CN111848151B - Magnesium aluminum lithium titanium phosphate LAMTP single-phase ceramic wave-absorbing material and preparation method and application thereof - Google Patents

Magnesium aluminum lithium titanium phosphate LAMTP single-phase ceramic wave-absorbing material and preparation method and application thereof Download PDF

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CN111848151B
CN111848151B CN202010797301.7A CN202010797301A CN111848151B CN 111848151 B CN111848151 B CN 111848151B CN 202010797301 A CN202010797301 A CN 202010797301A CN 111848151 B CN111848151 B CN 111848151B
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absorbing material
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陈丹
周影影
唐健江
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Xian Aeronautical University
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Abstract

The invention discloses a titanium magnesium aluminum lithium phosphate LAMTP single-phase ceramic wave-absorbing material and a preparation method and application thereof, wherein the preparation method comprises the following steps: the raw material is Li 2 CO 3 、NH 4 H 2 PO 4 、TiO 2 、Al 2 O 3 MgO, the ratio of the amounts of substances being 1.1 (0.65 + 0.5x): 3:1.7:0.15-0.5x: x and x are 0.01 to 0.1; after mixing, the raw materials are presintered at 880-920 ℃, and then plasma discharge sintering is carried out at 980-1020 ℃. The invention directly prepares the LAMTP single-phase ceramic wave-absorbing material with obvious wave-absorbing performance without adopting composite materials, and avoids the problems of oxidation and interface reaction when the composite materials are used for a long time.

Description

Magnesium aluminum lithium titanium phosphate LAMTP single-phase ceramic wave-absorbing material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of wave-absorbing material preparation, and relates to a titanium magnesium aluminum lithium phosphate LAMTP single-phase ceramic wave-absorbing material, and a preparation method and application thereof.
Background
With the further development of military science and technology, the modern information war provides the use requirement of the stealth performance of weapons at high temperature. The common high-temperature wave-absorbing material is usually compounded by adopting an absorbent and a substrate, wherein the substrate is usually made of high-temperature-resistant ceramic or glass, and the absorbent is usually a high-conductivity carbon material, such as SiC, znO and Ti 3 SiC 2 And the electromagnetic parameters are regulated and controlled by adjusting the type, content, size, morphology and distribution state of the absorbent. But the composite material has oxidation and interface reaction in long-term useAnd (5) problems are solved.
Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 From TiO 6 Hexahedron and PO 4 Skeleton structure composed of tetrahedrons, al 3+ The ions possibly being located either on tetrahedra or on hexahedrons, li + The ions shuttle in gaps of hexahedron and tetrahedron, and the ion conduction is high, so that the ion conduction type energy storage device is widely applied to the field of energy storage. With Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 The single-phase ceramic is used as a wave-absorbing material, the dielectric constant has a frequency dispersion effect, the absorption bandwidth can be effectively expanded, the loss mechanism is conductance loss, electromagnetic parameters can be regulated and controlled by adjusting the conductivity, the wave-absorbing performance is optimized, and the problems of interface reaction and diffusion existing in long-term use of the low-conductivity ceramic matrix/high-conductivity absorbent composite material can be solved. Currently, li prepared by solid phase method 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 The single-phase ceramic has a conductivity of 1 × 10 -4 S·cm -3 ～4×10 -4 S·cm -3 The conductivity of the material is yet to be improved; li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 The real part of the dielectric constant of the single-phase ceramic is 10.2-13.1, and the imaginary part is 2.2-3.3; in the X wave band, the absorption bandwidth with the reflectivity lower than-10 dB is 2.25GHz, the absorption bandwidth is still to be expanded, the lowest reflectivity is-13.4 dB, and the absorption peak is still to be deepened.
Therefore, in order to solve the above problems, it is necessary to use Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 The single-phase ceramic is modified to improve the conductivity, increase the absorption bandwidth and deepen the absorption peak so as to improve the wave-absorbing performance and enlarge the application range.
Disclosure of Invention
In order to achieve the purpose, the invention provides a titanium magnesium aluminum lithium phosphate LAMTP single-phase ceramic wave-absorbing material, a preparation method and application thereof, and solves the problem of Li in the prior art 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 The wave-absorbing performance of the single-phase ceramic needs to be improved.
Wherein, phosphorusThe acid titanium magnesium aluminum lithium is Li 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 The Chinese name of (2); LAMTP is Li 1.3+ x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 The English language of (1) is abbreviated.
