CN110270683A - A kind of Fe/ZrH2Nanocomposite particle and its preparation method and application - Google Patents
A kind of Fe/ZrH2Nanocomposite particle and its preparation method and application Download PDFInfo
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- CN110270683A CN110270683A CN201810220888.8A CN201810220888A CN110270683A CN 110270683 A CN110270683 A CN 110270683A CN 201810220888 A CN201810220888 A CN 201810220888A CN 110270683 A CN110270683 A CN 110270683A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
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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
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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
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Abstract
The invention discloses a kind of Fe/ZrH2Nanocomposite particle, it is with carbonyl iron dust and ZrH2Particle is primary raw material, is simply prepared by ball milling+stir mill method.The present invention is by combining ZrH2Particle obtains the Fe/ZrH with heat resistance to the distribution control technique of the stabilization of carbonyl iron dust microcosmic crystal boundary, Zr constituent content control technology and Zr2Compound particle；The Fe/ZrH2Within 20nm, the electromagnetic parameter of 2-18GHz is not substantially change crystallite dimension compound particle after 500 DEG C of heat treatment 1h, has good temperature tolerance, with important application prospects in fields such as heatproof wave absorbing agents.
Description
Technical field
The invention belongs to field of electronic materials, and in particular to a kind of Fe/ZrH2Nanocomposite particle and preparation method thereof
The application of sum.
Background technique
Microwave absorbing material is because it can absorb, decaying incident electromagnetic wave and converts it into extensive due to heat energy loss falls
Applied to military stealthy, electromagnetic shielding and human-body safety protection aspect.With the development of military technology, aircraft was flying
The temperature of skin can reach 300 DEG C or more in journey, and the temperature close to engine tail pipe is up to 500 DEG C or more.Therefore, heatproof
Absorbing material is of great significance to the Stealth Fighter under holding aircraft working condition.
The heatproof absorbing material developed at present according to the difference of loss mechanism be divided into dielectric loss type heatproof absorbing material and
Magnetic loss type heatproof absorbing material.The multiple dielectric that the drain performance of dielectric loss type heatproof absorbing material depends primarily on material is normal
Number (ε=ε '-i ε ")；This material by single loss mechanism due to being limited with the defect that thickness is big, absorption band is narrow.
The absorbent properties of magnetic loss type heatproof absorbing material depend primarily on the complex dielectric permittivity (ε=ε '-i ε ") and multiple magnetic conductance of wave absorbing agent
Rate (μ=μ '-i μ ") has two kinds of loss mechanisms of dielectric loss and magnetic loss, therefore it may be designed to 2.0mm thickness or less
Thin layer absorbing material, and its absorption band width is far longer than dielectric loss absorbing material, militarily has pole
Big application prospect.
In magnetic loss type heatproof absorbing material, since carbonyl iron dust has biggish saturation magnetization, become
The preferred material of wave absorbing agent.However, the temperature tolerance due to carbonyl iron dust is very poor, oxidation or microstructure are easy to happen in heating
Variation and complex dielectric permittivity and complex permeability are changed so that absorbing property be deteriorated.Exist for carbonyl iron dust
The problem of aoxidizing under high temperature, people have developed surface coating technology design preparation heatproof magnetism wave absorbing agent, 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 resin (Journal of Magnetism&
Magnetic Materials, 2015,374:345-349.) etc..However such methods not can avoid carbonyl iron dust microstructure
Change, such as the phenomenon that crystal grain is grown up, thus its complex dielectric permittivity and complex permeability still have biggish deterioration in heating.
Fig. 1 shows the carbonyl iron dusts after processing in room temperature and XRD diffraction pattern Jing Guo 500 DEG C of 1h vacuum heat treatments, by Scherrer formula
Calculating.The crystallite dimension of high-purity carbonyl iron dust is 9.2nm at room temperature, and the crystallite dimension by 500 DEG C of 1h vacuum heat treatments is
179.2nm.Fig. 2 indicates carbonyl iron dust in room temperature and electromagnetic parameter Jing Guo 500 DEG C of 1h vacuum heat treatments, it may be seen that answering
Dielectric constant obviously becomes larger, and complex permeability is decreased obviously.Therefore, how to solve to cause multiple dielectric normal because of the change of microstructure
The several and complex permeability this problem that changes becomes a technical problem of heatproof absorbing material preparation.
