CN101792186A - Method for preparing micaceous iron oxide by molten salt growth method - Google Patents
Method for preparing micaceous iron oxide by molten salt growth method Download PDFInfo
- Publication number
- CN101792186A CN101792186A CN 201010136709 CN201010136709A CN101792186A CN 101792186 A CN101792186 A CN 101792186A CN 201010136709 CN201010136709 CN 201010136709 CN 201010136709 A CN201010136709 A CN 201010136709A CN 101792186 A CN101792186 A CN 101792186A
- Authority
- CN
- China
- Prior art keywords
- iron mica
- iron
- growth method
- salt growth
- mica
- 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.)
- Pending
Links
Images
Abstract
The invention provides a method for preparing micaceous iron oxide, which has the advantages of controllable grain size and color change, high purity, complete and reliable production process, easy operation and high resource utilization rate, by a molten salt growth method. In the method, ammonium ferrous sulfate or ferrous sulfate or a mixture of ammonium ferrous sulfate and ferrous sulfate serving as an iron source and sulfates or chlorides or a mixture of sulfates and chlorides serving as a fluxing agent are mixed and melted to form the micaceous iron oxide, wherein the main component of the micaceous iron oxide is a-Fe2O3. The method has the advantages of low cost, easy operation, complete process, no toxicity, high chemical stability, high purity, high crystallinity, high heat resistance, easy realization of industrialization and the like.
Description
Technical field
The present invention relates to a kind ofly be source of iron, be the fused salt fusing assistant, adopt molten-salt growth method to prepare the method for iron mica, belong to the inorganic powder material preparation field with vitriol or muriate with ferrous ammonium sulphate or ferrous sulfate or both mixtures.
Background technology
The preparation method of iron mica mainly comprises two kinds of flake hematite and synthetic iron micas.Along with the development and utilization of natural resources, high-grade flake hematite mineral reserve constantly reduce, and advanced composite material is also more and more higher to the iron mica specification of quality.The synthetic iron mica has particle diameter controllable color, chemical stability height, purity height, well-crystallized and thermotolerance advantages of higher, the synthetic iron mica just progressively replaces flake hematite, applies in the industry such as rust-inhibiting paint, coating, pearly pigment.
In the existing synthetic iron mica technology, hydrothermal method is the maximum method of present synthetic mica ferric oxide research.Patent US4233283 adopts boric acid (H in hydrothermal method
3BO
3) or borate (MBO
3) prepare iron mica as crystal growth promoters, make the iron mica particle size range strengthen (reaching 150 microns), but only considered the promoter action of boric acid crystal growth promoters, do not considered boric acid usage quantity, hydro-thermal reaction crystallization medium sodium hydroxide (NaOH) concentration, hydro-thermal reaction Tc and hydro-thermal reaction crystallization time collaborative influence and regulating and controlling effect iron mica particle diameter and colour-change to the iron mica particle diameter.Patent EP0416648
,US4289746
,US3987156 does not use crystal growth promoters, and is not good enough to iron mica particle diameter and color regulating effect, and the iron mica particle diameter of preparing (below 100 microns) less than normal.Chinese patent 0610032440.0, though by regulating crystalline growth promotor boric acid addition, sodium hydroxide medium concentration, hydro-thermal reaction Tc etc., prepare the suitable iron mica of size and colour-change, but this kind method requires very strictness to the heat resisting and pressure resisting and the corrosion resistance of main device high pressure vessel, brings certain difficulty for real suitability for industrialized production.
Molten-salt growth method has been widely used in the ceramic powder that ceramic industry prepares specific function, and fused salt plays the effect of fusing assistant and reaction medium in the molten-salt growth method preparation process, and effectively the size and dimension of control crystal grain synthesizes the powder with specific morphology.European patent EP 0307486 is passed into oxygen-containing gas the FeCl that contains alkaline or alkaline-earth salts
2And FeCl
3In the melting salt, obtain iron mica through oxidizing reaction.It is low, simple to operate that this method has a cost, easily realizes industrialized advantage, but FeCl
2And FeCl
3Volatile shortcoming influences utilization ratio of raw materials.
Summary of the invention
The present invention is a source of iron with ferrous ammonium sulphate and ferrous sulfate, with vitriol or muriate is fusing assistant, provides a kind of and has adopted molten-salt growth method to prepare particle diameter and colour-change is controlled, purity is high, the method for complete reliable, the easy handling of production technique, iron mica that resource utilization is high.
