CN108977713B - A kind of preparation method of TiCN base metal-ceramic material - Google Patents
A kind of preparation method of TiCN base metal-ceramic material Download PDFInfo
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Abstract
The present invention relates to the preparation methods of TiCN base metal-ceramic material.It the following steps are included: (1) modifier powder preparation；(2) corresponding dosed powder and modifier powder are weighed respectively, are mixed and are configured to powder mixing；It adds paraffin and then is mixed ball milling, spray drying；By the stamping of powder molding after drying, over-voltage sintering is finally carried out, is filled with argon gas before sintering terminates, until sintering is completed.The present invention has at low cost, equipment and easy to operate, is easy to many advantages, such as industrializing, can prepare the TiCN base metal-ceramic material of material property excellent effect.
Description
The present invention is that application No. is the division Shens of the 201710416726.7, applying date on 06 06th, 2017 patent of invention
Please.
Technical field
The present invention relates to cermet material technical field more particularly to a kind of systems of modified TiCN base metal-ceramic material
Preparation Method.
Background technique
TiCN based composites have many advantages, such as excellent wear resistence, high-temperature behavior, lower cost, gradually in high temperature knot
The fields such as structure material, wear-resistant material, tool die material are widely applied.Preparing the metals such as high performance alloys, cermet
When based composites, cerium group light rare earth oxide is important additive and its indispensable component part.Light rare earth holds
The elements such as easy and oxygen, sulphur form high-melting-point chemical combination, and purification crystal boundary is played in metal-base composites, reaches raising intercrystalline
Interface binding power, to improve the purpose of material integral strength；And its atomic radius is big, can fill up metal and its composite wood
The crystal grain defect of material generates the limitans for hindering grain growth, can refine crystal grain.Cerium group light rare earth granular size and pattern are to gold
The intensity of metal-matrix composite material plays a crucial role.However it currently, is obtained using the conventional cerium group light rare earth oxide of addition is prepared
The modified metal based composites arrived, properties need to be further increased, and application range is also accordingly limited.To find out its cause,
This is mainly due to added existing cerium group light rare earth oxide itself, that there are patterns is different, Oxygen potential is not high, mostly hollow
Structure, and easily grow up, bond the defects of reunion, and then rare earth element is caused to be unevenly distributed in each crystal boundary of metal-base composites
It is even, crystal boundary can not be purified, the raising of material property effect is limited.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of TiCN base metal-ceramic material, made from the preparation method
Modified metal based composites have excellent performance.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of TiCN base metal-ceramic material, which comprises the following steps:
(1) according to each element stoichiometric ratio in reaction equation, corresponding sodium bicarbonate (NaHCO is weighed respectively3) and
Rare earth cerium salt is as reaction raw materials；Suitable cetyl trimethylammonium bromide (CTAB) is weighed again；By reaction raw materials, CTAB with
Suitable dehydrated alcohol mixing, then carries out planetary ball mill；Products therefrom is filtered, washing, appropriate dehydrated alcohol is added afterwards i.e.
Obtain predecessor slurry；Predecessor slurry is thermally decomposed with spray pyrolysis, obtains modifying agent nanometer spherical rare earth oxygen
Compound powder；
(2) according to the composition of target product, corresponding dosed powder and nanometer spherical RE oxide powder are weighed respectively,
It being mixed and is configured to powder mixing, wherein nanometer spherical RE oxide powder accounts for the 1%~5% of powder mixing total weight,
The paraffin for accounting for powder mixing total weight 1%~5% is added, to enable powder to form in molding；Mixing and ball milling later
36~48 hours, then be spray-dried, wherein the diameter for controlling nozzle is 0.5~0.8mm, and atomization temperature is 120~150
DEG C, so that powder is sprayed by nozzle forms spherical shape, and keep powder fully dispersed；The stamping of powder after drying is formed again, pressure
Pressing pressure is 100~160KN, 10~15s of pressure maintaining, finally carries out over-voltage sintering, and control furnace pressure is 4~6MPa when sintering,
Sintering temperature is 1400~1550 DEG C, to guarantee that the gas generated in sintering process is sufficiently discharged；Terminate preceding 10 in sintering~
20min is filled with 4MPa argon gas, to make metal-base composites full densification under the effect of the pressure during cooling,
Until sintering is completed.Up to modified metal based composites after the completion of sintering.
