CN108640672A - A kind of preparation method of light-weight magnesite-alumina spinel refractories - Google Patents
A kind of preparation method of light-weight magnesite-alumina spinel refractories Download PDFInfo
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- CN108640672A CN108640672A CN201810580194.5A CN201810580194A CN108640672A CN 108640672 A CN108640672 A CN 108640672A CN 201810580194 A CN201810580194 A CN 201810580194A CN 108640672 A CN108640672 A CN 108640672A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
- C04B35/443—Magnesium aluminate spinel
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9646—Optical properties
- C04B2235/9653—Translucent or transparent ceramics other than alumina
Abstract
The present invention provides a kind of light-weight magnesite-alumina spinel refractories MgOnAl2O3Preparation method, wherein 1≤n≤2, specifically include following steps：1) mixing and ball milling is added in magnesium oxide powder and alpha alumina powder, then removes solvent, be sieved, then through high temperature solid state reaction, sieving obtains magnesia-alumina spinel powder；2) magnesia-alumina spinel powder is put into graphite jig, then is placed in discharging plasma sintering equipment and is molded and is pre-sintered, obtain pre-sintered body；3) pre-sintered body is placed in Muffle furnace and is sintered again, then natural cooling, obtain the closed sintered body of open pore；4) the closed sintered body of open pore is handled through HIP sintering, gained sample obtains light-weight magnesite-alumina spinel refractories after polished processing again after sintering.This method is conducive to control sample composition and without can be obtained high consistency by adding sintering aid, can carry out large-scale industrial production using without sintering in pressure air, reducing production cost.
Description
Technical field
The invention belongs to field of transparent ceramic material preparation, and in particular to a kind of magnesium aluminate spinel MgOnAl2O3(1≤n
≤ 2) preparation method of crystalline ceramics.
Background technology
Light-weight magnesite-alumina spinel refractories material has high temperature resistant, resistant to chemical etching, excellent electrical insulation capability and mechanicalness
Can, there is good optical transmittance in 0.20-6.5 μ m wavelength ranges.Magnesium aluminate spinel is as solid solution, and performance is with change
It learns metering to change, this provides foundation technically to form controlled material performance by control.Aluminium oxide solid solution enters point
Spar lattice makes lattice constant reduce, and can improve its mechanical property, this transparent spinel ceramics to meet difference to answer
Requirement with field to performance.For example it is militarily used as transparent armor and material of infrared window, civilian aspect is held for pressure
Device window, high pressure fluorescent tube, photo-thermal exchanger, watchcase etc..
In terms of preparing light-weight magnesite-alumina spinel refractories, Gilde et al. uses business powder S30-CR, mixing 0.75wt%
LiF is raw material, and using 1620-1650 DEG C of hot pressed sintering 3h or 12h, 1500-1900 DEG C of hot isostatic pressing condition/100-200MPa is burnt
Knot 6h obtains transmitance at 3.39 μm>80% crystalline ceramics (Gilde G, Patel P, Patterson P, et al.,
Evaluation of Hot Pressing and Hot Isostastic Pressing Parameters on the
Optical Properties of Spinel[J].Journal of the American Ceramic Society,2005,
88(10):2747–2751.).Since sintering aid LiF causes at 632.8nm transmitance to only have 65% or so in crystal boundary enrichment, and
And since the addition sintering mechanism of LiF is liquid-phase sintering, the mode of liquid-phase sintering promotes crystal grain significantly to grow, before and after hot isostatic pressing
Crystallite dimension grows into 200-300 μm by 100 μm.Krell et al. uses the special MgAl of grain size 53nm2O4Powder uses
350MPa cold isostatic compactions, 1240-1260 DEG C of sintering under the conditions of no pressure, hot isostatic pressing is made average at less than 1300 DEG C
Light-weight magnesite-alumina spinel refractories (Krell A, Hutzler T, Klimke J, the et al., Fine- of 0.2-0.3 μm of crystallite dimension
Grained Transparent Spinel Windows by the Processing of Different Nanopowders
[J].Journal of the American Ceramic Society,2010,93(9):2656-2666.), thickness of sample 4-
Visible light region transmitance reaches 80% in the case of 10mm, and this method is high to material powder Particle size requirements, with high costs.
