CN108358628B - Mullite-zirconia composite ceramic and preparation method thereof - Google Patents

Mullite-zirconia composite ceramic and preparation method thereof Download PDF

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CN108358628B
CN108358628B CN201810030002.3A CN201810030002A CN108358628B CN 108358628 B CN108358628 B CN 108358628B CN 201810030002 A CN201810030002 A CN 201810030002A CN 108358628 B CN108358628 B CN 108358628B
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mullite
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ball milling
composite ceramic
zirconia
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CN108358628A (en
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骆丽杰
陈拥军
余辉
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Hainan University
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Abstract

The invention provides a preparation method of mullite-zirconia composite ceramic, which comprises the following steps: (1) weighing raw materials, wherein the raw materials comprise: alumina, silica, zirconia and titania; based on the total mass of the raw materials, the mass fraction of the zirconium dioxide is 50-70%; and the mass ratio of alumina to silica is greater than 72: 28; the titanium dioxide accounts for 1 to 3 percent; (2) carrying out wet ball milling on the raw materials, and drying after the ball milling is finished to obtain mixed powder; (3) and putting the mixed powder into a mould, and carrying out hot-pressing sintering in an inert atmosphere. Compared with the traditional mullite ceramic, the mullite-zirconia composite ceramic prepared by the invention has obviously improved mechanical properties, especially fracture toughness.

Description

Mullite-zirconia composite ceramic and preparation method thereof
Technical Field
The invention relates to the technical field of composite ceramic preparation, in particular to mullite-zirconia composite ceramic and a preparation method thereof.
Background
Mullite (3 Al)2O3·2SiO2) Ceramics have high melting point, high temperature strength, good creep resistance, high chemical stability, low thermal expansion coefficient and other excellent properties, and thus are widely used as traditional refractory materials and high temperature engineering ceramic parts. However, the fracture toughness of mullite is low at room temperature (about 2 MPa. m)1/2) And is susceptible to cracking. In addition, mullite is difficult to sinter densely. These disadvantages limit their use in advanced structural ceramics.
Disclosure of Invention
The embodiment of the invention aims to provide mullite-zirconia composite ceramic and a preparation method thereof, so as to achieve the aim of toughening mullite ceramic. The specific technical scheme is as follows:
the invention firstly provides a preparation method of mullite-zirconia composite ceramic, which comprises the following steps:
(1) weighing raw materials, wherein the raw materials comprise: alumina, silica, zirconia and titania; based on the total mass of the raw materials, the mass fraction of the zirconium dioxide is 50-70%; and the mass ratio of alumina to silica is greater than 72: 28; the titanium dioxide accounts for 1 to 3 percent;
(2) carrying out wet ball milling on the raw materials, and drying after the ball milling is finished to obtain mixed powder;
(3) and putting the mixed powder into a mould, and carrying out hot-pressing sintering in an inert atmosphere.
In some embodiments of the invention, the mass ratio of alumina to silica is 78 or less: 22.
in some embodiments of the invention, the mass fraction of zirconium dioxide is 59%, the mass fraction of silicon dioxide is 8.8%, the mass fraction of aluminum oxide is 31.2%, and the mass fraction of titanium dioxide is 1%, based on the total mass of the feedstock.
In some embodiments of the present invention, the wet ball milling in step (2) comprises: and placing the raw materials, the grinding medium and the dispersion medium in a ball mill for ball milling for 15-25 hours.
In some embodiments of the invention, the mass ratio of the grinding medium, raw material and dispersion medium is 3:1: 0.8; preferably, the grinding media are zirconia balls; the dispersion medium is ethanol.
In some embodiments of the present invention, the hot press sintering in step (3) comprises: heating to 1400-1650 deg.C, and maintaining for 0.5-3 hr under 30-60 MPa.
In some embodiments of the invention, the temperature ramp rate for hot press sintering is 10 ℃/minute.
In some embodiments of the present invention, the average particle size of each raw material is: alumina 150-250nm, silica 400-600nm, zirconia 300-500nm and titania 30-70 nm.
In some embodiments of the invention, the inert atmosphere in step (3) is a nitrogen or argon atmosphere.
The invention also provides the mullite-zirconia composite ceramic prepared by the preparation method.
