CN105732040B - A kind of microwave self- propagating method preparation Ti3AlC2Synthetic method - Google Patents

Abstract

A kind of microwave self- propagating method preparation Ti₃AlC₂Synthetic method, raw material Ti powder, TiC powder, Al powder, carbon dust, silica flour, glass putty are subjected to dispensing according to molar ratio first, be added equal quality ethyl alcohol stir evenly after, 25 times of quality agate ball of different sizes, 4 12h of ball milling on high speed ball mill is added.By the pulp centrifuged processing after ball milling, for 24 hours, 5 25MPa are dry-pressing formed in FIxed abrasive article for drying at room temperature after recycling powder, and isostatic cool pressing processing is then carried out in the pressure range of 120 200MPa.Block after isostatic cool pressing is put into self-control ceramic mold, the mold for filling sample is put into microwave reactor, 10 20min of furnace cooling after reaction, mold, which is moved to room temperature, cools down 10 20min, takes out the material of synthesis, is recycled after carrying out mechanical crushing.Present invention process is simple, energy-efficient, is well suited for industrialized production.

Description

A kind of microwave self- propagating method preparation Ti3AlC2Synthetic method

Technical field：The present invention relates to a kind of Ti₃AlC₂The preparation method of material more particularly to a kind of microwave self- propagating method Prepare Ti₃AlC₂Synthetic method.

Background technology：Ti₃AlC₂It is M₃AX₂A kind of new compound in system belongs to a kind of cermet material of stratiform Material.Ti₃AlC₂With space octahedron connection hexagonal layered structure feature, have concurrently metal and ceramics double grading, one Aspect its with good electric conductivity and thermal conductivity, higher elasticity modulus, thermal shock resistance, high temperature plasticity and machinability etc. Metalloid characteristic；And on the other hand, with high yield strength, high-melting-point, high thermal stability, highly oxidation resistant and corrosion etc. Typical ceramic characteristics.These excellent characteristics assign it in electromechanics, metallurgy, chemical industry, automobile, ship, petrochemical industry, space flight and national defence The potential using value space in equal fields.

Although Ti₃AlC₂Excellent properties attracted extensive concern both domestic and external.But due in Ti- Al-C ternary phase diagrams In, single Ti₃AlC₂Phase stable range is narrow, therefore preparation process is relative complex.Currently used preparation method has hot pressed sintering Method, HIP sintering method, discharge plasma sintering method, pulsed discharge plasma sintering process, machine-alloying, self- propagating are high Warm synthetic method, vacuum non-pressure sintering method, laser melting method etc..Wherein hot pressing, hot isostatic pressing or vacuum non-pressure sintering method this three Kind method is required to high temperature and longer soaking time to maintain the progress of reaction, so the actual consumption in reaction process is very Greatly.And discharge plasma sintering or pulsed discharge plasma sintering process need expensive Preparation equipment and high energy consumption.Swash Although the light fusion method reaction time is shorter, it requires Preparation equipment high, low yield, it is difficult to extensive use.And it is traditional Although self-propagating high-temperature energy consumption it is relatively low, be swift in response, it is simple for process, reaction process be difficult to control, exist in reaction process Prodigious temperature gradient, product purity are relatively low.Thus it is high-purity in production synthesis really to be able to batch application for current shortage Ti₃AlC₂The technical method of material.

Invention content：The invention aims to solve current Ti₃AlC₂In material synthesis processes when equipment costliness, reaction Between it is long, product purity is low, synthesis condition is harsh, material reaction yield uncontrollable especially for technique in current self- propagating method Low problem provides a kind of microwave self- propagating method preparation Ti using microwave high-temperature self- propagating technology₃AlC₂Synthetic method.

To achieve the above object, the technical solution adopted by the present invention is：A kind of microwave self- propagating method preparation Ti₃AlC₂Conjunction At method, detailed process is as follows：

(1) dispensing and ball milling：By raw material Ti powder (or TiH₂Powder), TiC powder, Al powder, carbon dust, silica flour, glass putty according to mole Than (1.9-3.2):(0-1.3):(1-1.3):(1- 2.2):(0-0.2):(0-0.1) carries out dispensing, and the second of equal quality is added After alcohol stirs evenly, 2-5 times of quality agate ball of different sizes, the ball milling 4-12h on high speed ball mill is added.

(2) dry and molding：By the pulp centrifuged processing after ball milling, after recycling powder drying at room temperature for 24 hours, in fixing mould Middle 5-25MPa is dry-pressing formed, and isostatic cool pressing processing is then carried out in the pressure range of 120-200MPa.

(3) microwave self-propagating synthesis：Block after isostatic cool pressing is put into self-control ceramic mold, mold passes through stringent Design has three layers of composite-like structures, and the mold short time, which bears internal-external temperature difference, will fill the mould of sample up to 600 DEG C or more Tool is put into microwave reactor, reaction power 200-2000W, reaction time 3-10min.The self-control ceramic mold is by inorganic Outer cover, ceramic buffer layer, positioning clamp pin, reaction module chamber, thermal insulation layer and ceramic backing composition.Ceramic buffer layer is in inorganic In outer cover.Thermal insulation layer is fixed on by positioning to clamp to sell in ceramic buffer layer, and reaction module chamber is in thermal insulation layer.Ceramic backing Lower end in inorganic housing.The ceramics buffer layer includes porous ceramics.

