CN103964475B - Cubic magnesium oxide powder and method for making thereof - Google Patents
Cubic magnesium oxide powder and method for making thereof Download PDFInfo
- Publication number
- CN103964475B CN103964475B CN201410048866.XA CN201410048866A CN103964475B CN 103964475 B CN103964475 B CN 103964475B CN 201410048866 A CN201410048866 A CN 201410048866A CN 103964475 B CN103964475 B CN 103964475B
- Authority
- CN
- China
- Prior art keywords
- magnesium oxide
- oxide powder
- cubic
- precursor
- magnesium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/02—Magnesia
- C01F5/06—Magnesia by thermal decomposition of magnesium compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/02—Magnesia
- C01F5/06—Magnesia by thermal decomposition of magnesium compounds
- C01F5/08—Magnesia by thermal decomposition of magnesium compounds by calcining magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/38—Particle morphology extending in three dimensions cube-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention provides cubic and the large magnesium oxide powder of median size and method for making thereof.The particle shape that this magnesium oxide powder scanning electron microscope is observed is cubic, and the accumulation 50% particle diameter (D obtained by laser diffraction and scattering formula particle size distribution
50) be more than 1.0 μm.This powder obtains by being burnt till in closed system under the total amount relative to this precursor is the existence of the halide ions of 0.5 ~ 30 quality % by magnesia precursor.
Description
Technical field
The present invention relates to cubic magnesium oxide powder and method for making thereof.
Background technology
Magnesium oxide (magnesia) is except being used as refractory materials; also be used as the raw material of the purposes of various additive or electronic component, phosphor raw material, various target raw material, superconducting thin film substrate raw material, tunnel magnetoresistance element (TMR element) tunnel barrier raw material, color plasma display panels (PDP) protective membrane raw material and PDP crystal magnesium oxide layer, attracted attention as the inorganic materials with purposes very widely.
Such as, as the formation of the magnesium oxide of PDP with the raw material of crystal magnesium oxide layer, require that the shape of primary particle is particle diameter large and narrow particle size distribution, the dispersed excellent crystalline powder of cubic, high purity, each crystallization.
As the method for making of magnesium oxide powder, mainly known (1) utilizes the vapor phase process of the oxidation of MAGNESIUM METAL, (2) based on the thermal decomposition method of the operation of will burn till at the temperature of the precursor such as magnesium hydroxide or magnesiumcarbonate more than heat decomposition temperature, and the method that the block obtained by electric smelting method is pulverized by (3).
Utilize vapor phase process can obtain the magnesium oxide powder of high purity, cubic, but its particle diameter is only less than 1 μm (with reference to patent documentation 1 and non-patent literature 1).In addition, also there is crystal surface and be attached with a large amount of particulates, surperficial sordid problem, and cubic particle and non-cubic shape particle mixes, the problem of single dispersing powder that not only formed by cubic particle.
Utilize the magnesium oxide powder of the better thermal decomposition method manufacture of productivity to have the angle of crystalline particle or the rib polygonal shape with circular arc, and be difficult to obtain macroparticle.Therefore, above-mentioned magnesium oxide powder can absorb carbon dioxide and moisture etc. in air, and this may impact the performance of magnesian natural characteristics.In a lot of situation, particle also can phase mutual coagulation, can only obtain the powder of bad dispersibility.
For overcoming the shortcoming in above-mentioned thermal decomposition method, describe the method for carrying out after being mixed with magnesia precursor or magnesium oxide by chloride ion burning till in patent documentation 2, and will filter, then carrying out the method for burning till after magnesium chloride brine and the mixing of alkaline sedimentation agent solution when not cleaning.Describe in the embodiment of the document and implement above-mentioned scheme of burning till in oxygen flow.Although thus obtained magnesian crystallization is cubic, its particle diameter is only about 0.2 μm, can only obtain the magnesium oxide powder (Fig. 2 (A) of the document) of particle phase mutual coagulation.
Patent documentation 1: Japanese Patent Laid-Open 1-282146 publication
Patent documentation 2: Japanese Patent Laid-Open 2006-36544 publication
Non-patent literature 1: " material ", Showa in November, 62, the 36th volume, No. 410,1157-1161 page
The announcement of invention
The present invention is the invention completed in view of above-mentioned present situation, its objective is and provides cubic and the large magnesium oxide powder of particle diameter and method for making thereof.
The present inventor has carried out various research repeatedly for solving the problem, found that, when utilizing thermal decomposition method magnesia precursor being burnt till thus manufacture magnesium oxide powder, burn till by implementing this under the existence of the halide ions of specified quantitative and in the closed system different from the firing condition of routine, can produce completely can not obtainable cubic and median size is the great magnesium oxide powder of more than 1 μm with existing method for making, thus completes the present invention.
