone easily peels off, easily tipping.And due to the thermal expansivity difference of differing materials, coating tool materials impact due to thermal stresses in process of cooling easily cracks, crackle easily produces and to material internal expansion, finally causes material failure from coatingsurface.In view of the foregoing, have human hair to understand by carry out the method that functionally graded metal pottery is prepared in surfaces nitrided processing in high temperature nitrogen environment, but the method technological process is longer, preparation efficiency is lower, and surface function gradient layer is thinner.
Summary of the invention
The object of the invention is the present situation for prior art, provide a kind of surface to there is very high hardness, wear resistance, red hardness, and heart portion has gradient-structure Ti (C, N) based ceramic metal and the high efficiency preparation method thereof of higher-strength.
To achieve these goals, technical scheme of the present invention is:
A kind of gradient-structure Ti (C, N) based ceramic metal, its composition quality umber is: C is that 6.5～7.5, N is that 1.5～2.5, Ti is that 36～45, Ni is that 25～32, Mo is that 13～18, W is 6～10.The raw material adopting is (Ti, Mo, W) (C, N), C, NiMo powder.
The present invention adopts the Ti (C of the relatively high and low non-normal tissue in normal carbon amount of Ni content, N) based ceramic metal is matrix, then adopt plasma nitrided method to prepare and in textura epidermoidea, be rich in TiN, Ti (C, the hard phase such as N), core is rich in Ni, the sintering metal of hard phase and metallic binding phase distribution gradient.Make the core of material have higher intensity, surface has higher hardness and wear resistance.Realize this purpose Ti (C, N) based ceramic metal, be characterized in, in moiety, C, N content are lower, are starkly lower than the sintering metal compound of normal range, and metal Ni content is higher.
The plasma nitrided gradient-structure Ti (C for preparing of the present invention, N) method of based ceramic metal, first preparation meets the compound of composition requirement, obtain sintered compact through batch mixing, moulding, degreasing, vacuum sintering successively, after its polishing and cleaning, pack in the plasma nitrided stove with high temperature assisted heating device and carry out nitriding processing.
Specifically comprise the steps:
(1) preparation meets the compound of following requirement, and its composition mass fraction is: C is that 6.5～7.5, N is that 1.5～2.5, Ti is that 36～45, Ni is that 25～32, Mo is that 13～18, W is 6～10.All the components is introduced by (Ti, Mo, W) (C, N), C, NiMo powder;
(2) batch mixing, compounding process carries out in planetary ball mill, and drum's speed of rotation is 180rpm, and the time is 24h;
(3) add forming agent, the forming agent adding is that concentration is the polyvinyl alcohol water solution of 7mass%, 3mass%～7mass% that additional proportion is compound;
(4) compression moulding, pressing pressure used is 250MPa;
(5) degreasing, carries out in higher than the vacuum oven of 10Pa in vacuum tightness, and the heat-up rate between 200～450 DEG C is 0.3～0.5 DEG C/min;
(6) vacuum sintering is carried out in vacuum sintering furnace, and vacuum tightness is higher than 5.0 × 10
-2pa, sintering temperature is 1410～1440 DEG C, soaking time is 50～70min;
(7) to carrying out plasma nitriding processing through above-mentioned operation gained sintered compact, in the plasma nitrided stove with high temperature assisted heating device, carry out, first working spaces is evacuated to the vacuum below 10Pa, being filled with Ar/N2 mixed gas does again, total gas pressure is 120～180Pa, two kinds of gas flow ratios are PAr/PN2=1/2, and workpiece voltage is 500～700V, nitriding treatment 3～5h at 1140～1200 DEG C.
