CN106745260A - A kind of method that utilization molten-salt growth method prepares copper-chrome black - Google Patents
A kind of method that utilization molten-salt growth method prepares copper-chrome black Download PDFInfo
- Publication number
- CN106745260A CN106745260A CN201611096064.1A CN201611096064A CN106745260A CN 106745260 A CN106745260 A CN 106745260A CN 201611096064 A CN201611096064 A CN 201611096064A CN 106745260 A CN106745260 A CN 106745260A
- Authority
- CN
- China
- Prior art keywords
- ball milling
- copper
- chrome black
- salt
- molten
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/14—Chromates; Bichromates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Abstract
A kind of method that utilization molten-salt growth method prepares copper-chrome black, belong to chemical materials preparation field, using molten-salt growth method synthetic spinel type copper-chrome black, with cupric oxide and chrome green as reaction raw materials, sodium chloride, potassium chloride are fused-salt medium, raw material is uniformly mixed with fused salt by high-energy ball milling, then has successfully prepared that particle diameter distribution is uniform, the perfect copper-chrome black spinel type pigment particle of crystal morphology through high-temperature calcination.Copper-chrome black properties of product prepared by molten-salt growth method are excellent, and its index of correlation is close with the performance indications of SA sol-gal process products made therebies, and is superior to commercially available prod.
Description
Technical field
The side of copper-chrome black is prepared the invention belongs to chemical materials preparation field, more particularly to a kind of utilization molten-salt growth method
Method.
Background technology
Molten-salt growth method is a kind of new powder synthesis process.It can occur at a lower temperature using some inorganic salts
The characteristics of melting, molten salt system is set up in lower temperature environments, raw material components more fast diffusion in this system is promoted with this
With react, formed target product.Because in molten salt system, raw material components exist with ionic condition, and reaction environment is in
Existing liquid so that the mobility of reactant is significantly increased, and surface-active and diffusion rate increase, so as to accelerate reaction speed
Degree so that target product can just be produced out under relatively low synthesis temperature.Therefore, compare with traditional solid phase method, melt
Salt method can substantially reduce synthesis temperature, shorten the reaction time.Using molten-salt growth method, can join by molten salt system and calcine technology
Several adjustment, better controls over the particle size and microscopic appearance of powder, improves the application performance of its material.Additionally, to synthesis
Product is cleaned, and after removal fused salt, just obtains the target powder of high-purity, and the salt isolated then can be reclaimed further, with
Recycle.In a word, molten-salt growth method greatlys save consumption reduction in terms of powder body material is prepared, and reduces production cost, and can be from
Pollution is eliminated in beginning of production, is conducive to the cleanly production of product.
The content of the invention
Present invention seek to address that above mentioned problem, there is provided a kind of method that utilization molten-salt growth method prepares copper-chrome black.
The technical scheme is that：
A kind of method that utilization molten-salt growth method prepares copper-chrome black, comprises the following steps：
(1) stoichiometrically n (Cu): n(Cr) = 1 :2 weigh a certain amount of cupric oxide and chrome green, tentatively
Being put in after mixing in QM-3SP2 type planetary ball mills carries out high speed ball milling, and selects absolute ethyl alcohol as ball milling solvent；
(2) oxide after ball milling is put in baking oven and is dried 1 hour at 80 DEG C, be then reentered into ball grinder, and by n
( KCl ) : n( NaCl ) : n( CuO ) : n( Cr2O3 )= 1:1:1:1 adds fused-salt medium, is made with absolute ethyl alcohol
It is solvent, ball milling is carried out again；
(3) mixture is put into air dry oven after wet-milling, and 2 h are dried at 100 DEG C；Crucible is transferred to after drying, is put
It is placed in Muffle furnace, is calcined in the range of 500 ~ 1000 DEG C, insulation a period of time, cools to room temperature with the furnace；
(4) powder after calcining is poured into the beaker for filling deionized water, and in the heating of digital display constant temperature blender with magnetic force, simultaneously magnetic force is stirred
A period of time is mixed, decompression suction filtration is then carried out while hot, repeatedly washing, suction filtration, until filtrate added drop-wise silver nitrate solution is no longer produced
White precipitate, stops suction filtration；
(5) filter cake dries 2h at 120 DEG C, and dry ball milling is then carried out again, obtains final product copper-chrome black product.
