CN101646624A - Cubic magnesium oxide powder and method for producing the same - Google Patents
Cubic magnesium oxide powder and method for producing the same Download PDFInfo
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Abstract
Disclosed is a magnesium oxide powder having a cubic shape and a large average particle diameter. Also disclosed is a method for producing such a magnesium oxide powder. Specifically disclosed is a magnesium oxide powder whose particles have a cubic shape when observed with a scanning electron microscope. This magnesium oxide powder has a 50% cumulative particle diameter (D50), as determined by alaser diffraction/scattering particle size distribution measuring method, of not less than 1.0 [mu]m. This powder can be obtained by firing a magnesium oxide precursor in the presence of 0.5-30% by mass of a halide ion relative to the total mass of the precursor in a closed system.
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; the purposes, phosphor raw material, various target raw material, superconducting thin film substrate that also is used as various additives or electronic component with raw material, tunnel magnetoresistance element (TMR element) with tunnel barrier raw material, color plasma display panels (PDP) with protective membrane raw material and PDP raw material with the crystal magnesium oxide layer, attracted attention as having very widely the inorganic materials of purposes.
For example, as being used to form the magnesium oxide of PDP with the raw material of crystal magnesium oxide layer, require primary particle be shaped as cubic, high purity, each crystalline particle diameter is big and size-grade distribution is narrow, dispersed good crystalline powder.
Method for making as 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 that precursors such as magnesium hydroxide or magnesiumcarbonate are burnt till under the temperature more than the heat decomposition temperature, and (3) method that will pulverize by the piece that the electric smelting method obtains.
Utilize vapor phase process can obtain the magnesium oxide powder of high purity, cubic, but its particle diameter only is less than 1 μ m (with reference to patent documentation 1 and non-patent literature 1).In addition, also exist crystal surface to be attached with a large amount of particulates, surperficial sordid problem, and the cubic particle and non-cubic particle mixes, be not the problem of single dispersed powders of only forming by the cubic particle.
Utilize the magnesium oxide powder of the better thermal decomposition method manufacturing of productivity to have the angle of crystalline particle or the polygonal shape that rib has circular arc, and be difficult to obtain macroparticle.Therefore, above-mentioned magnesium oxide powder can absorb Atmospheric Carbon Dioxide gas and moisture etc., and this may impact the performance of magnesian natural characteristics.Particle also can the phase mutual coagulation under a lot of situations, can only obtain the powder of bad dispersibility.
For overcoming the shortcoming in the above-mentioned thermal decomposition method, put down in writing in the patent documentation 2 chloride ion and the method for burning till after magnesium oxide precursor or magnesium oxide mix, and magnesium chloride brine and alkaline sedimentation agent solution have been mixed the method that the back is filtered, burnt till then under the situation of not cleaning.Put down in writing among the embodiment of the document and in oxygen flow, implemented above-mentioned scheme of burning till.Though thus obtained magnesian crystallization is a cubic, its particle diameter only is about 0.2 μ m, can only obtain the magnesium oxide powder (Fig. 2 of the document (A)) of particle phase mutual coagulation.
Patent documentation 1: Japanese patent laid-open 1-282146 communique
Patent documentation 2: the Japanese Patent spy opens the 2006-36544 communique
Non-patent literature 1: " material ", clear and in November, 62, the 36th volume, No. 410,1157-1161 page or leaf
The announcement of invention
The present invention is the invention of finishing in view of above-mentioned present situation, and its objective is provides cubic and big magnesium oxide powder and the method for making thereof of particle diameter.
The inventor has carried out various researchs repeatedly for addressing the above problem, found that, when utilizing thermal decomposition method that thereby the magnesium oxide precursor is burnt till the manufacturing magnesium oxide powder, burn till by in the presence of the halide ions of specified quantitative and in the closed system different, implementing this with the firing condition of routine, can produce with existing method for making fully can not obtainable cubic and median size be great magnesium oxide powder more than the 1 μ m, thereby finished the present invention.