Morita et al. (Morita K, Kim B N, Yoshida H, et al., Effect of loading schedule on
densification of MgAl2O4spinel during spark plasma sintering(SPS)processing
[J].Journal of the European Ceramic Society,2012,32(10):2303-2309.) use grain size
The business powder of 100-300nm is warming up to using plasma discharging vacuum-sintering with the heating rate of 10-100 DEG C/min
At 1000-1400 DEG C, Quick-pressing is sintered 20min to 80MPa in 10-300s, obtains MgAl2O4The crystal grain ruler of ceramics sample
Very little at 0.4 μm or so, but transmitance is undesirable, and the best sample of transmitance is that 100 DEG C/min rises to 1300 DEG C and pressurizes
It prepares, it is 74% that straight line transmittance, which is about at 35%, 2000nm, at 550nm.Dericioglu et al. association reactions be sintered and
Hot pressed sintering, is sintered 1h and in 1900 DEG C, 189MPa hip treatments under the conditions of 1400 DEG C, 50MPa, obtain n values be 1,
1.5 and 2 transparent spinel ceramics, but stoichiometry spinelle visible light transmittance only has 20-40%, aluminium riched spinel
It is not above 60% (Dericioglu F, Boccaccini AR, Dlouhy I, et al., Effect of Chemical
Composition on the Optical Properties and Fracture Toughness of Transparent
Magnesium Aluminate Spinel Ceramics[J].Materials Transactions,2005,46(5):996-
1003)。
As known from the above, the magnesium-aluminum spinel ceramic obtained in the prior art using the hot pressed sintering of addition auxiliary agent is generally deposited
Poor in grain size distribution homogeneity, crystalline ceramics mechanical property is poor, and the sintering aid added is enriched with to form the second phase
Reduce transmitance and mechanical performance；The magnesium aluminate spinel crystal grain that discharge plasma is sintered is smaller but due to the use of graphite mo(u)ld
Tool causes carbon pollution to reduce optical property；And the application requirement of light-weight magnesite-alumina spinel refractories its have both excellent optical property and
Mechanical performance, such as intensity and hardness.Although and traditional pressureless sintering mode prepare fine-crystal transparent ceramics succeed, it is right
Material powder requires very high, and diameter of particle requires 50nm hereinafter, manufacturing cost is consequently increased, therefore, prepare ingredient it is simple,
Having both the magnesium-aluminum spinel ceramic of excellent mechanical performance and optical property becomes research urgent problem to be solved at present.
Invention content
The purpose of the present invention is being directed to the deficiencies in the prior art, proposition is a kind of to prepare light-weight magnesite-alumina spinel refractories
Method, this method combination discharge plasma sintering, pressureless sintering and HIP sintering advantage, can reduce to raw material
The requirement of powder, and additive is not used, high-performance MgOnAl can be prepared2O3The transparent pottery of (1≤n≤2) spinelle
Porcelain, and controlled material performance can be designed by composition.
In order to solve the above technical problems, technical solution provided by the invention is：
A kind of light-weight magnesite-alumina spinel refractories MgOnAl is provided2O3Preparation method, wherein 1≤n≤2, specifically include with
Lower step：
1) preparation of magnesia-alumina spinel powder：By magnesium oxide powder and alpha-alumina powder in molar ratio 1：N is matched, according to
Ball material mass ratio 4:1 is added alumina balls and absolute ethyl alcohol mixing and ball milling for 24 hours, and then rotary evaporation removes solvent, crosses 100 mesh
Sieve, then through high temperature solid state reaction, finally cross 200 mesh and sieve to obtain high-purity, single-phase magnesia-alumina spinel powder；
2) molding and pre-sintering：Magnesia-alumina spinel powder obtained by step 1) is put into graphite jig, then is placed in electric discharge etc.
It is molded and is pre-sintered in ion agglomerating plant, obtain the pre-sintering of relative density 82-90% (i.e. porosity 10-18%)
Body；
3) pressureless sintering：Pre-sintered body obtained by step 2) is placed in Muffle furnace and is sintered again, then natural cooling,
Obtain the closed sintered body of open pore；
4) HIP sintering：The closed sintered body of open pore obtained by step 3) is handled through HIP sintering, is sintered
Gained sample obtains light-weight magnesite-alumina spinel refractories after polished processing again afterwards.
By said program, step 1) the magnesium oxide powder grain size is 100nm~1 μm, the alpha-alumina powder grain size
For 180nm~1 μm.
By said program, step 1) the high temperature solid state reaction condition is：10~15min is kept the temperature at 1350~1750 DEG C.
By said program, step 1) the magnesia-alumina spinel powder grain size is 180~1000nm.
By said program, step 2) is placed in discharging plasma sintering equipment the process conditions for being molded and being pre-sintered
For：Start to keep precompression 7.5MPa, continue when being warming up to 1300-1500 DEG C at room temperature with the rate of 10~200 DEG C/min with
The compression rate of 30MPa/min is forced into 20~40MPa, subsequent heat-insulation pressure keeping 1-30min.
By said program, sintering process conditions are step 3) again：It is warming up to 1500- with the heating rate of 10 DEG C/min
1650 DEG C, keep the temperature 1-25h.
By said program, the closed sintered body relative density of the step 3) open pore is 96-99%.Sintered body is set to reach
To the requirement of HIP sintering (general consistency can obtain preferable HIP sintering effect for 95% or more).By
Two-step sintering is already close to fine and close ceramics.
By said program, step 4) the HIP sintering process conditions are：Under inert atmosphere, in pressure 180-
It is sintered at 200MPa, 1500-1880 DEG C of temperature, sintering time 5-15h.
Discharge plasma is sintered by the present invention, pressureless sintering and HIP sintering combine, selection process sequence and item
Part, the first step first use SPS to be pre-sintered (spark plasma sintering discharge plasma sinterings), and obtained sample is in crystalline substance
Grain without grow in the case of (grain growth needs high temperature activated, and this dynamic process needs the time,
The present invention, using being rapidly heated, is kept the temperature in SPS sintering to 1300-1500 DEG C of (low sintering temperature) short time, is allowed ceramic fast
Speed densification, to allow grain growth to have little time to occur) pore size with very little, after being embodied in molding or being pre-sintered
The consistency for relying solely on the green body that particle packing obtains in sample consistency higher than tradition, to have in later stage pressureless sintering
There is very high sintering character.