The method that utilization molten-salt growth method of the present invention prepares copper-chrome black, step（1）The related ball milling parameter is：
M (agate grinds pearl): m( CuO + Cr2O3 ) = 2 :1, m (absolute ethyl alcohol): m( CuO + Cr2O3 ) = 0.4 :
1, ball milling method is positive and negative alternate operation, and its alternate cycle is 30 min/ time, and ball milling total time is 6 h.
The method that utilization molten-salt growth method of the present invention prepares copper-chrome black, step（2）The milling parameters are：
M (agate grinds pearl):M (mixture)=2:1, m (absolute ethyl alcohol):M (mixture)=0.4:1, ball milling method is still
Selection positive and negative alternate operation, its cycle is 30min/ times, and Ball-milling Time is 4 h.
The technical effects of the invention are that：
The method that utilization molten-salt growth method of the present invention prepares copper-chrome black, using molten-salt growth method synthetic spinel type copper-chrome black face
Material.With cupric oxide and chrome green as reaction raw materials, sodium chloride, potassium chloride are fused-salt medium, by high-energy ball milling by raw material
Uniformly mix with fused salt, then successfully prepared that particle diameter distribution is uniform, the perfect copper-chrome black point of crystal morphology is brilliant through high-temperature calcination
Stone-type pigment particles.Copper-chrome black properties of product prepared by molten-salt growth method are excellent, its index of correlation and SA sol-gal processes institute
The performance indications of product processed are close, and are superior to commercially available prod.
Specific embodiment
Embodiment 1
A kind of method that utilization molten-salt growth method prepares copper-chrome black, comprises the following steps：
(1) stoichiometrically n (Cu): n(Cr) = 1 :2 weigh a certain amount of cupric oxide and chrome green, tentatively
Being put in after mixing in QM-3SP2 type planetary ball mills carries out high speed ball milling, and selects absolute ethyl alcohol as ball milling solvent；
(2) oxide after ball milling is put in baking oven and is dried 1 hour at 80 DEG C, be then reentered into ball grinder, and by n
( KCl ) : n( NaCl ) : n( CuO ) : n( Cr2O3 )= 1:1:1:1 adds fused-salt medium, is made with absolute ethyl alcohol
It is solvent, ball milling is carried out again；
(3) mixture is put into air dry oven after wet-milling, and 2 h are dried at 100 DEG C；Crucible is transferred to after drying, is put
It is placed in Muffle furnace, is calcined at 500 DEG C, insulation a period of time, cools to room temperature with the furnace；
(4) powder after calcining is poured into the beaker for filling deionized water, and in the heating of digital display constant temperature blender with magnetic force, simultaneously magnetic force is stirred
A period of time is mixed, decompression suction filtration is then carried out while hot, repeatedly washing, suction filtration, until filtrate added drop-wise silver nitrate solution is no longer produced
White precipitate, stops suction filtration；
(5) filter cake dries 2h at 120 DEG C, and dry ball milling is then carried out again, obtains final product copper-chrome black product.
The method that utilization molten-salt growth method of the present invention prepares copper-chrome black, step（1）The related ball milling parameter is：
M (agate grinds pearl): m( CuO + Cr2O3 ) = 2 :1, m (absolute ethyl alcohol): m( CuO + Cr2O3 ) = 0.4 :
1, ball milling method is positive and negative alternate operation, and its alternate cycle is 30 min/ time, and ball milling total time is 6 h.
The method that utilization molten-salt growth method of the present invention prepares copper-chrome black, step（2）The milling parameters are：
M (agate grinds pearl):M (mixture)=2:1, m (absolute ethyl alcohol):M (mixture)=0.4:1, ball milling method is still
Selection positive and negative alternate operation, its cycle is 30min/ times, and Ball-milling Time is 4 h.
Oxide and molten chloride start to absorb heat, when temperature reaches the eutectic point 650 of sodium chloride and potassium chloride
DEG C when, chloride starts liquefaction, absorbs substantial amounts of heat, and at the same time oxide is dissolved in fused salt, mutual diverging flow, connects
Touch, and start to react, both common heat-absorbing actions, now spinel type crystal is slowly formed, and 800 DEG C are increased to temperature,
Substantially completely, hereafter two curves of DTA and TG tend to gentle to the brilliant reaction of this turn, substantially massless, thermal loss.
