CN100450970C - Atmospheric synthetic method for high purity titamum aluminum carbide ceramic powder - Google Patents

Abstract

The present invention discloses atmospheric synthesis process of high purity titanium aluminum carbide (Ti3AlC2) ceramic powder. High purity Ti3AlC2 ceramic powder is prepared through mixing Ti powder, Al powder, TiC powder and Sn as reaction assistant in the molar ratio of 1 to 1 to 1 to (0.1-0.2) for 5-10 hr; pressing at 10-50 MPa into block; and sintering in a high temperature furnace under protection of argon in the temperature raising rate of 15-50 deg.c/min and through maintaining at 1350-1550 deg.c for 5-15 min. The present invention has the advantages of simple apparatus, stable technological parameters, short Ti3AlC2 powder preparing period, high product purity and low cost, and is suitable for industrial production.

Description

The atmospheric synthesizing method of high purity titamum aluminum carbide ceramic powder

Technical field

The present invention relates to a kind of preparation method of ceramic powder, particularly high purity carbonization aluminium titanium Ti ₃AlC ₂The atmospheric synthesizing method of ceramic powder.

Background technology

Aluminium-titanium carbonate Ti ₃AlC ₂Have high conductivity, high heat conductance, anti-oxidant, heat shock resistance, corrosion-resistant, self-lubricating, easy premium properties such as processing.This novel lamellar double carbide integrates the advantage of metal and pottery, and structure set and function integration can be widely used in fields such as aerospace, petrochemical complex, communications and transportation, new forms of energy, electronic information.

At present, great majority research concentrates on hot pressing, hot isostatic pressing technique and prepares Ti ₃AlC ₂The compact block material.Document (J.Am.Ceram.Soc., 2000; 83[4]: 825) report, with Ti powder, Al ₄C ₃Powder and Graphite Powder 99 are raw material, and at 1400 ℃, hot isostatic pressing is 16 hours under the 70MPa pressure, prepares Ti ₃AlC ₂Block materials.Chinese invention patent 1 (ZL00123203.7) report, with Ti powder, Al powder and C powder is raw material, presses Ti: Al: C=3: 1: 2 molar ratio ingredient, with in-situ hot pressing/solid-liquid reaction method, 1200～1500 ℃, the following hot pressing of 25MPa pressure 0.5～4 hour, prepare Ti ₃AlC ₂Block materials.Chinese invention patent 2 (application number: 200610009694.0) report, with Ti powder, Al powder and C powder is raw material, press Ti: Al: C=67%: 23%: 10% weight ratio batching, utilize from spreading hot isostatic pressing method, under 180～225 tons pressure, prepared large size Ti ₃AlC ₂Block materials.

The characteristics of aforesaid method are 1. only to be fit to the preparation block materials, but to be not suitable for Ti ₃AlC ₂Synthesizing of powder; 2. there are TiC or Al in the final product ₂O ₃The impurity phase; 3. sintering time is long, time consumption and energy consumption, and efficient is low, causes the material cost height.

Because Ti ₃AlC ₂Have many premium propertiess, on engineering, need a large amount of high purity Tis ₃AlC ₂Powder is that raw material carries out the Ti that double sintering prepares various practicalities ₃AlC ₂And matrix material device; Or with it as additive, the high temperature self-lubricating composite of toughened and reinforced ceramic base and metal-base composites or synthesizing new etc.Therefore, high purity, low-cost Ti ₃AlC ₂Powder and synthetic method thereof are for Ti ₃AlC ₂The practical application of material has crucial meaning.

At preparation Ti ₃AlC ₂The powder aspect, at present mainly with Ti, Al and C powder are raw material, press Ti: Al: C=3: 1: 2 molar ratio ingredient, by combustion synthesis method (J.Eur.Ceram.Soc.2003,23:567; Rare Metals Materials and engineering .2003,32 (7): 561.) synthesize, but have following problem:

1) in the reaction process, a large amount of heat is emitted in Ti and C reaction, causes " thermal explosion " phenomenon appearance in the system, and system temperature is raise, and causes Al volatilization loss serious, thereby has changed the reaction ratio of each element in the system, influences the purity of synthetics.