It is above-mentioned that predecessor slurry is thermally decomposed with spray pyrolysis as advanced optimizing, specifically according to following step
It is rapid to carry out:
A. predecessor slurry is placed in rotary container, is pumped into the atomizer of spray pyrolysis unit and is prepared with micropump
Predecessor nanometer powder, wherein the charging rate of micropump is 50~100ml/min, and atomizer bore is 0.2~0.5mm,
Carrier gas is nitrogen, and 200~500ml/min of gas flow, atomization temperature is 100~150 DEG C；
B. resulting predecessor nanometer powder is brought into pyrolysis zone with carrier gas, carry out two-part heat resolve；Wherein, one
Duan Wendu is 200~250 DEG C, keeps the temperature 1 hour, removes the crystallization water；Two sections of temperature are 400~800 DEG C, keep the temperature 3~6 hours；So
It after decomposition product is blown into powder collector by carrier gas afterwards, is cooled to room temperature under gas shield, it is dilute to obtain modifying agent nanometer spherical
Native oxide powder.
As advanced optimizing, the dosage of above-mentioned cetyl trimethylammonium bromide is according to accounting for reaction raw materials gross mass 2%
~5% meter.
As advanced optimizing, above-mentioned planetary ball mill is specifically carried out according to following operation: by reaction raw materials, CTAB and appropriate
Dehydrated alcohol mixing after, then be packed into together with agate ball agate pot and carry out planetary ball mill, wherein reaction raw materials and agate ball
Weight ratio is 1:5~8, and ball milling speed is 300~500 revs/min, Ball-milling Time 5~10 hours of revolution.
As advanced optimizing, the washing operation in above-mentioned steps (1) is specifically to be washed with deionized 3~5 times.
It most specifically says, a kind of preparation method of TiCN base metal-ceramic material, which comprises the following steps:
(1) according to each element stoichiometric ratio in reaction equation, corresponding sodium bicarbonate (NaHCO is weighed respectively3)
2mol, rare-earth salts cerous nitrate (Ce (NO3)2·6H2O) 1mol is as reaction raw materials；It weighs again and accounts for the 2% of reaction raw materials gross mass
Cetyl trimethylammonium bromide (CTAB)；By weighed NaHCO3、Ce(NO3)2·6H2O, CTAB and suitable anhydrous second
Alcohol mixing, is packed into agate pot together with agate ball, wherein the weight ratio of reaction raw materials and agate ball is 1:5, then carries out planet
Ball milling, ball milling speed are 300 revs/min of revolution, and Ball-milling Time 5 hours, products therefrom was washed with deionized 3 times again after filtering,
Appropriate dehydrated alcohol is added and obtains predecessor slurry；Predecessor slurry is placed in rotary container, then is pumped into micropump
In the atomizer of spray pyrolysis unit, micropump charging rate is 50ml/min, and carrier gas is nitrogen, gas flow 300ml/min,
Atomizer bore is 0.2mm, and atomization temperature is 150 DEG C；Predecessor nanometer powder after atomization brings pyrolysis zone into carrier gas
It is divided to two sections to thermally decompose predecessor: one section 250 DEG C of temperature, keeps the temperature 1 hour, remove the crystallization water；It two sections 600 DEG C of temperature, protects
Temperature 5 hours；Then after decomposition product being blown into powder collector by carrier gas, it is cooled to room temperature under gas shield, obtains modifying agent and receive
The spherical cerium group light rare earth oxidate powder (CeO of rice2)；
(2) weight ratio and composition shown according to the form below weighs each dosed powder that corresponding granularity is less than or equal to 10um respectively,
And nanometer spherical rare earth oxide CeO obtained by step (1)2Powder carries out ingredient, is mixed and is configured to powder mixing:
| Powder | TiCN | WC | Mo | Co | CeO2Powder | It is total |
| Weight ratio % | 50 | 20 | 8 | 17 | 5 | 100 |
Again in the powder mixing prepared, the paraffin for accounting for its total weight 4.5% is added, after being mixed ball milling 48 hours
It is spray-dried, nozzle diameter 0.5mm, 125 DEG C of atomization temperature；By the stamping of powder molding after drying, pressing pressure
For 110KN, pressure maintaining 15s, over-voltage sintering is finally carried out, furnace pressure 5MPa when sintering, terminates in sintering by 1450 DEG C of sintering temperature
Preceding 15min is filled with 4MPa argon gas, until sintering is completed, up to TiCN base metal-ceramic material after the completion of sintering.
