CN110483058A - A kind of boride ceramics and its preparation method and application of superhard high intensity - Google Patents

A kind of boride ceramics and its preparation method and application of superhard high intensity Download PDF

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CN110483058A
CN110483058A CN201910727137.XA CN201910727137A CN110483058A CN 110483058 A CN110483058 A CN 110483058A CN 201910727137 A CN201910727137 A CN 201910727137A CN 110483058 A CN110483058 A CN 110483058A
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powder
boride
high intensity
boride ceramics
solid solution
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CN110483058B (en
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袁进豪
张岩
郭伟明
吴利翔
林华泰
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Guangdong University of Technology
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Guangdong University of Technology
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Abstract

The invention belongs to technical field of ceramic material, disclose a kind of boride ceramics and its preparation method and application of superhard high intensity.The boride ceramics is by ZrO2, WO3Mixed powder is obtained after ball milling and drying with unformed boron powder；Green body is made in mixed powder；The green body is warming up to 1500~1700 DEG C of calcinings under vacuum, it is polished, obtain (ZrxWy)B2Boride solid solution powder, 0.75≤x≤0.95,0.75≤y≤0.95；Using discharge plasma sintering, it is filled with protective atmosphere when boride solid solution powder is warming up to 1000~1400 DEG C, is warming up to 1800~2200 DEG C, pressurization 10~100MPa sintering is made.The relative density of the boride ceramics is 92~99.9%, and hardness is 16~30GPa, and fracture toughness is 2.4~5MPam1/2, compression strength is 200~650MPa.

Description

A kind of boride ceramics and its preparation method and application of superhard high intensity
Technical field
The invention belongs to technical field of ceramic material, a kind of boride ceramics more particularly, to superhard high intensity and Preparation method and application.
Background technique
Superhard material has important application in terms of aerospace, deep drilling exploration and material, and wherein Essential material in a kind of human lives.Novel superhard material can be by the ion of most covalent bond and fraction Key is constituted, and the transition metal element with high electron density is added in light element and prepares novel superhard material.Transition The experiment and theory study of race's light element type superhard material becomes that material, physics and chemistry etc. are multidisciplinary in recent years pays close attention to jointly Hot research problem.Zirconium boride has a high-intensitive and performances such as hardness, excellent electrical and thermal conductivity, corrosion-resistant, but its exist it is disconnected Split the deficiencies of toughness is lower, anti-oxidant ablation property is poor.Document report, pure zirconium boride ceramic have strong covalent bond, need height Temperature, high pressure or addition additive can just prepare fine and close ceramic material, and its fracture toughness is also lower.According to good Powder can effectively improve its sintering character.It is successfully prepared in patent CN201611021565.3 by the admittedly molten method of boron thermal reduction Powder diameter is small out, the high-quality powder being evenly distributed, but it does not report the performance of powder sintered rear ceramics, belongs to powder conjunction At field, it is not belonging to field of ceramic preparation.
WB2With high-melting-point, high rigidity, good electric conductivity and thermal conductivity, chemical stability and excellent wearability And the advantages that corrosion resistance.It is reported that W2B5Addition lead to B4The bending strength of C base composite ceramic increases and fracture toughness.So And in tungsten boron compound system, for WB2Research it is few.Likewise, ZrB2-WB2Report of the ceramics as research object Seldom, therefore about these materials and its characteristic there are also the places for much needing to study.
Summary of the invention
In order to solve above-mentioned the shortcomings of the prior art and disadvantage, primary and foremost purpose of the present invention is to provide a kind of superhard height The boride ceramics of intensity.There are uniform solid solution phases for the ceramics, have the advantages that high rigidity, high intensity.
Another object of the present invention is to provide the preparation method of the boride ceramics of above-mentioned superhard high intensity.
Still a further object of the present invention is to provide the application of the boride ceramics of above-mentioned superhard high intensity.
