CN101294055B - Radar wave absorbing agent and preparation method employing chemical plating technique - Google Patents
Radar wave absorbing agent and preparation method employing chemical plating technique Download PDFInfo
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- CN101294055B CN101294055B CN2008101145568A CN200810114556A CN101294055B CN 101294055 B CN101294055 B CN 101294055B CN 2008101145568 A CN2008101145568 A CN 2008101145568A CN 200810114556 A CN200810114556 A CN 200810114556A CN 101294055 B CN101294055 B CN 101294055B
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Abstract
The invention discloses a radar wave absorbent and the preparation method adopting the chemical plating process. The radar wave absorbent consists of a hollow microsphere and a metal plating layer enwrapping the surface of the hollow microspheres, wherein the metal plating layer with the thickness of 50 to 250 nm can contain elementary substance nickel (Ni), iron (Fe) or cobalt (Co) or can be a composite plating layer containing iron (Fe) 10 to 30wt% and cobalt (Co) 70 to 90wt%, or a composite plating layer containing iron (Fe) 10 to 30wt% and nickel (Ni) 70 to 90wt%, or a composite plating layer containing nickel (Ni) 50 to 70wt% and cobalt (Co) 30 to 50wt%, or a composite plating layer containing iron (Fe) 5 to 20wt%, cobalt (Co) 20 to 40wt% and nickel (Ni) being the rest. The radar wave absorbent has the relative dielectric constant of 20 to 70, the magnetic permeability of 1.5 to 2.0, and the density of 2.6 to 3.5 g/cm<3>. The radar wave absorbent has the maximal absorptivity of 20 dB at the electromagnetic wave frequency band of 2 to 18 GHz and the frequency width of 5 GHz larger than 10 dB.
Description
Technical field
The present invention relates to a kind of radar wave absorbing agent and preparation method thereof, more particularly say, be meant a kind of radar wave absorbing agent that adopts chemical plating technology at the surface clad coating of functionalization tiny balloon.
Background technology
Tiny balloon is a kind of inorganic powder, compares with metal powder, and less, high temperature resistant, antiacid alkali of density and oxidisability are strong.Handle if modification is carried out on its surface, realize surface metalation, then might solve big, the shortcomings such as high-temperature behavior is poor, anti-oxidant, acid and alkali-resistance ability of density that traditional absorbing material exists.At present, thus adopt suitable technology that the research that tiny balloon carries out surface modification preparation lightweight radar absorbing has been caused scholars' extensive concern.
Because the tiny balloon granularity is little, density is little and characteristics such as physicals excellence, the tiny balloon of surface metalation can replace the preparation that the bigger traditional wave absorbing agent of density is used for microwave absorbing coating, thereby solve that the density that traditional microwave absorbing coating exists is big, high-temperature behavior is poor, anti-oxidant and shortcoming such as acid and alkali-resistance ability, realize the target of absorbing material " thin, light, wide, strong ".
Summary of the invention
One of purpose of the present invention provides a kind of radar wave absorbing agent, and this radar wave absorbing agent is made up of tiny balloon and metal plating, and metal plating is coated on the surface of tiny balloon, and the thickness 50～250nm of metal plating.The composition of described metal plating can be nickel (Ni), iron (Fe) or the cobalt (Co) of simple substance, also can be the iron (Fe) that contains 10～30wt% and cobalt (Co) composite deposite of 70～90wt%, also can be the iron (Fe) that contains 10～30wt% and nickel (Ni) composite deposite of 70～90wt%, also can be the nickel (Ni) that contains 50～70wt% and cobalt (Co) composite deposite of 30～50wt%, also can be the iron (Fe) that contains 5～20wt%, the cobalt (Co) of 20～40wt% and nickel (Ni) composite deposite of surplus.The relative permittivity of this radar wave absorbing agent is 20～70, and magnetic permeability is 1.5～2.0; Density 2.6～the 3.5g/cm of radar wave absorbing agent
3
Another object of the present invention is to propose a kind of method for preparing radar wave absorbing agent, and this method has adopted chemical plating technology at tiny balloon surface system metal plating, thereby obtains the method for radar wave absorbing agent.
The present invention adopts the advantage of chemical plating technology preparation process: (1) adds coupling step in the pre-treatment process, improve the quantity of active site in the reactivation process by adding KH550, and the physical bond mode that changes original active site is a Chemical bond, improve the bonding force of active site with this, and then the bonding force of metal plating after the raising electroless plating, make coating have certain wear resistance, be difficult for being peeled off; (2) adopt the single stage method activating process, the stability and the shelf life of having improved plating bath, and can effectively improve the quantity of active site, and can be in reactivation process, by regulating Sn
2+Content, control the quantity of active Pd, thereby be applicable to different chemical plating cladding process; (3) prepare on tiny balloon by chemical plating technology and have nano level metal plating (composition metal coating), can be by adjusting the kind and the amount ratio of chemical plating technology parameter and metal-salt (iron, nickel, cobalt), obtain having the material of different relative permittivitys and relative magnetic permeability, thereby obtain radar wave absorbing agent of fine quality.
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
A kind of radar wave absorbing agent of the present invention is made up of tiny balloon and metal plating, and metal plating is coated on the surface of tiny balloon, and the thickness 50～250nm of metal plating.The composition of described metal plating can be nickel (Ni), iron (Fe) or the cobalt (Co) of simple substance, also can be the iron (Fe) that contains 10～30wt% and cobalt (Co) composite deposite of 70～90wt%, also can be the iron (Fe) that contains 10～30wt% and nickel (Ni) composite deposite of 70～90wt%, also can be the nickel (Ni) that contains 50～70wt% and cobalt (Co) composite deposite of 30～50wt%, also can be the iron (Fe) that contains 5～20wt%, the cobalt (Co) of 20～40wt% and nickel (Ni) composite deposite of surplus.