The technical scheme adopted by the invention is that the titanium magnesium aluminum lithium phosphate LAMTP single-phase ceramic wave-absorbing material has a chemical formula general formula of Li 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 And x is 0.01-0.1.
Further, li 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 Has a conductivity of 2X 10 -3 S·cm -3 ～5×10 -3 S·cm -3 (ii) a The Li 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 The real part range of the dielectric constant of (1) is 11.3 to 14.2, and the imaginary part range is 3.0 to 4.0.
The invention also aims to provide a preparation method of the titanium magnesium aluminum lithium phosphate LAMTP single-phase ceramic wave-absorbing material, which comprises the following steps:
s10, preparing raw materials: according to the quantity ratio of the substances 1.1X (0.65 + 0.5X): 3:1.7: (0.15-0.5 x): weighing Li in proportion of x 2 CO 3 、NH 4 H 2 PO 4 、TiO 2 、Al 2 O 3 MgO; wherein x is 0.01 to 0.1; the purity of each raw material is more than 99.99 percent; in order to compensate for the high-temperature volatilization of Li element, li in the raw material 2 CO 3 Is added in an amount of 10wt% more than the amount of the substance calculated in the stoichiometric ratio;
s20, primary ball milling and drying: mixing the prepared raw materials of S1, and then carrying out primary ball milling and drying treatment to obtain precursor powder; the purpose of performing ball milling for one time in S20 is to uniformly mix all the raw materials and prepare for S30 presintering to generate high-temperature solid-phase reaction;
s30, pre-burning: putting the precursor powder obtained in the step S20 into a crucible, transferring the crucible into an air furnace, and heating to 880 ℃ at the heating rate of 5 ℃/minKeeping the temperature at 920 ℃ for 4 to 8 hours, then cooling the product along with the furnace, and grinding the product to obtain single-phase Li 1.3+ x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 Coarsely grinding the particles; wherein, the crucible is preferably a corundum crucible;
wherein, in S30, the pre-sintering aims at synthesizing single-phase Li 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 (ii) a The pre-firing temperature and time are based on Li 2 CO 3 、NH 4 H 2 PO 4 、TiO 2 、Al 2 O 3 Reaction to form Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 When the temperature is below 880 ℃ or above 920 ℃ and the holding time is below 4h or above 8h, li cannot be synthesized as determined by the DSC curve 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 Or impurities appear, and Mg can not enter the Al position.
S30 obtaining single-phase Li of pre-sintered product 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 Can not be directly used as a wave-absorbing material because the wave-absorbing material can be used only by having higher density, if the precursor powder obtained by S20 is molded directly and then presintered by S30 to obtain a molded body or is directly used as a coating material, a large amount of air exists among particles of the molded body or the coating, the dielectric constant and the electric conduction loss of the molded body or the coating can be reduced, and the wave-absorbing performance of the molded body or the coating is influenced, therefore, the single-phase Li obtained by S30 must be used 1.3+ x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 The material with good wave absorption performance can be obtained only by carrying out densification treatment;
s40, secondary ball milling and drying: the single-phase Li obtained in S30 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 Carrying out secondary ball milling and drying treatment on the coarse ground particles to obtain single-phase Li 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 Finely grinding the particles;
s50, sintering: the single-phase Li obtained in S40 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 Placing the finely ground particles into a graphite mould, transferring the graphite mould into a plasma discharge sintering furnace, heating to 980-1020 ℃ at a heating rate of 80-120 ℃/min under the pressure condition of 20-40 MPa, preserving the heat for 4-8 min, and then cooling along with the furnace to obtain the material with the chemical formula of Li 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 The single-phase ceramic wave-absorbing material of LAMTP is prepared from magnesium aluminum lithium titanium phosphate.
Wherein, in S50, single-phase Li 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 The purpose of placing the fine ground particles into a graphite mould for plasma discharge sintering is as follows: by using the principle of sintering under pressure while discharging plasma, dense Li is obtained 1.3+x Al 0.3- x Mg x Ti 1.7 (PO 4 ) 3 Single-phase ceramic wave-absorbing material.
The shrinkage rate is calculated according to the volume difference of the samples before and after sintering, the sintering temperature is lower than 980 ℃, the samples are not compact, the sintering temperature is higher than 1020 ℃, the samples are over-sintered, and the shrinkage rate difference of the samples is large along with the change of the sintering temperature; when the sintering temperature is 980-1020 ℃, the shrinkage rate of the sample is unchanged along with the change of the sintering temperature, so that the sintering temperature is selected to be 980-1020 ℃. Because of different contents of doped Mg, the sintering temperature is within a range, and the sintering temperatures are slightly different for different contents.
