CN102181765B

CN102181765B - A (Ti, cr)3AlC2/Al2O3composite material and its preparation method

Info

Publication number: CN102181765B
Application number: CN 201010623870
Authority: CN
Inventors: 朱建锋; 韩娜; 杨海波; 林营; 王芬; 王莉丽
Original assignee: Shaanxi University of Science and Technology
Current assignee: Shaanxi Xinhui New Energy Technology Development Co Ltd
Priority date: 2010-12-31
Filing date: 2010-12-31
Publication date: 2013-03-20
Anticipated expiration: 2030-12-31
Also published as: CN102181765A

Abstract

A (Ti, Cr)3AlC2/Al2O3 composite material and a preparation method thereof. The method comprises a hot-press sintering process according to ratios of 43.06-72.82% by weight of Ti powder, 14.03-19.19% by weight of Al powder, 9.67-12.26% by weight of C powder, and 0.89-28.08% by weight of Cr2O3 powder, and a fine crystalline composite material with an Al2O3 dispersed phase strengthening a matrix phase Ti3AlC2 is prepared by a thermite reaction which allows the autogeny of a particle reinforcing phase during the generation of the matrix phase, and the matrix phase is treated by solid solution strengthening by Cr generated in the reaction; the material has highly-adjustable components, low sintering temperature, a uniform and compact structure, low cost, excellent mechanical properties, which widens the application scope of the composite material; additionally, the invention reduces the sintering temperature and the hot-pressing pressure, and the microcrystallization of crystal grains is realized during rapid sintering.

Description

A kind of (Ti, Cr) 3AlC 2/ Al 2O 3Matrix material and preparation method thereof

Technical field

The invention belongs to matrix material and make field, particularly a kind of (Ti, Cr) ₃AlC ₂/ Al ₂O ₃Matrix material and preparation method thereof.

Background technology

In recent years, _ 2 Ceramics material Ti ₃AlC ₂Attracted lot of domestic and foreign scholar's broad research with its excellent properties.Ti ₃AlC ₂Performance with metal as having at normal temperatures good thermal conductivity and electroconductibility, lower Vickers' hardness, higher Young's modulus and shearing modulus, at room temperature can be carried out traditional mechanical workout, can produce viscous deformation under comparatively high temps; This material has again the performance of pottery, such as high-melting-point, high high-temp stability and good antioxidant property.But this material also exists sintering temperature high, and temperature range is little, and the shortcoming such as hardness is low, intensity is smaller and limited its further application.

For improving Ti ₃AlC ₂The performance of material, people utilize the means of solid solution highly malleablized and Composite that it has been carried out study on the modification, have obtained preferably effect.Such as bibliographical information (Surface ﹠amp; Coatings Technology 203 (2009) 3595-3609) utilize simple substance Cr element to carry out the solid solution study on the modification, material mechanical performance is greatly improved, but the method raw materials cost is higher, and synthesis temperature is higher simultaneously, is unfavorable for its industrialization production; Also there is document (ScriptaMaterialia 50 (2004) 897-901) report to utilize Al ₂O ₃Particle can be to Ti ₃AlC ₂Material property carries out modification.But currently used method is all more single, simultaneously, on the preparation method mainly with Al ₂O ₃And Ti ₃AlC ₂Sintering is carried out in two kinds of powders mixing, perhaps with Al, C, TiO ₂For raw material high temperature generates Ti by reduction reaction ₃AlC ₂/ Al ₂O ₃Matrix material, but no matter all there is the temperature of reaction height in the sort of technique and the relatively low deficiency that waits of intensity, can't large-scale industrialized production.Document (Advanced Powder Technology 03 (2010) 1-4) has been reported and has been utilized high-energy ball milling to synthesize Ti ₃AlC ₂/ Al ₂O ₃The novel method of matrix material, the material that the method is synthesized is greatly improved in performance, but high-energy ball milling is difficult to suitability for industrialized production, simultaneously, matrix phase is not carried out the solid solution modification.Therefore, how to take effective approach, utilize cheap material to synthesize Al ₂O ₃The solid-solution type Ti of particle highly malleablized ₃AlC ₂Matrix material will become research emphasis from now on.