Gradient-structure Ti of the present invention (C, N) based ceramic metal, Thickness of Gradient Layer is greater than 30 μ m, within the scope of the cementation zone of 10 μ m, its surface hardness>=1700HV, the bending strength σ of material
b>=1750MPa, not only have higher hardness, wear resistance, red hardness, good chemical stability, with the advantage such as the low frictional coefficient of metal compole, and its obdurability is also very good, not only can on the advanced lathe of good stability, use as cutter, can also be used for domestic common lathe, compared with the Wimet of same rigidity, it can allow the depth of cut to improve 2-3 doubly, cutting speed improves more than 2 times, in the time of high-speed dry type cutting normalized steel, its durability can improve more than 6 times; With coated carbides and coating metal ceramic phase ratio, its composition and microstructure are mild to the transition of heart portion from material surface, there is no obvious interface, do not have the problem that causes disbonding because interface bond strength is low; The thickness of surface graded layer is thicker, more much bigger than the thickness of current common technology gained hard coat; Compared with coated carbides, this gradient-structure sintering metal can be saved the expensive resource such as WC, Co, and its manufacturing cost reduces greatly.
Embodiment
The raw material that following instance adopts is introduced by (Ti, Mo, W) (C, N), C, NiMo and plate-like WC powder.
Table 2 is compounds of 4 kinds of component prescriptions.Adopt respectively different processing parameters to be prepared into gradient-structure Ti (C, N) based ceramic metal, and measure respectively its surface hardness and bending strength.
The composition proportion of table 24 kind of compound
Embodiment 1
Prepare respectively compound by table 2, the compounding process of each compound carries out in planetary ball mill, and drum's speed of rotation is 180rpm, and the time is 24h; The add-on of the polyvinyl alcohol water solution of forming agent 7mass% is 3mass%, and compression moulding pressure used is 250MPa; Degreasing process carries out under higher than the condition of 10Pa in vacuum tightness, and the heat-up rate between 200-450 DEG C is 0.3 DEG C/min; The vacuum tightness of vacuum sintering is higher than 5.0 × 10
-2pa, sintering temperature is 1410 DEG C, soaking time is 70min.
Plasma nitriding is processed and is carried out in the plasma nitrided stove with high temperature assisted heating device, first working spaces is evacuated to the vacuum below 10Pa, then is filled with Ar/N
2mixed gas, total gas pressure is 120Pa, two kinds of gas flow ratios are P
ar/ P
n2=1/2, operating voltage is 500V, and treatment temp is 1140 DEG C, and the treatment time is 5h.
Under above-mentioned preparation process condition, the ceramic-metallic performance of heterogeneity proportioning is in table 3.
The performance of the different metal pottery that table 3 adopting process 1 is prepared
Embodiment 2
Prepare respectively compound by table 2, the compounding process of each compound carries out in planetary ball mill, and drum's speed of rotation is 180rpm, and the time is 24h; The add-on of the polyvinyl alcohol water solution of forming agent 7mass% is 5mass%, and compression moulding pressure used is 250MPa; Degreasing process carries out under higher than the condition of 10Pa in vacuum tightness, and the heat-up rate between 200-450 DEG C is 0.4 DEG C/min; The vacuum tightness of vacuum sintering is higher than 5.0 × 10
-2pa, sintering temperature is 1420 DEG C, soaking time is 60min.
Plasma nitriding is processed and is carried out in the plasma nitrided stove with high temperature assisted heating device, first working spaces is evacuated to the vacuum below 10Pa, then is filled with Ar/N
2mixed gas, total gas pressure is 140Pa, two kinds of gas flow ratios are P
ar/ P
n2=1/2, operating voltage is 600V, and treatment temp is 1160 DEG C, and the treatment time is 5h.
Under above-mentioned preparation process condition, the ceramic-metallic performance of heterogeneity proportioning is in table 4.
The performance of the different metal pottery that table 4 adopting process 1 is prepared
Embodiment 3
Prepare respectively compound by table 2, the compounding process of each compound carries out in planetary ball mill, and drum's speed of rotation is 180rpm, and the time is 24h; The add-on of the polyvinyl alcohol water solution of forming agent 7mass% is 7mass%, and compression moulding pressure used is 250MPa; Degreasing process carries out under higher than the condition of 10Pa in vacuum tightness, and the heat-up rate between 200-450 DEG C is 0.5 DEG C/min; The vacuum tightness of vacuum sintering is higher than 5.0 × 10
-2pa, sintering temperature is 1430 DEG C, soaking time is 50min.