Further, in S10, x takes a value of 0.04.
Further, in S20, the primary ball milling and drying specifically includes the following steps:
s21, primary ball milling: mixing the prepared raw materials in the step S10, pouring the mixture into a ball milling tank, adding a grinding ball, wherein the mass ratio of the ball to the material is 20;
s22, primary drying: and after the primary ball milling is finished, pouring out the precursor slurry in the ball milling tank, putting the precursor slurry into an oven with the temperature of 80 ℃ for primary drying after the absolute ethyl alcohol in the precursor slurry is completely volatilized to obtain a precursor material, grinding the precursor material, and sieving the ground precursor material by a 200-mesh sieve to obtain precursor powder. Wherein, the specific process of primary drying is as follows: pouring the precursor slurry in the ball milling tank into a clean stainless steel plate, then putting the plate into a fume hood, after the absolute ethyl alcohol of the precursor slurry is completely volatilized and becomes viscous, putting the plate into an oven at 80 ℃, and taking out the plate after the material is cracked and has no wet trace to obtain a precursor material;
further, in S30, the pre-firing specifically includes: putting the precursor powder obtained in the step S20 into a crucible, transferring the crucible into an air furnace, heating to 900 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 6 hours, cooling along with the furnace, and grinding the obtained product to obtain the single-phase Li 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 And (4) coarsely grinding the particles.
Further, in S40, secondary ball milling and drying specifically include:
s41, secondary ball milling: the single-phase Li obtained in S30 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 Pouring the coarsely ground particles into a ball milling tank, adding a milling ball, wherein the ball-material ratio is 30 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 Coarsely grinding the particles to 2/3 of the ball milling tank, and performing secondary ball milling at 300rad/min for 8h to obtain single-phase Li 1.3+ x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 Sizing agent; wherein, the purpose of secondary ball milling of S41 is to reduce the synthesized single-phase Li 1.3+x Al 0.3- x Mg x Ti 1.7 (PO 4 ) 3 The size of the coarse ground particles;
s42, secondary drying: after the secondary ball milling is finished, the single-phase Li in the ball milling tank is used 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 Pouring out the slurry until single-phase Li is obtained 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 After the absolute ethyl alcohol in the slurry is completely volatilizedPlacing the mixture into an oven at 80 ℃ for secondary drying to obtain single-phase Li 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 Material preparation; mixing single-phase Li 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 Grinding the materials, and sieving with a 200-mesh sieve to obtain single-phase Li 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 The particles are finely ground. Wherein, the specific process of secondary drying is as follows: single-phase Li in a ball milling tank 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 Pouring the slurry into a clean stainless steel plate, placing the plate into a fume hood, and waiting for single-phase Li 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 After the absolute ethyl alcohol of the slurry is volatilized and becomes viscous, the slurry is placed into an oven at 80 ℃, and the slurry is taken out after the materials are cracked and have no any wetting trace, so that the single-phase Li is obtained 1.3+ x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 And (3) feeding.
In S21 and S41, the ball milling tank is made of any one of stainless steel, nylon, polytetrafluoroethylene, alumina and zirconia; the grinding ball is made of any one of stainless steel, aluminum oxide and zirconium oxide.
Further, in S50, the sintering treatment specifically includes: the single-phase Li obtained in S40 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 Placing the fine ground particles into a graphite mold, transferring the graphite mold into a plasma discharge sintering furnace, heating to 1000 ℃ at a heating rate of 100 ℃/min under the pressure condition of 30MPa, preserving heat for 5min, and cooling along with the furnace to obtain Li 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 Single-phase ceramic wave-absorbing material.
Further, S40 obtained Single-phase Li 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 The finely ground particles can also be used as raw materials of stealth coatings to carry out supersonic plasma spraying on the surfaces of objects needing stealth to obtain Li 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 A single phase ceramic coating.
The invention also aims to provide an application of the titanium magnesium aluminum lithium phosphate LAMTP single-phase ceramic wave-absorbing material in the field of wave-absorbing materials.
The beneficial effects of the invention are:
(1) The invention utilizes low-valence element Mg to dope Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 So that the doping elements partially replace Al sites and reduce the Li content of the framework ion pairs + The binding force of ions optimizes Li + The channel size of ion migration increases the carrier Li + The quantity of the ions effectively improves the conductivity and the dielectric constant of the composite material, adjusts the frequency dispersion effect of the composite material and improves the wave absorbing performance of the composite material.