That is, the present invention relates to cubic magnesium oxide powder, this magnesium oxide powder is characterised in that, is cubic with the observed particle shape of scanning electron microscope, and the accumulation 50% particle diameter (D that is obtained by laser diffraction and scattering formula particle size distribution
50) be more than the 1.0 μ m.Here, be preferably the accumulation 10% particle diameter (D that obtains by laser diffraction and scattering formula particle size distribution
10) and accumulation 90% particle diameter (D
90) ratio D
90/ D
10Be below 10.0, the BET specific surface area is 5.0m
2Below/the g.In addition, being preferably purity is more than the 99.9 quality %.Be preferably described cubic magnesium oxide powder by with the magnesium oxide precursor be in total amount with respect to this precursor 0.5～30 quality % halide ions in the presence of in closed system, burn till and get.
The invention still further relates to the cubic magnesium oxide particle, this magnesia particle is characterised in that, is cubic with the observed particle shape of scanning electron microscope, and the length on this cubical one side is greater than 4.0 μ m; In addition, also relate to the magnesium oxide powder that comprises this cubic magnesium oxide particle.
The invention still further relates to the manufacture method of cubic magnesium oxide powder, the method is characterized in that, with the magnesium oxide precursor be in total amount with respect to this precursor 0.5～30 quality % halide ions in the presence of in closed system, burn till.Being preferably described magnesium oxide precursor is magnesium basic carbonate, magnesium hydroxide or their mixture.
Utilize the present invention, can obtain the big magnesium oxide powder of cubic and median size.Best is, utilize the present invention, can make the magnesium oxide powder with following characteristic: (1) particle shape is consistent to be cubic, (2) median size is greatly to more than the 1 μ m, (3) particle diameter unanimity, (4) do not contain particulate, cubic crystalline surface cleaning and level and smooth, (5) crystal grain is separated from one another, and is dispersed good.
The best mode that carries out an invention
The primary particle of magnesium oxide powder of the present invention be shaped as cubic.This shape can be determined with scanning electron microscope.In addition, cubic is not meant the cubes of the strictness on the geometry meaning, and is meant passing through the visual inspection microphotograph and can roughly be identified as cubical shape 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 big, particularly, satisfies the accumulation 50% particle diameter (D that is obtained by laser diffraction and scattering formula particle size distribution
50) be the above conditions of 1.0 μ m.Cubes magnesium oxide powder with so big median size is at first found by the inventor.This D
50Be preferably more than the 1.2 μ m, more preferably more than the 1.5 μ m.Think and in the scope of method for making of the present invention, can obtain D
50Be about the powder that 20 μ m are following or 10 μ m are following.In addition, D
50Being meso-position radius, being meant the particle diameter (μ m) that is equivalent to 50 volume % in the cumulative graph of granularity, is that a bigger side and a less side is the particle diameter of equivalent when with certain particle diameter powder being divided into two.
In addition, contain the micro mist this point more greatly and not about primary particle integral body, the specific surface area that the BET method of passing through of magnesium oxide powder of the present invention is measured is preferably 5.0m
2Below/the g.4.0m more preferably
2Below/the g, further 2.5m more preferably
2Below/the g, 1.0m particularly preferably
2Below/the g.
It is cubic that magnesium oxide powder of the present invention is preferably particle shape consistent, and the cubic crystal surface does not have particulate and adheres to, this surface cleaning and level and smooth.Therefore, magnesium oxide powder of the present invention is preferably the particle diameter unanimity, and promptly size-grade distribution is narrow, particularly, is preferably and satisfies the accumulation 10% particle diameter (D that is 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 below 10.0.More preferably below 6.0, particularly preferably below 4.5.
Magnesium oxide powder of the present invention is a high purity powdered form, and purity is preferably more than the 99.9 quality %, more preferably more than the 99.99 quality %.
Below, the manufacture method of magnesium oxide powder of the present invention is described.
Manufacture method of the present invention is based on thermal decomposition method, in the present invention, implement with the magnesium oxide precursor in total amount be with respect to this precursor 0.5～30 quality % halide ions in the presence of the operation of in closed system, burning till, make magnesium oxide powder by this.Thus, can make magnesium oxide powder with above-mentioned each characteristic.
As described magnesium oxide precursor, can be the precursor that in thermal decomposition method in the past, uses, be not particularly limited, can exemplify for example magnesium hydroxide, magnesium basic carbonate, magnesiumcarbonate, magnesium oxalate etc.Wherein, because the characteristic good of gained magnesium oxide powder, therefore preferred magnesium hydroxide, magnesium basic carbonate and their mixture.
