CN103951389B - A kind of preparation method of cobalt base oxide thermoelectric material - Google Patents
A kind of preparation method of cobalt base oxide thermoelectric material Download PDFInfo
- Publication number
- CN103951389B CN103951389B CN201410138341.5A CN201410138341A CN103951389B CN 103951389 B CN103951389 B CN 103951389B CN 201410138341 A CN201410138341 A CN 201410138341A CN 103951389 B CN103951389 B CN 103951389B
- Authority
- CN
- China
- Prior art keywords
- obtains
- temperature
- thermoelectric material
- base oxide
- powder
- 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.)
- Expired - Fee Related
Links
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
A preparation method for cobalt base oxide thermoelectric material, it relates to a kind of preparation method of thermoelectric material.The present invention will solve the low problem of existing cobalt-based thermoelectric material conductivity.Preparation method: with calcium nitrate, cobalt nitrate and citric acid for raw material, in outside magnetic field, complex reaction occurs, carries out self-propagating combustion by the colloid of acquisition, obtains powder presoma, and calcining obtains Ca further
3co
4o
9+ δpowder.Precompressed is carried out by under this powder outside magnetic field, then hot pressing further, finally the block after institute's hot pressing is sintered, obtain cobalt base oxide thermoelectric material.The present invention is for the preparation of cobalt base oxide thermoelectric material.
Description
Technical field
The present invention relates to a kind of preparation method of thermoelectric material.
Background technology
Ca
3co
4o
9+ δbase thermoelectricity material is a kind of natural super crystal lattice material, is suitable for working in 200 DEG C ~ 900 DEG C temperature ranges.It has non-oxidizability, nontoxic, cheap.Just because of these features, Ca
3co
4o
9+ δbase thermoelectricity material has caused extensive attention.Sol-gel and mechanical alloying two kinds of methods are mainly taked to obtain Ca at present
3co
4o
9+ δbase oxide material.And these two kinds of methods all have the appearance of a lot of defect struchures in material synthesis processes, cause conductivity and thermal conductivity to reduce simultaneously, make it apply limited.
Summary of the invention
The present invention will solve the low problem of existing cobalt-based thermoelectric material conductivity, and provides a kind of preparation method of cobalt base oxide thermoelectric material.
The preparation method of a kind of cobalt base oxide thermoelectric material of the present invention carries out according to the following steps:
One, calcium nitrate tetrahydrate, cabaltous nitrate hexahydrate and citric acid is taken as raw material; The mol ratio of described calcium nitrate tetrahydrate, cabaltous nitrate hexahydrate and citric acid is 3:4:21;
Two, the calcium nitrate tetrahydrate that step one takes is dissolved in deionized water, obtains calcium nitrate solution; Cabaltous nitrate hexahydrate step one taken is dissolved in deionized water, obtains cobalt nitrate solution; Citric acid step one taken is dissolved in deionized water, obtains citric acid solution;
Three, calcium nitrate solution step 2 obtained and cobalt nitrate solution mixing in the reactor, are then under the condition of 60 DEG C ~ 80 DEG C in temperature, drip the citric acid solution that step 2 obtains while stirring, obtain mixed solution in reactor;
Four, mixed solution step 3 obtained, under temperature is the condition of 80 DEG C ~ 100 DEG C, is then stirred to mixed solution pulverize red, transparent thick gel in the horizontal direction steady external magnetic field of 1000G ~ 5000G;
Five, red, transparent thick gel step 4 obtained is dry 10h ~ 16h in the baking oven of 180 DEG C ~ 220 DEG C in temperature, obtains xerogel;
Six, be placed on after the xerogel that step 5 obtains being ground to form powder on Electric stove and carry out self-propagating combustion, then the powder after self-propagating combustion is placed in Muffle furnace, be after sintering 4h ~ 8h under the condition of 450 DEG C ~ 600 DEG C in temperature, then be sinter 6h ~ 10h in the air furnace of 850 DEG C in temperature; Obtain Ca
3co
4o
9+ δpowder;
Seven, Ca step 6 obtained
3co
4o
9+ δpowder is precompressed slabbing in the steady external magnetic field of 3000G, then temperature be 200 DEG C ~ 300 DEG C, pressure carries out hot-forming under being the condition of 25MPa ~ 40MPa, obtain Ca
3co
4o
9+ δblock;
Eight, Ca step 7 obtained
3co
4o
9+ δblock is sinter 10h ~ 16h in the air furnace of 850 DEG C in temperature, obtains cobalt base oxide thermoelectric material.