Summary of the invention

In order to overcome the defective of above-mentioned prior art, the object of the present invention is to provide a kind of (Ti, Cr) ₃AlC ₂/ Al ₂O ₃Matrix material and preparation method thereof utilizes Ti-Al-C-Cr ₂O ₃System is raw material, prepares Al by thermite reaction reaction in－situ technique low temperature ₂O ₃The Ti that strengthens ₃AlC ₂Solid solution composite material; The method is utilized cheap oxide compound Cr ₂O ₃Substitute expensive metal simple-substance, reduced raw materials cost; Utilize the reaction heat of thermite reaction self, reduced the synthesis temperature of material, simultaneously generated in-situ Al ₂O ₃The wild phase particle is tiny, even, and the performance of material is greatly improved, and prepared material has high-strength, fine and close, high temperature resistant, machinable characteristics.

In order to achieve the above object, technical scheme of the present invention is achieved in that

A kind of (Ti, Cr) ₃AlC ₂/ Al ₂O ₃Matrix material, its initial feed be purity more than or equal to 99%, fineness is less than or equal to 200 purpose metal Ti powder, Al powder, C powder and metal oxide Cr ₂O ₃, carry out proportioning by following reaction formula:

3(1-x)Ti+(1+3x)Al+2C+3x/2Cr ₂O ₃→(Ti _1-xCr _x) ₃AlC ₂+3x/2Al ₂O ₃ (1)(x＝0.0064～0.2555)，

The result is: a kind of (Ti, Cr) ₃AlC ₂/ Al ₂O ₃Matrix material, the raw material moiety is: the Ti powder accounts for 43.06～72.82% of gross weight, and the Al powder accounts for 14.03～19.19% of gross weight, and the C powder accounts for 9.67～12.26% and Cr of gross weight ₂O ₃Powder accounts for 0.89～28.08% of gross weight.

A kind of (Ti, Cr) ₃AlC ₂/ Al ₂O ₃The composite manufacture method, step is as follows:

Step 1, at first with purity more than or equal to 99%, fineness is less than or equal to 200 purpose metal Ti powder, Al powder, carbon dust and metal oxide Cr ₂O ₃By following proportioning weighing, the Ti powder accounts for 43.06～72.82% of gross weight, and the Al powder accounts for 14.03～19.19% of gross weight, and the C powder accounts for 9.67～12.26% and Cr of gross weight ₂O ₃Powder accounts for 0.89～28.08% of gross weight;

Step 2, the batching in the step 1 is put into the alumina balls grinding jar carry out mixing and ball milling at planetary ball mill, take dehydrated alcohol as ball-milling medium, the rotating speed of ball mill is 600～900 rpms, material: ball: the mass ratio of ethanol=1: 3: 1, ball milling 0.5～1.5 hour;

Step 3, the ball milling powder of step 2 gained is lower dry 4～8 hours at 40～50 ℃;

Step 4, the dried powder of step 3 gained is packed in the graphite jig, under vacuum or argon gas condition, 1100 ℃～1400 ℃, the pressure hot pressed sintering of 5.0～30MPa 1～2 hour;

Step 5, the step 4 resulting materials is naturally cooled to room temperature can obtain (Ti, Cr) ₃AlC ₂/ Al ₂O ₃Matrix material.

(Ti, the Cr) that the present invention synthesized ₃AlC ₂/ Al ₂O ₃Matrix material is characterized in that: it is comprised of matrix phase and wild phase two portions, and matrix phase accounts for 81.5～99.5%% of matrix material gross weight, and wild phase accounts for the 0.5-18.5% of gross weight, and matrix phase is (Ti _1-x, Cr _x) ₃AlC ₂, wherein x gets 0.0064～0.2555, and wild phase is Al ₂O ₃If Al in the matrix material that generates ₂O ₃Growing amount does not have enhancing, toughness reinforcing Ti less than 0.5% of product quality ₃AlC ₂The effect of matrix, otherwise, if Al in the product ₂O ₃Phasor surpasses Ti ₃AlC ₂The content of matrix phase can not be referred to as Ti ₃AlC ₂Based composites, simultaneously, Al ₂O ₃Growing amount will be above 18.5%, excessive Al ₂O ₃Not only do not have and improve Ti ₃AlC ₂Effect, can worsen its performance on the contrary.Therefore determined above compositional range.

The present invention utilizes Ti powder, Al powder, C powder and Cr ₂O ₃Powder is raw material, by thermite reaction spontaneous particulates reinforcements Al in the process that matrix phase generates ₂O ₃The metal simple-substance Cr that restores simultaneously is to Ti ₃AlC ₂Carry out solution strengthening.Thereby prepared Al ₂O ₃The thin brilliant Ti of dispersion consolidatedization ₃AlC ₂Solid solution composite material.Because the material composition adjustability that this technique is synthesized is large, firing temperature is low, and even structure is fine and close, and cost is lower, and mechanical property is excellent, has widened the range of application of this matrix material.

