CN101108739A - Method of manufacturing alumine acid cuprous polycrystalline material with delafossite structure and manufacturing material thereof - Google Patents
Method of manufacturing alumine acid cuprous polycrystalline material with delafossite structure and manufacturing material thereof Download PDFInfo
- Publication number
- CN101108739A CN101108739A CNA2006100412026A CN200610041202A CN101108739A CN 101108739 A CN101108739 A CN 101108739A CN A2006100412026 A CNA2006100412026 A CN A2006100412026A CN 200610041202 A CN200610041202 A CN 200610041202A CN 101108739 A CN101108739 A CN 101108739A
- Authority
- CN
- China
- Prior art keywords
- polycrystalline material
- delafossite structure
- cuprous
- alumine
- ball milling
- 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.)
- Granted
Links
Images
Abstract
The invention discloses the preparation method and the materials for preparation of cuprous aluminate polycrystalline material of delafossite structure. The method is that (a) the cupric acetate and the aluminium-sec-butoxide are weighed according to the mol ratio of 1 : 0.99 to 1.01 between the copper and the aluminum; the cupric acetate is added into the blended solution of the citric acid, nitric acid and ethanol and is stirred until the cupric acetate is dissolved, after that, the aluminium-sec-butoxide is added into the cupric acetate blended solution and is stirred until dissolved and the precursor colloid is gained; (b) the precursor colloid is dried for at least one hour under 100 DEG C. to 150 DEG C. in turns and is thermally decomposed for 0.5 hour to 6 hours under 250 DEG C. to 350 DEG C. to gain the precursor powder, and then the powder is ball grinded; (c) the powder after ball grinder is sintered for 6 hours to 20 hours under 1080 DEG C. to 1200 DEG C. to produce the cuprous aluminate polycrystalline material of delafossite structure. The atomic per cent of the material is Cu : Al is equal to 0.95 to 0.98 : 1 and the electric transport mechanism is the typical P type semi-conductor behavior. The invention has simple process and easy control of operation condition, which is widely used in such fields as transparent electron devices, thermoelectric materials and room temperature smell sensor.
Description
Technical field the present invention relates to a kind of preparation method of alumine acid cuprous polycrystalline material of method for making and goods thereof, especially delafossite structure of polycrystalline material and the material of preparation thereof.
Alumine acid cuprous (the CuAlO of background technology delafossite structure
2) polycrystalline material is because of it has p type electrically conducting transparent performance, good thermoelectricity capability and room temperature foul smell sensing characteristics, have a wide range of applications in fields such as transparent electronics, thermoelectric material and room temperature foul smell transmitters.People have done some trials and effort in order to obtain it, as a kind of " CuAlO that discloses among the disclosed Japanese application for a patent for invention prospectus JP 2002-114515A on April 16th, 2002
2The manufacture method of film ".It is intended to provide a kind of manufacture method to produce CuAlO
2Film; Wherein, manufacture method adds aluminium alkoxide solution again for earlier venus crystals being dissolved in ethanol and the 2 → methyl cellosolve, afterwards, obtains to contain Cu through backflow and distillatory process
2++ Al
3+Precursor solution, then this forerunner's liquid solution is applied on the substrate, drying and in argon gas sintering produce CuAlO
2Base film.But, no matter be manufacture method, or its finished product, all exist weak point, at first, the finished product that use this manufacture method to produce only are film like, have limited its range of application; Secondly, many, the complicated operation of step of manufacturing, film needs sintering in argon gas, makes production cost be difficult to reduce; Once more, finished product CuAlO
2Base film is not pure phase CuAlO
2Polycrystalline material, but contain CuAlO
2, Cu
2O, CuAl
2O
4, composition such as CuO heterogeneous system.
The summary of the invention the technical problem to be solved in the present invention is for overcoming weak point of the prior art, provide a kind of preparation method easy, finished product are the preparation method of alumine acid cuprous polycrystalline material of delafossite structure of pure phase alumine acid cuprous polycrystalline material and the material of preparation thereof.