Plasma nitriding is processed and is carried out in the plasma nitrided stove with high temperature assisted heating device, first working spaces is evacuated to the vacuum below 10Pa, then is filled with Ar/N
2mixed gas is done, and total gas pressure is 160Pa, and two kinds of gas flow ratios are P
ar/ P
n2=1/2, operating voltage: 700V, treatment temp is 1180 DEG C, the treatment time is 4h.
Under above-mentioned preparation process condition, the ceramic-metallic performance of heterogeneity proportioning is in table 5.
The performance of the different metal pottery that table 5 adopting process 1 is prepared
Embodiment 4
Prepare respectively compound by table 2, the compounding process of each compound carries out in planetary ball mill, and drum's speed of rotation is 180rpm, and the time is 24h; The add-on of the polyvinyl alcohol water solution of forming agent 7mass% is 7mass%, and compression moulding pressure used is 250MPa; Degreasing process carries out under higher than the condition of 10Pa in vacuum tightness, and the heat-up rate between 200-450 DEG C is 0.3 DEG C/min; The vacuum tightness of vacuum sintering is higher than 5.0 × 10
-2pa, sintering temperature is 1440 DEG C, soaking time is 50min.
Plasma nitriding is processed and is carried out in the plasma nitrided stove with high temperature assisted heating device, first working spaces is evacuated to the vacuum below 10Pa, then is filled with Ar/N
2mixed gas is done, and total gas pressure is 180Pa, and two kinds of gas flow ratios are P
ar/ P
n2=1/2, operating voltage: 700V, treatment temp is 1200 DEG C, the treatment time is 3h.
Under above-mentioned preparation process condition, the ceramic-metallic performance of heterogeneity proportioning is in table 6.
The performance of the different metal pottery that table 6 adopting process 1 is prepared
In the time that in sintering metal matrix, Ni content is lower, after plasma nitridation process, the hardness of gained gradient-structure Ti (C, N) based ceramic metal is relatively high, and bending strength is relatively low, and vice versa.In claims span, its performance impact to material is limited.
Above-described embodiment does not limit the present invention in any way, and every employing is equal to replaces or technical scheme that the mode of equivalent transformation obtains all drops in protection scope of the present invention.
Claims (3)
1. gradient-structure Ti (C, a N) based ceramic metal, is characterized in that its composition quality umber is: C is that 6.5～7.5, N is that 1.5～2.5, Ti is that 36～45, Ni is that 25～32, Mo is that 13～18, W is 6～10.
2. gradient-structure Ti according to claim 1 (C, N) based ceramic metal, is characterized in that adopted raw material is for (Ti, Mo, W) (C, N), C, NiMo powder.
3. a plasma nitrided method of preparing gradient-structure Ti (C, N) based ceramic metal, is characterized in that comprising the steps:
(1) preparation meets the compound of following requirement, and its composition quality umber is: C is that 6.5～7.5, N is that 1.5～2.5, Ti is that 36～45, Ni is that 25～32, Mo is that 13～18, W is 6～10; Above-mentioned all the components is introduced by (Ti, Mo, W) (C, N), C, NiMo powder;
(2) batch mixing, compounding process carries out in planetary ball mill, and drum's speed of rotation is 180rpm, and the time is 24h;
(3) add forming agent, the forming agent adding is that concentration is the polyvinyl alcohol water solution of 7mass%, 3mass%～7mass% that additional proportion is compound;
(4) compression moulding, pressing pressure used is 250MPa;
(5) degreasing, carries out in higher than the vacuum oven of 10Pa in vacuum tightness, and the heat-up rate between 200～450 DEG C is 0.3～0.5 DEG C/min;
(6) vacuum sintering is carried out in vacuum sintering furnace, and vacuum tightness is higher than 5.0 × 10
-2pa, sintering temperature is 1410～1440 DEG C, soaking time is 50～70min;
(7) to carrying out plasma nitriding processing through above-mentioned operation gained sintered compact, in the plasma nitrided stove with high temperature assisted heating device, carry out, first working spaces is evacuated to the vacuum below 10Pa, be filled with again Ar/N2 mixed gas, total gas pressure is 120～180Pa, two kinds of gas flow ratios are PAr/PN2=1/2, and workpiece voltage is 500～700V, nitriding treatment 3～5h at 1140～1200 DEG C.