If described precursor contains more impurity, then the shape of gained magnesium oxide powder is not a cubic, but tends to become the polygon-shaped of band circular arc, so the impurity of precursor is to be advisable less.Particularly, as impurity level contained in the precursor, the total amount of remaining impurities is removed halide ions and is preferably below the 0.1 quality % when generating magnesium oxide by thermal decomposition method, more preferably below the 0.01 quality %.
Described burning till in the presence of halide ions carried out.As halide ions, can exemplify chloride ion, fluoride ion, bromide ion, iodide ion, use chloride ion usually.Concrete example as halide ionic compound can exemplify hydrochloric acid, ammonium chloride, sodium-chlor, Repone K, magnesium chloride etc.
The amount of halide ions with respect to the total amount of magnesium oxide precursor in the scope of 0.5～30 quality %.If the amount of halide ions is very few, then can't bring into play effect of the present invention, on the contrary, if too much, then magnesian crystallization is difficult to grow up.The scope of preferred 1.0～25 quality %, the more preferably scope of 10～25 quality %.
Halide ionic compound can be a magnesium oxide precursor itself, it can be material from the contained impurity of magnesium oxide precursor, it can be the by product that generates when modulating the magnesium oxide precursor by solution synthetic method, can be the material that is added into separately in the magnesium oxide precursor, also can be that form with for example gasiform hydrogenchloride etc. is added into the material in the gas atmosphere in the enclosed stove.In addition, also can wait the by product that generates when removing the contained impurity of magnesium oxide precursor fully and modulating magnesium oxide, be added into again in magnesium oxide precursor or the gas atmosphere then by cleaning.
Among the present invention, as the magnesium oxide precursor, preferably by the synthetic magnesium oxide precursor that obtains of solution.
The magnesium oxide precursor is under the situation of mixture of magnesium basic carbonate and magnesium hydroxide, when modulating this precursor by solution synthetic method, for example (1) mixes magnesium chloride brine and aqueous sodium hydroxide solution, obtain the magnesium hydroxide slurry, (2) with a part of carbonating of the magnesium hydroxide in this slurry, obtain comprising the slurry of magnesium basic carbonate and magnesium hydroxide, (3) filter this slurry, obtain the mixture of magnesium basic carbonate and magnesium hydroxide.Contain raw material thing magnesium chloride or by product sodium-chlor in this mixture as chloride ion.
In described operation (1), can be after obtaining the magnesium hydroxide slurry dilute with water, thereby the concentration of this slurry is adjusted to be preferably 50～100g/L, more preferably in the scope of 60～90g/L.This is because by reducing the concentration of slurry, can reduce the viscosity of slurry, and the carbonation reaction in the follow-up operation (2) is carried out equably.
In described operation (2), by described slurry is blown into carbon dioxide, with a part of carbonating of the magnesium hydroxide in the slurry.Preferred 40～80 ℃ of the temperature of this carbonation reaction.In this temperature range, carry out the reaction efficiency height apace to the conversion of magnesium basic carbonate from magnesium hydroxide.In this temperature range, also can obtain to have the magnesium basic carbonate of the good particle diameter of filtration efficiency and the mixture of magnesium hydroxide.
The consumption of the carbon dioxide that uses in the described carbonation reaction is the amount that the part of the magnesium hydroxide in the magnesium hydroxide slurry can be converted into magnesium basic carbonate, the mixture of magnesium basic carbonate and magnesium hydroxide is provided.The concrete usage quantity of carbon dioxide is with respect to preferred 0.2～2.0 molar equivalent of 1 mole magnesium hydroxide.In this scope, can obtain the mixture of good magnesium basic carbonate of filtration efficiency and magnesium hydroxide efficiently.
In described operation (3),, thereby obtain the mixture of magnesium basic carbonate and magnesium hydroxide with the solid form by the slurries filtration that comprises magnesium basic carbonate and magnesium hydroxide that obtains in will described operation (2).Contain chloride ion in this solid mixt, therefore can under the situation of not cleaning, directly be dried, be used for described later burning till then, also can clean this mixture with an amount of water, amount with the chloride ion in the filter cake is reduced to suitable level by this, carries out drying then and burns till.If clean fully, then the content of chloride ion is low excessively, can't obtain effect of the present invention, and usage quantity that therefore need be by rinse water, scavenging period etc. are controlled the degree of cleaning.But, also can after cleaning fully, chloride ion is removed fully, add halide ionic mixture separately.