(2) Li prepared by the invention 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 The single-phase ceramic wave-absorbing material has the conductivity of (2-5) multiplied by 10 -3 S·cm -3 In comparison with Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 Is improved by one order of magnitude; the real part of the dielectric constant is 11.3-14.2, the imaginary part is 3.0-4.0, compared with Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 The dielectric property of the dielectric ceramic is obviously improved; in the X wave band, the absorption bandwidth with the reflectivity lower than-10 dB is 2.98GHz, and the absorption bandwidth is more Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 Has obvious improvement, the lowest reflectivity is-17.2 dB, and the absorption peak is more Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 There is a significant deepening.
(3) Li prepared by the invention 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 (x is more than or equal to 0.01 and less than or equal to 0.1) the dielectric constant of the single-phase ceramic has a frequency dispersion effect, which is beneficial to the expansion of absorption bandwidth, and the polarization mechanism is thermionic relaxation polarization, li + The activation energy of ion migration determines the polarization capability, the loss mechanism is the conductance loss, and the conductivity determines the loss value.
(4) The invention directly prepares Li without adopting composite material 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 The single-phase ceramic wave-absorbing material avoids the problems of oxidation and interface reaction existing in the long-term use of the composite material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows Li obtained in example 3 of the present invention 1.34 Al 0.26 Mg 0.04 Ti 1.7 (PO 4 ) 3 XRD pattern of single-phase ceramic wave-absorbing material.
FIG. 2 shows Li obtained in example 3 of the present invention 1.34 Al 0.26 Mg 0.04 Ti 1.7 (PO 4 ) 3 SEM image of single-phase ceramic wave-absorbing material.
FIG. 3 is Li obtained in comparative example 1 of the present invention 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 Single-phase ceramic material and Li prepared in example 3 1.34 Al 0.26 Mg 0.04 Ti 1.7 (PO 4 ) 3 The dielectric constant curve diagram of the single-phase ceramic wave-absorbing material.
FIG. 4 shows Li obtained in example 3 of the present invention 1.34 Al 0.26 Mg 0.04 Ti 1.7 (PO 4 ) 3 Reflectivity curve diagrams of the single-phase ceramic wave-absorbing material under different thicknesses.
FIG. 5 shows Li in comparative example 1 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 Single-phase ceramic material and Li prepared in example 3 1.34 Al 0.26 Mg 0.04 Ti 1.7 (PO 4 ) 3 Reflectivity curve diagrams of the single-phase ceramic wave-absorbing material under respective optimal thicknesses.
Detailed Description
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.
Example 1
Li 1.31 Al 0.29 Mg 0.01 Ti 1.7 (PO 4 ) 3 The preparation method of the single-phase ceramic wave-absorbing material comprises the following steps:
(1) Preparing raw materials: according to the ratio of the amount of the substances of 0.7205:3:1.7:0.145: li was weighed in a proportion of 0.01 2 CO 3 、NH 4 H 2 PO 4 、TiO 2 、Al 2 O 3 MgO; wherein the purity of each raw material is more than 99.99%;
(2) And ball milling for the first time: mixing the prepared raw materials in the step (1), pouring the mixture into a polytetrafluoroethylene ball milling tank, adding zirconia grinding balls, wherein the ball-material mass ratio is 20;
(3) And (3) primary drying: after primary ball milling is finished, pouring the precursor slurry in the ball milling tank into a clean stainless steel plate, then putting the stainless steel plate into a fume hood, after absolute ethyl alcohol of the precursor slurry is completely volatilized and becomes viscous, putting the precursor slurry into an oven at 80 ℃, taking the precursor slurry out after the material is cracked and has no any wet trace (completely dried), obtaining a precursor material, manually grinding the precursor material by adopting an agate mortar until the precursor material is completely dispersed, and sieving the precursor material by using a 200-mesh sieve to obtain precursor powder;