Description of drawings

Fig. 1 is the material phase analysis result of example one gained sample; X-coordinate is diffraction angle, and ordinate zou is diffraction peak intensity, and wherein matrix phase is (Ti _0.9468Cr _0.0532) ₃AlC ₂Wild phase is Al ₂O ₃

Fig. 2 is the material phase analysis result of example two gained samples; X-coordinate is diffraction angle, and ordinate zou is diffraction peak intensity, and wherein matrix phase is (Ti _0.9740Cr _0.0260) ₃AlC ₂Wild phase is Al ₂O ₃

Embodiment

Embodiment one

A kind of (Ti, Cr) ₃AlC ₂/ Al ₂O ₃Matrix material, the raw material moiety is: 16.66%, the 1200 purpose C powder that 65.84%, the 200 purpose Al powder that 270 purpose Ti powder account for gross weight account for gross weight account for gross weight 10.47%, Cr ₂O ₃Powder accounts for 7.03% of gross weight.

The step of preparation process of present embodiment is as follows:

Step 1, at first with purity more than or equal to 99%, fineness is less than or equal to 200 purpose metal Ti powder, Al powder, carbon dust and metal oxide Cr ₂O ₃By following proportioning weighing, 16.66%, the 1200 purpose C powder that 65.84%, the 200 purpose Al powder that 270 purpose Ti powder account for gross weight account for gross weight account for gross weight 10.47%, Cr ₂O ₃Powder accounts for 7.03% of gross weight;

Step 2, the batching in the step 1 is put into the alumina balls grinding jar carry out mixing and ball milling at planetary ball mill, take dehydrated alcohol as ball-milling medium, the rotating speed of ball mill is 800 rpms, material: ball: the mass ratio of ethanol=1: 3: 1, ball milling 1 hour;

Step 3, the ball milling powder of step 2 gained is lower dry 6 hours at 44 ℃;

Step 4, the dried powder of step 3 gained is packed in the graphite jig, under vacuum condition, 1360 ℃, the pressure hot pressed sintering of 16MPa 2 hours;

(Ti, the Cr) that present embodiment synthesized ₃AlC ₂/ Al ₂O ₃Matrix material with reference to Fig. 1, is characterized in that, it is comprised of matrix phase and wild phase two portions, wherein matrix phase (Ti _0.9477, Cr _0.0523) ₃AlC ₂Account for 96% of gross weight, Al ₂O ₃Account for mutually 4% of product total mass.

Embodiment two

A kind of (Ti, Cr) ₃AlC ₂/ Al ₂O ₃Matrix material, the raw material moiety is: 15.95%, the 1200 purpose C powder that 69.73%, the 200 purpose Al powder that 270 purpose Ti powder account for gross weight account for gross weight account for gross weight 10.78%, Cr ₂O ₃Powder accounts for 3.54% of gross weight.

The step of preparation process of present embodiment is as follows:

Step 1, at first with purity more than or equal to 99%, fineness is less than or equal to 200 purpose metal Ti powder, Al powder, carbon dust and metal oxide Cr ₂O ₃By following proportioning weighing, 15.95%, the 1200 purpose C powder that 69.73%, the 200 purpose Al powder that 270 purpose Ti powder account for gross weight account for gross weight account for gross weight 10.78%, Cr ₂O ₃Powder accounts for 3.54% of gross weight;

Step 4, the dried powder of step 3 gained is packed in the graphite jig, under vacuum condition, 1250 ℃, the pressure hot pressed sintering of 16MPa 2 hours;

(Ti, the Cr) that present embodiment synthesized ₃AlC ₂/ Al ₂O ₃Matrix material is characterized in that, it is comprised of matrix phase and wild phase two portions, wherein matrix phase (Ti _0.9740, Cr _0.0260) ₃AlC ₂Account for 98% of gross weight, Al ₂O ₃Account for mutually product total mass 2%.

With reference to Fig. 2, show that this material matrix is by (Ti, Cr) ₃AlC ₂Phase contains a small amount of impurity TiC phase, and wild phase is Al ₂O ₃Phase.

Embodiment three

A kind of (Ti, Cr) ₃AlC ₂/ Al ₂O ₃Matrix material, the raw material moiety is: 17.96%, the 1200 purpose C powder that 57.89%, the 200 purpose Al powder that 270 purpose Ti powder account for gross weight account for gross weight account for gross weight 10.35%, Cr ₂O ₃Powder accounts for 13.80% of gross weight.