The invention has the following advantages:
The present invention provides a kind of preparation method of TiCN base metal-ceramic material, the preparation method have it is at low cost, set
It is standby and easy to operate, it is easy to many advantages, such as industrializing.It is by first reacting micella solid state reaction with spray-wall interaction
Combine, prepared that pattern is good, be evenly distributed, particle size is small, with high purity, and particle Oxygen potential it is big modifying agent nanometer it is real
Bulbus cordis shape rare earth oxide, and add the modifying agent prepare alloy during, rare earth element is evenly distributed on Metal Substrate
Each crystal boundary of composite material improves the effect of material property to reach effectively purification crystal boundary.Wherein, sharp in solid phase reaction
The spherical microreactor that micelle forma-tion is generated with CTAB effectively controls particle size and pattern, limits each Xiang Feijun of crystal
Even growth and grow up, prepared Oxygen potential is high, particle uniformly, the spherical predecessor of Nano grade, and cooperate two-part high temperature
Spray pyrolysis makes predecessor effectively remove the crystallization water in pyrolytic process and crystal grain is inhibited to grow up, while spray pyrolysis makes heat point
Particle after solution effectively keeps nanometer spherical and does not bond reunion, not will form hollow sub-microsphere, further ensures spherical shape
Pattern, has prepared that pattern is good, is evenly distributed, and particle size is less than 100nm, and purity is greater than 99.9%, and particle Oxygen potential is big
In the 90% solid spherical cerium group light rare earth oxide of nanometer, so mixing and ball milling, spray drying and etc. in make rare earth
Element sufficiently optimizes the heterogeneous microstructure of metal-base composites, assigns its superior impact of performance.
Detailed description of the invention
Fig. 1 is modifying agent nanometer spherical cerium group light rare earth oxidate powder (CeO prepared in the embodiment of the present invention 12)
SEM spectrum.
Fig. 2 is modifying agent nanometer spherical cerium group light rare earth oxidate powder (CeO prepared in the embodiment of the present invention 12)
Particle size distribution figure.
Fig. 3 is modifying agent nanometer spherical cerium group light rare earth oxidate powder (CeO prepared in the embodiment of the present invention 12)
XRD spectrum.
Fig. 4 is using ultra-fine CeO employed in customary preparation methods2The structural schematic diagram of powder.
Specific embodiment
The present invention is specifically described below by specific embodiment, it is pointed out here that following embodiment is served only for this hair
It is bright to be further described, it should not be understood as limiting the scope of the invention, the person skilled in the art of this field can root
Some nonessential modifications and adaptations are made to the present invention according to foregoing invention content.
Embodiment 1
A kind of preparation method of TiCN base metal-ceramic material, comprising the following steps:
(1) according to each element stoichiometric ratio in reaction equation, corresponding sodium bicarbonate (NaHCO is weighed respectively3)
2mol, rare-earth salts cerous nitrate (Ce (NO3)2·6H2O) 1mol is as reaction raw materials；It weighs again and accounts for the 2% of reaction raw materials gross mass
Cetyl trimethylammonium bromide (CTAB)；By weighed NaHCO3、Ce(NO3)2·6H2O, CTAB and suitable anhydrous second
Alcohol mixing, is packed into agate pot together with agate ball, wherein the weight ratio of reaction raw materials and agate ball is 1:5, then carries out planet
Ball milling, ball milling speed are 300 revs/min of revolution, and Ball-milling Time 5 hours, products therefrom was washed with deionized 3 times again after filtering,
Appropriate dehydrated alcohol is added and obtains predecessor slurry；Predecessor slurry is placed in rotary container, then is pumped into micropump
In the atomizer of spray pyrolysis unit, micropump charging rate is 50ml/min, and carrier gas is nitrogen, gas flow 300ml/min,
Atomizer bore is 0.2mm, and atomization temperature is 150 DEG C；Predecessor nanometer powder after atomization brings pyrolysis zone into carrier gas
It is divided to two sections to thermally decompose predecessor: one section 250 DEG C of temperature, keeps the temperature 1 hour, remove the crystallization water；It two sections 600 DEG C of temperature, protects
Temperature 5 hours；Then after decomposition product being blown into powder collector by carrier gas, it is cooled to room temperature under gas shield, obtains modifying agent and receive
The spherical cerium group light rare earth oxidate powder (CeO of rice2)；
(2) weight ratio and composition shown according to the form below weighs each dosed powder that corresponding granularity is less than or equal to 10um respectively,
And nanometer spherical rare earth oxide CeO obtained by step (1)2Powder carries out ingredient, is mixed and is configured to powder mixing:
| Powder | TiCN | WC | Mo | Co | CeO2Powder | It is total |
| Weight ratio % | 50 | 20 | 8 | 17 | 5 | 100 |
Again in the powder mixing prepared, the paraffin for accounting for its total weight 4.5% is added, after being mixed ball milling 48 hours
It is spray-dried, nozzle diameter 0.5mm, 125 DEG C of atomization temperature；By the stamping of powder molding after drying, pressing pressure
For 110KN, pressure maintaining 15s, over-voltage sintering is finally carried out, furnace pressure 5MPa when sintering, terminates in sintering by 1450 DEG C of sintering temperature
Preceding 15min is filled with 4MPa argon gas, until sintering is completed, up to TiCN base metal-ceramic material after the completion of sintering.
