CN110270683B - Fe/ZrH2 nanocrystalline composite particle and preparation method and application thereof - Google Patents

Fe/ZrH2 nanocrystalline composite particle and preparation method and application thereof Download PDF

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CN110270683B
CN110270683B CN201810220888.8A CN201810220888A CN110270683B CN 110270683 B CN110270683 B CN 110270683B CN 201810220888 A CN201810220888 A CN 201810220888A CN 110270683 B CN110270683 B CN 110270683B
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CN110270683A (en
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官建国
王彦淇
陈志宏
李维
赵素玲
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Wuhan Shuanghu Coating Co ltd
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Wuhan University of Technology WUT
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    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling

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Abstract

The invention discloses Fe/ZrH2Nanocrystalline composite particles comprising carbonyl iron powder and ZrH2The particles are used as main raw materials and are simply prepared by a ball milling and stirring method. The invention combines ZrH2The Fe/ZrH with temperature resistance is obtained by the stabilizing effect of the particles on the microscopic grain boundary of the carbonyl iron powder, the Zr element content control technology and the Zr distribution regulation and control technology2Composite particles; the Fe/ZrH2After the composite particles are subjected to heat treatment at 500 ℃ for 1h, the grain size is within 20nm, the electromagnetic parameters of 2-18GHz are not obviously changed, and the composite particles have good temperature resistance and important application prospects in the fields of temperature-resistant wave absorbing agents and the like.

Description

Fe/ZrH2Nanocrystalline composite particle and preparation method and application thereof
Technical Field
The invention belongs to the field of electronic materials, and particularly relates to Fe/ZrH2Nanocrystalline composite particles, a preparation method and application thereof.
Background
The microwave absorbing material can absorb and attenuate incident electromagnetic waves and convert the incident electromagnetic waves into heat energy to be lost, so that the microwave absorbing material is widely applied to the aspects of military stealth, electromagnetic shielding and human body safety protection. With the development of military technology, the temperature of the surface skin of an aircraft can reach more than 300 ℃ in the flying process, and the temperature close to the tail pipe of an engine can reach more than 500 ℃. Therefore, the temperature-resistant wave-absorbing material has important significance for keeping the stealth performance of the aircraft in the working state.
The temperature-resistant wave-absorbing materials developed at present are classified into dielectric loss type temperature-resistant wave-absorbing materials and magnetic loss type temperature-resistant wave-absorbing materials according to different loss mechanisms. The loss performance of the dielectric loss type temperature-resistant wave-absorbing material mainly depends on the complex dielectric constant (epsilon' -i epsilon) of the material; this material has the disadvantage of large thickness and narrow absorption band due to the limitation of a single loss mechanism. The absorption performance of the magnetic loss type temperature-resistant wave-absorbing material mainly depends on the complex dielectric constant (epsilon '-i epsilon ") and the complex permeability (mu-mu' -i mu") of the wave-absorbing agent, namely, the wave-absorbing material has two loss mechanisms of dielectric loss and magnetic loss, so that the wave-absorbing material can be designed into a thin-layer wave-absorbing material with the thickness of less than 2.0mm, the absorption frequency bandwidth of the wave-absorbing material is far greater than that of the dielectric loss wave-absorbing material, and the wave-absorbing material has great application prospect in military affairs.