The invention has the beneficial effects as follows:
Defect struchures in cobalt base oxide thermoelectric material prepared by the present invention often has non-sharing electron, in outside magnetic field, impurity, defect are split into two energy levels, the different orientation of corresponding electron spin respectively, as about external magnetic field 0.1T, just there will be electron spin resonance (or electron paramagnetic resonance).Therefore, the present invention intends at sol-gel synthesis Ca
3co
4o
9+ δsill presoma process and powder pre-binder process two step introduce external magnetic field, regulate and control the spin of non-sharing electron, the further orientation of induction spin, make material along c-axis preferred orientation, improve hole mobility, and then increase conductivity, reach the effect changing material morphology and improve thermoelectricity capability, thermoelectricity capability significantly improves.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the cobalt base oxide thermoelectric material that the present invention obtains;
Fig. 2 is X-ray diffractogram; Wherein A represents the X-ray diffractogram of the cobalt base oxide thermoelectric material that the present invention obtains, and B represents the X-ray diffractogram of cobalt base oxide thermoelectric material standard sample;
Fig. 3 is that conductivity varies with temperature curve; Wherein ▲ the conductivity of cobalt base oxide thermoelectric material that obtains for the present invention varies with temperature curve, and the conductivity of the cobalt base oxide thermoelectric material that ■ indicates without external magnetic field induction varies with temperature curve.
Embodiment
Embodiment one: the preparation method of a kind of cobalt base oxide thermoelectric material of present embodiment carries out according to the following steps:
One, calcium nitrate tetrahydrate, cabaltous nitrate hexahydrate and citric acid is taken as raw material; The mol ratio of described calcium nitrate tetrahydrate, cabaltous nitrate hexahydrate and citric acid is 3:4:21;
Two, the calcium nitrate tetrahydrate that step one takes is dissolved in deionized water, obtains calcium nitrate solution; Cabaltous nitrate hexahydrate step one taken is dissolved in deionized water, obtains cobalt nitrate solution; Citric acid step one taken is dissolved in deionized water, obtains citric acid solution;
Three, calcium nitrate solution step 2 obtained and cobalt nitrate solution mixing in the reactor, are then under the condition of 60 DEG C ~ 80 DEG C in temperature, drip the citric acid solution that step 2 obtains while stirring, obtain mixed solution in reactor;
Four, mixed solution step 3 obtained, under temperature is the condition of 80 DEG C ~ 100 DEG C, is then stirred to mixed solution pulverize red, transparent thick gel in the horizontal direction steady external magnetic field of 1000G ~ 5000G;
Five, red, transparent thick gel step 4 obtained is dry 10h ~ 16h in the baking oven of 180 DEG C ~ 220 DEG C in temperature, obtains xerogel;
Six, be placed on after the xerogel that step 5 obtains being ground to form powder on Electric stove and carry out self-propagating combustion, then the powder after self-propagating combustion is placed in Muffle furnace, be after sintering 4h ~ 8h under the condition of 450 DEG C ~ 600 DEG C in temperature, then be sinter 6h ~ 10h in the air furnace of 850 DEG C in temperature; Obtain Ca
3co
4o
9+ δpowder;
Seven, Ca step 6 obtained
3co
4o
9+ δpowder is precompressed slabbing in the steady external magnetic field of 3000G, then temperature be 200 DEG C ~ 300 DEG C, pressure carries out hot-forming under being the condition of 25MPa ~ 40MPa, obtain Ca
3co
4o
9+ δblock;
Eight, Ca step 7 obtained
3co
4o
9+ δblock is sinter 10h ~ 16h in the air furnace of 850 DEG C in temperature, obtains cobalt base oxide thermoelectric material;
Described calcium nitrate tetrahydrate, cabaltous nitrate hexahydrate and citric acid are for analyzing pure rank.
