CN101928985B

CN101928985B - Quadrilateral zinc oxide/ nickel ferrite material and preparation method thereof

Info

Publication number: CN101928985B
Application number: CN201010234974A
Authority: CN
Inventors: 于美; 胡建平; 刘建华; 王承; 李松梅; 刘鹏瑞
Original assignee: Beihang University
Current assignee: Beihang University
Priority date: 2010-07-23
Filing date: 2010-07-23
Publication date: 2012-10-03
Anticipated expiration: 2030-07-23
Also published as: CN101928985A

Abstract

The invention discloses a quadrilateral zinc oxide whisker/ nickel ferrite material and a preparation method thereof. The quadrilateral zinc oxide whisker/ nickel ferrite material has good wave absorbing performance, and the preparation method of the quadrilateral zinc oxide whisker/ nickel ferrite material realizes chemical plating for nickel ferrite on the surface of the quadrilateral zinc oxide whisker under the condition of low temperature (80 DEG C) so as to successfully prepare and obtain a layer of nickel ferrite on the surface of the quadrilateral zinc oxide whisker.

Description

A kind of four horn shapes zinc oxide/Ni ferrite material and preparation method thereof

Technical field

The present invention relates to a kind of four horn shapes zinc oxide/Ni ferrite material and preparation method thereof, particularly relate to a kind of method for preparing four horn shapes ZnOw/Ni ferrite material at four horn shape ZnOw surface chemical plating plated nickel ferrites.

Background technology

Four jiaos of ZnOws (T-ZnOw) are the lightweight whiskers of finding at present with regular three-dimensional four acicular structures.Because the singularity of its four angled construction and have that intensity height, modulus are high, high temperature resistant, wear-resisting, damping, noise reduction, ultraviolet ray absorbing functions, be widely used in fields such as chemical industry, light industry, electronics.In addition, this material microwave absorptive character have been given in the special construction of four horn shapes and the combination of multiple function.(Liu Jianhua such as Liu Jianhua; Sun Jie, Li Songmei, Chen Dongmei. the microwave electromagnetic performance of four-leg crystal whisker of zinc oxide. the matrix material journal; 2003; 20 (6): 121-124) mixture of T-ZnOw and paraffin has been carried out the research of microwave electromagnetic performance, found that T-ZnOw is the dielectric loss type material, had certain microwave absorbing property.Zhou Zuowan etc. (Zhou Zuowan, Peng Weiming, Deng sea. the application of ZnOw and matrix material thereof [J]. New Chemical Materials, 1999,26 (11): 13-15) T-ZnOw is discovered that in the 5-18GHz wave band, it inhales the ripple amount is 5-16.68dB.

Ferrite is to use magnetic loss type microwave absorbing material the most widely at present.As a kind of anisotropy soft magnetic materials, NiFe ₂O ₄Be a kind of very important ferrite, because Ni ²⁺Occupied octahedral site, and Fe ³⁺Occupied tetrahedral site, the two non-parallel rotation produces stronger reverse magnetic force distance, makes NiFe ₂O ₄Have higher saturation magnetization and coercive force, simultaneously because it has good magnetic, electromagnetic performance and chemicalstability, especially NiFe ₂O ₄Curie-point temperature reached 590 ℃, far above general Ferrite Material, it is used widely on field such as microwave superpower shield retaining, high frequency recording material, microwave device and electromagnetism be stealthy.

Ferrite chemical plating is a kind of technology that is different from traditional chemical plating, and it is a kind ofly can under low temperature (less than 100 ℃) condition, from solution, directly ferrite be plated on the chemical plating method on the matrix.This makes on the particle of resistance toheat difference or Powdered matrix plating ferrite film and then preparation high-performance wave-absorbing material become possibility.

Carrying out electroless plating plated nickel ferrite on the surface of four horn shape ZnOws, prepare four horn shapes ZnOw/Ni ferrite material at low temperatures, is the effective ways of preparation high-performance wave-absorbing material.