The purpose of the present invention is realized by following technical proposals:
A kind of boride ceramics of superhard high intensity, the boride ceramics is by ZrO2, WO3Add in unformed boron powder Solubilizer and ball-milling medium obtain mixed powder after ball milling and drying；Mixed powder is made by green body using mould pressing process；True The green body is warming up to 1500~1700 DEG C under empty condition to calcine, polished sieving obtains (ZrxWy)B2Boride melts admittedly Body powder, wherein 0.75≤x≤0.95,0.75≤y≤0.95；Using discharge plasma sintering, by boride solid solution powder It is filled with protective atmosphere when being warming up to 1000~1400 DEG C, then heats to 1800~2200 DEG C, pressurization 10~100MPa sintering system .
Preferably, the relative density of the boride ceramics is 92~99.9%, and hardness is 16~30GPa, fracture toughness For 2.4~5MPam1/2, compression strength is 200~650MPa.
Preferably, 0.75≤x≤0.95,0.75≤y≤0.95.
Preferably, the ZrO2And WO3Purity be 99~99.9wt%, ZrO2And WO3Partial size be 0.1~10 μm, institute The purity for stating unformed boron powder is 95~99wt%, and the partial size of the unformed boron powder is 0.1~10 μm.
Preferably, the described (ZrxWy)B2The purity of solid solution powder is 99~99.9wt%, (ZrxWy)B2Solid solution The partial size of powder is 0.1~1 μm, (the ZrxWy)B2The oxygen content of solid solution powder is 0.01~0.1wt%.
Preferably, the unformed boron powder and ZrO2Molar ratio be (3~5): 1, the unformed boron powder and WO3Rub You are than being (4~6): 1.
Preferably, the solvent is one or more of ethyl alcohol, acetone, methanol or butanol；The ball-milling medium is Si3N4、 WC or ZrO2；The protective atmosphere is N2Or Ar.
Preferably, the time of the ball milling is 10~48h, and the pressure of the molding is 1~10MPa, the molding when Between be 1~10min, the rate of the heating is 5~20 DEG C/min, and the time of the calcining is 0.5~3h.
Preferably, described to be warming up to 1000~1400 DEG C and the rate of heating when being warming up to 1800~2200 DEG C is 100~400 DEG C/min, the time of the sintering is 1~30min.
The preparation method of the boride ceramics of the superhard high intensity, comprises the following specific steps that:
S1. by ZrO2, WO3Solvent is added with unformed boron powder and ball-milling medium carries out ball milling mixing, is mixed after dry Powder；
S2. the green body after mixed powder being molded is put into graphite crucible, is warming up to 1500 with the rate of 5~20 DEG C/min ~1700 DEG C of 0.5~3h of heat preservation obtain (ZrxWy)B2Boride solid solution powder；
S3. by (ZrxWy)B2Boride solid solution powder is put into graphite jig, use discharge plasma sintering with 100~ 400 DEG C/min rate fills protective atmosphere when being warming up to 1000~1400 DEG C, then is warming up to 1800 with 100~400 DEG C/min rate ~2200 DEG C, (Zr is made in pressurization 10~100MPa sinteringxWy)B2Boride ceramics.
Application of the boride ceramics in superhigh temperature resistance to compression field.
It is raw material powder that the boride ceramics of superhard high intensity of the invention, which is by two kinds of metal oxides and unformed boron powder, Body, two-spot metal oxide obtain (Zr after Overheating TreatmentxWy)B2Boride powder, ZrO2And WO3Between melt admittedly, prepare (ZrxWy)B2Solid solution powder, this powder particle size is small, is evenly distributed, acceleration of sintering, it is easier to obtain fine and close boride Ceramics, and have excellent performance.
Compared with prior art, the invention has the following advantages:
1. the present invention is prepared for (Zr using boron thermal reduction methodxWy)B2Boride ceramic powders, the powder are purchased with by business Buy ZrB2/WB2Powder is small compared to purity is high, partial size, and component is uniform.