(4) Pre-burning: placing the precursor powder obtained in the step (3) into a corundum crucible, transferring the corundum crucible into an air furnace, heating to 880 ℃ at the heating rate of 5 ℃/min, preserving heat for 4 hours, and then cooling along with the furnace to obtain the productManually grinding the materials by an agate mortar to completely disperse the products to obtain single-phase Li 1.31 Al 0.29 Mg 0.01 Ti 1.7 (PO 4 ) 3 Coarsely grinding the particles;
(5) And (3) secondary ball milling: the single-phase Li obtained in the step (4) 1.31 Al 0.29 Mg 0.01 Ti 1.7 (PO 4 ) 3 Pouring the coarse ground particles into a polytetrafluoroethylene ball mill tank, adding zirconia grinding balls, wherein the ball-material ratio is 30 1.31 Al 0.29 Mg 0.01 Ti 1.7 (PO 4 ) 3 Coarsely grinding the particles to 2/3 of the ball milling tank, and performing secondary ball milling at 300rad/min for 8h to obtain single-phase Li 1.31 Al 0.29 Mg 0.01 Ti 1.7 (PO 4 ) 3 Sizing agent;
(6) And (3) secondary drying: after the secondary ball milling is finished, the single-phase Li in the ball milling tank is added 1.31 Al 0.29 Mg 0.01 Ti 1.7 (PO 4 ) 3 Pouring the slurry into a clean stainless steel plate, placing the plate into a fume hood, and waiting for single-phase Li 1.31 Al 0.29 Mg 0.01 Ti 1.7 (PO 4 ) 3 After the absolute ethyl alcohol of the slurry is volatilized and becomes viscous, the slurry is placed into an oven at 80 ℃, and the slurry is taken out after the material is cracked and has no any wetting trace (is completely dried), so that the single-phase Li is obtained 1.31 Al 0.29 Mg 0.01 Ti 1.7 (PO 4 ) 3 Material preparation; mixing single-phase Li 1.31 Al 0.29 Mg 0.01 Ti 1.7 (PO 4 ) 3 The material is manually ground by an agate mortar and sieved by a 200-mesh sieve to obtain single-phase Li 1.31 Al 0.29 Mg 0.01 Ti 1.7 (PO 4 ) 3 Finely grinding the particles;
(7) And (3) sintering: the single-phase Li obtained in S40 1.31 Al 0.29 Mg 0.01 Ti 1.7 (PO 4 ) 3 Placing the finely ground particles into a graphite mould, transferring the graphite mould into a plasma discharge sintering furnace, heating to 980 ℃ at a heating rate of 80 ℃/min under the pressure condition of 20MPa, preserving the heat for 4min, and then preserving the heat for 4minFurnace cooling to obtain Li 1.31 Al 0.29 Mg 0.01 Ti 1.7 (PO 4 ) 3 Single-phase ceramic wave-absorbing material.
Li obtained in example 1 1.31 Al 0.29 Mg 0.01 Ti 1.7 (PO 4 ) 3 The single-phase ceramic wave-absorbing material has the conductivity of 2 multiplied by 10 - 3 S·cm -3 。
Example 2
Li 1.4 Al 0.2 Mg 0.1 Ti 1.7 (PO 4 ) 3 The preparation method of the single-phase ceramic wave-absorbing material comprises the following steps:
the ratio in terms of the amount of substance in the division (1) was 0.77:3:1.7:0.1: li was weighed in a proportion of 0.1 2 CO 3 、NH 4 H 2 PO 4 、TiO 2 、Al 2 O 3 、MgO；
(3) Heating to 920 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 8 hours;
(7) Heating to 1020 ℃ at the heating rate of 120 ℃/min under the pressure condition of 40MPa, and keeping the temperature for 8min.
The remaining steps were the same as in example 1.
Li obtained in example 2 1.4 Al 0.2 Mg 0.1 Ti 1.7 (PO 4 ) 3 The single-phase ceramic wave-absorbing material has the conductivity of 4 multiplied by 10 - 3 S·cm -3 。
Example 3
Li 1.34 Al 0.26 Mg 0.04 Ti 1.7 (PO 4 ) 3 The preparation method of the single-phase ceramic wave-absorbing material comprises the following steps:
the ratio in terms of the amount of substances in the division (1) is 0.737:3:1.7:0.13: li was weighed in a proportion of 0.04 2 CO 3 、NH 4 H 2 PO 4 、TiO 2 、Al 2 O 3 、MgO；
(3) Heating to 900 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 6h;
(7) Heating to 1000 ℃ at a heating rate of 100 ℃/min under the pressure condition of 30MPa, and keeping the temperature for 5min.
The remaining steps were the same as in example 1.
