CN104761251B - A kind of reaction sintering method preparing magnesium aluminate spinel - Google Patents
A kind of reaction sintering method preparing magnesium aluminate spinel Download PDFInfo
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- CN104761251B CN104761251B CN201510145760.6A CN201510145760A CN104761251B CN 104761251 B CN104761251 B CN 104761251B CN 201510145760 A CN201510145760 A CN 201510145760A CN 104761251 B CN104761251 B CN 104761251B
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- aluminate spinel
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Abstract
The invention discloses a kind of reaction sintering method preparing magnesium aluminate spinel, feature is by dry green compact in resistance furnace, is warmed up at a temperature of 1250～1550 DEG C be incubated 0.5～16h with the heating rate of 4～16 DEG C/min；Heating rate with 4～16 DEG C/min is warmed up to insulation at a temperature of 1550～1750 DEG C and is less than 1.5h again；Cool to be incubated at a temperature of 1300～1600 DEG C 0.5～16h with the rate of temperature fall of 10～70 DEG C/min, then naturally cool to room temperature, can be prepared by the magnesium aluminate spinel that microstructure is uniform, consistency is high.Use the present invention, advantageously reduce sintering temperature and shortening temperature retention time at high temperature, reduce energy consumption；Improve the microstructure of magnesia-alumina spinel ceramic material, improve the mechanical performance of magnesia-alumina spinel ceramic material；Improve the anti-melt infiltration of magnesium aluminate spinel and the performance of corrosion.
Description
Technical field
The invention belongs to powder metallurgical technology, be specifically related to a kind of reaction sintering method preparing magnesium aluminate spinel.
Background technology
MgAl2O4Spinelle (MAS) is face-centered cubic crystal structure, thus MAS has some important properties, for example, and high-melting-point (2135 DEG C),
High mechanical properties, good resistance to chemical corrosion, good thermal shock resistance, good electrical insulating property, higher relative density (3.58g cm-3)。
MAS is widely used in the fields such as metallurgy, electrochemistry, chemistry.But, the aluminum-spinel of pure natural is very rare, industrial magnalium point
Spar is all the method synthesis by Prof. Du Yucang.It is divided into according to the difference of production technology: sintering spinelle and electric smelting spinelle.Due to electric smelting
Method is mainly intermittently operated, and the cooling of pour causes microstructural uneven, it is difficult to meet industrial requirements, so major part is to use sintering process
Prepare magnesium aluminate spinel.
Due to MgO and Al2O3Reacting can be with the volumetric expansion of 8% during generating MAS, so one-step calcination is difficult to obtain densification
MAS sintered body.In order to avoid generally using two steps annealing method to prepare the MAS of high-compactness before this problem, i.e. first more than 1500 DEG C
At a temperature of synthesis MAS powder, then grind, compressing after, at a temperature of higher than 1900 DEG C sinter.Due to the calcining of needs two step
Process, so the electricity consuming is very high, causes production cost very high.Attempt some new sintering methods for this forefathers and shorten sintering time or fall
Sintering temperature and low, for example, microwave sintering method, vaccum sintering process, discharge plasma sintering method etc., but these sintering methods need some high-end
Equipment, so being difficult to large-scale production and application.These solid phase method weak points are to be readily incorporated impurity in preparation process on the whole, and sintered article is pure
Spending low, particle is uneven and shape is difficult to control to, and additionally calcining heat is higher, production cost is high.The mechanical performance of magnesium-aluminum spinel ceramic is main
Depend on the microstructure of magnesium aluminate spinel, can realize improving the target of mechanical performance by reducing crystallite dimension under normal conditions.Additionally
The anti-melt infiltration of magnesium-aluminum spinel ceramic and decay resistance additionally depend on its sintering densification degree, by improving the densification of magnesium-aluminum spinel ceramic
Degree, the reduction porosity, improve anti-melt infiltration and resistance to melt corrosive nature.
During preparing magnesium-aluminum spinel ceramic, especially when sintering due to the effect of temperature, inevitably there is moving of crystal boundary in sintered body
The phenomenons such as shifting, causes the nodularization of hole assemble and grow up, the Size growth of crystal grain.Thus the design of sintering temperature control system can significantly affect the burning of pottery
Knot performance and microstructural homogeneity.Sintering temperature is too low or sintering time is too short, then can not occur or react can not be complete in reaction；Temperature is too high
Or overlong time, then the product grain generating is easily thick, and too high temperature is also possible to make raw material evaporate or decomposition product.For this, the present invention carries
Go out a kind of reaction sintering method preparing magnesium aluminate spinel, i.e. first calcine synthetic MgAl spinal；Then continue to be heated to a higher temperature, make
System obtains a thermodynamic driving force that be enough to grain boundary decision；Then fast cooling continues insulation to a certain lower temperature, thus suppresses crystal boundary
Migrate, and utilize grain boundary decision effect to make sample reach fine and close, advantageously form homogeneous microstructure simultaneously, promote magnesium-aluminum spinel ceramic machinery
The raising of performance.The reaction sintering of present invention advantage more maximum compared with conventional method is to prepare fine and close magnalium point crystalline substance by one section of reaction-sintered
Stone, additionally avoids long high temperature sintering, reduces the production cost of magnesium aluminate spinel.