That is, the present invention relates to cubic magnesium oxide powder, the feature of this magnesium oxide powder is, the particle shape observed with scanning electron microscope is cubic, and the accumulation 50% particle diameter (D obtained by laser diffraction and scattering formula particle size distribution
50) be more than 1.0 μm.Here, the accumulation 10% particle diameter (D obtained by laser diffraction and scattering formula particle size distribution is preferably
10) and accumulation 90% particle diameter (D
90) ratio D
90/ D
10be less than 10.0, BET specific surface area is 5.0m
2/ below g.In addition, being preferably purity is more than 99.9 quality %.Be preferably described cubic magnesium oxide powder to obtain by magnesia precursor is burnt till under the total amount relative to this precursor is the existence of the halide ions of 0.5 ~ 30 quality % in closed system.
The invention still further relates to cubic magnesium oxide particle, the feature of this magnesia particle is, the particle shape observed with scanning electron microscope is cubic, and this cubical length is greater than 4.0 μm; In addition, the magnesium oxide powder comprising this cubic magnesium oxide particle is also related to.
The invention still further relates to the manufacture method of cubic magnesium oxide powder, the method is characterized in that, magnesia precursor is burnt till under the total amount relative to this precursor is the existence of the halide ions of 0.5 ~ 30 quality % in closed system.Being preferably described magnesia precursor is magnesium basic carbonate, magnesium hydroxide or their mixture.
Utilize the present invention, can cubic be obtained and the large magnesium oxide powder of median size.It is preferred that, utilize the present invention, the magnesium oxide powder with following characteristic can be manufactured: (1) particle shape is unanimously cubic, (2) median size is greatly to more than 1 μm, (3) particle diameter is consistent, (4) not containing particulate, the clean surface of cubic crystallization and level and smooth, (5) crystal grain is separated from one another, dispersed excellent.
The best mode carried out an invention
The shape of the primary particle of magnesium oxide powder of the present invention is cubic.This shape can be determined with scanning electron microscope.In addition, cubic does not refer to the strict cubes in geometry meaning, and refers to can roughly be identified as cubical shape by visual inspection microphotograph as shown in Fig. 1 ~ 5.The primary particle of the cubic of magnesium oxide powder of the present invention can not condense, but separated from one another, therefore has the character of favorable dispersity.
The median size of magnesium oxide powder of the present invention is large, specifically, meets the accumulation 50% particle diameter (D obtained by laser diffraction and scattering formula particle size distribution
50) be the condition of more than 1.0 μm.First the cubes magnesium oxide powder with so large median size is found by the present inventor.This D
50preferably more than 1.2 μm, more preferably more than 1.5 μm.Think in the scope of method for making of the present invention, can D be obtained
50be about the powder of less than 20 μm or less than 10 μm.In addition, D
50being meso-position radius, referring in the cumulative graph of granularity the particle diameter (μm) being equivalent to 50 volume %, is the particle diameter that larger side and less side are equivalent when being divided into two by powder with certain particle diameter.
In addition, about primary particle entirety more greatly and not containing micro mist this point, the specific surface area preferably 5.0m measured by BET method of magnesium oxide powder of the present invention
2/ below g.More preferably 4.0m
2/ below g, further more preferably 2.5m
2/ below g, particularly preferably 1.0m
2/ below g.
Magnesium oxide powder of the present invention is preferably particle shape unanimously for cubic, and cubic crystal surface adheres to without particulate, this clean surface and level and smooth.Therefore, it is consistent that magnesium oxide powder of the present invention is preferably particle diameter, i.e. narrow particle size distribution, specifically, is preferably the accumulation 10% particle diameter (D meeting and obtained by laser diffraction and scattering formula particle size distribution
10) and accumulation 90% particle diameter (D
90) ratio D
90/ D
10it is the condition of less than 10.0.More preferably less than 6.0, particularly preferably less than 4.5.
Magnesium oxide powder of the present invention is high purity powdered form, and purity is more than 99.9 quality % preferably, more preferably more than 99.99 quality %.
Below, the manufacture method of magnesium oxide powder of the present invention is described.
Manufacture method of the present invention, based on thermal decomposition method, in the present invention, is implemented the operation of being burnt till in closed system under the total amount relative to this precursor is the existence of the halide ions of 0.5 ~ 30 quality % by magnesia precursor, is manufactured magnesium oxide powder by this.Thus, the magnesium oxide powder with above-mentioned each characteristic can be manufactured.
As described magnesia precursor, can be the precursor used in thermal decomposition method in the past, be not particularly limited, such as magnesium hydroxide, magnesium basic carbonate, magnesiumcarbonate, magnesium oxalate etc. can be exemplified.Wherein, due to the characteristic good of gained magnesium oxide powder, therefore preferred magnesium hydroxide, magnesium basic carbonate and their mixture.
