CN101698910B - Method for preparing ferromagnetic alumina-based ceramic metal through thermal explosion combustion synthesis - Google Patents

Method for preparing ferromagnetic alumina-based ceramic metal through thermal explosion combustion synthesis Download PDF

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CN101698910B
CN101698910B CN2009101849433A CN200910184943A CN101698910B CN 101698910 B CN101698910 B CN 101698910B CN 2009101849433 A CN2009101849433 A CN 2009101849433A CN 200910184943 A CN200910184943 A CN 200910184943A CN 101698910 B CN101698910 B CN 101698910B
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alumina
powder
nio
diluent
based ceramic
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CN101698910A (en
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潘冶
陆韬
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Hai Zhongshan Synthetic Fiber Co ltd
Southeast University
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Southeast University
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Abstract

The invention relates to a method for preparing ferromagnetic alumina-based ceramic metal through thermal explosion combustion synthesis. In the method, one or two of Al-Co2O3 and Al-NiO are taken as a reaction system, and the method comprises the following steps: adding a diluent and a combustion improver into the Al-Co2O3 or the Al-NiO to obtain mixed powder, wherein the mass ratio of the Al-Co2O3 or the Al-NiO to the diluent is 1:1-1:6, the diluent is one or two of Al2O3 and Ni, and the added combustion improver is polyfluortetraethylene of which the amount is 1 to 2 percent of the mass of Al; ball-milling, drying and grinding the mixed powder to make the mean grain size of the mixed powder between 1.5 and 1.8 microns; obtaining a pre-cast block of which the relative density is 60 to 70 percent through compaction; placing the pre-cast block into a graphite casting mould; heating the whole graphite casting mould through a resistance furnace until a thermal explosion reaction is generated; and applying an axial pressure of 1.2 to 1.5 MPa to obtain the ferromagnetic alumina-based ceramic metal of which the compactness is 95 to 96 percent.