The present invention realizes by following manner:
With ferrous ammonium sulphate or ferrous sulfate or both mixtures is source of iron, is fusing assistant with vitriol or muriate or both mixtures, fusion after mixing and iron mica, the main component of described iron mica is a-Fe
2O
3, the pressure range during described fusion is 101.325kPa ± 10kPa.
Reaction equation:
2
FeSO 4 (NH 4 ) 2 SO 4 ·6H 2 O 
Fe 2 O 3 +14H 2 O+4NH 3 +SO 2? +3SO 3
Wherein said vitriol is sodium sulfate or vitriolate of tartar or both mixtures, and described muriate is sodium-chlor or Repone K or both mixtures, and described fusing assistant consumption with the ratio of the amount of substance of source of iron consumption is: 2 ~ 3:1.
Concrete preparation method is as follows:
Take by weighing ferrous ammonium sulphate or ferrous sulfate, vitriol or muriate, thorough mixing, and put into the mortar grinding to 20 ~ 700 μ m, then mixture is packed in corundum crucible or the porcelain crucible, crucible is put into the reaction smelting furnace, speed by 5 ℃/min heats up, reach 800 ± 5 ℃ and be incubated 30 ~ 40min, follow-up continuing is warming up to 900-1200 ℃, and keeps temperature 5 ~ 7h, programmed cooling (5 ℃/10min), after treating that sample is cooled to room temperature, the water that adds 85 ~ 95 ℃ stirs, and the water of adding and the mass ratio of sample are 50:1, and the agglomerating fusing assistant is dissolved in the water, use a large amount of washed with de-ionized water behind the suction filtration, to clarification of water,, the filter cake drying in 100 ℃ loft drier that obtains is made iron mica to remove residual ion.
Prepared iron mica is rectangle, square or irregular laminar, particle diameter is 20-200 μ m, purity is greater than 98wt%.
When mixing, abundant mixing at ferrous ammonium sulphate and fused salt (fusing assistant), can grind in case of necessity.The maximum feature of fused salt is the ion melt, and the fused salt that we select for use is respectively vitriol (sodium sulfate and vitriolate of tartar) or muriate (sodium-chlor and Repone K).
In temperature-rise period, need keep constant temperature for some time when rising to 800 ℃, about 30 minutes by room temperature.Fused salt is fusion, and the melt of salt plays the effect of solvent and reaction medium, and the former composition of promotion reactant dissolves and transforms to product.
In pyroreaction crystallization iron mica process, by discovering: the kind of fused salt (fusing assistant), each component proportions of fused salt and consumption, pyroreaction sintering temperature and pyroreaction sintering time have a significant effect to iron mica particle diameter and colour-change.Form the following factors of iron mica by the regulation and control pyroreaction, can be more reasonably to the controlled preparation of iron mica particle diameter and color:
(1) kind of fused salt (fusing assistant): adopt two class fused salts; Vitriol (sodium sulfate and vitriolate of tartar) molten salt system is preferable selection, and gained iron mica particle diameter is big and evenly, whiter, impurity is fewer; And the product particle diameter that muriate (sodium-chlor and Repone K) molten salt system generates is less, be a large amount of red materials, and fused salt boils closely at high temperature.
(2) each component proportions of fused salt: vitriol (sodium sulfate and vitriolate of tartar), sodium sulfate: vitriolate of tartar=80:20(mol ratio); Muriate (sodium-chlor and Repone K), sodium-chlor: Repone K=50:50(mol ratio).
(3) (S is fused salt SO in the influence of fused salt consumption: S=4 ~ 6
4 2-Or Cl
-The Fe deserved with theory
2O
3Mol ratio) time, the particle diameter of iron mica is best; The fused salt consumption does not have the due effect of fused salt very little the time, and is not good because of the inhomogeneous morphology microstructure that causes of production concentration, and agglomeration arranged; When the fused salt consumption was too much, too much flux had hindered the growth of ferric oxide crystal grain, and provided condition for growing up unusually of minority crystal grain.
(4) influence of pyroreaction sintering temperature: when sintering range was 900-1200 ° of C, the crystal structure degree was higher, and color is better, and surface topography is smooth.
(5) influence of pyroreaction sintering time: when the sintering time scope was 5-7h, the product pattern was essentially smooth smooth, and the colourimetric number of product and excitation purity thereof are all preferable.