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Cited By (8)
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| CN104630530A (en) * | 2015-01-29 | 2015-05-20 | 南京航空航天大学 | Preparation method of Ti(C, N)-based metal ceramic of gradient structure |
| CN105296840A (en) * | 2015-11-03 | 2016-02-03 | 合肥海源机械有限公司 | Method for manufacturing automobile engine camshaft |
| CN106565244A (en) * | 2016-11-09 | 2017-04-19 | 哈尔滨东安发动机（集团）有限公司 | Surface nitriding method for particle-reinforced ternary layered ceramic part |
| CN106756168A (en) * | 2016-12-12 | 2017-05-31 | 南京航空航天大学 | The method that one kind prepares Ti (C, N) based ceramic metal based on carbon thermal reduction molybdenum trioxide |
| CN111590070A (en) * | 2020-05-23 | 2020-08-28 | 自贡硬质合金有限责任公司 | Sintering method of YT hard alloy |
| CN113737076A (en) * | 2021-09-08 | 2021-12-03 | 王淅茹 | Low-nitrogen high-toughness Ti (C, N) cermet matrix and preparation process thereof |
| CN114752835A (en) * | 2022-03-18 | 2022-07-15 | 南京航空航天大学 | Ti (C, N) -based metal ceramic with honeycomb structure and preparation method thereof |
| CN115449661A (en) * | 2022-08-22 | 2022-12-09 | 三峡大学 | Cermet material with gradient structure and preparation method thereof |
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| CN101565790A (en) * | 2009-06-03 | 2009-10-28 | 南京航空航天大学 | Gradient structure carbon nano-tube enhanced Ti(C, N)-based metal ceramic and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104630530A (en) * | 2015-01-29 | 2015-05-20 | 南京航空航天大学 | Preparation method of Ti(C, N)-based metal ceramic of gradient structure |
| CN105296840A (en) * | 2015-11-03 | 2016-02-03 | 合肥海源机械有限公司 | Method for manufacturing automobile engine camshaft |
| CN106565244A (en) * | 2016-11-09 | 2017-04-19 | 哈尔滨东安发动机（集团）有限公司 | Surface nitriding method for particle-reinforced ternary layered ceramic part |
| CN106756168A (en) * | 2016-12-12 | 2017-05-31 | 南京航空航天大学 | The method that one kind prepares Ti (C, N) based ceramic metal based on carbon thermal reduction molybdenum trioxide |
| CN106756168B (en) * | 2016-12-12 | 2018-05-22 | 南京航空航天大学 | The method that one kind prepares Ti (C, N) based ceramic metal based on carbon thermal reduction molybdenum trioxide |
| CN111590070A (en) * | 2020-05-23 | 2020-08-28 | 自贡硬质合金有限责任公司 | Sintering method of YT hard alloy |
| CN113737076A (en) * | 2021-09-08 | 2021-12-03 | 王淅茹 | Low-nitrogen high-toughness Ti (C, N) cermet matrix and preparation process thereof |
| CN114752835A (en) * | 2022-03-18 | 2022-07-15 | 南京航空航天大学 | Ti (C, N) -based metal ceramic with honeycomb structure and preparation method thereof |
| CN114752835B (en) * | 2022-03-18 | 2022-10-25 | 南京航空航天大学 | Ti (C, N) -based metal ceramic with honeycomb structure and preparation method thereof |
| CN115449661A (en) * | 2022-08-22 | 2022-12-09 | 三峡大学 | Cermet material with gradient structure and preparation method thereof |
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