Description

The thermal explosion burning synthesis for preparing is equipped with the preparation method of ferromagnetic alumina-based ceramic metal
Technical field
The present invention relates to a kind of get everything ready preparation method of ferromagnetic alumina-based ceramic metal of thermal explosion burning synthesis for preparing that utilizes.
Background technology
Alumina-ceramic is owing to abundant, the performance of its raw material superior becomes most widely used engineering materials.With aluminium oxide as matrix material, form the alumina-based ceramic metal material by adding ductile metal, can be when improving alumina substrate fragility, high-strength, high hard, the low-density of performance alumina substrate and good chemical stability characteristics are expanded the range of application of aluminium oxide ceramics.By compound second-phase metallic particles with functional characteristic (magnetic property, dielectric properties etc.) in alumina substrate, can be when improving alumina substrate mechanical property and processability, formation has the novel high-performance material of mechanical property and functional characteristic concurrently, to satisfy the application of the bad working environments occasions such as high temperature, high corrosion.
Ceramic-metallic preparation method mainly contains powder sintering, pickling process and pressure sintering etc., and these three kinds of technologies have all experienced an agglomerating stage.Utilization based on the thermal explosion burning synthesis for preparing of thermite reaction be equipped with technology in the process of preparation alumina-based ceramic metal, have be swift in response, advantages such as technology is simple, production efficiency height, having changed especially conventional sintering technology length consuming time, characteristics that energy consumption is high in the reaction moulding process, is a kind of technology of preparing efficiently.
Summary of the invention
The purpose of this invention is to provide the preparation method that a kind of thermal explosion burning synthesis for preparing is equipped with ferromagnetic alumina-based ceramic metal, by the present invention can obtain fine and close, possess ferromagnetic alumina-based ceramic metal material.
The present invention adopts following technical scheme:
Step 1: with Al-Co 2O 3With among the Al-NiO one or both as reaction system, at Al-Co 2O 3Perhaps add diluent and combustion adjuvant among the Al-NiO, obtain mixed-powder, described Al-Co 2O 3Perhaps the mass ratio of the addition of Al-NiO and diluent is 1: 1-1.6, described diluent are Al 2O 3With among the Ni one or both, the combustion adjuvant of interpolation is polytetrafluoroethylene (PTFE), and its addition is the 1-2% of Al quality.
Step 2: with mixed powder by behind the ball milling, drying, grinding, the median size of mixed powder is 1.5-1.8 μ m, obtain the prefabricated section of relative density 60-70% by pressed compact, prefabricated section is inserted graphite casting mould, by resistance furnace graphite casting mould is carried out integral body and be heated to thermal explosion reaction generation, apply axle pressure 1.2-1.5MPa, obtain the ferromagnetic alumina-based ceramic metal of density 95-96%.
Compared with prior art, the present invention has following advantage:
1, abundant raw material, cost is lower, and preparation equipment is simple.
2, preparation process is rapid, and energy consumption is few, product phase interface cleaning, and foreign matter content is low.
3, react under the high heat release condition at thermal explosion, just can obtain fine and close alumina-based ceramic metal by lower pressure.
4, be compound in the alumina substrate by metal Co, Ni and Co-Ni alloy, can in the mechanical property that improves alumina-ceramic, obtain ferromegnetism, expand the range of application of alumina-based ceramic metal.
Description of drawings
Fig. 1 thermal explosion synthesizer synoptic diagram.
Fig. 2 Al 2O 3-Co cermet SEM figure.
Fig. 3 Al 2O 3-Co cermet XRD figure.
Fig. 4 Al 2O 3-Co ceramet group physical efficiency spectrogram.
Fig. 5 Al 2O 3-Co cermet Metal Phase can spectrogram.
Fig. 6 Al 2O 3-Co cermet hysteresis curve figure.
Fig. 7 is by adding the synthetic Al of Ni powder 2O 3-(Co-50Ni) cermet SEM schemes.
Fig. 8 is by adding the synthetic Al of Ni powder 2O 3-(Co-50Ni) cermet XRD schemes.
Fig. 9 is by adding the synthetic Al of Ni powder 2O 3-(Co-50Ni) ceramet group physical efficiency spectrogram.
Figure 10 is by adding the synthetic Al of Ni powder 2O 3-(Co-50Ni) the cermet Metal Phase can spectrogram.
Figure 11 is by adding the synthetic Al of Ni powder 2O 3-(Co-50Ni) cermet hysteresis curve figure.
Figure 12 generates the Al of Co-50Ni by reaction 2O 3-(Co-50Ni) cermet SEM schemes.
Figure 13 generates the Al of Co-50Ni by reaction 2O 3-(Co-50Ni) cermet XRD schemes.
Figure 14 generates the Al of Co-50Ni by reaction 2O 3-(Co-50Ni) ceramet group physical efficiency spectrogram.
Figure 15 generates the Al of Co-50Ni by reaction 2O 3-(Co-50Ni) the cermet Metal Phase can spectrogram.
Figure 16 generates the Al of Co-50Ni by reaction 2O 3-(Co-50Ni) cermet hysteresis curve figure.
Embodiment
A kind of thermal explosion burning synthesis for preparing is equipped with the preparation method of ferromagnetic alumina-based ceramic metal:
Step 1: with Al-Co 2O 3With among the Al-NiO one or both as reaction system, at Al-Co 2O 3Perhaps add diluent and combustion adjuvant among the Al-NiO, obtain mixed-powder, described Al-Co 2O 3Perhaps the mass ratio of the addition of Al-NiO and diluent is 1: 1-1.6, present embodiment can select 1: 1,1: 1.6 or 1: 1.2, and described diluent is Al 2O 3With among the Ni one or both, the combustion adjuvant of interpolation is polytetrafluoroethylene (PTFE), and its addition is the 1-2% of Al quality, and present embodiment can select 1%, 2% or 1.4%,