The preparation method of the mullite-zirconia composite ceramic provided by the invention adjusts the proportion of alumina and silica in the ceramic raw material to be larger than 3Al in mullite2O3·2SiO2To promote equiaxed growth of mullite grains (72: 28); 50% -The addition of 70% zirconium dioxide can also inhibit the growth of columnar mullite grains. In addition, the sintering aids titanium dioxide and ZrO2、Al2O3The solid solution reaction is carried out between the mullite and the glass phase, the glass phase property of a crystal boundary is improved, and the low-viscosity glass phase condition required by the columnar growth of mullite grains cannot be realized; and the hot-pressing sintering process is adopted to further promote the equiaxial growth of the mullite, so that the aim of improving the mullite microstructure is fulfilled. Compared with the traditional mullite ceramic, the mechanical property, especially the fracture toughness of the finally obtained mullite-zirconia composite ceramic is obviously improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an X-ray diffraction pattern of mullite-zirconia composite ceramic made in examples 1-4;
FIG. 2 is a scanning electron micrograph of the mullite-zirconia composite ceramic produced in examples 1 to 4; in the figure, the dotted circle marks the position of the air hole, the single-direction solid arrow marks the groove left by the pulled-out particles, the double-direction solid arrow marks the size of the particles, and the hollow single-direction arrow marks the crack on the section.
Detailed Description
The inventors have made extensive and intensive studies to solve the problem of poor toughness of mullite ceramics, and have found, without being limited to any theory, that the adjustment of alumina (Al)2O3) With silicon dioxide (SiO)2) The mass ratio of the alumina to the silica is more than 72:28, so that the equiaxial growth of mullite grains can be promoted; zirconium dioxide (ZrO) is added into the formula2) By utilizing the stress-induced phase change toughening mechanism, the ferroelastic toughening mechanism and the microcrack toughening mechanismThe high-efficiency toughening effect is generated; the hot-pressing sintering can manufacture compact mullite ceramic at a lower temperature and promote the equiaxial growth of mullite grains; the inventors have further found that titanium dioxide (TiO)2) The solid solution reaction of the zirconium dioxide, the aluminum oxide and the mullite can reduce the formation of a glass phase in the composite ceramic and stabilize tetragonal zirconium dioxide (t-ZrO)2) The phase function improves the glass phase property of the grain boundary, so that the low-viscosity glass phase condition required by the columnar growth of the mullite grains cannot be realized, and the equiaxial growth of the mullite grains is promoted; based on the above, the invention provides a preparation method of mullite-zirconia composite ceramic, which is characterized in that the equiaxial growth of mullite is cooperatively controlled through the four aspects to obtain the mullite-zirconia composite ceramic with high fracture toughness; the method comprises the following steps:
(1) weighing raw materials, wherein the raw materials comprise: alumina, silica, zirconia and titania; based on the total mass of the raw materials, the mass fraction of the zirconium dioxide is 50-70%; and the mass ratio of alumina to silica is greater than 72: 28; the titanium dioxide accounts for 1 to 3 percent;
(2) carrying out wet ball milling on the raw materials, and drying after the ball milling is finished to obtain mixed powder;
(3) and putting the mixed powder into a mould, and carrying out hot-pressing sintering in an inert atmosphere.
It should be noted that the raw materials used in the present invention can be industrial grade products, and unless otherwise specified, the raw materials used in the present invention are conventional raw materials used in the preparation of ceramics and related fields, and are commercially available to those skilled in the art. For example, in some embodiments of the present invention, the average particle size of each raw material is: alumina 150-250nm, silica 400-600nm, zirconia 300-500nm and titania 30-70 nm. In other embodiments of the present invention, zirconium dioxide is selected to be 3 mol% Y2O3Stabilized ZrO2(3Y-ZrO2)。
Preferably, in some embodiments of the present invention, the mass ratio of alumina to silica is 78 or less: 22. more specifically, in some embodiments of the present invention, the mass fraction of zirconium dioxide is 59%, the mass fraction of silicon dioxide is 8.8%, and the mass fraction of aluminum oxide is 31.2%, based on the total mass of the ceramic starting material.
In some embodiments of the invention, step (2) is specifically: placing the raw materials, the grinding medium and the dispersion medium in a ball mill for ball milling for 15-25 hours; then the mixture is dried in a vacuum drying oven at 60 ℃ and then is sieved by a 100-mesh sieve to obtain uniform mixed powder. In the specific implementation process, the powder agglomerated after being dried can be ground according to actual needs, for example, in an agate mortar to disperse the powder.