Li obtained in example 3 1.34 Al 0.26 Mg 0.04 Ti 1.7 (PO 4 ) 3 The single-phase ceramic wave-absorbing material has the conductivity of 5 multiplied by 10 - 3 S·cm -3 。
Example 4
Li 1.37 Al 0.23 Mg 0.07 Ti 1.7 (PO 4 ) 3 The preparation method of the single-phase ceramic wave-absorbing material comprises the following steps:
the ratio in terms of the amount of substances in the division (1) is 0.754:3:1.7:0.115: li was weighed in a proportion of 0.07 2 CO 3 、NH 4 H 2 PO 4 、TiO 2 、Al 2 O 3 、MgO；
The remaining steps were the same as in example 3.
Li obtained in example 4 1.34 Al 0.26 Mg 0.04 Ti 1.7 (PO 4 ) 3 The single-phase ceramic wave-absorbing material has the conductivity of 4.5 multiplied by 10 -3 S·cm -3 。
Comparative example 1
Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 The preparation method of the single-phase ceramic material comprises the following steps:
the ratio in terms of the amount of substance in the division (1) is 0.65:3:1.7: li was weighed in a proportion of 0.15 2 CO 3 、NH 4 H 2 PO 4 、TiO 2 、Al 2 O 3 ；
The remaining steps were the same as in example 3.
Li of comparative example 1 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 Conductivity of single phase ceramic material 2X 10 -4 S·cm -3 。
Experimental example 1
For L obtained in example 3i 1.34 Al 0.26 Mg 0.04 Ti 1.7 (PO 4 ) 3 XRD test is carried out on the single-phase ceramic wave-absorbing material, and the test result is shown in figure 1. As shown in FIG. 1, the crystalline phase of the wave-absorbing material prepared in example 1 of the present invention is Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 The diffraction peak at the position of the single phase is at a position closer to Li than that of the diffraction peak at the position of 24 DEG to 25 DEG as seen from the enlarged image of the diffraction peak at the position of the single phase 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 The diffraction peak at the position shifts to a small angle in pure phase, which indicates that the wave-absorbing material prepared in the embodiment has the existence of a doped product magnesium, and the diffraction peak shifts to a small angle according to a Bragg equation 2dsin theta = n lambda, wherein d is the interplanar spacing, theta is the diffraction angle, lambda is the wavelength, n is the reflection order, and the decrease of the diffraction angle indicates the increase of the interplanar spacing, thereby further proving that the ionic radius is larger than that of Al 3+
Figure BDA0002626136050000081
Ionic Mg 2+
Figure BDA0002626136050000082
Successful ion doping into Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 Formation of Li 1.34 Al 0.26 Mg 0.04 Ti 1.7 (PO 4 ) 3 Single-phase ceramic wave-absorbing material. Wherein the dotted line position in the enlarged view of diffraction peaks at positions 24 to 25 ℃ in FIG. 1 represents undoped Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 The diffraction peak of (4).
Experimental example 2
For Li prepared in example 3 1.34 Al 0.26 Mg 0.04 Ti 1.7 (PO 4 ) 3 SEM test is carried out on the microscopic morphology of the single-phase ceramic wave-absorbing material, and the test result is shown in figure 2. As can be seen from FIG. 2, li obtained in example 3 1.34 Al 0.26 Mg 0.04 Ti 1.7 (PO 4 ) 3 The grain size of the single-phase ceramic wave-absorbing material is between 1 mu m and 18 mu m, and the compactness is uniformAbove 95%.
Experimental example 3
For Li prepared in example 3 1.34 Al 0.26 Mg 0.04 Ti 1.7 (PO 4 ) 3 The wave-absorbing performance of the single-phase ceramic wave-absorbing material is tested, and the test results are shown in figures 3-5.
First, li obtained in example 3 1.34 Al 0.26 Mg 0.04 Ti 1.7 (PO 4 ) 3 Single-phase ceramic wave-absorbing material and Li prepared in comparative example 1 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 The dielectric constant of the single-phase ceramic material was tested and the dielectric constant curve is shown in fig. 3. As can be seen from FIG. 3, li obtained in example 3 1.34 Al 0.26 Mg 0.04 Ti 1.7 (PO 4 ) 3 Single-phase ceramic wave-absorbing material and Li prepared in comparative example 1 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 The dielectric constant of the single-phase ceramic material shows a frequency dispersion effect along with the change of frequency. Li obtained in comparative example 1 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 The real part of the dielectric constant of the single-phase ceramic material is 10.2-13.1, and the imaginary part is 2.2-3.3. Li obtained in example 3 1.34 Al 0.26 Mg 0.04 Ti 1.7 (PO 4 ) 3 The real part of the dielectric constant of the single-phase ceramic wave-absorbing material is 11.3-14.2, and the imaginary part is 3.0-4.0, which are all increased compared with the comparative example 1.
