CN111592349A - Fe-doped CuAlO2High-temperature wave-absorbing ceramic and preparation method thereof - Google Patents

Fe-doped CuAlO2High-temperature wave-absorbing ceramic and preparation method thereof Download PDF

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CN111592349A
CN111592349A CN202010500998.7A CN202010500998A CN111592349A CN 111592349 A CN111592349 A CN 111592349A CN 202010500998 A CN202010500998 A CN 202010500998A CN 111592349 A CN111592349 A CN 111592349A
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苏进步
李萍
王成兵
王维科
赵霞霖
张鹏奎
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Shaanxi University of Science and Technology
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Abstract

The invention discloses Fe-doped CuAlO2A high-temperature wave-absorbing ceramic and a preparation method thereof belong to the technical field of wave-absorbing material preparation. In the preparation method, Fe is used for doping CuAlO2Changing CuAlO2The conductivity and the electromagnetic parameters of the alloy are adopted to generate CuAl with x less than or equal to 0.21‑xFexO2Sintering the powder into ceramic, adopting Cu source substance, Al source substance and Fe source substance as reactants, and preparing the Fe-doped CuAlO by ball milling process and presintering sintering binder removal process2High-temperature wave-absorbing ceramic. The preparation method has the advantages of good process stability, wide raw material application range and low cost, and can be popularized to the mass production of the material. Fe-doped CuAlO prepared by adopting the preparation method2High-temperature wave-absorbing ceramic with chemical formula of CuAl1‑ xFexO2X is less than or equal to 0.2, and the introduction of Fe causes CuAl1‑xFexO2The ceramic has larger dielectric loss, magnetic property and high temperature resistance, so that the finally prepared Fe-doped CuAlO2The high-temperature wave-absorbing ceramic has high temperature resistance and excellent wave-absorbing performance, and can be widely applied to high and new technology industries such as aerospace and aviation.

Description

Fe-doped CuAlO2High-temperature wave-absorbing ceramic and preparation method thereof
Technical Field
The invention belongs to the technical field of wave-absorbing material preparation, and relates to Fe-doped CuAlO2High-temperature wave-absorbing ceramic and a preparation method thereof.
Background
The research on wave-absorbing materials was first started in the military and was called "stealth materials". At present, with the rapid development of electromagnetic technologies such as computers, transformer substations, wireless communication and the like, the problem of electromagnetic pollution caused by the rapid development of the information technology is increasingly emphasized by people. How to prevent and treat electromagnetic pollution is an inevitable major problem in this century, and the existing wave-absorbing material is widely applied to the fields of anti-electromagnetic interference, electromagnetic compatibility, stealth technology and the like of communication and navigation systems aiming at the problem of electromagnetic pollution.
In terms of the wave-absorbing principle of the wave-absorbing material, in order to obtain a wave-absorbing material with excellent performance, the wave-absorbing material should have excellent electromagnetic impedance matching characteristics and electromagnetic loss performance. Meanwhile, in application, the wave-absorbing material is required to have a wider absorption frequency band and high absorption rate to electromagnetic waves, and also required to meet the characteristics of light weight, thin wave-absorbing powder, good thermal stability, good corrosion resistance, moisture resistance and the like. Therefore, research and development of novel ceramic wave-absorbing materials become a current focus.
CuAlO2As a material with a delafossite structure, the material has received attention of researchers due to the advantages of low price of raw materials for preparation and the like. CuAlO2Is a superlattice material with delafossite structure, Cu layer and AlO2Stacked alternately along the c-axis. CuAlO2Is a p-type semiconductor having hole-conducting property, and each Cu in the O-Cu-O structure+Providing 1 electron, while the equilibrium state requires the Cu atom to provide 2 electronsThe pair of the photon and 2 oxygen atoms around the photon will generate 1 hole inevitably, and the hole carrier will be localized strongly due to the strong O-p hybridization of the valence band, showing p-type conduction, and it is hopeful to be applied in the wave-absorbing material field.