Summary of the invention
Aiming at the shortcomings in the prior art, the object of the present invention is to provide a kind of Fe/ZrH2Nanocomposite particle, it with
ZrH2Particle and carbonyl iron dust are that raw material is combined through mechanical force, wherein ZrH2Uniform particle is distributed in the nanocrystalline crystal boundary of iron, can
Effectively inhibit that iron is nanocrystalline grows up, promotes its temperature tolerance etc.；It is used as microwave absorbing material, can express excellent heatproof and inhale
Wave performance, after 500 DEG C of heat treatment electromagnetic parameter do not change substantially.
To achieve the above object, the invention adopts a technical scheme as:
A kind of Fe/ZrH2Nanocomposite particle, it is in spherical or sheet；Including Fe it is nanocrystalline and be distributed its grain boundaries
ZrH2Particle, wherein Fe nanocrystalline crystallite dimension is 8-20nm.
In above scheme, the Fe/ZrH2Nanocomposite particle is with ZrH2Powder and carbonyl iron dust are raw material, carry out ball milling
It forms.
Preferably, the Fe/ZrH2Nanocomposite particle is with ZrH2Powder and carbonyl iron dust are raw material, successively carry out ball milling
It is ground with stirring.
A kind of above-mentioned Fe/ZrH2The preparation method of nanocomposite particle includes the following steps: ZrH2Particle and carbonyl
Iron powder is mixed, and is subsequently placed in ball mill and is carried out ball milling, separates and collects powder；Obtain the Fe/ZrH2Nanocomposite grain
Son.
Above-mentioned another kind Fe/ZrH21) preparation method of nanocomposite particle includes the following steps: ZrH2Particle and
Carbonyl iron dust is mixed, and is subsequently placed in ball mill, carries out ball milling, and separate and collect powder；2) by powder obtained by step 1)
It is placed in and stirs in grinding jar, carry out stirring mill, be finally separating abrading-ball and product, drying to get Fe/ZrH2Nanocomposite particle.
In above scheme, the ZrH2The mass ratio of powder and carbonyl iron dust is 1:(4-200).
In above scheme, the purity of iron is 99wt.% or more in the carbonyl iron dust.
In above scheme, the Ball-milling Time is 20h or more；Stirring time consuming is 1h or more.
In above scheme, in the ball-milling technology, for the ball milling speed used for 200-300rpm, ratio of grinding media to material is (15-30):
1。
In above scheme, ball-milling medium is used as using n-hexane or ethyl alcohol etc. in the ball-milling technology, additive amount is
ZrH2The 5~55% of powder and carbonyl iron dust gross mass.
Described to stir in grinding process in above scheme, what is used stirs mill frequency as 5-20Hz, and ratio of grinding media to material is (60-120): 1.
In above scheme, described stir in grinding process stirs grinding media, additive amount ZrH using the conduct such as ethyl alcohol2Powder and carbonyl
3-8 times of base iron powder gross mass.
According to Fe/ZrH obtained by above scheme2The application of nanocomposite particle is suitable as heatproof wave absorbing agent, is passing through
Electromagnetic parameter does not change substantially after 500 DEG C of heat treatment, takes into account electromagnetic performance and heat resistance.
The principle that the present invention uses are as follows:
The present invention uses mechanical force composite means, utilizes ZrH2Itself good thermal stability and antioxygenic property, and
ZrH2Molecule is easy to hinder the nanocrystalline characteristic grown up of iron in cyrystal boundary segregation, makes a nanometer ZrH using ball grinding method first2Particle is more
It dissipates and is distributed in the nanocrystalline grain boundaries of iron, be conducive to that iron crystal grain is inhibited to grow up, promote the heat resistance of carbonyl iron dust；Then it carries out
Mill processing is stirred, gained Fe/ZrH is further promoted2The electromagnetic performance of compound particle, is used as microwave absorbing material, can express
Excellent heat resistance and electromagnetic wave absorption performance out.