Summary of the invention

The present invention has successfully prepared a kind of well behaved absorbing material, and concrete summary of the invention is following:

Four horn shape ZnOws can adopt oxidation style to make.Basic technology is heated to 1000 ℃ for ceramic crucible is put into retort furnace.Zinc powder and iron powder are put into crucible by a certain percentage, behind the insulation 5min, close retort furnace, take out the crucible air cooling, can obtain product to room temperature.Four horn shape ZnOws also can be bought through businessman and obtain.

Above-mentioned surface is covered with one deck Ni ferrite (NiFe ₂O ₄) the chemical plating method of four horn shape ZnOws do

(1) get four horn shape ZnOw 0.1-0.4g, water washes repeatedly;

(2) in the reaction vessel that has whipping appts, add 80mL water, and feed protective gas, be heated to 80 ℃;

(3) be incubated and add four horn shape ZnOws, stir;

(4) drip the FeCl of 0.2～0.4mol/L respectively with the interpolation speed of 1～2ml/min and 4～5ml/min ₂4H ₂O, NiCl ₂6H ₂The mixing solutions 45mL of O, and 90mL is with the CH of 1: 2 volume ratio blended 2～5mol/L ₃COONH ₄The NaNO of solution and 1-3g/L ₂Solution, and the pH that controls reaction solution in the reaction vessel in real time is between 7-8;

(5) more than the insulation reaction 10min, after having reacted repeatedly filtration and washing obtain product.

Wherein reaction vessel is preferably four-hole boiling flask in the step (2), and protective gas is nitrogen or rare gas element;

Stirring velocity is 200-500r/min in the step (3), preferably uses 300-400r/min;

FeCl in the step (4) ₂4H ₂O, NiCl ₂6H ₂The mixing solutions of O is FeCl ₂4H ₂O and NiCl ₂6H ₂The O mol ratio be 2: 1 formulated.

During step (4) control pH, use pH meter to measure the feedback bath pH value, pH value of solution is in specifying the pH scope in the whole electroless plating process to keep to drip pH adjustment agent, and pH adjustment agent is a NaOH solution, and ammoniacal liquor or other do not influence the basic soln that technology is carried out;

The water that uses in steps be deionized water.

The some samples that prepare are carried out the XRD test; Relevant for the obvious characteristic peak of ferrite and zinc oxide, carry out EDS and analyze, elemental nickel, iron, zinc are arranged; And nickel is about 1: 2 with the atomicity ratio of iron; Show and contain Ni ferrite and zinc oxide in this product, carry out SEM thereafter and observe that can obviously observe the whisker surface has Ni ferrite to generate.

The present invention has realized at low temperatures four horn shape ZnOws being carried out ferrite chemical plating, and at four horn shape ZnOw surface preparation Ni ferrites, the four horn shapes ZnOw/Ni ferrite material of preparation has microwave absorbing property.The filler that this product can be used as microwave absorbing coating uses, and has broad application prospects.

Description of drawings

Fig. 1 is the XRD figure of the crystal whisker materials of four horn shapes ZnOw/Ni ferrite material of preparing;

Fig. 2 is the SEM photo of crystal whisker materials of the four horn shapes ZnOw/Ni ferrite material of embodiment 1 preparation;

Fig. 3 is that four horn shapes ZnOw/Ni ferrite material and the paraffin mass ratio of embodiment 1 preparation is to mix at 2: 1; Process coaxial sample; The reflectance curve figure of product under the different thickness of testing its electromagnetic parameter and calculating according to transmission line theory, range of frequency is 2～18GHz;

Fig. 4 is that four horn shapes ZnOw/Ni ferrite material and the paraffin mass ratio of embodiment 2 preparation is to mix at 2: 1; Process coaxial sample; The reflectance curve figure of product under the different thickness of testing its electromagnetic parameter and calculating according to transmission line theory, range of frequency is 2～18GHz;

Fig. 5 is that four horn shapes ZnOw/Ni ferrite material and the paraffin mass ratio of embodiment 3 preparation is to mix at 2: 1; Process coaxial sample; The reflectance curve figure of product under the different thickness of testing its electromagnetic parameter and calculating according to transmission line theory, range of frequency is 2～18GHz.