The preparation method of the alumine acid cuprous polycrystalline material of delafossite structure comprises colloidal sol → gel method, particularly it is finished according to the following steps: (a) mol ratio by copper and aluminium is 1: 0.99～1.01, behind weighing venus crystals and the aluminium secondary butylate, venus crystals is added citric acid, in nitric acid and the alcoholic acid mixing solutions, being stirred to venus crystals dissolves fully, wherein, the mol ratio of venus crystals and citric acid is 1: 3～7, the mol ratio of venus crystals and nitric acid is 1: 6～18, the volume ratio of nitric acid and dehydrated alcohol is 1: 3～7, afterwards, in the mixed liquid of venus crystals, add aluminium secondary butylate and be stirred to dissolving fully, obtain forerunner's colloid; (b) earlier forerunner's colloid is obtained precursor powder in 0.5～6 hour at least 1 hour, 250～350 ℃ following pyrolysis of 100～150 ℃ of following dryings successively, again precursor powder is carried out ball milling; (c) with the precursor powder behind the ball milling in 1080～1200 ℃ of following sintering 6～20 hours, make the alumine acid cuprous polycrystalline material of delafossite structure.
Further improvement as the preparation method of the alumine acid cuprous polycrystalline material of delafossite structure, described ball milling is for to place ball grinder to carry out ball milling on planetary ball mill precursor powder, wherein, ratio of grinding media to material is 15～30: 1, and the rotating speed of ball milling is 300～500rpm, time to be at least 20 hours; Described after to the precursor powder sintering behind the ball milling, earlier to its grinding, pressed compact, again with it in 1080～1200 ℃ of following sintering 0.5～6 hour, make the alumine acid cuprous polycrystalline material of block delafossite structure; Described pressed compact places the mould of desired shape to carry out the single shaft press forming for the alumine acid cuprous polycrystalline material with pulverous delafossite structure.
The alumine acid cuprous polycrystalline material of the delafossite structure of preparation method's preparation of the alumine acid cuprous polycrystalline material of use delafossite structure comprises copper and aluminium element, particularly the alumine acid cuprous polycrystalline material of (a) said delafossite structure is to be made by the raw material of following ratio: the mol ratio by copper and aluminium is 1: 0.99～1.01, metering venus crystals and aluminium secondary butylate; (b) the atomic percent Cu of the alumine acid cuprous polycrystalline material of said delafossite structure: Al=0.95～0.98: 1, its electronic transport mechanism is the behavior of typical p N-type semiconductorN.
Beneficial effect with respect to prior art is that one, the alumine acid cuprous polycrystalline material of the delafossite structure that makes are powdery, are convenient on this basis as required it be made desired shape, to adapt to various application scenarios; Its two, preparation technology is simple, operational condition is easy to control, the stoichiometric ratio of material can accurately be controlled, material tends to spontaneous formation and is subjected to major defects in preparation process.Neither need reflux in the preparation and the distillatory process, also not be used in sintering in the argon gas, make production cost be reduced significantly, make it be easy to large-scale industrial production, be beneficial to the commercial applications of its product; They are three years old, after using field emission scanning electron microscope, x-ray diffractometer, field emission scanning electron microscope incidental X-ray energy spectrum analyser and resistance measuring instrument to characterize respectively to the alumine acid cuprous polycrystalline material of the delafossite structure that repeatedly makes, from the stereoscan photograph that obtains as can be known, the epigranular of the powder of polycrystalline material, narrowly distributing does not have any coacervate.By X-ray diffracting spectrum as can be known, polycrystalline material is the 3R-CuAlO of delafossite structure
2The polycrystalline phase becomes mutually even, and does not contain dephasign.By X-ray energy spectrum figure as can be known, polycrystalline material is elementary composition by copper, aluminium and three kinds of oxygen; The element percentage composition table of the polycrystalline material that obtains after as calculated with the data among the X-ray energy spectrum figure is as follows:
| Element | Weight % | Atom % |
| O K Al K Cu K adds up to | 30.05 21.35 48.60 100.00 | 54.69 23.04 22.27 |
Can find out the atomic percent Cu of polycrystalline material: Al=0.95～0.98: 1 from this table.By transporting measuring result figure as can be known, the electronic transport mechanism of polycrystalline material is the behavior of typical p N-type semiconductorN.