Below technology of the present invention is described in further details.Technology of the present invention divides following three phases to carry out:
(1) reactant mixes with fused salt
Press 1g source of iron ferrous ammonium sulphate (FeSO
4(NH
4)
2SO
46H
2O) with 0.80 ~ 0.90gNa
2SO
4With 0.20 ~ 0.25gK
2SO
4Mixed; Or 1g source of iron ferrous ammonium sulphate (FeSO
4(NH
4)
2SO
46H
2O) or FeSO
4Mixed with 0.18 ~ 0.23gNaCl and 0.25 ~ 0.30gKCl.Thorough mixing also grinds, and packs in corundum crucible or the porcelain crucible, puts into High Temperature Furnaces Heating Apparatus, and High Temperature Furnaces Heating Apparatus was communicated with extraneous the maintenance.
(2) high temperature sintering reaction
Reaction mixture pack into corundum crucible or porcelain crucible.Fused salt be sulfate mixture in crucible, the reaction mass volume can reach crucible volumetrical 2/3; Fused salt be chloride mix in crucible because the fusing point of molten chloride is lower, the reaction mass body is no more than crucible volumetrical 1/3; Temperature controller when temperature reaches 800 ° of C, keeps 30min, thermal pretreatment by the speed temperature programming of 5 ℃/min; Continue to heat up and reach assigned temperature and be incubated certain hour, according to required iron mica particle diameter and color, by 900-1200 ° of C of control sintering temperature, with the pyroreaction sintering time, the sintering time scope is 5-7h, realizes the controlled preparation to iron mica particle diameter and color.
(3) high temperature sintering aftertreatment
After the high temperature sintering reactive crystallization was finished, programmed cooling was to room temperature, with the reaction product in the crucible, in the water-bath of deionized water about 90 ℃, stir fully washing, the agglomerating fusing assistant is dissolved in the water, use a large amount of washed with de-ionized water behind the suction filtration again, to remove residual ion.With the filter cake dry about 1h in 100 ℃ loft drier that obtains.Dried filter cake texture is loose, finally obtains the sheet mica iron oxide product.
The present invention prepares the iron mica of particle diameter and controllable color by the pyroreaction molten-salt growth method.Prepared iron mica vitriol is as fused salt, and synthetic product sheet is big, and optical effect is better, and impurity is fewer; And less, a large amount of red crystallite of product sheet that chlorate generates as fused salt, and at the bottom of the crucible crucible with the crucible wall on residual black impurity.
The present invention has following advantage:
Molten-salt growth method can significantly reduce synthesis temperature and shorten the reaction times, because the formation of the melt of salt strengthens the flowability of reacted constituent in liquid phase, velocity of diffusion improves; Fused salt is evenly distributed on again between the iron mica particle of generation, stops the mutual binding between the particle, so the iron mica uniform particles that molten-salt growth method makes does not have reunion, or only pettiness is reunited.
Molten-salt growth method can be controlled iron mica coating of particles and size.Shape and size are relevant with surface energy and interfacial energy between reactant and the salt-melting, and surface energy and interfacial energy have the trend that is tending towards reducing, so molten-salt growth method synthetic iron mica has controlled pattern.By changing the kind and the consumption of used salt, reaction times and temperature of reaction, thereby prepare the controlled iron mica of size and colour-change, its median size variation range is 20-200mm, and the colour-change scope is that canescence, red-brown, red-purple are to black purple.
In addition, molten-salt growth method also can help the removing of impurity in reaction process and cleaning process subsequently, and sodium sulfate and vitriolate of tartar, sodium-chlor and Repone K are all soluble in water.The high-purity reaction product of final formation.
In sum, the inventive method has that cost is low, simple to operate, complete process, nontoxic, controllable color, chemical stability height, purity height, well-crystallized, thermotolerance is high and easily realize industrialized advantage.
Institute of the present invention synthetic iron mica is square, rectangle or irregular laminar crystal, and main component is α
_Fe
2O
3The change of size scope is 20-200 μ m, colour-change from canescence, red-brown, red-purple to black purple, purity is (mass percent) more than 98%, even particle size distribution, light sense and stereoscopic sensation are strong, face reflectivity height, enough physical strengths are arranged, characteristics such as fabulous sticking power, opacifying power, tinting strength, shielding, fast light, heat-resisting, weathering resistance are arranged.