The following table 1 show the physical property comparison of obtained TiCN base metal-ceramic material sample；Wherein, sample B is
Modifying agent spherical nanoparticle CeO in added this example 12TiCN base metal-ceramic material obtained by powder；Sample A is to use
Technique identical with the preparation process of above-mentioned TiCN based ceramic metal, but the CeO that corresponding replacement is conventional using addition2Superfines
(as shown in Fig. 4, be sheet, average-size 300nm) and obtained TiCN base metal-ceramic material.
Table 1
It can be seen that: the toughness and intensity of sample B is substantially better than sample A, illustrates that the heterogeneous microstructure of sample B is more preferable, crystal boundary
It is purified, performance improves.
In addition, respectively with reference to the accompanying drawings known to 1,2 and 3: modifying agent nanometer spherical cerium group light rare earth oxidate powder (CeO2)
Grain is medicine ball, and particle is uniform, nonadherent, be distributed；Size distribution is in normal distribution, and D50 is less than 100nm, illustrates that particle is equal
Even, average particle size particle size is less than 100nm；It is cerium oxide characteristic peak shown in Fig. 3, illustrates that object is cerium oxide.
Modifying agent nanometer spherical cerium group light rare earth oxidate powder (CeO2) detection:
Through the CeO in detection modifying agent product2Content is greater than 99.9%.(being free of adsorption O)
ICP (plasma spectrum) analyzes result:
| Element | Pr | Gd | Yb | Tb | Pm | Sm | Eur | Fe | Na | K | Mn | Zn | Mg | Cr | Al | CeO2 |
| Content (ppm) | 15 | 12 | 10 | 16 | 20 | 11 | 10 | 30 | 10 | 10 | 12 | 10 | 10 | 10 | 11 | > 99.9% |
Oxygen carbon analyzes result:
| Element | O (wherein chemical combination O content 35.6%) | C |
| Content % | 43.7% | 0.21% |
Embodiment 2
A kind of preparation method of TiCN base metal-ceramic material, comprising the following steps:
(1) according to each element stoichiometric ratio in reaction equation, corresponding 3mol sodium bicarbonate is weighed respectively
(NaHCO3), 2mol rare-earth salts lanthanum nitrate (La (NO3)3·6H2O reaction raw materials) are used as；It weighs again and accounts for reaction raw materials gross mass
3.5% cetyl trimethylammonium bromide (CTAB)；By weighed NaHCO3、La(NO3)3·6H2O, CTAB and suitable nothing
Water-ethanol mixing, is packed into agate pot together with agate ball, wherein the weight ratio of reaction raw materials and agate ball is 1:6, is then carried out
Planetary ball mill, ball milling speed are 400 revs/min of revolution, and Ball-milling Time 7.5 hours, products therefrom was washed with deionized water again after filtering
It washs 4 times, appropriate dehydrated alcohol is added and obtains predecessor slurry；Predecessor slurry is placed in rotary container, then uses micropump
It is pumped into the atomizer of spray pyrolysis unit, micropump charging rate is 80ml/min, and carrier gas is nitrogen, gas flow
400ml/min, atomizer bore are 0.45mm, and atomization temperature is 150 DEG C；Predecessor nanometer powder carrier gas band after atomization
Enter two sections of thermal decomposition differentiation to thermally decompose predecessor: one section 240 DEG C of temperature, keeping the temperature 1.5 hours, remove the crystallization water；Two sections
700 DEG C of temperature, keep the temperature 6 hours；Then after decomposition product being blown into powder collector by carrier gas, room temperature is cooled under gas shield, i.e.,
Modifier powder is made；