As the further embodiment of beneficial effect, the one, place ball grinder on planetary ball mill, to carry out ball milling at least 20 hours precursor powder, guaranteed the epigranular, uniform of precursor powder, for subsequent processing is laid a good foundation; The 2nd, to behind powder sintered behind the ball milling,, can make block polycrystalline material once more to its grinding, pressed compact and sintering; The 3rd, pressed compact is that the alumine acid cuprous polycrystalline material with pulverous delafossite structure places the mould of desired shape to carry out the single shaft press forming, and is not only simple but also can obtain the block polycrystalline material of desired shape.
Description of drawings is described in further detail optimal way of the present invention below in conjunction with accompanying drawing.
Fig. 1 is the CuAlO to the delafossite structure that makes
2Polycrystalline material use take the photograph behind LEO 1530 type field emission scanning electron microscopes (SEM) the observation surface topography the SEM photo;
Fig. 2 is the CuAlO to the delafossite structure that makes
2Polycrystalline material uses the XRD figure spectrum that obtains after the test of Phillips X ' Pert type X-ray diffraction (XRD) instrument, and the X-coordinate among the figure is that diffraction angle, ordinate zou are relative intensity.By the position of each diffraction peak in the XRD figure and relative intensity as can be known, this polycrystalline material is the 3R-CuAlO of delafossite structure
2The polycrystalline phase;
Fig. 3 is the CuAlO to the delafossite structure that makes
2Polycrystalline material uses the EDS figure that obtains after the test of the Sirion 200FEG type incidental X-ray energy spectrum of scanning electronic microscope (EDS) analyser, and the X-coordinate among the figure is that energy, ordinate zou are relative intensity.This EDS figure explanation, polycrystalline material is elementary composition by copper, aluminium and three kinds of oxygen;
Fig. 4 is the CuAlO to the delafossite structure that makes
2Polycrystalline material use obtain after the resistance measuring instrument test transport measuring result figure, the X-coordinate among the figure is that temperature, ordinate zou are resistance value.As can be seen from Figure, the specific conductivity of polycrystalline material raises with temperature and enlarges markedly, and is the semi-conductor electrical conductive behavior.(220K～320K) can meet Arrhenius hot activation pattern well, intensity of activation Ea is about 0.20eV at institute's temperature measuring area.Be lower than the warm area of 220K, log σ is by (1/T)
1/4The rule linearity reduces, and meets the range hopping model better.
Embodiment at first makes with ordinary method or buys venus crystals, aluminium secondary butylate, citric acid, nitric acid and ethanol from market, then,
Embodiment 1: finish preparation according to the following steps order: (a) mol ratio by copper and aluminium is 1: 0.99, behind weighing venus crystals and the aluminium secondary butylate, venus crystals is added in citric acid, nitric acid and the alcoholic acid mixing solutions, is stirred to venus crystals and dissolves fully; Wherein, the mol ratio of venus crystals and citric acid is that the mol ratio of 1: 3, venus crystals and nitric acid is that the volume ratio of 1: 18, nitric acid and dehydrated alcohol is 1: 7.Afterwards, in the mixed liquid of venus crystals, add aluminium secondary butylate and be stirred to dissolving fully, obtain forerunner's colloid.(b) forerunner's colloid was obtained precursor powder in 6 hours in 100 ℃ of dry down 3 hours, 250 ℃ following pyrolysis successively.Afterwards, precursor powder is carried out ball milling; Ball milling is for to place ball grinder to carry out ball milling on planetary ball mill precursor powder, and wherein, ratio of grinding media to material is 15: 1, and the rotating speed of ball milling is that 500rpm, time are 25 hours.(c) with the precursor powder behind the ball milling in 1080 ℃ of following sintering 20 hours, make alumine acid cuprous polycrystalline material as Fig. 1 and the delafossite structure shown in curve among Fig. 2, Fig. 3, Fig. 4.Perhaps after to the precursor powder sintering behind the ball milling, earlier to its grinding, pressed compact, again with it in 1080 ℃ of following sintering 6 hours, wherein, grinding is with aforesaid ball milling, pressed compact places the mould of desired shape to carry out the single shaft press forming for the alumine acid cuprous polycrystalline material with pulverous delafossite structure, thereby makes the alumine acid cuprous polycrystalline material as Fig. 1 and the blocky delafossite structure shown in curve among Fig. 2, Fig. 3, Fig. 4.
