CN106187136B - Zirconium 40# mullites and preparation method thereof - Google Patents
Zirconium 40# mullites and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of zirconium 40# mullites, the specific steps are：(1) preparation of zirconium 40# mullite precursors, the preparation of (two) zirconium 40# mullites：The zirconium 40# mullite precursors that step (1) obtains are prepared as raw material, zirconium 40# mullite precursors are placed on pre-oxidation 1h~1.5h in 150~180 DEG C of Muffle furnaces, pre-oxidation zirconium 40# mullite precursors are prepared, then pre-oxidation zirconium 40# mullite precursors are carried out first time calcining again, it is then transferred into argon gas atmosphere and carries out second of calcining, zirconium 40# mullites are prepared.The present invention by multistep calcine technology, not only can impurity content in reduction system, reduce system hole, while improving the compactness of mullite, be conducive to improve the mechanical performance of mullite；It is with important application prospects.
Description
Technical field
The present invention relates to mullite technical fields, are a kind of zirconium 40# mullites and preparation method thereof specifically.
Background technology
Mullite (or Mo Naishi) is that a series of mineral being made of aluminosilicate are referred to as, and mullite is Al2O3-SiO2System
In unique stable binary compound；Mullite has excellent high temperature thermal stability, low coefficient of thermal expansion and heat transfer, high
Creep resistance, resistant to chemical etching, suitable intensity and fracture toughness；Mixing condition is formed within the scope of component ratio, can tied
Various external cations are introduced in structure.Therefore the features such as its high temperature resistant, intensity high thermal conductivity coefficient are small, and energy-saving effect is notable is fitted
For petroleum cracking stove, metallurgical hot-blast stove, ceramic roller kiln, tunnel oven, electroceramics shuttle kiln, removing appts. of glass crucible and various electric furnaces
Liner.
Mullite crystal whisker is a kind of mullite crystal of specific form, therefore, except distinctive wear-resisting with mullite ontology
Damage functional, high temperature resistance is excellent (1750 DEG C), and resistance to high temperature oxidation coefficient of thermal expansion is smaller, in addition the mechanical property under high temperature
Can extremely excellent (such as elevated temperature strength high, thermal shock resistance is good, high-temerature creep is small), and since the internal flaw of whisker is smaller,
With especially excellent mechanical property, therefore, mullite crystal whisker is that a kind of excellent composite material is used for strengthening and toughening material, mesh
The preparation method of preceding mullite mainly has mineral decomposition method, molten-salt growth method, VLS growth methods, oxide-doped method etc..
102040373 A zirconium mullites of Chinese patent CN and its processing technology.With γ-Al2O3, zircon sand be raw material, lead to
Control raw material composition and auxiliary agent are crossed to prepare zirconium mullite.The more traditional mullite of zirconium mullite produced has more excellent
The performances such as wearability, shaking property of heat resistanceheat resistant, chemerosiveness resistent.
104261810 A one kind composite diphase materials containing zirconium mullite of Chinese patent CN and preparation method thereof,：First with Discarding Type
Sand and alumina mix for raw material, using polyvinyl alcohol as dispersing binder, are made through 5~10h of ball milling, then by the slurry spraying after ball milling
Grain, mechanical pressing, green body after molding keeps the temperature 3~5 hours under the conditions of 1600~1700 DEG C, natural cooling to get containing zirconium not
Carry out stone composite diphase material.Invention has the characteristics that production cost is low, environmental pollution is small and is easy to industrialized production, and prepared contains zirconium
Mullite complex phase material has lower coefficient of thermal expansion and good thermal shock resistance, use scope wide.
A kind of chromium zirconium mullite refractory materials of 103496992 A of Chinese patent CN and preparation method thereof.By with electric smelting not
It is that aggregate is sintered forming using zircon powder, schmigel, chrome oxide green as article substrate part to come stone or fused mullite,
Prepared chromium zirconium mullite refractory product is mainly used in glass melter, glass melting furnaces and steel, chemical industry kiln, heat resistanceheat resistant punching
Hit function admirable, high temperature it is anti-burst apart, the high temperature handling characteristics such as high temperature anti-slag ability is strong, does not peel off.
Invention content
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of zirconium 40# mullites and preparation method thereof.
