CN103449386B - A kind of powder with ultrahigh negative thermal expansion coefficient and preparation method thereof - Google Patents
A kind of powder with ultrahigh negative thermal expansion coefficient and preparation method thereof Download PDFInfo
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- CN103449386B CN103449386B CN201310376901.6A CN201310376901A CN103449386B CN 103449386 B CN103449386 B CN 103449386B CN 201310376901 A CN201310376901 A CN 201310376901A CN 103449386 B CN103449386 B CN 103449386B
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Abstract
The present invention relates to negative thermal expansion material, refer in particular to a kind of powder with ultrahigh negative thermal expansion coefficient and preparation method thereof; The molecular formula of described powder is Mn
3zn
0.5ag
0.5n, by Mn, Zn, Ag, N element forms, and its atomic ratio is: Mn:Zn:Ag:N=6:1:1:2, and its crystalline structure is anti-perovskite cubic structure, and at 298 K≤T≤316K, its average line negative expansion coefficient is-81 × 10
-6/ K; This material has good electrical and thermal conductivity performance, and chemically stable is strong, and physical strength is high, and preparation technology is simple, and therefore in aerospace, electronic component, the field such as optical element and opticfiber communication has broad application prospects.
Description
Technical field
The present invention relates to negative thermal expansion material, refer in particular to a kind of powder with ultrahigh negative thermal expansion coefficient and preparation method thereof; Be specifically related to a kind of manganese nitrogen compound Mn
3zn
0.5ag
0.5n, it has ultrahigh negative thermal expansion coefficient near room temperature, and the absolute value of its thermal expansivity reaches 10
-5the order of magnitude; This material has good electrical and thermal conductivity performance, and chemically stable is strong, and physical strength is high, and preparation technology is simple, and therefore in aerospace, electronic component, the field such as optical element and opticfiber communication has broad application prospects.
Background technology
Material is heated and occurs volumetric shrinkage, is referred to as negative expansion phenomenon, and negative thermal expansion material receives international concern from 20th century, is a kind of special new function material; The application of negative thermal expansion material can reduce the impact of temperature on components and parts, eliminate the internal stress destruction that thermal expansion causes, the performance of raising equipment and precision, increase the service life, such as, negative thermal expansion material can be used for manufacturing precision optical instrument, and the accurate light as systems such as visual telescope, laser equipment, optical-fibre communications focuses on and beam path alignment, makes it not by the impact of temperature fluctuation; The surface of high-accuracy optical frames adopts Zero-expansion material making coatings, can prevent from causing optical property to reduce because of temperature variation, in addition, in the electronics industry, controllable thermal expansion material can with the thermal expansion matching of matrix silicon, control the thermal expansion of printed-wiring board (PWB) and radiator element.
Nineteen ninety-five, Sleight research group has found negative thermal expansion material ZrW
2o
8, after this, negative thermal expansion material becomes a wonderful work in Materials science, researchs and develops AM so far
2o
7(M=V, P), AM
2o
8, A
2m
3o
12(M=W, Mo), M (CN)
2and Mn
3aN (A=Ge, Cu, Zn, Sn etc.) series, wherein Mn
3the focus that AN series is studied in nearly ten years especially; This type of negative thermal expansion material has very large advantage compared with other series, by carrying out the thermal expansivity of controlled material in A position doped element, and just can reach near-zero thermal expansion with single-phase material, preparation technology is simple, and there is good physicals, apply more extensive; The Mn found at present
3aN negative thermal expansion material, its negative expansion coefficient is greatly about-5 ~-38 × 10
-6/ K, as Mn
3zn
0.6sn
0.4its thermal expansivity of N is maximum so far, reaches α=-38 × 10 at 410-440K
-6/ K, we are by using Ag doped with Mn
3znN compound obtains a kind of powder near room temperature with ultrahigh negative thermal expansion coefficient coefficient, and its thermal expansivity is approximately-81 × 10
-6/ K, the thermal expansivity of this material is twice many than the thermal expansivity of all manganese nitrogen compound negative thermal expansion materials of existing discovery.