Embodiment 2: finish preparation according to the following steps order: (a) mol ratio by copper and aluminium is 1: 0.99, behind weighing venus crystals and the aluminium secondary butylate, venus crystals is added in citric acid, nitric acid and the alcoholic acid mixing solutions, is stirred to venus crystals and dissolves fully; Wherein, the mol ratio of venus crystals and citric acid is that the mol ratio of 1: 4, venus crystals and nitric acid is that the volume ratio of 1: 15, nitric acid and dehydrated alcohol is 1: 6.Afterwards, in the mixed liquid of venus crystals, add aluminium secondary butylate and be stirred to dissolving fully, obtain forerunner's colloid.(b) forerunner's colloid was obtained precursor powder in 4.5 hours in 115 ℃ of dry down 2.5 hours, 275 ℃ following pyrolysis successively.Afterwards, precursor powder is carried out ball milling; Ball milling is for to place ball grinder to carry out ball milling on planetary ball mill precursor powder, and wherein, ratio of grinding media to material is 19: 1, and the rotating speed of ball milling is that 450rpm, time are 24 hours.(c) with the precursor powder behind the ball milling in 1100 ℃ of following sintering 17 hours, make alumine acid cuprous polycrystalline material as Fig. 1 and the delafossite structure shown in curve among Fig. 2, Fig. 3, Fig. 4.Perhaps after to the precursor powder sintering behind the ball milling, earlier to its grinding, pressed compact, again with it in 1100 ℃ of following sintering 4.5 hours, wherein, grinding is with aforesaid ball milling, pressed compact places the mould of desired shape to carry out the single shaft press forming for the alumine acid cuprous polycrystalline material with pulverous delafossite structure, thereby makes the alumine acid cuprous polycrystalline material as Fig. 1 and the blocky delafossite structure shown in curve among Fig. 2, Fig. 3, Fig. 4.
Embodiment 3: finish preparation according to the following steps order: (a) mol ratio by copper and aluminium is 1: 1, behind weighing venus crystals and the aluminium secondary butylate, venus crystals is added in citric acid, nitric acid and the alcoholic acid mixing solutions, is stirred to venus crystals and dissolves fully; Wherein, the mol ratio of venus crystals and citric acid is that the mol ratio of 1: 5, venus crystals and nitric acid is that the volume ratio of 1: 12, nitric acid and dehydrated alcohol is 1: 5.Afterwards, in the mixed liquid of venus crystals, add aluminium secondary butylate and be stirred to dissolving fully, obtain forerunner's colloid.(b) forerunner's colloid was obtained precursor powder in 3 hours in 130 ℃ of dry down 2 hours, 300 ℃ following pyrolysis successively.Afterwards, precursor powder is carried out ball milling; Ball milling is for to place ball grinder to carry out ball milling on planetary ball mill precursor powder, and wherein, ratio of grinding media to material is 23: 1, and the rotating speed of ball milling is that 400rpm, time are 23 hours.(c) with the precursor powder behind the ball milling in 1140 ℃ of following sintering 13 hours, make alumine acid cuprous polycrystalline material as Fig. 1 and the delafossite structure shown in curve among Fig. 2, Fig. 3, Fig. 4.Perhaps after to the precursor powder sintering behind the ball milling, earlier to its grinding, pressed compact, again with it in 1140 ℃ of following sintering 3 hours, wherein, grinding is with aforesaid ball milling, pressed compact places the mould of desired shape to carry out the single shaft press forming for the alumine acid cuprous polycrystalline material with pulverous delafossite structure, thereby makes the alumine acid cuprous polycrystalline material as Fig. 1 and the blocky delafossite structure shown in curve among Fig. 2, Fig. 3, Fig. 4.