(2) weight ratio and composition shown according to the form below weighs each dosed powder that corresponding granularity is less than or equal to 10um respectively,
And modifier powder obtained by step (1) carries out ingredient, is mixed and is configured to powder mixing:
| Powder | TiCN | WC | Mo | Co | Modifier powder | It is total |
| Weight ratio % | 50 | 20 | 9 | 16.5 | 4.5 | 100 |
Again in the powder mixing prepared, the paraffin for accounting for its total weight 3.5% is added, after being mixed ball milling 40 hours
It is spray-dried, nozzle diameter 0.7mm, 135 DEG C of atomization temperature；By the stamping of powder molding after drying, pressing pressure
For 150KN, pressure maintaining 12s, over-voltage sintering is finally carried out, furnace pressure 5MPa when sintering, terminates in sintering by 1400 DEG C of sintering temperature
Preceding 18min is filled with 4MPa argon gas, until sintering is completed, up to TiCN base metal-ceramic material after the completion of sintering.
Embodiment 3
A kind of preparation method of TiCN base metal-ceramic material, comprising the following steps:
(1) according to each element stoichiometric ratio in reaction equation, corresponding sodium bicarbonate (NaHCO is weighed respectively3)
3mol, rare-earth salts samarium sulphate (Sm2(SO4)3) 2mol is as reaction raw materials；Weigh again account for reaction raw materials gross mass 4.5% ten
Six alkyl trimethyl ammonium bromides (CTAB)；By weighed NaHCO3、Sm2(SO4)3, CTAB mixed with suitable dehydrated alcohol, with
Agate ball is packed into agate pot together, wherein the weight ratio of reaction raw materials and agate ball is 1:8, then carries out planetary ball mill, ball milling
Speed is 480 revs/min of revolution, and Ball-milling Time 9.5 hours, products therefrom was washed with deionized 5 times again after filtering, and is added appropriate
Dehydrated alcohol obtains predecessor slurry；Predecessor slurry is placed in rotary container, then is pumped into spray pyrolysis with micropump
In the atomizer of device, micropump charging rate is 100ml/min, and carrier gas is nitrogen, gas flow 500ml/min, atomization spray
Mouthpiece diameter is 0.50mm, and atomization temperature is 150 DEG C；Predecessor nanometer powder after atomization brings thermal decomposition into carrier gas and distinguishes two sections
Predecessor is thermally decomposed: one section 250 DEG C of temperature, keeping the temperature 1.5 hours, removes the crystallization water；Two sections 800 DEG C of temperature, heat preservation 6 is small
When；Then after decomposition product being blown into powder collector by carrier gas, it is cooled to room temperature under gas shield, obtains modifier powder；
(2) weight ratio and composition shown according to the form below weighs each dosed powder that corresponding granularity is less than or equal to 10um respectively,
And modifier powder obtained by step (1) carries out ingredient, is mixed and is configured to powder mixing:
| Powder | TiCN | WC | Mo | Co | Modifier powder | It is total |
| Weight ratio % | 51.5 | 18 | 8.5 | 18.5 | 3.5 | 100 |
Again in the powder mixing prepared, the paraffin for accounting for its total weight 2.5% is added, after being mixed ball milling 48 hours
It is spray-dried, nozzle diameter 0.8mm, 145 DEG C of atomization temperature；By the stamping of powder molding after drying, pressing pressure
For 145KN, pressure maintaining 12s, over-voltage sintering is finally carried out, furnace pressure 6MPa when sintering, terminates in sintering by 1500 DEG C of sintering temperature
Preceding 20min is filled with 4MPa argon gas, until sintering is completed, up to TiCN base metal-ceramic material after the completion of sintering.
