CN103787407A - Method for preparing nano TiCN/Al2O3 composite powder through reactive ball milling - Google Patents
Method for preparing nano TiCN/Al2O3 composite powder through reactive ball milling Download PDFInfo
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- CN103787407A CN103787407A CN201310725365.6A CN201310725365A CN103787407A CN 103787407 A CN103787407 A CN 103787407A CN 201310725365 A CN201310725365 A CN 201310725365A CN 103787407 A CN103787407 A CN 103787407A
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Abstract
The invention discloses a method for preparing nano TiCN/Al2O3 composite powder through reactive ball milling. The method comprises the steps of mixing rutile powder, Al powder, graphite powder and urea (analytically pure) in a mole ratio of 3: 4: 2.7: 0.15, filling mixture, together with grinding balls, in a ball milling tank, wherein ratio of the balls to the materials is (20-30): 1, and carrying out ball milling for 40-80 hours in a high-energy ball mill, wherein raw materials react under the function of ball milling to form TiCN/Al2O3 composite powder which is less than 2 microns in granularity, 0.71 microns in average particle size and less than 10nm in grain size. The method disclosed by the invention is simple in synthesis process, low in synthesis temperature, small in grain size of synthesized powder, high in powder sintering activity and favorable for reducing powder sintering temperature.
Description
Technical field
The present invention relates to a kind of TiCN/Al
2o
3the preparation method of composite powder, particularly relates to a kind of reaction ball milling legal system for nano TiC N/Al
2o
3the method of composite powder.
Background technology
TiCN/Al
2o
3composite powder has that fusing point is high, hardness is large, frictional coefficient is low, toughness and the plurality of advantages such as thermal conductivity is good, all has a very wide range of applications in cutting, grinding and high-abrasive material field.Traditional TiCN/Al
2o
3composite powder is by TiCN and Al
2o
3two kinds of powder are formed by directly mixing, and in the situation that powder size is very thin, conventionally can cause that powder absorption impurity is more, powder mixes inhomogeneous.Solid-phase synthesis, carbothermic method, self propagating high temperature synthesis method in the synthetic method of traditional TiCN, synthesis temperature higher (1000 ℃ of >) conventionally, energy consumption is large, and synthetic TiCN coarse grains is unfavorable to follow-up sintering.Chemical Vapor deposition process and microwave process for synthesizing can reduce synthesis temperature, and synthetic powder crystal grain is tiny, but complex process, efficiency are lower, and synthetic cost is higher.The series of advantages such as it is little that reaction ball milling method has synthetic powder grain fineness number, and powder sintered activity is high, simple, the applicable suitability for industrialized production of synthesis technique.Normally take Ti powder, C powder as raw material, at mobile N
2or NH
3high-energy ball milling under atmosphere, but Ti powder price is higher, and pass into mobile N
2or NH
3need the ball mill of particular design.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of reaction ball milling legal system for nano TiC N/Al
2o
3the method of composite powder, the method raw materials cost is low, synthesis temperature low (room temperature), energy consumption is little, and equipment and process is simple.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of reaction ball milling legal system is for nano TiC N/Al
2o
3the method of composite powder, concrete steps are as follows:
1), by golden red stone flour, Al powder, Graphite Powder 99 and urea in molar ratio 3:4 ~ 4.05:2 ~ 2.7:0.1 ~ 0.2 mix;
2) above-mentioned mixed powder and abrading-ball are packed in ball grinder, the mass ratio of abrading-ball and mixed powder is 20～30:1;
3) after filling, ball grinder is covered tightly, sealed, and be placed on ball mill and start ball milling, drum's speed of rotation >=600r/min, ball milling 40～80 hours under room temperature;
4) under argon gas condition, from ball grinder, take out powder, remove urea decomposition product remaining in powder through soaked in absolute ethyl alcohol, through seasoning, finally obtain nano TiC N/Al
2o
3composite powder.