Compared with prior art, the invention has the benefit that
1) present invention uses ZrH2Composite modified preparation Fe/ZrH is carried out to carbonyl iron dust2Nanocomposite particle, nanometer
ZrH2Particle equably can play pinning crystal boundary in the nanocrystalline crystal boundary of iron by Dispersed precipitate, hinder the nanocrystalline work grown up of iron
With improving its heat resistance.
2) present invention makes iron powder and ZrH using simple ball milling+stir mill method, first progress ball milling2Particle is sufficiently compound,
Utilize ZrH2It is easy to hinder the nanocrystalline principle grown up of iron in cyrystal boundary segregation, promotes the heat resistance of carbonyl iron dust, then carry out
It stirs mill processing and further promotes gained Fe/ZrH2The electromagnetic performance of nanocomposite particle；The preparation process being related to is simple, easy
Control, can guarantee the heat resistance and electromagnetic performance of products therefrom simultaneously.
3) present invention gained Fe/ZrH2Nanocomposite particle is still able to maintain stable electricity after 500 DEG C of operating temperature
Magnetic parameter has in potential use of the aircraft on heatproof absorbing material.
Detailed description of the invention
Fig. 1 is the XRD spectrum of room temperature and the carbonyl iron dust after 500 DEG C are heat-treated 1h；
Fig. 2 is the electromagnetic parameter of room temperature and the carbonyl iron dust after 500 DEG C are heat-treated 1h；
Fig. 3 is the carbonyl iron dust XRD diffraction pattern that embodiment 1 uses；
Fig. 4 is the nanometer ZrH that embodiment 1 uses2The XRD diffraction pattern of particle；
Fig. 5 is 1 gained Fe/ZrH of embodiment2The SEM of nanocomposite particle schemes
Fig. 6 is 1 gained Fe/ZrH of embodiment2Nanocomposite particle selected diffraction electronic pattern master drawing；
Fig. 7 is 1 gained Fe/ZrH of embodiment2A) the surface topography TEM of nanocomposite particle schemes；B) energy spectrum diagram；C) iron
The distribution map of element；D) distribution map of zr element；
Fig. 8 be 1 products therefrom of embodiment at room temperature and by 500 DEG C be heat-treated 1h after XRD spectrum；
Fig. 9 be 1 products therefrom of embodiment at room temperature and by 500 DEG C be heat-treated 1h after electromagnetic parameter；
Figure 10 be 2 products therefrom of embodiment at room temperature and by 500 DEG C be heat-treated 1h after XRD spectrum；
Figure 11 be 2 products therefrom of embodiment at room temperature and by 500 DEG C be heat-treated 1h after electromagnetic parameter；
Figure 12 be 3 products therefrom of embodiment at room temperature and by 500 DEG C be heat-treated 1h after XRD spectrum；
Figure 13 be 3 products therefrom of embodiment at room temperature and by 500 DEG C be heat-treated 1h after electromagnetic parameter；
Figure 14 is 4 gained Fe/ZrH of embodiment2The SEM of compound particle schemes；
Figure 15 be 4 products therefrom of embodiment at room temperature and by 500 DEG C be heat-treated 1h after XRD spectrum；
Figure 16 be 4 products therefrom of embodiment at room temperature and by 500 DEG C be heat-treated 1h after electromagnetic parameter；
Figure 17 is 1 gained Fe/ZrH of comparative example2The SEM of stuff and other stuff schemes；
Figure 18 be 1 products therefrom of comparative example at room temperature and by 500 DEG C be heat-treated 1h after XRD spectrum；
Figure 19 be 1 products therefrom of comparative example at room temperature and by 500 DEG C be heat-treated 1h after electromagnetic parameter.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
In following embodiment, carbonyl iron dust that the carbonyl iron dust that uses provides for a Jiangsu day company.