With iron mica of the present invention is base material, the pearl effect dyestuff of making, can be widely used in makeup, printing-ink, parasol, leather, food product pack and outdoor architecture finishing material finish paint, and large-scale steel framed structure rust-inhibiting paint, the tinting material of rubber, plastics, asbestos and leatheroid product and weighting agent or the like.
Description of drawings
Fig. 1 prepares the method flow diagram of iron mica for molten-salt growth method.
Fig. 2 is among the present invention, is the iron mica of fusing assistant preparation with vitriol.
Fig. 3 is among the present invention, is the iron mica of fusing assistant preparation with the muriate.
Embodiment
Below be several specific embodiment of the present invention, further specify the present invention, but the present invention be not limited only to this.
Embodiment 1
With 10g source of iron ferrous ammonium sulphate (FeSO
4(NH
4)
2SO
46H
2O), 8.80gNa
2SO
4, 2.53gK
2SO
4Mix grinding, in the corundum crucible of packing into, reaction mixture is put into the reaction smelting furnace, temperature controller is by the speed temperature programming of 5 ℃/min, and temperature reaches 800 ℃, constant temperature 30min, thermal pretreatment; Continue intensification and reach 950 ℃ of insulations 6 hours, back programmed cooling.After being cooled to room temperature, product is transferred in the beaker, adds the 90ml deionized water, in the water-bath about 90 ℃, stir fully washing, the agglomerating fusing assistant is dissolved in the water, use a large amount of washed with de-ionized water behind the suction filtration again, to remove residual ion.With the filter cake dry about 1h in 100 ℃ loft drier that obtains.Dried filter cake texture is loose, finally obtains the sheet mica iron oxide product.Thick 1 ~ the 20mm of gained iron mica grain, median size is 110 μ m.The iron mica product colour is red-purple to canescence, and metalluster is stronger, detects irregular thin slice (as shown in Figure 2) with the microphotograph method.
Embodiment 2
With 7g source of iron ferrous sulfate FeSO
47H
2O, 2.24gNaCl, 2.85gKCl mix grinding, in the porcelain crucible of packing into, reaction mixture are put into the reaction smelting furnace, and temperature controller is by the speed temperature programming of 5 ℃/min, and temperature reaches 800 ℃, constant temperature 30min, thermal pretreatment; Continue intensification and reach 900 ℃ of insulations 6 hours, back programmed cooling.After being cooled to room temperature, product is the splash shape, covers all internal surfaces of crucible.Product is transferred in the beaker, adds the 90ml deionized water, in the water-bath about 90 ℃, stir fully washing, the agglomerating fusing assistant is dissolved in the water, use a large amount of washed with de-ionized water behind the suction filtration again, to remove residual ion.With the filter cake dry about 1h in 100 ℃ loft drier that obtains.Dried filter cake texture is loose, finally obtains the sheet mica iron oxide product.Thick 1 ~ the 20mm of gained iron mica grain, median size is 60 μ m.The iron mica product colour takes on a red color or red-brown, and metalluster is stronger, detects irregular thin slice with the microphotograph method, and a small amount of reunion (as shown in Figure 3) is arranged.
Embodiment 3
With 7g source of iron ferrous sulfate (FeSO
47H
2O), 8.80gNa
2SO
4, 2.53gK
2SO
4Mix grinding, in the corundum crucible of packing into, reaction mixture is put into the reaction smelting furnace, temperature controller is by the speed temperature programming of 5 ℃/min, and temperature reaches 800 ℃, constant temperature 30min, thermal pretreatment; Continue intensification and reach 950 ℃ of insulations 6 hours, back programmed cooling.After being cooled to room temperature, product is transferred in the beaker, adds the 90ml deionized water, in the water-bath about 90 ℃, stir fully washing, the agglomerating fusing assistant is dissolved in the water, use a large amount of washed with de-ionized water behind the suction filtration again, to remove residual ion.With the filter cake dry about 1h in 100 ℃ loft drier that obtains.Dried filter cake texture is loose, finally obtains the sheet mica iron oxide product.Thick 1 ~ the 20mm of gained iron mica grain, median size is 110 μ m.The iron mica product colour is red-brown, red-purple to atropurpureus, and metalluster is stronger, detects square or irregular thin slice with the microphotograph method.