If described precursor is containing more impurity, then the shape of gained magnesium oxide powder is not cubic, but tends to become the polygon-shaped of band circular arc, and therefore the impurity of precursor is to be advisable less.Specifically, as impurity level contained in precursor, total amount removing halide ions preferably below the 0.1 quality % of the impurity remained when generating magnesium oxide by thermal decomposition method, more preferably below 0.01 quality %.
Described burning till is carried out under the existence of halide ions.As halide ions, chloride ion, fluoride ion, bromide ion, iodide ion can be exemplified, usually use chloride ion.As the concrete example of the compound of halide ion, hydrochloric acid, ammonium chloride, sodium-chlor, Repone K, magnesium chloride etc. can be exemplified.
The amount of halide ions relative to the total amount of magnesia precursor in the scope of 0.5 ~ 30 quality %.If the amount of halide ions is very few, then cannot play effect of the present invention, on the contrary, if too much, then magnesian crystallization is difficult to grow up.The preferably scope of 1.0 ~ 25 quality %, the more preferably scope of 10 ~ 25 quality %.
The compound of halide ion can be magnesia precursor itself, it can be the material from the impurity contained by magnesia precursor, it can be the by product by generating during solution synthetic method modulation magnesia precursor, can be the material be added into separately in magnesia precursor, also can be added into the material in the gas atmosphere in enclosed stove with the form of the hydrogenchloride of such as gaseous state etc.In addition, the by product generated when also can be removed the impurity contained by magnesia precursor fully by cleaning etc. and be modulated magnesium oxide, is then added in magnesia precursor or gas atmosphere again.
In the present invention, as magnesia precursor, the magnesia precursor obtained preferably by solution synthesis.
When magnesia precursor is the mixture of magnesium basic carbonate and magnesium hydroxide, when being modulated this precursor by solution synthetic method, such as (1) is by magnesium chloride brine and aqueous sodium hydroxide solution mixing, obtain magnesium hydroxide slurry, (2) by a part of carbonating of the magnesium hydroxide in this slurry, obtain the slurry comprising magnesium basic carbonate and magnesium hydroxide, (3) filter this slurry, obtain the mixture of magnesium basic carbonate and magnesium hydroxide.In this mixture containing raw material thing magnesium chloride or side product chlorinated sodium as chloride ion.
In described operation (1), can after obtaining magnesium hydroxide slurry dilute with water, thus the concentration of this slurry to be adjusted in the scope of preferably 50 ~ 100g/L, more preferably 60 ~ 90g/L.This is because the concentration by reducing slurry, the viscosity of slurry can be reduced, the carbonation reaction in follow-up operation (2) is carried out equably.
In described operation (2), by being blown into carbon dioxide to described slurry, by a part of carbonating of the magnesium hydroxide in slurry.The temperature of this carbonation reaction preferably 40 ~ 80 DEG C.In this temperature range, carry out rapidly from magnesium hydroxide to the conversion of magnesium basic carbonate, reaction efficiency is high.Also can obtain in this temperature range and there is the magnesium basic carbonate of the excellent particle diameter of filtration efficiency and the mixture of magnesium hydroxide.
The consumption of the carbon dioxide used in described carbonation reaction is the amount that a part for the magnesium hydroxide in magnesium hydroxide slurry can be converted into magnesium basic carbonate, provide the mixture of magnesium basic carbonate and magnesium hydroxide.Magnesium hydroxide preferably 0.2 ~ 2.0 molar equivalent of concrete usage quantity relative to 1 mole of carbon dioxide.The mixture of the excellent magnesium basic carbonate of filtration efficiency and magnesium hydroxide can be obtained efficiently within the scope of this.
In described operation (3), by the slurries filtration comprising magnesium basic carbonate and magnesium hydroxide will obtained in described operation (2), thus obtain the mixture of magnesium basic carbonate and magnesium hydroxide in solid form.Containing chloride ion in this solid mixt, therefore directly can be dried when not cleaning, then burn till for described later, also this mixture can be cleaned with appropriate water, by this amount of the chloride ion in filter cake is reduced to suitable level, then carries out drying and burn till.If cleaned fully, then the content of chloride ion is too low, cannot obtain effect of the present invention, therefore needs to be controlled by the degree to cleaning such as usage quantity, scavenging period of rinse water.But, also after carrying out fully cleaning, being removed completely by chloride ion, the mixture of halide ion can be added separately.