Summary of the invention
The object of the present invention is to provide one to have ultrahigh negative thermal expansion coefficient coefficient in certain temperature range interval, its negative expansion coefficient reaches-81 × 10
-6the Mn of/K
3zn
0.5ag
0.5n powder, be the manganese nitrogen compound so far with maximum negative expansion coefficient, this material can be used for aerospace, microelectronic device, and optical information propagates the field such as device and material of construction.
A kind of powder body material with the anti-perovskite structure of negative heat expansion characteristics of the present invention, its molecular formula is Mn
3zn
0.5ag
0.5n, by Mn, Zn, Ag, N element forms, and its atomic ratio is Mn:Zn:Ag:N=6:1:1:2, and its crystalline structure is anti-perovskite cubic structure.
Mn in the present invention
3zn
0.5ag
0.5n powder body material, at 298 K≤T≤316K, is the change (T1 ﹤ T2) of specimen length between temperature T1 and T2 according to the calculation formula α=Δ L/ (L Δ T) of mean coefficient of linear thermal expansion, Δ L; L is the original length of sample; Δ T is the temperature head between temperature T2 and T1, and its average line negative expansion coefficient is-81 × 10
-6/ K, the thermal expansivity of the negative thermal expansion material more found is twice left and right, as shown in Figure 1.
A kind of Mn with ultrahigh negative thermal expansion coefficient characteristic of the present invention
3zn
0.5ag
0.5the preparation method of N powder body material, it comprises the following steps:
(1) taking purity is the manganese powder of 99.9% and the Zinc oxide powder of 99.7%, mol ratio is ZnO:Mn=1:3, then put it in tube furnace, under the atmosphere of high-purity ammonia (>=99.999%) of flowing, with the ramp to 750 DEG C of 10 DEG C/min, be incubated 10 hours, furnace cooling, synthesis Mn
3znN powder;
(2) taking purity is the manganese powder of 99.9% and the silver oxide powder of 99.7%, and mol ratio is Ag
2o:Mn=1:6, then puts it in tube furnace, under the atmosphere of high-purity ammonia (>=99.999%) of flowing, with the ramp to 350 DEG C of 10 DEG C/min, is incubated 10 hours, furnace cooling, synthesis Mn
3agN powder;
(3) according to mol ratio Mn
3znN:Mn
3agN=1:1, takes Mn
3znN powder and Mn
3agN powder, mixes, and grinds and sieve in agate mortar;
(4) powdered sample is evenly poured in little porcelain boat, less porcelain boat put into silica tube and vacuumize simultaneously, then sealed silica envelope;
(5) silica tube is put in tube furnace, be warming up to 850 DEG C, be incubated 20 hours, be cooled to room temperature, powered-down, cool to room temperature with the furnace, namely obtain target product Mn
3zn
0.5ag
0.5n.
Tool of the present invention has the following advantages: a kind of anti-perovskite structure powder material with ultrahigh negative thermal expansion coefficient characteristic of the present invention, it is at 298 K≤T≤316K, and its average line negative expansion coefficient is-81 × 10
-6/ K, nearly greatly about one times of the thermal expansivity of the negative thermal expansion material more found; The negative expansion of such material is isotropic, and structure is very stable, and this material also has good electrical and thermal conductivity performance; Higher physical strength; Abundant raw material source, and preparation condition easily realizes.
Accompanying drawing explanation
Fig. 1 is Mn
3zn
0.5ag
0.5the specimen length that N powder body material is tested through TMA varies with temperature curve.
Specific embodiments
A kind of powder body material with anti-perovskite structure with atomic negative heat expansion characteristics of the present invention, its molecular formula is Mn
3zn
0.5ag
0.5n, by Mn, Zn, Ag, N element forms, and its atomic ratio is Mn:Zn:Ag:N=6:1:1:2, and its crystalline structure is anti-perovskite cubic structure.
