CN104451265B - Ni-based alloy magnetic microwave absorbing material and preparation method thereof - Google Patents

Abstract

The invention discloses a Ni-based alloy magnetic microwave absorbing material and a preparation method thereof. The stoichiometric proportions of a molecular formula of the magnetic microwave absorbing material are as follows: 16.67% of Pr, 83.33%-75% of Ni and 0-8.33% of Fe. The Ni-based alloy magnetic microwave absorbing material is prepared by the following main steps: smelting Pr, Fe and Ni metals, of which the purities are greater than or equal to 99.50% as raw materials under argon or vacuum protection; carrying out heat treatment on a cast ingot at 600-1100 DEG C under vacuum or argon protection; quenching with ice water; and grinding into powder and carrying out ball milling to form powder after mechanically crushing. The Ni-based alloy disclosed by the invention has the advantages of relatively good microwave absorbing effect, wide absorbing frequency band, simple preparation process, high antioxidant resistance and the like in a 2-18GHz of microwave band; and the Ni-based alloy magnetic microwave absorbing material disclosed by the invention is suitable for preparation of microwave absorbing products of requiring wide absorbing frequency band, good wave absorbing property and high corrosion resistance in the magnetic wave absorbing material.

Description

Ni based alloy magnetic microwave absorbing material and preparation method thereof

Technical field

The invention belongs to microwave material field, specifically Ni based alloy magnetic absorbing material and preparation method thereof.

Background technology

Owing to electronic equipment, mobile communication use more and more universal in daily life, and these electronic machines, equipment work As time the electromagnetic wave that gives off, not only can disturb the normal work of other electronic machines around, and the body and mind of the mankind can be good for Health brings threat.In order to solve the harm that electromagnetic radiation is brought, people have carried out substantial amounts of research work.Wherein at microwave ripple In section (especially in 2～18GHz frequency ranges), by utilizing electromagnetic wave absorbing material that electromagnetic wave energy is converted into other forms Energy, the radiation suppressing electromagnetic wave with this and interference, there is preferable effect.As electromagnetic wave absorbing material being coated in TV, sound On the surface of the electronic product such as sound, the mechanical, electrical brain of VCD, mobile communication, electromagnetic wave leakage can be made to drop to below safety limit (little In 10 microwatts/every square centimeter), it is ensured that health.It is applied to radar, microwave medical apparatus and instruments, broken microwave machine etc. set In Bei, the electromagenetic wave radiation injury to operator's health can be reduced to a certain extent.Microwave absorbing material is applied to In construction material, the ghost problems caused because of tall and big building reflection electromagnetic wave can be solved.And use magnetic microwave absorption The microwave dark room that material makes also is widely used in the fields such as radar, telecommunications and Aero-Space.Additionally, magnetic microwave Absorbing material is improving compatibility airborne, that boat carries radar equipment, and improving the aspects such as overall performance also has wide application empty Between, it can be seen that the application market of magnetic microwave absorbing material is the hugest.

Traditional absorbing material mainly has ferrite-type and magnetic metal (alloy) micropowder etc..Although ferrite is hundreds of It is most widely used and maximally effective electromagnetism interference material in MHz frequency range, low yet with its saturation magnetization, but 2 ～microwave magnetic permeability is less under 18GHz frequency range, wave-sucking performance is poor, and matching thickness thicker (Centimeter Level), therefore ferrite material Expect in the application of this frequency range by great limitation.And lamellar soft magnetic metal micropowder is high due to Curie temperature, Heat stability is good, have Preferably saturation magnetization and grain shape effect, can obtain under 2～18GHz frequency ranges simultaneously higher complex permeability and Relatively low eddy-current loss, matching thickness less (grade), as radio-radar absorber, there is good application prospect, and current Most magnetically soft alloy micropowders is applied to be mainly Fe, Co, Ni and alloy powder etc. thereof.

Absorbing property is good in exploitation, absorption band width, oxidation resistance and corrosion resistance and good, temperature stability material good, former The novel magnetic absorbing material that material is abundant, preparation technology is easily mastered and production cost is low is a research emphasis from now on, with Deepization of research and development, difficulty can become increasing, but the magnetic suction ripple that market price good to performance is the lowest Material again in the urgent need to, develop inexpensive electromagnetic wave absorbing material and be always world investigation of materials worker Study hotspot.