Embodiment 1
A kind of Fe/ZrH2Nanocomposite particle, preparation method include the following steps:
1) by 19.4g carbonyl iron dust and 0.6g ZrH2Powder is put into ball grinder (ZrH2Quality of the particle in composite granule
Score is 3wt.%), the stainless steel abrading-ball of 10mm and 6mm is weighed according to the ratio of grinding media to material of 20:1, the ratio of sizes of balls is 3:2；
The analytically pure n-hexane of 10ml is added as dispersing agent；Ball mill is set as positive and negative rotation alternate mode, is rotated each time
Period is 5h, and centre stops 20min, sets Ball-milling Time as 80h, revolving speed 260rpm/min；300 mesh mistakes are used after the completion of ball milling
Mesh separates ball and powder；
2) powder obtained by 10g step 1) is taken, the zirconia ball that diameter is 6mm is weighed with the mass ratio (ratio of grinding media to material) of 80:1,
Powder and ball addition are stirred in grinding jar, and 100ml ethyl alcohol is added thereto as grinding media is stirred, it is 8h that time consuming is stirred in setting, is stirred
Mill frequency is 10Hz；After stirring mill, used mesh separation ball and ethyl alcohol powder mixed liquor, with magnet adsorbed the disk of mesh with
Separating alcohol and powder；Powder is put into baking oven, sets drying temperature as 60 DEG C, drying time 1h obtains the Fe/ZrH2
Nanocomposite particle.
Fig. 5 is the scanning electron microscope (SEM) photograph of the present embodiment products therefrom, can be seen that products therefrom structure in the form of sheets in figure, piece
Thickness is about 0.6 μm；
Fig. 6 is the selective electron diffraction style figure of the present embodiment products therefrom, we can clearly observe from figure
ZrH2(111), (112) crystal face and iron (110), (211) crystal face, in addition to this do not find other peaks, it was demonstrated that ZrH2In ball
There is no decomposing during mill；
Fig. 7 is TEM the and EDS energy spectrum diagram of the present embodiment.Do not have to find the presence of oxygen element in power spectrum, illustrate in ball milling
In the process there is no oxidation, Zr element is all from ZrH2。
For the temperature tolerance for detecting products therefrom, a certain amount of Fe/ZrH is taken2Nanocomposite particle is placed in crucible, is put into
In Muffle furnace, the heating rate of 8 DEG C/min is heated to keeping the temperature 1h at 500 DEG C, is cooled to in-furnace temperature and then takes out sample,
And carry out XRD test.
Fig. 8 is Fe/ZrH obtained by the present embodiment2Nanocomposite particle is at room temperature and after 500 DEG C of heat treatment 1h
XRD diagram calculates the Fe/ZrH of heat treatment front and back according to Scherrer formula2The crystallite dimension of the Fe of compound particle be 10.2nm and
19.7nm.According to Fig. 1 and Fig. 8, by calculating, the lattice parameter of carbonyl iron dust is 0.2844nm, Fe/ZrH2Compound particle iron
Lattice parameter is 0.2844nm.The lattice parameter of iron does not change in the two, so as to prove that the system is Fe/ZrH2It receives
The brilliant compound particle (being not incorporated into iron intracell, cause lattice parameter altering) of rice, Figure 18 Fe/ZrH2Stuff and other stuff, but not
Have a possibility that stability of crystal grain, the information of complex chart 1, Fig. 8 and Figure 18, exclusion stuff and other stuff, alloy, it is however generally that
For not incorporating the impurity of lattice, there is the characteristic in cyrystal boundary segregation, it can therefore be concluded that ZrH2Particle segregation is nanocrystalline in iron
Grain boundaries.
Shown by Fig. 1, before compound, carbonyl iron dust after 500 DEG C, the heat treatment of 1h crystallite dimension by
9.2nm increases to 179.2nm increasing degree and is up to 1848%, and present invention gained Fe/ZrH2Compound particle passes through 500 DEG C, 1h
Heat treatment after crystallite dimension only increase 93.1%, far below the carbonyl iron dust before non-combined processing.
Fig. 9 be the present embodiment products therefrom at room temperature and by 500 DEG C be heat-treated 1h after electromagnetic parameter testing map, knot
Fruit shows, gained sheet Fe/ZrH2The electromagnetic parameter of nanocomposite particle before heat treatment after there is no significantly changing,
With good heat resistance.