In some embodiments of the invention, the mass ratio of the grinding medium, raw material and dispersion medium is 3:1: 0.8; preferably, the grinding media are zirconia balls; the dispersion medium is ethanol. The ball milling may be carried out in a planetary ball mill.
In some embodiments of the present invention, the hot press sintering in step (3) comprises: heating to 1400-1650 deg.C, and maintaining for 0.5-3 hr under 30-60 MPa. More preferably, the temperature is raised to 1500-1550 ℃ and the temperature is kept for 0.5-1 hour.
In the present invention, the inert atmosphere may be various atmospheres inert to the raw material; in some embodiments of the invention, the sexual atmosphere may be a nitrogen or argon atmosphere, preferably a nitrogen atmosphere for cost reasons.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
First, it is to be noted that each raw material and relevant equipment used in the following examples are commercially available unless otherwise specified.
In the following examples, the parameters of each powder raw material were as follows:
SiO2: 500nm, the purity is 99.9 percent,
Al2O3: 200nm, the purity is 99.99 percent,
3Y-ZrO2: 400nm, the purity is 99.9 percent,
TiO2: 50nm and 99.9 percent of purity.
Preparation example of mullite-zirconia composite ceramic
Example 1
(1) Weighing the following raw materials: 2.64g SiO2、9.36g Al2O3、17.7g 3Y-ZrO2And 0.3g TiO2；
(2) The weighed raw materials are mixed and placed in a ball milling tank according to the mass ratio of ball to material to ethanol of 3:1:0.8, and ball milling is carried out for 24 hours at the ball milling speed of 300 revolutions per minute. Separating ball mill and slurry after ball milling, placing the slurry in a vacuum drying oven at 60 ℃ for drying for 24 hours, fully removing ethanol, then grinding the powder which is agglomerated into blocks after drying by using an agate mortar for 10 minutes, and sieving by using a 100-mesh sieve to obtain mixed powder.
(3) Weighing 20g of the sieved mixed powder, placing the powder in a hot-pressing graphite mold with the diameter of 42mm, and isolating the graphite mold and the powder by using graphite paper. Heating to 1450 ℃ at a heating rate of 10 ℃/min, preserving heat for 0.5 hour and maintaining the pressure at 30 MPa; and then naturally cooling to room temperature to obtain the mullite-zirconia composite ceramic.
Example 2
(1) Weighing the following raw materials: 2.64g SiO2、9.36g Al2O3、17.7g 3Y-ZrO2And 0.3g TiO2；
(2) The weighed raw materials are mixed and placed in a ball milling tank according to the mass ratio of ball to material to ethanol of 3:1:0.8, and ball milling is carried out for 24 hours at the ball milling speed of 300 revolutions per minute. Separating ball mill and slurry after ball milling, placing the slurry in a vacuum drying oven at 60 ℃ for drying for 24 hours, fully removing ethanol, then grinding the powder which is agglomerated into blocks after drying by using an agate mortar for 10 minutes, and sieving by using a 100-mesh sieve to obtain mixed powder.
(3) Weighing 20g of the sieved mixed powder, placing the powder in a hot-pressing graphite mold with the diameter of 42mm, and isolating the graphite mold and the powder by using graphite paper. Heating to 1500 ℃ at the heating rate of 10 ℃/min, preserving heat for 0.5 hour and maintaining the pressure for 30 MPa; and then naturally cooling to room temperature to obtain the mullite-zirconia composite ceramic.
Example 3
(1) Weighing the following raw materials: 2.64g SiO2、9.36g Al2O3、17.7g 3Y-ZrO2And 0.3g TiO2；
(2) The weighed raw materials are mixed and placed in a ball milling tank according to the mass ratio of ball to material to ethanol of 3:1:0.8, and ball milling is carried out for 24 hours at the ball milling speed of 300 revolutions per minute. Separating ball mill and slurry after ball milling, placing the slurry in a vacuum drying oven at 60 ℃ for drying for 24 hours, fully removing ethanol, then grinding the powder which is agglomerated into blocks after drying by using an agate mortar for 10 minutes, and sieving by using a 100-mesh sieve to obtain mixed powder.