Claims (6)
1. method that adopts molten-salt growth method to prepare iron mica, it is characterized in that with ferrous ammonium sulphate or ferrous sulfate or both mixtures be source of iron, with vitriol or muriate or both mixtures is fusing assistant, fusion after mixing and iron mica, the main component of described iron mica is a-Fe
2O
3
2. a kind of method that adopts molten-salt growth method to prepare iron mica according to claim 1, it is characterized in that: described vitriol is sodium sulfate or vitriolate of tartar or both mixtures, described muriate is sodium-chlor or Repone K or both mixtures, and described fusing assistant consumption with the ratio of the amount of substance of source of iron consumption is: 1 ~ 3:1.
3. a kind of method that adopts molten-salt growth method to prepare iron mica according to claim 2 is characterized in that: described vitriol is the mixture of sodium sulfate and vitriolate of tartar, and the ratio of its amount of substance is 4:1.
4. a kind of method that adopts molten-salt growth method to prepare iron mica according to claim 2 is characterized in that: described muriate is the mixture of sodium-chlor and Repone K, and the ratio of its amount of substance is 1:1.
5. according to claim 1,2, a kind of method that adopts molten-salt growth method to prepare iron mica described in 3 or 4, it is characterized in that: take by weighing ferrous ammonium sulphate or ferrous sulfate, vitriol or muriate, thorough mixing, and put into the mortar grinding to 20 ~ 700 μ m, then mixture is packed in corundum crucible or the porcelain crucible, crucible is put into the reaction smelting furnace, heat up by the speed of 5 ℃/min, reach 800 ± 5 ℃ and be incubated 30 ~ 40min, follow-uply continuously be warming up to 900-1200 ℃, and maintenance temperature 5 ~ 7h, programmed cooling (5 ℃/10min), treat that sample is cooled to room temperature after, the water that adds 85 ~ 95 ℃ stirs, the water that adds and the mass ratio of sample are 50:1, the agglomerating fusing assistant is dissolved in the water, uses a large amount of washed with de-ionized water behind the suction filtration, to clarification of water, to remove residual ion, the filter cake drying in 100 ℃ loft drier that obtains is made iron mica.
6. according to claim 1,2,3,4 or 5 described a kind of methods that adopt molten-salt growth method to prepare iron mica is characterized in that: prepared iron mica is rectangle, square or irregular laminar, and particle diameter is 20-200 μ m, and purity is greater than 98wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010136709 CN101792186A (en) | 2010-03-31 | 2010-03-31 | Method for preparing micaceous iron oxide by molten salt growth method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010136709 CN101792186A (en) | 2010-03-31 | 2010-03-31 | Method for preparing micaceous iron oxide by molten salt growth method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101792186A true CN101792186A (en) | 2010-08-04 |
Family
ID=42585144
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010136709 Pending CN101792186A (en) | 2010-03-31 | 2010-03-31 | Method for preparing micaceous iron oxide by molten salt growth method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101792186A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445426A (en) * | 2014-11-28 | 2015-03-25 | 衡阳市金化科技有限公司 | Method for producing iron oxide yellow and iron oxide red by brine and ferrous sulphate solution obtained by production of titanium dioxide |
| CN106865623A (en) * | 2017-04-06 | 2017-06-20 | 东北大学 | One kind prepares γ Fe using iron oxide phosphorus2O3The method of powder |
| CN110446687A (en) * | 2017-06-30 | 2019-11-12 | 株式会社Lg化学 | For producing the method for nickel oxide nano particle and using the nickel oxide nano particle of its production |
| CN112897592A (en) * | 2021-01-25 | 2021-06-04 | 中国科学院广州地球化学研究所 | Micro-nano iron oxide mineral color developing agent and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4624845A (en) * | 1983-02-24 | 1986-11-25 | Laundon Roy D | Process for preparing an iron oxide |
| CN1318518C (en) * | 2005-05-27 | 2007-05-30 | 华南理工大学 | Process for preparing iron oxide red by using sulfuric acid crystal seed mixed acid method and products thereby |
-
2010