The chemical plating technology system of employing radar wave absorbing agent of the present invention includes following steps:
The first step: the choosing of body material
Body material is the tiny balloon of particle diameter 1～20 μ m;
In the present invention, to choose the main component that Qinhuangdao glass microballon company limited produces be SiO to tiny balloon
2And Al
2O
3Tiny balloon;
Second step: to the pre-treatment of matrix
(A) preparation alkali cleaning treatment solution
The alkali cleaning treatment solution is made up of sodium hydroxide (NaOH) and deionized water;
The sodium hydroxide (NaOH) that adds 10～20g in the deionized water of consumption: 500ml;
(B) alkali washing process
The tiny balloon that first step is chosen adds in the alkali cleaning treatment solution;
The alkali cleaning condition: 60～80 ℃ alkali cleaning temperature, under the condition of power 500W, magnetic agitation disperses to make first reaction solution behind reaction 60～90min;
First reaction solution is washed acquisition first product;
Washing condition: under room temperature (25 ℃) condition, first reaction solution is diluted (adding 800～1000ml deionized water in every 100ml first reaction solution dilutes) with deionized water, behind sedimentation 60～90min supernatant liquid is removed, repeats 2～3 times after acquisition first product;
In the present invention, adopting washing is with the Na in first reaction solution on the basis that does not influence the tiny balloon dispersiveness
+, OH
-And the impurities in raw materials removal, thereby obtain first product.
(C) preparation coupling processing liquid
Coupling processing liquid is by silane coupling agent and ethanol (C
2H
5OH) form;
Ethanol (the C of consumption: 500ml
2H
5OH) silane coupling agent that adds 0.5～2g in;
Described silane coupling agent can be a γ-An Bingjisanyiyangjiguiwan, trade mark KH550.
(D) coupling process
First product is added in the coupling processing liquid;
Coupling condition:, under the condition of power 500W, behind ultra-sonic dispersion reaction 6～8h, leave standstill 3～5min and make second reaction solution 35～50 ℃ coupling temperature;
Second reaction solution is carried out suction filtration obtain second product;
The suction filtration condition: under room temperature (25 ℃) condition, the vacuum tightness of regulating suction filtration vacuum instrument is-0.1MPa to obtain second product behind suction filtration time 5～10min;
In the present invention, adopting suction filtration is with the coupling agent in second reaction solution, ethanol (C
2H
5OH) remove, thereby obtain second product.
(E) preparation activation treatment liquid
Activation treatment liquid is by tin protochloride (SnCl
22H
2O), sodium stannate (Na
2SnO
3), Palladous chloride (PdCl
2), hydrochloric acid (HCl) and deionized water form;
Add 1～2g tin protochloride (SnCl in the hydrochloric acid of consumption: 100ml (HCl)
22H
2O) and the Palladous chloride (PdCl of 0.2～0.5g
2), add 12.5～50g tin protochloride (SnCl behind reaction 10～20min
22H
2O), the sodium stannate (Na of 2～4g
2SnO
3) and the deionized water of 400ml;
(F) activating process
Second product is added in the activation treatment liquid;
Activation condition:, under the condition of power 500W, behind ultra-sonic dispersion reaction 30～60min, leave standstill 3～5min and make the 3rd reaction solution 50～70 ℃ activation temperature;
The 3rd reaction solution is carried out suction filtration obtain third product;
The suction filtration condition: under room temperature (25 ℃) condition, the vacuum tightness of regulating suction filtration vacuum instrument is-0.1MPa to obtain third product behind suction filtration time 5～10min;
In the present invention, adopting suction filtration is with the Sn in the 3rd reaction solution
2+, Sn
4+, Pd
2+, Cl
-And H
+Remove, wherein Sn
4+Be at Sn
2+With Palladous chloride (PdCl
2) chemical reaction takes place obtain.
(G) preparation dispergation treatment solution
The dispergation treatment solution is made up of hydrochloric acid (HCl) and deionized water;
The hydrochloric acid (HCl) that adds 50～100ml in the deionized water of consumption: 500ml;
(H) separate adhesive process
The 3rd reaction product is added in the dispergation treatment solution;
Dispergation condition:, under the condition of power 500W, behind ultra-sonic dispersion reaction 1～3min, leave standstill 3～5min and make the 4th reaction solution 35～50 ℃ dispergation temperature;
The 4th reaction solution is carried out suction filtration obtain the 4th product;
The suction filtration condition: under room temperature (25 ℃) condition, the vacuum tightness of regulating suction filtration vacuum instrument is-0.1MPa to obtain the 4th product behind suction filtration time 5～10min;
In the present invention, adopting suction filtration is with the Sn in the 4th reaction solution
2+And Cl
-And H
+Remove, thereby obtain the 4th product.Sn wherein
2+Be attached on the tiny balloon of the 4th product;
The 4th product is put into loft drier, behind dry 3～4h under 90～110 ℃ the condition, make the 5th product;
The 3rd step: electroless plating is handled
(A) preparation chemical plating fluid
Chemical plating fluid is by metal-salt, inferior sodium phosphate (NaH
2PO
2), trisodium citrate (Na
3C
6H
5O
7) and the deionized water composition; Described metal-salt is single nickel salt (NiSO
46H
2O), rose vitriol (CoSO
47H
2O) and ferrous sulfate (FeSO
47H
2O) a kind of in or two kinds or three kinds.