Preferably, described rutile Powder Particle Size < 10 μ m, purity > 99.5%, described Al Powder Particle Size < 10 μ m, purity > 99.5%, described Graphite Powder 99 granularity < 10 μ m, purity > 99.0%; Described urea is analytical pure.
Preferably, described golden red stone flour, Al powder, Graphite Powder 99 and urea mol ratio are 3:4:2.7:0.5.
Preferably, described abrading-ball is stainless steel abrading-ball.
Nano TiC N/Al prepared by aforesaid method
2o
3the brilliant tiny < 10nm of composite powder, granularity is tiny, and evenly granularity is less than 2 μ m, and mean particle size is 0.71 μ m, TiCN and Al in composite powder
2o
3mol ratio is 3:2.
The beneficial effect that adopts technique scheme to produce is: the 1) low (TiO of the method raw materials cost
2/ 10th of a not enough Ti of price, urea price is also compared with N
2and NH
3cheap), synthesis temperature low (room temperature), energy consumption is little, and equipment and process is simple, synthetic TiCN/Al
2o
3composite powder is original position synthetic powder, and powder mixes, and absorption impurity is few, and powder particle size and grain fineness number are tiny, are conducive to sintering.
2) the inventive method utilizes reaction ball milling method that golden red stone flour, Al powder, Graphite Powder 99 and urea are at room temperature carried out to ball milling, the TiCN of preparation and Al
2o
3composite powder granularity is less than 2 μ m, and mean particle size is 0.71 μ m, and grain fineness number is less than 10nm, excellent property.
Accompanying drawing explanation
Fig. 1 is golden red stone flour, Al powder, and Graphite Powder 99 and urea in molar ratio 3:4:2.7:0.15 mix, the raw material XRD spectra during without ball milling;
Fig. 2 is golden red stone flour, Al powder, and Graphite Powder 99 and urea in molar ratio 3:4:2.7:0.15 mix, the powder X-ray RD spectrogram after different ratio of grinding media to material and different Ball-milling Time ball milling.(a): ratio of grinding media to material is 20:1, Ball-milling Time 40h; (b): ratio of grinding media to material is 25:1, Ball-milling Time 60h; (c): ratio of grinding media to material is 30:1, Ball-milling Time 80h;
Fig. 3 is golden red stone flour, Al powder, and Graphite Powder 99 and urea in molar ratio 3:4:2.7:0.15 mix, after different ratio of grinding media to material and different Ball-milling Time ball milling, and the XRD spectra of powder after 1100 ℃ of vacuum annealings.(a): ratio of grinding media to material is 20:1, Ball-milling Time 40h; (b): ratio of grinding media to material is 25:1, Ball-milling Time 60h; (c): ratio of grinding media to material is 30:1, Ball-milling Time 80h;
Fig. 4 is golden red stone flour, Al powder, and Graphite Powder 99 and urea in molar ratio 3:4:2.7:0.15 mix, and ratio of grinding media to material is 20:1, the SEM photo of powder after ball milling 40h;
Fig. 5 is golden red stone flour, Al powder, and Graphite Powder 99 and urea in molar ratio 3:4:2.7:0.15 mix, and ratio of grinding media to material is 20:1, the TEM photo of powder after ball milling 40h.(a): single particle powder bright field image (b): powder selected area electron diffraction spot;
Fig. 6 is golden red stone flour, Al powder, and Graphite Powder 99 and urea in molar ratio 3:4:2.7:0.15 mix, and ratio of grinding media to material is 20:1, the particle size distribution figure of powder after ball milling 40h.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation.
