CN104911385A - A kind of ultrafine ceramic particle ultrafine Cu-based composite material with Ti2SnC as precursor and preparation method thereof - Google Patents

Abstract

An ultra-fine Cu-based composite material with ultra-fine ceramic particles using Ti ₂ SnC as a precursor and a preparation method thereof. The composite material uses micron-sized Ti ₂ SnC with a volume content of 3-50% and micron-sized Cu as starting materials. After the reaction, ultrafine TiC _0.5 particles are uniformly dispersed in the Cu(Sn) matrix, and the Cu grains are also are refined to the submicron level. The preparation method of the composite material is as follows: uniformly mix Ti ₂ SnC powder and Cu powder on a ball mill, shape it under a pressure of 120-250 MPa, put it into a high-temperature furnace, protect it with argon, and raise the furnace temperature to 1100-1250 ℃, keep warm for 30-60 minutes, and after cooling, ultra-fine ceramic particles and ultra-fine Cu-based composite materials can be obtained. The preparation method of the present invention has the remarkable characteristics of simple process and convenient operation; the superfine Cu-based composite material of ultrafine ceramic particles of the present invention has the characteristics of high strength, high ductility, wear resistance and corrosion resistance, and can be widely used in military industry Equipment, high-speed railway, aerospace and other fields, such as high-strength box shell materials, etc.

Description

A kind of ultrafine ceramic particle ultrafine Cu-based composite material with Ti2SnC as precursor and preparation method thereof

technical field

The invention relates to an ultrafine Cu _- based composite material with ultrafine ceramic particles using Ti2SnC as a precursor and a preparation method thereof.

Background technique

Copper-based materials with high yield strength, high ductility, wear resistance and corrosion resistance, because of their high characteristics and easy processing and molding, they have great applications in military equipment, high-speed railways, aerospace and other fields, such as high-strength box shells materials etc. However, for general copper-based materials, high strength and high ductility cannot be obtained at the same time. Copper has good plastic deformation ability, but its yield strength is low. Generally, work hardening and grain boundary strengthening are used to improve the strength by hindering the movement of dislocations and increasing the density of dislocation barriers. In recent years, the strength and hardness of copper materials have been greatly improved by means of ceramic phase particles to reinforce Cu-based composites. However, these methods often come at the cost of sacrificing the ductility and ductility of the copper substrate. The method of reducing the size of ceramic particles, refining the Cu matrix and in-situ generating ceramic particle reinforcement phase to obtain a strong interface with metal materials is a more effective method for improving the plasticity and toughness of particle-reinforced Cu-based composites.

Ti ₂ SnC is a new type of ternary carbide ceramic, which contains both covalent bonds and metal bonds, and integrates the advantages of ceramics and metals, such as high mechanical strength, excellent thermal shock resistance, good electrical conductivity and Ease of processing etc. Ti ₂ SnC belongs to a layered hexagonal crystal structure, in which nearly densely packed Ti layers intersect with Sn atomic layers, C atoms fill the octahedral positions between Ti layers, and Sn atoms are located in the center of trigonal columns with large spaces, Ti ₆ C octahedral edge sharing. In their structures, the bonding between Ti atoms and C atoms (i.e., nanoscale TiC _0.5 groups) is a strong covalent bond, while the bonding between Ti atoms and Sn atoms is weak, similar to layered graphite, and the interlayer combined by van der Waals forces. For this reason, the sliding between layers perpendicular to the c-axis is easy to occur under the action of external force, and the Sn atoms are more likely to escape from their positions. These unique nano-layered crystal structures, pyrolysis and external force dissolution behaviors make us think that Ti ₂ SnC ceramics can be used as a precursor to add to Cu melt, because Cu has a strong solid solution binding force with Sn in Ti ₂ SnC, Sn atoms can be dissolved out to obtain nano-TiC _0.5 groups, and TiC _0.5 has good wettability with Cu, and can be used as a nucleating agent or refiner for Cu alloys. In this way, the nano-TiC _0.5 group can not only serve as a nucleating agent to refine the grains of the Cu matrix, but also act as an effective nano-reinforcement to strengthen the Cu-based composite material. The composite material prepared in this way will have both high strength and high ductility. But the work in this area has not been reported yet.

Contents of the invention

The object of the present invention is to provide a Cu-based composite material refined with ultrafine ceramic particles using Ti ₂ SnC as a precursor and a preparation method thereof.

