CN112292016B - Preparation method of rare earth composite wave-absorbing material - Google Patents
Preparation method of rare earth composite wave-absorbing material Download PDFInfo
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- CN112292016B CN112292016B CN202011287009.7A CN202011287009A CN112292016B CN 112292016 B CN112292016 B CN 112292016B CN 202011287009 A CN202011287009 A CN 202011287009A CN 112292016 B CN112292016 B CN 112292016B
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/288—Sulfides
- C01F17/294—Oxysulfides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q17/00—Devices for absorbing waves radiated from an antenna; Combinations of such devices with active antenna elements or systems
Abstract
The invention relates to a preparation method of a rare earth composite wave-absorbing material, which takes Nd-MOF as a precursor and prepares Nd through a one-step pyrolysis method 2 O 2 S/C rare earth composite wave-absorbing material. The rare earth composite wave-absorbing material prepared by simple pyrolysis has the characteristics of high stability and light weight; through a semiconductor Nd 2 O 2 S is compounded with the porous carbon material, so that the rare earth composite wave-absorbing material shows excellent microwave absorption performance at a thinner thickness, the matching thickness is 2.56 and mm at the frequency of 12.72GHz, and the optimal RL value can reach-52.3 and dB. The preparation method is simple, uniform in compounding, stable in material performance, low in cost and suitable for industrial production.
Description
Technical Field
The invention relates to a preparation method of a rare earth composite wave-absorbing material, and in particular relates to the technical field of microwave wave-absorbing materials.
Background
With the continuous advancement of high-tech communication and information technology, the potential impact of electromagnetic interference or pollution on human health and electronic safety is a widely focused problem. Various solutions have been adopted to overcome electromagnetic radiation pollution, with microwave absorbing materials being considered as one of the most promising solutions. At present, most electromagnetic wave absorbers have poor microwave absorption performance and stability and thick thickness. Therefore, there is a need for an electromagnetic wave absorbing material that has both strong absorption, a thin thickness, and high stability. Up to now, dielectric loss absorbents containing carbonaceous materials, conductive polymers and the like, and magnetic loss materials such as ferrites, magnetic metals and the like have been widely reported, but their production methods are complicated and costly. Yao Zhengjun et al synthesized Ni 0.5 Zn 0.5 NdxFe 2-x O 4 The composite material exhibits good microwave absorption properties, and a maximum reflection loss value (RL) at x=0.04, at 4.4GHz and 8.5 mm thickness max ) An effective absorption bandwidth (RL) of-20.8 dB at a thickness of 8.5 mm<-10 dB) is 3.2 GHz (Kun Qian, zhengjun Yao, haiyan Lin, et al The influence of Nd substitution in Ni-Zn ferrites for the improved microwave absorption properties Ceramics International, 2020, 46:227-235.). Wang Lei et al synthesized Nd 23.25 Fe 36.75 Co 40 The composite material shows better microwave absorption performance, and the maximum reflection loss value (RL at 4.8 GHz and 1.8 mm thickness max ) Also, it is only-19.7 dB (Lei Wang, peihao Lin, shunkang Pan, et al Microwave absorbing properties of NdFeCo magnetic powder Journal of Rare Earths, 2012, 30:529-533.). The wave absorbing material containing rare earth neodymium has the strongest microwave absorption performance which is weaker and can only reach about-20 dB, and thicker material thickness is needed to obtain the maximum reflection loss value.
Nd 2 O 3 Is an important semiconductor mainly used as a colorant of glass and ceramics, and is a raw material for manufacturing metal neodymium and a raw material for manufacturing ferromagnetic neodymium-iron-boron. In addition, nd 2 O 3 Has unique magnetic and dielectric properties, while Nd 2 O 2 S and Nd 2 O 3 With similar properties, one sulfur atom occupies the lattice site of the oxygen atom, so that more lattice defects are obtained, and the loss capacity is enhanced. Lower band gaps are beneficial to improving dielectric constant, dielectric loss and wave absorbing capability. Thus, nd 2 O 2 S is expected to be an excellent microwave absorbing material.
Disclosure of Invention
Aiming at the problems of complex preparation method, strict equipment requirement, high cost and the like of the existing carbon-based microwave absorbing material, the invention provides a method for preparing a rare earth composite wave absorbing material by taking Nd-MOF as a template.
The invention relates to a preparation method of a rare earth composite wave-absorbing material, which takes Nd-MOF as a template to prepare Nd 2 O 2 The S/C rare earth composite wave-absorbing material comprises the following specific steps:
step 1: dissolving neodymium nitrate hexahydrate, thiophene diacid and ammonium acetate in a mixed solution of deionized water and ethanol, transferring to a high-pressure reaction kettle, preserving heat for 2-4 days at 100 ℃, alternately centrifuging and washing the obtained product with deionized water and absolute ethanol for three times respectively, and finally carrying out vacuum drying at 50-60 ℃ to obtain a blocky Nd-MOF crystal;
wherein: the mol ratio of the neodymium nitrate hexahydrate to the thiophene diacid to the ammonium acetate is 0.3-0.5:0.7-1.0:3-5, the dosage ratio of the thiophene diacid to the deionized water is 0.8-1.2 mmol:8-12 mL, and the volume ratio of the deionized water to the ethanol is 1.0:1.0-1.2;
step 2: heating the block Nd-MOF crystal from room temperature to 600-900 ℃ in nitrogen atmosphere, roasting for 2-4 hours, and naturally cooling to room temperature in nitrogen atmosphere to obtain a rare earth composite wave-absorbing material; the process temperature rise/fall rate is 2-5 ℃/min.