At present, the wave-absorbing material in the fields of normal temperature and medium and low temperature is designed and applied more mature, and the research on the high-temperature wave-absorbing material is relatively lagged all the time. The search for better high temperature absorbents has also been a continuing effort by researchers. In recent years, various novel absorbents emerge endlessly, but the raw materials are expensive, and the wave-absorbing performance is reduced due to high-temperature oxidation. In addition, carbon materials such as carbon black and carbon nanotubes can also be used for high-temperature wave-absorbing performance. However, under the condition of no external coating protection, the carbon-based wave-absorbing material is generally applied at a temperature below 400 ℃, and the carbon material is oxidized due to the temperature rise to cause the wave-absorbing performance to be reduced. Generally, the purpose of increasing the application temperature can be achieved by preparing an anti-oxidation layer on the surface of the carbon material, but the preparation process is complex and the price is high.
Therefore, the research on how to prepare the wave-absorbing material applied to the high-temperature field with reasonable cost investment and convenient and simplified preparation process is always the focus of research of workers in the field.
Disclosure of Invention
In order to overcome the disadvantages of the prior art, the invention aims to provide Fe-doped CuAlO2High-temperature wave-absorbing ceramic and a preparation method thereof. The preparation method has the characteristics of good process stability, cheap raw materials and low preparation cost, and the Fe-doped CuAlO prepared by the method2High-temperature wave-absorbing ceramic with chemical formula of CuAl1-xFexO2X is less than or equal to 0.2, and has excellent high-temperature wave-absorbing performance.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses Fe-doped CuAlO2The preparation method of the high-temperature wave-absorbing ceramic comprises the following steps:
1)CuAl1-xFexO2preparation of high temperature absorbents
Uniformly mixing a Cu source substance, an Al source substance and a Fe source substance by ball milling to obtain a mixed material; uniformly grinding the mixed materials, drying, sieving to obtain 200-mesh powder, presintering the powder at 1100-1200 ℃ for 0.5-4.0 h, and cooling to obtain CuAl1-xFexO2A high temperature absorbent;
2) fe-doped CuAlO2Preparation of high-temperature wave-absorbing ceramic
To CuAl1-xFexO2Adding 1-5% g/mL PVA sol into a high-temperature absorbent, grinding, sieving by a 80-mesh sieve to obtain green body powder, pressing the green body powder, and sintering to remove glue to obtain a green body; treating the blank at 1000-1200 ℃ for 0.5-4 h, and cooling to obtain Fe-doped CuAlO2High-temperature wave-absorbing ceramic.
Preferably, in the step 1), the reaction charge ratio of the Cu source substance, the Al source substance and the Fe source substance is 0.5: 1-0.8: 0-0.2 in terms of the ratio of the amounts of the Cu, Al and Fe substances.
Preferably, in step 1), the Cu source substance includes Cu2O, CuO and Cu (OH)2One or a mixture of several of them.
Preferably, in step 1), the Al source substance includes Al2O3And Al (OH)3One or a mixture of several of them.
Preferably, in step 1), the Fe source substance includes Fe2O3、Fe3O4、FeO、Fe(OH)2And Fe (OH)3One or a mixture of several of them.
Preferably, in the step 2), (1% -5%) g/mL of PVA sol is added in CuAl1-xFexO20.5-1% of the high-temperature absorbent.
Preferably, in the step 2), the operation condition of green powder pressing is that the pressure is 20MPa, and the pressure is maintained for 60 s; the sintering and glue discharging operation condition is that the temperature is kept for 2 hours at 650 ℃.
The invention also discloses Fe-doped CuAlO prepared by the preparation method2High-temperature wave-absorbing ceramic with chemical formula of CuAl1-xFexO2，x≤0.2。
Preferably, the Fe-doped CuAlO2The reflectivity of the high-temperature wave-absorbing ceramic in the range of 25-1000 ℃ and 8.2-12.4 GHz is less than-10 dB.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses Fe-doped CuAlO2Preparation method of high-temperature wave-absorbing ceramic, wherein Fe is doped with CuAlO2Changing CuAlO2The conductivity and the electromagnetic parameters of the alloy are adopted to generate CuAl with x less than or equal to 0.21-xFexO2The powder is then sintered into a ceramic. According to the preparation method, the Cu source substance, the Al source substance and the Fe source substance are used as reactants, so that the cost investment can be effectively reduced, the preparation method has a large using value, the raw materials are fully and uniformly mixed by adopting ball milling and then uniformly ground in a matching manner, the presintering is facilitated to obtain a product with a uniform structure, the presintering operation is designed, the gas generated in the reaction of the raw materials can be prevented from being introduced into a final product, a large number of air holes are formed, the density is reduced, and the compactness and the structural uniformity of the finally prepared ceramic material can be improved. The preparation method disclosed by the invention has the advantages of good process stability, wide raw material application range and low cost, and can be popularized to mass production of the material.
