CN101239814A - Aluminum oxide-titanium carbonitride-titanium nickel composite material and preparation method thereof - Google Patents

Abstract

The invention relates to an aluminum oxide-titanium carbonitride-titanium nickel composite material and a preparation method thereof. The volume percentage of the composite material is: Al ₂ O ₃ : 60-94, Ti(C,N): 5-35, Ti+ Ni: 1-12; preparation process steps: the first step is raw material mixing and drying: (1) raw material Al ₂ O ₃ powder and TiCN powder are mixed with ball milling medium and surfactant, ball milled and dried; (2) raw material Ti powder and Ni powder are mixed with ball milling medium, and ball milling is dried, and the atomic ratio of titanium and nickel is 1:1～1:4; (3) The powder after step (1) and (2) is mixed and dried is added into ball milling medium and mixed , ball milling, drying, the addition of Ti and Ni powders is 1 to 12vol%, the second step is powder forming and sintering: the mixed powder after step (3) is added to the hot-pressed furnace, in an argon atmosphere, the temperature is 1400 ~1700°C, hot press forming at a pressure of 25~35MPa. The invention has the advantages that the hardness, strength and toughness of the comprehensive properties of the material are obviously improved, and it is more suitable for the cutting tool material used in the machinery industry.

Description

Aluminum oxide-titanium carbonitride-titanium nickel composite material and preparation method thereof

technical field

The invention relates to a ceramic composite material and a preparation method thereof, in particular to an aluminum oxide-titanium carbonitride-titanium nickel composite material and a preparation method thereof.

Background technique

With the development of high and new technologies, the machining industry has put forward more stringent and demanding requirements for tool materials. For example, processing materials with higher hardness, higher cutting efficiency, finishing and realizing unmanned operation, etc., this requires improving the strength, toughness, wear resistance and thermal shock resistance of tool materials. Alumina ceramic materials have the characteristics of high melting point, high compressive strength and corrosion resistance, but because Al ₂ O ₃ ceramic materials are brittle, low in tensile strength and poor in impact resistance, they should be widely used in practice as tool materials , must improve the mechanical properties of the material. Over the years, countries have successively proposed a variety of toughening and strengthening methods and advanced technology. Add reinforcement phases such as: TiN, Ti(C, N), TiB ₂ , SiC, (W, Ti)C, WC, Mo ₂ C, ZrO ₂ , Y ₂ O ₃ and other components to ceramic materials, and use the second phase 3. Particle dispersion strengthening, fiber reinforcement, whisker toughening, phase change toughening or synergistic toughening and reinforcement of the third phase material improve the performance of ceramic materials. Chinese patent CN1911856A (published on February 14, 2007) provides a chromium carbide and titanium carbonitride dispersion toughened alumina matrix composite material and a preparation method thereof. The volume percentage of its components is: 5-30% Cr ₃ C ₂ , 5-30% Ti(C,N), 0.2-2% Y ₂ O ₃ , 0.2-1% MgO, and the rest is Al ₂ O ₃ . The purpose is to simultaneously increase the hardness of the material through the effects of Cr ₃ C ₂ and Ti(C,N).

Contents of the invention

The purpose of the present invention is to develop an alumina-titanium carbonitride-titanium-nickel composite material and its preparation method for the defects of the aluminum oxide/titanium carbonitride (Al ₂ O ₃ /Ti(C,N)) composite material. , improve the comprehensive performance, hardness, strength and toughness of ceramic composite materials, and further provide a tool material that is more suitable for the mechanical industry.

The aluminum oxide-titanium carbonitride-titanium nickel composite material developed by the invention has the following volume percentages of components: Al ₂ O ₃ : 60-94, Ti(C,N): 5-35, Ti+Ni: 1-12. The comprehensive performance of the composite material is that the hardness HV is 20-21GPa, the strength is 600-800MPa, and the fracture toughness is 7-9MPa·m ^1/2 .