The purpose of the present invention is achieved through the following technical solutions：
A kind of zirconium 40# mullites, density are 2.85~3.05g/cm3, mass fraction of the zr element in zirconium 40# mullites
It is 0.4~4.0%, the molar ratio of aluminium and element silicon is 1: 0.6~1: 0.7.
A kind of preparation method of zirconium 40# mullites, the specific steps are：
(1) preparation of zirconium 40# mullite precursors
According to proportioning, metasilicic acid is added in the polymeric aluminum chlorides solution for being 30% to mass fraction, after dissolving, then 35~
Zirconium nitrate is added under the conditions of 45 DEG C, retention time 15min obtains mixed complex system, then molten to mixed complex system
Sodium hydroxide solution is added in liquid, system pH is made to maintain 8~9, reacts 30~45min, after system not after occurring precipitating, obtains
To complex compound sediment, supernatant is filtered out, is then freezed for 24 hours at -10~-5 DEG C again, then using the method for freeze-drying, it is dry
Required zirconium 40# mullite precursors are prepared in sample；
The molar ratio of the aluminium polychloride and metasilicic acid is 1: 0.4~1: 0.5；
The mass values of zirconium nitrate and aluminium polychloride are 1: 50~1: 300；
A concentration of 0.1~0.5mol/L of the sodium hydroxide solution；
The volume ratio of sodium hydroxide and polymeric aluminum chlorides solution is 1: 10~50；
Aluminium polychloride is the polymer forms of aluminium chloride, and as silicon source, aqueous solution is acidity, is usually used in sewage disposal
Flocculant；And the present invention enables zirconium ion and aluminium ion by the suction-operated to metal ion zirconium of aluminium polychloride
Accurate combination is carried out, complex coordination compound is formed；
Metasilicic acid has abundant silicon source structure, after zirconium ion is complexed in aluminium polychloride, with the sodium knot in sodium hydroxide
It closes, produces sodium metasilicate, and sodium metasilicate produces silicon dioxide structure under the conditions of 150 DEG C, while in aluminium polychloride and zirconium
After ion complexation, produce aluminum hydroxide precipitation under alkaline condition, to drive zirconium ion and aluminium hydroxide precipitation and partially
The precipitation of sodium metasilicate is co-precipitated production simultaneously, is conducive to the stability of later stage composition of raw materials intermediate ion ingredient in calcination process, from
And improve the calcination product quality of material；And the complex ion for being co-precipitated generation avoids phase existing for direct physical blending
Being difficult to for state itself is compatible, interface is excessive and the problem of being difficult to calcine forming；
Using the method for collosol and gel, with nano level blending dispersion technology, realizes and come into full contact with and be blended in raw material point
It dissipates, avoids the process of lapping that conventional grinding and mixing method needs high speed permanent, while also solving the inorganic of multi phase state structure
Sintering process activation energy is excessive between powder, and the self aggregation state of waste of energy and inorganic particle itself causes material to be given birth to
Local defect is easy tod produce during production, influences the yield rate of product；
Freeze Drying Technique prepares nano-powder material in sol-gel has boundless application, can be most
The combining form and geometry for keeping element in material of limits, therefore after drying, powder body material porosity keeps complete,
Conducive to the calcination process in later stage；
(2) preparation of zirconium 40# mullites
The zirconium 40# mullite precursors that step (1) obtains are prepared as raw material, zirconium 40# mullite precursors are placed
1h~1.5h is pre-oxidized in 150~180 DEG C of Muffle furnaces, pre-oxidation zirconium 40# mullite precursors is prepared, then again pre-
Zirconium oxide 40# mullite precursors carry out first time calcining, are then transferred into argon gas atmosphere and carry out second of calcining, are prepared into
To zirconium 40# mullites；
First time calcine technology is：0.5~1.0h is calcined under the conditions of 550~650 DEG C in oxygen atmosphere；
The temperature of second of calcining is 1500~1650 DEG C, and the time is 1~1.5h；
The sodium metasilicate made in zirconium 40# mullite precursors is produced using first step pre-oxidation by earth silicon material, together
When so that the pore structure of material is improved, while being calcined in second step high-temperature oxygen, extra sodium ion burnt, goes to clean
Matter, then the further high-temperature burning process in argon inert gas again, not only makes the structure of mullite more perfect, simultaneously also
System hole can be reduced, the compactness of mullite is improved, improves the mechanical performance of mullite.