Next, for Li obtained in example 3 1.34 Al 0.26 Mg 0.04 Ti 1.7 (PO 4 ) 3 The reflectivity curves of the single-phase ceramic wave-absorbing material under different thicknesses are tested, and the test result is shown in figure 4. As can be seen from fig. 4, the absorption peak shifts to a low frequency as the thickness increases. By selecting the thickness having the widest absorption bandwidth as the optimum thickness at the thinnest possible thickness, li obtained in example 3 1.34 Al 0.26 Mg 0.04 Ti 1.7 (PO 4 ) 3 The optimal thickness of the single-phase ceramic wave-absorbing material is 2.1mm.
Finally, li obtained in example 3 1.34 Al 0.26 Mg 0.04 Ti 1.7 (PO 4 ) 3 Single-phase ceramic wave-absorbing material and Li prepared in comparative example 1 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 The reflectivity curves of the single-phase ceramic materials at the respective optimum thicknesses were tested, and the test results are shown in fig. 5. As can be seen from FIG. 5, li obtained in comparative example 1 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 The optimal thickness of the single-phase ceramic material is 2.2mm, the bandwidth with the reflectivity lower than-10 dB in an X wave band is 2.25GHz, and the minimum reflectivity is-13.4 dB. Example 3 Li in comparison to comparative example 1 1.34 Al 0.26 Mg 0.04 Ti 1.7 (PO 4 ) 3 The optimal thickness of the single-phase ceramic wave-absorbing material is 2.1mm, the optimal thickness is reduced compared with that of a comparative example 1, the bandwidth with the reflectivity lower than-10 dB in an X wave band is 2.98GHz, the bandwidth is obviously increased compared with that of the comparative example 1, the minimum reflectivity is-17.2 dB, and the absorption peak is deeper. This is due to the Li prepared in example 3 1.34 Al 0.26 Mg 0.04 Ti 1.7 (PO 4 ) 3 Proper amount of Mg is doped into single-phase ceramic wave-absorbing material 2+ After ionization, li with proper size is obtained + The ion migration channel reduces the migration activation energy and obviously improves Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 The conductivity of the ceramic increases the conductivity loss and obtains better wave-absorbing performance.
It is noted that, in this application, relational terms such as first, second, third, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrases "comprising a," "8230," "8230," or "comprising" does not exclude the presence of additional like elements in a process, method, article, or apparatus that comprises the element.
All the embodiments in the present specification are described in a related manner, and the same and similar parts among the embodiments may be referred to each other, and each embodiment focuses on differences from other embodiments.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.

Claims (8)

1. A preparation method of a titanium magnesium aluminum lithium phosphate LAMTP single-phase ceramic wave-absorbing material is characterized by comprising the following steps:
s10, preparing raw materials: ratio of the amounts of substances according to 1.1 × (0.65 + 0.5x): 3:1.7: (0.15-0.5 x): x ratio of Li to 2 CO 3 、NH 4 H 2 PO 4 、TiO 2 、Al 2 O 3 MgO; wherein the value of x is 0.01-0.1;
s20, primary ball milling and drying: mixing the raw materials prepared in the step S10, and then carrying out primary ball milling and drying treatment to obtain precursor powder;
s30, pre-burning: putting the precursor powder obtained in the step S20 into a crucible, transferring the crucible into an air furnace, heating to 880-920 ℃ at the heating rate of 5 ℃/min, preserving the heat for 4-8 h, cooling along with the furnace, and grinding the obtained product to obtain the single-phase Li 1.3+x Al 0.3- x Mg x Ti 1.7 (PO 4 ) 3 Coarsely grinding the particles;
s40, secondary ball milling and drying: the single-phase Li obtained in S30 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 Carrying out secondary ball milling and drying treatment on the coarse ground particles to obtain single-phase Li 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 Finely grinding the particles;
s50, sintering: the single-phase Li obtained in S40 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 Placing the finely ground particles into a graphite mould, transferring the graphite mould into a plasma discharge sintering furnace, heating to 980-1020 ℃ at a heating rate of 80-120 ℃/min under the pressure condition of 20-40 MPa, preserving the heat for 4-8 min, and then cooling along with the furnace to obtain the material with the chemical formula of Li 1.3+x Al 0.3- x Mg x Ti 1.7 (PO 4 ) 3 The LAMTP single-phase ceramic wave-absorbing material is prepared by mixing the titanium phosphate, the magnesium aluminum lithium phosphate and the LAMTP single-phase ceramic wave-absorbing material;
the titanium magnesium aluminum lithium phosphate LAMTP single-phase ceramic wave-absorbing material has a chemical formula general formula of Li 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 The value of x is 0.01-0.1;
the Li 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 Has a conductivity of 2X 10 -3 S·cm -1 ～5×10 -3 S·cm -1 (ii) a The Li 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 The real part of the dielectric constant of (1) ranges from 11.3 to 14.2, and the imaginary part ranges from 3.0 to 4.0.