Embodiment 1
By golden red stone flour (granularity < 10 μ m, purity > 99.5%), Al powder (granularity < 10 μ m, purity > 99.5%), Graphite Powder 99 (granularity < 10 μ m, purity > 99.0%) and urea (analytical pure) 3:4:2.7:0.15 mixing in molar ratio, the XRD spectra of mixed powder is shown in Fig. 1.Mixed powder is sealed in stainless steel jar mill together with stainless steel abrading-ball, and ratio of grinding media to material is 20:1, and ball radius is 5-10 ㎜.Reaction ball milling carries out on GN-2 type high energy ball mill (Ke Te vacuum mechanical & electrical equipment factory of Shenyang City).Drum's speed of rotation is 600r/min, and Ball-milling Time is 40h.Powder after ball milling is carried out to XRD analysis, the results are shown in Figure 2(a), in figure, can only see the diffraction peak of TiCN, can't see Al
2o
3diffraction peak, consider that XRD, to amorphous and very tiny nanocrystalline insensitive of crystal grain, therefore carries out the powder after ball milling 1100 ℃ of vacuum annealings, if there is Al
2o
3amorphous or nanometer crystalline phase, annealing after crystal grain will grow up, in XRD spectra, will reflect normally, experiment showed, the Al that really has amorphous or nanometer crystalline phase
2o
3generate (seeing Fig. 3 (a)).Meanwhile, utilize scanning electron microscope (SEM) and transmission electron microscope (TEM) to carry out microscopic appearance to powder and observe and electron diffraction pattern analysis, (seeing Fig. 4, Fig. 5).Can find out from SEM photo, the granularity of synthetic powder is less than 2 μ m, most of powder size below 1 μ m, (see figure 6) consistent with laser particle size analysis result.Transmission electron microscope bright field image shows, the polycrystal that powder particle is made up of many small grains, and crystal particle scale is at 4-6nm, and this calculates with utilizing Scherrer formula the grain fineness number consistent (seeing Fig. 2 (a)) that XRD result obtains.
Embodiment 2
By golden red stone flour (granularity < 10 μ m, purity > 99.5%), Al powder (granularity < 10 μ m, purity > 99.5%), Graphite Powder 99 (granularity < 10 μ m, purity > 99.0%) and urea (analytical pure) 3:4:2.7:0.15 mixing in molar ratio, be sealed in stainless steel jar mill together with stainless steel abrading-ball, ratio of grinding media to material is 25:1,, ball radius is 5-10 ㎜.Reaction ball milling carries out on GN-2 type high energy ball mill (Ke Te vacuum mechanical & electrical equipment factory of Shenyang City).Drum's speed of rotation is 600r/min, and Ball-milling Time is 60h.Powder after ball milling is carried out to XRD analysis, the results are shown in Figure 2(b), the grain fineness number of utilizing Scherrer formula calculating XRD result to obtain synthetic TiCN powder is 4 ~ 7nm.In figure, can only see the diffraction peak of TiCN, can't see Al
2o
3diffraction peak, consider that XRD, to amorphous and very tiny nanocrystalline insensitive of crystal grain, therefore carries out the powder after ball milling 1100 ℃ of vacuum annealings, if there is Al
2o
3amorphous or nanometer crystalline phase, annealing after crystal grain will grow up, XRD will reflect normally, experiment showed, the Al that really has amorphous or nanometer crystalline phase
2o
3generate (seeing Fig. 3 (b)).Other analyses are substantially the same manner as Example 1, and result is same as embodiment 1.
Embodiment 3
By golden red stone flour (granularity < 10 μ m, purity > 99.5%), Al powder (granularity < 10 μ m, purity > 99.5%), Graphite Powder 99 (granularity < 10 μ m, purity > 99.0%) and urea (analytical pure) 3:4:2.7:0.15 mixing in molar ratio, seal together with stainless steel abrading-ball with stainless steel jar mill in, ratio of grinding media to material is 30:1, and ball radius is 5-10 ㎜.Reaction ball milling carries out on GN-2 type high energy ball mill (Ke Te vacuum mechanical & electrical equipment factory of Shenyang City).Drum's speed of rotation is 600r/min, and Ball-milling Time is 80h.Powder after ball milling is carried out to XRD analysis, the results are shown in Figure 2(c), the grain fineness number of utilizing Scherrer formula calculating XRD result to obtain synthetic TiCN powder is 5 ~ 8nm.In figure, can only see the diffraction peak of TiCN, can't see Al
2o
3diffraction peak, consider that XRD, to amorphous and very tiny nanocrystalline insensitive of crystal grain, therefore carries out the powder after ball milling 1100 ℃ of vacuum annealings, if there is Al
2o
3amorphous or nanometer crystalline phase, annealing after crystal grain will grow up, XRD will reflect normally, experiment showed, the Al that really has amorphous or nanometer crystalline phase
2o
3generate (seeing Fig. 3 (c)).Other analyses are substantially the same manner as Example 1, and result is same as embodiment 1.