The usefulness of the present invention and the prior art：
A kind of zirconium 40# mullites of the present invention and preparation method thereof, the method that collosol and gel is total to using ionic adsorption, by poly-
Suction-operated of the aluminium chloride to zirconium ion is closed, zirconium ion is made to be complexed with aluminium element, reduces the activation energy of zirconium ion doping, is conducive to not
Carry out the generation of stone crystal；Metasilicic acid has abundant silicon source structure simultaneously, after zirconium ion is complexed in aluminium polychloride, with hydroxide
Sodium in sodium combines, and produces sodium metasilicate, silicon dioxide structure is produced under the conditions of 150 DEG C using sodium metasilicate, while poly-
Aluminium chloride is closed with after zirconium ion complexing, aluminum hydroxide precipitation is produced under alkaline condition, to drive zirconium ion and aluminium hydroxide
Precipitation and the precipitation of sodium metasilicate be co-precipitated production simultaneously, conducive to later stage composition of raw materials intermediate ion ingredient in calcination process
Stability improve raw material proportioning uniformity to improve the calcination product quality of material；And be co-precipitated the complexing of generation from
Son avoid phase itself existing for direct physical blending be difficult to it is compatible, interface is excessive and the problem of being difficult to calcine forming；
By multistep calcine technology, not only can impurity content in reduction system, reduce system hole, while improving the densification of mullite
Property, it is conducive to improve the mechanical performance of mullite；A kind of zirconium 40# mullites of the present invention and preparation method thereof have in ceramic roasting field
There is important application prospect.
Description of the drawings
Fig. 1 is a kind of preparation technology flow chart of zirconium 40# mullites of the present invention and preparation method thereof；
Specific implementation mode
A kind of specific implementation mode of zirconium 40# mullites of the present invention presented below and preparation method thereof.
Embodiment 1
A kind of preparation method of zirconium 40# mullites, the specific steps are：
(1) preparation of zirconium 40# mullite precursors
According to proportioning, metasilicic acid is added in the polymeric aluminum chlorides solution for being 30% to mass fraction, after dissolving, then 35~
Zirconium nitrate is added under the conditions of 45 DEG C, retention time 15min obtains mixed complex system, then molten to mixed complex system
Sodium hydroxide solution is added in liquid, system pH is made to maintain 8~9, reacts 30~45min, after system not after occurring precipitating, obtains
To complex compound sediment, supernatant is filtered out, is then freezed for 24 hours at -10~-5 DEG C again, then using the method for freeze-drying, it is dry
Required zirconium 40# mullite precursors are prepared in sample；
The molar ratio of the aluminium polychloride and metasilicic acid is 1: 0.4；
The mass values of zirconium nitrate and aluminium polychloride are 1: 50；
A concentration of 0.1mol/L of the sodium hydroxide solution；
The volume ratio of sodium hydroxide and polymeric aluminum chlorides solution is 1: 10；
Aluminium polychloride is the polymer forms of aluminium chloride, and as silicon source, aqueous solution is acidity, is usually used in sewage disposal
Flocculant；And suction-operated of the present invention by aluminium polychloride to metal ion zirconium, enable zirconium ion and aluminium ion into
The accurate combination of row, forms complex coordination compound；
Metasilicic acid has abundant silicon source structure, after zirconium ion is complexed in aluminium polychloride, with the sodium knot in sodium hydroxide
It closes, produces sodium metasilicate, and sodium metasilicate produces silicon dioxide structure under the conditions of 150 DEG C, while in aluminium polychloride and zirconium
After ion complexation, produce aluminum hydroxide precipitation under alkaline condition, to drive zirconium ion and aluminium hydroxide precipitation and partially
The precipitation of sodium metasilicate is co-precipitated production simultaneously, is conducive to the stability of later stage composition of raw materials intermediate ion ingredient in calcination process, from
And improve the calcination product quality of material；And the complex ion for being co-precipitated generation avoids phase existing for direct physical blending
Being difficult to for state itself is compatible, interface is excessive and the problem of being difficult to calcine forming；
Using the method for collosol and gel, with nano level blending dispersion technology, realizes and come into full contact with and be blended in raw material point