Content of the invention
The purpose of the present invention is intended to overcome deficiency of the prior art, provides a kind of reaction sintering method preparing magnesium aluminate spinel.Use the present invention,
The magnesium aluminate spinel that microstructure is homogeneous, consistency is high can be prepared, and production cost is low.Improve magnesium-aluminum spinel ceramic according to reaction sintering method
Microstructure and sintering character, improve the mechanical performance of magnesia-alumina spinel ceramic material, anti-melt infiltration and resistance to melt corrosive nature, can be extensive
It is applied in non-ferrous metal metallurgy industry, steel industry and petrochemical industry.
It is an object of the invention to be accomplished by.
Magnesia raw material and aluminum raw material are mixed by a kind of reaction sintering method preparing magnesium aluminate spinel, at high-energy ball milling, compressing, after being dried,
Reacted sintering prepares magnesium-aluminum spinel ceramic；Use reaction-sintered step as follows successively: with the heating rate of 4～16 DEG C/min be warmed up to 1250～
It is incubated 0.5～16h at a temperature of 1550 DEG C；Heating rate with 4～16 DEG C/min is warmed up at a temperature of 1550～1750 DEG C be incubated be less than again
1.5h；Cool to be incubated at a temperature of 1300～1600 DEG C 0.5～16h with the rate of temperature fall of 10～70 DEG C/min, then naturally cool to room temperature.
In said method, reaction-sintered preferred steps is as follows successively: be warmed up at a temperature of 1300～1500 DEG C protect with the heating rate of 5～10 DEG C/min
Temperature 1～15h；It is warmed up to insulation at a temperature of 1600～1700 DEG C with the heating rate of 5～15 DEG C/min and be less than 1h；With 20～60 DEG C/min
Rate of temperature fall cool at a temperature of 1350～1550 DEG C be incubated 1～15h, then naturally cool to room temperature.
In said method, magnesia raw material and aluminum raw material are respectively with Al2O3, MgO meter, in molar ratio be Al2O3: the ratio of MgO=1:1 weighs mixing.
In said method, magnesia raw material includes one or more the mixture in magnesium carbonate, magnesium hydroxide, magnesia.
In said method, aluminum raw material includes one or more the mixture in aluminium carbonate, aluminium hydroxide, aluminum oxide.
In said method, the impurity content of magnesia raw material is less than 5wt.%, and the impurity content of aluminum raw material is less than 5wt.%.
In said method, high-energy-milling is: Ball-milling Time 1～10h, rotating speed 10～100r/min, ratio of grinding media to material 1:1～5:1.
In said method, ball-milling additive includes one or more the mixture in ethanol, ethylene glycol and glycerine.
Compressing in said method is compressing under hydraulic press, and briquetting pressure is 50～200MPa, and the dwell time is 1～10min.
In said method compressing after material is placed in insulating box at a temperature of 120～160 DEG C, is dried 5～12h.
Compared with prior art, the present invention has the advantage that
(1) using the magnesium-aluminum spinel ceramic that the present invention obtains, magnesium aluminate spinel synthetic ratio is high, and impurity content is few, purity is high；
(2) using the magnesium-aluminum spinel ceramic that the present invention obtains, particle size is little, and microstructure is homogeneous, and consistency is high, and high-temperature holding time
Short, energy consumption is relatively low；
(3) preparation technology of the present invention is simple, easily operates, practical.
Brief description:
Fig. 1 present invention prepares the sintering step schematic diagram of magnesium aluminate spinel；
The XRD of the magnesium aluminate spinel that Fig. 2 present invention prepares；
The SEM figure of the magnesium aluminate spinel that Fig. 3 present invention prepares.
Detailed description of the invention
The invention will be further described for example given below plan, but is not to be construed as limiting the scope of the invention, the skill in this field
Art personnel the present invention is made according to the content of the invention described above some nonessential improve and adjust, still fall within protection scope of the present invention.