Summary of the invention

Problem to be solved by this invention is just to provide a kind of Ni based alloy magnetic absorbing material and preparation method thereof, this Material have in 2～18GHz microwave bands absorption band width, wave absorbing efficiency height, Heat stability is good, oxidation resistance strong and The advantages such as corrosion resistance and good.

The Ni based alloy magnetic absorbing material of the present invention, the stoichiometric proportion of its molecular formula is: Pr16.67, Ni83.33～ 75.00, Fe0～8.33.

The method preparing PrNiFe alloy electromagnetic wave absorbing material, comprises following key step:

(1) with Pr, Fe, Ni metal of purity >=99.50% as raw material, by following stoichiometric proportion Pr_16.67Ni_{83.3～ 75}Fe_0～8.33Dispensing；

(2) melting under argon or vacuum protection；

(3) ingot casting carries out heat treatment in 600～1100 DEG C under vacuum or argon shield；

(4) coarse crushing is milled powder process；

(5) pulverized powder.

Described melting, is carried out in the non-consumable arc furnace of standard, in order to ensure the homogeneity of ingredients of alloy, need to turn over Peritectic refines 3～4 times；

Described heat treatment process includes being incubated 48～120 hours, shrend afterwards.Heat treatment temperature with 900～1050 DEG C is Preferably, temperature retention time is with 72～120 hours preferably；

Described powder process of milling uses Achates alms bowl mill to mill 30 minutes, sieves afterwards under 300 mesh sieves；

Described pulverized powder uses ball milling, and the coarse powder after zirconia ball and coarse crushing is put into oxidation by 15:1～20:1 mass ratio In zirconium tank, ethanol do protectant in the case of, ball milling 20～40h, drum's speed of rotation is 300～350 revs/min；

Product reflectance R and the detection of electromagnetic parameter:

In PrNiFe alloy powder: the ratio mixing of paraffin=4:1 (mass ratio), make internal diameter and external diameter is respectively 3mm And 7mm, thickness is the coaxial sample of about 3.5mm, uses HP8722ES microwave vector network analyzer to measure sample respectively 2 ～the complex dielectric permittivity of 18GHz frequency range and complex permeability.Use that following formula calculates under the different-thickness of single-layer absorber is anti- Penetrate rate R:

$R=-20\lg \left|\frac{z\tanh (\mathrm{jk}\·d)-z_0}{z\tanh (\mathrm{jk}\·d)+z_0}\right|$

K in formula is propagation constantZ is natural impedanceIts Middle z₀For the natural impedance of vacuum, μ₀、ε₀It is respectively permeability of vacuum, permittivity of vacuum and microwave absorbing coating thickness, ε ' and ε " with d Being real part and the imaginary part of complex dielectric permittivity, μ ' and μ respectively " is respectively real part and the imaginary part of complex permeability.

Testing result: the PrNiFe alloy electromagnetic wave absorbing material of the present invention, when PrNiFe alloy powder and paraffin press 4:1's Ratio (mass ratio) is mixed into complex, and in 2～18GHz microwave bands, microwave absorbing coating thickness is between 1.0～4.0mm, compound Thing is respectively provided with preferable wideband effect.When composite thickness is 2.5mm, the reflectance peak minimum of microwave be can reach- 30.8dB, and there is preferable wideband effect.When thickness is 1.5mm, by Pr_16.67Ni_83.33The minimum of made complex Reflectance value also can reach-26.6dB.Alloy powder after ball-milling technology processes and the complex made by paraffin, 2 ～in 18GHz microwave band, microwave absorbing coating thickness between 1.0～2.0mm, the minimum reflectance peak value of complex be respectively less than- 10dB (absorbance is more than 90%), and there is preferable wideband effect.When composite thickness is 2.0mm, its minimum reflectance Peak value can reach about-29.0dB.And when thickness is only 1mm, minimum reflectance peak value at 17.2GHz frequency also up to To about-28.9dB, there is preferable application potential.