Defect struchures in cobalt base oxide thermoelectric material prepared by present embodiment often has non-sharing electron, in outside magnetic field, impurity, defect are split into two energy levels, the different orientation of corresponding electron spin respectively, as about external magnetic field 0.1T, just there will be electron spin resonance (or electron paramagnetic resonance).Therefore, the present invention intends at sol-gel synthesis Ca
3co
4o
9+ δsill presoma process and powder pre-binder process two step introduce external magnetic field, regulate and control the spin of non-sharing electron, the further orientation of induction spin, make material along c-axis preferred orientation, improve hole mobility, and then increase conductivity, reach the effect changing material morphology and improve thermoelectricity capability, thermoelectricity capability significantly improves.
Embodiment two: present embodiment and embodiment one unlike: step 3, under temperature is the condition of 70 DEG C, drips the citric acid solution that step 2 obtains while stirring in reactor.Other is identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: step 4 is stirred to mixed solution pulverize red, transparent thick gel in the horizontal direction steady external magnetic field of 1500G.Other is identical with embodiment one or two.
Embodiment four: present embodiment and embodiment one to three unlike: step 4 is stirred to mixed solution pulverize red, transparent thick gel in the horizontal direction steady external magnetic field of 2000G.Other is identical with embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: step 4 is stirred to mixed solution pulverize red, transparent thick gel in the horizontal direction steady external magnetic field of 3000G.Other is identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: step 4 is stirred to mixed solution pulverize red, transparent thick gel in the horizontal direction steady external magnetic field of 4000G.Other is identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six unlike: step 5 is dry 12h in the baking oven of 200 DEG C in temperature.Other is identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: after step 7 sinters 6h under temperature is the condition of 500 DEG C, then be sinter 8h in the air furnace of 850 DEG C in temperature; Obtain Ca
3co
4o
9+ δpowder.Setting like this, is in order to further organics removal, corresponds to actual needs.Other is identical with one of embodiment one to seven.
By following verification experimental verification beneficial effect of the present invention:
Test one: a kind of preparation method of cobalt base oxide thermoelectric material carries out according to the following steps:
One, 14.16g calcium nitrate tetrahydrate, 23.28g cabaltous nitrate hexahydrate and 88.2g citric acid is taken by mass fraction;
Two, the calcium nitrate tetrahydrate that step one takes is dissolved in 60mL deionized water, obtains calcium nitrate solution; Cabaltous nitrate hexahydrate step one taken is dissolved in 80mL deionized water, obtains cobalt nitrate solution; Citric acid step one taken is dissolved in 150mL deionized water, obtains citric acid solution;
Three, calcium nitrate solution step 2 obtained and cobalt nitrate solution mixing in the reactor, are then under the condition of 70 DEG C in temperature, drip the citric acid solution that step 2 obtains while stirring, obtain mixed solution in reactor;
Four, mixed solution step 3 obtained, under temperature is the condition of 80 DEG C, is then stirred to mixed solution pulverize red, transparent thick gel in the horizontal direction steady external magnetic field of 1500G;
Five, red, transparent thick gel step 4 obtained is dry 10h in the baking oven of 200 DEG C in temperature, obtains xerogel;
Six, be placed on after the xerogel that step 5 obtains being ground to form powder on Electric stove and carry out self-propagating combustion, then the powder after self-propagating combustion is placed in Muffle furnace, be after sintering 4h under the condition of 450 DEG C in temperature, then be sinter 6h in the air furnace of 850 DEG C in temperature; Obtain Ca
3co
4o
9+ δpowder;
Seven, Ca step 6 obtained
3co
4o
9+ δpowder is precompressed slabbing in the steady external magnetic field of 3000G, then temperature be 200 DEG C, pressure carries out hot-forming under being the condition of 30MPa, obtain Ca
3co
4o
9+ δblock;
Eight, Ca step 7 obtained
3co
4o
9+ δblock is sinter 12h in the air furnace of 850 DEG C in temperature, obtains cobalt base oxide thermoelectric material.