Embodiment 2
A kind of Fe/ZrH2Nanocomposite particle, preparation method include the following steps:
1) by 18.4g carbonyl iron dust and 1.6g ZrH2Powder is put into ball grinder (ZrH2Quality of the particle in composite granule
Score is 8wt.%), the stainless steel abrading-ball of 10mm and 6mm is weighed according to the ratio of grinding media to material of 20:1, the ratio of sizes of balls is 3:2；
The analytically pure n-hexane of 10ml is added as dispersing agent；Ball mill is set as positive and negative rotation alternate mode, is rotated each time
Period is 5h, and centre stops 20min, sets Ball-milling Time as 100h, revolving speed 240rpm/min；300 mesh are used after the completion of ball milling
It looks over so as to check sieve separation ball and powder；
2) powder obtained by 10g step 1) is taken, the zirconia ball that diameter is 6mm is weighed with the mass ratio (ratio of grinding media to material) of 80:1,
Powder and ball addition are stirred in grinding jar, and 100ml ethyl alcohol is added thereto as grinding media is stirred, it is 10h that time consuming is stirred in setting, is stirred
Mill frequency is 8Hz；After stirring mill, used mesh separation ball and ethyl alcohol powder mixed liquor, with magnet adsorbed the disk of mesh with
Separating alcohol and powder；Powder is put into baking oven, sets drying temperature as 60 DEG C, drying time 1h obtains the Fe/ZrH2
Nanocomposite particle.
For the temperature tolerance for detecting products therefrom, a certain amount of Fe/ZrH is taken2Nanocomposite particle is placed in crucible, is put into
In Muffle furnace, the heating rate of 8 DEG C/min is heated to keeping the temperature 1h at 500 DEG C, is cooled to in-furnace temperature and then takes out sample,
And carry out XRD test.
Figure 10 is Fe/ZrH obtained by the present embodiment2Nanocomposite particle is at room temperature and after 500 DEG C of heat treatment 1h
XRD diagram calculates Fe/ZrH after being heat-treated at room temperature with 500 DEG C according to Scherrer formula2The crystallite dimension of compound particle iron is 9.6nm
And 16.5nm.According to Fig. 1 and Figure 10, by calculating, the lattice parameter of carbonyl iron dust is 0.2844nm, Fe/ZrH2It is nanocrystalline multiple
The lattice parameter for closing iron in particle is 0.2844nm, so as to prove that the system is Fe/ZrH2Nanocomposite particle, without
It is alloy system.Fig. 1 is shown, before compound, nanocrystalline carbonyl iron dust crystallite dimension after the heat treatment of 500 DEG C of 1h
179.2nm increasing degree is increased to by 9.2nm and is up to 1848%, and Fe/ZrH2Compound particle is after the heat treatment of 500 DEG C of 1h
The crystallite dimension of iron only increases 71.9%, far below the carbonyl iron dust before non-combined processing.
Figure 11 be the present embodiment products therefrom at room temperature and by 500 DEG C be heat-treated 1h after electromagnetic parameter testing map,
The results show that gained sheet Fe/ZrH2The electromagnetic parameter of compound particle before heat treatment after there is no significantly changing, have
Good heat resistance.
Embodiment 3
A kind of Fe/ZrH2Nanocomposite particle, preparation method include the following steps:
1) by 19g carbonyl iron dust and 1g ZrH2Powder is put into ball grinder (ZrH2Mass fraction of the particle in composite granule
For 5wt.%), the stainless steel abrading-ball of 10mm and 6mm is weighed according to the ratio of grinding media to material of 20:1, the ratio of sizes of balls is 3:2；Again plus
Enter the analytically pure n-hexane of 15ml as dispersing agent；Ball mill is set as positive and negative rotation alternate mode, the period rotated each time
For 5h, centre stops 20min, sets Ball-milling Time as 60h, revolving speed 250rpm/min；Mesh is crossed with 300 mesh after the completion of ball milling
Separate ball and powder；
2) powder obtained by 10g step 1) is taken, the zirconia ball that diameter is 6mm is weighed with the mass ratio (ratio of grinding media to material) of 80:1,
Powder and ball addition are stirred in grinding jar, and 100ml ethyl alcohol is added thereto as grinding media is stirred, it is 9h that time consuming is stirred in setting, is stirred
Mill frequency is 12Hz；After stirring mill, used mesh separation ball and ethyl alcohol powder mixed liquor, with magnet adsorbed the disk of mesh with
Separating alcohol and powder；Powder is put into baking oven, sets drying temperature as 60 DEG C, drying time 1h obtains the Fe/ZrH2
Nanocomposite particle.