The invention have the advantage that the PrNiFe alloy electromagnetic wave absorbing material of the present invention, have in 2～18GHz microwave bands Preferably Microwave Absorption Properties, absorption band width, and it is preferable to have temperature stability, and oxidation resistance is strong, preparation technology letter The features such as list.In electromagnetic wave absorbing material, the Ni based alloy magnetic absorbing material of the present invention is applicable to preparation and has absorption band Wide, absorbing property is good, Heat stability is good and the strong microwave absorption product of oxidation resistance.

Accompanying drawing explanation

Fig. 1 is the preparation method process chart of the present invention；

Fig. 2 is the Pr of non-ball milling_16.67Ni_83.33Alloy electromagnetic wave absorbing material test result figure；

Fig. 3 is the Pr of non-ball milling_16.67Ni₈₀Fe_3.33Alloy electromagnetic wave absorbing material test result figure；

Fig. 4 is the Pr of non-ball milling_16.67Ni₇₅Fe_8.33Alloy electromagnetic wave absorbing material test result figure；

Fig. 5 is the Pr after ball milling 20h_16.67Ni₈₀Fe_3.33Alloy electromagnetic wave absorbing material test result figure；

Fig. 6 is the Pr after ball milling 40h_16.67Ni₈₀Fe_3.33Alloy electromagnetic wave absorbing material test result figure.

Detailed description of the invention

Embodiment 1:

Preparation Pr_16.67Ni_83.33Atomic percent electromagnetic wave absorbing material be embodied as step:

1) by equal >=99.50% Pr, Ni metal of purity, by Pr_16.67Ni_83.33The stoichiometric proportion dispensing of molecular formula；

2) melting in the electric arc furnace of standard under argon shield, uniform in order to ensure the composition of alloy, upset is molten repeatedly Refine 3～4 times；

3) ice water quenching after melted ingot casting being incubated 120 hours under vacuum protection at 1000 DEG C；

4) alloy pig obtained is broken into granularity and is respectively less than the coarse powder of 0.5mm, then sieve under 300 mesh sieves；

The ratio mixing of Product checking: in alloy powder: paraffin=4:1 (mass ratio), makes internal diameter and external diameter is respectively 3mm and 7mm, thickness, at the coaxial sample of 3.0～about 4.0mm, uses HP8722ES microwave vector network analyzer to survey respectively Amount sample is in the complex permeability of 2～18GHz frequency ranges, complex dielectric permittivity.Then following formula calculating simulation is used to go out single-layer absorber Reflectance R at thickness 1.4mm, 1.5mm, 1.6mm, 1.7mm, 1.8mm respectively.

$R=-20\lg \left|\frac{z\tanh (\mathrm{jk}\·d)-z_0}{z\tanh (\mathrm{jk}\·d)+z_0}\right|$

K in formula is propagation constantZ is natural impedanceIts Middle z₀For the natural impedance of vacuum, μ₀、ε₀It is respectively permeability of vacuum, permittivity of vacuum and microwave absorbing coating thickness, ε ' and ε " with d Being real part and the imaginary part of complex dielectric permittivity, μ ' and μ respectively " is respectively real part and the imaginary part of complex permeability.

The performance test results:

Fig. 2 is Pr_16.67Ni_83.33Powder body/paraffin complex thickness in 2～18GHz microwave bands be respectively 1.4mm, Reflectance when 1.5mm, 1.6mm, 1.7mm, 1.8mm.Can obtain from figure: in the middle of all thickness, the absorption peak of complex It is respectively less than-10dB (absorbance is more than 90%), and there is preferable wideband effect；When composite thickness is 1.5mm, At 13.68GHz frequency, minimum reflectance peak value is about-26.6dB.