The rare earth composite microwave absorbing material is mixed with paraffin as a base material to obtain the microwave absorbing agent, wherein the mass ratio of the mixing materials is 1:0.8-1.2.
The invention has the beneficial effects that:
1. the invention relates to a semiconductor Nd 2 O 2 S is compounded with the porous carbon material, and the graphitization degree of the composite material is changed by changing the temperature rising rate, the calcination temperature and the calcination time, so that the impedance matching is regulated and controlled. After the rare earth composite wave-absorbing material is proportioned with the paraffin, the excellent microwave absorption performance can be ensured under the condition of lower coating thickness, the matching thickness is 2.56mm at the frequency of 12.72GHz, and the optimal RL value can reach-52.3 dB.
2. Compared with the existing preparation of the carbon-based microwave absorbing material, the preparation method provided by the invention has the advantages of simplicity, uniform compounding, stable material performance and low production cost, and is suitable for industrial production.
Drawings
FIG. 1 shows Nd of the invention 2 O 2 S/C-800X-ray diffraction pattern;
FIG. 2 shows Nd prepared in example 1 of the present invention 2 O 2 Reflection loss spectrum of S/C-800 composite wave-absorbing material;
FIG. 3 shows the present inventionNd prepared in EXAMPLE 2 2 O 2 Reflection loss spectrum of S/C-900 composite wave-absorbing material;
Nd 2 O 2 S/C-800 and Nd 2 O 2 S/C-900 is the calcined product of Nd-MOFs at 800 and 900 degrees, respectively.
Detailed Description
Example 1
Step 1: 0.1752g of neodymium nitrate hexahydrate, 0.136g of thiophene diacid and 0.308g of ammonium acetate are dissolved in a mixed solution of 8mL of deionized water and 8mL of ethanol together, then the mixed solution is transferred into a high-pressure reaction kettle, the temperature is kept for 3 days at 100 ℃, and the obtained product is respectively washed by centrifugation and three times alternately with deionized water and absolute ethanol; finally, placing the mixture in a vacuum oven, and drying the mixture at the temperature of 50 ℃ under vacuum to obtain a blocky Nd-MOF crystal;
step 2: heating up the block Nd-MOF crystal from room temperature to 800 ℃ and roasting for 2 hours under the condition of nitrogen atmosphere and a heating/cooling rate of 5 ℃/min, and naturally cooling to room temperature under the nitrogen atmosphere to obtain Nd 2 O 2 S/C-800 composite wave-absorbing material.
Step 3: the prepared hollow Nd 2 O 2 The S/C-800 composite material and the paraffin substrate are uniformly mixed to form a circular ring, and the mass of the composite material and the mass of the paraffin are respectively 0.05g and 0.05g.
The electromagnetic parameters of the material are measured by a vector network analyzer, and according to the transmission line theory, the reflection loss of the material on electromagnetic waves is calculated by the following equation through complex dielectric constant and complex magnetic permeability under given frequency and the thickness of the wave absorbing material.
Example 2
Step 1: dissolving 0.1752g neodymium nitrate hexahydrate, 0.136g thiophene diacid and 0.308g ammonium acetate into a mixed solution of 8mL deionized water and 8mL ethanol, transferring into a high-pressure reaction kettle, preserving heat for 3 days at 100 ℃, and respectively and alternately centrifuging and washing the obtained product with deionized water and absolute ethanol for three times; finally, placing the mixture in a vacuum oven, and drying the mixture at the temperature of 50 ℃ under vacuum to obtain a blocky Nd-MOF crystal;
step 2: heating up the block Nd-MOF crystal from room temperature to 900 ℃ and roasting for 2 hours under the condition of nitrogen atmosphere and a heating/cooling rate of 5 ℃/min, and naturally cooling to room temperature under the nitrogen atmosphere to obtain Nd 2 O 2 S/C-900 composite wave-absorbing material.
Step 3: the prepared hollow Nd 2 O 2 The S/C-900 composite material and the paraffin substrate are uniformly mixed to form a circular ring, and the mass of the composite material and the mass of the paraffin are respectively 0.05g and 0.05g.
This embodiment differs from embodiment 1 in that: the calcination temperature of the bulk Nd-MOF crystals was 900 degrees.
Nd of FIG. 1 of the present invention 2 O 2 S/C-800X-ray diffraction pattern, by XRD analysis, the synthesized Nd was studied 2 O 2 The crystal structure and phase composition of the S/C-800 sample. In general, 12 peaks shown in 26.11, 29.16, 37.30, 45.96, 48.13, 53.99, 55.37, 60.76, 62.35, 69.11, 74.75 and 75.23 correspond to Nd, respectively 2 O 2 S (100), (101), (102), (110), (103), (004), (201), (104), (113), (005), (211) and (105) cubic crystal planes.