2. reaction raw materials of the invention are just single-phase solid solution powder, compared to two kinds boride high-energy ball millings are obtained mixed Closing raw material powder, physically uniformity, this method have reached the chemical uniformity of raw material components.This is also beneficial to its agglomerated material Homogeneous solid solution phase formation, also energy saving and cost.
3. the present invention is by ZrB2In admittedly melt WB2, since raw material is solid solution powder, original can be promoted by forming solid solution Son diffusion, can realize densified sintering product at low temperature, improve sintering character, so that the consistency of material is improved, mechanical property Improved.
4. the present invention uses WB2It is melted admittedly as the second phase, since its hardness is high and is incompressible material, this makes (ZrxWy)B2The hardness of boride is greatly improved with compressive property.
Detailed description of the invention
Fig. 1 is (Zr in embodiment 10.95W0.05)B2The XRD spectrum of boride powder.
Fig. 2 is (Zr in embodiment 10.95W0.05)B2The SEM photograph of boride powder.
Fig. 3 is (Zr in embodiment 10.95W0.05)B2The fracture apperance of boride ceramics.
Fig. 4 is ZrB in comparative example 12The fracture apperance of ceramics.
Specific embodiment
The contents of the present invention are further illustrated combined with specific embodiments below, but should not be construed as limiting the invention. Unless otherwise specified, the conventional means that technological means used in embodiment is well known to those skilled in the art.Except non-specifically Illustrate, reagent that the present invention uses, method and apparatus is the art conventional reagents, method and apparatus.
Embodiment 1
1. with ZrO2(purity 99.9% of powder, 1 μm of partial size), WO3(purity 99.9% of powder, 1 μm of partial size) powder with Unformed boron powder (purity 95.6%, 1 μm of partial size) is raw material, unformed boron powder and ZrO2Molar ratio be 4:1, the nothing is fixed Type boron powder and WO3Molar ratio be 5:1.Using ethyl alcohol as solvent, with Si3N4Ball is ball-milling medium, is mixed on roll-type ball mill For 24 hours, mixed-powder is obtained after drying；
2. the green body after mixed-powder is molded 1min with the pressure of 2MPa is put into graphite crucible, with the speed of 10 DEG C/min Rate heats up 1600 DEG C of heat preservation 1h, and after vacuum heat treatment, polished sieving obtains (Zr0.95W0.05)B2Boride solid solution powder.
3. by (Zr0.95W0.05)B2Boride solid solution powder is put into graphite jig, will with 300 DEG C/min heating rate Temperature rises to 2000 DEG C, keeps the temperature 10min, and pressurize 30MPa, fills Ar gas at 1200 DEG C, by discharge plasma sintering, is made (Zr0.95W0.05)B2Boride ceramics.
As laser particle size analysis measure the present embodiment made from (Zr0.95W0.05)B2The partial size of boride solid solution powder It is 0.4 μm, the oxygen content in the boride solid solution powder is 0.08wt%, (Zr0.95W0.05)B2Boride ceramics it is opposite Density is 98.1%, hardness 19.6GPa, fracture toughness 3.52MPam1/2, compression strength 420MPa.
Fig. 1 is (Zr in the present embodiment0.95W0.05)B2The XRD spectrum of boride solid solution powder, from figure 1 it appears that (Zr is only detected0.95W0.05)B2Independent ZrO is not detected in the peak of solid solution2Or WO3Peak, it was demonstrated that boron thermal response is complete, Also independent ZrB is not detected2Or WB2Peak, it was demonstrated that ZrB2With WB2Gu molten complete.Fig. 2 is in the present embodiment (Zr0.95W0.05)B2The SEM photograph of boride solid solution powder, as can be seen from Figure 2 its particle diameter distribution is uniform, and particle is tiny. Fig. 3 is (Zr in the present embodiment0.95W0.05)B2The fracture apperance of boride ceramics, from figure 3, it can be seen that (Zr0.95W0.05)B2 The fracture mode of boride ceramics is transgranular fracture, there is partial rivers style, therefore its toughness improves, entire fracture Pattern color is uniform, illustrates after discharge plasma sintering, (Zr0.95W0.05)B2Boride ceramics only exists single-phase, with XRD As a result consistent, and it only has a small amount of stomata, successfully prepares fine and close superhard (Zr0.95W0.05)B2Boride ceramics.