Furthermore, as the Cu source substance, the Al source substance and the Fe source substance can all select a plurality of substances containing the element as reactants, the preparation method has good application and popularization, is beneficial to controlling the investment of preparation cost, and has good industrial application value.
The invention also discloses Fe-doped CuAlO prepared by the preparation method2The high-temperature wave-absorbing ceramic has a chemical formula of CuAl1-xFexO2X is less than or equal to 0.2, due to CuAl1-xFexO2The ceramic has large dielectric loss, and the incident electromagnetic wave is attenuated through dielectric polarization relaxation loss, so that the electromagnetic energy is converted into heat energy to be lost. Further, Fe3+So that CuAl is introduced1-xFexO2The ceramic has certain magnetic property, and the magnetic loss mechanism further loses incident electromagnetic wavesAnd (4) consuming. Simultaneously CuAl1-xFexO2Belongs to a high temperature resistant material, the high temperature wave absorbing performance of which is basically the same as the wave absorbing performance at normal temperature, so that the Fe-doped CuAlO disclosed by the invention2The high-temperature wave-absorbing ceramic has the advantages of temperature resistance and excellent wave-absorbing performance, and can be widely applied to high and new technology industries such as aerospace and aviation.
Drawings
FIG. 1 is an XRD (X-ray diffraction) spectrum of the high-temperature wave-absorbing ceramic prepared in the embodiments 1-4 of the invention when the scanning angle is 10-80 degrees;
FIG. 2 is an XRD (X-ray diffraction) spectrum of the high-temperature wave-absorbing ceramic prepared in the embodiments 1-4 of the invention when the scanning angle is 30-40 degrees;
FIG. 3 is an SEM micro-morphology diagram of the high-temperature wave-absorbing ceramic prepared in the embodiments 1-4 of the invention; wherein (a) is example 1; (b) example 2 was used; (c) example 3 was used; (d) example 4 was used;
FIG. 4 is a reflectivity curve diagram of the high-temperature wave-absorbing ceramic prepared in example 1 of the present invention at different thicknesses;
FIG. 5 is a reflectivity curve diagram of the high-temperature wave-absorbing ceramic prepared in example 2 according to the present invention at different thicknesses;
FIG. 6 is a reflectivity curve diagram of the high-temperature wave-absorbing ceramic prepared in embodiment 3 of the present invention at different thicknesses;
FIG. 7 is a reflectivity curve diagram of the high-temperature wave-absorbing ceramic prepared in example 4 according to the present invention at different thicknesses;
FIG. 8 is a reflectivity curve diagram of the high-temperature wave-absorbing ceramic prepared in example 2 of the present invention at different temperatures.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
Example 1
The embodiment of the invention aims to provide high-temperature wave-absorbing ceramic with cheap raw materials and low preparation cost and a preparation method thereof, wherein the chemical formula of the high-temperature wave-absorbing ceramic is CuAlO2。
Step 1: preparation of CuAlO2High temperature absorbent
Cu with the stoichiometric ratio of 0.5:1 is firstly added2O、Al(OH)3The raw materials are fully and uniformly mixed, then presintered at high temperature and cooled along with a furnace.
CuAlO2The preparation method of the high-temperature absorbent is carried out according to the following steps:
s1, weighing: weighing Cu according to stoichiometric ratio2O、Al(OH)3；
S2, ball milling: weighing Cu2O、Al(OH)3Pouring the mixture into a ball milling tank, adding grinding balls, deionized water and absolute ethyl alcohol, and performing ball milling after flooding;
s3, drying: after the ball milling is finished, putting the mixed slurry in the ball milling tank into an oven for drying after the absolute ethyl alcohol is completely volatilized;
s4, grinding: manually grinding the dried material by using an agate mortar, completely dispersing the hardened material obtained by drying, and then sieving the material by using a 200-mesh sieve;
s5, pre-burning: heating the sieved material to 1200 deg.C, keeping the temperature for 2.0h, and cooling with the furnace to obtain CuAlO2A high temperature absorbent.
Step 2: preparation of CuAlO2High-temperature wave-absorbing ceramic
Pre-burning to obtain CuAlO2Tabletting and sintering high-temperature absorbent powder to prepare CuAlO2High-temperature wave-absorbing ceramic.