The magnesium oxide precursor is under the situation of magnesium hydroxide, and when modulating this precursor by solution synthetic method, for example (1) mixes magnesium chloride brine and aqueous sodium hydroxide solution, obtains the magnesium hydroxide slurry, and (2) filter this slurry, obtain solid-state magnesium hydroxide.Contain raw material thing magnesium chloride or by product sodium-chlor in this solids as chloride ion.
In described operation (1), be preferably dilute with water after obtaining the magnesium hydroxide slurry, thereby the concentration of this slurry is adjusted to is preferably 50～100g/L, more preferably in the scope of 60～90g/L, then by its slaking being made the magnesium hydroxide particles in this slurry grow up.Can improve the filtration efficiency in the operation (2) by this.Described slaking condition is not particularly limited, and under agitation at high temperature keeps certain hour to get final product in slurry.Curing temperature for example is to get final product about 80～150 ℃, and the curing time is to get final product about several minutes～a few hours.
In described operation (2), filter by the magnesium hydroxide slurry that will obtain in the described operation (1), thereby obtain solid-state magnesium hydroxide.Because this solids contains chloride ion, therefore it is carried out aforesaid processing and get final product.
In the magnesian method for making based on thermal decomposition method of the present invention, need in the presence of halide ions and in closed system, carry out burning till of magnesium oxide precursor.Closed system among the present invention is meant that the gas that is present in the space of burning till in fact flows out, in fact also do not have the system of gas from the approximate sealing of outside inflow to the outside, is different from the process for calcining of the routine of carrying out when the air flow stream of opening or make these gases under atmosphere such as atmosphere or oxygen is crossed.Among the present invention, by in closed system, burning till, thereby halide ions can not splashed to the outside, but stay in the container that burns till, participate in magnesium oxide powder crystalline developmental process fully, obtain the great cubic crystalline powder of median size by this.
In this closed system for example burn till can be by using the inflow and outflow that does not have atmosphere gas in fact the closed electric furnace or with raw material add can be airtight crucible in carry out.Temperature when burning till can be about 600 ℃～1400 ℃, preferably about 1200 ℃.If the temperature when burning till is too high, then the gained crystallization may be condensed, dispersed variation.Firing time is relevant with temperature, is generally about 1～10 hour.For example, under temperature was situation about 1200 ℃, firing time was advisable with about 5 hours.In addition, the speed when heating up for burning till is not particularly limited, and is to get final product about 5～10 ℃/minute.
Atmosphere when this burns till is not particularly limited, and can exemplify for example atmosphere, oxygen, nitrogen, argon gas etc., owing to impurity contained in the precursor can be removed as oxidizing gas, so preferred atmosphere or oxygen atmosphere.
By burning till under the described condition, the big cubic magnesium oxide powder of median size is grown up, but owing to burn till in confined conditions, and therefore impurity such as described halide ionic compound can't be removed fully, thereby sneaks in the powder after burning till.In order to reduce the mixed volume of this halide ionic compound, improve the purity of magnesium oxide powder, preferably in described closed system, carry out in the manufacture method of the present invention further in open system, carrying out burning till the second time behind the once-firing.
This twice firing can be burning till of carrying out in common open system, and for example can use has gas furnace that atmosphere gas flows or the electric furnace under the oxygen flow to wait under air atmosphere to carry out.Gas in temperature during twice firing, time and the stove is not particularly limited, as long as can remove impurity such as halide ionic compound, be not particularly limited, but owing to crystalline growth can be finished by once-firing, so the time of twice firing also can be shorter.
Utilize method for making of the present invention, can obtain the magnesia particle of the cubic with great particle diameter shown in Figure 4.When observing this cubic particle with scanning electron microscope, the length on cubical one side is greater than 4.0 μ m.So big, do not have particulate, a cleaning surfaces and level and smooth cubic particle report not also up to now.Think that in the scope of method for making of the present invention the length that can obtain cubical one side is below the 20 μ m or the particle below 10 μ m.The magnesium oxide powder that comprises this particle is also included within the 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 embodiment.
Among the following embodiment, according to the various rerum naturas of sequential determination as follows etc.
(1) scanning electron microscope (SEM) observation
Use scanning electron microscope (trade(brand)name: JSM-5410, Jeol Ltd. (JEOL) system) to take the SEM composograph, observe particle shape, and measure the length on one side of cubic magnesium oxide.