It dissipates, avoids the process of lapping that conventional grinding and mixing method needs high speed permanent, while also solving the inorganic of multi phase state structure
Sintering process activation energy is excessive between powder, and the self aggregation state of waste of energy and inorganic particle itself causes material to be given birth to
Local defect is easy tod produce during production, influences the yield rate of product；
Freeze Drying Technique prepares nano-powder material in sol-gel has boundless application, can be most
The combining form and geometry for keeping element in material of limits, therefore after drying, powder body material porosity keeps complete,
Conducive to the calcination process in later stage；
(2) preparation of zirconium 40# mullites
The zirconium 40# mullite precursors that step (1) obtains are prepared as raw material, zirconium 40# mullite precursors are placed
1h~1.5h is pre-oxidized in 150~180 DEG C of Muffle furnaces, pre-oxidation zirconium 40# mullite precursors is prepared, then again pre-
Zirconium oxide 40# mullite precursors carry out first time calcining, are then transferred into argon gas atmosphere and carry out second of calcining, are prepared into
To zirconium 40# mullites；
First time calcine technology is：0.5~1.0h is calcined under the conditions of 550~650 DEG C in oxygen atmosphere；
The temperature of second of calcining is 1500~1650 DEG C, and the time is 1~1.5h；
The sodium metasilicate made in zirconium 40# mullite precursors is produced using first step pre-oxidation by earth silicon material, together
When so that the pore structure of material is improved, while being calcined in second step high-temperature oxygen, extra sodium ion burnt, goes to clean
Matter, then the further high-temperature burning process in argon inert gas again, not only makes the more perfect of mullite structure, simultaneously also
System hole can be reduced, the compactness of mullite is improved, improves the mechanical performance of mullite.
Embodiment 2
A kind of preparation method of zirconium 40# mullites, the specific steps are：
(1) preparation of zirconium 40# mullite precursors
According to proportioning, metasilicic acid is added in the polymeric aluminum chlorides solution for being 30% to mass fraction, after dissolving, then 35~
Zirconium nitrate is added under the conditions of 45 DEG C, retention time 15min obtains mixed complex system, then molten to mixed complex system
Sodium hydroxide solution is added in liquid, system pH is made to maintain 8~9, reacts 30~45min, after system not after occurring precipitating, obtains
To complex compound sediment, supernatant is filtered out, is then freezed for 24 hours at -10~-5 DEG C again, then using the method for freeze-drying, it is dry
Required zirconium 40# mullite precursors are prepared in sample；
The molar ratio of the aluminium polychloride and metasilicic acid is 1: 0.44；
The mass values of zirconium nitrate and aluminium polychloride are 1: 150；
A concentration of 0.35mol/L of the sodium hydroxide solution；
The volume ratio of sodium hydroxide and polymeric aluminum chlorides solution is 1: 32；
Aluminium polychloride is the polymer forms of aluminium chloride, and as silicon source, aqueous solution is acidity, is usually used in sewage disposal
Flocculant；And suction-operated of the present invention by aluminium polychloride to metal ion zirconium, enable zirconium ion and aluminium ion into
The accurate combination of row, forms complex coordination compound；
Metasilicic acid has abundant silicon source structure, after zirconium ion is complexed in aluminium polychloride, with the sodium knot in sodium hydroxide
It closes, produces sodium metasilicate, and sodium metasilicate produces silicon dioxide structure under the conditions of 150 DEG C, while in aluminium polychloride and zirconium
After ion complexation, produce aluminum hydroxide precipitation under alkaline condition, to drive zirconium ion and aluminium hydroxide precipitation and partially
The precipitation of sodium metasilicate is co-precipitated production simultaneously, is conducive to the stability of later stage composition of raw materials intermediate ion ingredient in calcination process, from
And improve the calcination product quality of material；And the complex ion for being co-precipitated generation avoids phase existing for direct physical blending
Being difficult to for state itself is compatible, interface is excessive and the problem of being difficult to calcine forming；
Using the method for collosol and gel, with nano level blending dispersion technology, realizes and come into full contact with and be blended in raw material point
It dissipates, avoids the process of lapping that conventional grinding and mixing method needs high speed permanent, while also solving the inorganic of multi phase state structure