Embodiment 1
Impurity content is the magnesia of 4wt.% and the aluminum oxide that impurity content is 1wt.%, by MgO:Al2O3Mol ratio is 1:1 proportioning, at rotating speed
Ball milling 1h, the powder that ball milling is obtained pressurize 1min under 50MPa under conditions of being 1:1 for 10r/min and ratio of grinding media to material, compressing, green compact
It is dried at a temperature of 120 DEG C.It is placed in the green compact being dried in chamber type electric resistance furnace, be warmed up to the temperature of 1300 DEG C with the heating rate of 5 DEG C/min
Lower insulation 2h, then the heating rate with 5 DEG C/min, be warmed up at a temperature of 1600 DEG C be incubated 0.1h, the then rate of temperature fall with 30 DEG C/min,
Cool to be incubated at a temperature of 1350 DEG C 2h, then naturally cool to room temperature.The consistency of its magnesium-aluminum spinel ceramic obtaining is 93%, counter-bending
Intensity is 150MPa.
Embodiment 2
Impurity content is the magnesia raw material that the magnesium hydroxide of 3wt.% mixes with magnesia, and impurity content is that the aluminium carbonate of 2wt.% mixes with aluminum oxide
Aluminum raw material, by MgO:Al2O3Mol ratio is 1:1 proportioning, and ball milling 4h under conditions of rotating speed is 30r/min and ratio of grinding media to material is 2:1, by ball milling
The powder obtaining pressurize 5min under 100MPa, compressing, green compact are dried at a temperature of 120 DEG C.The green compact being dried are placed in box
It in resistance furnace, is warmed up at a temperature of 1400 DEG C be incubated 2h, then the heating rate with 8 DEG C/min with the heating rate of 8 DEG C/min, is warmed up to 1650 DEG C
At a temperature of insulation 0.5h, the then rate of temperature fall with 40 DEG C/min, cool to be incubated at a temperature of 1450 DEG C 5h, then naturally cool to room temperature.
The consistency of its magnesium-aluminum spinel ceramic obtaining is 96%, and flexural strength is 180MPa.
Embodiment 3
Impurity content is the magnesia raw material that the magnesium hydroxide of 2wt.% mixes with magnesium carbonate, and impurity content is that the aluminium carbonate of 3wt.% mixes with aluminium hydroxide
Aluminum raw material, by MgO:Al2O3Mol ratio is 1:1 proportioning, and ball milling 8h under conditions of rotating speed is 60r/min and ratio of grinding media to material is 3:1, by ball
The powder that mill obtains pressurize 8min under 150MPa, compressing, green compact are dried at a temperature of 120 DEG C.The green compact being dried are placed in case
It in formula resistance furnace, is warmed up at a temperature of 1450 DEG C be incubated 10h, then the heating rate with 10 DEG C/min with the heating rate of 10 DEG C/min, heats up
It is incubated 0.8h, the then rate of temperature fall with 50 DEG C/min at a temperature of 1680 DEG C, cool to be incubated at a temperature of 1500 DEG C 10h, more naturally cold
But to room temperature.The consistency of its magnesium-aluminum spinel ceramic obtaining is 98%, and flexural strength is 200MPa.
Embodiment 4
Impurity content is the magnesia raw material of the magnesium carbonate of 1wt.%, magnesium hydroxide and magnesia mixing, and impurity content is the aluminium carbonate of 4wt.%, hydrogen-oxygen
Change the aluminum raw material that aluminium mixes with aluminum oxide, by MgO:Al2O3Mol ratio is 1:1 proportioning, at the bar that rotating speed is 100r/min and ratio of grinding media to material is 5:1
Ball milling 10h under part, the powder obtaining ball milling pressurize 10min under 200MPa, compressing, green compact are dried at a temperature of 120 DEG C.Will
The green compact being dried are placed in chamber type electric resistance furnace, are warmed up at a temperature of 1500 DEG C be incubated 15h with the heating rate of 5 DEG C/min, then with 10 DEG C/min
Heating rate, be warmed up at a temperature of 1700 DEG C be incubated 1h, the then rate of temperature fall with 60 DEG C/min, cool at a temperature of 1550 DEG C be incubated
15h, then naturally cool to room temperature.The consistency of its magnesium-aluminum spinel ceramic obtaining is 99%, and flexural strength is 220MPa.
Claims (10)
1. prepare a reaction sintering method for magnesium aluminate spinel, magnesia raw material and aluminum raw material are mixed, at high-energy ball milling, compressing, dry
After dry, reacted sintering prepares magnesium-aluminum spinel ceramic；It is characterized in that, use reaction-sintered step as follows successively: with the liter of 4～16 DEG C/min
Insulation 0.5～16h at a temperature of temperature ramp to 1250～1550 DEG C；Heating rate with 4～16 DEG C/min is warmed up to 1550～1750 DEG C again
At a temperature of insulation be less than 1.5h；Cool to be incubated at a temperature of 1300～1600 DEG C 0.5～16h with the rate of temperature fall of 10～70 DEG C/min, so
After naturally cool to room temperature.