For the temperature tolerance for detecting products therefrom, a certain amount of Fe/ZrH is taken2Compound particle is placed in crucible, is put into Muffle furnace
Interior, the heating rate of 8 DEG C/min is heated to keeping the temperature 1h at 500 DEG C, is cooled to in-furnace temperature and then takes out sample, and carries out
XRD test.
Figure 12 is Fe/ZrH obtained by the present embodiment2Nanocomposite particle is at room temperature and after 500 DEG C of heat treatment 1h
XRD diagram calculates Fe/ZrH after being heat-treated at room temperature with 500 DEG C according to Scherrer formula2The crystallite dimension of compound particle is 10.6nm
And 17.2nm.According to Fig. 1 and Figure 12, by calculating, the lattice parameter of original carbonyl iron dust is 0.2844nm, Fe/ in this example
ZrH2The lattice parameter of iron is 0.2844nm in compound particle.The two lattice parameter does not change, so as to prove the body
System is Fe/ZrH2Nanocomposite particle, rather than alloy system.Before compound, nanocrystalline carbonyl iron dust passes through 500
Crystallite dimension increases to 179.2nm increasing degree by 9.2nm and is up to 1848% after the heat treatment of DEG C 1h, and Fe/ZrH2Compound grain
Son crystallite dimension after the heat treatment of 500 DEG C of 1h only increases 62.3%, far below the carbonyl iron dust before non-combined processing.
Figure 13 be the present embodiment products therefrom at room temperature and by 500 DEG C be heat-treated 1h after electromagnetic parameter testing map,
The results show that gained sheet Fe/ZrH2The electromagnetic parameter of compound particle before heat treatment after there is no significantly changing, have
Good heat resistance.
Embodiment 4
A kind of Fe/ZrH2Nanocomposite particle, preparation method is roughly the same with embodiment 1, the difference is that: it should
Fe/ZrH2Compound particle is handled without mill is stirred.
Figure 14 is that the SEM of the present embodiment products therefrom schemes, and the compound particle is in near-spherical as we can see from the figure.
Figure 15 be the present embodiment products therefrom at room temperature and by 500 DEG C be heat-treated 1h after XRD spectrum.According to Scherrer public affairs
Fe/ZrH after formula calculating is heat-treated with 500 DEG C at room temperature2The crystallite dimension of compound particle is 9.9nm and 19.5nm.According to Fig. 1 with
Figure 14, by calculating, the lattice parameter of original high-purity carbonyl iron dust is 0.2844nm, Fe/ZrH2The lattice parameter of middle iron is
0.2844nm.The two lattice parameter does not change, so as to prove that the system is Fe/ZrH2Nanocomposite particle, and
It is not alloy system.Before compound, nanocrystalline carbonyl iron dust after the heat treatment of 500 DEG C of 1h crystallite dimension by
9.2nm increases to 179.2nm increasing degree and is up to 1848%, and Fe/ZrH2Compound particle is brilliant after the heat treatment of 500 DEG C of 1h
Particle size only increases 96.1%, far below the carbonyl iron dust before non-combined processing.Fe/ZrH in comparative example 12Compound particle
Still there is good temperature tolerance；
Figure 16 be the present embodiment products therefrom at room temperature and by 500 DEG C be heat-treated 1h after electromagnetic parameter.The results show that
Gained sheet Fe/ZrH2The electromagnetic parameter of compound particle before heat treatment after there is no significantly changing, have good resistance to
Warm nature energy.But it is compared with embodiment 1, the complex permeability in the present embodiment is significantly lower than embodiment 1, illustrates that the present invention used stirs
Grinding process is remarkably improved Fe/ZrH2The complex permeability of compound particle.