Embodiment 2

Preparation Pr_16.67Ni₈₀Fe_3.33Atomic percent electromagnetic wave absorbing material be embodied as step:

1) by equal >=99.50% Pr, Fe, Ni metal of purity, by Pr_16.67Ni₈₀Fe_3.33The stoichiometric proportion of molecular formula is joined Material；

2) melting in the electric arc furnace of standard under argon shield, uniform in order to ensure the composition of alloy, upset is molten repeatedly Refine 3～4 times；

3) ice water quenching after melted ingot casting being incubated 72 hours under vacuum protection at a temperature of 1050 DEG C；

4) alloy pig obtained is broken into granularity and is respectively less than the coarse powder of 0.5mm, then sieve under 300 mesh sieve；

The ratio mixing of Product checking: in alloy powder: paraffin=4:1 (mass ratio), makes external diameter and internal diameter is respectively 7mm and 3mm, thickness, at the coaxial sample of 3.0～about 4.0mm, is measured and is calculated same embodiment 1, then use computer journey Sequence simulates thickness and is respectively the reflectance of 1.5mm, 2.0mm, 2.5mm, 3.0mm, 3.5mm, 4.0mm.

The performance test results:

Fig. 3 is Pr_16.67Ni₈₀Fe_3.33Powder body/paraffin complex thickness in 2～18GHz microwave bands be respectively 1.5mm, Reflectance when 2.0mm, 2.5mm, 3.0mm, 3.5mm, 4.0mm.Can obtain from figure: when composite thickness is 2.5～4.0mm Time, this complex has preferable microwave absorption effect at C-band (4～8GHz), when thickness is 4.0mm, at 4.56GHz Minimum reflectance value reaches-19.7dB.

Embodiment 3

Preparation Pr_16.67Ni₇₅Fe_8.33Atomic percent electromagnetic wave absorbing material be embodied as step:

1) by equal >=99.50% Pr, Fe, Ni metal of purity, by Pr_16.67Ni₇₅Fe_8.33The stoichiometric proportion of molecular formula is joined Material；

2) melting in the electric arc furnace of standard under argon shield, uniform in order to ensure the composition of alloy, upset is molten repeatedly Refine 3～4 times；

3) ice water quenching after melted ingot casting being incubated 90 hours under vacuum protection at a temperature of 1050 DEG C；

4) alloy pig obtained is broken into granularity and is respectively less than the coarse powder of 0.5mm, then sieve under 300 mesh sieve；

The ratio mixing of Product checking: in alloy powder: paraffin=4:1 (mass ratio), makes external diameter and internal diameter is respectively 7mm and 3mm, thickness, at the coaxial sample of 3.0～about 4.0mm, is measured and is calculated same embodiment 1, then use computer journey Sequence simulates thickness and is respectively the reflectance of 2.4mm, 2.5mm, 2.6mm, 2.7mm, 2.8mm.

The performance test results:

Fig. 4 is Pr_16.67Ni₇₅Ni_8.33Powder body/paraffin complex thickness in 2～18GHz microwave bands be respectively 2.4mm, Reflectance when 2.5mm, 2.6mm, 2.7mm, 2.8mm.Can obtain from figure: in all of thickness, at 2～18GHz microwave ripples Section, minimum reflectance peak value is respectively less than-10dB (absorbance is more than 90%), and has preferable wideband effect；When complex is thick When degree is for 2.5mm, at 9.12GHz frequency, minimum reflectance value reaches about-30.8dB.

Embodiment 4

Preparation Pr_16.67Ni₈₀Fe_3.33Atomic percent electromagnetic wave absorbing material be embodied as step:

1) by equal >=99.50% Pr, Fe, Ni metal of purity, by Pr_16.67Ni₈₀Fe_3.33The stoichiometric proportion of molecular formula is joined Material；

2) melting in the electric arc furnace of standard under argon shield, uniform in order to ensure the composition of alloy, upset is molten repeatedly Refine 3 times；

3) ice water quenching after melted ingot casting being incubated 72 hours under vacuum protection at a temperature of 1050 DEG C；

4) alloy pig obtained is broken into granularity and is respectively less than the coarse powder of 0.5mm；

5) broken alloy coarse powder and zirconia ball are put in zirconium oxide tank by the mass ratio of 15:1, protect at dehydrated alcohol Protecting lower ball milling 20h, drum's speed of rotation is 300r/min；

The ratio mixing of Product checking: in alloy powder: paraffin=4:1 (mass ratio), makes external diameter and internal diameter is respectively 7mm and 3mm, thickness, at the coaxial sample of 3.0～about 4.0mm, is measured and is calculated same embodiment 1, then use computer journey Sequence simulates thickness and is respectively the reflectance of 1.6mm, 1.8mm, 2.0mm.