As calcining heat is constantly raised, the characteristic diffraction peak intensity continuous enhancing of copper chromite, when calcining heat reaches
At 850 DEG C, the principal character diffraction maximum of copper-chrome black occurs completely, and crystal development is complete, can be crystallized at a temperature of this
Perfect pure spinel-type CuCr2O4, 2 θ values corresponding to its each diffraction maximum are and CuCr2O4The data of standard PDF cards are complete
It is complete to coincide, illustrate that synthesized powder is pure spinel-type CuCr2O4.Hereafter when calcining heat is increased to 950 DEG C, diffraction maximum
Intensity is further enhanced, crystalline form gets over perfection.
When calcination temperature is 550 DEG C, its main component is cupric oxide and chrome green, copper-chrome black does not occur
Spinel type crystal.When calcining heat reaches 650 DEG C, positive spinel type copper-chrome black crystal is now indistinctly can see, but still have
The oxide of substantial amounts of copper and chromium mixes therebetween.It can be seen that a large amount of spinel-types from 750 DEG C of SEM photographs of calcination product
Crystal, until 850 DEG C of oxide total overall reaction generation spinel-type CuCr2O4Crystal, powder particle is tiny, and dispersiveness is good
It is good, almost there is not agglomeration.Hereafter, as the continuation of temperature increases, the particle diameter of pigment particles becomes big and skewness
It is even, cause agglomeration to produce because of high temperature sintering.
When temperature is increased to 950 DEG C from 750 DEG C, the dispersiveness of copper-chrome black sample is deteriorated, and the distribution of particles of particle is gradually
Moved to the scope of greater particle size, and 850 DEG C of D50 of sample are also substantially than 750 DEG C and 950 DEG C of samples are good, experiment table
When bright calcining heat is 850 DEG C, the particle diameter distribution of its copper-chrome black sample is relatively best.Main cause is in 750 DEG C of calcinings, still
There is minimal amount of copper-chrome black crystal formation not develop completely, occur that lattice is damaged, missing, cause particle diameter distribution uneven.
Using molten-salt growth method synthetic powder material, fused-salt medium forms liquid phase after being melted down, and crystal grain is just in this liquid phase ring
Grown in border, therefore the consumption of fused salt influences the pattern and particle diameter of synthetic powder particle to a certain extent.In general
When the mol ratio of fused salt and reaction raw materials increases, i.e., the consumption of fused salt increases, and reactive ion can be made to divide in reaction system
Dissipate uniform, so that for the growth of crystal provides relatively wide space.
Different fused salt consumptions is incubated the copper-chrome black that 3 h generate single spinel crystal phase at 850 DEG C；With fused salt
The increase of amount, diffraction peak intensity gradually increases, and crystal development is more complete.Because when fused salt consumption is relatively low, although reach
Liquid phase environment is formd at the eutectic point of sodium chloride and potassium chloride, but because the amount of liquid phase is relatively low, it is difficult to make particle in this liquid
Fully spread in phase system, particle can only carry out the movement of relatively short distance mostly, it is interparticle to be fully contacted more difficult, cause nothing
Method forms bulky grain crystal.When the consumption of fused salt increases, liquid phase relative will increase during melting, in the liquid phase environment, grain
Son can carry out remote travel motion, contact with each other frequently, and bulky grain merges short grained probability and increases therewith, so that just
In the formation of larger particles.When the mol ratio of fused salt and reaction raw materials is 1.5:When 1.Result above shows, the increasing of fused salt consumption
Added with the development beneficial to crystal, when the amount ratio of fused salt and raw material is 1.5:When 1, product has been crystallized completely, and crystal grain is fully sent out
Educate；But when fused salt consumption is excessive, the powder after calcining needs to carry out the washing of long period, suction filtration treatment, easily causes
The fused salt ion residues of amount are in powder.The above analysis, determines that fused salt is with the suitable mol ratio of the amount of raw material
1.5:1。
850 DEG C be incubated 2h after, the spinel-type copper-chrome black for being generated with octahedron be its main pattern, relatively
The copper-chrome black spinelle quantity of irregular spherical morphology is more, and octahedral shape grain diameter be all higher than it is irregular spherical
Grain diameter；When holding time to 3h, the copper-chrome black spinel-type amounts of particles of irregular spherical morphology is substantially reduced, and
The spinelle quantity of shape of octahedron is relative to be increased, and particle diameter increase, crystal morphology is more perfect.Hereafter, holding time is worked as
It is 4h and 5h, the octahedra spinelle pattern of copper-chrome black is more regular, and particle further increases.It can be seen that, when the timing of calcining heat one,
Increasing soaking time can effectively improve the crystallinity of spinel crystal；But extension soaking time, energy consumption increases.