The beneficial effects of the present invention are：1) compared with existing magnesium-aluminum spinel ceramic technology of preparing, the present invention is without burning
Auxiliary agent is tied, is suitble to conventional powder, and form controllable, in conjunction with the advantage of different sintering processings, obtains the uniform green body of structure
Be conducive to be sintered, using without pressure air calcination, reduce production cost, can be produced in batches under existing working condition,
Save equipment investment；2) the magnesium-aluminum spinel ceramic product that the present invention prepares has both good mechanical property and optical property,
And controlled material performance can be designed by composition.
Description of the drawings
Fig. 1 is the full spectrum transmitance figure of the transparent magnesium aluminium spinel ceramics prepared by embodiment 1；
Fig. 2 is the photograph in kind after the potsherd polishing of the transparent magnesium aluminium spinel ceramics prepared by embodiment 1；
Fig. 3 is the SEM microstructure photographs of sample after pressureless sintering in embodiment 1；
Fig. 4 is the SEM microstructure photographs of the transparent magnesium aluminium spinel ceramics prepared by embodiment 1；
Fig. 5 is the full spectrum transmitance figure of the transparent magnesium aluminium spinel ceramics prepared by embodiment 2；
Fig. 6 is the photograph in kind after the potsherd polishing of the transparent magnesium aluminium spinel ceramics prepared by embodiment 2；
Fig. 7 is the SEM microstructure photographs of sample after pressureless sintering in embodiment 2；
Fig. 8 is the SEM microstructure photographs of the transparent magnesium aluminium spinel ceramics prepared by embodiment 2；
Fig. 9 is the full spectrum transmitance figure of the transparent magnesium aluminium spinel ceramics prepared by embodiment 3；
Figure 10 is the photograph in kind after the potsherd polishing of the transparent magnesium aluminium spinel ceramics prepared by embodiment 3；
Figure 11 is the SEM microstructure photographs of sample after pressureless sintering in embodiment 3；
Figure 12 is the SEM microstructure photographs of the transparent magnesium aluminium spinel ceramics prepared by embodiment 3；
Figure 13 is the full spectrum transmitance figure of the magnesium-aluminum spinel ceramic prepared by comparative example 1；
Figure 14 is the photograph in kind after the potsherd polishing of the magnesium-aluminum spinel ceramic prepared by comparative example 1；
Figure 15 is the SEM microstructure photographs of the magnesium-aluminum spinel ceramic prepared by comparative example 1；
Figure 16 is the SEM microstructure photographs of magnesium-aluminum spinel ceramic after pressureless sintering in comparative example 2.
Specific implementation mode
Embodiment 1
A kind of light-weight magnesite-alumina spinel refractories MgOAl2O3, preparation method is as follows：
It is respectively that 28.33% and 71.67% weigh magnesia (average grain diameter 100nm) and alpha-oxidation according to mass percent
Aluminium (average grain diameter 180nm) amounts to 150g, according to ball material mass ratio 4:1 is added alumina balls and absolute ethyl alcohol mixing and ball milling for 24 hours,
Then rotary evaporation removes solvent, sieves with 100 mesh sieve, then is sintered 10min in 1350 DEG C of solid phase reactions, finally crosses 200 mesh and sieves to obtain
MgO·Al2O3Spinel powder, powder average grain diameter are 180nm；
By the MgOAl of above-mentioned preparation2O3Spinel powder is put into graphite jig, then by mold be put into electric discharge etc. from
Precharge 7.5MPa is carried out in the insulation quilt of sub- agglomerating plant, uses the heating rate heating mould of 100 DEG C/min to arrive at room temperature
1425 DEG C, 20MPa, subsequent heat-insulation pressure keeping 1min are forced into the compression rate of 30MPa/min when temperature reaches maximum temperature,
The pre-sintered body that relative density is 82% (porosity 18%) is obtained after natural cooling；
The pre-sintered body of above-mentioned preparation is placed in Muffle furnace, 4h is sintered in 1575 DEG C with the heating rate of 10 DEG C/min,
Then natural cooling obtains the closed sintered body of open pore of consistency 98%；
The above-mentioned closed sintered body of gained open pore is placed in 1500 DEG C, carries out heat etc. in the Ar compression rings border of pressure 180MPa
Static pressure sintering processes 5h；Finally sample is cut, polished and polished with precision gas cutting machine, surface grinding machine, diamond polishing liquid, is obtained
To light-weight magnesite-alumina spinel refractories, photo is as shown in Figure 2.
The ceramic body 2mm thickness that the present embodiment obtains straight line transmittance at 550nm is 75%, infrared region highest straight line
Transmitance is 83%；Vickers hardness hv 1=13.91 ± 0.44GPa.
It is the full spectrum transmitance figure of light-weight magnesite-alumina spinel refractories manufactured in the present embodiment, as seen from the figure 2mm as shown in Figure 1
Straight line transmittance of the sample of thickness at 550nm is 75%, and infrared region highest straight line transmittance is 83%, shows that sample has
There is good optical property.