2) " thermal explosion " phenomenon causes temperature big ups and downs in the stove, the intravital heating member of infringement stove.Even add sintering aid (as B ₂O ₃, low melting components such as NaF) and reduce the thermal explosion degree, because the volatilization of low melting point constituent element can cause the corrosion of body of heater internal heating spare and the pollution of environment.

3) there is TiC impurity phase in the product usually.The existence of TiC has not only influenced Ti ₃AlC ₂The purity of powder, and to Ti ₃AlC ₂The high conductivity of material, self-lubricating and excellent specific property such as can process disadvantageous effect is all arranged;

When 4) burning was synthetic, temperature was wayward, and the processing parameter instability.

Summary of the invention

Technical problem to be solved by this invention is, changes traditionally with Ti, and Al and C powder are the synthetic Ti of initial batching ₃AlC ₂The problem that exists directly adopts Ti, and Al and TiC powder are raw material, and interpolation Sn is a reaction promoter, in wide temperature range, in the short period of time, realizes high purity and low-cost Ti with the normal pressure synthesis technology ₃AlC ₂The large-scale production of powder.

Technical scheme of the present invention is:

High purity Ti ₃AlC ₂The atmospheric synthesizing method of ceramic powder:

(1) be raw material with Ti powder, Al powder and TiC powder, Sn is a reaction promoter, presses Ti: Al: TiC: Sn=1: 1: 1: the molar ratio ingredient of (0.1～0.2);

(2) above-mentioned batching and agate ball are put into ball grinder, on ball mill, do and mixed 5～10 hours;

(3) with the above-mentioned batching that mixes briquetting under 10～50MPa pressure;

(4) above-mentioned briquetting is placed High Temperature Furnaces Heating Apparatus, argon shield atmosphere rises to 1350～1550 ℃ with the temperature rise rate of 15～50 ℃/min with furnace temperature, and soaking time is 5～15min, is cooled to room temperature, obtains high purity Ti ₃AlC ₂Powder.

Beneficial effect of the present invention is:

The first, the present invention is according to Ti: Al: TiC=1: 1: 1 molar ratio ingredient, normal pressure synthesis Ti ₃AlC ₂Ti with the synthetic equal in quality of this prescription ₃AlC ₂Powder, and Ti: Al: C=3: 1: 2 prescription is compared, and has reduced the content of raw material powder, has reduced cost.

The second, technical process of the present invention is simple, in the vacuum oven of routine, and under argon gas (or vacuum) protective atmosphere, synthetic Ti ₃AlC ₂Powder purity height, generated time is short, the synthesis temperature wide ranges, processing parameter is stable, is applicable to large-scale production.

The 3rd, with Ti, Al and C traditional proportioning synthesize Ti ₃AlC ₂Process in, must have the reaction of Ti and C to generate TiC, again by TiC and Ti-Al compound reaction generation Ti ₃AlC ₂But with respect to Ti ₃AlC ₂Formation speed, the generation of TiC has hysteresis quality in the system, has reduced Ti ₃AlC ₂Resultant velocity.If directly adopt TiC, reaction process and the step of Ti-C have been reduced, as long as reach temperature, just TiC generates Ti with Ti-Al compound direct reaction ₃AlC ₂, make Ti ₃AlC ₂Resultant velocity obviously accelerate;

The 4th, in batching, adopt TiC to replace whole C and part Ti, avoided the generation of thermal explosion reaction in conventional Ti-Al-C system, can not cause the fluctuation of temperature, reduced the high temperature loss problem of Al, sintering process parameter is easy to stablize, and helps system components and generates by design proportion, guarantees high purity Ti ₃AlC ₂Synthetic.

The 4th, the present invention adopts Sn to be as the advantage of reaction promoter: 1. in the temperature more than 232 ℃, because liquid phase appears in the fusing of Sn, each component is tending towards homogenizing, helps reaction in the environment that liquid phase exists and carries out; 2. Sn can remedy the volatilization loss of Al in the reaction building-up process, promotes Ti ₃AlC ₂Formation; 3. after reaction was finished, the Sn atom entered Ti ₃AlC ₂Form sosoloid in the lattice, and can not be present in mutually in the product, therefore to Ti with impurity ₃AlC ₂The purity and the characteristic of powder do not have substantial effect.