Embodiment 4: finish preparation according to the following steps order: (a) mol ratio by copper and aluminium is 1: 1.01, behind weighing venus crystals and the aluminium secondary butylate, venus crystals is added in citric acid, nitric acid and the alcoholic acid mixing solutions, is stirred to venus crystals and dissolves fully; Wherein, the mol ratio of venus crystals and citric acid is that the mol ratio of 1: 6, venus crystals and nitric acid is that the volume ratio of 1: 9, nitric acid and dehydrated alcohol is 1: 4.Afterwards, in the mixed liquid of venus crystals, add aluminium secondary butylate and be stirred to dissolving fully, obtain forerunner's colloid.(b) forerunner's colloid was obtained precursor powder in 2 hours in 140 ℃ of dry down 1.5 hours, 325 ℃ following pyrolysis successively.Afterwards, precursor powder is carried out ball milling; Ball milling is for to place ball grinder to carry out ball milling on planetary ball mill precursor powder, and wherein, ratio of grinding media to material is 27: 1, and the rotating speed of ball milling is that 350rpm, time are 21 hours.(c) with the precursor powder behind the ball milling in 1170 ℃ of following sintering 9 hours, make alumine acid cuprous polycrystalline material as Fig. 1 and the delafossite structure shown in curve among Fig. 2, Fig. 3, Fig. 4.Perhaps after to the precursor powder sintering behind the ball milling, earlier to its grinding, pressed compact, again with it in 1170 ℃ of following sintering 2 hours, wherein, grinding is with aforesaid ball milling, pressed compact places the mould of desired shape to carry out the single shaft press forming for the alumine acid cuprous polycrystalline material with pulverous delafossite structure, thereby makes the alumine acid cuprous polycrystalline material as Fig. 1 and the blocky delafossite structure shown in curve among Fig. 2, Fig. 3, Fig. 4.
Embodiment 5: finish preparation according to the following steps order: (a) mol ratio by copper and aluminium is 1: 1.01, behind weighing venus crystals and the aluminium secondary butylate, venus crystals is added in citric acid, nitric acid and the alcoholic acid mixing solutions, is stirred to venus crystals and dissolves fully; Wherein, the mol ratio of venus crystals and citric acid is that the mol ratio of 1: 7, venus crystals and nitric acid is that the volume ratio of 1: 6, nitric acid and dehydrated alcohol is 1: 3.Afterwards, in the mixed liquid of venus crystals, add aluminium secondary butylate and be stirred to dissolving fully, obtain forerunner's colloid.(b) forerunner's colloid was obtained precursor powder in 0.5 hour in 150 ℃ of dry down 1 hour, 350 ℃ following pyrolysis successively.Afterwards, precursor powder is carried out ball milling; Ball milling is for to place ball grinder to carry out ball milling on planetary ball mill precursor powder, and wherein, ratio of grinding media to material is 30: 1, and the rotating speed of ball milling is that 300rpm, time are 20 hours.(c) with the precursor powder behind the ball milling in 1200 ℃ of following sintering 6 hours, make alumine acid cuprous polycrystalline material as Fig. 1 and the delafossite structure shown in curve among Fig. 2, Fig. 3, Fig. 4.Perhaps after to the precursor powder sintering behind the ball milling, earlier to its grinding, pressed compact, again with it in 1200 ℃ of following sintering 0.5 hour, wherein, grinding is with aforesaid ball milling, pressed compact places the mould of desired shape to carry out the single shaft press forming for the alumine acid cuprous polycrystalline material with pulverous delafossite structure, thereby makes the alumine acid cuprous polycrystalline material as Fig. 1 and the blocky delafossite structure shown in curve among Fig. 2, Fig. 3, Fig. 4.
Obviously, those skilled in the art can carry out various changes and modification and not break away from the spirit and scope of the present invention to the material of the preparation method of the alumine acid cuprous polycrystalline material of delafossite structure of the present invention and preparation thereof.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.
Claims (5)
1. the preparation method of the alumine acid cuprous polycrystalline material of a delafossite structure comprises sol-gel method, it is characterized in that finishing according to the following steps:
(a) mol ratio by copper and aluminium is 1: 0.99～1.01, behind weighing venus crystals and the aluminium secondary butylate, venus crystals is added in citric acid, nitric acid and the alcoholic acid mixing solutions, being stirred to venus crystals dissolves fully, wherein, the mol ratio of venus crystals and citric acid is 1: 3～7, the mol ratio of venus crystals and nitric acid is 1: 6～18, the volume ratio of nitric acid and dehydrated alcohol is 1: 3～7, afterwards, in the mixed liquid of venus crystals, add aluminium secondary butylate and be stirred to dissolving fully, obtain forerunner's colloid;
(b) earlier forerunner's colloid is obtained precursor powder in 0.5～6 hour at least 1 hour, 250～350 ℃ following pyrolysis of 100～150 ℃ of following dryings successively, again precursor powder is carried out ball milling;
(c) with the precursor powder behind the ball milling in 1080～1200 ℃ of following sintering 6～20 hours, make the alumine acid cuprous polycrystalline material of delafossite structure.