2. The method for preparing a LAMTP single-phase ceramic wave-absorbing material of magnesium aluminum lithium titanium phosphate according to claim 1, wherein in S10, the value of x is 0.04.
3. The preparation method of the titanium magnesium aluminum lithium phosphate LAMTP single-phase ceramic wave-absorbing material according to claim 1, wherein in S20, the primary ball milling and drying specifically comprise the following steps:
s21, primary ball milling: mixing the prepared raw materials in the step S10, pouring the mixture into a ball milling tank, adding grinding balls, wherein the mass ratio of the ball materials is 20;
s22, primary drying: and after the primary ball milling is finished, pouring out the precursor slurry in the ball milling tank, putting the precursor slurry into an oven at 80 ℃ for primary drying after the absolute ethyl alcohol in the precursor slurry is completely volatilized to obtain a precursor material, grinding the precursor material, and sieving by using a 200-mesh sieve to obtain precursor powder.
4. The method for preparing a titanium magnesium aluminum lithium phosphate LAMTP single-phase ceramic wave-absorbing material according to claim 1, wherein in S30, the pre-sintering specifically comprises the following steps: putting the precursor powder obtained in the step S20 into a crucible, transferring the crucible into an air furnace, heating to 900 ℃ at the heating rate of 5 ℃/min, preserving the heat for 6 hours, cooling along with the furnace, and grinding the obtained product to obtain the single-phase Li 1.3+ x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 And (4) coarsely grinding the particles.
5. The preparation method of the LAMTP single-phase ceramic wave-absorbing material of claim 1, wherein in S40, the secondary ball milling and drying specifically comprise:
s41, secondary ball milling: the single-phase Li obtained in S30 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 Pouring the coarsely ground particles into a ball milling tank, adding a milling ball, wherein the ball-material ratio is 30 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 Coarsely grinding the particles to 2/3 of the ball milling tank, and performing secondary ball milling at 300rad/min for 8h to obtain single-phase Li 1.3+x Al 0.3- x Mg x Ti 1.7 (PO 4 ) 3 Sizing agent;
s42, secondary drying: after the secondary ball milling is finished, the single-phase Li in the ball milling tank is added 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 Pouring out the slurry until single-phase Li is obtained 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 After the absolute ethyl alcohol in the slurry is completely volatilized, the slurry is placed into an oven at 80 ℃ for secondary drying to obtain single-phase Li 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 Material preparation; mixing single-phase Li 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 Grinding the materials, and sieving with a 200-mesh sieve to obtain single-phase Li 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 The particles are finely ground.
6. The preparation method of the LAMTP single-phase ceramic wave-absorbing material of claim 1, wherein in S50, the sintering treatment specifically comprises the following steps: the single-phase Li obtained in S40 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 Placing the fine ground particles into a graphite mold, transferring the graphite mold into a plasma discharge sintering furnace, heating to 1000 ℃ at a heating rate of 100 ℃/min under the pressure condition of 30MPa, preserving heat for 5min, and cooling along with the furnace to obtain Li 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 Single-phase ceramic wave-absorbing material.
7. The method for preparing LAMTP single-phase ceramic wave-absorbing material of claim 1, wherein the single-phase Li obtained in S40 is 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 The finely ground particles can also be used as raw materials of stealth coatings to carry out supersonic plasma spraying on the surfaces of objects needing stealth to obtain Li 1.3+x Al 0.3-x Mg x Ti 1.7 (PO 4 ) 3 A single phase ceramic coating.
8. The application of the LAMTP single-phase ceramic wave-absorbing material prepared by the preparation method of the LAMTP single-phase ceramic wave-absorbing material of the magnesium aluminum lithium titanium phosphate according to claim 1 in the field of wave-absorbing materials.
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