CuAlO2The preparation method of the high-temperature wave-absorbing ceramic comprises the following steps:
s1, preparing sol, adding 1g of PVA into 100ml of deionized water, heating, continuously stirring to dissolve the PVA, and cooling for later use;
s2, tabletting, namely putting a certain amount of the pre-sintered sample obtained in the step 1 into a mortar, dripping 1% of glue, continuously grinding, sieving by a 80-mesh sieve after 30min, tabletting by a tabletting machine under the pressure of 20MPa, and maintaining the pressure for 60S.
S3, sintering, namely placing the pressed green body in a muffle furnace for sintering, preserving heat at 650 ℃ for 2h for binder removal, treating at 1200 ℃ for 2h, then cooling along with the furnace, taking out a sample after the temperature of the furnace is lower than 150 ℃, and obtaining the CuAlO2High-temperature wave-absorbing ceramic.
Example 2
The embodiment of the invention aims to provide a high-temperature wave-absorbing ceramic with cheap raw materials and low preparation cost and a preparation method thereof, wherein the chemical formula of the high-temperature wave-absorbing ceramic is CuAl0.97Fe0.03O2。
Step 1: preparation of CuAl0.97Fe0.03O2High temperature absorbent
Cu with the stoichiometric ratio of 0.5:0.97:0.03 is firstly added2O、Al(OH)3、Fe(OH)3The raw materials are fully and uniformly mixed, then presintered at high temperature and cooled along with a furnace.
CuAl0.97Fe0.03O2The preparation method of the high-temperature absorbent is carried out according to the following steps:
s1, weighing: weighing Cu according to stoichiometric ratio2O、Al(OH)3And Fe (OH)3；
S2, ball milling: weighing Cu2O、Al(OH)3And Fe (OH)3Pouring the mixture into a ball milling tank, adding grinding balls, deionized water and absolute ethyl alcohol, and performing ball milling after flooding;
s3, drying: after the ball milling is finished, putting the mixed slurry in the ball milling tank into an oven for drying after the absolute ethyl alcohol is completely volatilized;
s4, grinding: manually grinding the dried material by using an agate mortar, completely dispersing the hardened material obtained by drying, and then sieving the material by using a 200-mesh sieve;
s5, pre-burning: heating the sieved material to 1200 ℃, preserving heat for 2.0h, and then cooling along with the furnace to obtain CuAl0.97Fe0.03O2A high temperature absorbent.
Step 2: preparation of CuAl0.97Fe0.03O2High-temperature wave-absorbing ceramic
Pre-sintering to obtain CuAl0.97Fe0.03O2Tabletting and sintering the high-temperature absorbent powder to prepare CuAl0.97Fe0.03O2High-temperature wave-absorbing ceramic.
CuAl0.97Fe0.03O2The preparation method of the high-temperature wave-absorbing ceramic comprises the following steps:
s1, preparing sol, adding 1g of PVA into 100ml of deionized water, heating, continuously stirring to dissolve the PVA, and cooling for later use;
s2, tabletting, namely putting a certain amount of the pre-sintered sample obtained in the step 1 into a mortar, dripping 1% of glue, continuously grinding, sieving by a 80-mesh sieve after 30min, tabletting by a tabletting machine under the pressure of 20MPa, and maintaining the pressure for 60S.
S3, sintering, namely placing the pressed green body in a muffle furnace for sintering, preserving heat at 650 ℃ for 2h for binder removal, treating at 1200 ℃ for 2h, cooling along with the furnace, taking out a sample when the temperature of the furnace is lower than 150 ℃, and obtaining the CuAl0.97Fe0.03O2High-temperature wave-absorbing ceramic.
Example 3
The embodiment of the invention aims to provide the high-temperature wave-absorbing ceramic with cheap raw materials and low preparation cost and the preparation method thereofThe chemical formula of the preparation method is CuAl0.91Fe0.09O2。
Step 1: preparation of CuAl0.91Fe0.09O2High temperature absorbent
Cu with the stoichiometric ratio of 0.5:0.91:0.09 is firstly added2O、Al(OH)3、Fe(OH)3The raw materials are fully and uniformly mixed, then presintered at high temperature and cooled along with a furnace.