Sintering process activation energy is excessive between powder, and the self aggregation state of waste of energy and inorganic particle itself causes material to be given birth to
Local defect is easy tod produce during production, influences the yield rate of product；
Freeze Drying Technique prepares nano-powder material in sol-gel has boundless application, can be most
The combining form and geometry for keeping element in material of limits, therefore after drying, powder body material porosity keeps complete,
Conducive to the calcination process in later stage；
(2) preparation of zirconium 40# mullites
The zirconium 40# mullite precursors that step (1) obtains are prepared as raw material, zirconium 40# mullite precursors are placed
1h~1.5h is pre-oxidized in 150~180 DEG C of Muffle furnaces, pre-oxidation zirconium 40# mullite precursors is prepared, then again pre-
Ceria-zirconia 40# mullite precursors carry out first time calcining, are then transferred into argon gas atmosphere and carry out second of calcining, system
It is standby to obtain zirconium 40# mullites；
First time calcine technology is：0.5~1.0h is calcined under the conditions of 550~650 DEG C in oxygen atmosphere；
The temperature of second of calcining is 1500~1650 DEG C, and the time is 1~1.5h；
The sodium metasilicate made in zirconium 40# mullite precursors is produced using first step pre-oxidation by earth silicon material, together
When so that the pore structure of material is improved, while being calcined in second step high-temperature oxygen, extra sodium ion burnt, goes to clean
Matter, then the further high-temperature burning process in argon inert gas again, not only makes the more perfect of mullite structure, simultaneously also
System hole can be reduced, the compactness of mullite is improved, improves the mechanical performance of mullite.
Embodiment 3
A kind of preparation method of zirconium 40# mullites, the specific steps are：
(1) preparation of zirconium 40# mullite precursors
According to proportioning, metasilicic acid is added in the polymeric aluminum chlorides solution for being 30% to mass fraction, after dissolving, then 35~
Zirconium nitrate is added under the conditions of 45 DEG C, retention time 15min obtains mixed complex system, then molten to mixed complex system
Sodium hydroxide solution is added in liquid, system pH is made to maintain 8~9, reacts 30~45min, after system not after occurring precipitating, obtains
To complex compound sediment, supernatant is filtered out, is then freezed for 24 hours at -10~-5 DEG C again, then using the method for freeze-drying, it is dry
Required zirconium 40# mullite precursors are prepared in sample；
The molar ratio of the aluminium polychloride and metasilicic acid is 1: 0.5；
The mass values of zirconium nitrate and aluminium polychloride are 1: 300；
A concentration of 0.5mol/L of the sodium hydroxide solution；
The volume ratio of sodium hydroxide and polymeric aluminum chlorides solution is 1: 50；
Aluminium polychloride is the polymer forms of aluminium chloride, and as silicon source, aqueous solution is acidity, is usually used in sewage disposal
Flocculant；And suction-operated of the present invention by aluminium polychloride to metal ion zirconium, enable zirconium ion and aluminium ion into
The accurate combination of row, forms complex coordination compound；
Metasilicic acid has abundant silicon source structure, after zirconium ion is complexed in aluminium polychloride, with the sodium knot in sodium hydroxide
It closes, produces sodium metasilicate, and sodium metasilicate produces silicon dioxide structure under the conditions of 150 DEG C, while in aluminium polychloride and zirconium
After ion complexation, produce aluminum hydroxide precipitation under alkaline condition, to drive zirconium ion and aluminium hydroxide precipitation and partially
The precipitation of sodium metasilicate is co-precipitated production simultaneously, is conducive to the stability of later stage composition of raw materials intermediate ion ingredient in calcination process, from
And improve the calcination product quality of material；And the complex ion for being co-precipitated generation avoids phase existing for direct physical blending
Being difficult to for state itself is compatible, interface is excessive and the problem of being difficult to calcine forming；
Using the method for collosol and gel, with nano level blending dispersion technology, realizes and come into full contact with and be blended in raw material point
It dissipates, avoids the process of lapping that conventional grinding and mixing method needs high speed permanent, while also solving the inorganic of multi phase state structure
Sintering process activation energy is excessive between powder, and the self aggregation state of waste of energy and inorganic particle itself causes material to be given birth to