Technical scheme of the present invention:

1. The present invention uses Ti ₂ SnC as the precursor ultra-fine ceramic particle ultra-fine Cu-based composite material, which is characterized in that: the initial raw material is micron-sized Ti ₂ SnC with a volume content of 3-50%, and the rest is micron-sized Cu; the final product is sub-micron or nano-sized TiC _0.5 particles uniformly dispersed in the Cu(Sn) matrix, and the Cu grains are also refined to the sub-micron level;

2. A method for preparing an ultrafine ceramic particle ultrafine Cu _- based composite material using Ti2SnC as a precursor, characterized in that: the method comprises the following steps:

Step 1, batching: batching Ti ₂ SnC powder and Cu powder according to the following ratio:

Ti2SnC= ₃ ～50vol.%,

Cu=97～50vol.%;

Among them, the particle size of Ti ₂ SnC powder is 5-10 μm, and the particle size of Cu powder is 50-70 μm;

Step 2, mixing ingredients: adding 200-400 grams of agate balls to every 100 grams of the above ingredients, and ball milling for 2-4 hours;

Step 3, pre-press molding: put a certain quality of mixed powder into a steel mold, and apply a pressure of 120-250MPa to compact the powder in the mold;

Step 4, sintering: Put the formed block into a high-temperature furnace, and under the protection of argon, raise the temperature of the furnace to 1100-1250°C at a heating rate of 10-30°C/min, keep it warm for 30-60min, and then The temperature is lowered at a rate of 10-30° C./min, and after cooling, an ultrafine Cu-based composite material with ultrafine ceramic particles is obtained.

The beneficial effects that the present invention has:

The present invention uses Ti2SnC as the precursor of the ultrafine ceramic particle ultrafine Cu _- based composite material, and its product is submicron or nanometer TiC _0.5 particles uniformly dispersed in the Cu(Sn) matrix, and the Cu crystal grains are also Refined to the sub-micron level, its composite material has the characteristics of high strength, high ductility, wear resistance and corrosion resistance. The superfine ceramic particle superfine Cu-based composite material prepared by the present invention, its strength and wear resistance increase with the increase of the initial Ti ₂ SnC content, and the ductility decreases with the increase of the initial Ti ₂ SnC content; for the present invention For the application of composite materials, an appropriate raw material ratio of Ti ₂ SnC and Cu can be selected according to actual use requirements; the preparation method of the present invention has the remarkable characteristics of simple process, convenient operation, and low cost.

The ultra-fine ceramic particle ultra-fine Cu-based composite material with Ti ₂ SnC as the precursor of the present invention has the characteristics of high strength and high ductility, wear resistance, corrosion resistance, etc., and can be widely used in military equipment, high-speed railway, aerospace and other fields , such as high-strength box shell materials, etc.

Description of drawings

Fig. 1 is the SEM photograph of the ultrafine ceramic particles TiC _0.5 reinforced Cu-based composite material with Ti2SnC as the precursor of the present invention, and Fig _. 2 is the SEM photograph of the ultrafine Cu grain matrix exposed after the ceramic particles are corroded .

Detailed ways

Implementation Mode 1

Weigh 2.2 grams of Ti ₂ SnC powder with a purity of 98.5% and a particle size of 5 μm, and 97.8 grams of Cu powder with a purity of 99.8% and a particle size of 50 μm, add 200 grams of agate balls after mixing, and ball mill the mixture for 2 hours. Put it into a Φ50 steel mold, and apply a pressure of 120MPa to compact the powder in the mold. Put the above block into a high-temperature furnace, and under the protection of argon, press a heating rate of 10°C/min. The temperature of the furnace was raised to 1100° C., kept for 30 minutes, and then cooled at a rate of 10° C./min. After cooling, an ultrafine Cu-based composite material with ultrafine ceramic particles was obtained.

It is measured that the TiC _0.5 particles of the composite material are about 200-300nm, the Cu crystal grains are about 0.8-1μm, the yield strength of the composite material is 100MPa, the compressive strength is 295MPa, and the elongation is 53%.

Implementation mode two

Weigh 7.33 grams of Ti ₂ SnC powder with a purity of 98.5% and a particle size of 10 μm, and 92.67 grams of Cu powder with a purity of 99.8% and a particle size of 70 μm. After mixing, add 400 grams of agate balls and ball mill the mixture for 2 hours. Put it into a Φ76 steel mold, and apply a pressure of 250MPa to compact the powder in the mold, put the above block into a high-temperature furnace, and under the protection of argon, press the heating rate of 20°C/min. The temperature of the furnace was raised to 1150° C., kept for 45 minutes, and then cooled at a rate of 30° C./min. After cooling, an ultrafine Cu-based composite material with ultrafine ceramic particles was obtained.

It is measured that the TiC _0.5 particles of the above composite material are about 150-200nm, the Cu crystal grains are about 0.3-0.5μm, the yield strength of the composite material is 225MPa, the compressive strength is 562MPa, and the elongation is 46%.