CuAl0.91Fe0.09O2The preparation method of the high-temperature absorbent is carried out according to the following steps:
s1, weighing: weighing Cu according to stoichiometric ratio2O、Al(OH)3And Fe (OH)3；
S2, ball milling: weighing Cu2O、Al(OH)3And Fe (OH)3Pouring the mixture into a ball milling tank, adding grinding balls, deionized water and absolute ethyl alcohol, and performing ball milling after flooding;
s3, drying: after the ball milling is finished, putting the mixed slurry in the ball milling tank into an oven for drying after the absolute ethyl alcohol is completely volatilized;
s4, grinding: manually grinding the dried material by using an agate mortar, completely dispersing the hardened material obtained by drying, and then sieving the material by using a 200-mesh sieve;
s5, pre-burning: heating the sieved material to 1200 ℃, preserving heat for 2.0h, and then cooling along with the furnace to obtain CuAl0.91Fe0.09O2A high temperature absorbent.
Step 2: preparation of CuAl0.91Fe0.09O2High-temperature wave-absorbing ceramic
Pre-sintering to obtain CuAl0.91Fe0.09O2Tabletting and sintering the high-temperature absorbent powder to prepare CuAl0.91Fe0.09O2High-temperature wave-absorbing ceramic.
CuAl0.91Fe0.09O2The preparation method of the high-temperature wave-absorbing ceramic comprises the following steps:
s1, preparing sol, adding 1g of PVA into 100ml of deionized water, heating, continuously stirring to dissolve the PVA, and cooling for later use;
s2, tabletting, namely putting a certain amount of the pre-sintered sample obtained in the step 1 into a mortar, dripping 1% of glue, continuously grinding, sieving by a 80-mesh sieve after 30min, tabletting by a tabletting machine under the pressure of 20MPa, and maintaining the pressure for 60S.
S3, sintering, namely placing the pressed green body in a muffle furnace for sintering, preserving heat at 650 ℃ for 2h for binder removal, treating at 1200 ℃ for 2h, cooling along with the furnace, taking out a sample when the temperature of the furnace is lower than 150 ℃, and obtaining the CuAl0.91Fe0.09O2High-temperature wave-absorbing ceramic.
Example 4
The embodiment of the invention aims to provide a high-temperature wave-absorbing ceramic with cheap raw materials and low preparation cost and a preparation method thereof, wherein the chemical formula of the high-temperature wave-absorbing ceramic is CuAl0.82Fe0.18O2。
Step 1: preparation of CuAl0.82Fe0.18O2High temperature absorbent
Cu with the stoichiometric ratio of 0.5:0.82:0.18 is firstly added2O、Al(OH)3、Fe(OH)3The raw materials are fully and uniformly mixed, then presintered at high temperature and cooled along with a furnace.
CuAl0.82Fe0.18O2The preparation method of the high-temperature absorbent is carried out according to the following steps:
s1, weighing: weighing Cu according to stoichiometric ratio2O、Al(OH)3And Fe (OH)3；
S2, ball milling: weighing Cu2O、Al(OH)3And Fe (OH)3Pouring the mixture into a ball milling tank, adding grinding balls, deionized water and absolute ethyl alcohol, and performing ball milling after flooding;
s3, drying: after the ball milling is finished, putting the mixed slurry in the ball milling tank into an oven for drying after the absolute ethyl alcohol is completely volatilized;
s4, grinding: manually grinding the dried material by using an agate mortar, completely dispersing the hardened material obtained by drying, and then sieving the material by using a 200-mesh sieve;
s5, pre-burning: heating the sieved material to 1200 ℃, preserving heat for 2.0h, and then cooling along with the furnace to obtain CuAl0.82Fe0.18O2A high temperature absorbent.
Step 2: preparation of CuAl0.82Fe0.18O2High-temperature wave-absorbing ceramic
Pre-sintering to obtain CuAl0.82Fe0.18O2Tabletting and sintering the high-temperature absorbent powder to prepare CuAl0.82Fe0.18O2High-temperature wave-absorbing ceramic.
CuAl0.82Fe0.18O2The preparation method of the high-temperature wave-absorbing ceramic comprises the following steps:
s1, preparing sol, adding 1g of PVA into 100ml of deionized water, heating, continuously stirring to dissolve the PVA, and cooling for later use;
s2, tabletting, namely putting a certain amount of the pre-sintered sample obtained in the step 1 into a mortar, dripping 1% of glue, continuously grinding, sieving by a 80-mesh sieve after 30min, tabletting by a tabletting machine under the pressure of 20MPa, and maintaining the pressure for 60S.