Trisodium citrate (the Na that adds 20～110g in the deionized water of consumption: 500ml
3C
6H
5O
7), the metal-salt of 8～40g and the inferior sodium phosphate (NaH of 8.5～42.5g
2PO
2);
In chemical plating fluid, add ammoniacal liquor (NH
3H
2O) pH=8.5～10 of the described chemical plating fluid of adjusting obtain chemical plating fluid;
(B) chemical plating technology
The 5th product that makes is put into chemical plating fluid;
The electroless plating condition: 70～90 ℃ electroless plating temperature, under the condition of power 500W, react 60～120min under the condition of ultra-sonic dispersion after, leave standstill 3～5min and make the 5th reaction solution;
The 5th reaction solution is carried out suction filtration obtain the 6th product;
The suction filtration condition: under room temperature (25 ℃) condition, the vacuum tightness of regulating suction filtration vacuum instrument is-0.1MPa to obtain the 6th product behind suction filtration time 5～10min;
In the present invention, adopting suction filtration is with the C in the 5th reaction solution
6H
5O
7 3-, H
2PO
3 -, Na
+Remove with metal ion, thereby obtain the 6th product.Described metal ion can be Ni
2+, Co
2+Or Fe
2+, also can be Ni
2+With Co
2+Metal ion, also can be Ni
2+With Fe
2+Metal ion, also can be Fe
2+With Co
2+Metal ion, also can be Ni
2+, Co
2+And Fe
2+Metal ion.
The 6th product is put into loft drier, behind dry 3～4h under 90～110 ℃ the condition, make the 7th product, i.e. the radar wave absorbing agent of clad metal coating on tiny balloon.
Embodiment 1:
(the KW-10 tiny balloon that glass microballon company limited in Qinhuangdao produces, main component is SiO to the tiny balloon that this routine radar wave absorbing agent is particle diameter 5～10 μ m
2And Al
2O
3), the metal-plated nickel dam forms, the metal-plated nickel dam is coated on the surface of tiny balloon, and the thickness 250nm of metal-plated nickel dam.
Adopt the preparation process of chemical plating technology clad metal nickel layer on tiny balloon as follows:
The first step: the choosing of body material
Body material is the KW-10 tiny balloon of particle diameter 5～10 μ m;
Second step: to the pre-treatment of matrix
(A) preparation alkali cleaning treatment solution
The alkali cleaning treatment solution is made up of sodium hydroxide (NaOH) and deionized water;
The sodium hydroxide (NaOH) that adds 10g in the deionized water of consumption: 500ml;
(B) alkali washing process
The tiny balloon that first step is chosen adds in the alkali cleaning treatment solution;
The alkali cleaning condition: 80 ℃ alkali cleaning temperature, under the condition of power 500W, magnetic agitation disperses to make first reaction solution behind (the high-power magnetic stirring apparatus of 88-1, Changzhou Guohua Electric Appliance Co., Ltd. produces) reaction 90min;
First reaction solution is washed acquisition first product;
The washing condition: under 25 ℃ of conditions, in first reaction solution of 100ml, add the 800ml deionized water and stirring and evenly dilute, behind the sedimentation 60min supernatant liquid is removed, repeats 2 times after acquisition first product;
In the present invention, adopting washing is with the Na in first reaction solution on the basis that does not influence the tiny balloon dispersiveness
+, OH
-And the impurities in raw materials removal, thereby obtain first product.
(C) preparation coupling processing liquid
Coupling processing liquid is by γ-An Bingjisanyiyangjiguiwan (KH550) and ethanol (C
2H
5OH) form;
Ethanol (the C of consumption: 500ml
2H
5OH) the Y-aminopropyl triethoxysilane that adds 0.5g in;
(D) coupling process
First product is added in the coupling processing liquid;
Coupling condition:, under the condition of power 500W, behind ultra-sonic dispersion (KQ-500B type ultrasonic cleaner, Kunshan Ultrasonic Instruments Co., Ltd. produces) the reaction 8h, leave standstill 3min and make second reaction solution 50 ℃ coupling temperature;
Second reaction solution is carried out suction filtration obtain second product;
The suction filtration condition: under 25 ℃ of conditions, the vacuum tightness of regulating suction filtration vacuum instrument (SHZ-III type recirculated water vacuum pump) is-0.1MPa to obtain second product behind the suction filtration time 5min;
In the present invention, adopting suction filtration is to add 40% removal and the adding ethanol (C of the consumption of coupling agent in second reaction solution
2H
5OH) 95% of consumption is removed, thereby obtains second product.
(E) preparation activation treatment liquid
Activation treatment liquid is by tin protochloride (SnCl
22H
2O), sodium stannate (Na
2SnO
3), Palladous chloride (PdCl
2), hydrochloric acid (HCl) and deionized water form;
Add 1g tin protochloride (SnCl in the hydrochloric acid of consumption: 100ml (HCl)
22H
2O) and the Palladous chloride (PdCl of 0.2g
2), add 12.5g tin protochloride (SnCl behind the reaction 20min
22H
2O), the sodium stannate (Na of 2g
2SnO
3) and the deionized water of 400ml;
(F) activating process
Second product is added in the activation treatment liquid;
Activation condition:, under the condition of power 500W, behind ultra-sonic dispersion (KQ-500B type ultrasonic cleaner, Kunshan Ultrasonic Instruments Co., Ltd. produces) the reaction 60min, leave standstill 3min and make the 3rd reaction solution 70 ℃ activation temperature;
The 3rd reaction solution is carried out suction filtration obtain third product;
The suction filtration condition: under 25 ℃ of conditions, the vacuum tightness of regulating suction filtration vacuum instrument (SHZ-III type recirculated water vacuum pump) is-0.1MPa to obtain third product behind the suction filtration time 5min;
In the present invention, adopting suction filtration is with the Sn in the 3rd reaction solution
2+, Sn
4+, Pd
2+, Cl
-And H
+Remove, wherein Sn
4+Be at Sn
2+With Palladous chloride (PdCl
2) chemical reaction takes place obtain.