Fig. 3 is that the SEM of sample (the closed sintered body of open pore of consistency 98%) after pressureless sintering in the present embodiment is aobvious
Microstructural photographs, grain size distribution is uniform in sample as seen from the figure, and average grain size is 1 μm or so.
Fig. 4 is the SEM microstructure photographs of the light-weight magnesite-alumina spinel refractories prepared by the present embodiment, micro- as seen from the figure
Structure keeps uniform, and average grain size is about 1.9 μm.By compared with the microstructure (Fig. 3) before HIP sintering, table
Crystallite dimension variation is little in bright hot isostatic pressing.
Embodiment 2
A kind of light-weight magnesite-alumina spinel refractories MgO1.44Al2O3, preparation method is as follows：
It is respectively that 21.54% and 78.46% weigh magnesia (average grain diameter 100nm) and Alpha-alumina according to mass fraction
(average grain diameter 180nm) amounts to 150g, according to ball material mass ratio 4:1 is added alumina balls and absolute ethyl alcohol mixing and ball milling for 24 hours, so
Rotary evaporation removes solvent afterwards, sieves with 100 mesh sieve, then is sintered 10min in 1350 DEG C of solid phase reactions, finally crosses 200 mesh and sieves to obtain
MgO·1.44Al2O3The average particle diameter size of spinel powder, powder is 225nm；
By the MgO1.44Al of above-mentioned preparation2O3Spinel powder is put into graphite jig, and mold is then put into electric discharge
Precharge 7.5MPa is carried out in the insulation quilt of plasma sintering equipment, uses the heating rate heated mould of 100 DEG C/min at room temperature
Have to 1400 DEG C, 30MPa, subsequent heat-insulation pressure keeping are forced into the compression rate of 30MPa/min when temperature reaches maximum temperature
10min obtains the pre-sintered body that relative density is 90% after natural cooling；
The pre-sintered body of above-mentioned preparation is placed in Muffle furnace, 5h is sintered in 1575 DEG C with the heating rate of 10 DEG C/min,
Then natural cooling obtains the closed sintered body of open pore of consistency 98%；
The above-mentioned closed sintered body of gained open pore is placed in 1500 DEG C, carries out heat etc. in the Ar compression rings border of pressure 180MPa
Static pressure sintering processes 15h；Finally sample is cut, polished and polished with precision gas cutting machine, surface grinding machine, diamond polishing liquid,
Light-weight magnesite-alumina spinel refractories are obtained, photo is as shown in Figure 6.
The ceramic body 2mm thickness that the present embodiment obtains straight line transmittance at 550nm is 65%, infrared region highest straight line
Transmitance is 80%；Vickers hardness hv 1=13.90 ± 0.20GPa.
Fig. 5 is the full spectrum transmitance figure of light-weight magnesite-alumina spinel refractories manufactured in the present embodiment, as seen from the figure 2mm thickness
Straight line transmittance of the sample at 550nm is 65%, and infrared region highest straight line transmittance is 80%, and it is good to show that sample has
Optical property.
Fig. 7 is that the SEM of sample (the closed sintered body of open pore of consistency 98%) after pressureless sintering in the present embodiment is aobvious
Microstructural photographs, grain size distribution is uniform in sample as seen from the figure, and average grain size is 1 μm or so.
Fig. 8 is the SEM microstructure photographs of the light-weight magnesite-alumina spinel refractories prepared by the present embodiment, micro- as seen from the figure
Structure keeps uniform, and average grain size is about 1.9 μm.By compared with the microstructure (Fig. 7) before HIP sintering, table
Crystallite dimension variation is little in bright hot isostatic pressing.
Embodiment 3
A kind of light-weight magnesite-alumina spinel refractories MgO1.8Al2O3, preparation method is as follows：
It is respectively that 18.01% and 81.99% weigh magnesia (average grain diameter 200nm) and Alpha-alumina according to mass fraction
(average grain diameter 400nm) amounts to 150g, according to ball material mass ratio 4:1 is added alumina balls and absolute ethyl alcohol mixing and ball milling for 24 hours, so
Rotary evaporation removes solvent afterwards, sieves with 100 mesh sieve, then is sintered 15min in 1680 DEG C of solid phase reactions, finally crosses 200 mesh and sieves to obtain
MgO·1.8Al2O3The average particle diameter size of spinel powder, powder is 600nm；
By the MgO1.8Al of above-mentioned preparation2O3Spinel powder is put into graphite jig, and mold is then put into electric discharge etc.
Precharge 7.5MPa is carried out in the insulation quilt of ion agglomerating plant, uses the heating rate heating mould of 10 DEG C/min to arrive at room temperature
1300 DEG C, 40MPa, subsequent heat-insulation pressure keeping are forced into the compression rate of 30MPa/min when temperature reaches maximum temperature
30min obtains the pre-sintered body that relative density is 89% after natural cooling；
The pre-sintered body of above-mentioned preparation is placed in Muffle furnace, 2h is sintered in 1650 DEG C with the heating rate of 10 DEG C/min,
Then natural cooling obtains the closed sintered body of open pore of consistency 98%；
The above-mentioned closed sintered body of gained open pore is placed in 1880 DEG C, carries out heat etc. in the Ar compression rings border of pressure 180MPa
Static pressure sintering processes 5h；Finally sample is cut, polished and polished with precision gas cutting machine, surface grinding machine, diamond polishing liquid, is obtained
To light-weight magnesite-alumina spinel refractories, photo is as shown in Figure 10.