In the magnetic loss type temperature-resistant wave-absorbing material, carbonyl iron powder has higher saturation magnetization intensity, so the carbonyl iron powder is the preferred material of the wave-absorbing agent. However, since carbonyl iron powder has poor temperature resistance, oxidation or microstructure change easily occurs at the time of temperature rise, so that the complex permittivity and complex permeability are changed, and the wave absorbing performance is deteriorated. Aiming at the problem of the oxidation of carbonyl iron powder at high temperature, people develop the surface coating technology to design and prepare a temperature-resistant magnetic wave absorber, such as Fe @ SiO2(Physica B Condensed Matter,2011,406(4):777-780)、Fe@Al2O3(Acta Metallurgica Slovaca Conference,2010, No.2, S.2010.) and Fe @ Silicone (Journal of Magnetism)&Magnetic Materials,2015,374: 345-. However, the method cannot avoid the microstructure change of carbonyl iron powder, such as the phenomenon of large crystal grain growth, and the complex dielectric constant and the complex permeability of carbonyl iron powder still have large deterioration at the temperature rise. Fig. 1 shows the XRD diffractogram of the processed carbonyl iron powder at room temperature and after 1h vacuum heat treatment at 500 deg.c, calculated by the scherrer equation. The grain size of the high-purity carbonyl iron powder at room temperature is 9.2nm, and the grain size after 1h of vacuum heat treatment at 500 ℃ is 179.2 nm. Fig. 2 shows the electromagnetic parameters of carbonyl iron powder after vacuum heat treatment at room temperature and 500 ℃ for 1h, and we can see that the complex dielectric constant is obviously increased and the complex permeability is obviously reduced. Therefore, how to solve the problem of the change of the microstructureThe problem that the complex dielectric constant and the complex magnetic permeability are changed becomes a technical problem for preparing the temperature-resistant wave-absorbing material.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide Fe/ZrH2Nanocrystalline composite particles of ZrH2The particles and carbonyl iron powder are compounded by mechanical force, wherein ZrH2The particles are uniformly distributed in the grain boundary of the iron nanocrystalline, so that the growth of the iron nanocrystalline can be effectively inhibited, the temperature resistance of the iron nanocrystalline is improved, and the like; the material is used as a microwave absorbing material, can show excellent temperature resistance and wave absorption performance, and basically does not change the electromagnetic parameters after heat treatment at 500 ℃.
In order to achieve the purpose, the invention adopts the technical scheme that:
Fe/ZrH2Nanocrystalline composite particles, which are spherical or plate-shaped; comprises Fe nano-crystals and ZrH distributed at the grain boundary2Particles, wherein the grain size of the Fe nanocrystals is 8-20 nm.
In the scheme, the Fe/ZrH2The nanocrystalline composite particle is ZrH2The powder and carbonyl iron powder are used as raw materials and are prepared by ball milling.
Preferably, the Fe/ZrH2The nanocrystalline composite particle is ZrH2The powder and carbonyl iron powder are taken as raw materials and are sequentially subjected to ball milling and stirring milling to obtain the powder.
Fe/ZrH2The preparation method of the nanocrystalline composite particle comprises the following steps: reacting ZrH2Mixing the particles with carbonyl iron powder, then placing the mixture into a ball mill for ball milling, and separating and collecting powder; obtaining the Fe/ZrH2A nanocrystalline composite particle.
The other Fe/ZrH2The preparation method of the nanocrystalline composite particle comprises the following steps: 1) reacting ZrH2Mixing the particles with carbonyl iron powder, then placing the mixture in a ball mill for ball milling, and separating and collecting powder; 2) placing the powder obtained in the step 1) into a stirring and grinding tank, stirring and grinding, finally separating grinding balls from the product, and drying to obtain Fe/ZrH2A nanocrystalline composite particle.
In the above scheme, theZrH2The mass ratio of the powder to the carbonyl iron powder is 1 (4-200).
In the above scheme, the purity of iron in the carbonyl iron powder is 99 wt.% or more.
In the scheme, the ball milling time is more than 20 hours; the stirring and milling time is more than 1 h.
In the scheme, the ball milling speed adopted in the ball milling process is 200-300rpm, and the ball-material ratio is (15-30): 1.
In the scheme, n-hexane or ethanol and the like are used as ball milling media in the ball milling process, and the addition amount of the n-hexane or ethanol is ZrH25-55% of the total mass of the powder and the carbonyl iron powder.
In the scheme, in the stirring and grinding process, the stirring and grinding frequency is 5-20Hz, and the ball-material ratio is (60-120): 1.
In the scheme, ethanol and the like are used as stirring and grinding media in the stirring and grinding process, and the addition amount of the ethanol and the like is ZrH23-8 times of the total mass of the powder and the carbonyl iron powder.
Fe/ZrH obtained according to the scheme2The application of the nanocrystalline composite particles is suitable for being used as a temperature-resistant wave absorbing agent, electromagnetic parameters are basically not changed after heat treatment at 500 ℃, and both the electromagnetic performance and the temperature resistance are taken into consideration.