(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 (Ri Machine dress) Co., Ltd.'s system) mensuration accumulation 10% particle diameter (D
10), the accumulation 50% particle diameter (D
50) and accumulation 90% particle diameter (D
90).
(3) BET specific area measuring method
Use specific area measuring device (trade(brand)name: Macsorb1210, mountain skill (マ ウ Application テ Star Network) Co., Ltd.'s system) by the gas adsorption method measurement the specific area.
(4) magnesian purity testing method
Magnesian purity from 100 quality % deduct the impurity level that records summation and value calculate.
(5) magnesian impurity level assay method
Make recruitment CP apparatus for analyzing luminosity (trade(brand)name: SPS-1700, Seiko electronics (セ イ コ one イ Application ス Star Le メ Application Star) Co., Ltd.'s system) that sample is dissolved in the acid back and measure magnesian impurity level (Si, Al, Ca, Fe, V, Cr, Mn, Ni, Zn, B, Zr, Cu, Na, K, Cl).
(6) the halogenide flow measurement method of magnesium oxide precursor
Use ICP apparatus for analyzing luminosity (trade(brand)name: SPS-1700, Seiko Electronics Co., Ltd system) to measure the halogenide amount of magnesium oxide 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, stirs with the speed of the 100～150rpm magnesium hydroxide slurry after to the dilution of 30L, and be blown into water vapour simultaneously, the liquid temperature is adjusted to 60 ℃.Then, the flow with 10L/ minute is blown into CO the liquid temperature being remained in 60 ℃ from the bottom of jar
2The carbon dioxide of concentration 100 capacity % 3 hours (0.8 molar equivalent) is transformed to magnesium basic carbonate with the part magnesium hydroxide.
Then, filter this slurry, the gained filter cake is washed with the 20L ion exchanged water.Then, with drying machine with 120 ℃ with this filtration cakes torrefaction 10 hours, obtain precursor.By the result of X-ray diffraction analysis as can be known, precursor is magnesium hydroxide and magnesium basic carbonate (chemical formula: 4MgCO
3Mg (OH)
28H
2O and 4MgCO
3Mg (OH)
24H
2O) mixture.At this moment, measure the content of chloride ion contained in the above-mentioned precursor, the result is 3 quality %.
Then, use does not have the closed electric furnace of the inflow and outflow of atmosphere gas under air atmosphere, with 6 ℃/minute heat-up rates with the mixture of this magnesium hydroxide and magnesium basic carbonate, be that precursor is heated to 1200 ℃, under this temperature, kept 5 hours then, burn till by this, form magnesium oxide powder.Use has the gas furnace of atmosphere gas inflow and outflow with 1200 ℃ this magnesium oxide powder further to be carried out 1 hour burning till under air atmosphere.Get the Fig. 1 that the results are shown in of magnesium oxide powder with scanning electron microscope (15000 times) observation post.Observed crystalline shape almost all is a cubic, and particle shape is very consistent.In addition, on one side the cubic crystalline is about about 1 μ m D
90/ D
10Little, size-grade distribution that hence one can see that is very narrow.Different with Fig. 9 described later is, crystal surface does not have particulate to adhere to, and crystal surface is level and smooth, clean.And the cubic crystalline particle is separated from one another well.
Embodiment 2
Except that the consumption with the ion exchanged water in the washing step changes 10L into, by the step identical with embodiment 1 obtain magnesium basic carbonate and magnesium hydroxide mixture, be precursor, obtain magnesium oxide powder then.Here, the content of contained chloride ion is 8 quality % in the described precursor.Get the Fig. 2 that the results are shown in of magnesium oxide powder with scanning electron microscope (15000 times) observation post.Compare with embodiment 1, on one side the cubic crystalline increases to about about 1.5 μ m.
Embodiment 3
Except that not implementing washing step, by the step identical with embodiment 1 obtain magnesium basic carbonate and magnesium hydroxide mixture, be precursor, obtain magnesium oxide powder then.Here, the content of contained chloride ion is 14 quality % in the described precursor.Get the Fig. 3 that the results are shown in of magnesium oxide powder with scanning electron microscope (15000 times) observation post.Compare with embodiment 1, on one side the cubic crystalline increases to about about 2 μ m.