Embodiment

To combine accompanying drawing and embodiment that the present invention is done further detailed description below.

Embodiment 1

(1) get four horn shape ZnOw 0.1g, it is subsequent use to wash the back repeatedly with deionized water;

(2) in four-hole boiling flask, add the 80ml deionized water, magnetic agitation also feeds protective gas nitrogen, is heated to 80 ℃;

(3) be incubated and add four horn shape ZnOws, stir (300r/min);

(4) drip the FeCl of 0.2mol/L respectively with the speed of 1mL/min and 4mL/min ₂4H ₂O solution 45mL, and 90mL is with the CH of 1: 2 volume ratio blended 2mol/L ₃COONH ₄The NaNO of solution and 1.5g/L ₂Solution uses pH meter to measure the feedback bath pH value simultaneously, drips NaOH solution simultaneously to keep in the whole electroless plating process in the four-hole boiling flask pH of reaction solution liquid 7.5;

(5) reaction obtains product with the deionized water filtration and washing after 45 minutes repeatedly.

Embodiment 2

(1) get four horn shape ZnOw 0.2g, it is subsequent use to wash the back repeatedly with deionized water;

(3) after the homo(io)thermism, add four horn shape ZnOws, stir (400r/min);

(4) drip the FeCl of 0.4mol/L respectively with the speed of 2mL/min and 5mL/min ₂4H ₂O solution 45mL, and 90mL is with the CH of 1: 2 volume ratio blended 2mol/L ₃COONH ₄The NaNO of solution and 3g/L ₂Solution uses pH meter to measure the feedback bath pH value, drips NaOH solution to keep in the whole electroless plating process in the four-hole boiling flask pH of reaction solution 7;

(5) reaction is 30 minutes, obtains product with the deionized water filtration and washing repeatedly.

Embodiment 3

(1) get four horn shape ZnOw 0.4g, it is subsequent use to wash the back repeatedly with deionized water;

(2) in reaction vessel, add the 80ml deionized water, magnetic agitation also feeds protective gas nitrogen, is heated to 80 ℃;

(3) after the homo(io)thermism, add four horn shape ZnOws, stir (300r/min);

(4) drip the FeCl of 0.4mol/L respectively with the speed of 2mL/min and 5mL/min ₂4H ₂O solution 45mL, and 90mL is with the CH of 1: 2 volume ratio blended 2mol/L ₃COONH ₄The NaNO of solution and 4g/L ₂Solution uses pH meter to measure the feedback bath pH value, and dropping ammonia solution is to keep in the whole electroless plating process in the reaction vessel pH of reaction solution between 8;

(5) reaction obtained product with the deionized water filtration and washing after 60 minutes.

Claims

1. horn shape ZnOw/Ni ferrite preparation methods is characterized in that, concrete preparing method's step is:

(1) get four horn shape ZnOw 0.1-0.4g, water washes repeatedly;

(2) adding 80mL water in the four-hole boiling flask reaction vessel that has whipping appts, and feeding nitrogen or rare gas element are heated to 80 ℃ as protective gas;

(3) be incubated and add four horn shape ZnOws, stir, stirring velocity is 200-500r/min;

(4) drip the FeCl of 0.2～0.4mol/L respectively with the interpolation speed of 1～2ml/min and 4～5ml/min ₂4H ₂O, NiCl ₂6H ₂The mol ratio of O is 2: 1 mixing solutions 45mL, and 90mL is with the CH of 1: 2 volume ratio blended 2～5mol/L ₃COONH ₄The NaNO of solution and 1-3g/L ₂Solution, and the pH that controls reaction solution in the reaction vessel in real time is between 7-8;

(5) more than the insulation reaction 10min, filtration and washing repeatedly after having reacted obtains to have at the coating surface of four horn shape ZnOws the product of one deck Ni ferrite;

Wherein, pH adjustment agent is that NaOH solution, ammoniacal liquor or other do not influence the basic soln that technology is carried out, and the water that is used in steps is deionized water.