Embodiment 2
1. with ZrO2(purity 99.9% of powder, 2 μm of partial size), WO3(purity 99.9% of powder, 2 μm of partial size) powder with Unformed boron powder (purity 95.6%, 2 μm of partial size) is raw material, unformed boron powder and ZrO2Molar ratio be 3:1, the nothing is fixed Type boron powder and WO3Molar ratio be 5:1.Using ethyl alcohol as solvent, with Si3N4Ball is ball-milling medium, is mixed on roll-type ball mill For 24 hours, mixed-powder is obtained after drying；
2. the green body after mixed-powder is molded 1min with the pressure of 3MPa is put into graphite crucible, with the speed of 15 DEG C/min Rate heats up 1500 DEG C of heat preservation 1h, and after vacuum heat treatment, polished sieving obtains (Zr0.90W0.10)B2Boride solid solution powder.
3. by (Zr0.90W0.10)B2Boride solid solution powder is put into graphite jig, will with 300 DEG C/min heating rate Temperature rises to 2000 DEG C, keeps the temperature 10min, and pressurize 30MPa, fills Ar gas at 1200 DEG C, by discharge plasma sintering, is made (Zr0.90W0.10)B2Boride ceramics.
Resulting (the Zr of the present embodiment is measured by laser particle size analysis0.90W0.10)B2The partial size of boride solid solution powder It is 0.4 μm, the oxygen content in the boride solid solution powder is 0.06wt%, (Zr0.90W0.10)B2Boride ceramics it is opposite Density is 98.5%, hardness 22.3GPa, fracture toughness 3.84MPam1/2, compression strength 483MPa.
Embodiment 3
1. with ZrO2(purity 99.9% of powder, 4 μm of partial size), WO3(purity 99.9% of powder, 4 μm of partial size) powder with Unformed boron powder (purity 95.6%, 5 μm of partial size) is raw material, unformed boron powder and ZrO2Molar ratio be 4:1, the nothing is fixed Type boron powder and WO3Molar ratio be 6:1.Using ethyl alcohol as solvent, with Si3N4Ball is ball-milling medium, is mixed on roll-type ball mill For 24 hours, mixed-powder is obtained after drying；
2. the green body after mixed-powder is molded 2min with the pressure of 4MPa is put into graphite crucible, with the speed of 20 DEG C/min Rate heats up 1700 DEG C of heat preservation 1h, and after vacuum heat treatment, polished sieving obtains (Zr0.85W0.15)B2Boride solid solution powder.
3. by (Zr0.85W0.15)B2Boride solid solution powder is put into graphite jig, will with 300 DEG C/min heating rate Temperature rises to 2000 DEG C, keeps the temperature 10min, and pressurize 30MPa, fills Ar gas at 1200 DEG C, by discharge plasma sintering, is made (Zr0.85W0.15)B2Boride ceramics.
(the Zr that the present embodiment obtains is measured by laser particle size analysis0.85W0.15)B2The partial size of boride solid solution powder It is 0.3 μm, the oxygen content in the boride solid solution powder is 0.05wt%, (Zr0.85W0.15)B2Boride ceramics it is opposite Density is 99.3%, hardness 27.2GPa, fracture toughness 4.52MPam1/2, compression strength 533MPa.
Embodiment 4
1. with ZrO2(purity 99.9% of powder, 3 μm of partial size) and unformed boron powder (purity 95.6%, 4 μm of partial size) is Raw material, unformed boron powder and ZrO2Molar ratio be 3:1, the unformed boron powder and WO3Molar ratio be 5:1.With ethyl alcohol For solvent, with Si3N4Ball is ball-milling medium, is mixed on roll-type ball mill for 24 hours, obtains mixed-powder after dry；
2. the green body after mixed-powder is molded 1min with the pressure of 2MPa is put into graphite crucible, with the speed of 15 DEG C/min Rate heats up 1600 DEG C of heat preservation 0.5h, after vacuum heat treatment, polished sieving, and acquisition (Zr0.80W0.20)B2Boride solid solution powder End.