Implementation Mode Three

Weigh 15.12 grams of Ti ₂ SnC powder with a purity of 98.5% and a particle size of 7 μm, and 84.88 grams of Cu powder with a purity of 99.8% and a particle size of 60 μm. After mixing, add 300 grams of agate balls and ball mill the mixture for 4 hours. Put it into a steel mold of Φ50, and apply a pressure of 200MPa to compact the powder in the mold, put the above block into a high-temperature furnace, and under the protection of argon, press a heating rate of 30°C/min. The temperature of the furnace was raised to 1170°C, kept at a temperature of 60 minutes, and then lowered at a rate of 20°C/min. After cooling, an ultrafine Cu-based composite material with ultrafine ceramic particles was obtained.

It is measured that the TiC _0.5 particles of the composite material are about 60-80nm, the Cu crystal grains are about 0.1-0.2μm, the yield strength of the composite material is 335MPa, the compressive strength is 870MPa, and the elongation is 38%.

Implementation Mode Four

Weigh 23.39 grams of Ti ₂ SnC powder with a purity of 98.5% and a particle size of 7 μm, and 76.61 grams of Cu powder with a purity of 99.8% and a particle size of 50 μm. After mixing, add 300 grams of agate balls and ball mill the mixture for 4 hours. Put it into a Φ50 steel mold, and apply a pressure of 200MPa to compact the powder in the mold, put the above block into a high-temperature furnace, and under the protection of argon, press a heating rate of 20°C/min. The temperature of the furnace was raised to 1200° C., kept for 40 minutes, and then cooled at a rate of 20° C./min. After cooling, an ultrafine Cu-based composite material with ultrafine ceramic particles was obtained.

It is measured that the TiC _0.5 particles of the composite material are about 80-100 nm, the Cu crystal grains are about 0.2-0.3 μm, the yield strength of the composite material is 483 MPa, the compressive strength is 1162 MPa, and the elongation is 29%.

Implementation Mode Five

Weigh 41.6 grams of Ti ₂ SnC powder with a purity of 98.5% and a particle size of 7 μm, and 58.4 grams of Cu powder with a purity of 99.8% and a particle size of 50 μm, add 400 grams of agate balls after mixing, and ball mill the mixture for 4 hours. Put it into a steel mold of Φ76, and apply a pressure of 250MPa to compact the powder in the mold, put the above block into a high-temperature furnace, and under the protection of argon, press a heating rate of 15°C/min. The temperature of the furnace was raised to 1250°C, kept for 30 minutes, and then lowered at a rate of 10°C/min. After cooling, the superfine Cu-based composite material with ultrafine ceramic particles was obtained.

It is measured that the TiC _0.5 particles of the above composite material are about 150-200nm, the Cu crystal grains are about 0.5-0.7μm, the yield strength of the composite material is 662MPa, the compressive strength is 1080MPa, and the elongation is 10.2%.

Claims (2)

1. one kind with Ti ₂snC is the superfine ceramic granular superfine Cu based composites of presoma, it is characterized in that: initial feed is micron-sized Ti ₂its volume content of SnC is 3 ~ 50%, and all the other are micron-sized Cu; Final product is submicron order or nano level TiC _0.5even particulate dispersion is in Cu (Sn) matrix, and Cu crystal grain is also refined as submicron order level.

2. one kind with Ti ₂snC is the preparation method of the superfine ceramic granular superfine Cu based composites of presoma, it is characterized in that: the method comprises the following steps:

Step 1, batching: by Ti ₂snC powder and Cu powder are prepared burden in following ratio:

Ti ₂SnC＝3～50vol.％，

Cu＝97～50vol.％；

Wherein Ti ₂the granularity of SnC powder is 5 ~ 10 μm, and the granularity of Cu powder is 50 ~ 70 μm;

Step 2, batch mixing: the agate ball adding 200 ~ 400 grams in every 100 grams of above-mentioned batchings, ball milling 2 ~ 4 hours;

Step 3, pre-molding: the mixed powder of certain mass is loaded in steel die, and applies the pressure of 120 ~ 250MPa, make the powder compaction moulding in mould;

Step 4; sintering: the block after shaping is put into High Temperature Furnaces Heating Apparatus; under argon shield; by the temperature rise rate of 10 ~ 30 DEG C/min; furnace temperature is risen to 1100 ~ 1250 DEG C, insulation 30 ~ 60min, then lowers the temperature with the speed of 10 ~ 30 DEG C/min; after cooling, namely obtain superfine ceramic granular superfine Cu based composites.