The invention adopts the following principle:
the invention adopts a mechanical force composite method and utilizes ZrH2Good thermal stability and oxidation resistance, and ZrH2The molecule is easy to segregate in the grain boundary to block the growth of iron nanometer crystal, firstly, the ball milling method is adopted to lead the nanometer ZrH2The particles are dispersed and distributed at the crystal boundary of the iron nanocrystalline, so that the growth of iron grains is inhibited, and the temperature resistance of the carbonyl iron powder is improved; then stirring and grinding are carried out to further promote the obtained Fe/ZrH2The composite particles have electromagnetic performance, and can show excellent temperature resistance and electromagnetic wave absorption performance when used as a microwave absorption material.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention adopts ZrH2Preparation of Fe/ZrH by carrying out composite modification on carbonyl iron powder2Nanocrystalline compositeComposite particles, nano ZrH2The particles can be uniformly dispersed in the grain boundary of the iron nanocrystalline, so that the grain boundary is pinned, the growth of the iron nanocrystalline is hindered, and the temperature resistance of the iron nanocrystalline is improved.
2) The invention adopts a simple ball milling and stirring method, firstly ball milling is carried out to ensure that iron powder and ZrH are mixed2Particles are fully compounded by ZrH2The principle that the grain boundary segregation is easy to hinder the growth of iron nano-crystals is adopted, the temperature resistance of carbonyl iron powder is improved, and then the obtained Fe/ZrH is further improved by stirring and grinding2The electromagnetic properties of the nanocrystalline composite particles; the related preparation process is simple and easy to control, and the temperature resistance and the electromagnetic property of the obtained product can be ensured at the same time.
3) Fe/ZrH obtained by the invention2The nanocrystalline composite particles can still maintain stable electromagnetic parameters at the working temperature of 500 ℃, and have potential application in temperature-resistant wave-absorbing materials for aircrafts.
Drawings
FIG. 1 is an XRD pattern of carbonyl iron powder after heat treatment at room temperature and 500 ℃ for 1 h;
FIG. 2 shows the electromagnetic parameters of carbonyl iron powder after heat treatment at room temperature and 500 ℃ for 1 hour;
FIG. 3 is an XRD diffractogram of carbonyl iron powder used in example 1;
FIG. 4 shows a ZrH nanopowder used in example 12XRD diffractogram of the particles;
FIG. 5 shows Fe/ZrH of example 12SEM image of nanocrystalline composite particle
FIG. 6 shows Fe/ZrH of example 12Selecting a diffraction electron pattern diagram of the nanocrystalline composite particles;
FIG. 7 shows Fe/ZrH of example 12A) a TEM image of the surface morphology of the nanocrystalline composite particles; b) an energy spectrum; c) distribution diagram of iron element; d) distribution diagram of zirconium element;
FIG. 8 is an XRD pattern of the product obtained in example 1 at room temperature and after heat treatment at 500 ℃ for 1 h;
FIG. 9 shows the electromagnetic parameters of the product obtained in example 1 at room temperature and after a heat treatment at 500 ℃ for 1 hour;
FIG. 10 is an XRD pattern of the product obtained in example 2 at room temperature and after heat treatment at 500 ℃ for 1 h;
FIG. 11 shows the electromagnetic parameters of the product obtained in example 2 at room temperature and after a heat treatment at 500 ℃ for 1 hour;
FIG. 12 is an XRD pattern of the product obtained in example 3 at room temperature and after heat treatment at 500 ℃ for 1 h;
FIG. 13 shows the electromagnetic parameters of the product obtained in example 3 at room temperature and after a heat treatment at 500 ℃ for 1 hour;
FIG. 14 shows Fe/ZrH of example 42SEM images of the composite particles;
FIG. 15 is an XRD pattern of the product obtained in example 4 at room temperature and after heat treatment at 500 ℃ for 1 h;
FIG. 16 shows the electromagnetic parameters of the product obtained in example 4 at room temperature and after a heat treatment at 500 ℃ for 1 hour;
FIG. 17 shows Fe/ZrH obtained in comparative example 12SEM images of the mixed particles;
FIG. 18 is an XRD pattern of the product obtained in comparative example 1 at room temperature and after heat treatment at 500 ℃ for 1 h;
FIG. 19 shows the electromagnetic parameters of the product obtained in comparative example 1 at room temperature and after a heat treatment at 500 ℃ for 1 hour.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
In the following examples, the carbonyl iron powder used is that provided by Jiangsu Tianyi.