3. by (Zr0.80W0.20)B2Boride solid solution powder is put into graphite jig, will with 200 DEG C/min heating rate Temperature rises to 2000 DEG C, keeps the temperature 5min, and pressurize 30MPa, fills Ar gas at 1200 DEG C, by discharge plasma sintering, is made (Zr0.80W0.20)B2Boride ceramics.
(the Zr that the present embodiment obtains is measured by laser particle size analysis0.80W0.20)B2The partial size of boride solid solution powder It is 0.1 μm, the oxygen content in the boride solid solution powder is 0.03wt%, (Zr0.80W0.20)B2Boride ceramics it is opposite Density is 99.5%, hardness 28.6GPa, fracture toughness 4.89MPam1/2, compression strength 573MPa.
Embodiment 5
4. with ZrO2(purity 99.9% of powder, 1 μm of partial size) and unformed boron powder (purity 95.6%, 1 μm of partial size) is Raw material, unformed boron powder and ZrO2Molar ratio be 4:1, the unformed boron powder and WO3Molar ratio be 5:1.It is molten with ethyl alcohol Agent, with Si3N4Ball is ball-milling medium, is mixed on roll-type ball mill for 24 hours, obtains mixed-powder after dry；
5. the green body after mixed-powder is molded 1min with the pressure of 2MPa is put into graphite crucible, with the speed of 15 DEG C/min Rate heats up 1600 DEG C of heat preservation 1h, and after vacuum heat treatment, polished sieving obtains (Zr0.75W0.25)B2Boride solid solution powder.
6. by (Zr0.75W0.25)B2Boride solid solution powder is put into graphite jig, will with 150 DEG C/min heating rate Temperature rises to 2000 DEG C, keeps the temperature 15min, and pressurize 40MPa, fills Ar gas at 1200 DEG C, by discharge plasma sintering, is made (Zr0.75W0.25)B2Boride ceramics.
(the Zr that the present embodiment obtains is measured by laser particle size analysis0.75W0.25)B2The partial size of boride solid solution powder It is 0.1 μm, the oxygen content in the boride solid solution powder is 0.02wt%, (Zr0.75W0.25)B2Boride ceramics it is opposite Density is 99.9%, hardness 29.5GPa, fracture toughness 4.98MPam1/2, compression strength 646MPa.
Comparative example 1
1. with ZrO2(purity 99.9% of powder, 1 μm of partial size) and unformed boron powder (purity 95.6%, 1 μm of partial size) is Raw material, unformed boron powder and ZrO2Molar ratio be 4:1.Using ethyl alcohol as solvent, with Si3N4Ball is ball-milling medium, in roll-type ball It is mixed on grinding machine for 24 hours, obtains mixed-powder after dry；
2. the green body after mixed-powder is molded 1min with the pressure of 2MPa is put into graphite crucible, with the speed of 10 DEG C/min Rate heats up 1600 DEG C of heat preservation 1h, and after vacuum heat treatment, polished sieving obtains ZrB2Boronation zirconium powder.
3. by ZrB2Boronation zirconium powder is put into graphite jig, and temperature is risen to 2000 DEG C with 300 DEG C/min heating rate, 10min is kept the temperature, pressurize 30MPa, fills Ar gas at 1200 DEG C, and by discharge plasma sintering, ZrB is made2Zirconium boride ceramic.
The ZrB that the present embodiment obtains is measured by laser particle size analysis2Zirconium boride powder diameter is 0.8 μm, the boronation Oxygen content in zirconium powder is 0.1wt%, ZrB2The relative density of zirconium boride ceramic is 92.1%, hardness 16GPa, is broken tough Property is 2.4MPam1/2, compression strength 202MPa.