The preparation method of above-mentioned composite material of the present invention, carries out as follows:

Raw material mixing and drying:

(1) The raw material Al ₂ O ₃ powder and TiCN powder are mixed and called A mixed powder, mixed with ball milling medium and surfactant, and ball milled. The ratio of raw materials is: Al ₂ O ₃ powder is 60-94vol%, Ti( C _1-X N _X ) powder is 5-35vol%, wherein X= _0.3-0.7 , the amount of surfactant added is 0-3vol% of the total amount of raw material _Al2O3 powder and TiCN powder, and the ball milling time is 12-24 hours; the ball-milled material is put into an oven, and dried for 24 to 48 hours at a temperature of 60°C or 120°C;

(2) The raw material Ti powder and Ni powder are mixed and called B mixed powder mixed with ball milling media, ball milled, the ratio of titanium and nickel atoms is 1:1 to 1:4, the ball milling time is 12 to 24 hours, and then put into a vacuum oven In the oven, dry at a temperature of 60°C for 24 to 48 hours;

(3) Mix and dry the powder in steps (1) and (2), add ball milling medium and mix evenly, ball mill for 12-24 hours, then put it in a vacuum oven, dry at 60°C for 24-48 hours, B mixed powder The addition amount is 1-12vol% of the total amount of the two mixed powders of A and B, and the balance is the mixed powder of A;

Powder forming and sintering:

The mixed powder treated in step (3) is hot-pressed in a hot-press furnace under the protection of argon at a temperature of 1400-1700°C and a pressure of 25-35 MPa for 5-30 minutes.

Raw materials used in the present invention: Al ₂ O ₃ powder: particle size d ₅₀ is 0.1-10 μm, purity Al ₂ O ₃ content>99.9%; Ti(C _1-X N _X ): particle size d ₅₀ is 0.1-10 μm, content> 99.9%, where X=0.3-0.7; Ti powder: particle size d ₅₀ is 0.1-10 μm, purity Ti content >99.9%; Ni powder: particle size d ₅₀ is 0.1-10 μm, purity content > 99.9%.

The surfactant is selected from polyethylene carboxylate, and the ball milling medium is selected from absolute ethanol or deionized water.

The powder mixed and ball-milled in the above step (2) or step (3) is put into an oven for vacuum drying, and the vacuum degree is 1×10 ⁻¹ MPa.

The advantages and positive effects produced by the present invention are: the present invention uses aluminum oxide/titanium carbide, that is, Al ₂ O ₃ /Ti(C, N) composite material as the matrix, and it is the present invention to improve the strength and toughness of the cutting tool material by adding NiTi specialty. Adding Ni and Ti to ceramics, the metal can improve the toughness of the material through particle toughening, and under certain conditions, Ni and Ti will form intermetallic compounds NiTi, Ti ₂ Ni and TiNi ₃ and form a liquid phase during sintering. This is very beneficial to reduce the sintering temperature of the composite material, inhibit the decomposition of Ti(C,N) during high temperature sintering, and promote the sintering densification of the material. In addition, the present invention also adds surfactant polycarboxylate in the powder mixing process, which can effectively improve the uniformity of _Al2O3 /Ti(C, N) powder mixing, reduce powder _{agglomeration} , and improve the density and mechanical properties of the material. performance.

The comprehensive properties of the above-mentioned composite material produced by the present invention reach: the hardness Hv is 20-21GPa, the strength is 600-800MPa, and the fracture toughness is 7-10MPa·m ^1/2 , which can fully meet the performance requirements of machining tool materials.

Detailed ways

Example 1 Preparation and properties of (Al ₂ O ₃ -5vol%TiC _0.5 N _0.5 )-1vol% (Ti+Ni) composite material

Add TiC _0.5 N _0.5 powder (particle size d ₅₀ of 0.1 μm, purity > 99.90%) with a volume percentage of 5 to Al ₂ O ₃ powder (particle size d ₅₀ is 0.1 μm, purity > 99.90%), dilute with absolute ethanol The aluminum oxide ball is used as the ball milling medium, the ball is milled for 12 hours, and then dried in an oven at 60° C. for 24 hours to obtain Al ₂ O ₃ -5vol% TiC _0.5 N _0.5 mixed powder. Mix Ti powder and Ni powder in an atomic ratio of 1:1, use absolute ethanol as the ball milling medium, and stainless steel balls as the balls, mill for 12 hours, and then put them in a vacuum oven at 60°C for 48 hours to dry at a vacuum degree of 1 ×10 ^-1 MPa to obtain Ti-Ni mixed powder. Add the mixed Ti-Ni mixed powder with a volume percentage of 1 to the mixed Al ₂ O ₃ -5vol% TiC _0.5 N _0.5 mixed powder, use absolute ethanol as the ball milling medium, stainless steel balls as the balls, and mill for 12 hours, and then dried in a 60°C vacuum oven for 24 hours with a vacuum degree of 1×10 ^-1 MPa. The mixed powder is hot-pressed in a hot-press furnace. The hot pressing temperature is 1700° C., the sintering pressure is 35 MPa, the hot pressing time is 30 min, and the hot pressing atmosphere is argon. The hardness (Hv) of the material was determined by the Vickers indentation hardness method; the strength of the material was detected by the three-point bending strength test; the fracture toughness of the material was detected by the single edge notch beam method (SENB); the material was detected by scanning electron microscopy (SEM). microstructure and fracture. The test results of material properties are: hardness (Hv) 20GPa, three-point bending strength 600MPa, fracture toughness 7.1MPa·m ^1/2 .