Local defect is easy tod produce during production, influences the yield rate of product；
Freeze Drying Technique prepares nano-powder material in sol-gel has boundless application, can be most
The combining form and geometry for keeping element in material of limits, therefore after drying, powder body material porosity keeps complete,
Conducive to the calcination process in later stage；
(2) preparation of zirconium 40# mullites
The zirconium 40# mullite precursors that step (1) obtains are prepared as raw material, zirconium 40# mullite precursors are placed
1h~1.5h is pre-oxidized in 150~180 DEG C of Muffle furnaces, pre-oxidation zirconium 40# mullite precursors is prepared, then again pre-
Ceria-zirconia 40# mullite precursors carry out first time calcining, are then transferred into argon gas atmosphere and carry out second of calcining, system
It is standby to obtain zirconium 40# mullites；
First time calcine technology is：0.5~1.0h is calcined under the conditions of 550~650 DEG C in oxygen atmosphere；
The temperature of second of calcining is 1500~1650 DEG C, and the time is 1~1.5h；
The sodium metasilicate made in zirconium 40# mullite precursors is produced using first step pre-oxidation by earth silicon material, together
When so that the pore structure of material is improved, while being calcined in second step high-temperature oxygen, extra sodium ion burnt, goes to clean
Matter, then the further high-temperature burning process in argon inert gas again, not only makes the more perfect of mullite structure, simultaneously also
System hole can be reduced, the compactness of mullite is improved, improves the mechanical performance of mullite.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, without departing from the inventive concept of the premise, can also make several improvements and modifications, these improvements and modifications also should be regarded as
In protection scope of the present invention.
Claims (6)
1. a kind of preparation method of zirconium 40# mullites, which is characterized in that its specific steps are：
（One）The preparation of zirconium 40# mullite precursors
Metasilicic acid is added in the polymeric aluminum chlorides solution for being 30% to mass fraction, after dissolving, then is added under the conditions of 35~45 DEG C
Zirconium nitrate, retention time 15min obtain mixed complex system, and hydroxide then is added into mixed complex system solution
Sodium solution makes system pH maintain 8~9, reacts 30~45min, after precipitation no longer occurs in system, obtains complex compound sediment,
Supernatant is filtered out, then for 24 hours, then using the method for freeze-drying, drying sample is prepared for freezing at -10~-5 DEG C again
Required zirconium 40# mullite precursors；
（Two）The preparation of zirconium 40# mullites
Step（One）Obtained zirconium 40# mullite precursors are raw material, and zirconium 40# mullite precursors are placed on 150~180
1h~1.5h is pre-oxidized in DEG C Muffle furnace, pre-oxidation zirconium 40# mullite precursors is prepared, then again pre-oxidation zirconium 40#
Mullite precursor carries out first time calcining, is then transferred into argon gas atmosphere and carries out second of calcining, zirconium 40# is prepared not
Carry out stone；
The zirconium 40# mullites, density are 2.85~3.05 g/cm3, zr element is in the mass fraction of zirconium 40# mullites
0.4~4.0%, the molar ratio of aluminium and element silicon is 1:0.6~1:0.7.
2. a kind of preparation method of zirconium 40# mullites as described in claim 1, which is characterized in that in zirconium 40# mullite forerunners
In the preparation of body, the molar ratio of the aluminium polychloride and metasilicic acid is 1：0.4~1：0.5.
3. a kind of preparation method of zirconium 40# mullites as described in claim 1, which is characterized in that in zirconium 40# mullite forerunners
In the preparation of body, the mass values of zirconium nitrate and aluminium polychloride are 1：50~1：300.
4. a kind of preparation method of zirconium 40# mullites as described in claim 1, which is characterized in that in zirconium 40# mullite forerunners
In the preparation of body, a concentration of 0.1~0.5mol/L of the sodium hydroxide solution.
5. a kind of preparation method of zirconium 40# mullites as described in claim 1, which is characterized in that
In the preparation of zirconium 40# mullites, first time calcine technology is：It is calcined under the conditions of 550~650 DEG C in oxygen atmosphere
0.5~1.0h.
6. a kind of preparation method of zirconium 40# mullites as described in claim 1, which is characterized in that
In the preparation of zirconium 40# mullites, the temperature of second of calcining is 1500~1650 DEG C, and the time is 1~1.5h.
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