When magnesia precursor is magnesium hydroxide, when being modulated this precursor by solution synthetic method, such as (1), by magnesium chloride brine and aqueous sodium hydroxide solution mixing, obtains magnesium hydroxide slurry, (2) filter this slurry, obtain solid-state magnesium hydroxide.In this solids containing raw material thing magnesium chloride or side product chlorinated sodium as chloride ion.
In described operation (1), be preferably dilute with water after obtaining magnesium hydroxide slurry, thus the concentration of this slurry is adjusted in the scope of preferably 50 ~ 100g/L, more preferably 60 ~ 90g/L, then by its slaking being made the magnesium hydroxide particles in this slurry grow up.The filtration efficiency in operation (2) can be improved by this.Described cooking conditions is not particularly limited, and slurry is under agitation at high temperature kept certain hour.Curing temperature is such as about 80 ~ 150 DEG C, and the curing time is about several minutes ~ a few hours.
In described operation (2), filtered by the magnesium hydroxide slurry will obtained in described operation (1), thus obtain solid-state magnesium hydroxide.Because this solids contains chloride ion, therefore it is processed as above.
Of the present invention based in the magnesian method for making of thermal decomposition method, need to carry out burning till of magnesia precursor under the existence of halide ions and in closed system.The approximate system closed that closed system in the present invention refers to that the gas in the space that is present in and carries out burning till externally does not flow out in fact, in fact also do not have gas to flow into from outside, the process for calcining of routine being different under the atmosphere such as air or oxygen opening or carrying out while the air-flow of these gases is flow through.In the present invention, by burning till in closed system, thus halide ions externally can not be splashed, but stay in the container carrying out burning till, participate in the developmental process of magnesium oxide powder crystallization fully, obtain the great cubic crystalline powder of median size by this.
In this closed system burning till such as by use there is no in fact the closed electric furnace of the inflow and outflow of atmosphere gas or raw material is added can be airtight crucible in carry out.Temperature when burning till can be 600 DEG C ~ about 1400 DEG C, preferably about 1200 DEG C.If temperature when burning till is too high, then gained crystallization may be condensed, dispersed variation.Firing time is relevant with temperature, is generally 1 ~ 10 hours.Such as, when temperature is about 1200 DEG C, firing time is advisable with 5 hours.In addition, for speed when carrying out burning till and heat up is not particularly limited, it is about 5 ~ 10 DEG C/min.
Atmosphere when this burns till is not particularly limited, and can exemplify such as air, oxygen, nitrogen, argon gas etc., owing to impurity contained in precursor can be removed as oxidizing gas, and therefore preferred atmosphere or oxygen atmosphere.
By burning till under described condition, the large cubic magnesium oxide powder of median size is grown up, but owing to burning till in confined conditions, and therefore the impurity such as compound of described halide ion cannot be removed fully, thus in being mixed into the powder after burning till.In order to reduce the mixed volume of the compound of this halide ion, improving the purity of magnesium oxide powder, in open system, carrying out second time further after preferably carrying out once-firing in described closed system in manufacture method of the present invention and burning till.
This twice firing can be burning till of carrying out in common open system, and the electric furnace etc. under the gas furnace such as, having atmosphere gas to flow under can being used in air atmosphere or oxygen flow carries out.Gas in temperature during twice firing, time and stove is not particularly limited, as long as the impurity such as the compound of halide ion can be removed, be not particularly limited, but can be completed by once-firing due to crystalline growth, therefore the time of twice firing also can be shorter.
Utilize method for making of the present invention, the magnesia particle with the cubic of great particle diameter shown in Fig. 4 can be obtained.When observing this cubic particle with scanning electron microscope, cubical length is greater than 4.0 μm.So large, there is no particulate, surface cleaning and level and smooth cubic particle also do not report up to now.Think in the scope of method for making of the present invention, the particle of cubical length below 20 μm or below 10 μm can be obtained.The magnesium oxide powder comprising this particle is also included within scope of the present invention.
Embodiment
The present invention will be described in more detail to disclose embodiment below, but the present invention is not limited to these embodiments.
In following embodiment, according to the various physical property of sequential determination etc. as follows.
(1) scanning electron microscope (SEM) observation
Use scanning electron microscope (trade(brand)name: JSM-5410, Jeol Ltd. (JEOL) make) shooting SEM composograph, observe particle shape, and measure cubic magnesium oxide length.
(2) laser diffraction and scattering formula particle size distribution method
Use laser diffraction and scattering formula particle size distribution device (trade(brand)name: HIRA, day machine dress (Machine dress) Co., Ltd.'s system) measure accumulation 10% particle diameter (D
10), accumulate 50% particle diameter (D
50) and accumulation 90% particle diameter (D
90).
(3) BET specific surface area assay method
Use specific area measuring device (trade(brand)name: Macsorb1210, mountain skill (マ ウ Application テ ッ Network) Co., Ltd.'s system) by gas adsorption method measurement the specific area.