Description of drawings

Fig. 1 is the Ti of normal pressure synthesis method preparation of the present invention ₃AlC ₂The X-ray diffraction of ceramic powder (XRD) collection of illustrative plates.

Embodiment

Embodiment one:

1) press Ti: Al: TiC: Sn=1: 1: 1: 0.1 molar ratio ingredient takes by weighing Ti powder 24.6 grams, Al powder 13.9 grams, TiC powder 30.8 grams, Sn powder 6.1 grams.

2) above-mentioned batching was put into the ball grinder batch mixing 5 hours.

3) batching that will mix is pressed into block under the pressure of 10MPa.

4) above-mentioned briquetting is put into High Temperature Furnaces Heating Apparatus, argon shield atmosphere rises to 1350 ℃ with the temperature rise rate of 30 ℃/min with furnace temperature, and soaking time is 15min, promptly makes high purity Ti ₃AlC ₂Powder, the X-ray diffraction of powder (XRD) collection of illustrative plates is seen accompanying drawing 1.As seen from the figure, the product purity height, impurity such as no TiC exists mutually in XRD figure spectrum.

Embodiment two:

1) press Ti: Al: TiC: Sn=1: 1: 1: 0.1 molar ratio ingredient takes by weighing Ti powder 24.6 grams, Al powder 13.9 grams, TiC powder 30.8 grams, Sn powder 6.1 grams.

2) above-mentioned batching was put into the ball grinder batch mixing 5 hours.

3) batching that will mix is pressed into block under the pressure of 10MPa.

4) above-mentioned briquetting is put into High Temperature Furnaces Heating Apparatus, argon shield atmosphere rises to 1400 ℃ with the temperature rise rate of 40 ℃/min with furnace temperature, and soaking time is 10min, makes high purity Ti ₃AlC ₂Powder, its XRD result is identical with embodiment one.

Embodiment three:

1) press Ti: Al: TiC: Sn=1: 1: 1: 0.15 molar ratio ingredient takes by weighing Ti powder 28.7 grams, Al powder 16.2 grams, TiC powder 35.9 grams, Sn powder 10.7 grams.

2) above-mentioned batching was put into the ball grinder batch mixing 6 hours.

3) batching that will mix is pressed into block under the pressure of 30MPa.

4) above-mentioned briquetting is put into High Temperature Furnaces Heating Apparatus, argon shield atmosphere rises to 1450 ℃ with the temperature rise rate of 40 ℃/min with furnace temperature, and soaking time is 15min, makes high purity Ti ₃AlC ₂Powder, its XRD result is identical with embodiment one.

Embodiment four:

1) press Ti: Al: TiC: Sn=1: 1: 1: 0.15 molar ratio ingredient takes by weighing Ti powder 28.7 grams, Al powder 16.2 grams, TiC powder 35.9 grams, Sn powder 10.7 grams.

2) above-mentioned batching was put into the ball grinder batch mixing 10 hours.

3) batching that will mix is pressed into block under the pressure of 50MPa.

4) above-mentioned briquetting is put into High Temperature Furnaces Heating Apparatus, argon shield atmosphere rises to 1500 ℃ with the temperature rise rate of 20 ℃/min with furnace temperature, and soaking time is 5min, makes high purity Ti ₃AlC ₂Powder, its XRD result is identical with embodiment one.

Claims (1)

1. the atmospheric synthesizing method of high purity titamum aluminum carbide ceramic powder is characterized in that:

(1) be raw material with Ti powder, Al powder and TiC powder, Sn is a reaction promoter, presses Ti: Al: TiC: Sn=1: 1: 1: the molar ratio ingredient of (0.1～0.2);

(2) above-mentioned batching and agate ball are put into ball grinder, on ball mill, do and mixed 5～10 hours;

(3) with the above-mentioned batching that mixes briquetting under 10～50MPa pressure;

(4) above-mentioned briquetting is placed High Temperature Furnaces Heating Apparatus, argon shield atmosphere rises to 1350～1550 ℃ with the temperature rise rate of 15～50 ℃/min with furnace temperature, and soaking time is 5～15min, obtains high purity Ti ₃AlC ₂Powder.

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