Example 1
Fe/ZrH2The preparation method of the nanocrystalline composite particle comprises the following steps:
1) 19.4g of carbonyl iron powder and 0.6g of ZrH2Putting the powder into a ball milling tank (ZrH)2The mass fraction of the particles in the composite powder is 3 wt.%), weighing stainless steel grinding balls of 10mm and 6mm according to the ball-to-material ratio of 20:1, wherein the ratio of large balls to small balls is 3: 2; then 10ml of analytically pure n-hexane is added as a dispersing agent; setting the ball mill to be in a positive and negative rotation alternating mode, wherein the period of each rotation is 5h, stopping for 20min in the middle, and setting the ball milling timeThe rotating speed is 260rpm/min for 80 h; after the ball milling is finished, separating the balls and the powder by using a 300-mesh sieve;
2) taking 10g of the powder obtained in the step 1), weighing zirconia balls with the diameter of 6mm according to the mass ratio (ball-to-material ratio) of 80:1, adding the powder and the balls into a stirring and grinding tank, adding 100ml of ethanol serving as a stirring and grinding medium, setting the stirring and grinding time to be 8h, and setting the stirring and grinding frequency to be 10 Hz; after the stirring and grinding are finished, screening a mixed solution of the separation ball and the ethanol powder by using a sieve, and adsorbing a disc of the sieve by using a magnet to separate the ethanol and the powder; putting the powder into a drying oven, setting the drying temperature to be 60 ℃ and the drying time to be 1h to obtain the Fe/ZrH2A nanocrystalline composite particle.
FIG. 5 is a scanning electron micrograph of the product obtained in this example, wherein it can be seen that the product obtained has a lamellar structure with a platelet thickness of about 0.6 μm;
FIG. 6 is a plot of the selected area electron diffraction pattern of the product obtained in this example, from which ZrH can be clearly observed2And (2) crystal planes of (111) and (112) and (110) and (211) crystal planes of iron, and no other peak is found, and ZrH is proved2No decomposition occurs during the ball milling process;
FIG. 7 shows TEM and EDS energy spectra of this example. No oxygen element exists in the energy spectrum, which indicates that no oxidation occurs in the ball milling process, and all Zr elements come from ZrH2。
In order to detect the temperature resistance of the obtained product, a certain amount of Fe/ZrH is taken2And (3) placing the nanocrystalline composite particles into a crucible, placing the crucible into a muffle furnace, heating the crucible to 500 ℃ at a heating rate of 8 ℃/min, preserving the temperature for 1h, taking out the sample after the temperature in the furnace is cooled, and carrying out XRD test.
FIG. 8 shows Fe/ZrH obtained in this example2XRD patterns of the nanocrystalline composite particles after heat treatment at room temperature and 500 ℃ for 1h are calculated according to the Sherrer formula, and Fe/ZrH before and after heat treatment is calculated2The grain sizes of Fe of the composite particles were 10.2nm and 19.7 nm. According to FIG. 1 and FIG. 8, the lattice parameter of carbonyl iron powder is calculated to be 0.2844nm, Fe/ZrH2The lattice parameter of the composite particle iron is 0.2844 nm. The lattice parameter of iron in the two is not changed, so that the system is proved to be Fe/ZrH2Nanocrystalline composite particles (not doped into the interior of the iron lattice, causing a change in lattice parameter), FIG. 18 is Fe/ZrH2Although the mixed particles do not have the stability of crystal grains, it can be estimated that ZrH is segregated in the grain boundary for impurities not incorporated into crystal lattices in general, excluding the possibility of mixed particles and alloys, from the information of fig. 1, 8 and 182The particles segregate at the grain boundaries of the iron nanocrystals.
As shown in figure 1, the grain size of the carbonyl iron powder is increased by up to 1848% after the carbonyl iron powder is subjected to heat treatment at 500 ℃ for 1h before being compounded, and the grain size is increased from 9.2nm to 179.2nm, while the Fe/ZrH obtained by the invention2After the composite particles are subjected to heat treatment at 500 ℃ for 1h, the grain size is only increased by 93.1 percent and is far lower than that of carbonyl iron powder before the composite treatment.
FIG. 9 is a graph showing electromagnetic parameter test patterns of the product obtained in this example after heat treatment at room temperature and 500 ℃ for 1h, and the result shows that the obtained flaky Fe/ZrH2The electromagnetic parameters of the nanocrystalline composite particles do not change obviously before and after heat treatment, and the nanocrystalline composite particles have good temperature resistance.