The manufacture method of present embodiment may further comprise the steps:

Step 1, at first with purity more than or equal to 99%, fineness is less than or equal to 200 purpose metal Ti powder, Al powder, carbon dust and metal oxide Cr ₂O ₃By following proportioning weighing, 17.96%, the 1200 purpose C powder that 57.89%, the 200 purpose Al powder that 270 purpose Ti powder account for gross weight account for gross weight account for gross weight 10.35%, Cr ₂O ₃Powder accounts for 13.80% of gross weight;

(Ti, the Cr) that present embodiment synthesized ₃AlC ₂/ Al ₂O ₃Matrix material is characterized in that, it is comprised of matrix phase and wild phase two portions, wherein matrix phase (Ti _0.8886, Cr _0.1114) ₃AlC ₂Account for 92% of gross weight, Al ₂O ₃Account for mutually product total mass 8%.

Claims

1. one kind (Ti, Cr) ₃AlC ₂/ Al ₂O ₃The composite manufacture method is characterized in that, step is as follows: step 1, at first with purity more than or equal to 99%, fineness is less than or equal to 200 purpose metal Ti powder, Al powder, carbon dust and metal oxide Cr ₂O ₃By following proportioning weighing, the Ti powder accounts for 43.06～72.82% of gross weight, and the Al powder accounts for 14.03～19.19% of gross weight, and the C powder accounts for 9.67～12.26% and Cr of gross weight ₂O ₃Powder accounts for 0.89～28.08% of gross weight;

Step 2, the batching in the step 1 is put into the alumina balls grinding jar carry out mixing and ball milling at planetary ball mill, take dehydrated alcohol as ball-milling medium, the rotating speed of ball mill is 600～900 rpms, material: ball: the mass ratio=1:3:1 of ethanol, ball milling 0.5～1.5 hour;

Step 5, the step 4 resulting materials is naturally cooled to room temperature get final product.

2. a kind of (Ti, Cr) according to claim 1 ₃AlC ₂/ Al ₂O ₃The composite manufacture method is characterized in that, step is as follows:

Step 1, at first with purity more than or equal to 99%, fineness is less than or equal to 200 purpose metal Ti powder, Al powder, carbon dust and metal oxide Cr ₂O ₃By following proportioning weighing, 16.66%, the 1200 purpose C powder that 65. 84%, the 200 purpose Al powder that 270 purpose Ti powder account for gross weight account for gross weight account for gross weight 10.47%, Cr ₂O ₃Powder accounts for 7.03% of gross weight;

Step 2, the batching in the step 1 is put into the alumina balls grinding jar carry out mixing and ball milling at planetary ball mill, take dehydrated alcohol as ball-milling medium, the rotating speed of ball mill is 800 rpms, material: ball: the mass ratio=1:3:1 of ethanol, ball milling 1 hour;

3. a kind of (Ti, Cr) according to claim 1 ₃AlC ₂/ Al ₂O ₃The composite manufacture method is characterized in that, step is as follows:

4. one kind (Ti, Cr) ₃AlC ₂/ Al ₂O ₃Solid solution composite material is characterized in that, it is comprised of matrix phase and wild phase two portions, and matrix phase accounts for 81.5～99.5% of matrix material gross weight, and wild phase accounts for the 0.5-18.5% of gross weight, and matrix phase is (Ti _1-x, Cr _x) ₃AlC ₂, wherein x gets 0.0064～0.2555, and wild phase is Al ₂O ₃

5. a kind of (Ti, Cr) according to claim 4 ₃AlC ₂/ Al ₂O ₃Solid solution composite material is characterized in that, it is comprised of matrix phase and wild phase two portions, and matrix phase accounts for 96% of matrix material gross weight, and wild phase accounts for 4% of gross weight, and matrix phase is (Ti _0.9477, Cr _0.0523) ₃AlC ₂, wild phase is Al ₂O ₃

6. a kind of (Ti, Cr) according to claim 4 ₃AlC ₂/ Al ₂O ₃Solid solution composite material is characterized in that, it is comprised of matrix phase and wild phase two portions, and matrix phase accounts for 98% of matrix material gross weight, and wild phase accounts for 2% of gross weight, and matrix phase is (Ti _0.9740, Cr _0.0260) ₃AlC ₂, wild phase is Al ₂O ₃