(3) Weighing 20g of the sieved mixed powder, placing the powder in a hot-pressing graphite mold with the diameter of 42mm, and isolating the graphite mold and the powder by using graphite paper. Heating to 1500 ℃ at the heating rate of 10 ℃/min, preserving heat for 1 hour and maintaining the pressure at 30 MPa; and then naturally cooling to room temperature to obtain the mullite-zirconia composite ceramic.
Example 4
(1) Weighing the following raw materials: 2.64g SiO2、9.36g Al2O3、17.7g 3Y-ZrO2And 0.3g TiO2；
(2) The weighed raw materials are mixed and placed in a ball milling tank according to the mass ratio of ball to material to ethanol of 3:1:0.8, and ball milling is carried out for 24 hours at the ball milling speed of 300 revolutions per minute. Separating ball mill and slurry after ball milling, placing the slurry in a vacuum drying oven at 60 ℃ for drying for 24 hours, fully removing ethanol, then grinding the powder which is agglomerated into blocks after drying by using an agate mortar for 10 minutes, and sieving by using a 100-mesh sieve to obtain mixed powder.
(3) Weighing 20g of the sieved mixed powder, placing the powder in a hot-pressing graphite mold with the diameter of 42mm, and isolating the graphite mold and the powder by using graphite paper. Heating to 1600 ℃ at a heating rate of 10 ℃/min, preserving heat for 1 hour and maintaining the pressure at 30 MPa; and then naturally cooling to room temperature to obtain the mullite-zirconia composite ceramic.
Example 5
Example 5 differs from example 3 in that: the formula of the raw materials is as follows: 3.6g SiO2、9.9g Al2O3、15.9g3Y-ZrO2And 0.6g TiO2(ii) a The pressure is kept at 40 MPa.
Example 6
Example 6 differs from example 3 in that: the formula of the raw materials is as follows: 2.25g SiO2、6.75g Al2O3、20.1g 3Y-ZrO2And 0.9g TiO2(ii) a The pressure for maintaining the pressure is 60 MPa.
Characterization of
The mullite-zirconia composite ceramics prepared in examples 1-4 were characterized by X-ray diffraction, (XRD) X-ray diffraction (XRD) instrument test of D8Advanced type, brueck, germany (Cu K α target,
Figure BDA0001546219090000071
the results are shown in FIG. 1.
Fig. 1 (a) shows XRD of the composite ceramic of example 1, and it can be seen that the phase composition of the composite ceramic prepared in example 1 includes: mullite (Mullite), tetragonal zirconium dioxide (t-ZrO)2) Monoclinic zirconium dioxide (m-ZrO)2) Alumina (Al)2O3) And zirconium silicate (ZrSiO)4)。
Fig. 1 (b) shows XRD of the composite ceramic of example 2, and it can be seen that the phase composition of the composite ceramic prepared in example 2 includes: mullite (Mullite), tetragonal zirconium dioxide (t-ZrO)2) And monoclinic zirconium dioxide (m-ZrO)2)。
In fig. 1, (c) is XRD of the composite ceramic of example 3, and it can be seen that the phase composition of the composite ceramic prepared in example 3 includes: mullite (Mullite), tetragonal zirconium dioxide (t-ZrO)2) And monoclinic zirconium dioxide (m-ZrO)2)。
Fig. 1 (d) shows XRD of the composite ceramic of example 4, and it can be seen that the phase composition of the composite ceramic prepared in example 4 includes: mullite (Mullite), tetragonal zirconium dioxide (t-ZrO)2) And monoclinic zirconium dioxide (m-ZrO)2)。
Scanning electron microscope characterization was performed on the mullite-zirconia composite ceramics prepared in examples 1 to 4, (hitachi high new S-4800 cold field emission scanning electron microscope), and the results are shown in fig. 2;
FIG. 2 (a) is a scanning electron micrograph of the composite ceramic of example 1, and it can be seen that the microstructure of the ceramic is characterized by fine mullite grains but pores distributed on the mullite matrix.
FIG. 2 (b) is a scanning electron micrograph of the composite ceramic of example 3, and it can be seen from the micrograph that the microstructure of the ceramic is characterized by fine mullite grains, fewer pores, and a large number of grains pulled out to leave grooves.
FIG. 2 (c) is a SEM photograph of the composite ceramic of example 4. As can be seen from the figure, the microstructure of the ceramic is characterized by large mullite grains, no pores, and a large number of cracks in the cross section that propagate in the mullite matrix and grain boundaries.