As can be seen from FIG. 2, the product Nd 2 O 2 S/C-800 the strongest reflection loss was-52.3 dB at a frequency of 12.7GHz and a matching thickness of 2.56 mm. As can be seen from FIG. 3, the product Nd 2 O 2 S/C-900 has a strongest reflection loss of-66.4 dB at a frequency of 7.24GHz and a matching thickness of 4.47mm, an effective bandwidth of 3.32GHz, and a maximum effective bandwidth of 4.92GHz at a matching thickness of 3.0 mm.
Claims (1)
1. A preparation method of a rare earth composite wave-absorbing material is characterized by comprising the following steps: the method takes Nd-MOF as a template to prepare Nd 2 O 2 The S/C rare earth composite wave-absorbing material comprises the following specific steps:
step 1: dissolving neodymium nitrate hexahydrate, thiophene diacid and ammonium acetate in a mixed solution of deionized water and ethanol, transferring to a high-pressure reaction kettle, preserving heat for 2-4 days at 100 ℃, alternately centrifuging and washing the obtained product with deionized water and absolute ethanol for three times respectively, and finally carrying out vacuum drying at 50-60 ℃ to obtain a blocky Nd-MOF crystal;
wherein: the mol ratio of the neodymium nitrate hexahydrate to the thiophene diacid to the ammonium acetate is 0.3-0.5:0.7-1.0:3-5, the dosage ratio of the thiophene diacid to the deionized water is 0.8-1.2 mmol:8-12 mL, and the volume ratio of the deionized water to the ethanol is 1.0:1.0-1.2;
step 2: heating the block Nd-MOF crystal from room temperature to 600-900 ℃ in nitrogen atmosphere, roasting for 2-4 hours, and naturally cooling to room temperature in nitrogen atmosphere to obtain a rare earth composite wave-absorbing material; the process temperature rise/fall rate is 2-5 ℃/min.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010063949A (en) * | 2008-09-08 | 2010-03-25 | Toyota Motor Corp | Oxygen absorbing and desorbing material and catalyst containing the same for cleaning exhaust gas |
| CN102105557A (en) * | 2008-07-23 | 2011-06-22 | 皇家飞利浦电子股份有限公司 | Gd2O2S material for use in CT applications |
| CN106947465A (en) * | 2017-03-27 | 2017-07-14 | 大连海事大学 | Core shell structure rare-earth oxide sulfate X-ray luminescence nano-particle and preparation method thereof |
| CN108726556A (en) * | 2018-08-21 | 2018-11-02 | 中国科学院包头稀土研发中心 | A kind of preparation method of rare-earth sulfide and/or rare-earth oxide sulfate colorant |
| CN110203960A (en) * | 2019-06-28 | 2019-09-06 | 南阳师范学院 | A kind of rare earth oxysulfide and preparation method thereof as lube oil additive |
| CN110615807A (en) * | 2019-10-17 | 2019-12-27 | 中国海洋大学 | Rare earth metal organic complex wave-absorbing material and preparation method thereof |
| CN110746931A (en) * | 2019-11-18 | 2020-02-04 | 南昌航空大学 | Method for preparing ITO/porous carbon composite wave-absorbing material by taking In-MOFs as template |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7393516B2 (en) * | 2003-01-31 | 2008-07-01 | Seo Dong-Kyun | Preparation of metal chalcogenides from reactions of metal compounds and chalcogen |
-
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102105557A (en) * | 2008-07-23 | 2011-06-22 | 皇家飞利浦电子股份有限公司 | Gd2O2S material for use in CT applications |
| JP2010063949A (en) * | 2008-09-08 | 2010-03-25 | Toyota Motor Corp | Oxygen absorbing and desorbing material and catalyst containing the same for cleaning exhaust gas |
| CN106947465A (en) * | 2017-03-27 | 2017-07-14 | 大连海事大学 | Core shell structure rare-earth oxide sulfate X-ray luminescence nano-particle and preparation method thereof |
| CN108726556A (en) * | 2018-08-21 | 2018-11-02 | 中国科学院包头稀土研发中心 | A kind of preparation method of rare-earth sulfide and/or rare-earth oxide sulfate colorant |
| CN110203960A (en) * | 2019-06-28 | 2019-09-06 | 南阳师范学院 | A kind of rare earth oxysulfide and preparation method thereof as lube oil additive |
| CN110615807A (en) * | 2019-10-17 | 2019-12-27 | 中国海洋大学 | Rare earth metal organic complex wave-absorbing material and preparation method thereof |
| CN110746931A (en) * | 2019-11-18 | 2020-02-04 | 南昌航空大学 | Method for preparing ITO/porous carbon composite wave-absorbing material by taking In-MOFs as template |
Non-Patent Citations (1)
| Title |
|---|
| 马禄彬.稀土硫（氧）化物的热解法制备及其性能研究.2011,(2011年第09期),第12-27页. * |
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