S3, sintering, namely placing the pressed green body in a muffle furnace for sintering, preserving heat at 650 ℃ for 2h for binder removal, treating at 1200 ℃ for 2h, cooling along with the furnace, taking out a sample when the temperature of the furnace is lower than 150 ℃, and obtaining the CuAl0.82Fe0.18O2High-temperature wave-absorbing ceramic.
Example 5
The embodiment of the invention aims to provide a high-temperature wave-absorbing ceramic with cheap raw materials and low preparation cost and a preparation method thereof, wherein the chemical formula of the high-temperature wave-absorbing ceramic is CuAl0.8Fe0.2O2。
Step 1: preparation of CuAl0.82Fe0.18O2High temperature absorbent
Cu with the stoichiometric ratio of 0.5:0.8:0.2 is firstly added2O、Al(OH)3、Fe(OH)3The raw materials are fully and uniformly mixed, then presintered at high temperature and cooled along with a furnace.
CuAl0.82Fe0.18O2The preparation method of the high-temperature absorbent is carried out according to the following steps:
s1, weighing: weighing Cu according to stoichiometric ratio2O、Al(OH)3And Fe (OH)3；
S2, ball milling: weighing Cu2O、Al(OH)3And Fe (OH)3Pouring the mixture into a ball milling tank, adding grinding balls, deionized water and absolute ethyl alcohol, and performing ball milling after flooding;
s3, drying: after the ball milling is finished, putting the mixed slurry in the ball milling tank into an oven for drying after the absolute ethyl alcohol is completely volatilized;
s4, grinding: manually grinding the dried material by using an agate mortar, completely dispersing the hardened material obtained by drying, and then sieving the material by using a 200-mesh sieve;
s5, pre-burning: heating the sieved material to 1200 ℃, preserving heat for 4.0h, and then cooling along with the furnace to obtain CuAl0.8Fe0.182O2A high temperature absorbent.
Step 2: preparation of CuAl0.8Fe0.2O2High-temperature wave-absorbing ceramic
Pre-sintering to obtain CuAl0.8Fe0.2O2Tabletting and sintering the high-temperature absorbent powder to prepare CuAl0.8Fe0.2O2High-temperature wave-absorbing ceramic.
CuAl0.8Fe0.2O2The preparation method of the high-temperature wave-absorbing ceramic comprises the following steps:
s1, preparing sol, adding 5g of PVA into 100ml of deionized water, heating, continuously stirring to dissolve the PVA, and cooling for later use;
s2, tabletting, namely putting a certain amount of the pre-sintered sample obtained in the step 1 into a mortar, dripping 1% of glue, continuously grinding, sieving by a 80-mesh sieve after 30min, tabletting by a tabletting machine under the pressure of 20MPa, and maintaining the pressure for 60S.
S3, sintering, namely placing the pressed green body in a muffle furnace for sintering, preserving heat at 650 ℃ for 2h for binder removal, treating at 1200 ℃ for 4h, cooling along with the furnace, taking out a sample when the temperature of the furnace is lower than 150 ℃, and obtaining the CuAl0.8Fe0.2O2High-temperature wave-absorbing ceramic.
Example 6
The embodiment of the invention aims to provide the high-temperature wave-absorbing ceramic with cheap raw materials and low preparation costPorcelain with chemical formula of CuAl and preparation method thereof0.8Fe0.2O2。
Step 1: preparation of CuAl0.82Fe0.18O2High temperature absorbent
Cu with the stoichiometric ratio of 0.5:0.8:0.2 is firstly added2O、Al(OH)3、Fe(OH)3The raw materials are fully and uniformly mixed, then presintered at high temperature and cooled along with a furnace.
CuAl0.82Fe0.18O2The preparation method of the high-temperature absorbent is carried out according to the following steps:
s1, weighing: weighing Cu according to stoichiometric ratio2O、Al(OH)3And Fe (OH)3；
S2, ball milling: weighing Cu2O、Al(OH)3And Fe (OH)3Pouring the mixture into a ball milling tank, adding grinding balls, deionized water and absolute ethyl alcohol, and performing ball milling after flooding;
s3, drying: after the ball milling is finished, putting the mixed slurry in the ball milling tank into an oven for drying after the absolute ethyl alcohol is completely volatilized;
s4, grinding: manually grinding the dried material by using an agate mortar, completely dispersing the hardened material obtained by drying, and then sieving the material by using a 200-mesh sieve;
s5, pre-burning: heating the sieved material to 1100 deg.C, maintaining the temperature for 0.5h, and cooling in furnace to obtain CuAl0.8Fe0.182O2A high temperature absorbent.