(G) preparation dispergation treatment solution
The dispergation treatment solution is made up of hydrochloric acid (HCl) and deionized water;
The hydrochloric acid (HCl) that adds 50ml in the deionized water of consumption: 500ml;
(H) separate adhesive process
The 3rd reaction product is added in the dispergation treatment solution;
Dispergation condition:, under the condition of power 500W, behind ultra-sonic dispersion (KQ-500B type ultrasonic cleaner, Kunshan Ultrasonic Instruments Co., Ltd. produces) the reaction 3min, leave standstill 3min and make the 4th reaction solution 35 ℃ dispergation temperature;
The 4th reaction solution is carried out suction filtration obtain the 4th product;
The suction filtration condition: under 25 ℃ of conditions, the vacuum tightness of regulating suction filtration vacuum instrument (SHZ-III type recirculated water vacuum pump) is-0.1MPa to obtain the 4th product behind the suction filtration time 5min;
In the present invention, adopting suction filtration is with the Sn in the 4th reaction solution
2+And Cl
-And H
+Remove, thereby obtain the 4th product.Sn wherein
2+Be attached on the tiny balloon of the 4th product;
The 4th product is put into loft drier, behind dry 4h under 90 ℃ the condition, make the 5th product;
The 3rd step: electroless plating is handled
(A) preparation chemical plating fluid
Chemical plating fluid is by single nickel salt (NiSO
46H
2O), inferior sodium phosphate (NaH
2PO
2), trisodium citrate (Na
3C
6H
5O
7) and the deionized water composition;
Trisodium citrate (the Na that adds 20g in the deionized water of consumption: 500ml
3C
6H
5O
7), the single nickel salt (NiSO of 8g
46H
2O) and the inferior sodium phosphate (NaH of 8.5g
2PO
2);
In chemical plating fluid, add ammoniacal liquor (NH
3H
2O) pH=8.5 of the described chemical plating fluid of adjusting obtains chemical plating fluid;
(B) chemical plating technology
The 5th product that makes is put into chemical plating fluid;
Electroless plating condition:, under the condition of power 500W, behind the reaction 60min, leave standstill 3min and make the 5th reaction solution under the condition of ultra-sonic dispersion (KQ-500B type ultrasonic cleaner, Kunshan Ultrasonic Instruments Co., Ltd. produces) 70 ℃ electroless plating temperature;
The 5th reaction solution is carried out suction filtration obtain the 6th product;
The suction filtration condition: under 25 ℃ of conditions, the vacuum tightness of regulating suction filtration vacuum instrument (SHZ-III type recirculated water vacuum pump) is-0.1MPa to obtain the 6th product behind the suction filtration time 5min;
In the present invention, adopting suction filtration is with the C in the 5th reaction solution
6H
5O
7 3-, H
2PO
3 -, Na
+, Ni
2+Remove, thereby obtain the 6th product.
The 6th product is put into loft drier, behind dry 4h under 90 ℃ the condition, make the 7th product, be i.e. the radar wave absorbing agent of clad metal nickel layer on tiny balloon.
The radar wave absorbing agent (KW-10 tiny balloon+metal nickel dam) that adopts above-mentioned technology to make, the relative permittivity when coating thickness is 250nm is 50, and relative magnetic permeability is 1.5, and the density of radar wave absorbing agent is 3.5g/cm
3The relative permittivity of KW-10 tiny balloon is 4, and relative magnetic permeability is 1.The radar wave absorbing agent of KW-10 tiny balloon+metal nickel dam is 20dB in the maximum absorbance of 2～18GHz hertzian wave frequency range, is 5GHz greater than the frequency range of 10dB.
Adopt above-mentioned same process chemical plating metal cobalt (Co) layer on the KW-10 tiny balloon, the relative permittivity when coating thickness is 250nm is 40, and relative magnetic permeability is 1.4, and the density of radar wave absorbing agent is 3.5g/cm
3The radar wave absorbing agent of KW-10 tiny balloon+layer of metal cobalt is 20dB in the maximum absorbance of 2～18GHz hertzian wave frequency range, is 5GHz greater than the frequency range of 10dB.
Adopt above-mentioned same process chemical plating metal iron (Fe) layer on the KW-10 tiny balloon, the relative permittivity when coating thickness is 250nm is 60, and relative magnetic permeability is 2.0, and the density of radar wave absorbing agent is 3.4g/cm
3The radar wave absorbing agent of KW-10 tiny balloon+metallic iron layer is 20dB in the maximum absorbance of 2～18GHz hertzian wave frequency range, is 6GHz greater than the frequency range of 10dB.
Embodiment 2:
This routine radar wave absorbing agent is that KW-10 tiny balloon, the metal nickel plating+iron+cobalt layer of particle diameter 10～20 μ m formed, and metal nickel plating+iron+cobalt layer is coated on the surface of tiny balloon, and the thickness 150nm of metal-plated nickel dam.The mass percent of iron is 15 in metal nickel plating+iron+cobalt layer, and the mass percent of cobalt is 40, and surplus is a nickel.
Adopt chemical plating technology as follows in the preparation process that the KW-10 tiny balloon surface of particle diameter 10～20 μ m coats the thick metal nickel plating+iron+cobalt layer of 150nm:
The first step: the choosing of body material
Body material is the KW-10 tiny balloon of particle diameter 10～20 μ m;
Second step: to the pre-treatment of matrix
(A) preparation alkali cleaning treatment solution
The alkali cleaning treatment solution is made up of sodium hydroxide (NaOH) and deionized water;
The sodium hydroxide (NaOH) that adds 15g in the deionized water of consumption: 500ml;
(B) alkali washing process
The tiny balloon that first step is chosen adds in the alkali cleaning treatment solution;
The alkali cleaning condition: 70 ℃ alkali cleaning temperature, under the condition of power 500W, magnetic agitation disperses to make first reaction solution behind (the high-power magnetic stirring apparatus of 88-1, Changzhou Guohua Electric Appliance Co., Ltd. produces) reaction 75min;
First reaction solution is repeatedly washed acquisition first product;
The washing condition: under 25 ℃ of conditions, in first reaction solution of 100ml, add the 1000ml deionized water and stirring and evenly dilute, behind the sedimentation 75min supernatant liquid is removed, repeats 3 times after acquisition first product;
In the present invention, adopting washing is with the Na in first reaction solution on the basis that does not influence the tiny balloon dispersiveness
+, OH
-And the impurities in raw materials removal, thereby obtain first product.