Fig. 4 is ZrB in this comparative example2The fracture apperance of ceramics, figure 4, it is seen that ZrB2The fracture mode of ceramics is equal For grain boundary fracture, therefore its brittleness is larger, and toughness is lower, and with the presence of a large amount of stomatas, illustrates pure ZrB2Ceramics are difficult densified sintering product.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, it is other it is any without departing from the spirit and principles of the present invention made by change, modification, substitution, combination and simplify, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (10)

1. a kind of boride ceramics of superhard high intensity, which is characterized in that the boride ceramics is by ZrO2, WO3With it is unformed Solvent and ball-milling medium are added in boron powder, obtain mixed powder after ball milling and drying；Mixed powder is made using mould pressing process Green body；The green body is warming up to 1500~1700 DEG C under vacuum conditions to calcine, polished sieving obtains (ZrxWy)B2Boron Compound solid solution powder, wherein 0.75≤x≤0.95,0.75≤y≤0.95；Using discharge plasma sintering, boride is consolidated Melt powder is filled with protective atmosphere when being warming up to 1000~1400 DEG C, then heats to 1800~2200 DEG C, and pressurization 10~ 100MPa sintering is made.
2. the boride ceramics of superhard high intensity according to claim 1, which is characterized in that the unformed boron powder and ZrO2Molar ratio be (3~5): 1, the unformed boron powder and WO3Molar ratio be (4~6): 1.
3. the boride ceramics of superhard high intensity according to claim 1, which is characterized in that the phase of the boride ceramics It is 92~99.9% to density, hardness is 16~30GPa, and fracture toughness is 2.4~5MPam1/2, compression strength be 200~ 650MPa。
4. the boride ceramics of superhard high intensity according to claim 1, which is characterized in that (the ZrxWy)B2Solid solution The purity of powder is 99~99.9wt%, (ZrxWy)B2The partial size of solid solution powder is 0.1~1 μm, (the ZrxWy)B2 The oxygen content of solid solution powder is 0.01~0.1wt%.
5. the boride ceramics of superhard high intensity according to claim 1, which is characterized in that the solvent is ethyl alcohol, third One or more of ketone, methanol or butanol；The ball-milling medium is Si3N4, WC or ZrO2。
6. the boride ceramics of superhard high intensity according to claim 1, which is characterized in that the protective atmosphere is N2Or Ar。
7. the boride ceramics of superhard high intensity according to claim 1, which is characterized in that the time of the ball milling is 10 ~48h, the pressure of the molding are 1~10MPa, and the time of the molding is 1~10min, and the rate of the heating is 5~20 DEG C/min, the time of the calcining is 0.5~3h.
8. the boride ceramics of superhard high intensity according to claim 1, which is characterized in that it is described be warming up to 1000~ The rate of 1400 DEG C and heating when being warming up to 1800~2200 DEG C is 100~400 DEG C/min, and the time of the sintering is 1 ~30min.
9. the preparation method of the boride ceramics of superhard high intensity according to claim 1-8, which is characterized in that It comprises the following specific steps that:
S1. by ZrO2, WO3Solvent is added with unformed boron powder and ball-milling medium carries out ball milling mixing, obtains mixed powder after dry Body；
S2. the green body after mixed powder being molded is put into graphite crucible, 1500 are warming up to the rate of 5~20 DEG C/min~ 1700 DEG C of 0.5~3h of heat preservation obtain (ZrxWy)B2Boride solid solution powder；
S3. by (ZrxWy)B2Boride solid solution powder is put into graphite jig, uses discharge plasma sintering with 100~400 DEG C/min rate fills protective atmosphere when being warming up to 1000~1400 DEG C, then 1800 are warming up to 100~400 DEG C/min rate~ 2200 DEG C, (Zr is made in pressurization 10~100MPa sinteringxWy)B2Boride ceramics.
10. application of the boride ceramics of any one of the claim 1~8 superhard high intensity in superhigh temperature resistance to compression field.
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