The ceramic body 2mm thickness that the present embodiment obtains straight line transmittance at 550nm is 70%, infrared region highest straight line
Transmitance is 85%；Vickers hardness hv 1=12.40 ± 0.25GPa.
Fig. 9 show the full spectrum transmitance figure of light-weight magnesite-alumina spinel refractories manufactured in the present embodiment, and 2mm is thick as seen from the figure
Straight line transmittance of the sample of degree at 550nm is 70%, and infrared region highest straight line transmittance is 85%, shows that sample has
Good optical property.
Figure 11 is that the SEM of sample (the closed sintered body of open pore of consistency 98%) after pressureless sintering in the present embodiment is aobvious
Microstructural photographs, grain size distribution is uniform in sample as seen from the figure, and average grain size is 2 μm or so.
Figure 12 is the SEM microstructure photographs of light-weight magnesite-alumina spinel refractories manufactured in the present embodiment, micro- as seen from the figure
Structure keeps uniform, and average grain size is about 200 μm.Pass through (Figure 11), heat etc. compared with the crystallite dimension after pressureless sintering
Significant growth has occurred in crystal grain in static pressure sintering, this may be caused by HIP sintering temperature is higher.
Embodiment 4
A kind of light-weight magnesite-alumina spinel refractories MgO2Al2O3, preparation method is as follows：
It is respectively 16.50% and 83.50% to weigh magnesia (1 μm of average grain diameter) and Alpha-alumina according to mass fraction
(1 μm of average grain diameter) amounts to 150g, according to ball material mass ratio 4:1 is added alumina balls and absolute ethyl alcohol mixing and ball milling for 24 hours, then
Rotary evaporation removes solvent, sieves with 100 mesh sieve, then is sintered 15min in 1750 DEG C of solid phase reactions, finally crosses 200 mesh and sieves to obtain MgO
2Al2O3The average particle diameter size of spinel powder, powder is 1 μm；
By the MgO2Al of above-mentioned preparation2O3Spinel powder is put into graphite jig, then by mold be put into electric discharge etc. from
Precharge 7.5MPa is carried out in the insulation quilt of sub- agglomerating plant, uses the heating rate heating mould of 200 DEG C/min to arrive at room temperature
1500 DEG C, 30MPa, subsequent heat-insulation pressure keeping are forced into the compression rate of 30MPa/min when temperature reaches maximum temperature
10min obtains the pre-sintered body that relative density is 87% after natural cooling；
The pre-sintered body of above-mentioned preparation is placed in Muffle furnace, 2h is sintered in 1650 DEG C with the heating rate of 10 DEG C/min,
Then natural cooling obtains the closed sintered body of open pore of consistency 98%；
The above-mentioned closed sintered body of gained open pore is placed in 1880 DEG C, carries out heat etc. in the Ar compression rings border of pressure 180MPa
Static pressure sintering processes 5h；Finally sample is cut, polished and polished with precision gas cutting machine, surface grinding machine, diamond polishing liquid, is obtained
To light-weight magnesite-alumina spinel refractories.
The ceramic body 2mm thickness that the present embodiment obtains straight line transmittance at 550nm is 50%, infrared region highest straight line
Transmitance is 75%；Vickers hardness hv 1=12.70 ± 0.31GPa.Crystallite dimension is about 200 μm.
Embodiment 5
A kind of light-weight magnesite-alumina spinel refractories MgOAl2O3, preparation method is as follows：
It is respectively that 28.33% and 71.67% weigh magnesia (average grain diameter 240nm) and alpha-oxidation according to mass percent
Aluminium (average grain diameter 300nm) amounts to 150g, according to ball material mass ratio 4:1 is added alumina balls and absolute ethyl alcohol mixing and ball milling for 24 hours,
Then rotary evaporation removes solvent, sieves with 100 mesh sieve, then is sintered 10min in 1350 DEG C of solid phase reactions, finally crosses 200 mesh and sieves to obtain
MgO·Al2O3The average particle diameter size of spinel powder, powder is 300nm；
By the MgOAl of above-mentioned preparation2O3Spinel powder is put into graphite jig, then by mold be put into electric discharge etc. from
Precharge 7.5MPa is carried out in the insulation quilt of sub- agglomerating plant, uses the heating rate heating mould of 10 DEG C/min to arrive at room temperature
1425 DEG C, 20MPa, subsequent heat-insulation pressure keeping are forced into the compression rate of 30MPa/min when temperature reaches maximum temperature
10min obtains the pre-sintered body that relative density is 82% after natural cooling；
The pre-sintered body of above-mentioned preparation is placed in Muffle furnace, 25h is sintered in 1500 DEG C with the heating rate of 10 DEG C/min,
Then natural cooling obtains the closed sintered body of open pore of consistency 98%；
The above-mentioned closed sintered body of gained open pore is placed in 1590 DEG C, carries out heat etc. in the Ar compression rings border of pressure 180MPa
Static pressure sintering processes 5h；Finally sample is cut, polished and polished with precision gas cutting machine, surface grinding machine, diamond polishing liquid, is obtained
To light-weight magnesite-alumina spinel refractories.