Step 2: preparation of CuAl0.8Fe0.2O2High-temperature wave-absorbing ceramic
Pre-sintering to obtain CuAl0.8Fe0.2O2Tabletting and sintering the high-temperature absorbent powder to prepare CuAl0.8Fe0.2O2High-temperature wave-absorbing ceramic.
CuAl0.8Fe0.2O2The preparation method of the high-temperature wave-absorbing ceramic comprises the following steps:
s1, preparing sol, adding 1g of PVA into 100ml of deionized water, heating, continuously stirring to dissolve the PVA, and cooling for later use;
s2, tabletting, namely putting a certain amount of the pre-sintered sample obtained in the step 1 into a mortar, dripping 1% of glue, continuously grinding, sieving by a 80-mesh sieve after 30min, tabletting by a tabletting machine under the pressure of 20MPa, and maintaining the pressure for 60S.
S3, sintering, namely placing the pressed green body in a muffle furnace for sintering, preserving heat at 650 ℃ for 2h for binder removal, treating at 1000 ℃ for 0.5h, cooling along with the furnace, taking out a sample when the temperature of the furnace is lower than 150 ℃, and obtaining the CuAl0.8Fe0.2O2High-temperature wave-absorbing ceramic.
The invention is described in further detail below with reference to the accompanying drawings:
FIG. 1 shows CuAl with different doping amounts at a scan angle of 10-80 deg1-xFexO2XRD pattern of (a). By comparing the trend and peak size of each curve in the graph, it can be known that a small amount of Fe is present3+Can replace CuAlO2Al in (1)3+This is because of Fe3+With Al3+The ionic radii are close and the valence states are the same. With the increase of the Fe doping amount, a new phase FeAl appears2O4And CuAlO2While CuO and Cu appear2Diffraction peak of O. This indicates that when Fe is incorporated in excess (12% or more), FeAl is formed by the reaction2O4The presence of this material inhibits CuAl1-xFexO2And (4) growing crystal grains.
FIG. 2 shows CuAl with different doping amounts at a scanning angle of 30-40 DEG1-xFexO2XRD pattern of (a). With the increase of the Fe doping amount, CuAl1-xFexO2Is constantly decreasing and moving towards low angles, which is Fe3+Continuously replace CuAlO2Middle Al3+The result of (1).
FIG. 3 shows CuAl with different Fe doping amounts1-xFexO2And performing SEM test pattern of morphology characterization on the ceramic sample. Wherein (a) is the micro-morphology of an undoped sample, the surface structure is compact, the grain boundary is fuzzy, and a small amount of air holes appear. (b) To (c) is Fe-doped CuAl1-xFexO2(x ═ 0.03,0.09) of sampleCompared with an undoped sample, the grain size of the sample is slightly reduced, a part of large grains are evolved into small grains, the grain boundary is clear, and the number of air holes is obviously increased. (d) Is Fe doped CuAl1- xFexO2The microstructure of the sample (x is 0.18), compared with the undoped sample, the surface of the sample has larger holes due to the generation of a new phase, the grain size is slightly increased, and the adhesion phenomenon of partial grains occurs.
FIG. 4 shows a ceramic sample with an Fe doping amount of 0, which has an optimum thickness of 4mm, a lowest absorption peak at a frequency of 9.6GHz, and a reflectance of approximately-8.5 dB.
FIG. 5 shows a ceramic sample with an Fe doping amount of 0.03, which has an optimum thickness of 3.3mm, a lowest absorption peak at a frequency of 10.4GHz, and a reflectance of approximately-50.0 dB.
FIG. 6 shows a ceramic sample with an Fe doping amount of 0.09, the optimum thickness is 2.4mm, the lowest value of the absorption peak is at a frequency of 10.3GHz, and the reflectivity is approximately-10.0 dB.
FIG. 7 shows a ceramic sample with 0.18 Fe doping, and a 7mm sample with a reflectivity of approximately-30.0 dB at a frequency of 9.0 GHz.