2. the reaction sintering method preparing magnesium aluminate spinel according to claim 1, it is characterised in that use reaction-sintered step successively such as
Under: it is warmed up at a temperature of 1300～1500 DEG C be incubated 1～15h with the heating rate of 5～10 DEG C/min；Heating rate with 5～15 DEG C/min
It is warmed up to insulation at a temperature of 1600～1700 DEG C and be less than 1h；Cool at a temperature of 1350～1550 DEG C with the rate of temperature fall of 20～60 DEG C/min
Insulation 1～15h, then to naturally cool to room temperature.
3. the reaction sintering method preparing magnesium aluminate spinel according to claim 1, it is characterised in that magnesia raw material and aluminum raw material are respectively
With Al2O3, MgO meter, in molar ratio be Al2O3: the ratio of MgO=1:1 weighs mixing.
4. the reaction sintering method preparing magnesium aluminate spinel according to claim 1 or 3, it is characterised in that magnesia raw material include magnesium carbonate,
One or more mixture in magnesium hydroxide, magnesia.
5. the reaction sintering method preparing magnesium aluminate spinel according to claim 1 or 3, it is characterised in that aluminum raw material include aluminium carbonate,
One or more mixture in aluminium hydroxide, aluminum oxide.
6. the reaction sintering method preparing magnesium aluminate spinel according to claim 1 or 3, it is characterised in that the impurity content of magnesia raw material
Less than 5wt.%, the impurity content of aluminum raw material is less than 5wt.%.
7. the reaction sintering method preparing magnesium aluminate spinel according to claim 1, it is characterised in that high-energy-milling is: during ball milling
Between 1～10h, rotating speed 10～100r/min, ratio of grinding media to material 1:1～5:1.
8. the reaction sintering method preparing magnesium aluminate spinel according to claim 1 or 7, it is characterised in that ball-milling additive include ethanol,
One or more mixture in ethylene glycol and glycerine.
9. the reaction sintering method preparing magnesium aluminate spinel according to claim 1, it is characterised in that compressing is to press under hydraulic press
Making type, briquetting pressure is 50～200MPa, and the dwell time is 1～10min.
10. the reaction sintering method preparing magnesium aluminate spinel according to claim 1 or 9, it is characterised in that after compressing, material is put
It is dried 5～12h at a temperature of 120～160 DEG C in insulating box.
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| CN111902383B (en) | 2018-03-28 | 2022-12-16 | 日本碍子株式会社 | Composite sintered body, semiconductor manufacturing apparatus component, and method for manufacturing composite sintered body |
| CN110655412A (en) * | 2019-11-13 | 2020-01-07 | 山东恒嘉高纯铝业科技股份有限公司 | Preparation method of high-purity sintered spinel |
| CN111499371A (en) * | 2020-04-08 | 2020-08-07 | 哈尔滨工业大学 | Preparation method of magnesia-alumina spinel transparent ceramic |
| KR20230012573A (en) * | 2020-07-13 | 2023-01-26 | 헤레우스 코나믹 노스 아메리카 엘엘씨 | Ceramic sintered body containing magnesium aluminate spinel |
| CN112266241A (en) * | 2020-11-03 | 2021-01-26 | 江苏省陶瓷研究所有限公司 | Magnesium aluminate spinel porous ceramic and preparation method thereof |
| CN112573935B (en) * | 2021-01-08 | 2022-06-21 | 郑州大学 | Preparation method of forsterite-magnalium spinel heat-insulating refractory material |
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| JPS6272556A (en) * | 1985-09-25 | 1987-04-03 | 三菱マテリアル株式会社 | Manufacture of fine polycrystal mgal2o4 spinel |
| CN101265082A (en) * | 2008-04-24 | 2008-09-17 | 烁光特晶科技有限公司 | Method for preparing transparent magnesium-aluminum spinel ceramic |
| CN101580383A (en) * | 2009-06-25 | 2009-11-18 | 福州大学 | Magnesia-alumina spinel material prepared by waste activated alumina and preparation method thereof |
| CN102936022B (en) * | 2012-10-17 | 2015-03-11 | 河南科技大学 | High purity nano-scale magnesium-aluminum spinel synthesis method |
| CN104150895B (en) * | 2014-08-01 | 2016-04-06 | 中南大学 | A kind of low temperature preparation method of aluminum-spinel |
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