Test a cobalt base oxide thermoelectric material density obtained about 90%, crystal grain 40% preferred orientation.
Test two: a kind of preparation method of cobalt base oxide thermoelectric material carries out according to the following steps:
One, 14.16g calcium nitrate tetrahydrate, 23.28g cabaltous nitrate hexahydrate and 88.2g citric acid is taken by mass fraction;
Two, the calcium nitrate tetrahydrate that step one takes is dissolved in 60mL deionized water, obtains calcium nitrate solution; Cabaltous nitrate hexahydrate step one taken is dissolved in 80mL deionized water, obtains cobalt nitrate solution; Citric acid step one taken is dissolved in 150mL deionized water, obtains citric acid solution;
Three, calcium nitrate solution step 2 obtained and cobalt nitrate solution mixing in the reactor, are then under the condition of 70 DEG C in temperature, drip the citric acid solution that step 2 obtains while stirring, obtain mixed solution in reactor;
Four, mixed solution step 3 obtained, under temperature is the condition of 80 DEG C, is then stirred to mixed solution pulverize red, transparent thick gel in the horizontal direction steady external magnetic field of 3000G;
Five, red, transparent thick gel step 4 obtained is dry 10h in the baking oven of 200 DEG C in temperature, obtains xerogel;
Six, be placed on after the xerogel that step 5 obtains being ground to form powder on Electric stove and carry out self-propagating combustion, then the powder after self-propagating combustion is placed in Muffle furnace, be after sintering 4h under the condition of 450 DEG C in temperature, then be sinter 6h in the air furnace of 850 DEG C in temperature; Obtain Ca
3co
4o
9+ δpowder;
Seven, Ca step 6 obtained
3co
4o
9+ δpowder is precompressed slabbing in the steady external magnetic field of 3000G, then temperature be 200 DEG C, pressure carries out hot-forming under being the condition of 30MPa, obtain Ca
3co
4o
9+ δblock;
Eight, Ca step 7 obtained
3co
4o
9+ δblock is sinter 12h in the air furnace of 850 DEG C in temperature, obtains cobalt base oxide thermoelectric material.
Test the two cobalt base oxide thermoelectric material densityes obtained about 90%, crystal grain 60% preferred orientation.
Test three: a kind of preparation method of cobalt base oxide thermoelectric material carries out according to the following steps:
One, 14.16g calcium nitrate tetrahydrate, 23.28g cabaltous nitrate hexahydrate and 88.2g citric acid is taken by mass fraction;
Two, the calcium nitrate tetrahydrate that step one takes is dissolved in 60mL deionized water, obtains calcium nitrate solution; Cabaltous nitrate hexahydrate step one taken is dissolved in 80mL deionized water, obtains cobalt nitrate solution; Citric acid step one taken is dissolved in 150mL deionized water, obtains citric acid solution;
Three, calcium nitrate solution step 2 obtained and cobalt nitrate solution mixing in the reactor, are then under the condition of 70 DEG C in temperature, drip the citric acid solution that step 2 obtains while stirring, obtain mixed solution in reactor;
Four, mixed solution step 3 obtained, under temperature is the condition of 80 DEG C, is then stirred to mixed solution pulverize red, transparent thick gel in the horizontal direction steady external magnetic field of 5000G;
Five, red, transparent thick gel step 4 obtained is dry 10h in the baking oven of 200 DEG C in temperature, obtains xerogel;
Six, be placed on after the xerogel that step 5 obtains being ground to form powder on Electric stove and carry out self-propagating combustion, then the powder after self-propagating combustion is placed in Muffle furnace, be after sintering 4h under the condition of 450 DEG C in temperature, then be sinter 6h in the air furnace of 850 DEG C in temperature; Obtain Ca
3co
4o
9+ δpowder;
Seven, Ca step 6 obtained
3co
4o
9+ δpowder is precompressed slabbing in the steady external magnetic field of 3000G, then temperature be 200 DEG C, pressure carries out hot-forming under being the condition of 30MPa, obtain Ca
3co
4o
9+ δblock;
Eight, Ca step 7 obtained
3co
4o
9+ δblock is sinter 12h in the air furnace of 850 DEG C in temperature, obtains cobalt base oxide thermoelectric material.