The inventive method is with rutile (TiO
2) powder, aluminium powder, Graphite Powder 99 and urea is raw material, at room temperature carries out reaction ball milling, original position is synthesized TiCN/Al
2o
3composite powder, the grain fineness number < 10nm of synthetic powder, granularity is less than 2 μ m, and mean particle size is 0.71 μ m, TiCN and Al in composite powder
2o
3mol ratio is 3:2.
Claims (4)
1. a reaction ball milling legal system is for nano TiC N/Al
2o
3the method of composite powder, is characterized in that: described method steps is as follows:
1), by golden red stone flour, Al powder, Graphite Powder 99 and urea in molar ratio 3:4 ~ 4.05:2 ~ 2.7:0.1 ~ 0.2 mix;
2) above-mentioned mixed powder and abrading-ball are packed in ball grinder, the mass ratio of abrading-ball and mixed powder is 20～30:1;
3) after filling, ball grinder is covered tightly, sealed, and be placed on ball mill and start ball milling, drum's speed of rotation >=600r/min, ball milling 40～80 hours under room temperature;
4) under argon gas condition, from ball grinder, take out powder, remove urea decomposition product remaining in powder through soaked in absolute ethyl alcohol, through seasoning, finally obtain nano TiC N/Al
2o
3composite powder.
2. reaction ball milling legal system according to claim 1 is for nano TiC N/Al
2o
3the method of composite powder, it is characterized in that: described rutile Powder Particle Size < 10 μ m, purity > 99.5%, described Al Powder Particle Size < 10 μ m, purity > 99.5%, described Graphite Powder 99 granularity < 10 μ m, purity > 99.0%; Described urea is analytical pure.
3. reaction ball milling legal system according to claim 1 is for nano TiC N/Al
2o
3the method of composite powder, is characterized in that: described golden red stone flour, Al powder, Graphite Powder 99 and urea mol ratio are 3:4:2.7:0.5.
4. reaction ball milling legal system according to claim 1 is for nano TiC N/Al
2o
3the method of composite powder, is characterized in that: described abrading-ball is stainless steel abrading-ball.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103991889A (en) * | 2014-06-11 | 2014-08-20 | 天津大学 | Method for preparing alumina nano-wires and nano-rods by ball-milling in liquid phase |
| RU2568555C1 (en) * | 2014-07-08 | 2015-11-20 | Российская Федерация, от имени которой выступает Министерство промышленности и торговли Российской Федерации (Минпромторг России) | Method of producing nanostructured conglomerated powdered material for coating by gas-dynamic and thermal spraying |
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| CN1559912A (en) * | 2004-03-02 | 2005-01-05 | 山东大学 | Preparation process for three elemental compound powder material of titanium carbonitride |
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|---|---|---|---|---|
| JPS6360283A (en) * | 1986-08-29 | 1988-03-16 | Mitsubishi Metal Corp | Surface-coated hard metal for cutting tool having excellent breakage resistance |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103991889A (en) * | 2014-06-11 | 2014-08-20 | 天津大学 | Method for preparing alumina nano-wires and nano-rods by ball-milling in liquid phase |
| CN103991889B (en) * | 2014-06-11 | 2015-09-09 | 天津大学 | Liquid phase ball milling prepares the method for alumina nanowires and nanometer rod |
| RU2568555C1 (en) * | 2014-07-08 | 2015-11-20 | Российская Федерация, от имени которой выступает Министерство промышленности и торговли Российской Федерации (Минпромторг России) | Method of producing nanostructured conglomerated powdered material for coating by gas-dynamic and thermal spraying |
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