Embodiment 2
A kind of method that utilization molten-salt growth method prepares copper-chrome black, comprises the following steps：
(1) stoichiometrically n (Cu): n(Cr) = 1 :2 weigh a certain amount of cupric oxide and chrome green, tentatively
Being put in after mixing in QM-3SP2 type planetary ball mills carries out high speed ball milling, and selects absolute ethyl alcohol as ball milling solvent；
(2) oxide after ball milling is put in baking oven and is dried 1 hour at 80 DEG C, be then reentered into ball grinder, and by n
( KCl ) : n( NaCl ) : n( CuO ) : n( Cr2O3 )= 1:1:1:1 adds fused-salt medium, is made with absolute ethyl alcohol
It is solvent, ball milling is carried out again；
(3) mixture is put into air dry oven after wet-milling, and 2 h are dried at 100 DEG C；Crucible is transferred to after drying, is put
It is placed in Muffle furnace, is calcined in the range of 850 DEG C, insulation a period of time, cools to room temperature with the furnace；
(4) powder after calcining is poured into the beaker for filling deionized water, and in the heating of digital display constant temperature blender with magnetic force, simultaneously magnetic force is stirred
A period of time is mixed, decompression suction filtration is then carried out while hot, repeatedly washing, suction filtration, until filtrate added drop-wise silver nitrate solution is no longer produced
White precipitate, stops suction filtration；
(5) filter cake dries 2h at 120 DEG C, and dry ball milling is then carried out again, obtains final product copper-chrome black product.
The method that utilization molten-salt growth method of the present invention prepares copper-chrome black, step（1）The related ball milling parameter is：
M (agate grinds pearl): m( CuO + Cr2O3 ) = 2 :1, m (absolute ethyl alcohol): m( CuO + Cr2O3 ) = 0.4 :
1, ball milling method is positive and negative alternate operation, and its alternate cycle is 30 min/ time, and ball milling total time is 6 h.
The method that utilization molten-salt growth method of the present invention prepares copper-chrome black, step（2）The milling parameters are：
M (agate grinds pearl):M (mixture)=2:1, m (absolute ethyl alcohol):M (mixture)=0.4:1, ball milling method is still
Selection positive and negative alternate operation, its cycle is 30min/ times, and Ball-milling Time is 4 h
When temperature is increased to 950 DEG C from 750 DEG C, the dispersiveness variation of copper-chrome black sample, the distribution of particles of particle gradually to compared with
The scope movement of big particle diameter, and 850 DEG C of D50 of sample test and show to forge also substantially than 750 DEG C and 950 DEG C of samples are good
When burning temperature is 850 DEG C, the particle diameter distribution of its copper-chrome black sample is relatively best.Main cause is that, in 750 DEG C of calcinings, still there is pole
A small amount of copper-chrome black crystal formation is not developed completely, occurs that lattice is damaged, missing, causes particle diameter distribution uneven.When calcining heat is
850 DEG C, spinelle crystal formation is developed completely, crystal is full, therefore grain diameter size is relatively close to, and is evenly distributed.Further rise
High-temperature, copper-chrome black crystal causes agglomeration largely to occur because of high temperature sintering, and the particle of greater particle size starts appearance, particle diameter
Skewness.The above analysis, it is determined that suitable calcining heat is 850 DEG C.
The average grain diameter of product prepared by molten-salt growth method is more than product prepared by stearic acid gel method, but molten-salt growth method is made
Standby copper-chrome black product regular crystal forms, defect are few, thus, it is still relatively low that it absorbs oil mass.Extremely low hydrotrope amount and volatilization
Thing amount shows that product component is difficult volatilization, insoluble CuCr2O4Spinel crystal, purity are high, and reaction raw materials conversion is very complete
Entirely；Resistance to elevated temperatures then shows that the lattice of product keeps stabilization under high-temperature, further illustrates regular crystal forms of product, complete
It is beautiful.