(4) magnesian purity testing method
Magnesian purity deducts the summation of the impurity level recorded from 100 quality % and the value obtained calculates.
(5) magnesian impurity level assay method
Magnesian impurity level (Si, Al, Ca, Fe, V, Cr, Mn, Ni, Zn, B, Zr, Cu, Na, K, Cl) is measured after using ICP apparatus for analyzing luminosity (trade(brand)name: SPS-1700, Seiko electronics (セ イ コ ー イ Application ス Star Le メ Application Star) Co., Ltd.'s system) sample to be dissolved in acid.
(6) the halogenide flow measurement method of magnesia precursor
ICP apparatus for analyzing luminosity (trade(brand)name: SPS-1700, Seiko Electronics Co., Ltd system) is used to measure the halogenide amount of magnesia precursor.
Embodiment 1
Make magnesium chloride (MgCl
2) aqueous solution and sodium hydroxide (NaOH) reactant aqueous solution, obtain magnesium hydroxide (Mg (OH)
2) slurry.With ion exchanged water, this magnesium hydroxide slurry is diluted to slurry concentration 75g/L, with the speed of 100 ~ 150rpm, the magnesium hydroxide slurry after the dilution of 30L is stirred, and be blown into water vapour simultaneously, liquid temperature is adjusted to 60 DEG C.Then, CO is blown into from the bottom of tank with the flow of 10L/ minute liquid temperature being remained on while 60 DEG C
2the carbon dioxide 3 hours (0.8 molar equivalent) of concentration 100 capacity %, is transformed to magnesium basic carbonate by part magnesium hydroxide.
Then, filter this slurry, with 20L ion exchanged water, gained filter cake is washed.Then, with drying machine with 120 DEG C by this filtration cakes torrefaction 10 hours, obtain precursor.From the result of X-ray diffraction analysis, precursor is magnesium hydroxide and magnesium basic carbonate (chemical formula: 4MgCO
3mg (OH)
28H
2o and 4MgCO
3mg (OH)
24H
2o) mixture.Now, measure the content of chloride ion contained in above-mentioned precursor, result is 3 quality %.
Then, the closed electric furnace of the inflow and outflow of atmosphere gas is not had under being used in air atmosphere, with the heat-up rate of 6 DEG C/min, this magnesium hydroxide and the mixture of magnesium basic carbonate, i.e. precursor are heated to 1200 DEG C, then keep 5 hours at such a temperature, burn till by this, form magnesium oxide powder.The gas furnace of atmosphere gas inflow and outflow is had to carry out 1 hour burning till with 1200 DEG C further to this magnesium oxide powder under being used in air atmosphere.The result of observing gained magnesium oxide powder with scanning electron microscope (15000 times) is shown in Fig. 1.The shape of the crystallization observed is almost all cubic, and particle shape is very consistent.In addition, cubic crystallization be about about 1 μm, D
90/ D
10little, it can thus be appreciated that size-grade distribution is very narrow.With Fig. 9 described later unlike, crystal surface does not have particulate to adhere to, and crystal surface is level and smooth, clean.And cubic crystalline particle is separated from one another well.
Embodiment 2
Except the consumption of the ion exchanged water in washing step is changed into except 10L, obtained mixture, the i.e. precursor of magnesium basic carbonate and magnesium hydroxide by the step identical with embodiment 1, then obtain magnesium oxide powder.Here, the content of contained in described precursor chloride ion is 8 quality %.The result of observing gained magnesium oxide powder with scanning electron microscope (15000 times) is shown in Fig. 2.Compared with embodiment 1, cubic crystallization be increased to about about 1.5 μm.
Embodiment 3
Except not implementing except washing step, being obtained mixture, the i.e. precursor of magnesium basic carbonate and magnesium hydroxide by the step identical with embodiment 1, then obtaining magnesium oxide powder.Here, the content of contained in described precursor chloride ion is 14 quality %.The result of observing gained magnesium oxide powder with scanning electron microscope (15000 times) is shown in Fig. 3.Compared with embodiment 1, cubic crystallization be increased to about about 2 μm.
Embodiment 4
Except changing the consumption of the ion exchanged water in washing step into 30L, after washing, with ion exchanged water by 6N hydrochloric acid about 10 times, then be added into beyond the filter cake before drying, obtained mixture, the i.e. precursor of magnesium basic carbonate and magnesium hydroxide by the step identical with embodiment 1, then obtain magnesium oxide powder.Here, the content of contained in described precursor chloride ion is 20 quality %.The result of observing gained magnesium oxide powder with scanning electron microscope (15000 times) is shown in Fig. 4.Cubic crystallization while reach about about 4 μm, define great cubic magnesium oxide particle.