FIG. 8 is a graph showing reflectance curves at different temperatures for a ceramic sample having an Fe content of 0.03, and it can be found that CuAl is present1- xFexO2The ceramic has excellent wave absorbing performance within the temperature range of 25-1000 ℃.
In conclusion, the invention discloses a method for preparing Fe-doped CuAlO by a simple solid-phase reaction method2High-temperature wave-absorbing ceramic with chemical formula of CuAl1-xFexO2X is less than or equal to 0.2, and the prepared Fe is doped with CuAlO by XRD and SEM2The high-temperature wave-absorbing ceramic powder is characterized, electromagnetic parameters of the high-temperature wave-absorbing ceramic powder are tested by a waveguide method, and the high-temperature wave-absorbing ceramic powder has excellent high-temperature wave-absorbing performance through calculation.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (10)

1. Fe-doped CuAlO2The preparation method of the high-temperature wave-absorbing ceramic is characterized by comprising the following steps of:
1)CuAl1-xFexO2preparation of high temperature absorbents
Uniformly mixing a Cu source substance, an Al source substance and a Fe source substance by ball milling to obtain a mixed material; uniformly grinding the mixed material, drying and sieving to obtain powder, presintering the powder at 1100-1200 ℃ for 0.5-4.0 h, and cooling to obtain CuAl1-xFexO2A high temperature absorbent;
2) fe-doped CuAlO2Preparation of high-temperature wave-absorbing ceramic
To CuAl1-xFexO2Adding 1-5% g/mL PVA sol into a high-temperature absorbent, grinding and sieving to obtain green body powder, pressing the green body powder, and sintering to remove glue to obtain a green body; treating the blank at 1000-1200 ℃ for 0.5-4 h, and cooling to obtain Fe-doped CuAlO2High-temperature wave-absorbing ceramic.
2. Fe doped CuAlO according to claim 12The preparation method of the high-temperature wave-absorbing ceramic is characterized in that in the step 1), the reaction charge ratio of the Cu source substance, the Al source substance and the Fe source substance is 0.5: 1-0.8: 0-0.2 in terms of the amount ratio of the Cu, Al and Fe substances.
3. Fe doped CuAlO according to claim 12The preparation method of the high-temperature wave-absorbing ceramic is characterized in that in the step 1), the Cu source substance comprises Cu2O, CuO and Cu (OH)2One or a mixture of several of them.
4. Fe doped CuAlO according to claim 12The preparation method of the high-temperature wave-absorbing ceramic is characterized in that in the step 1), the Al source substance comprises Al2O3And Al (OH)3One or a mixture of several of them.
5. Fe doped CuAlO according to claim 12The preparation method of the high-temperature wave-absorbing ceramic is characterized in that in the step 1), Fe source substances comprise Fe2O3、Fe3O4、FeO、Fe(OH)2And Fe (OH)3One or a mixture of several of them.
6. Fe doped CuAlO according to claim 12The preparation method of the high-temperature wave-absorbing ceramic is characterized in that in the step 2), the addition amount of (1% -5%) g/mL PVA sol is CuAl1-xFexO20.5-1% of the high-temperature absorbent.
7. Fe doped CuAlO according to claim 12The preparation method of the high-temperature wave-absorbing ceramic is characterized in that in the step 2), the operation condition of green body powder pressing is that the pressure is 20MPa, and the pressure is maintained for 60 s; the sintering and glue discharging operation condition is that the temperature is kept for 2 hours at 650 ℃.
8. Fe doped CuAlO according to claim 12The preparation method of the high-temperature wave-absorbing ceramic is characterized in that powder of 200 meshes is obtained by sieving in the step 1), and green powder of 80 meshes is obtained by sieving in the step 2).
9. Fe-doped CuAlO prepared by the preparation method of any one of claims 1 to 82The high-temperature wave-absorbing ceramic is characterized in that the chemical formula is CuAl1-xFexO2，x≤0.2。
10. Fe doped CuAlO according to claim 92The high-temperature wave-absorbing ceramic is characterized in that the Fe is doped with CuAlO2The reflectivity of the high-temperature wave-absorbing ceramic in the range of 25-1000 ℃ and 8.2-12.4 GHz is less than-10 dB.
CN202010500998.7A 2020-06-04 2020-06-04 Fe-doped CuAlO2High-temperature wave-absorbing ceramic and preparation method thereof Pending CN111592349A (en)

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Application publication date: 20200828