The ceramic body 2mm thickness that the present embodiment obtains straight line transmittance at 550nm is 65%, infrared region highest straight line
Transmitance is 80%；Vickers hardness hv 1=13.49 ± 0.14GPa.Average grain size is about 15 μm.
Embodiment 6
A kind of light-weight magnesite-alumina spinel refractories MgO1.44Al2O3, preparation method is as follows：
It is respectively that 21.54% and 78.46% weigh magnesia (average grain diameter 500nm) and Alpha-alumina according to mass fraction
(average grain diameter 4500nm) amounts to 150g, according to ball material mass ratio 4:1 is added alumina balls and absolute ethyl alcohol mixing and ball milling for 24 hours,
Then rotary evaporation removes solvent, sieves with 100 mesh sieve, then is sintered 10min in 1650 DEG C of solid phase reactions, finally crosses 200 mesh and sieves to obtain
MgO·1.44Al2O3The average particle diameter size of spinel powder, powder is 500nm；
By the MgO1.44Al of above-mentioned preparation2O3Spinel powder is put into graphite jig, and mold is then put into electric discharge
Precharge 7.5MPa is carried out in the insulation quilt of plasma sintering equipment, uses the heating rate heated mould of 100 DEG C/min at room temperature
Have to 1400 DEG C, 30MPa, subsequent heat-insulation pressure keeping are forced into the compression rate of 30MPa/min when temperature reaches maximum temperature
1min obtains the pre-sintered body that relative density is 85% after natural cooling；
The pre-sintered body of above-mentioned preparation is placed in Muffle furnace, 25h is sintered in 1550 DEG C with the heating rate of 10 DEG C/min,
Then natural cooling obtains the closed sintered body of open pore of consistency 98%；
The above-mentioned closed sintered body of gained open pore is placed in 1590 DEG C, carries out heat etc. in the Ar compression rings border of pressure 180MPa
Static pressure sintering processes 5h；Finally sample is cut, polished and polished with precision gas cutting machine, surface grinding machine, diamond polishing liquid, is obtained
To light-weight magnesite-alumina spinel refractories.
The ceramic body 2mm thickness that the present embodiment obtains straight line transmittance at 550nm is 70%, infrared region highest straight line
Transmitance is 82%；Vickers hardness hv 1=13.49 ± 0.28GPa.Average grain size is about 50 μm.
Embodiment 7
A kind of light-weight magnesite-alumina spinel refractories MgO1.44Al2O3, preparation method is as follows：
It is respectively that 21.54% and 78.46% weigh magnesia (average grain diameter 100nm) and Alpha-alumina according to mass fraction
(average grain diameter 180nm) amounts to 150g, according to ball material mass ratio 4:1 is added alumina balls and absolute ethyl alcohol mixing and ball milling for 24 hours, so
Rotary evaporation removes solvent afterwards, sieves with 100 mesh sieve, then is sintered 10min in 1650 DEG C of solid phase reactions, finally crosses 200 mesh and sieves to obtain
MgO·1.44Al2O3The average particle diameter size of spinel powder, powder is 225nm；
By the MgO1.44Al of above-mentioned preparation2O3Spinel powder is put into graphite jig, and mold is then put into electric discharge
Precharge 7.5MPa is carried out in the insulation quilt of plasma sintering equipment, uses the heating rate heated mould of 100 DEG C/min at room temperature
Have to 1425 DEG C, 30MPa, subsequent heat-insulation pressure keeping are forced into the compression rate of 30MPa/min when temperature reaches maximum temperature
1min obtains the pre-sintered body that relative density is 88% after natural cooling；
The pre-sintered body of above-mentioned preparation is placed in Muffle furnace, 25h is sintered in 1550 DEG C with the heating rate of 10 DEG C/min,
Then natural cooling obtains the closed sintered body of open pore of consistency 98%；
The above-mentioned closed sintered body of gained open pore is placed in 1590 DEG C, carries out heat etc. in the Ar compression rings border of pressure 180MPa
Static pressure sintering processes 15h；Finally sample is cut, polished and polished with precision gas cutting machine, surface grinding machine, diamond polishing liquid,
Obtain light-weight magnesite-alumina spinel refractories.
The ceramic body 2mm thickness that the present embodiment obtains straight line transmittance at 550nm is 62%, infrared region highest straight line
Transmitance is 80%；Vickers hardness hv 1=13.44 ± 0.19GPa.Average grain size is about 50 μm.