Step 2: with mixed powder by behind the ball milling, drying, grinding, the median size of mixed powder is 1.5-1.8 μ m, specifically, the median size of described mixed powder is 1.5,1.7 or 1.8 μ m, obtain the prefabricated section of relative density 60-70% by pressed compact, prefabricated section is inserted graphite casting mould, by resistance furnace graphite casting mould is carried out integral body and be heated to thermal explosion reaction generation, apply axle pressure 1.2-1.5MPa, present embodiment can select 1.2,1.3 or 1.5MPa for use, obtains the ferromagnetic alumina-based ceramic metal of density 95-96%.
It is as follows that the present invention utilizes the thermal explosion burning synthesis for preparing to be equipped with the technology of ferromagnetic alumina-based ceramic metal:
1, by the design of reaction system composition, obtain reactant ratio, the thinner addition, the reaction system adiabatic temperature is controlled between metal boiling point and the aluminum oxide fusing point under the theoretical condition, and the guarantee system sufficient reacting is not but violent, and sample does not splash.
2, reactant ratio and the thinner addition weighing reaction powder that obtains according to technology 1, add the polymer poly tetrafluoroethylene simultaneously as ignition dope, as grinding aid, use aluminum oxide ball milling jar to carry out ball milling speed 300r/min ball milling 6-8 hour with dehydrated alcohol.
3, the slurry that obtains behind the ball milling is inserted drying basin, be not higher than under 70 ℃ the condition vacuum-drying 4 hours, and the dried powder of acquisition is inserted mortar and ground evenly.
4, dried powder is carried out pressed compact on press, pressure 50MPa obtains Φ 20mm * 10mm right cylinder prefabricated section, relative density 60-70%.
5, brill aperture in prefabricated section top is used to place thermocouple temperature measurement, and prefabricated section is placed graphite casting mould, provides axle pressure by the graphite drift.
6, by the whole heating of resistance furnace, utilize temperature monitor Real Time Observation prefabricated section variations in temperature, when temperature curve climbs fast, the thermal explosion reaction takes place, axial compressive force 1.2-1.5MPa acts on response sample by the graphite drift, the exhaust passage is left at graphite drift middle part, and the residual gas in the sample can outwards be escaped by the exhaust passage.After reaction finished, pressurize 10 seconds removed pressure apparatus, and sample takes out air cooling from casting mold, obtained finished product.
Embodiment 1: with Al powder, Co 2O 3Powder is as reaction raw materials, Al 2O 3Powder adds 2% polytetrafluorethylepowder powder of Al opaque amount as combustion adjuvant as diluent, is made into the reaction powder.By Composition Design, can obtain the Al of Co mass fraction 25-30% 2O 3-Co cermet.To react powder and carry out ball milling, drying after the grinding, is pressed into Φ 20mm * 10mm cylinder prefabricated section, initial relative density 60%.Prefabricated section is inserted graphite casting mould, put into process furnace, begin heating from room temperature with the speed of 1.53 ℃/s.At 680 ℃ the thermal explosions reaction takes place, apply axial compressive force 1.2-1.5MPa in reaction moment, pressurize was taken out the sample air cooling after 10 seconds.As shown in Figure 2, the metal Co particle size is no more than 10 μ m, and even dispersion is distributed in the matrix, and the sample of acquisition is through test, and density surpasses 95%, saturation magnetization 42emu/g, coercive force 61Oe.
Embodiment 2: with Al powder, Co 2O 3Powder is as reaction raw materials, Al 2O 3Powder adds simultaneously the Co that the Ni powder is used for and reaction generates and forms the Co-Ni alloy as diluent, takes into account simultaneously as reaction diluent, adds 2% polytetrafluorethylepowder powder of Al opaque amount as combustion adjuvant, is made into the reaction powder.By Composition Design, can obtain the Al of Co-Ni alloy mass mark 40-45% 2O 3-(Co-50Ni) cermet.To react powder and carry out ball milling, drying after the grinding, is pressed into Φ 20mm * 10mm cylinder prefabricated section, initial relative density 60%.Prefabricated section is inserted graphite casting mould, put into process furnace, begin heating from room temperature with the speed of 1.53 ℃/s.At 910 ℃ the thermal explosions reaction takes place, apply axial compressive force 1.2-1.5MPa in reaction moment, pressurize was taken out the sample air cooling after 10 seconds.As shown in Figure 7, synthetic Co-50Ni alloy infiltrates in the matrix space under pressure, forms network-like distribution, and the sample of acquisition is through test, and density surpasses 96%, saturation magnetization 48emu/g, coercive force 12Oe.