Example 2
Fe/ZrH2The preparation method of the nanocrystalline composite particle comprises the following steps:
1) 18.4g of carbonyl iron powder and 1.6g of ZrH2Putting the powder into a ball milling tank (ZrH)2The mass fraction of the particles in the composite powder is 8 wt.%), and stainless steel grinding balls with the diameter of 10mm and stainless steel grinding balls with the diameter of 6mm are weighed according to the ball-to-material ratio of 20:1, wherein the ratio of the large balls to the small balls is 3: 2; then 10ml of analytically pure n-hexane is added as a dispersing agent; setting the ball mill to be in a positive and negative rotation alternating mode, wherein the period of each rotation is 5h, the middle rotation is stopped for 20min, the ball milling time is set to be 100h, and the rotating speed is 240 rpm/min; after the ball milling is finished, separating the balls and the powder by using a 300-mesh sieve;
2) taking 10g of the powder obtained in the step 1), weighing zirconia balls with the diameter of 6mm according to the mass ratio (ball-to-material ratio) of 80:1, adding the powder and the balls into a stirring and grinding tank, adding 100ml of ethanol serving as a stirring and grinding medium, setting the stirring and grinding time to be 10h, and setting the stirring and grinding frequency to be 8 Hz; after the stirring and grinding are finished, the ethanol powder is mixed with a sieve separating ballMixing the solution, and adsorbing the sieved plate with a magnet to separate ethanol and powder; putting the powder into a drying oven, setting the drying temperature to be 60 ℃ and the drying time to be 1h to obtain the Fe/ZrH2A nanocrystalline composite particle.
In order to detect the temperature resistance of the obtained product, a certain amount of Fe/ZrH is taken2And (3) placing the nanocrystalline composite particles into a crucible, placing the crucible into a muffle furnace, heating the crucible to 500 ℃ at a heating rate of 8 ℃/min, preserving the temperature for 1h, taking out the sample after the temperature in the furnace is cooled, and carrying out XRD test.
FIG. 10 shows Fe/ZrH obtained in this example2XRD patterns of the nanocrystalline composite particles at room temperature and after heat treatment at 500 ℃ for 1h are calculated according to the Sherry formula, and Fe/ZrH of the nanocrystalline composite particles at room temperature and after heat treatment at 500 ℃ is calculated according to the Sherry formula2The grain sizes of the composite iron particles were 9.6nm and 16.5 nm. According to FIG. 1 and FIG. 10, the lattice parameter of carbonyl iron powder is calculated to be 0.2844nm, Fe/ZrH2The lattice parameter of iron in the nanocrystalline composite particles is 0.2844nm, so that the system is proved to be Fe/ZrH2Nanocrystalline composite particles, rather than alloy systems. FIG. 1 shows that the grain size of nanocrystalline carbonyl iron powder increases up to 1848% after heat treatment at 500 ℃ for 1h without being compounded, and the grain size increases from 9.2nm to 179.2nm, while Fe/ZrH2After the composite particles are subjected to heat treatment at 500 ℃ for 1h, the grain size of the iron is only increased by 71.9 percent and is far lower than that of the carbonyl iron powder before the composite treatment.
FIG. 11 is a graph showing electromagnetic parameter test patterns of the product obtained in this example after heat treatment at room temperature and 500 ℃ for 1h, and the result shows that the obtained flaky Fe/ZrH2The electromagnetic parameters of the composite particles do not change obviously before and after heat treatment, and the composite particles have good temperature resistance.