Example 2

The composition of the alumina-based composite material in this example is (Al ₂ O ₃ -25vol% TiC _0.3 N _0.7 )-8vol% (Ti+Ni) in Al ₂ O ₃ powder (particle size d ₅₀ is 0.5 μm, purity > 99.9 %) was added TiC _0.3 N _0.7 powder with a volume percentage of 25 (particle size d ₅₀ is 0.3 μm, purity > 99.9%), with deionized water as the ball milling medium, alumina balls as the balls, ball milled for 20 hours, and then placed Dry in an oven at 120° C. for 48 hours to obtain Al ₂ O ₃ -5vol% TiC _0.5 N _0.5 mixed powder. Ti powder (particle size d ₅₀ is 0.5 μm, purity > 99.9%) and Ni powder (particle size d ₅₀ is 0.5 μm, purity > 99.9%) are mixed in an atomic ratio of 1:2, and absolute ethanol is used as a ball milling medium. The stainless steel balls were used as grinding balls, which were milled for 24 hours and then dried in a vacuum oven at 60°C for 24 hours with a vacuum degree of 1×10 ^-1 MPa to obtain Ti-Ni mixed powder. Add the mixed Ti-Ni mixed powder with a volume percentage of 8 to the mixed Al ₂ O ₃ -25vol% TiC _0.5 N _0.5 mixed powder, use absolute ethanol as the ball milling medium, stainless steel balls as the balls, and ball mill for 24 hours, and then dried in a vacuum oven at 60°C for 36 hours. The mixed powder is hot-pressed in a hot-press furnace. The hot-pressing temperature is 1500° C., the sintering pressure is 30 MPa, the hot-pressing time is 15 minutes, and the hot-pressing atmosphere is argon. The test results of material properties after hot pressing are: hardness (Hv) 20GPa, three-point bending strength 716MPa, fracture toughness 9.1MPa·m ^1/2 .

Example 3

The composition of the alumina-based composite material in this example is (Al ₂ O ₃ -35vol% TiC _0.3 N _0.7 )-12vol% (Ti+Ni) in Al ₂ O ₃ powder (particle size d ₅₀ is 3 μm, purity > 99.9%) ) with a volume percentage of 35 TiC _0.5 N _0.5 powder (particle size d ₅₀ is 3 μm, purity >99.9%), the preparation of Al ₂ O ₃ -35vol% TiC _0.3 N _0.7 mixed powder is as described in Example 1. Ti powder (particle size _d50 is 2 μm, purity>99.9%) and Ni powder (particle size _d50 is 2 μm, purity>99.9%) are mixed at an atomic ratio of 1:4, and the preparation of the mixed powder is as described in Example 1. Add the mixed Ti-Ni mixed powder with a volume percentage of 12 to the mixed Al ₂ O ₃ -35vol% TiC _0.3 N _0.7 mixed powder, use absolute ethanol as the ball milling medium, stainless steel balls as the balls, and ball mill for 18 hours, and then dried in a 60°C vacuum oven for 24 hours with a vacuum degree of 1×10 ^-1 MPa. The mixed powder is hot-pressed in a hot-press furnace. The hot-pressing temperature is 1550° C., the sintering pressure is 30 MPa, the hot-pressing time is 10 minutes, and the hot-pressing atmosphere is argon. The test results of the material properties after hot pressing are: hardness (Hv) 21GPa, three-point bending strength 816MPa, fracture toughness 9.8MPa·m ^1/2 .