Embodiment 4
The consumption that removes the ion exchanged water in the washing step changes 30L into, after washing, with ion exchanged water 6N hydrochloric acid is diluted about 10 times, be added into then beyond the dry preceding filter cake, by the step identical with embodiment 1 obtain magnesium basic carbonate and magnesium hydroxide mixture, be precursor, obtain magnesium oxide powder then.Here, the content of contained chloride ion is 20 quality % in the described precursor.Get the Fig. 4 that the results are shown in of magnesium oxide powder with scanning electron microscope (15000 times) observation post.The cubic crystalline reaches about about 4 μ m on one side, has formed 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, stirs with the speed of the 500～600rpm magnesium hydroxide slurry after to the dilution of 30L, and utilize autoclave that the liquid temperature is remained on 115 ℃ simultaneously, hydro-thermal reaction 1 hour.Then, filter this slurry, the gained filter cake is washed with the 30L ion exchanged water.Then, with drying machine with 120 ℃ with this filtration cakes torrefaction 10 hours, obtain precursor.At this moment, measure the content of chloride ion contained in the above-mentioned precursor, the result is 1 quality %.Then, use the closed electric furnace of the inflow and outflow that under air atmosphere, does not have atmosphere gas, this precursor is heated to 1200 ℃, under this temperature, kept 5 hours then, burn till by this, generate magnesium oxide powder with 6 ℃/minute heat-up rates.Use has the gas furnace of atmosphere gas inflow and outflow with 1200 ℃ this magnesium oxide powder further to be carried out 1 hour burning till under air atmosphere.Get the Fig. 5 that the results are shown in of magnesium oxide powder with scanning electron microscope (15000 times) observation post.Observed crystalline shape almost all is a cubic, and particle shape is very consistent.In addition, on one side the cubic crystalline is about about 0.5 μ m D
90/ D
10Little, hence one can see that, and the size-grade distribution width is very narrow.
Comparative example 1
Except that using the gas furnace that the atmosphere gas inflow and outflow is arranged under the air atmosphere is implemented to burn till, operate similarly to Example 1, obtain magnesium oxide powder.Get the Fig. 6 that the results are shown in of magnesium oxide powder with scanning electron microscope (15000 times) observation post.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 that the consumption with the ion exchanged water in the washing step changes 50L into, by the step identical with embodiment 1 obtain magnesium basic carbonate and magnesium hydroxide mixture, be precursor, obtain magnesium oxide powder then.Here, the content of contained chloride ion is 0.1 quality % in the described precursor.Get the Fig. 7 that the results are shown in of magnesium oxide powder with scanning electron microscope (15000 times) observation post.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 contains magnesium hydroxide (Da Taihao (タ テ ホ) chemical industry Co., Ltd. system, purity 99 quality %, primary particle size 0.3～0.5 μ m, the specific surface area 30～40m of the impurity about 1 quality %
2/ g) as magnesian precursor.Contained chlorine dose is 0.5 quality %.Then, use the closed electric furnace of the inflow and outflow that under air atmosphere, does not have atmosphere gas, this magnesium hydroxide is heated to 1200 ℃, under this temperature, kept 5 hours then, burn till by this, generate magnesium oxide powder with 6 ℃/minute heat-up rates.Use has the gas furnace of atmosphere gas inflow and outflow with 1200 ℃ this magnesium oxide powder further to be carried out 1 hour burning till under air atmosphere.Get the Fig. 8 that the results are shown in of magnesium oxide powder with scanning electron microscope (15000 times) observation post.Containing under the lower situation of impurity, MgO purity about 1 quality %, though the particle growth has taken place gained magnesium oxide, crystal form is not a cubes.
Comparative example 4
Observe commercially available Fig. 9 that the results are shown in that utilizes magnesium oxide powder that vapor phase process makes with scanning electron microscope (15000 times).Though comprise the cubic crystallization, meanwhile, fine particulate crystallization is adhered in a large number, and the surface is unholiness.