(C) preparation coupling processing liquid
Coupling processing liquid is by γ-An Bingjisanyiyangjiguiwan (KH550) and ethanol (C
2H
5OH) form;
Ethanol (the C of consumption: 500ml
2H
5OH) the Y-aminopropyl triethoxysilane that adds 1g in;
(D) coupling process
First product is added in the coupling processing liquid;
Coupling condition:, under the condition of power 500W, behind ultra-sonic dispersion (KQ-500B type ultrasonic cleaner, Kunshan Ultrasonic Instruments Co., Ltd. produces) the reaction 7h, leave standstill 4min and make second reaction solution 40 ℃ coupling temperature;
Second reaction solution is carried out suction filtration obtain second product;
The suction filtration condition: under 25 ℃ of conditions, the vacuum tightness of regulating suction filtration vacuum instrument (SHZ-III type recirculated water vacuum pump) is-0.1MPa to obtain second product behind the suction filtration time 8min;
In the present invention, adopting suction filtration is to add 45% removal and the adding ethanol (C of the consumption of coupling agent in second reaction solution
2H
5OH) 98% of consumption is removed, thereby obtains second product.
(E) preparation activation treatment liquid
Activation treatment liquid is by tin protochloride (SnCl
22H
2O), sodium stannate (Na
2SnO
3), Palladous chloride (PdCl
2), hydrochloric acid (HCl) and deionized water form;
Add 1.5g tin protochloride (SnCl in the hydrochloric acid of consumption: 100ml (HCl)
22H
2O) and the Palladous chloride (PdCl of 0.4g
2), add 37.5g tin protochloride (SnCl behind the reaction 15min
22H
2O), the sodium stannate (Na of 3g
2SnO
3) and the deionized water of 400ml;
(F) activating process
Second product is added in the activation treatment liquid;
Activation condition:, under the condition of power 500W, behind ultra-sonic dispersion (KQ-500B type ultrasonic cleaner, Kunshan Ultrasonic Instruments Co., Ltd. produces) the reaction 45min, leave standstill 4min and make the 3rd reaction solution 60 ℃ activation temperature;
The 3rd reaction solution is carried out suction filtration obtain third product;
The suction filtration condition: under 25 ℃ of conditions, the vacuum tightness of regulating suction filtration vacuum instrument (SHZ-III type recirculated water vacuum pump) is-0.1MPa to obtain third product behind the suction filtration time 8min;
In the present invention, adopting suction filtration is with the Sn in the 3rd reaction solution
2+, Sn
4+, Pd
2+, Cl
-And H
+Remove, wherein Sn
4+Be at Sn
2+With Palladous chloride (PdCl
2) chemical reaction takes place obtain.
(G) preparation dispergation treatment solution
The dispergation treatment solution is made up of hydrochloric acid (HCl) and deionized water;
The hydrochloric acid (HCl) that adds 75ml in the deionized water of consumption: 500ml;
(H) separate adhesive process
The 3rd reaction product is added in the dispergation treatment solution;
Dispergation condition:, under the condition of power 500W, behind ultra-sonic dispersion (KQ-500B type ultrasonic cleaner, Kunshan Ultrasonic Instruments Co., Ltd. produces) the reaction 2min, leave standstill 4min and make the 4th reaction solution at 40 ℃ sensitizing temperature;
The 4th reaction solution is carried out suction filtration obtain the 4th product;
The suction filtration condition: under 25 ℃ of conditions, the vacuum tightness of regulating suction filtration vacuum instrument (SHZ-III type recirculated water vacuum pump) is-0.1MPa to obtain the 4th product behind the suction filtration time 8min;
In the present invention, adopting suction filtration is with the Sn in the 4th reaction solution
2+And Cl
-And H
+Remove, thereby obtain the 4th product.Sn wherein
2+Be attached on the tiny balloon of the 4th product;
The 4th product is put into loft drier, behind dry 3.5h under 100 ℃ the condition, make the 5th product;
The 3rd step: electroless plating is handled
(A) preparation chemical plating fluid
Chemical plating fluid is by single nickel salt (NiSO
46H
2O), rose vitriol (CoSO
47H
2O), ferrous sulfate (FeSO
47H
2O), inferior sodium phosphate (NaH
2PO
2), trisodium citrate (Na
3C
6H
5O
7) and the deionized water composition;
Trisodium citrate (the Na that adds 51.5g in the deionized water of consumption: 500ml
3C
6H
5O
7), the single nickel salt (NiSO of 8g
46H
2O), the rose vitriol (CoSO of 8g
47H
2O), the ferrous sulfate (FeSO of 16g
47H
2O) and the inferior sodium phosphate (NaH of 21.5g
2PO
2);
In chemical plating fluid, add ammoniacal liquor (NH
3H
2O) pH=9 of the described chemical plating fluid of adjusting obtains chemical plating fluid;
(B) chemical plating technology
The 5th product that makes is put into chemical plating fluid;
Electroless plating condition:, under the condition of power 500W, behind the reaction 90min, leave standstill 4min and make the 5th reaction solution under the condition of ultra-sonic dispersion (KQ-500B type ultrasonic cleaner, Kunshan Ultrasonic Instruments Co., Ltd. produces) 80 ℃ electroless plating temperature;
The 5th reaction solution is carried out suction filtration obtain the 6th product;
The suction filtration condition: under 25 ℃ of conditions, the vacuum tightness of regulating suction filtration vacuum instrument (SHZ-III type recirculated water vacuum pump) is-0.1MPa to obtain the 6th product behind the suction filtration time 8min;
In the present invention, adopting suction filtration is with the C in the 5th reaction solution
6H
5O
7 3-, H
2PO
3 -, Na
+And Ni
2+Remove, thereby obtain the 6th product.