Embodiment 3: present embodiment is with Al-Co 2O 3With Al-NiO as reaction system, specifically, with Al powder, Co 2O 3Powder and NiO powder be as reaction raw materials, Al 2O 3Powder adds 2% polytetrafluorethylepowder powder of Al opaque amount as combustion adjuvant as diluent, is made into the reaction powder.Pass through Al-Co 2O 3Obtain the Co-Ni alloy with two thermit reactions of Al-NiO.By Composition Design, can obtain the Al of alloy mass mark 25-30% 2O 3-(Co-50Ni) cermet.To react powder and carry out ball milling, drying after the grinding, is pressed into Φ 20mm * 10mm cylinder prefabricated section, initial relative density 60%.Prefabricated section is inserted graphite casting mould, put into process furnace, begin heating from room temperature with the speed of 1.53 ℃/s.At 890 ℃ the thermal explosions reaction takes place, apply axial compressive force 1.2-1.5MPa in reaction moment, pressurize was taken out the sample air cooling after 10 seconds.As shown in figure 12, the Co-50Ni alloy out-of-shape that reaction generates, size is no more than 10 μ m, and even dispersion is distributed in the matrix, and the sample of acquisition is through test, and density surpasses 96%, saturation magnetization 30emu/g, coercive force 29Oe.
Embodiment 4: with Al powder, NiO powder as reaction raw materials, Al 2O 3Powder adds 2% polytetrafluorethylepowder powder of Al opaque amount as combustion adjuvant as diluent, is made into the reaction powder.By Composition Design, can obtain the Al of Ni mass fraction 25-30% 2O 3-Ni cermet.To react powder and carry out ball milling, drying after the grinding, is pressed into Φ 20mm * 10mm cylinder prefabricated section, initial relative density 60%.Prefabricated section is inserted graphite casting mould, put into process furnace, begin heating from room temperature with the speed of 1.53 ℃/s.After the thermal explosion reaction takes place, apply axial compressive force 1.2-1.5MPa in reaction moment, pressurize was taken out the sample air cooling after 10 seconds.Metal Ni particle size is no more than 10 μ m, and even dispersion is distributed in the matrix, and the sample of acquisition is through test, and density surpasses 95%.
Embodiment 5: as reaction raw materials, the Ni powder is as thinner with Al powder, NiO powder, and 2% polytetrafluorethylepowder powder that adds Al opaque amount is made into the reaction powder as ignition dope.By Composition Design, can obtain the Al of Ni mass fraction 45-50% 2O 3-Ni cermet.To react powder and carry out ball milling, drying after the grinding, is pressed into Φ 20mm * 10mm cylinder prefabricated section, initial relative density 60%.Prefabricated section is inserted graphite casting mould, put into process furnace, begin heating from room temperature with the speed of 1.53 ℃/s.After the thermal explosion reaction takes place, apply axial compressive force 1.2-1.5MPa in reaction moment, pressurize was taken out the sample air cooling after 10 seconds.Metal Ni particle size is evenly distributed in the matrix at 15-20 μ m, and the sample of acquisition is through test, and density surpasses 95%.
With reference to Fig. 1,1, body of heater, 2, sample, 3, pressure punch, 4, venting hole, 5, graphite casting mould, 6, go up the graphite cushion block, 7, graphite cushion block down.
With reference to Fig. 2, the Al for preparing among the embodiment 1 2O 3The ceramic-metallic SEM figure of-Co shows that the metal Co phase size on average is no more than 10 μ m, and even dispersion is distributed in the matrix.
With reference to Fig. 3, the Al for preparing among the embodiment 1 2O 3The ceramic-metallic XRD figure of-Co shows that the composition of product is mainly Al mutually 2O 3, α-Co and β-Co.
With reference to Fig. 4, the Al for preparing among the embodiment 1 2O 3The energy spectrogram of-Co cermet matrix phase shows that the component of matrix phase is Al and O.
With reference to Fig. 5, the Al for preparing among the embodiment 1 2O 3The energy spectrogram of-Co cermet Metal Phase shows that Metal Phase be pure Co.
With reference to Fig. 6, the Al for preparing among the embodiment 1 2O 3The ceramic-metallic hysteresis curve figure of-Co shows Al 2O 3-Co cermet has ferromagnetism, saturation magnetization 30emu/g, coercivity 29Oe.
With reference to Fig. 7, the Al for preparing among the embodiment 2 2O 3-(Co-50Ni) ceramic-metallic SEM figure shows the Co-50Ni alloy under pressure, infiltrates in the matrix space, forms network-like distribution.
With reference to Fig. 8, the Al for preparing among the embodiment 2 2O 3-(Co-50Ni) ceramic-metallic XRD figure shows that the composition of product is mainly Al mutually 2O 3With the Co-Ni alloy.
With reference to Fig. 9, the Al for preparing among the embodiment 2 2O 3-(Co-50Ni) cermet matrix phase can show that the component of matrix phase is Al and O by spectrogram.
With reference to Figure 10, the Al for preparing among the embodiment 2 2O 3-(Co-50Ni) the cermet Metal Phase can show that the Metal Phase component is Co and Ni by spectrogram.
With reference to Figure 11, the Al for preparing among the embodiment 2 2O 3-(Co-50Ni) ceramic-metallic hysteresis curve shows Al 2O 3-(Co-50Ni) cermet has ferromagnetism, saturation magnetization 48emu/g, coercivity 12Oe.
With reference to Figure 12, the Al for preparing among the embodiment 3 2O 3-(Co-50Ni) ceramic-metallic SEM figure shows the Co-50Ni alloy out-of-shape that reaction generates, and size is no more than 10 μ m, and even dispersion is distributed in the matrix.
With reference to Figure 13, the Al for preparing among the embodiment 3 2O 3-(Co-50Ni) ceramic-metallic XRD figure shows that the composition of product is mainly Al mutually 2O 3With the Co-Ni alloy.
With reference to Figure 14, the Al for preparing among the embodiment 3 2O 3-(Co-50Ni) cermet matrix phase can show that the component of matrix phase is Al and O by spectrogram.
With reference to Figure 15, the Al for preparing among the embodiment 3 2O 3-(Co-50Ni) the cermet Metal Phase can show that the Metal Phase component is Co and Ni by spectrogram.
With reference to Figure 16, the Al for preparing among the embodiment 3 2O 3-(Co-50Ni) ceramic-metallic hysteresis curve shows Al 2O 3-(Co-50Ni) cermet has ferromagnetism, saturation magnetization 30emu/g, coercivity 29Oe.