Claims (3)
1. a kind of method that utilization molten-salt growth method prepares copper-chrome black, it is characterised in that comprise the following steps：
(1) stoichiometrically n (Cu): n(Cr) = 1 :2 weigh a certain amount of cupric oxide and chrome green, tentatively
Being put in after mixing in QM-3SP2 type planetary ball mills carries out high speed ball milling, and selects absolute ethyl alcohol as ball milling solvent；
(2) oxide after ball milling is put in baking oven and is dried 1 hour at 80 DEG C, be then reentered into ball grinder, and by n
( KCl ) : n( NaCl ) : n( CuO ) : n( Cr2O3)= 1:1:1:1 adds fused-salt medium, is made with absolute ethyl alcohol
It is solvent, ball milling is carried out again；
(3) mixture is put into air dry oven after wet-milling, and 2 h are dried at 100 DEG C；Crucible is transferred to after drying, is put
It is placed in Muffle furnace, is calcined in the range of 500 ~ 1000 DEG C, insulation a period of time, cools to room temperature with the furnace；
(4) powder after calcining is poured into the beaker for filling deionized water, and in the heating of digital display constant temperature blender with magnetic force, simultaneously magnetic force is stirred
A period of time is mixed, decompression suction filtration is then carried out while hot, repeatedly washing, suction filtration, until filtrate added drop-wise silver nitrate solution is no longer produced
White precipitate, stops suction filtration；
(5) filter cake dries 2h at 120 DEG C, and dry ball milling is then carried out again, obtains final product copper-chrome black product.
2. the method that utilization molten-salt growth method according to claim 1 prepares copper-chrome black, it is characterised in that：Step（1）Institute
Stating related ball milling parameter is：M (agate grinds pearl): m( CuO + Cr2O3) = 2 :1, m (absolute ethyl alcohol): m( CuO +
Cr2O3) = 0.4 :1, ball milling method is positive and negative alternate operation, and its alternate cycle is 30 min/ time, and ball milling total time is 6
h。
3. the method that utilization molten-salt growth method according to claim 1 prepares copper-chrome black, it is characterised in that：Step（2）Institute
Stating milling parameters is：M (agate grinds pearl):M (mixture)=2:1, m (absolute ethyl alcohol):M (mixture)=
0.4 :1, ball milling method still selects positive and negative alternate to run, and its cycle is 30min/ times, and Ball-milling Time is 4 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611096064.1A CN106745260A (en) | 2016-12-02 | 2016-12-02 | A kind of method that utilization molten-salt growth method prepares copper-chrome black |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611096064.1A CN106745260A (en) | 2016-12-02 | 2016-12-02 | A kind of method that utilization molten-salt growth method prepares copper-chrome black |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106745260A true CN106745260A (en) | 2017-05-31 |
Family
ID=58883687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611096064.1A Pending CN106745260A (en) | 2016-12-02 | 2016-12-02 | A kind of method that utilization molten-salt growth method prepares copper-chrome black |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106745260A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108059187A (en) * | 2017-12-29 | 2018-05-22 | 华南协同创新研究院 | Copper-chrome black and preparation method and application is precipitated in a kind of low Cr VI |
| CN108102427A (en) * | 2017-12-29 | 2018-06-01 | 华南协同创新研究院 | A kind of sub-micron ceramic pigment color containing cobalt black and its preparation method and application |
| CN112340777A (en) * | 2020-10-30 | 2021-02-09 | 中科立民新材料（扬州）有限公司 | Method for synthesizing pure lanthanum chromate at low temperature, lanthanum chromate synthesized by method and application of lanthanum chromate |
| CN113860368A (en) * | 2020-11-17 | 2021-12-31 | 中国科学院青海盐湖研究所 | Copper-chromium black, low-temperature preparation method and application thereof |
| CN113943017A (en) * | 2020-07-16 | 2022-01-18 | 中国石油天然气股份有限公司 | Treatment method of copper-chromium black raw material and copper-chromium black |
-
2016
- 2016-12-02 CN CN201611096064.1A patent/CN106745260A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108059187A (en) * | 2017-12-29 | 2018-05-22 | 华南协同创新研究院 | Copper-chrome black and preparation method and application is precipitated in a kind of low Cr VI |