The performance test results:

Fig. 5 is Pr_16.67Ni₈₀Fe_3.33Powder body/paraffin complex thickness in 2～18GHz microwave bands be respectively 1.6mm, Reflectance when 1.8mm, 2.0mm.Can obtain from figure: in all of thickness, at 2～18GHz microwave bands, minimum reflectance Peak value is respectively less than-10dB (absorbance is more than 90%), and has preferable wideband effect；When composite thickness is 2.0mm, At 10.24GHz frequency, minimum reflectance peak value reaches about-18.9dB.

Embodiment 5

Preparation Pr_16.67Ni₈₀Fe_3.33Atomic percent electromagnetic wave absorbing material be embodied as step:

1) by equal >=99.50% Pr, Fe, Ni metal of purity, by Pr_16.67Ni₈₀Fe_3.33The stoichiometric proportion of molecular formula is joined Material；

2) melting in the electric arc furnace of standard under argon shield, uniform in order to ensure the composition of alloy, upset is molten repeatedly Refine 3 times；

3) ice water quenching after melted ingot casting being incubated 72 hours under vacuum protection at a temperature of 1050 DEG C；

4) alloy pig obtained is broken into granularity and is respectively less than the coarse powder of 0.5mm；

5) broken alloy coarse powder and zirconia ball are put in zirconium oxide tank by the mass ratio of 20:1, protect at dehydrated alcohol Protecting lower ball milling 40h, drum's speed of rotation is 350r/min；

The ratio mixing of Product checking: in alloy powder: paraffin=4:1 (mass ratio), makes external diameter and internal diameter is respectively 7mm and 3mm, thickness, at the coaxial sample of 3.0～about 4.0mm, is measured and is calculated same embodiment 1, then use computer journey Sequence simulates thickness and is respectively the reflectance of 1.0mm, 1.8mm, 2.0mm.

The performance test results:

Fig. 6 is Pr_16.67Ni₈₀Fe_3.33Powder body/paraffin complex thickness in 2～18GHz microwave bands be respectively 1.0mm, Reflectance when 1.8mm, 2.0mm.Can obtain from figure: in all of thickness, at 2～18GHz microwave bands, minimum reflectance Peak value is respectively less than-10dB (absorbance is more than 90%), and has preferable wideband effect；When composite thickness is 2.0mm, At 8.64GHz frequency, minimum reflectance peak value reaches about-29.0dB.When thickness is only 1mm, minimum reflectance peak value exists About-28.9dB is can reach at 17.2GHz frequency.

Claims (6)

1. a Ni based alloy magnetic absorbing material, is characterized in that: the atomic percent of its molecular formula is: Pr 16.67, Ni 83.33~75、Fe 0~8.33。

2. the preparation method of the Ni based alloy magnetic absorbing material described in claim 1, is characterized in that, comprises following main step Rapid:

(1) with Pr, Fe, Ni metal of purity >=99.50% as raw material, by following atomic percent Pr_16.67Ni_83.33~75 Fe _0~8.33Dispensing；

(2) melting under argon or vacuum protection；

(3) ingot casting carries out heat treatment in 600～1100 DEG C under vacuum or argon shield；

(4) coarse crushing is milled powder process；

(5) pulverized powder.

Preparation method the most according to claim 2, is characterized in that, carries out melting in non-consumable arc furnace, overturns 3～4 Secondary.

Preparation method the most according to claim 2, is characterized in that, heat treatment process includes being incubated 48～120 hours, carries out afterwards Ice water quenching.

Preparation method the most according to claim 2, is characterized in that, after coarse powder processed employing Mechanical Crushing is ground in coarse crushing, uses agate Nao alms bowl mill is milled 30 minutes, sieves afterwards under 300 mesh sieves.

Preparation method the most according to claim 2, is characterized in that, pulverized powder uses ball milling, thick after zirconia ball and coarse crushing Powder is put in zirconium oxide tank by 15:1～20:1 mass ratio, ethanol do protectant in the case of, ball milling 20h～40h, ball mill Rotating speed is 300 ~ 350 revs/min.