The 6th product is put into loft drier, behind dry 3.5h under 100 ℃ the condition, make the 7th product, be i.e. the radar wave absorbing agent of clad metal coating on tiny balloon.
The radar wave absorbing agent (KW-10 tiny balloon+metallic nickel+cobalt+iron layer) that adopts above-mentioned technology to make, the relative permittivity when coating thickness is 150nm is 70, and relative magnetic permeability is 2.0, and the density of radar wave absorbing agent is 3.0g/cm
3The relative permittivity of KW-10 tiny balloon is 4, and relative magnetic permeability is 1.The radar wave absorbing agent of KW-10 tiny balloon+metallic nickel+cobalt+iron layer is 15dB in the maximum absorbance of 2～18GHz hertzian wave frequency range, is 3GHz greater than the frequency range of 10dB.
Embodiment 3:
This routine radar wave absorbing agent is that KW-10 tiny balloon, the metal cobalt plating+iron layer of particle diameter 1～20 μ m formed, and metal cobalt plating+iron layer is coated on the surface of tiny balloon, and the thickness 50nm of metal-plated nickel dam.
Adopt chemical plating technology at tiny balloon surface clad cobalt plating+iron layer, its preparation process is as follows:
The first step: the choosing of body material
Body material is the KW-10 tiny balloon of particle diameter 1～20 μ m;
Second step: to the pre-treatment of matrix
(A) preparation alkali cleaning treatment solution
The alkali cleaning treatment solution is made up of sodium hydroxide (NaOH) and deionized water;
The sodium hydroxide (NaOH) that adds 20g in the deionized water of consumption: 500ml;
(B) alkali washing process
The tiny balloon that first step is chosen adds in the alkali cleaning treatment solution;
The alkali cleaning condition: 60 ℃ alkali cleaning temperature, under the condition of power 500W, magnetic agitation disperses to make first reaction solution behind (the high-power magnetic stirring apparatus of 88-1, Changzhou Guohua Electric Appliance Co., Ltd. produces) reaction 60min;
First reaction solution is repeatedly washed acquisition first product;
The washing condition: under 25 ℃ of conditions, in first reaction solution of 100ml, add the 900ml deionized water and stirring and evenly dilute, behind the sedimentation 60min supernatant liquid is removed, repeats 3 times after acquisition first product;
In the present invention, adopting washing is with the Na in first reaction solution on the basis that does not influence the tiny balloon dispersiveness
+, OH
-And the impurities in raw materials removal, thereby obtain first product.
(C) preparation coupling processing liquid
Coupling processing liquid is by γ-An Bingjisanyiyangjiguiwan (KH550) and ethanol (C
2H
5OH) form;
Ethanol (the C of consumption: 500ml
2H
5OH) the Y-aminopropyl triethoxysilane that adds 2g in;
(D) coupling process
First product is added in the coupling processing liquid;
Coupling condition:, under the condition of power 500W, behind ultra-sonic dispersion (KQ-500B type ultrasonic cleaner, Kunshan Ultrasonic Instruments Co., Ltd. produces) the reaction 6h, leave standstill 5min and make second reaction solution 35 ℃ coupling temperature;
Second reaction solution is carried out suction filtration obtain second product;
The suction filtration condition: under 25 ℃ of conditions, the vacuum tightness of regulating suction filtration vacuum instrument (SHZ-III type recirculated water vacuum pump) is-0.1MPa to obtain second product behind the suction filtration time 10min;
In the present invention, adopting suction filtration is to add 50% removal and the adding ethanol (C of the consumption of coupling agent in second reaction solution
2H
5OH) 95% of consumption is removed, thereby obtains second product.
(E) preparation activation treatment liquid
Activation treatment liquid is by tin protochloride (SnCl
22H
2O), sodium stannate (Na
2SnO
3), Palladous chloride (PdCl
2), hydrochloric acid (HCl) and deionized water form;
Add 2g tin protochloride (SnCl in the hydrochloric acid of consumption: 100ml (HCl)
22H
2O) and the Palladous chloride (PdCl of 0.5g
2), add 50g tin protochloride (SnCl behind the reaction 10min
22H
2O), the sodium stannate (Na of 4g
2SnO
3) and the deionized water of 400ml;
(F) activating process
Second product is added in the activation treatment liquid;
Activation condition:, under the condition of power 500W, behind ultra-sonic dispersion (KQ-500B type ultrasonic cleaner, Kunshan Ultrasonic Instruments Co., Ltd. produces) the reaction 30min, leave standstill 5min and make the 3rd reaction solution 50 ℃ activation temperature;
The 3rd reaction solution is carried out suction filtration obtain third product;
The suction filtration condition: under room temperature (25 ℃) condition, the vacuum tightness of regulating suction filtration vacuum instrument (SHZ-III type recirculated water vacuum pump) is-0.1MPa to obtain third product behind the suction filtration time 10min;
In the present invention, adopting suction filtration is with the Sn in the 3rd reaction solution
2+, Sn
4+, Pd
2+, Cl
-And H
+Remove, wherein Sn
4+Be at Sn
2+With Palladous chloride (PdCl
2) chemical reaction takes place obtain.