Embodiment 5
Make magnesium chloride solution (MgCl
2) react with sodium hydroxide solution (NaOH), obtain magnesium hydroxide (Mg (OH)
2) slurry.With ion exchanged water, this magnesium hydroxide slurry is diluted to slurry concentration 75g/L, with the speed of 500 ~ 600rpm, the magnesium hydroxide slurry after the dilution of 30L is stirred, and utilize autoclave that liquid temperature is remained on 115 DEG C simultaneously, hydro-thermal reaction 1 hour.Then, filter this slurry, with 30L ion exchanged water, gained filter cake is washed.Then, with drying machine with 120 DEG C by this filtration cakes torrefaction 10 hours, obtain precursor.Now, measure the content of chloride ion contained in above-mentioned precursor, result is 1 quality %.Then, under being used in air atmosphere, there is no the closed electric furnace of the inflow and outflow of atmosphere gas, with the heat-up rate of 6 DEG C/min, this precursor is heated to 1200 DEG C, then keep 5 hours at such a temperature, burn till by this, generate magnesium oxide powder.The gas furnace of atmosphere gas inflow and outflow is had to carry out 1 hour burning till with 1200 DEG C further to this magnesium oxide powder under being used in air atmosphere.The result of observing gained magnesium oxide powder with scanning electron microscope (15000 times) is shown in Fig. 5.The shape of the crystallization observed is almost all cubic, and particle shape is very consistent.In addition, cubic crystallization be about about 0.5 μm, D
90/ D
10little, it can thus be appreciated that breadth of particle size distribution is very narrow.
Comparative example 1
Except have under being used in air atmosphere the gas furnace of atmosphere gas inflow and outflow implement burn till except, operate similarly to Example 1, obtain magnesium oxide powder.The result of observing gained magnesium oxide powder with scanning electron microscope (15000 times) is shown in Fig. 6.Cubic is not grown in the crystallization of gained magnesium oxide powder, and particle diameter is also little, and each particle condenses.
Comparative example 2
Except the consumption of the ion exchanged water in washing step is changed into except 50L, obtained mixture, the i.e. precursor of magnesium basic carbonate and magnesium hydroxide by the step identical with embodiment 1, then obtain magnesium oxide powder.Here, the content of contained in described precursor chloride ion is 0.1 quality %.The result of observing gained magnesium oxide powder with scanning electron microscope (15000 times) is shown in Fig. 7.Cubic is not grown in the crystallization of gained magnesium oxide powder, and particle diameter is also little, and each particle condenses.
Comparative example 3
Use magnesium hydroxide (Da Taihao (タ テ ホ) chemical industry Co., Ltd. system, purity 99 quality %, primary particle size 0.3 ~ 0.5 μm, the specific surface area 30 ~ 40m of the impurity containing about 1 quality %
2/ g) as magnesian precursor.Contained chlorine dose is 0.5 quality %.Then, under being used in air atmosphere, there is no the closed electric furnace of the inflow and outflow of atmosphere gas, with the heat-up rate of 6 DEG C/min, this magnesium hydroxide is heated to 1200 DEG C, then keep 5 hours at such a temperature, burn till by this, generate magnesium oxide powder.The gas furnace of atmosphere gas inflow and outflow is had to carry out 1 hour burning till with 1200 DEG C further to this magnesium oxide powder under being used in air atmosphere.The result of observing gained magnesium oxide powder with scanning electron microscope (15000 times) is shown in Fig. 8.When lower containing the impurity of about 1 quality %, MgO purity, although gained magnesium oxide there occurs grain growth, crystal form is not cubes.
Comparative example 4
The result of observing the commercially available magnesium oxide powder utilizing vapor phase process to make with scanning electron microscope (15000 times) is shown in Fig. 9.Although comprise cubic crystallization, meanwhile, fine particulate crystallization is adhered in a large number, and surface is unholiness.
Comparative example 5
The result of observing commercially available magnesium oxide powder with scanning electron microscope (15000 times) is shown in Figure 10.Crystallization is not cubic, and particle diameter is also little, and each particle condenses.
The physics value of the magnesium oxide powder of embodiment 1 ~ 5 and comparative example 1 ~ 5 and the measurement result of impurity level are shown in table 1 and table 2.
[table 1]
[table 2]
The possibility that industry utilizes
Cubic magnesium oxide powder of the present invention is useful as the raw material etc. of additive, packing material, electronic component raw material, pharmaceuticals, use for laboratory reagent, various target raw material, superconducting thin film basilar membrane raw material, TMR element tunnel barrier raw material, PDP protective membrane raw material and PDP crystal magnesium oxide layer.