| CN108102427A (en) * | 2017-12-29 | 2018-06-01 | 华南协同创新研究院 | A kind of sub-micron ceramic pigment color containing cobalt black and its preparation method and application |
| CN108059187B (en) * | 2017-12-29 | 2020-03-24 | 华南协同创新研究院 | Low hexavalent chromium separated copper-chromium black pigment and preparation method and application thereof |
| CN108102427B (en) * | 2017-12-29 | 2020-10-09 | 华南协同创新研究院 | Submicron cobalt-containing black ceramic pigment and preparation method and application thereof |
| CN113943017A (en) * | 2020-07-16 | 2022-01-18 | 中国石油天然气股份有限公司 | Treatment method of copper-chromium black raw material and copper-chromium black |
| CN113943017B (en) * | 2020-07-16 | 2023-12-26 | 中国石油天然气股份有限公司 | Copper-chromium black raw material treatment method and copper-chromium black |
| CN112340777A (en) * | 2020-10-30 | 2021-02-09 | 中科立民新材料（扬州）有限公司 | Method for synthesizing pure lanthanum chromate at low temperature, lanthanum chromate synthesized by method and application of lanthanum chromate |
| CN113860368A (en) * | 2020-11-17 | 2021-12-31 | 中国科学院青海盐湖研究所 | Copper-chromium black, low-temperature preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106745260A (en) | A kind of method that utilization molten-salt growth method prepares copper-chrome black | |
| CN101913659B (en) | Battery-grade cobaltosic oxide preparation method | |
| CN102627454B (en) | Preparation method for indium tin oxide (ITO) powder and preparation method for ITO sintering body | |
| CN110818430B (en) | Uniform high-entropy oxide ceramic submicron spherical powder and preparation method thereof | |
| CN111217402A (en) | Hexahydric spinel type iron-cobalt-chromium-manganese-copper-zinc series high-entropy oxide and powder preparation method thereof | |
| CN111233454A (en) | Preparation method of spinel type iron-cobalt-chromium-manganese-magnesium series high-entropy oxide powder | |
| CN101880160A (en) | Method for preparing CaCu3Ti4O12 powder | |
| CN109261980A (en) | A kind of preparation method of heavy alloy tungsten powder | |
| CN108503224A (en) | It is a kind of using gangue and rice hull ash as devitrified glass of primary raw material and preparation method thereof | |
| CN1042377C (en) | Method for synthetizing positive electrode material in lithium ion battery | |
| CN111470859A (en) | Hexahydric spinel type iron-cobalt-chromium-manganese-magnesium-zinc series high-entropy oxide and powder preparation method thereof | |
| CN112430090A (en) | Method for preparing lanthanum lithium zirconate solid electrolyte by coprecipitation method | |
| CN113830829A (en) | Flaky bismuth titanate strontium barium template crystal grain and preparation method thereof | |
| CN113800480A (en) | N-type bismuth telluride-based thermoelectric material and preparation method and application thereof | |
| CN111233456A (en) | Hexahydric spinel type Fe-Co-Cr-Mn-Ni-Zn series high-entropy oxide and powder preparation method thereof | |
| CN111348910A (en) | Hexahydric spinel type iron-cobalt-chromium-manganese-nickel-copper series high-entropy oxide and powder preparation method thereof | |
| CN114715925A (en) | Flaky alpha alumina and preparation method thereof | |
| CN113889563A (en) | P-type bismuth telluride-based thermoelectric material and preparation method and application thereof | |
| CN110183214A (en) | The preparation method of porous hollow bowl-type alumina powder material and aluminium oxide ceramics | |
| CN108529672A (en) | Chemical coprecipitation produces yttrium stable zirconium oxide spherical powder production technology used for hot spraying | |
| CN113603356A (en) | Black pigment with strong absorption to visible light and preparation method thereof | |
| CN106083001A (en) | Nanocrystalline blue ceramic corundum abrasive and preparation method thereof | |
| CN110697776B (en) | Preparation method of spherical nano chromium sesquioxide | |
| CN102432341B (en) | Submicron-nanometer level red ceramic pigment and manufacturing method thereof | |
| CN111146435A (en) | Spherical-like lithium manganate material and preparation method of raw material manganese dioxide thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170531 |
|
| WD01 | Invention patent application deemed withdrawn after publication |