(G) preparation dispergation treatment solution
The dispergation treatment solution is made up of hydrochloric acid (HCl) and deionized water;
The hydrochloric acid (HCl) that adds 100ml in the deionized water of consumption: 500ml;
(H) separate adhesive process
The 3rd reaction product is added in the dispergation treatment solution;
Dispergation condition:, under the condition of power 500W, behind ultra-sonic dispersion (KQ-500B type ultrasonic cleaner, Kunshan Ultrasonic Instruments Co., Ltd. produces) the reaction 1min, leave standstill 5min and make the 4th reaction solution 50 ℃ dispergation temperature;
The 4th reaction solution is carried out suction filtration obtain the 4th product;
The suction filtration condition: under 25 ℃ of conditions, the vacuum tightness of regulating suction filtration vacuum instrument (SHZ-III type recirculated water vacuum pump) is-0.1MPa to obtain the 4th product behind the suction filtration time 10min;
In the present invention, adopting suction filtration is with the Sn in the 4th reaction solution
2+And Cl
-And H
+Remove, thereby obtain the 4th product.Sn wherein
2+Be attached on the tiny balloon of the 4th product;
The 4th product is put into loft drier, behind dry 3h under 110 ℃ the condition, make the 5th product;
The 3rd step: electroless plating is handled
(A) preparation chemical plating fluid
Chemical plating fluid is by rose vitriol (CoSO
47H
2O), ferrous sulfate (FeSO
47H
2O), inferior sodium phosphate (NaH
2PO
2), trisodium citrate (Na
3C
6H
5O
7) and the deionized water composition;
Trisodium citrate (the Na that adds 110g in the deionized water of consumption: 500ml
3C
6H
5O
7), the single nickel salt (CoSO of 20g
47H
2O), 20g ferrous sulfate (FeSO
47H
2O) and the inferior sodium phosphate (NaH of 42.5g
2PO
2);
In chemical plating fluid, add ammoniacal liquor (NH
3H
2O) pH=10 of the described chemical plating fluid of adjusting obtains chemical plating fluid;
(B) chemical plating technology
The 5th product that makes is put into chemical plating fluid;
Electroless plating condition:, under the condition of power 500W, behind the reaction 120min, leave standstill 5min and make the 5th reaction solution under the condition of ultra-sonic dispersion (KQ-500B type ultrasonic cleaner, Kunshan Ultrasonic Instruments Co., Ltd. produces) 90 ℃ electroless plating temperature;
The 5th reaction solution is carried out suction filtration obtain the 6th product;
The suction filtration condition: under 25 ℃ of conditions, the vacuum tightness of regulating suction filtration vacuum instrument (SHZ-III type recirculated water vacuum pump) is-0.1MPa to obtain the 6th product behind the suction filtration time 10min;
In the present invention, adopting suction filtration is with the C in the 5th reaction solution
6H
5O
7 3-, H
2PO
3 -, Na
+, Co
2+ and Fe
2+Remove, thereby obtain the 6th product.
The 6th product is put into loft drier, behind dry 4h under 110 ℃ the condition, make the 7th product, be i.e. the radar wave absorbing agent of clad metal coating on tiny balloon.
The radar wave absorbing agent (KW-10 tiny balloon+cobalt metal+iron layer) that adopts above-mentioned technology to make, the relative permittivity when coating thickness is 50nm is 60, and relative magnetic permeability is 1.4, and the density of radar wave absorbing agent is 2.65g/cm
3The relative permittivity of KW-10 tiny balloon is 4, and relative magnetic permeability is 1.The radar wave absorbing agent of KW-10 tiny balloon+cobalt metal+iron layer is 10dB in the maximum absorbance of 2～18GHz hertzian wave frequency range, is 3GHz greater than the frequency range of 8dB.
Adopt above-mentioned same process chemical plating metal cobalt+nickel dam on the KW-10 tiny balloon, the relative permittivity when coating thickness is 50nm is 50, and relative magnetic permeability is 1.5, and the density of radar wave absorbing agent is 2.60g/cm
3The radar wave absorbing agent of KW-10 tiny balloon+metallic nickel+cobalt layer is 10dB in the maximum absorbance of 2～18GHz hertzian wave frequency range, is 3GHz greater than the frequency range of 8dB.
Adopt above-mentioned same process chemical plating metal iron+nickel dam on the KW-10 tiny balloon, the relative permittivity when coating thickness is 50nm is 70, and relative magnetic permeability is 1.8, and the density of radar wave absorbing agent is 2.71g/cm
3The radar wave absorbing agent of KW-10 tiny balloon+metallic nickel+iron layer is 10dB in the maximum absorbance of 2～18GHz hertzian wave frequency range, is 4GHz greater than the frequency range of 8dB.