The simple declaration of accompanying drawing
Fig. 1 is the electron micrograph of the magnesium oxide powder obtained in embodiment 1.
Fig. 2 is the electron micrograph of the magnesium oxide powder obtained in embodiment 2.
Fig. 3 is the electron micrograph of the magnesium oxide powder obtained in embodiment 3.
Fig. 4 is the electron micrograph of the magnesium oxide powder obtained in embodiment 4.
Fig. 5 is the electron micrograph of the magnesium oxide powder obtained in embodiment 5.
Fig. 6 is the electron micrograph of the magnesium oxide powder obtained in comparative example 1.
Fig. 7 is the electron micrograph of the magnesium oxide powder obtained in comparative example 2.
Fig. 8 is the electron micrograph of the magnesium oxide powder of comparative example 3.
Fig. 9 is the electron micrograph of the magnesium oxide powder of comparative example 4.
Figure 10 is the electron micrograph of the magnesium oxide powder of comparative example 5.
Claims (5)
1. a cubic magnesium oxide powder, is characterized in that,
The particle shape observed with scanning electron microscope is cubic, and
The accumulation 50% particle diameter D obtained by laser diffraction and scattering formula particle size distribution
50it is more than 1.0 μm; The accumulation 10% particle diameter D obtained by laser diffraction and scattering formula particle size distribution
10with accumulation 90% particle diameter D
90ratio D
90/ D
10be less than 10.0;
Magnesium oxide purity is more than 99.9 quality %.
2. cubic magnesium oxide powder as claimed in claim 1, it is characterized in that, BET specific surface area is 5.0m
2/ below g.
3. cubic magnesium oxide powder as claimed in claim 1 or 2, it is characterized in that, after magnesia precursor is burnt till under the total amount relative to this precursor is the existence of the halide ions of 0.5 ~ 30 quality % in closed system, in open system, carry out second time burn till and obtain.
4. the manufacture method of magnesium oxide powder according to claim 1, it is characterized in that, after magnesia precursor is burnt till under the total amount relative to this precursor is the existence of the halide ions of 0.5 ~ 30 quality % in closed system, in open system, carry out second time burn till, obtained magnesium oxide purity is the magnesium oxide powder of more than 99.9 quality %.
5. manufacture method as claimed in claim 4, it is characterized in that, described magnesia precursor is magnesium basic carbonate, magnesium hydroxide or their mixture.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007019739A JP5016935B2 (en) | 2007-01-30 | 2007-01-30 | Cubic magnesium oxide powder and process for producing the same |
| JP2007-019739 | 2007-01-30 | ||
| CN200880003274A CN101646624A (en) | 2007-01-30 | 2008-01-22 | Cubic magnesium oxide powder and method for producing the same |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880003274A Division CN101646624A (en) | 2007-01-30 | 2008-01-22 | Cubic magnesium oxide powder and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103964475A CN103964475A (en) | 2014-08-06 |
| CN103964475B true CN103964475B (en) | 2015-10-21 |
Family
ID=39673877
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880003274A Pending CN101646624A (en) | 2007-01-30 | 2008-01-22 | Cubic magnesium oxide powder and method for producing the same |
| CN201410048866.XA Active CN103964475B (en) | 2007-01-30 | 2008-01-22 | Cubic magnesium oxide powder and method for making thereof |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880003274A Pending CN101646624A (en) | 2007-01-30 | 2008-01-22 | Cubic magnesium oxide powder and method for producing the same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5016935B2 (en) |
| KR (1) | KR101173728B1 (en) |
| CN (2) | CN101646624A (en) |
| TW (1) | TWI432380B (en) |
| WO (1) | WO2008093565A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5476826B2 (en) * | 2009-07-14 | 2014-04-23 | 堺化学工業株式会社 | Magnesium oxide particles, production method thereof, heat dissipating filler, resin composition, heat dissipating grease and heat dissipating coating composition |
| JP5415215B2 (en) * | 2009-10-02 | 2014-02-12 | タテホ化学工業株式会社 | Magnesium oxide powder having excellent dispersibility and method for producing the same |
| KR101193261B1 (en) * | 2011-04-12 | 2012-10-19 | 엘에스전선 주식회사 | Manufacturing method of magnesium oxide particles with controlled size |
| CN104755424A (en) | 2012-10-31 | 2015-07-01 | 宇部材料工业株式会社 | Magnesium oxide powder |
