CN103787407B - Reaction ball milling legal system is for nano TiC N/Al 2o 3the method of composite powder - Google Patents
Reaction ball milling legal system is for nano TiC N/Al 2o 3the method of composite powder Download PDFInfo
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- CN103787407B CN103787407B CN201310725365.6A CN201310725365A CN103787407B CN 103787407 B CN103787407 B CN 103787407B CN 201310725365 A CN201310725365 A CN 201310725365A CN 103787407 B CN103787407 B CN 103787407B
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Abstract
The invention discloses a kind of reaction ball milling legal system for nano TiC N/Al
2o
3the method of composite powder, it is by golden red stone flour, Al powder, Graphite Powder 99 and urea (analytical pure) in molar ratio 3:4:2.7:0.15 mixing after and abrading-ball together load in ball grinder, ratio of grinding media to material is 20 ~ 30:1, in high energy ball mill, carry out ball milling, Ball-milling Time is 40 ~ 80h.React between raw material under ball action, form granularity and be less than 2 μm, mean particle size is 0.71 μm, and grain fineness number is less than TiCN and Al of 10nm
2o
3composite powder.Synthesis technique of the present invention is simple, and synthesis temperature is low, and synthetic powder grain fineness number is tiny, can improve the sintering activity of powder, contributes to the sintering temperature reducing powder.
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 when powder size is very thin, usually can cause that powder adsorption impurity is more, powder mixing is uneven.Solid-phase synthesis, carbothermic method, self-propagating high-temperature synthesis in the synthetic method of traditional TiCN, usual synthesis temperature higher (> 1000 DEG C), energy consumption is large, and the TiCN coarse grains of synthesis 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 synthesis 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 with Ti powder, C powder for raw material, flowing N
2or NH
3high-energy ball milling under atmosphere, but Ti powder price is higher, and pass into the N of flowing
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, and 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 3:4 ~ 4.05:2 in molar ratio ~ 2.7:0.1 ~ 0.2 mixes;
2) load in ball grinder by above-mentioned mixed powder and abrading-ball, the mass ratio of abrading-ball and mixed powder is 20 ~ 30:1;
3) ball grinder is covered tightly, seal after filling, 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 μm, purity > 99.5%, described Al Powder Particle Size < 10 μm, purity > 99.5%, described Graphite Powder 99 granularity < 10 μm, 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 fine uniform, granularity is less than 2 μm, and mean particle size is 0.71 μm, TiCN and Al in composite powder
2o
3mol ratio is 3:2.
The beneficial effect adopting technique scheme to produce is: the 1) low (TiO of the method raw materials cost
2price less than 1/10th of Ti, urea price also comparatively N
2and NH
3cheap), synthesis temperature low (room temperature), energy consumption is little, and equipment and process is simple, the TiCN/Al of synthesis
2o
3composite powder is fabricated in situ powder, and powder mixes, and adsorbing contaminant is few, powder particle size and grain fineness number tiny, be conducive to sintering.
2) the inventive method utilizes reaction ball milling method golden red stone flour, Al powder, Graphite Powder 99 and urea at room temperature to be carried out ball milling, TiCN and Al of preparation
2o
3composite powder granularity is less than 2 μm, and mean particle size is 0.71 μm, and grain fineness number is less than 10nm, excellent property.
Accompanying drawing explanation
Fig. 1 is golden red stone flour, Al powder, and the 3:4:2.7:0.15 mixing in molar ratio of Graphite Powder 99 and urea, without raw material XRD spectra during ball milling;
Fig. 2 is golden red stone flour, Al powder, the 3:4:2.7:0.15 mixing in molar ratio of Graphite Powder 99 and urea, 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, the 3:4:2.7:0.15 mixing in molar ratio of Graphite Powder 99 and urea, after different ratio of grinding media to material and different Ball-milling Time ball milling, and the XRD spectra of powder after 1100 DEG C 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, the 3:4:2.7:0.15 mixing in molar ratio of Graphite Powder 99 and urea, 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 the 3:4:2.7:0.15 mixing in molar ratio of Graphite Powder 99 and urea, 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 the 3:4:2.7:0.15 mixing in molar ratio of Graphite Powder 99 and urea, 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 μm, purity > 99.5%), Al powder (granularity < 10 μm, purity > 99.5%), Graphite Powder 99 (granularity < 10 μm, 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 XRD analysis, the results are shown in Figure 2(a), the diffraction peak of TiCN can only be seen in figure, can't see Al
2o
3diffraction peak, consider that XRD is to amorphous and very tiny nanocrystalline insensitive of crystal grain, therefore carries out 1100 DEG C of vacuum annealings by the powder after ball milling, if there is Al
2o
3amorphous or nanometer crystalline phase, annealing after crystal grain will grow up, will reflect normally in XRD spectra, experiment prove, really have the Al of amorphous or nanometer crystalline phase
2o
3generate (see 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, (see Fig. 4, Fig. 5).As can be seen from SEM photo, the granularity of synthetic powder is less than 2 μm, most of powder size below 1 μm, (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, crystal particle scale at 4-6nm, this and the grain fineness number consistent (see Fig. 2 (a)) utilizing Scherrer formulae discovery XRD result to obtain.
