CN101323464A - Multiactivating preparation of titanium carbonitride nanopowder - Google Patents
Multiactivating preparation of titanium carbonitride nanopowder Download PDFInfo
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- CN101323464A CN101323464A CNA200710049299XA CN200710049299A CN101323464A CN 101323464 A CN101323464 A CN 101323464A CN A200710049299X A CNA200710049299X A CN A200710049299XA CN 200710049299 A CN200710049299 A CN 200710049299A CN 101323464 A CN101323464 A CN 101323464A
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Abstract
A multiple activation preparation method used for preparing a titanium carbonitride nano-powder adopts titanium oxide, titanium powder and carbon powder as materials and sequentially adopts the following steps of: material preparing, charging, mechanical milling, discharging, (charging), (hot processing), purifying, drying and sifting. The technology of the method is simple and the cost and the reaction temperature is low. The titanium carbonitride nano-powder with diverse carbon contents can be synthesized through controlling the proportioning ratio between titanium and titanium oxide, time of mechanical milling and the following hot processing, etc. The titanium carbonitride powder prepared through the method appears as a ball shape and has better dispersity, with average granularity which is less than 100nm and purity which is greater than 99 percent.
Description
One, technical field
The present invention relates to a kind of multiple activation preparation method of titanium carbonitride nano powder.
Two, background technology
In cutter material, consider that from over-all properties, Financial cost and the utilization of resources equal angles base titanium carbonitride all has advantage than tungsten carbide base carbide alloy.Discover, less than the sub-micro of 1 μ m, ultra-fine, nanometer hard phase powdered preparation or add modified metal-ceramic, can improve the use properties of base titanium carbonitride greatly with granularity.At present, the method for preparing the titanium carbonitride fine powder has plasma method, is 02125986.0 as application number, and name is called the Chinese patent application of " technology of preparing titanium carbonitride ceramic powder body by utilizing plasma chemial gas phase synthesis method "; Combustion synthesis method is 200510010013.8 as application number, and name is called the Chinese patent application of " burning synthesis method of sub-micron titanium carbide nitride powder "; The high energy mechanical ball milled is 200510042366.6 as application number, and name is called the Chinese patent application of " preparation method of nano-carbon titanium nitride powder "; Cryochem process is 200410023706.6 as application number, and name is called the Chinese patent application of " preparation method of titanium carbonitride ternary compound powder body material " or the like.
Analyze aforesaid method, can find that they generally have the raw materials cost height, technology is loaded down with trivial details, synthetic product granularity is big, output (rate) is lower, one or more shortcomings of apparatus expensive or the like, therefore limited it in industrial large-scale production.
Three, summary of the invention
We are in two Chinese invention patent applications of 200510021718.X and 200610022475.6 at application number, propose the pyrocarbon nitrogenizing reaction by nano-titanium oxide and nano-carbon powder respectively and prepared the method for titanium carbonitride ultrafine powder in conjunction with subsequent ball milling, and by mechanical activation nano raw material in advance and in conjunction with the hot nitrogenizing reaction of follow-up lesser temps carbon, thereby prepare the method for titanium carbonitride nanometer powder.For in the hot nitrogenizing reaction temperature of low-carbon (LC) more, or even room temperature directly prepares the nanometer product, the present invention proposes at first to add a certain amount of metallic titanium powder, the novel method of mechanical ball milling raw mix synthesis of nano titanium carbonitride in nitrogen containing atmosphere then in titanium oxide and carbon dust raw material.
Principle of the present invention is: Ti-C-N
2The reaction of the synthetic titanium carbonitride of system is a strong exothermal reaction, and this is reflected at, and liberated heat can activate TiO in mechanical activation or the subsequent heat treatment
2-C-N
2Be thermo-negative reaction, and then this reaction can be carried out under than the lower temperature of simple mechanical activation.
Method provided by the invention is a raw material with titanium oxide, titanium valve, carbon dust, and processing step is as follows:
1, batching
Titanium, titanium oxide mol ratio were more than or equal to 1.2: 1;
2, charging
The ball grinder of earlier confected materials being packed into feeds nitrogenous gas again in ball grinder;
3, mechanical ball milling
Mechanical ball milling raw material for some time on high energy ball mill;
4, get material
In vacuum glove box, take out the ball milling material;
Annotate: reacted in mechanical milling process as mixing raw material and finish, then following steps 5,6 are omitted.
5, charging
The ball milling material is put into the crucible of carbon tube furnace;
6, thermal treatment
(1) closed system
Begin heating when certain vacuum is spent when being extracted in the carbon tube furnace, thermal treatment temp is 800～1050 ℃, and the time is 0～1h (if necessary, needing to feed a certain amount of nitrogen before arriving thermal treatment temp in stove);
(2) open system
Applying argon gas in carbon tube furnace (or nitrogen) is to being a bit larger tham 1 standard atmospheric pressure, and through-flow more moving argon gas (or nitrogen) and intensification are simultaneously heated, and thermal treatment temp is 800～1100 ℃, and the time is 0～1h;
7, purify
Refilter ball milling or thermal treatment product soaked 24h in 5～10% hydrochloric acid after;
8, drying
Product powder after oven dry is purified;
9, sieve
To dry the product powder sieve product.
Method synthetic product provided by the invention is the titanium carbonitride solid-solution powder, and its particle is spherical, and is better dispersed, and the average product granularity is below 100nm, and purity reaches (the XRD figure spectrum goes up the inclusion-free peak) more than 99%.