Claims (1)

1. a thermal explosion burning synthesis for preparing is equipped with the preparation method of ferromagnetic alumina-based ceramic metal, it is characterized in that:
Step 1: with Al-Co 2O 3A kind of as reaction system with among the Al-NiO is at Al-Co 2O 3Perhaps add diluent and combustion adjuvant among the Al-NiO, obtain mixed-powder, described Al-Co 2O 3Perhaps the mass ratio of the addition of Al-NiO and diluent is 1: 1-1.6, described diluent are Al 2O 3With among the Ni one or both, the combustion adjuvant of interpolation is polytetrafluoroethylene (PTFE), and its addition is the 1-2% of Al quality,
Step 2: with mixed powder by behind the ball milling, drying, grinding, the median size of mixed powder is 1.5-1.8 μ m, obtain the prefabricated section of relative density 60-70% by pressed compact, prefabricated section is inserted graphite casting mould, by resistance furnace graphite casting mould is carried out integral body and be heated to thermal explosion reaction generation, apply axle pressure 1.2-1.5MPa, obtain the ferromagnetic alumina-based ceramic metal of density 95-96%.
CN2009101849433A 2009-10-21 2009-10-21 Method for preparing ferromagnetic alumina-based ceramic metal through thermal explosion combustion synthesis Expired - Fee Related CN101698910B (en)

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CN106048365A (en) * 2016-05-31 2016-10-26 合肥正浩机械科技有限公司 Alsimay composite metal ceramic seal ring and preparation method thereof
CN107012380B (en) * 2017-03-31 2018-12-14 东南大学 A kind of preparation method of Self- propagating Sintering Synthetic founding high-entropy alloy
CN108543935B (en) * 2018-04-12 2020-09-18 北京科技大学 Method for preparing metal-based SHS (super thin-layer high-resolution) wear-resistant coating by combining 3D (three-dimensional) printing with vacuum lost foam

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