Example 3
Fe/ZrH2The preparation method of the nanocrystalline composite particle comprises the following steps:
1) 19g of carbonyl iron powder and 1g of ZrH2Putting the powder into a ball milling tank (ZrH)2The mass fraction of the particles in the composite powder is 5 wt.%), and stainless steel grinding balls with the diameter of 10mm and stainless steel grinding balls with the diameter of 6mm are weighed according to the ball-to-material ratio of 20:1, wherein the ratio of the large balls to the small balls is 3: 2; 15ml of analytically pure n-hexane were added asA dispersant; setting the ball mill to be in a positive and negative rotation alternating mode, wherein the period of each rotation is 5h, the middle rotation is stopped for 20min, the ball milling time is set to be 60h, and the rotating speed is 250 rpm/min; after the ball milling is finished, separating the balls and the powder by using a 300-mesh sieve;
2) taking 10g of the powder obtained in the step 1), weighing zirconia balls with the diameter of 6mm according to the mass ratio (ball-to-material ratio) of 80:1, adding the powder and the balls into a stirring and grinding tank, adding 100ml of ethanol serving as a stirring and grinding medium, setting the stirring and grinding time to be 9h, and setting the stirring and grinding frequency to be 12 Hz; after the stirring and grinding are finished, screening a mixed solution of the separation ball and the ethanol powder by using a sieve, and adsorbing a disc of the sieve by using a magnet to separate the ethanol and the powder; putting the powder into a drying oven, setting the drying temperature to be 60 ℃ and the drying time to be 1h to obtain the Fe/ZrH2A nanocrystalline composite particle.
In order to detect the temperature resistance of the obtained product, a certain amount of Fe/ZrH is taken2And (3) placing the composite particles into a crucible, placing the crucible into a muffle furnace, heating the crucible to 500 ℃ at a heating rate of 8 ℃/min, preserving the temperature for 1h, taking out a sample after the temperature in the furnace is cooled, and carrying out XRD test.
FIG. 12 shows Fe/ZrH obtained in this example2XRD patterns of the nanocrystalline composite particles at room temperature and after heat treatment at 500 ℃ for 1h are calculated according to the Sherry formula, and Fe/ZrH of the nanocrystalline composite particles at room temperature and after heat treatment at 500 ℃ is calculated according to the Sherry formula2The grain sizes of the composite particles were 10.6nm and 17.2 nm. According to FIGS. 1 and 12, the lattice parameter of the original carbonyl iron powder is calculated to be 0.2844nm, in this example Fe/ZrH2The lattice parameter of the iron in the composite particles was 0.2844 nm. The lattice parameters of the two are not changed, so that the system can be proved to be Fe/ZrH2Nanocrystalline composite particles, rather than alloy systems. Before compounding, the grain size of the nanocrystalline carbonyl iron powder is increased from 9.2nm to 179.2nm by up to 1848 percent after the nanocrystalline carbonyl iron powder is subjected to heat treatment at 500 ℃ for 1h, and Fe/ZrH2After the composite particles are subjected to heat treatment at 500 ℃ for 1h, the grain size is only increased by 62.3 percent and is far lower than that of the carbonyl iron powder before the composite treatment.
FIG. 13 is a graph showing electromagnetic parameter test patterns of the product obtained in this example after heat treatment at room temperature and 500 ℃ for 1h, and the result shows that the obtained flaky Fe/ZrH2Of composite particlesThe electromagnetic parameters do not change obviously before and after the heat treatment, and the heat-resistant material has good temperature resistance.
Example 4
Fe/ZrH2The preparation method of the nanocrystalline composite particle is substantially the same as that of example 1, except that: the Fe/ZrH2The composite particles were not subjected to milling treatment.
FIG. 14 is an SEM photograph of the product obtained in this example, in which it can be seen that the composite particles are spheroidal.
FIG. 15 is an XRD pattern of the product obtained in this example after heat treatment at room temperature and 500 ℃ for 1 h. Calculating Fe/ZrH after heat treatment at room temperature and 500 ℃ according to the Sherrer formula2The grain sizes of the composite particles were 9.9nm and 19.5 nm. According to the graph shown in FIG. 1 and FIG. 14, the lattice parameter of the original high-purity carbonyl iron powder is calculated to be 0.2844nm, Fe/ZrH2The lattice parameter of the medium iron is 0.2844 nm. The lattice parameters of the two are not changed, so that the system can be proved to be Fe/ZrH2Nanocrystalline composite particles, rather than alloy systems. Before compounding, the grain size of the nanocrystalline carbonyl iron powder is increased from 9.2nm to 179.2nm by up to 1848 percent after the nanocrystalline carbonyl iron powder is subjected to heat treatment at 500 ℃ for 1h, and Fe/ZrH2After the composite particles are subjected to heat treatment at 500 ℃ for 1h, the grain size is only increased by 96.1 percent and is far lower than that of carbonyl iron powder before the composite treatment. Fe/ZrH in comparative example 12The composite particles still have good temperature resistance;
FIG. 16 shows the electromagnetic parameters of the product obtained in this example after a heat treatment at room temperature and 500 ℃ for 1 hour. The results show that the obtained flaky Fe/ZrH2The electromagnetic parameters of the composite particles do not change obviously before and after heat treatment, and the composite particles have good temperature resistance. However, compared with example 1, the complex permeability in this example is significantly lower than that in example 1, which shows that the stirring and milling process adopted by the invention can significantly improve Fe/ZrH2Complex permeability of the composite particles.