- 2010-03-31 CN CN 201010136709 patent/CN101792186A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4624845A (en) * | 1983-02-24 | 1986-11-25 | Laundon Roy D | Process for preparing an iron oxide |
| CN1318518C (en) * | 2005-05-27 | 2007-05-30 | 华南理工大学 | Process for preparing iron oxide red by using sulfuric acid crystal seed mixed acid method and products thereby |
Non-Patent Citations (3)
| Title |
|---|
| 《中国优秀博硕士学位论文全文数据库（硕士） 工程科技I辑 》 20060515 王晓霞 熔盐法合成片状氧化铁粉体的研究 摘要，第21，22，28，32，42页 1-6 , 第5期 2 * |
| 《化工新型材料》 20040731 邓三毛等 片状氧化物粉体的合成与性能 7，13-15 1-6 第32卷, 第7期 2 * |
| 《涂料工业》 20090831 袁晰等 珠光颜料用片状氧化铁的助熔剂法合成研究 第34-37页 1-6 第39卷, 第8期 2 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445426A (en) * | 2014-11-28 | 2015-03-25 | 衡阳市金化科技有限公司 | Method for producing iron oxide yellow and iron oxide red by brine and ferrous sulphate solution obtained by production of titanium dioxide |
| CN106865623A (en) * | 2017-04-06 | 2017-06-20 | 东北大学 | One kind prepares γ Fe using iron oxide phosphorus2O3The method of powder |
| CN106865623B (en) * | 2017-04-06 | 2018-04-10 | 东北大学 | One kind prepares γ Fe using scale oxide2O3The method of powder |
| CN110446687A (en) * | 2017-06-30 | 2019-11-12 | 株式会社Lg化学 | For producing the method for nickel oxide nano particle and using the nickel oxide nano particle of its production |
| CN110446687B (en) * | 2017-06-30 | 2022-04-05 | 株式会社Lg化学 | Method for producing nickel oxide nanoparticles and nickel oxide nanoparticles produced using the same |
| CN112897592A (en) * | 2021-01-25 | 2021-06-04 | 中国科学院广州地球化学研究所 | Micro-nano iron oxide mineral color developing agent and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101786902B (en) | Preparation method for zirconium silicate wrapped cadmium sulfide selenide scarlet pigment | |
| CN101148779B (en) | Preparation method for potassium titanate crystal whisker | |
| CN109054452A (en) | Copper-chromium black pigment and preparation method thereof | |
| CN107055609B (en) | A kind of preparation method of ultra-pure 3Y yttrium stable zirconium oxides | |
| CN101792186A (en) | Method for preparing micaceous iron oxide by molten salt growth method | |
| CN107342408A (en) | Improve spherical doping Co3O4The method of yield and application | |
| CN103862038A (en) | Extra-coarse hard alloy parcel powder and preparation method thereof | |
| CN109728262A (en) | Anode material for lithium-ion batteries and its preparation method and application | |
| CN109678193A (en) | A kind of preparation method of ceria nanoparticles | |
| CN107150127A (en) | The preparation method of spherical cobalt powder | |
| CN109370264A (en) | Mechanical force and chemical prepares high-performance iron oxide red/clay mineral hybrid pigment method | |
| CN106745260A (en) | A kind of method that utilization molten-salt growth method prepares copper-chrome black | |
| CN107601561B (en) | The preparation method of nanometer pucherite yellow uitramarine | |
| CN106745303B (en) | A kind of three-dimensional flower ball-shaped cadmium ferrite bismuth meal body and preparation method thereof | |
| CN103880410B (en) | Method of synthesizing ZnO-Cr2O3-Fe2O3-series humidity-sensitive ceramic sintered powder by molten-salt growth method | |
| CN104843787A (en) | Preparation method of cubic lanthanum zirconate nanometer monocrystal | |
| CN102659392A (en) | Preparation method of calcined alumina powder for black ceramics | |
| CN101913657A (en) | Preparation method of flake ferric oxide | |
| CN108102433B (en) | Method for preparing high-thermal stability clay mineral-iron red hybrid pigment by utilizing coprecipitation technology | |
| CN114436332A (en) | Hydroxyl chromic oxide with bottom-center orthogonal structure and preparation method of chromic oxide | |
| CN108529672A (en) | Chemical coprecipitation produces yttrium stable zirconium oxide spherical powder production technology used for hot spraying | |
| CN110697776A (en) | Preparation method of spherical nano chromium sesquioxide | |
| CN105623316A (en) | Iron-red-series low-gloss lamellar pigment and preparation method thereof | |
| CN103613958B (en) | Environment-friendly titanium pigment prepared by using complexation-precipitation process | |
| CN108640158A (en) | A kind of preparation method of high-purity hexagonal sheet-like barium ferrite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Open date: 20100804 |