The present invention has following advantage:
1, need not subsequent heat treatment or the only follow-up lesser temps thermal treatment of need;
The nano-carbon titanium nitride that 2, can synthesize various carbon contents by control titanium/titanium oxide proportioning, high-energy ball milling time, subsequent heat treatment technology etc.;
3, synthetic titanium carbonitride purity is higher, and particle is thin, and particle size distribution range is narrower;
4, raw material is more cheap, and domestic manufacturer can supply in batches;
5, equipment, technology are simple, are convenient to operation.
Four, description of drawings
Fig. 1 is a kind of process flow sheet according to the multiple activation preparation method of nano-carbon titanium nitride provided by the present invention.
Five, embodiment
Embodiment 1:
In the present embodiment, raw material is titanium oxide, titanium valve, carbon dust, by technical process Fig. 1 following processing step is arranged:
(1) batching
The mol ratio of titanium valve and titanium oxide is 2.0: 1;
(2) charging
The ball grinder of earlier confected materials being packed into feeds N again in ball grinder
2/ Ar mixed gas;
(3) mechanical ball milling
High energy dry grinding raw mix on the self-control vibromill, ball material weight ratio is 30: 1, and drum's speed of rotation is 700rpm/min, and the ball milling time is 40h;
(4) get material
In vacuum glove box, take out the ball milling material;
(5) charging
A certain amount of ball milling material is put into the crucible of carbon tube furnace;
(6) thermal treatment
With being extracted into vacuum tightness in the carbon tube furnace is 2.0 * 10
-2Begin heating during MPa, to 1050 ℃ of insulation 1h with 20 ℃/min;
(7) purify
Refilter the thermal treatment product soaked 24h in 10% hydrochloric acid after;
(8) drying
Product powder after oven dry is purified;
(9) sieve
To dry the product powder sieve product.
Embodiment 2:
In the present embodiment, raw material is titanium oxide, titanium valve, carbon dust, by technical process Fig. 1 following processing step is arranged:
(1) batching
The mol ratio of titanium valve and titanium oxide is 2.5: 1;
(2) charging
The ball grinder of earlier confected materials being packed into feeds N again in ball grinder
2/ Ar mixed gas;
(3) mechanical ball milling
High energy dry grinding raw mix on the self-control vibromill, ball material weight ratio is 30: 1, and drum's speed of rotation is 700rpm/min, and the ball milling time is 100h;
(4) get material
In vacuum glove box, take out the ball milling material;
(5) purify
Refilter the ball milling product soaked 24h in 10% hydrochloric acid after;
(6) drying
Product powder after oven dry is purified;
(7) sieve
To dry the product powder sieve product.
Claims (1)
1, a kind of multiple activation preparation method of titanium carbonitride nano powder is characterized in that with titanium oxide, titanium valve, carbon dust be raw material, and its processing step is as follows:
1, batching
Titanium, titanium oxide mol ratio were more than or equal to 1.2: 1;
2, charging
The ball grinder of earlier confected materials being packed into feeds nitrogenous gas again in ball grinder;
3, mechanical ball milling
Mechanical ball milling raw material for some time on high energy ball mill;
4, get material
In vacuum glove box, take out the ball milling material;
Annotate: reacted in mechanical milling process as mixing raw material and finish, then following steps 5,6 are omitted.
5, charging
The ball milling material is put into the crucible of carbon tube furnace;
6, thermal treatment
(1) closed system
Begin heating when certain vacuum is spent when being extracted in the carbon tube furnace, thermal treatment temp is 800～1050 ℃, and the time is 0～1h (if necessary, needing to feed a certain amount of nitrogen before arriving thermal treatment temp in stove);
(2) open system
Applying argon gas in carbon tube furnace (or nitrogen) is to being a bit larger tham 1 standard atmospheric pressure, and through-flow more moving argon gas (or nitrogen) and intensification are simultaneously heated, and thermal treatment temp is 800～1100 ℃, and the time is 0～1h;
7, purify
Refilter ball milling or thermal treatment product soaked 24h in 5～10% hydrochloric acid after;
8, drying
Product powder after oven dry is purified;
9, sieve
To dry the product powder sieve product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710049299A CN100590075C (en) | 2007-06-14 | 2007-06-14 | Multiactivating preparation of titanium carbonitride nanopowder |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710049299A CN100590075C (en) | 2007-06-14 | 2007-06-14 | Multiactivating preparation of titanium carbonitride nanopowder |
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| CN101323464A true CN101323464A (en) | 2008-12-17 |
| CN100590075C CN100590075C (en) | 2010-02-17 |
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| CN200710049299A Active CN100590075C (en) | 2007-06-14 | 2007-06-14 | Multiactivating preparation of titanium carbonitride nanopowder |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104046828A (en) * | 2014-05-15 | 2014-09-17 | 四川大学 | High energy ball milling process-containing preparation method for nanometer multi-element composite crystal grain growth inhibitor |
| CN110980667A (en) * | 2019-12-25 | 2020-04-10 | 株洲鸿达实业有限公司 | Micro-nano TiCN powder and preparation method and application thereof |
| CN113004048A (en) * | 2021-03-10 | 2021-06-22 | 滁州学院 | Preparation method of titanium oxycarbonitride ceramic powder |
-
2007
- 2007-06-14 CN CN200710049299A patent/CN100590075C/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104046828A (en) * | 2014-05-15 | 2014-09-17 | 四川大学 | High energy ball milling process-containing preparation method for nanometer multi-element composite crystal grain growth inhibitor |
| CN110980667A (en) * | 2019-12-25 | 2020-04-10 | 株洲鸿达实业有限公司 | Micro-nano TiCN powder and preparation method and application thereof |
| CN113004048A (en) * | 2021-03-10 | 2021-06-22 | 滁州学院 | Preparation method of titanium oxycarbonitride ceramic powder |
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| Publication number | Publication date |
|---|---|
| CN100590075C (en) | 2010-02-17 |
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