2. the preparation method of the alumine acid cuprous polycrystalline material of delafossite structure according to claim 1, it is characterized in that ball milling is to place ball grinder to carry out ball milling on planetary ball mill precursor powder, wherein, ratio of grinding media to material is 15～30: 1, and the rotating speed of ball milling is 300～500rpm, time to be at least 20 hours.
3. the preparation method of the alumine acid cuprous polycrystalline material of delafossite structure according to claim 1, it is characterized in that after the precursor powder sintering behind the ball milling, earlier to its grinding, pressed compact, again with it in 1080～1200 ℃ of following sintering 0.5～6 hour, make the alumine acid cuprous polycrystalline material of block delafossite structure.
4. the preparation method of the alumine acid cuprous polycrystalline material of delafossite structure according to claim 3 is characterized in that pressed compact is that alumine acid cuprous polycrystalline material with pulverous delafossite structure places the mould of desired shape to carry out the single shaft press forming.
5. the alumine acid cuprous polycrystalline material of the delafossite structure of the preparation method of an alumine acid cuprous polycrystalline material that uses the described delafossite structure of claim 1 preparation comprises copper and aluminium element, it is characterized in that:
(a) alumine acid cuprous polycrystalline material of said delafossite structure is to be made by the raw material of following ratio: the mol ratio by copper and aluminium is 1: 0.99～1.01, metering venus crystals and aluminium secondary butylate;
(b) the atomic percent Cu of the alumine acid cuprous polycrystalline material of said delafossite structure: Al=0.95～0.98: 1, its electronic transport mechanism is the behavior of typical p N-type semiconductorN.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100412026A CN100494064C (en) | 2006-07-19 | 2006-07-19 | Method of manufacturing alumine acid cuprous polycrystalline material with delafossite structure and manufacturing material thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100412026A CN100494064C (en) | 2006-07-19 | 2006-07-19 | Method of manufacturing alumine acid cuprous polycrystalline material with delafossite structure and manufacturing material thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101108739A true CN101108739A (en) | 2008-01-23 |
| CN100494064C CN100494064C (en) | 2009-06-03 |
Family
ID=39041034
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100412026A Expired - Fee Related CN100494064C (en) | 2006-07-19 | 2006-07-19 | Method of manufacturing alumine acid cuprous polycrystalline material with delafossite structure and manufacturing material thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100494064C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101767810B (en) * | 2009-10-30 | 2011-11-09 | 陕西科技大学 | Method for preparing CuAlO2 powder |
| CN103601256A (en) * | 2013-11-29 | 2014-02-26 | 中国工程物理研究院电子工程研究所 | Method for preparing high single-phase delafossite structure silver cobaltate polycrystalline powder |
| CN108680609A (en) * | 2018-03-15 | 2018-10-19 | 中国科学院合肥物质科学研究院 | It is a kind of using p-type delafossite structure oxide as room temperature ammonia gas sensor of sensitive material and preparation method thereof |
| RU2781013C2 (en) * | 2020-03-13 | 2022-10-04 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Южно-Уральский государственный гуманитарно-педагогический университет" ФГБОУ ВО "ЮУрГГПУ" | Method for production of copper aluminate with delafossite structure |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3527944B2 (en) * | 2000-10-02 | 2004-05-17 | 独立行政法人産業技術総合研究所 | Method for producing CuAlO2 thin film by chemical process |
| DE10323625B3 (en) * | 2003-05-21 | 2005-01-05 | Hahn-Meitner-Institut Berlin Gmbh | Process for the preparation of transparent p-type CuAIO2 and its use |
-
2006
- 2006-07-19 CN CNB2006100412026A patent/CN100494064C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101767810B (en) * | 2009-10-30 | 2011-11-09 | 陕西科技大学 | Method for preparing CuAlO2 powder |
| CN103601256A (en) * | 2013-11-29 | 2014-02-26 | 中国工程物理研究院电子工程研究所 | Method for preparing high single-phase delafossite structure silver cobaltate polycrystalline powder |