(4) material recovery：Mold is moved to room temperature and cools down 10- 20min, takes out synthesis by furnace cooling 10-20min after reaction Material is recycled after carrying out mechanical crushing.

The technology of the present invention advantage：

(1) uniform, controllable is reacted：Using microwave self-propagating synthesis technology, overcome traditional resistor silk ignite or outside ignite from Sprawling technique causes local temperature excessively high, reacts the shortcomings that there are temperature gradients, and reaction is uniformly synthesized powder purity height, leads to simultaneously Cross control microwave power, isostatic mold block size, processing time can indirect control synthesis temperature and time, inhibit reaction in other The generation of dephasign.

(2) energy-efficient：Using the ceramic mold of simple three-layer composite structure and an easy microwave generator, reaction Without heating, while the characteristics of using itself deoxygenation self-expanding, reaction whole process is without being passed through inert gas or taking out true Vacancy is managed, and is swift in response, equipment is cheap.

(3) high reaction activity and compactness：The a large amount of volatilizations as aluminium melts of traditional self- propagating technology, generating a large amount of cavities makes Reactivity reduces, and thermal insulation layer is arranged in mold reaction internal layer in this technology, and due to reacting thermal expansion, internal-response is kept very High temperature generates certain expansion, since the effect of thermal insulation layer makes internal generation certain pressure, plays the work of hot pressing synthesis indirectly With, make reaction have high activity and compactness.

(4) environmental-friendly, pollution is low：Self-propagating reaction unavoidably will produce a large amount of dust, this can be to air, water body etc. It causes seriously to pollute.This technology nested porous wave transparent ceramics in reacting mold second layer transition zone, can be to produce in adsorption reaction Raw dust, 99% or more flue dust can be absorbed by the excessive layer of mold in entire reaction process, and pollution is low, environmental-friendly.

Description of the drawings：

Fig. 1 is the structural schematic diagram for making ceramic mold by oneself.

Specific implementation mode：

As shown in Figure 1：It makes ceramic mold by oneself and pin 3, reaction module chamber is clamped by inorganic housing 6, ceramic buffer layer 1, positioning 4, thermal insulation layer 2 and ceramic backing 5 form.Ceramic buffer layer 1 is in inorganic housing 6.Thermal insulation layer 2 clamps pin 3 by positioning and consolidates It is scheduled in ceramic buffer layer 1, reaction module chamber 4 is in thermal insulation layer 2.Ceramic backing 5 is in the lower end of inorganic housing 6.

Embodiment 1

73g titanium valves, 20g aluminium powders, 14g carbon dusts are weighed, 108.8g ethyl alcohol, 217.6g agate balls is added in 1.8g silica flours.It is put into With the speed ball milling 6h of 300r/min in ball grinder.Pulp centrifuged removal supernatant liquor,

Drying at room temperature for 24 hours, be pressed into block after the shape of requirement in isostatic pressed by small pressure molding machine 5MPa Machine 120MPa compactings are fine and close.Then block is put into homemade ceramic mold, is moved in microwave reactor, microwave treatment 3min, Room temperature cools down 15min again after furnace cooling 15min, and the material mechanical for taking out synthesis crushes acquisition sample.

Embodiment 2

80g hydride powders, 16g aluminium powders, 14g carbon dusts, 1.2g silica flours are weighed, 112g ethyl alcohol, 224g agates is added in 0.8g glass puttys Nao balls.It is put into the speed ball milling 4h with 400r/min in ball grinder.Pulp centrifuged removal supernatant liquor, drying at room temperature for 24 hours, lead to Small-sized pressure forming machine 10MPa is crossed to be pressed into block after the shape of requirement in isostatic pressing machine 160MPa compacting densifications.Then block Body is put into homemade ceramic mold, is moved in microwave reactor, microwave treatment 5min, and room temperature cools down again after furnace cooling 15min 20min, the material mechanical for taking out synthesis crush acquisition sample.

Embodiment 3

Weigh 52g titanium valves, 14g aluminium powders, 7g carbon dusts, 30g carbonized titanium powders, 1.5g silica flours, 1g glass puttys, addition 105.5g second Alcohol, 250g agate balls.It is put into the speed ball milling 6h with 600r/min in ball grinder.Pulp centrifuged removal supernatant liquor, in room temperature Drying for 24 hours, is pressed into after the shape of requirement by small pressure molding machine 15MPa and causes block in isostatic pressing machine 150MPa compactings It is close.Then block is put into homemade ceramic mold, is moved in microwave reactor, microwave treatment 5min, room again after furnace cooling 20min The cooling 20min of temperature, the material mechanical for taking out synthesis crush acquisition sample.