FIG. 2 (d) is a scanning electron micrograph of the composite ceramic of example 2, and it can be seen from the micrograph that the microstructure of the ceramic is characterized by fine mullite grains, fewer pores, and a large number of grains pulled out to leave grooves.
Performance testing
The mullite-zirconia composite ceramics prepared in examples 1 to 6 were tested for relative density, flexural strength, fracture toughness and Rockwell hardness, and the test results are shown in Table 1.
Test method
(1) The relative density is calculated according to the following formula:
ρphase (C)＝VMeasuring/VTheory of things
Where ρ isPhase (C)Is relative density, VMeasuringFor the sample volume, V, measured by Archimedes drainage methodTheory of thingsIs the theoretical volume value of the material calculated according to the formula.
(2) Bending strength: a three-point bending method is adopted, and particularly, the bending strength test method is based on GB/T6569-2006 fine ceramic.
(3) Fracture toughness according to the test method of American Standard ASTM-E399.
(4) Rockwell hardness HRA is the hardness determined using a 60Kg load and a diamond cone indenter.
TABLE 1
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6
Relative density/%) 97.5 98.5 98.5 97.9 98.9 98.6
Flexural Strength/MPa 570 674 596 428 549 668
Fracture toughness/MPa.m1/2 9.95 11 12 7 8.95 11.32
Rockwell hardness/HRA 86 91 90 90 89.1 89.8
As can be seen from the data in Table 1, the mullite-zirconia composite ceramic prepared by the method provided by the invention has the advantages of high strength, high toughness, high hardness and the like, and the traditional mullite ceramic (the fracture toughness is about 2 MPa-m)1/2) Compared with the prior art, the mechanical property, especially the fracture toughness, is obviously improved.
Further, it can be seen that when the sintering temperature is higher than 1450 ℃ and lower than 1600 ℃, for example, when the sintering process is kept at 1500 ℃ for about 30-60 minutes, the prepared mullite-zirconia composite ceramic has purer phases, finer grain sizes, fewer pores, and a large number of grains on the cross section, which are pulled out of the residual grooves, and has no crack propagation, and the mechanical properties are better.
The mullite-zirconia composite ceramic and the preparation method thereof provided by the invention are described in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its central concept. It should be noted that it would be apparent to those skilled in the art that various changes and modifications can be made in the invention without departing from the principles of the invention, and such changes and modifications are intended to be covered by the appended claims.

Claims (6)

1. A preparation method of mullite-zirconia composite ceramic is characterized by comprising the following steps:
(1) weighing raw materials, wherein the raw materials comprise: alumina, silica, zirconia and titania; based on the total mass of the raw materials, the mass fraction of the zirconium dioxide is 50-70%; and the mass ratio of alumina to silica is greater than 72:28, and is not more than 78: 22; the titanium dioxide accounts for 1 to 3 percent;
(2) carrying out wet ball milling on the raw materials, and drying after the ball milling is finished to obtain mixed powder;
(3) putting the mixed powder into a mould, and carrying out hot-pressing sintering in a nitrogen or argon atmosphere; the hot-pressing sintering comprises the following steps: heating to 1400-1650 deg.C, maintaining for 0.5-3 hr, and maintaining at 30-60 MPa;
wherein the average particle size of each raw material is as follows: alumina 150-250nm, silica 400-600nm, zirconia 300-500nm and titania 30-70 nm.
2. The method according to claim 1, wherein the mass fraction of zirconium dioxide is 59%, the mass fraction of silicon dioxide is 8.8%, the mass fraction of aluminum oxide is 31.2%, and the mass fraction of titanium dioxide is 1%, based on the total mass of the raw materials.
3. The method of claim 1, wherein the wet ball milling in step (2) comprises: and placing the raw materials, the grinding medium and the dispersion medium in a ball mill for ball milling for 15-25 hours.
4. The method according to claim 3, wherein the mass ratio of the grinding medium, the raw material and the dispersion medium is 3:1: 0.8; the grinding medium is zirconia balls; the dispersion medium is ethanol.
5. The method of claim 1, wherein the hot press sintering is carried out at a ramp rate of 10 ℃/minute.
6. The mullite-zirconia composite ceramic produced by the production method according to any one of claims 1 to 5.
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