Mn in the present invention
3zn
0.5ag
0.5n powder body material, at 298 K≤T≤316K, its average line negative expansion coefficient is-81 × 10
-6/ K, nearly greatly about one times of the negative expansion coefficient of the negative thermal expansion material more found, the negative expansion behavior that the present invention finds is isotropy, and its negative expansion performance temperature is interval more than room temperature.
A kind of Mn with negative heat expansion characteristics of the present invention
3zn
0.5ag
0.5the preparation method of N powder body material, it comprises the following steps:
(1) taking purity is the manganese powder of 99.9% and the Zinc oxide powder of 99.7%, mol ratio is ZnO:Mn=1:3, then put it in tube furnace, under the atmosphere of high-purity ammonia (99.999%) of flowing, with the ramp to 750 DEG C of 10 DEG C/min, be incubated 10 hours, furnace cooling, synthesis Mn
3znN powder;
(2) taking purity is the manganese powder of 99.9% and the silver oxide powder of 99.7%, and mol ratio is Ag
2o:Mn=1:6, then puts it in tube furnace, under the atmosphere of high-purity ammonia (99.999%) of flowing, with the ramp to 350 DEG C of 10 DEG C/min, is incubated 10 hours, furnace cooling, synthesis Mn
3agN powder;
(3) according to mol ratio Mn
3znN:Mn
3agN=1:1, takes Mn
3znN powder and Mn
3agN powder, mixes, ground 200 mesh sieves in agate mortar;
(4) powdered sample is evenly poured in little porcelain boat, less porcelain boat put into silica tube and be evacuated to 10 simultaneously
-5pa, then sealed silica envelope;
(5) silica tube is put in tube furnace, be warming up to 850 DEG C, be incubated 20 hours, be cooled to room temperature, powered-down, cool to room temperature with the furnace, namely obtain target product Mn
3zn
0.5ag
0.5n.
Claims (6)
1. there is a powder for ultrahigh negative thermal expansion coefficient, it is characterized in that: the molecular formula of described powder is Mn
3zn
0.5ag
0.5n, by Mn, Zn, Ag, N element forms, and its atomic ratio is: Mn:Zn:Ag:N=6:1:1:2, and its crystalline structure is anti-perovskite cubic structure, and at 298 K≤T≤316K, its average line negative expansion coefficient is-81 × 10
-6/ K;
The described raw powder's production technology with ultrahigh negative thermal expansion coefficient, comprises the steps:
(1) take manganese powder and Zinc oxide powder, mol ratio is ZnO:Mn=1:3, then puts it in tube furnace, under the atmosphere of flowing ammonia, is warming up to 750 DEG C, is incubated 10 hours, furnace cooling, synthesis Mn
3znN powder;
(2) take manganese powder and silver oxide powder, mol ratio is Ag
2o:Mn=1:6, then puts it in tube furnace, under the atmosphere of flowing ammonia, is warming up to 350 DEG C, is incubated 10 hours, furnace cooling, synthesis Mn
3agN powder;
(3) according to mol ratio Mn
3znN:Mn
3agN=1:1, takes Mn
3znN powder and Mn
3agN powder, mixes, and grinds and sieve in agate mortar;
(4) powdered sample is evenly poured in little porcelain boat, less porcelain boat put into silica tube and vacuumize simultaneously, then sealed silica envelope;
(5) silica tube is put in tube furnace, be warming up to 850 DEG C, be incubated 20 hours, be cooled to room temperature, powered-down, cool to room temperature with the furnace, namely obtain target product Mn
3zn
0.5ag
0.5n.