Test the three cobalt base oxide thermoelectric material densityes obtained about 90%, crystal grain 90% preferred orientation.
Fig. 1 is the scanning electron microscope (SEM) photograph of the cobalt base oxide thermoelectric material that the present invention obtains; Fig. 2 is X-ray diffractogram; Wherein A represents the X-ray diffractogram of the cobalt base oxide thermoelectric material that the present invention obtains, and B represents the X-ray diffractogram of cobalt base oxide thermoelectric material standard sample; Fig. 3 is that conductivity varies with temperature curve; Wherein ▲ the conductivity of cobalt base oxide thermoelectric material that obtains for the present invention varies with temperature curve, and the conductivity of the cobalt base oxide thermoelectric material that ■ indicates without external magnetic field induction varies with temperature curve; The cobalt base oxide thermoelectric material that obtains of the present invention is compared with the material obtained without external magnetic field as shown in Figure 1, Figure 2 and Figure 3, crystal grain is obviously strengthened along c-axis orientation, electron mobility is increased and then conductivity increase, and then thermoelectricity capability is expected to increase substantially.
Claims (1)
1. a preparation method for cobalt base oxide thermoelectric material, is characterized in that the preparation method of cobalt base oxide thermoelectric material carries out according to the following steps:
One, 14.16g calcium nitrate tetrahydrate, 23.28g cabaltous nitrate hexahydrate and 88.2g citric acid is taken by mass fraction;
Two, the calcium nitrate tetrahydrate that step one takes is dissolved in 60mL deionized water, obtains calcium nitrate solution; Cabaltous nitrate hexahydrate step one taken is dissolved in 80mL deionized water, obtains cobalt nitrate solution; Citric acid step one taken is dissolved in 150mL deionized water, obtains citric acid solution;
Three, calcium nitrate solution step 2 obtained and cobalt nitrate solution mixing in the reactor, are then under the condition of 70 DEG C in temperature, drip the citric acid solution that step 2 obtains while stirring, obtain mixed solution in reactor;
Four, mixed solution step 3 obtained, under temperature is the condition of 80 DEG C, is then stirred to mixed solution pulverize red, transparent thick gel in the horizontal direction steady external magnetic field of 5000G;
Five, red, transparent thick gel step 4 obtained is dry 10h in the baking oven of 200 DEG C in temperature, obtains xerogel;
Six, be placed on after the xerogel that step 5 obtains being ground to form powder on Electric stove and carry out self-propagating combustion, then the powder after self-propagating combustion is placed in Muffle furnace, be after sintering 4h under the condition of 450 DEG C in temperature, then be sinter 6h in the air furnace of 850 DEG C in temperature; Obtain Ca
3co
4o
9+ δpowder;
Seven, Ca step 6 obtained
3co
4o
9+ δpowder is precompressed slabbing in the steady external magnetic field of 3000G, then temperature be 200 DEG C, pressure carries out hot-forming under being the condition of 30MPa, obtain Ca
3co
4o
9+ δblock;
Eight, Ca step 7 obtained
3co
4o
9+ δblock is sinter 12h in the air furnace of 850 DEG C in temperature, obtains cobalt base oxide thermoelectric material; Described cobalt base oxide thermoelectric material density is 90%, and preferable grain orientation is 90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410138341.5A CN103951389B (en) | 2014-04-08 | 2014-04-08 | A kind of preparation method of cobalt base oxide thermoelectric material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410138341.5A CN103951389B (en) | 2014-04-08 | 2014-04-08 | A kind of preparation method of cobalt base oxide thermoelectric material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103951389A CN103951389A (en) | 2014-07-30 |
| CN103951389B true CN103951389B (en) | 2015-12-30 |
Family