Claims (1)
1. method that adopts chemical plating technology to prepare radar wave absorbing agent is characterized in that the following step is arranged:
The first step: the choosing of body material
Body material is the tiny balloon of particle diameter 1～20 μ m;
Second step: to the pre-treatment of matrix
(A) preparation alkali cleaning treatment solution
The alkali cleaning treatment solution is made up of sodium hydroxide and deionized water;
The sodium hydroxide that adds 10～20g in the deionized water of consumption: 500ml;
(B) alkali washing process
The tiny balloon that first step is chosen adds in the alkali cleaning treatment solution;
The alkali cleaning condition: 60～80 ℃ alkali cleaning temperature, under the condition of power 500W, magnetic agitation disperses to make first reaction solution behind reaction 60～90min;
First reaction solution is washed acquisition first product;
The washing condition: under 25 ℃ of conditions, first reaction solution is diluted with deionized water, adds 800～1000ml deionized water in promptly every 100ml first reaction solution and dilute, behind sedimentation 60～90min supernatant liquid is removed, repeats 2～3 times after acquisition first product;
(C) preparation coupling processing liquid
Coupling processing liquid is by silane coupling agent and ethanol C
2H
5OH forms;
The ethanol C of consumption: 500ml
2H
5The silane coupling agent that adds 0.5～2g among the OH;
Described silane coupling agent can be a γ-An Bingjisanyiyangjiguiwan, trade mark KH550;
(D) coupling process
First product is added in the coupling processing liquid;
Coupling condition:, under the condition of power 500W, behind ultra-sonic dispersion reaction 6～8h, leave standstill 3～5min and make second reaction solution 35～50 ℃ coupling temperature;
Second reaction solution is carried out suction filtration obtain second product;
The suction filtration condition: under 25 ℃ of conditions, the vacuum tightness of regulating suction filtration vacuum instrument is-0.1MPa to obtain second product behind suction filtration time 5～10min;
(E) preparation activation treatment liquid
Activation treatment liquid is by tin protochloride SnCl
22H
2O, sodium stannate Na
2SnO
3, Palladous chloride PdCl
2, hydrochloric acid and deionized water form;
Add 1～2g tin protochloride SnCl in the hydrochloric acid of consumption: 100ml
22H
2The Palladous chloride PdCl of O and 0.2～0.5g
2, add 12.5～50g tin protochloride SnCl behind reaction 10～20min
22H
2The sodium stannate Na of O, 2～4g
2SnO
3Deionized water with 400ml;
(F) activating process
Second product is added in the activation treatment liquid;
Activation condition:, under the condition of power 500W, behind ultra-sonic dispersion reaction 30～60min, leave standstill 3～5min and make the 3rd reaction solution 50～70 ℃ activation temperature;
The 3rd reaction solution is carried out suction filtration obtain third product;
The suction filtration condition: under 25 ℃ of conditions, the vacuum tightness of regulating suction filtration vacuum instrument is-0.1MPa to obtain third product behind suction filtration time 5～10min;
(G) preparation dispergation treatment solution
The dispergation treatment solution is made up of hydrochloric acid and deionized water;
The hydrochloric acid that adds 50～100ml in the deionized water of consumption: 500ml;
(H) separate adhesive process
The 3rd reaction product is added in the dispergation treatment solution;
Dispergation condition:, under the condition of power 500W, behind ultra-sonic dispersion reaction 1～3min, leave standstill 3～5min and make the 4th reaction solution 35～50 ℃ dispergation temperature;
The 4th reaction solution is carried out suction filtration obtain the 4th product;
The suction filtration condition: under 25 ℃ of conditions, the vacuum tightness of regulating suction filtration vacuum instrument is-0.1MPa to obtain the 4th product behind suction filtration time 5～10min;
The 4th product is put into loft drier, behind dry 3～4h under 90～110 ℃ the condition, make the 5th product;
The 3rd step: electroless plating is handled
(A) preparation chemical plating fluid
Chemical plating fluid is by metal-salt, inferior sodium phosphate NaH
2PO
2, trisodium citrate Na
3C
6H
5O
7Form with deionized water; Described metal-salt is single nickel salt NiSO
46H
2O, rose vitriol CoSO
47H
2O and ferrous sulfate FeSO
47H
2A kind of among the O or two kinds or three kinds;
The trisodium citrate Na that adds 20～110g in the deionized water of consumption: 500ml
3C
6H
5O
7, the metal-salt of 8～40g and the inferior sodium phosphate NaH of 8.5～42.5g
2PO
2
In chemical plating fluid, add pH=8.5～10 that ammoniacal liquor is regulated described chemical plating fluid, obtain chemical plating fluid;
(B) chemical plating technology
The 5th product that makes is put into chemical plating fluid;
The electroless plating condition: 70～90 ℃ electroless plating temperature, under the condition of power 500W, react 60～120min under the condition of ultra-sonic dispersion after, leave standstill 3～5min and make the 5th reaction solution;
The 5th reaction solution is carried out suction filtration obtain the 6th product;
The suction filtration condition: under 25 ℃ of conditions, the vacuum tightness of regulating suction filtration vacuum instrument is-0.1MPa to obtain the 6th product behind suction filtration time 5～10min;
The 6th product is put into loft drier, behind dry 3～4h under 90～110 ℃ the condition, make the 7th product, i.e. the radar wave absorbing agent of clad metal coating on tiny balloon.
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| CN101962763B (en) * | 2009-07-22 | 2012-06-06 | 比亚迪股份有限公司 | Chemical plating peptizing liquid and method for performing non-metal surface treatment |
| CN101941076A (en) * | 2010-08-06 | 2011-01-12 | 华南理工大学 | Method for preparing multilayer hollow metal microspheres for electromagnetic wave absorbing material |
| CN103801707B (en) * | 2012-11-14 | 2016-04-13 | 广东信力材料科技有限公司 | The preparation method of hud typed microwave absorbing material |
| CN109111719B (en) * | 2017-06-26 | 2022-12-13 | 洛阳尖端技术研究院 | Wave-absorbing material and preparation method thereof |
| CN109233743B (en) * | 2018-10-25 | 2021-11-09 | 中北大学 | Light wave-absorbing composite material with coal ash-based core-shell structure and preparation method thereof |
| CN110541162A (en) * | 2019-09-11 | 2019-12-06 | 中国人民解放军火箭军工程大学 | method for coating magnetic metal film on surface of wave-absorbing material |
| CN111763931A (en) * | 2020-07-15 | 2020-10-13 | 上海大学 | Preparation method of nickel-plated glass microspheres and product |
| CN113583536A (en) * | 2021-07-26 | 2021-11-02 | 苏州市万利成制桶有限公司 | Formula and manufacturing process of outer-layer stab-resistant coating of environment-friendly metal barrel |
| CN115505910B (en) * | 2022-10-25 | 2023-10-27 | 北京航空航天大学 | Magnetic metal @ SiC wave-absorbing powder and preparation method thereof |
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