Comparative example 5
Observe the Figure 10 that the results are shown in of commercially available magnesium oxide powder with scanning electron microscope (15000 times).Crystallization is not a 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]
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| MgO (quality %) | ??99.9 | ??99.9 | ??99.9 | ??99.9 | ??99.99 |
| SEM photo range estimation shape | Cubes | Cubes | Cubes | Cubes | Cubes |
| SEM photo particle diameter (μ m) | ??1 | ??1.5 | ??2 | ??4 | ??0.5 |
| ??D 10(μm) | ??0.54 | ??0.75 | ??2.31 | ??3.48 | ??0.32 |
| ??D 50(μm) | ??1.50 | ??2.41 | ??5.31 | ??6.13 | ??1.05 |
| ??D 90(μm) | ??3.07 | ??4.0 | ??9.74 | ??10.55 | ??1.90 |
| ??D 90/D 10 | ??5.7 | ??5.3 | ??4.2 | ??3.0 | ??5.9 |
| Specific surface area (m 2/g) | ??3.15 | ??2.36 | ??0.93 | ??0.80 | ??4.73 |
[table 2]
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| MgO (quality %) | ??99.9 | ??99.9 | ??99.0 | ??99.9 | ??99.9 |
| SEM photo range estimation shape | Non-cubes | Non-cubes | Non-cubes | Cubes, particulate adheres in a large number | Non-cubes |
| SEM photo particle diameter (μ m) | ??0.1 | ??0.2 | ??2～3 | ??1 | ??0.2 |
| ??D 10(μm) | ??0.29 | ??0.31 | ??3.80 | ??0.42 | ??1.11 |
| ??D 50(μm) | ??2.26 | ??1.04 | ??11.85 | ??0.95 | ??3.81 |
| ??D 90(μm) | ??4.89 | ??1.94 | ??140.32 | ??9.12 | ??46.53 |
| ??D 90/D 10 | ??16.9 | ??6.3 | ??37.0 | ??21.7 | ??41.9 |
| Specific surface area (m 2/g) | ??15.5 | ??5.78 | ??0.63 | ??8.09 | ??23.6 |
The possibility of utilizing on the industry
Cubic magnesium oxide powder of the present invention is useful with the raw material of crystal magnesium oxide layer etc. with diaphragm raw material and PDP with tunnel barrier raw material, PDP with raw material, TMR element with raw material, pharmaceuticals, use for laboratory reagent, various target raw material, superconducting thin film basilar memebrane as additive, packing material, electronic component.
The simple declaration of accompanying drawing
Fig. 1 is the electron micrograph of the magnesium oxide powder that obtains among the embodiment 1.
Fig. 2 is the electron micrograph of the magnesium oxide powder that obtains among the embodiment 2.
Fig. 3 is the electron micrograph of the magnesium oxide powder that obtains among the embodiment 3.
Fig. 4 is the electron micrograph of the magnesium oxide powder that obtains among the embodiment 4.
Fig. 5 is the electron micrograph of the magnesium oxide powder that obtains among the embodiment 5.
Fig. 6 is the electron micrograph of the magnesium oxide powder that obtains in the comparative example 1.
Fig. 7 is the electron micrograph of the magnesium oxide powder that obtains in the 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 (9)
1. a cubic magnesium oxide powder is characterized in that,
With the observed particle shape of scanning electron microscope is cubic, and
The accumulation 50% particle diameter D that obtains by laser diffraction and scattering formula particle size distribution
50Be more than the 1.0 μ m.
2. cubic magnesium oxide powder as claimed in claim 1 is characterized in that, the accumulation 10% particle diameter D that is obtained by laser diffraction and scattering formula particle size distribution
10With accumulation 90% particle diameter D
90Ratio D
90/ D
10Be below 10.0.
3. cubic magnesium oxide powder as claimed in claim 1 or 2 is characterized in that, the BET specific surface area is 5.0m
2Below/the g.
4. cubic magnesium oxide powder as claimed in claim 1 or 2 is characterized in that, magnesium oxide purity is more than the 99.9 quality %.
5. cubic magnesium oxide powder as claimed in claim 1 or 2 is characterized in that, by with the magnesium oxide precursor be in total amount with respect to this precursor 0.5～30 quality % halide ions in the presence of in closed system, burn till and get.
6. a cubic magnesium oxide particle is characterized in that,
The particle shape that records with scanning electron microscope is a cubic, and
The length on this cubical one side is greater than 4.0 μ m.
7. a magnesium oxide powder is characterized in that, comprises the described cubic magnesium oxide particle of claim 6.
8. the manufacture method of a magnesium oxide powder is characterized in that, with the magnesium oxide precursor be in total amount with respect to this precursor 0.5～30 quality % halide ions in the presence of in closed system, burn till.
9. manufacture method as claimed in claim 8 is characterized in that, described magnesium oxide precursor is magnesium basic carbonate, magnesium hydroxide or their mixture.
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