ID=51328780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410138341.5A Expired - Fee Related CN103951389B (en) | 2014-04-08 | 2014-04-08 | A kind of preparation method of cobalt base oxide thermoelectric material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103951389B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108531182A (en) * | 2018-05-31 | 2018-09-14 | 陕西科技大学 | Thermoelectric material area load Ca2MgSi2O7：Eu2+, Dy3+The preparation method of long after glow luminous material |
| CN109735310B (en) * | 2019-01-16 | 2021-04-16 | 南京航空航天大学 | Full-spectrum photo-thermal conversion heat storage material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157482A (en) * | 2007-09-19 | 2008-04-09 | 哈尔滨工业大学 | Modified Ca-Co-O system doped transition metal composite oxides and preparation method thereof |
-
2014
- 2014-04-08 CN CN201410138341.5A patent/CN103951389B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157482A (en) * | 2007-09-19 | 2008-04-09 | 哈尔滨工业大学 | Modified Ca-Co-O system doped transition metal composite oxides and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| High temperature thermoelectric properties of Ca3Co4O9+δ by auto-combustion synthesis and spark plasma sintering;Wu Ningyu et al.;《Journal of the European Ceramic Society》;20131109;第34卷;第926页"2. Experimental procedure"部分 * |
| Thermoelectric properties of highly grain-aligned and densified Co-based oxide ceramics;Zhou Yuqin et al.;《JOURNAL OF APPLIED PHYSICS》;20030301;第93卷(第5期);摘要，第2657页右栏第2段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103951389A (en) | 2014-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104478006B (en) | Preparation method of tricobalt tetraoxide mesoporous nanosheets | |
| CN110970170B (en) | Preparation method of FeTeSe polycrystalline superconductor | |
| CN104211388A (en) | Preparation method of M-shaped strontium ferrite SrFe12O19 suitable for being sintered at low temperature | |
| CN105293499A (en) | Preparation method of B,N-codoped silicon carbide nano wave-absorbing material | |
| CN103951389B (en) | A kind of preparation method of cobalt base oxide thermoelectric material | |
| CN101481243A (en) | Method for directly preparing MnZn ferrite material from nanocrystalline MnZn powder | |
| CN104386657B (en) | The preparation method of a kind of high-crystallinity boron nitride | |
| CN103588474B (en) | Preparation method of magneto-electricity composite ceramic with coating structure | |
| CN115286377A (en) | Hexagonal SrFe 12 O 19 Preparation method of ferrite-based composite permanent magnetic ferrite | |
| CN104495944A (en) | Method for preparing nitrogen-doped bismuth ferrite nano powder | |
| CN105693246B (en) | A kind of preparation method of yttrium oxide transparent ceramic | |
| CN105016395A (en) | Nano ferrite material, and preparation method thereof | |
| CN103730635A (en) | Combustion method for preparing Li1.1Ni0.5Co0.2Mn0.3O2 lithium ion battery anode material | |
| CN101412544B (en) | Preparation of layered cobalt oxide | |
| CN103664155B (en) | Ultrahigh-Bs (saturation magnetic flux density) low-loss MnZn powder ferrite material and making method thereof | |
| CN105399418A (en) | Preparation method of high-performance sodium niobate dielectric ceramic powder | |
| CN105036148B (en) | Preparation method for flowerlike Li2Si2O5 powder | |
| CN104876285A (en) | Construction method of magnetic nickel ferrite nanorod | |
| CN103086749B (en) | In-situ synthesis method of zirconium silicate encapsulated carbon black pigment by microwave heating | |
| CN104961162B (en) | A kind of method that single pure phase bismuth ferric material is prepared based on Lithium ions compensation | |
| CN103193279A (en) | Method for preparing high electric magnetic resistance material strontium cobalt molybdenum oxide | |
| CN102584330B (en) | Laser preparation method of lanthanum molybdate based oxygen ion conductor | |
| CN107266040B (en) | Rapid preparation of multiphase composite CaMnO3Method for base oxide thermoelectric material | |
| CN103626198B (en) | A kind of synthetic method of nickelous borate | |
| CN101798093A (en) | Method for preparing calcium silicate nanowires in batches at low cost |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151230 |