| CN103601256B (en) * | 2013-11-29 | 2016-05-11 | 中国工程物理研究院电子工程研究所 | A kind of method of preparing the silver-colored polycrystal powder of high single phase property delafossite structure cobalt acid |
| CN108680609A (en) * | 2018-03-15 | 2018-10-19 | 中国科学院合肥物质科学研究院 | It is a kind of using p-type delafossite structure oxide as room temperature ammonia gas sensor of sensitive material and preparation method thereof |
| CN108680609B (en) * | 2018-03-15 | 2021-02-09 | 中国科学院合肥物质科学研究院 | Room-temperature ammonia gas sensor taking p-type delafossite structure oxide as sensitive material and preparation method thereof |
| RU2781013C2 (en) * | 2020-03-13 | 2022-10-04 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Южно-Уральский государственный гуманитарно-педагогический университет" ФГБОУ ВО "ЮУрГГПУ" | Method for production of copper aluminate with delafossite structure |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100494064C (en) | 2009-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101423243B (en) | La doped SrTiO3 base oxide pyroelectric material and preparation method | |
| Li et al. | Enhanced aging and thermal shock performance of Mn 1.95− x Co 0.21 Ni 0.84 Sr x O 4 NTC ceramics | |
| Jesurani et al. | Phase formation and high dielectric constant of calcium copper titanate using sol–gel route | |
| Jesurani et al. | Dielectric properties of Zr doped CaCu3Ti4O12 synthesized by sol–gel route | |
| Ji et al. | Preparation and characterization of Ce0. 8Y0. 2− xCuxO2− δ as electrolyte for intermediate temperature solid oxide fuel cells | |
| Singh et al. | Dielectric properties of zinc doped nanocrystalline calcium copper titanate synthesized by different approach | |
| Ashuri et al. | Al-doped Li 7 La 3 Zr 2 O 12 garnet-type solid electrolytes for solid-state Li-Ion batteries | |
| Weng et al. | Synthesis of lead zirconate titanate–cobalt ferrite magnetoelectric particulate composites via an ethylenediaminetetraacetic acid–citrate gel process | |
| Cui et al. | Fabrication of nano-grained negative temperature coefficient thermistors with high electrical stability | |
| Chanu et al. | Study on the structural and electrical properties of YMnO3 co-substituted with transition metal ions at Mn-site and their conduction mechanism | |
| CN100494064C (en) | Method of manufacturing alumine acid cuprous polycrystalline material with delafossite structure and manufacturing material thereof | |
| Wang et al. | Synthesis of doped ZnO nanopowders in alcohol–water solvent for varistors applications | |
| Han et al. | Microstructure and thermoelectric properties of La0. 1Dy0. 1SrxTiO3 ceramics | |
| Chakravarty et al. | Relaxation dynamics and hopping mechanism in Mg-doped BaFe0. 5Nb0. 5O3 complex perovskite | |
| Jesurani et al. | Dielectric properties of Erbium doped CaCu 3 Ti 4 O 12 prepared by sol–gel self combustion method | |
| Rautio et al. | Effect of synthesis method variables on particle size in the preparation of homogeneous doped nano ZnO material | |
| Puri et al. | Significant enhancement in thermoelectric power factor of bulk nanostructured calcium cobalt oxide ceramics | |
| Wang et al. | Preparation and characterization of CaCu 3 Ti 4 O 12 powders by non-hydrolytic sol–gel method | |
| Muguerra et al. | Improvement of the thermoelectric properties of [Bi1. 68Ca2O4− δ] RS [CoO2] 1.69 cobaltite by chimie douce methods | |
| Zhao et al. | NTC thermo-sensitive ceramics with low B value and high resistance at low temperature in Li-doped Mn 0.6 Ni 0.9 Co 1.5 O 4 system | |
| Katsuyama et al. | Synthesis of NaxCo2O4 by the hydrothermal hot-pressing and its thermoelectric properties | |
| CN1091084C (en) | Low (or negative)-expansibility complex-phase ceramic and its preparing process | |
| JPH08231223A (en) | Thermoelectric conversing material | |
| Verma et al. | Influence of Ba doping on the electrical behaviour of La0. 9Sr0. 1Al0. 9Mg0. 1O3− δ system for a solid electrolyte | |
| Hwan Jo et al. | Low-temperature sintering of dense lanthanum silicate electrolytes with apatite-type structure using an organic precipitant synthesized nanopowder |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090603 Termination date: 20100719 |