Comparative example 1
Fe/ZrH2Mixing the particles, carbonyl iron powder and ZrH with the same ball-to-feed ratio and the same processing method as those of example 12Dispersing by ultrasonic dispersion according to the proportion of example 1Realizing carbonyl iron powder and ZrH2Mechanical mixing of Fe/ZrH prepared in this way2The mixed particles differ most from example 1 by ZrH in comparative example 12Only mechanical mixing is achieved, whereas Fe/ZrH in example 12ZrH in composite particles2Is dispersedly distributed in the grain boundary of the Fe nanocrystalline and is Fe/ZrH2Composite particles.
FIG. 17 is an SEM photograph of the product obtained in comparative example 1, in which it is seen that nano-ZrH2The particles and the flaky carbonyl iron powder are distributed in a mixed state.
FIG. 18 is an XRD pattern of the product obtained in this comparative example at room temperature and after heat treatment at 500 ℃ for 1 hour. Calculating Fe/ZrH after heat treatment at room temperature and 500 ℃ according to the Sherrer formula2The grain sizes of the composite particles were 9.9nm and 162.4 nm. According to FIG. 4 and FIG. 18, the lattice parameter of the original carbonyl iron powder is calculated to be 0.2844nm, Fe/ZrH2Has a lattice parameter of 0.2844 nm. The lattice parameters of the two are not changed, which proves that the dispersion of the ultrasonic disperser can not realize Fe and ZrH2Alloyed, however Fe/ZrH2ZrH of mixed particles2The ZrH in examples 1 to 3 was indirectly demonstrated because it failed to stabilize the grain size2Distributed at the nanocrystalline grain boundary of Fe to form Fe/ZrH2Composite particles, ZrH2Plays a role of pinning the grain boundary to prevent the Fe nanocrystalline grains from growing.
FIG. 19 shows the electromagnetic parameters of the product obtained in the comparative example at room temperature and after heat treatment at 500 ℃ for 1 hour, and it can be seen that Fe/ZrH was obtained after heat treatment at 500 DEG C2The complex dielectric constant of the mixed particles is obviously increased, and the complex permeability is obviously reduced; the temperature resistance is poor.
It is apparent that the above embodiments are only examples for clearly illustrating and do not limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are therefore intended to be included within the scope of the invention as claimed.

Claims (5)

1. Fe/ZrH2The nanocrystalline composite particle consists of Fe nanocrystalline and ZrH distributed in the grain boundary2Compounding the particles; the grain size of the Fe nanocrystalline is 8-20 nm;
it is formed by ZrH2The powder and carbonyl iron powder are taken as raw materials and are sequentially subjected to ball milling and stirring milling to form the powder; the ball milling time is more than 20 h; the stirring and milling time is more than 1 h.
2. Fe/ZrH according to claim 12The preparation method of the nanocrystalline composite particles is characterized by comprising the following steps: reacting ZrH2Mixing the particles with carbonyl iron powder, then placing the mixture into a ball mill for ball milling, and separating and collecting powder; obtaining the Fe/ZrH2A nanocrystalline composite particle.
3. Fe/ZrH according to claim 12The preparation method of the nanocrystalline composite particles is characterized by comprising the following steps: 1) reacting ZrH2Mixing the particles with carbonyl iron powder, then placing the mixture into a ball mill for ball milling, and separating and collecting powder; 2) and (2) placing the powder obtained in the step 1) into a stirring and grinding tank, stirring and grinding, finally separating grinding balls and products, and drying to obtain the Fe/ZrH2 nanocrystalline composite particles.
4. The production method according to claim 3, wherein the ZrH2The mass ratio of the powder to the carbonyl iron powder is 1 (4-200).
5. Fe/ZrH as defined in claim 12The application of the nanocrystalline composite particles is characterized in that the nanocrystalline composite particles are used as a temperature-resistant wave absorbing agent.
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