Embodiment 4
A kind of preparation method of TiCN base metal-ceramic material, comprising the following steps:
(1) according to each element stoichiometric ratio in reaction equation, corresponding sodium bicarbonate (NaHCO is weighed respectively3)
3mol, rare-earth salts europium chloride (EuCl3.6H2O) 2mol is as reaction raw materials；It weighs again and accounts for the 5% of reaction raw materials gross masses
Cetyl trimethylammonium bromide (CTAB)；By weighed NaHCO3、EuCl3.6H2O, CTAB is mixed with suitable dehydrated alcohol,
Agate pot is packed into together with agate ball, wherein the weight ratio of reaction raw materials and agate ball is 1:7, then carries out planetary ball mill, ball
Grinding speed is 500 revs/min of revolution, and Ball-milling Time 10 hours, products therefrom was washed with deionized 5 times again after filtering, and is added suitable
Amount dehydrated alcohol obtains predecessor slurry；Predecessor slurry is placed in rotary container, then is pumped into spraying heat with micropump
In the atomizer for solving device, micropump charging rate is 60ml/min, and carrier gas is nitrogen, gas flow 300ml/min, atomization spray
Mouthpiece diameter is 0.30mm, and atomization temperature is 135 DEG C；Predecessor nanometer powder after atomization brings thermal decomposition into carrier gas and distinguishes two sections
Predecessor is thermally decomposed: one section 235 DEG C of temperature, keeping the temperature 1 hour, removes the crystallization water；Two sections 650 DEG C of temperature, heat preservation 6 is small
When；Then after decomposition product being blown into powder collector by carrier gas, it is cooled to room temperature under gas shield, obtains modifier powder；
(2) weight ratio and composition shown according to the form below weighs each dosed powder that corresponding granularity is less than or equal to 10um respectively,
And modifier powder obtained by step (1) carries out ingredient, is mixed and is configured to powder mixing:
| Powder | TiCN | WC | Mo | Co | Modifier powder | It is total |
| Weight ratio % | 50 | 20 | 8 | 17 | 5 | 100 |
Again in the powder mixing prepared, be added and account for the paraffin of its total weight 5%, be mixed ball milling 48 hours it is laggard
Row spray drying, nozzle diameter 0.6mm, 150 DEG C of atomization temperature；By the stamping of powder molding after drying, pressing pressure is
160KN, pressure maintaining 14s finally carry out over-voltage sintering, and furnace pressure 4.5MPa when sintering, terminates in sintering by 1550 DEG C of sintering temperature
Preceding 15min is filled with 4MPa argon gas, until sintering is completed, up to TiCN base metal-ceramic material after the completion of sintering.
Claims (4)
1. a kind of preparation method of TiCN base metal-ceramic material, which comprises the following steps:
(1) according to each element stoichiometric ratio in reaction equation, corresponding sodium bicarbonate (NaHCO is weighed respectively3) and cerium
Salt is as reaction raw materials；Suitable cetyl trimethylammonium bromide (CTAB) is weighed again；By reaction raw materials, CTAB with it is suitable
Dehydrated alcohol mixing, then carries out planetary ball mill；After filtering by products therefrom, be washed with deionized 3~5 times, it is added appropriate
Dehydrated alcohol obtains predecessor slurry；Predecessor slurry is thermally decomposed with spray pyrolysis, obtains modifying agent nanometer
Spherical rare-earth oxide powder；
It is described that predecessor slurry is thermally decomposed with spray pyrolysis, specifically follow the steps below:
A. predecessor slurry is placed in rotary container, is pumped into the atomizer of spray pyrolysis unit with micropump and prepares forerunner
Object nanometer powder, wherein the charging rate of micropump is 50~100mL/min, and atomizer bore is 0.2~0.5mm, carrier gas
For nitrogen, 200~500mL/min of gas flow, atomization temperature is 100~150 DEG C；
B. resulting predecessor nanometer powder is brought into pyrolysis zone with carrier gas, carry out two-part heat resolve；Wherein, a Duan Wen
Degree is 200~250 DEG C, keeps the temperature 1 hour, removes the crystallization water；Two sections of temperature are 400~800 DEG C, keep the temperature 3~6 hours；Then by
After decomposition product is blown into powder collector by carrier gas, it is cooled to room temperature under gas shield；
(2) according to the composition of target product, corresponding dosed powder and nanometer spherical RE oxide powder are weighed respectively, by it
It is mixedly configured into powder mixing, wherein nanometer spherical RE oxide powder accounts for the 1%~5% of powder mixing total weight, adds
The paraffin of powder mixing total weight 1%~5% is accounted for, to enable powder to form in molding；Mixing and ball milling 36~48 is small later
When, then be spray-dried, wherein the diameter for controlling nozzle is 0.5~0.8mm, and atomization temperature is 120~150 DEG C, so that
Powder is sprayed by nozzle forms spherical shape, and keeps powder fully dispersed；The stamping of powder after drying is formed again, pressing pressure is
100~160 kN, 10~15s of pressure maintaining finally carry out over-voltage sintering, and control furnace pressure is 4~6MPa, sintering temperature when sintering
Degree is 1400~1550 DEG C, to guarantee that the gas generated in sintering process is sufficiently discharged；Terminate preceding 10~20min in sintering to be filled with
4MPa argon gas, to make metal-base composites full densification under the effect of the pressure during cooling, until sintering
It completes.