Comparative example 1
Prepare a kind of magnesium aluminate spinel MgOAl2O3Ceramics, method are as follows：
It is respectively that 28.33% and 71.67% weigh magnesia (average grain diameter 100nm) and Alpha-alumina according to mass fraction
(average grain diameter 180nm) amounts to 150g, synthesizes MgOAl using method same as Example 12O3Spinel powder, powder
Average particle diameter size be 180nm；
By the MgOAl of above-mentioned preparation2O3Spinel powder is put into steel die, applies axial compressive force 20MPa pressurizes
1min carries out preforming；To the sample after preforming under the conditions of 180MPa pressurize 5min, carry out cold isostatic compaction (instrument type
Number：China Aviation Industry Chuanxi Machinery Factory, LDJ320/700-400) obtain the biscuit of ceramics that consistency is 50%；By ceramic element
Base is placed in Muffle furnace, is sintered 4h in 1575 DEG C with the heating rate of 10 DEG C/min, is obtained the magnesium aluminate spinel of consistency 98%
Ceramics sample；Sample after two-step sintering is put into 1500 DEG C, carries out at HIP sintering in the Ar compression rings border of pressure 180MPa
Manage 5h；Finally sample is cut, polished and polished with precision gas cutting machine, surface grinding machine, diamond polishing liquid, it is brilliant to obtain magnalium point
Feldspar, photo are as shown in figure 14.
Ceramic body 2mm thickness prepared by this comparative example straight line transmittance at 550nm is 36.9%, and infrared region highest is straight
Line transmitance is 70%；Vickers hardness hv 1=13.10 ± 0.33GPa.
It is the full spectrum transmitance figure of the magnesium-aluminum spinel ceramic prepared by this comparative example, as seen from the figure 2mm as shown in figure 13
Straight line transmittance of the sample of thickness at 550nm is 36.9%, and infrared region highest straight line transmittance is 70%, shows sample
Optical property it is poor；
Figure 15 is the SEM microstructure photographs of transparent magnesium aluminium spinel ceramics manufactured in the present embodiment, micro- as seen from the figure
Structure is poor, and average grain size is 13 μm, and grain size distribution is wider, and smaller crystallite dimension is 3 μm, larger crystal grain ruler
It is very little to reach 17 μm.
Compared with Example 1, the magnesium-aluminum spinel ceramic crystallite dimension that prepared by this comparative example is larger, and crystallite dimension point
Cloth is wider, causes transmitance relatively low, and mechanical property also decreases, and limits its application in window material.
Comparative example 2
Prepare MgO1.44Al2O3Ceramics, method are as follows：
It is respectively that 21.54% and 78.46% weigh magnesia (average grain diameter 100nm) and Alpha-alumina according to mass fraction
(average grain diameter 180nm) amounts to 150g, synthesizes MgO1.44Al using method same as Example 22O3Spinel powder,
The average particle diameter size of powder is 225nm；
By the MgO1.44Al of above-mentioned preparation2O3Spinel powder is put into steel die, is applied axial compressive force 20MPa and is protected
1min is pressed to carry out preforming；To the sample after preforming under the conditions of 180MPa pressurize 5min, carry out cold isostatic compaction (instrument
Model：China Aviation Industry Chuanxi Machinery Factory, LDJ320/700-400) obtain the biscuit of ceramics that consistency is 50%；It will be ceramic
Biscuit is placed in Muffle furnace, and 15h, the cause of obtained magnesium-aluminum spinel ceramic are sintered in 1575 DEG C with the heating rate of 10 DEG C/min
Density is only 82%, and gained sample does not reach the requirement of HIP sintering.
Figure 16 is the SEM microstructure photographs of gained magnesium-aluminum spinel ceramic after the pressureless sintering of this comparative example, as seen from the figure
Occurs Local Priority densification in microstructure, and intercrystalline has the open pore of connection, this consistency 82% corresponding thereto
Mutually confirm.
Compared with Example 2, the green body that same powder obtains in this comparative example is in 1575 DEG C of pressureless sintering 15h, consistency
Only up to 82%, air hole structure keeps open pore state；Same powder first passes through discharge plasma sintering in embodiment 2, then
The hole sintered body of holding one's breath of consistency 98% is obtained by mutually synthermal pressureless sintering 6h, and is successfully applied to hot isostatic pressing burning
Knot prepares the crystalline ceramics that crystallite dimension is 1.9 μm.
Each raw material and the bound of each raw material of the present invention cited by the present invention, the bound of technological parameter, section take
Value can realize the present invention, embodiment numerous to list herein；It is every according to the technical essence of the invention to above example institute
Any simple modification, equivalent variations or the modification made, within the scope of still falling within technical scheme of the present invention.
Claims (8)
1. a kind of light-weight magnesite-alumina spinel refractories MgOnAl2O3Preparation method, wherein 1≤n≤2, which is characterized in that specific
Include the following steps：
1) preparation of magnesia-alumina spinel powder：By magnesium oxide powder and alpha-alumina powder in molar ratio 1：N is matched, according to ball material
Mass ratio 4:1 is added alumina balls and absolute ethyl alcohol mixing and ball milling for 24 hours, and then rotary evaporation removes solvent, sieves with 100 mesh sieve, then
Through high temperature solid state reaction, finally crosses 200 mesh and sieve to obtain high-purity, single-phase magnesia-alumina spinel powder；
2) molding and pre-sintering：Magnesia-alumina spinel powder obtained by step 1) is put into graphite jig, then is placed in plasma discharging
It is molded and is pre-sintered in agglomerating plant, obtain the pre-sintered body of relative density 82-90%；
3) pressureless sintering：Pre-sintered body obtained by step 2) is placed in Muffle furnace and is sintered again, then natural cooling, obtains
The closed sintered body of open pore；
4) HIP sintering：The closed sintered body of open pore obtained by step 3) is handled through HIP sintering, institute after sintering
Sample obtains light-weight magnesite-alumina spinel refractories after polished processing again.