2. a kind of raw powder's production technology with ultrahigh negative thermal expansion coefficient as claimed in claim 1, is characterized in that comprising the steps:
(1) take manganese powder and Zinc oxide powder, mol ratio is ZnO:Mn=1:3, then puts it in tube furnace, under the atmosphere of flowing ammonia, is warming up to 750 DEG C, is incubated 10 hours, furnace cooling, synthesis Mn
3znN powder;
(2) take manganese powder and silver oxide powder, mol ratio is Ag
2o:Mn=1:6, then puts it in tube furnace, under the atmosphere of flowing ammonia, is warming up to 350 DEG C, is incubated 10 hours, furnace cooling, synthesis Mn
3agN powder;
(3) according to mol ratio Mn
3znN:Mn
3agN=1:1, takes Mn
3znN powder and Mn
3agN powder, mixes, and grinds and sieve in agate mortar;
(4) powdered sample is evenly poured in little porcelain boat, less porcelain boat put into silica tube and vacuumize simultaneously, then sealed silica envelope;
(5) silica tube is put in tube furnace, be warming up to 850 DEG C, be incubated 20 hours, be cooled to room temperature, powered-down, cool to room temperature with the furnace, namely obtain target product Mn
3zn
0.5ag
0.5n.
3. a kind of raw powder's production technology with ultrahigh negative thermal expansion coefficient as claimed in claim 2, is characterized in that: the mass percentage of described manganese powder is: 99.9%; The mass percentage of described Zinc oxide powder is: 99.7%; The mass percentage of described silver oxide powder is: 99.7%.
4. a kind of raw powder's production technology with ultrahigh negative thermal expansion coefficient as claimed in claim 2, is characterized in that: the temperature rise rate of described step (1) and step (2) is 10 DEG C/min; The volumn concentration of ammonia is >=99.999%.
5. a kind of raw powder's production technology with ultrahigh negative thermal expansion coefficient as claimed in claim 2, is characterized in that: the grinding of described step (3) is sieved and referred to ground 200 mesh sieves.
6. a kind of raw powder's production technology with ultrahigh negative thermal expansion coefficient as claimed in claim 2, is characterized in that: the finger that vacuumizes in described step (4) is evacuated to 10
-5pa.
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| CN103449386B true CN103449386B (en) | 2015-08-05 |
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| CN109133938A (en) * | 2018-10-09 | 2019-01-04 | 上海交通大学 | A kind of regulation method of preparation and its negative expansion behavior of negative thermal expansion material |
| CN111943206B (en) * | 2020-08-28 | 2021-10-12 | 郑州轻工业大学 | Vacancy anti-perovskite Mn3Preparation method and application of AlC |
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2013
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Non-Patent Citations (2)
| Title |
|---|
| Magnetovolume Effect and Negative Thermal Expansion in Mn3(Cu1xGex)N;Koshi Takenaka et al.;《Materials Transactions》;20060315;第47卷(第3期);471-474 * |
| Tuning the range, magnitude, and sign of the thermal expansion in intermetallic Mn3(Zn, M)x N(M = Ag, Ge);Cong Wang et al.;《PHYSICAL REVIEW B》;20120614;第85卷;220103 1-5 * |
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Effective date of registration: 20171130 Address after: 212005 South Xu Road, Zhenjiang, Zhenjiang, Jiangsu Patentee after: JIANGSU HUIZHI INTELLECTUAL PROPERTY SERVICES CO., LTD. Address before: Zhenjiang City, Jiangsu Province, 212013 Jingkou District Road No. 301 Patentee before: Jiangsu University |
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Effective date of registration: 20191226 Address after: 225200 No. 88 Wenchang East Road, Jiangdu District, Yangzhou, Jiangsu. Patentee after: Yangzhou (Jiangdu) New Energy Automobile Industry Research Institute of Jiangsu University Address before: 212005 South Xu Road, Zhenjiang, Zhenjiang, Jiangsu Patentee before: JIANGSU HUIZHI INTELLECTUAL PROPERTY SERVICES CO., LTD. |