Example 4

The composition of the alumina-based composite material in this example is (Al ₂ O ₃ -25vol% TiC _0.3 N _0.7 )-10vol% (Ti+Ni) in Al ₂ O ₃ powder (particle size d ₅₀ 10 μm, purity > 99.9%) TiC _0.3 N _0.7 powder (particle size d ₅₀ 8 μm, purity >99.9%) was added to the mixture at a volume percentage of 25, and the preparation of Al ₂ O ₃ -25 vol% TiC _0.3 N _0.7 mixed powder was as described in Example 2. Ti powder (particle size _d50 is 8 μm, purity>99.9%) and Ni powder (particle size _d50 is 8 μm, purity>99.9%) are mixed in an atomic ratio of 1:3, and the preparation of the mixed powder is as described in Example 1. Add the mixed Ti-Ni mixed powder with a volume percentage of 10 to the mixed Al ₂ O ₃ -25vol% TiC _0.3 N _0.7 mixed powder, use absolute ethanol as the ball milling medium, stainless steel balls as the balls, and ball mill for 24 hours, and then dried in a 60°C vacuum oven for 48 hours with a vacuum degree of 1×10 ^-1 MPa. The mixed powder is hot-pressed in a hot-press furnace. The hot pressing temperature is 1400° C., the sintering pressure is 25 MPa, the hot pressing time is 5 min, and the hot pressing atmosphere is argon. The test results of material properties after hot pressing are: hardness (Hv) 21GPa, three-point bending strength 806MPa, fracture toughness 8.8MPa·m ^1/2 .

Claims (5)

1, a kind of aluminum oxide-titanium carbonitride-titanium nickel composite material is characterized in that the moiety percent by volume is: Al ₂O ₃: 60～94, and Ti (C, N): 5～35, Ti+Ni:1～12.

2,, it is characterized in that processing step is as follows according to the preparation method of the described aluminum oxide-titanium carbonitride of claim 1-titanium nickel composite material:

Raw material mixes and is dry:

(1) with raw material A l ₂O ₃Powder and TiCN powder mixes are called the A mixed powder, mix with ball-milling medium, tensio-active agent, ball milling, and its proportioning raw materials is: Al ₂O ₃Powder is 60～94vol%, Ti (C _1-XN _X) powder is 5～35vol%, X=0.3～0.7 wherein, the surfactant add-on is raw material A l ₂O ₃0～3vol% of powder and TiCN powder total amount, the ball milling time is 12～24 hours; Material behind the ball milling adds baking oven, is under 60 ℃ or 120 ℃ in temperature, dry 24～48 hours;

(2) raw material Ti powder and Ni powder mixes are called the B mixed powder mixes with ball-milling medium, ball milling, titanium and nickle atom proportioning be 1: 1～1: 4,12～24 hours ball milling time, put into vacuum drying oven then, temperature be 60 ℃ dry 24～48 hours down;

(3) with the powder behind step (1) and (2) combination drying, behind the adding ball-milling medium mixing, ball milling 12～24 hours, put into vacuum drying oven then, 60 ℃ of dryings 24～48 hours, B mixed powder add-on was 1～12vol% of A and two kinds of mixed powder total amounts of B, and surplus is the A mixed powder;

Powder forming and sintering:

Mixed powder after step (3) handled adds in the hot pressing furnace, and under argon shield, temperature is 1400～1700 ℃, and pressure is hot pressing 5～30 minutes under 25～35MPa.

3, according to the preparation method of the described aluminum oxide-titanium carbonitride of claim 2-titanium nickel composite material, it is characterized in that described tensio-active agent selects poly carboxylic acid second fat for use, ball-milling medium is selected dehydrated alcohol or deionized water for use.

4, according to the preparation method of the described aluminum oxide-titanium carbonitride of claim 2-titanium nickel composite material, it is characterized in that mixed powder is put into drying under the baking oven vacuum in step (2) or the step (3), vacuum tightness is 1 * 10 ^-1MPa.

5, according to the preparation method of the described aluminum oxide-titanium carbonitride of claim 2-titanium nickel composite material, it is characterized in that raw material A l ₂O ₃Powder: granularity d ₅₀Be 0.1～10 μ m, purity Al ₂O ₃Content＞99.9%; Ti (C _1-XN _X): granularity d ₅₀Be 0.1～10 μ m, content＞99.9%, wherein X=0.3～0.7; Ti powder: granularity d ₅₀Be 0.1～10 μ m, purity Ti content＞99.9%; Ni powder: granularity d ₅₀Be 0.1～10 μ m, purity content＞99.9%.