Comparative example 1
A kind of Fe/ZrH2Stuff and other stuff, by ratio of grinding media to material same as Example 1, the identical carbonyl iron dust of processing method and ZrH2
Carbonyl iron dust and ZrH are realized by ultrasonic disperse instrument by proportion described in embodiment 12Mechanical mixture, prepare under this method
Fe/ZrH2The ZrH that stuff and other stuff and the maximum difference of embodiment 1 are in comparative example 12Only realize mechanical mixture, and embodiment
Fe/ZrH in 12ZrH in compound particle2Dispersed precipitate is Fe/ZrH in the nanocrystalline crystal boundary of Fe2Compound particle.
Figure 17 is that the SEM of 1 products therefrom of comparative example schemes, and is found out in figure, nanometer ZrH2Particle and flaky carbonyl iron powder are presented
Admixture distribution.
Figure 18 be this comparative example products therefrom at room temperature and by 500 DEG C be heat-treated 1h after XRD spectrum.According to Scherrer public affairs
Fe/ZrH after formula calculating is heat-treated with 500 DEG C at room temperature2The crystallite dimension of compound particle is 9.9nm and 162.4nm.According to Fig. 4
With Figure 18, by calculating, the lattice parameter of original carbonyl iron dust is 0.2844nm, Fe/ZrH2Lattice parameter be 0.2844nm.
The two lattice parameter does not change, it was demonstrated that by the peptizaiton of ultrasonic disperse instrument, can not achieve Fe and ZrH2Alloy
Change, however Fe/ZrH2The ZrH of stuff and other stuff2It can not play the role of size of stable grain, it can be in indirect proof Examples 1 to 3
ZrH2The nanocrystalline grain boundaries of Fe are distributed in, Fe/ZrH is formed2Compound particle, ZrH2Playing pinning crystal boundary hinders Fe nanocrystalline
The effect that crystal grain is grown up.
Figure 19 be comparative example products therefrom at room temperature and by 500 DEG C be heat-treated 1h after electromagnetic parameter, it can be seen that warp
After 500 DEG C of heat treatments, Fe/ZrH2The complex dielectric permittivity of stuff and other stuff obviously becomes larger, and complex permeability is decreased obviously；Heat resistance compared with
Difference.
Obviously, above-described embodiment is only intended to clearly illustrate made example, and is not the limitation to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And the obvious variation or change therefore amplified
It moves within still in the protection scope of the invention.
Claims (9)
1. a kind of Fe/ZrH2Nanocomposite particle, it is by Fe is nanocrystalline and ZrH2Particle is combined.
2. Fe/ZrH according to claim 12Nanocomposite particle, which is characterized in that the Fe nanocrystalline crystal grain ruler
Very little is 8-20nm.
3. Fe/ZrH according to claim 12Nanocomposite particle, which is characterized in that it is with ZrH2Powder and carbonyl iron dust
For raw material, carries out ball milling and form.
4. Fe/ZrH according to claim 12Nanocomposite particle, which is characterized in that it is with ZrH2Powder and carbonyl iron dust
For raw material, successively carry out ball milling and stir to grind.
5. Fe/ZrH described in claim 12The preparation method of nanocomposite particle, which comprises the steps of: will
ZrH2Particle and carbonyl iron dust are mixed, and are subsequently placed in ball mill and are carried out ball milling, separate and collect powder；Obtain the Fe/ZrH2
Nanocomposite particle.
6. Fe/ZrH described in claim 12The preparation method of nanocomposite particle, which comprises the steps of: 1)
By ZrH2Particle and carbonyl iron dust are mixed, and are subsequently placed in ball mill and are carried out ball milling, separate and collect powder；2) by step 1)
Gained powder, which is placed in, to be stirred in grinding jar, carries out stirring mill, is finally separating abrading-ball and product, drying to get Fe/ZrH2Nanocomposite grain
Son.
7. preparation method according to claim 5 or 6, which is characterized in that the ZrH2The mass ratio of powder and carbonyl iron dust is
1:(4~200).
8. preparation method according to claim 5 or 6, which is characterized in that the Ball-milling Time is 20h or more；When stirring mill
Between be 1h or more.
9. a kind of Fe/ZrH2The application of nanocomposite particle, which is characterized in that be used as heatproof wave absorbing agent.
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