2. preparation method according to claim 1, which is characterized in that step 1) the magnesium oxide powder grain size is 100nm
~1 μm, the alpha-alumina powder grain size is 180nm~1 μm.
3. preparation method according to claim 1, which is characterized in that step 1) the high temperature solid state reaction condition is：
10~15min is kept the temperature at 1350~1750 DEG C.
4. preparation method according to claim 1, which is characterized in that step 1) the magnesia-alumina spinel powder grain size is
180~1000nm.
5. preparation method according to claim 1, which is characterized in that step 2) be placed in discharging plasma sintering equipment into
Row molding and the process conditions of pre-sintering are：Start to keep precompression 7.5MPa, at room temperature with the rate liter of 10~200 DEG C/min
Temperature to continuation at 1300-1500 DEG C is forced into 20~40MPa, subsequent heat-insulation pressure keeping 1- with the compression rate of 30MPa/min
30min。
6. preparation method according to claim 1, which is characterized in that sintering process conditions are step 3) again：With 10 DEG C/
The heating rate of min is warming up to 1500-1650 DEG C, keeps the temperature 1-25h.
7. preparation method according to claim 1, which is characterized in that the closed sintered body of the step 3) open pore is opposite
Consistency is 96-99%.
8. preparation method according to claim 1, which is characterized in that step 4) the HIP sintering process conditions
For：Under inert atmosphere, it is sintered at pressure 180-200MPa, 1500-1880 DEG C of temperature, sintering time 5-15h.
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| CN111499371A (en) * | 2020-04-08 | 2020-08-07 | 哈尔滨工业大学 | Preparation method of magnesia-alumina spinel transparent ceramic |
| CN111807828A (en) * | 2020-07-07 | 2020-10-23 | 上海衡益特陶新材料有限公司 | Preparation method of low-cost magnesia-alumina spinel transparent ceramic product |
| CN111848184A (en) * | 2020-07-30 | 2020-10-30 | 武汉理工大学 | High-aluminum-content magnesia-alumina spinel transparent ceramic powder and preparation method thereof |
| CN112174645A (en) * | 2020-09-27 | 2021-01-05 | 中国科学院上海光学精密机械研究所 | Method for preparing compact nano-crystalline ceramic |
| CN113200746A (en) * | 2021-04-30 | 2021-08-03 | 中国科学院上海光学精密机械研究所 | Method for preparing infrared transparent ceramic through pressureless rapid sintering |
| WO2022015688A1 (en) * | 2020-07-13 | 2022-01-20 | Heraeus Conamic North America Llc | Ceramic sintered body comprising magnesium aluminate spinel |
| CN114477990A (en) * | 2022-01-26 | 2022-05-13 | 中国科学院上海硅酸盐研究所 | Method for preparing high-density magnesia-alumina spinel ceramic through low-temperature pressureless sintering |
| CN114538913A (en) * | 2022-02-17 | 2022-05-27 | 大连海事大学 | Pure-phase nano MgAl with high sintering activity2O4Powder and preparation method and application thereof |
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| CN111499371A (en) * | 2020-04-08 | 2020-08-07 | 哈尔滨工业大学 | Preparation method of magnesia-alumina spinel transparent ceramic |
| CN111807828A (en) * | 2020-07-07 | 2020-10-23 | 上海衡益特陶新材料有限公司 | Preparation method of low-cost magnesia-alumina spinel transparent ceramic product |
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| CN116018329B (en) * | 2020-07-13 | 2024-01-02 | 贺利氏科纳米北美有限责任公司 | Ceramic sintered body comprising magnesium aluminate spinel |
| CN111848184A (en) * | 2020-07-30 | 2020-10-30 | 武汉理工大学 | High-aluminum-content magnesia-alumina spinel transparent ceramic powder and preparation method thereof |
| CN112174645A (en) * | 2020-09-27 | 2021-01-05 | 中国科学院上海光学精密机械研究所 | Method for preparing compact nano-crystalline ceramic |
| CN112174645B (en) * | 2020-09-27 | 2022-05-31 | 中国科学院上海光学精密机械研究所 | Method for preparing compact nano-crystalline ceramic |
| CN113200746A (en) * | 2021-04-30 | 2021-08-03 | 中国科学院上海光学精密机械研究所 | Method for preparing infrared transparent ceramic through pressureless rapid sintering |
| CN114477990A (en) * | 2022-01-26 | 2022-05-13 | 中国科学院上海硅酸盐研究所 | Method for preparing high-density magnesia-alumina spinel ceramic through low-temperature pressureless sintering |
| CN114477990B (en) * | 2022-01-26 | 2023-03-07 | 中国科学院上海硅酸盐研究所 | Method for preparing high-density magnesia-alumina spinel ceramic through low-temperature pressureless sintering |
| CN114538913A (en) * | 2022-02-17 | 2022-05-27 | 大连海事大学 | Pure-phase nano MgAl with high sintering activity2O4Powder and preparation method and application thereof |
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Application publication date: 20181012 |