Embodiment 4

80g titanium valves, 24g aluminium powders, 18g carbon dusts, 9g carbonized titanium powders are weighed, 133g ethyl alcohol, 300g agates is added in 2g glass puttys Ball.It is put into the speed ball milling 8h with 600r/min in ball grinder.Pulp centrifuged removal supernatant liquor, drying at room temperature for 24 hours, lead to Small-sized pressure forming machine 20MPa is crossed to be pressed into block after the shape of requirement in isostatic pressing machine 180MPa compacting densifications.Then block Body is put into homemade ceramic mold, is moved in microwave reactor, microwave treatment 8min, and room temperature cools down again after furnace cooling 20min 20min, the material mechanical for taking out synthesis crush acquisition sample.

Embodiment 5

Weigh 55g hydride powders, 18g aluminium powders, 6g carbon dusts, carbonized titanium powder 30g silica flours, 2g silica flours, 1g glass puttys, addition 112g ethyl alcohol, 400g agate balls.It is put into the speed ball milling 10h with 600r/min in ball grinder.Pulp centrifuged removal upper layer is clear Liquid, drying at room temperature for 24 hours, be pressed into block after the shape of requirement in isostatic pressing machine by small pressure molding machine 20MPa 200MPa compactings are fine and close.Then block is put into homemade ceramic mold, is moved in microwave reactor, microwave treatment 10min, stove Room temperature cools down 20min again after cold 20min, and the material mechanical for taking out synthesis crushes acquisition sample.

Claims (3)

1. a kind of microwave self- propagating method prepares Ti₃AlC₂Synthetic method, detailed process is as follows：

(1) dispensing and ball milling：By raw material Ti powder, TiC powder, Al powder, carbon dust, silica flour, glass putty according to molar ratio (1.9-3.2):(0- 1.3):(1-1.3):(1-2.2):(0-0.2):(0-0.1) carry out dispensing, be added equal quality ethyl alcohol stir evenly after, add Enter 2-5 times of quality agate ball of different sizes, the ball milling 4-12h on high speed ball mill；

(2) dry and molding：By the pulp centrifuged processing after ball milling, after recycling powder drying at room temperature for 24 hours, the 5- in fixing mould 25MPa is dry-pressing formed, and isostatic cool pressing processing is then carried out in the pressure range of 120-200MPa；

(3) microwave self-propagating synthesis：Block after isostatic cool pressing is put into self-control ceramic mold, mold is set by stringent Meter has three layers of composite-like structures, and the mold short time, which bears internal-external temperature difference, will fill the mold of sample up to 600 DEG C or more It is put into microwave reactor, reaction power 200-2000W, reaction time 3-10min；The self-control ceramic mold is by inorganic outer Cover, ceramic buffer layer, positioning clamp pin, reaction module chamber, thermal insulation layer and ceramic backing composition, and ceramic buffer layer is in inorganic outer In cover, thermal insulation layer is fixed on by positioning to clamp to sell in ceramic buffer layer, and reaction module chamber is in thermal insulation layer, at ceramic backing In the lower end of inorganic housing；

(4) material recovery：Mold is moved to room temperature and cools down 10-20min, takes out the material of synthesis by furnace cooling 10-20min after reaction, It is recycled after carrying out mechanical crushing.

2. a kind of microwave self- propagating method as described in claim 1 prepares Ti₃AlC₂Synthetic method, it is characterised in that：Described Ceramic buffer layer includes porous ceramics.

3. a kind of microwave self- propagating method prepares Ti₃AlC₂Synthetic method, detailed process is as follows：

(1) dispensing and ball milling：By raw material TiH₂Powder, TiC powder, Al powder, carbon dust, silica flour, glass putty are according to molar ratio (1.9-3.2): (0-1.3):(1-1.3):(1-2.2):(0-0.2):(0-0.1) carry out dispensing, be added equal quality ethyl alcohol stir evenly after, 2-5 times of quality agate ball of different sizes, the ball milling 4-12h on high speed ball mill is added；

(2) dry and molding：By the pulp centrifuged processing after ball milling, after recycling powder drying at room temperature for 24 hours, the 5- in fixing mould 25MPa is dry-pressing formed, and isostatic cool pressing processing is then carried out in the pressure range of 120-200MPa；

(3) microwave self-propagating synthesis：Block after isostatic cool pressing is put into self-control ceramic mold, mold is set by stringent Meter has three layers of composite-like structures, and the mold short time, which bears internal-external temperature difference, will fill the mold of sample up to 600 DEG C or more It is put into microwave reactor, reaction power 200-2000W, reaction time 3-10min；The self-control ceramic mold is by inorganic outer Cover, ceramic buffer layer, positioning clamp pin, reaction module chamber, thermal insulation layer and ceramic backing composition, and ceramic buffer layer is in inorganic outer In cover, thermal insulation layer is fixed on by positioning to clamp to sell in ceramic buffer layer, and reaction module chamber is in thermal insulation layer, at ceramic backing In the lower end of inorganic housing；

(4) material recovery：Mold is moved to room temperature and cools down 10-20min, takes out the material of synthesis by furnace cooling 10-20min after reaction, It is recycled after carrying out mechanical crushing.