Embodiment 2
By golden red stone flour (granularity < 10 μm, purity > 99.5%), Al powder (granularity < 10 μm, purity > 99.5%), Graphite Powder 99 (granularity < 10 μm, purity > 99.0%) and urea (analytical pure) 3:4:2.7:0.15 mixing in molar ratio, be sealed in together with stainless steel abrading-ball in stainless steel jar mill, 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 XRD analysis, the results are shown in Figure 2(b), the grain fineness number utilizing Scherrer formulae discovery XRD result to obtain synthesizing TiCN powder is 4 ~ 7nm.The diffraction peak of TiCN can only be seen in figure, can't see Al
2o
3diffraction peak, consider that XRD is to amorphous and very tiny nanocrystalline insensitive of crystal grain, therefore carries out 1100 DEG C of vacuum annealings by the powder after ball milling, if there is Al
2o
3amorphous or nanometer crystalline phase, annealing after crystal grain will grow up, XRD will reflect normally, experiment prove, really have the Al of amorphous or nanometer crystalline phase
2o
3generate (see 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 μm, purity > 99.5%), Al powder (granularity < 10 μm, purity > 99.5%), Graphite Powder 99 (granularity < 10 μm, 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, 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 XRD analysis, the results are shown in Figure 2(c), the grain fineness number utilizing Scherrer formulae discovery XRD result to obtain synthesizing TiCN powder is 5 ~ 8nm.The diffraction peak of TiCN can only be seen in figure, can't see Al
2o
3diffraction peak, consider that XRD is to amorphous and very tiny nanocrystalline insensitive of crystal grain, therefore carries out 1100 DEG C of vacuum annealings by the powder after ball milling, if there is Al
2o
3amorphous or nanometer crystalline phase, annealing after crystal grain will grow up, XRD will reflect normally, experiment prove, really have the Al of amorphous or nanometer crystalline phase
2o
3generate (see 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, in-situ synthesizing TiC N/Al
2o
3composite powder, the grain fineness number < 10nm of synthetic powder, granularity is less than 2 μm, and mean particle size is 0.71 μm, 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 3:4 ~ 4.05:2 in molar ratio ~ 2.7:0.1 ~ 0.2 mixes;
2) load in ball grinder by above-mentioned mixed powder and abrading-ball, the mass ratio of abrading-ball and mixed powder is 20 ~ 30:1;
3) ball grinder is covered tightly, seal after filling, 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 μm, purity > 99.5%, described Al Powder Particle Size < 10 μm, purity > 99.5%, described Graphite Powder 99 granularity < 10 μm, 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, and 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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| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1083587A (en) * | 1993-09-20 | 1994-03-09 | 中国科学院力学研究所 | The mat heat separator reduces the cryonetic wind tunnel of stagnation temperature |
| CN1559912A (en) * | 2004-03-02 | 2005-01-05 | 山东大学 | Preparation process for three elemental compound powder material of titanium carbonitride |
| CN101723670A (en) * | 2009-12-03 | 2010-06-09 | 陕西科技大学 | Ti(CxN1-x)/Al2O3 composite material and preparation method thereof |
| CN103130506A (en) * | 2013-03-15 | 2013-06-05 | 长沙伟徽高科技新材料股份有限公司 | Method for preparing superfine titanium carbonitride |
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|---|---|---|---|---|
| JP2571772B2 (en) * | 1986-08-29 | 1997-01-16 | 三菱マテリアル株式会社 | Surface coated cutting tool with excellent fracture resistance |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1083587A (en) * | 1993-09-20 | 1994-03-09 | 中国科学院力学研究所 | The mat heat separator reduces the cryonetic wind tunnel of stagnation temperature |
| CN1559912A (en) * | 2004-03-02 | 2005-01-05 | 山东大学 | Preparation process for three elemental compound powder material of titanium carbonitride |
| CN101723670A (en) * | 2009-12-03 | 2010-06-09 | 陕西科技大学 | Ti(CxN1-x)/Al2O3 composite material and preparation method thereof |
| CN103130506A (en) * | 2013-03-15 | 2013-06-05 | 长沙伟徽高科技新材料股份有限公司 | Method for preparing superfine titanium carbonitride |
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