2. the preparation method of TiCN base metal-ceramic material as described in claim 1, it is characterised in that: the cetyl
The dosage of trimethylammonium bromide is according to the meter for accounting for reaction raw materials gross mass 2%~5%.
3. the preparation method of TiCN base metal-ceramic material as claimed in claim 1 or 2, it is characterised in that: the planet ball
Grinding tool body is carried out according to following operation: after reaction raw materials, CTAB are mixed with suitable dehydrated alcohol, then being filled together with agate ball
Enter agate pot and carry out planetary ball mill, wherein the weight ratio of reaction raw materials and agate ball is 1:5~8, and ball milling speed is revolution 300
~500 revs/min, Ball-milling Time 5~10 hours.
4. a kind of preparation method of TiCN base metal-ceramic material, which comprises the following steps:
(1) according to each element stoichiometric ratio in reaction equation, corresponding sodium bicarbonate 2mol, Ce (NO is weighed respectively3)2·
6H2O 1mol is as reaction raw materials；The 2% cetyl trimethylammonium bromide CTAB for accounting for reaction raw materials gross mass is weighed again；It will
Weighed NaHCO3、Ce(NO3)2·6H2O, CTAB is mixed with suitable dehydrated alcohol, and agate pot is packed into together with agate ball,
In, the weight ratio of reaction raw materials and agate ball is 1:5, then carries out planetary ball mill, and ball milling speed is 300 revs/min of revolution, ball milling
Time 5 hours, products therefrom was washed with deionized 3 times again after filtering, and appropriate dehydrated alcohol is added and obtains predecessor slurry；
Predecessor slurry is placed in rotary container, then is pumped into the atomizer of spray pyrolysis unit with micropump, micropump charging
Speed is 50mL/min, and carrier gas is nitrogen, and gas flow 300mL/min, atomizer bore is 0.2mm, atomization temperature 150
℃；Predecessor nanometer powder after atomization is brought two sections of thermal decomposition differentiation into carrier gas and is thermally decomposed to predecessor: a Duan Wendu
250 DEG C, 1 hour is kept the temperature, removes the crystallization water；Two sections 600 DEG C of temperature, keep the temperature 5 hours；Then decomposition product is blown into collection by carrier gas
After powder device, it is cooled to room temperature under gas shield, obtains modifying agent nanometer spherical cerium group light rare earth oxide CeO2Powder；
(2) by TiCN powder weight than 50%, WC powder weight ratio 20%, Mo powder weight than 8%, Co powder weight than 17%, CeO2
Powder weight ratio 5% adds up to 100% weight ratio and composition, and it is each less than or equal to 10 μm to weigh corresponding granularity respectively
Nanometer spherical rare earth oxide CeO obtained by dosed powder and step (1)2Powder carries out ingredient, is mixed and is configured to
Powder mixing；
Again in the powder mixing prepared, the paraffin for accounting for its total weight 4.5% is added, is carried out after being mixed ball milling 48 hours
Spray drying, nozzle diameter 0.5mm, 125 DEG C of atomization temperature；By the stamping of powder molding after drying, pressing pressure is
110kN, pressure maintaining 15s finally carry out over-voltage sintering, furnace pressure 5MPa when sintering, and 1450 DEG C of sintering temperature, before sintering terminates
15min is filled with 4MPa argon gas, until sintering is completed, up to TiCN base metal-ceramic material after the completion of sintering.
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