| US11884553B2 (en) | 2020-12-25 | 2024-01-30 | Ube Material Industries, Ltd. | Magnesium oxide powder, thermally conductive filler, resin composition, and production method for magnesium oxide powder |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1750221A (en) * | 2004-09-16 | 2006-03-22 | 日本先锋公司 | Plasma display panel |
| CN1836305A (en) * | 2003-09-26 | 2006-09-20 | 日本先锋公司 | Plasma display panel and method for producing same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3980569B2 (en) * | 2004-04-19 | 2007-09-26 | 宇部マテリアルズ株式会社 | Magnesium oxide |
| JP4873680B2 (en) * | 2004-07-22 | 2012-02-08 | 独立行政法人物質・材料研究機構 | Method for producing cubic magnesia powder |
| JP5108218B2 (en) * | 2005-09-28 | 2012-12-26 | 日本化学工業株式会社 | Magnesium oxide powder, precursor for magnesium oxide molded body, manufacturing method thereof, magnesium oxide molded body, and magnesium oxide sintered body pellet |
-
2007
- 2007-01-30 JP JP2007019739A patent/JP5016935B2/en active Active
-
2008
- 2008-01-22 CN CN200880003274A patent/CN101646624A/en active Pending
- 2008-01-22 KR KR1020097016041A patent/KR101173728B1/en active IP Right Grant
- 2008-01-22 WO PCT/JP2008/050783 patent/WO2008093565A1/en active Application Filing
- 2008-01-22 CN CN201410048866.XA patent/CN103964475B/en active Active
- 2008-01-28 TW TW97103055A patent/TWI432380B/en active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1836305A (en) * | 2003-09-26 | 2006-09-20 | 日本先锋公司 | Plasma display panel and method for producing same |
| CN1750221A (en) * | 2004-09-16 | 2006-03-22 | 日本先锋公司 | Plasma display panel |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101173728B1 (en) | 2012-08-13 |
| KR20090104088A (en) | 2009-10-05 |
| TWI432380B (en) | 2014-04-01 |
| WO2008093565A1 (en) | 2008-08-07 |
| JP2008184366A (en) | 2008-08-14 |
| CN103964475A (en) | 2014-08-06 |
| TW200844052A (en) | 2008-11-16 |
| JP5016935B2 (en) | 2012-09-05 |
| CN101646624A (en) | 2010-02-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bensalah et al. | Hydrothermal synthesis of nanocrystalline hydroxyapatite from phosphogypsum waste | |
| Shi et al. | Synthesis of zinc oxide nanoparticles with strong, tunable and stable visible light emission by solid-state transformation of Zn (II)–organic coordination polymers | |
| TWI483899B (en) | Magnesium oxide powder having good dispersibility and method for producing same | |
| Yang et al. | Synthesis of lithium manganese oxide in different lithium-containing fluxes | |
| CN103964475B (en) | Cubic magnesium oxide powder and method for making thereof | |
| Dong et al. | Surfactant-free fabrication of CaTiO 3 butterfly-like dendrite via a simple one-step hydrothermal route | |
| CN101679860B (en) | Oxide luminophor | |
| Zhou et al. | Morphology-controlled synthesis of Co3O4 by one step template-free hydrothermal method | |
| Liang et al. | Low temperature synthesis of LiSi 2 N 3 nanobelts via molten salt nitridation and their photoluminescence properties | |
| JPWO2008123566A1 (en) | Carbonate group-containing magnesium hydroxide particles and method for producing the same | |
| Ercan et al. | The effects of urea content on the structural, thermal and morphological properties of MgO nanopowders | |
| TWI386369B (en) | Magnesium oxide powder | |
| JP5588815B2 (en) | Gallium oxide powder | |
| Pei et al. | Cd2Ge2O6 nanowires grown by a simple hydrothermal route | |
| Lei et al. | Synthesis and morphological control of MnCO3 and Mn (OH) 2 by a complex homogeneous precipitation method | |
| JP4873680B2 (en) | Method for producing cubic magnesia powder | |
| JP5081438B2 (en) | Method for producing magnesium oxide | |
| JP2001354416A (en) | Method for manufacturing aragonite type calcium carbonate | |
| Akhtar et al. | Synthesis and Characterization of uniform Fine particles of Manganese Oxide and its Morphological Stability towards Calcination Rates. | |
| JP2006151712A (en) | HIGHLY DISPERSIBLE Ca-Mg COMPOSITE CARBONATES AND METHOD FOR PRODUCING THE SAME | |
| JP5058475B2 (en) | Alumina and production method thereof | |
| Wang et al. | Continuous and Scalable Synthesis of Prussian Blue Analogues with Tunable Structure and Composition in Surfactant‐Free Microreactor for Stable Zinc‐Ion Storage | |
| KR20230116777A (en) | Niobium oxide particles and method for producing niobium oxide particles | |
| Lazău et al. | Compounds formation in the MeO-Al2O3 (Me2+= Mg2+, Ca2+) system by unconventional methods | |
| JP2007246362A (en) | Method for manufacturing titanium oxide precursor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |