CN104402057A

CN104402057A - Spinel ferrite nanoparticle preparation method

Info

Publication number: CN104402057A
Application number: CN201410548060.7A
Authority: CN
Inventors: 刘青芳; 曹德让; 潘丽宁; 王建波
Original assignee: Lanzhou University
Current assignee: Lanzhou University
Priority date: 2014-10-16
Filing date: 2014-10-16
Publication date: 2015-03-11

Abstract

The present invention discloses a spinel ferrite (MFe2O4) nanoparticle preparation method, which comprises: matching one or a plurality of metal M salts capable of being dissolved in DMF and an iron salt capable of being dissolved in DMF according to an atom molar ratio of M to Fe of 1:2, mixing the M salt, the Fe salt and 1-10 times by mass of DMF, uniformly stirring to obtain a transparent solution, and sintering the solution for 1-6 h at a temperature of 600-1100 DEG C so as to obtain the spinel ferrite MFe2O4 nanoparticle. With the spinel ferrite (MFe2O4) nanoparticle preparation method of the present invention, the defects in the prior art can be overcome, the prepared ferrite nanoparticle has characteristics of small size and uniform size, and the method has advantages of rapid production rate, high yield, high benefit, easy large-batch industrial production and the like.

Description

Prepare the method for ferrospinel nano particle

Technical field

The invention belongs to magnetic Nano material and manufacture field, specifically the present invention relates to a kind of ferrospinel (MFe ₂o ₄) preparation method of nano particle.

Background technology

In recent years, magnetic nanoparticle illustrates its application prospect widely in magnetic-sensitive elements, microwave coating, biomedicine and in the industry such as other chemical catalysis.Ferrospinel, as important magneticsubstance, has that initial permeability is high, resistivity high, is widely used in magnetic recording media, pigment, catalyzes and synthesizes, the field such as ceramic post sintering raw material, electronic instrument microwave communication device, magnetic fillers.The market requirement of China's current ferrospinel differential is in rising trend, and existing production technology comparatively backwardness, and product category is few, and quality is low.Along with the develop rapidly of the high-tech industries such as electronic industry, ferritic demand is also and then increased sharply.With this in the urgent need to improving product quality and yield, develop new synthetic technology.

In existing conventional art, prepare ferritic method have: sol-gel method, coprecipitation method, hydrothermal method etc., because magneticsubstance is easily reunited, the magnetic nanoparticle usually obtained does not have good dispersiveness.

The product of the powder obtained by sol-gel method has the advantages such as chemical uniformity is good, particle is thin, sintering temperature is low.But this requirement of putting method condition is to external world higher, wayward, and cost is higher, for industrialization, also compares and is difficult to realize on a large scale.

Though the powder grain of hydrothermal method preparation is grown complete, particle is little and be evenly distributed, can obtain the magnetic nanoparticle that purity is high, reunion degree is little, coking property is good, but the method needs adjust ph, and gained particle size is uneven.

Precipitator method technique is simple, and obtained particulates' properties is good, and has the advantages such as reactant chemically reactive is high, product powder mixes, fine size, but easily reunites with the nano powder that this method is synthesized, and need carry out finishing to product, limits its application.In addition, the tensio-active agent of precipitator method use and the pH value of reaction system all can have an impact to the performance of product.

Although the patent about ferrite nanometer particle preparation method having had part to improve in prior art (patent No. publication number: CN 102424570 A, CN 101486492 A, CN 101696108 A, CN 102225866 A etc.), but the raw material type of these methods (comprising traditional method) major part needs preparation before this and process is many, such as need: sodium acetate, ethylene glycol, Pentyl alcohol, acid, alkali, organic solvent etc., or need adjust ph (pH value regulates to be needed to add other acid or alkaline matters), or need some auxiliarys or tensio-active agent (such as macromolecule dispersing agent, how far hydrochlorate, citric acid etc.), and treating processes (needs ultrasonic, temperature adjustment etc.) and follow-up work more (subsequent operation needs to add other medicines as acetone breakdown of emulsion, the separating for several times precipitations such as ethanol, eccentric cleaning etc.), process is loaded down with trivial details.

Because prior art has above-mentioned deficiency, develop a kind of novelty, simple, convenient, efficient and particle size distribution prepares ferrospinel nano particle uniformly method is significant.

Summary of the invention

The invention provides in a kind of letter newly and overcome prior art deficiency, ferrospinel (MFe can be prepared more simple, cheap, efficiently ₂o ₄) method.

The method preparing ferrospinel nano particle of the present invention is M:Fe=1:2 proportioning by one or more metal M salt dissolving in DMF and the molysite that dissolves in DMF in atomic molar ratio, be that the DMF of M salt and Fe salt quality and 1 ~ 10 times mixes again by M salt and Fe salt and quality, be stirred for transparent solution, again previous solu is sintered 1 ~ 6 hour at 600 DEG C ~ 1100 DEG C, obtain ferrospinel MFe ₂o ₄nano particle.

Sintering temperature of the present invention more than 800 DEG C after to NiFe ₂o ₄dispersiveness has impact, and sintering time is long, and can affect the size of particle, related experiment shows, the sintering temperature of the best of the present invention is 650 DEG C ~ 750 DEG C, and best sintering time is 2 ~ 4 hours, can obtain dispersed best nano particle like this.

The method preparing ferrospinel nano particle of the present invention overcomes the deficiency such as loaded down with trivial details process and complicated post-processed of prior art, adjust ph is not needed in whole preparation process, without any need for auxiliary or tensio-active agent, only need by DMF, together with the Fe salt dissolving in DMF is dissolved in other metal-salt (M salt), by a step solvent sintered method, ferrospinel nano particle can be obtained, and gained ferrite nanometer particle size is little and even, there is throughput rate fast, output is high, high efficiency and be easy to industrial advantage in enormous quantities.

Accompanying drawing explanation

Fig. 1 is that the present invention prepares ferrospinel (MFe ₂o ₄) Production Flow Chart schematic diagram.In Fig. 1, (a) is for dissolving in the M salt of DFM, b () is for dissolving in the molysite of DFM, c () represents DMF, (d) representative sinters 1 ~ 6 hour at 600 DEG C ~ 1100 DEG C, the ferrospinel (MFe prepared by (e) representative ₂o ₄) nano particle.

Ni ferrite (the NiFe that Fig. 2 is embodiment 1, prepared by embodiment 2, embodiment 3 ₂o ₄), vectolite (CoFe ₂o ₄) XRD figure sheet.

Fig. 3 is nickel-zinc ferrite (NiZnFe prepared by the different sintering temperature of embodiment 4 ₂o ₄) XRD figure sheet.

Fig. 4 is Ni ferrite (NiFe prepared by embodiment 1 ₂o ₄) SEM picture.

Fig. 5 is vectolite (CoFe prepared by embodiment 2 ₂o ₄) SEM picture.

Fig. 6 is nickel-zinc ferrite (NiZnFe prepared by embodiment 3 ₂o ₄) SEM picture.

Fig. 7 and Fig. 8 is Ni ferrite (NiFe prepared by the different sintering temperature of embodiment 4 ₂o ₄) SEM picture.

Fig. 9 is the Ni ferrite (NiFe of embodiment 1, embodiment 2 and embodiment 3 preparation ₂o ₄), vectolite (CoFe ₂o ₄) and nickel-zinc ferrite (NiZnFe ₂o ₄) VSM picture.

Figure 10 is Ni ferrite (NiFe prepared by the different sintering temperature of embodiment 4 ₂o ₄) VSM picture.

Embodiment

Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.

According to the step shown in Fig. 1, a () represents M salt, b () represents trivalent iron salt, c () represents medicine DMF, the requirements for pharmaceuticals molar ratio of preparation be M:Fe=1:2 (if M is multiple element, then these elements total atomic mol and with the mole atom amount of Fe than being 1:2.Such as Mn _0.6zn _0.4fe ₂o ₄, mole summation of Mn and Zn is 0.6+0.4=1), be then dissolved in certain volume (c).Further, we are put into calculated (a) (b) (c) mixing in crucible, are then stirred for transparent solution.Further, retort furnace is put into filling the crucible that clear solution puts, 1 ~ 6 hour is sintered (in order to reduce costs at 600 DEG C ~ 1100 DEG C, at usual selection 650 DEG C, sintering can obtain good result as preparation condition in 2 hours), wait having sintered products therefrom in rear crucible and be ferrospinel (MFe ₂o ₄) nano particle.

Embodiment 1: preparation NiFe ₂o ₄nano particle

According to the step shown in Fig. 1, (a) represents medicine Ni (NO ₃) ₂6H ₂o (b) represents medicine Fe (NO ₃) ₃9H ₂o, (c) represents medicine DMF, and the requirements for pharmaceuticals molar ratio of preparation is Ni:Fe=1:2, is then dissolved in certain volume (c).Such as, in order to ensure Ni:Fe=1:2, if DMF gets 15 mL, then Ni (NO ₃) ₂6H ₂o is 0.2 mol/L quality is 0.8724 g, Fe (NO ₃) ₃9H ₂it is 2.424 g that O gets 0.4 mol/L quality.Then calculated (a) (b) (c) mixing is put in crucible, is then stirred for transparent solution.Then putting into retort furnace filling the crucible that clear solution puts, at 650 DEG C, sintering 2 hours, wait having sintered products therefrom in rear crucible and be NiFe ₂o ₄nano particle.

Embodiment 2: preparation CoFe ₂o ₄nano particle.

According to the step shown in Fig. 1, (a) represents medicine Co (NO ₃) ₂6H ₂o (b) represents medicine Fe (NO ₃) ₃9H ₂o, (c) represents medicine DMF, and the requirements for pharmaceuticals molar ratio of preparation is Co:Fe=1:2, is then dissolved in certain volume (c).Such as, in order to ensure Co:Fe=1:2, if DMF gets 15 mL, then Co (NO ₃) ₂6H ₂o is 0.2 mol/L quality is 0.87309 g, Fe (NO ₃) ₃9H ₂it is 2.424 g that O gets 0.4 mol/L quality.Subsequently, calculated (a) (b) (c) mixing is put in crucible, is then stirred for transparent solution.Then putting into retort furnace by filling the crucible that clear solution puts, at 650 DEG C, sintering 2 hours, wait having sintered products therefrom in rear crucible and be CoFe ₂o ₄nano particle.

Embodiment 3: preparation NiZnFe ₂o ₄nano particle.

According to the step shown in Fig. 1, (a) represents medicine Ni (NO ₃) ₂6H ₂o and Zn (NO ₃) ₂6H ₂o (b) represents medicine Fe (NO ₃) ₃9H ₂o, (c) represents medicine DMF, and the requirements for pharmaceuticals molar ratio of preparation is (Ni+Zn): Fe=1:2, is then dissolved in certain volume (c).Such as, in order to ensure (Ni+Zn): Fe=1:2, if DMF gets 15 mL, then Ni (NO ₃) ₂6H ₂o is 0.1 mol/L quality is 0.4362 g, Zn (NO ₃) ₂6H ₂o is 0.1 mol/L quality is 0.4462 g, Fe (NO ₃) ₃9H ₂it is 2.424 g that O gets 0.4 mol/L quality.Further, we are put into calculated (a) (b) (c) mixing in crucible, are then stirred for transparent solution.Then putting into retort furnace filling the crucible that clear solution puts, at 650 DEG C, sintering 2 hours, wait having sintered products therefrom in rear crucible and be NiZnFe ₂o ₄nano particle.

Embodiment 4: prepare NiFe under differing temps ₂o ₄nano particle.

Implement according to the step in embodiment 1, only change and sinter 2 hours at 600 DEG C, 700 DEG C, 800 DEG C, 900 DEG C, wait having sintered products therefrom in rear crucible and be NiFe ₂o ₄nano particle

Embodiment 1, embodiment 2 and the NiFe prepared by embodiment 3 ₂o ₄, CoFe ₂o ₄and NiZnFe ₂o ₄x-ray diffraction spectrogram as shown in Figure 2, show this NiFe ₂o ₄, CoFe ₂o ₄, NiZnFe ₂o ₄nano particle is Spinel; From the NiFe shown in Fig. 4 ₂o ₄coFe shown in [(a) (b)], Fig. 5 ₂o ₄niZnFe shown in [(c) (d)] and Fig. 6 ₂o ₄the SEM photo of [(e) (f)] can be found out, ferritic particle size uniformity, and mean size is 30 nm, the phenomenon such as not reunite.NiFe in Fig. 9 and Figure 10 ₂o ₄, CoFe ₂o ₄and NiZnFe ₂o ₄vSM result show, prepared NiFe ₂o ₄, CoFe ₂o ₄and NiZnFe ₂o ₄there is higher saturation magnetization, wherein NiFe ₂o ₄be 31 emu/g, coercive force 239 Oe; CoFe ₂o ₄be 65 emu/g, coercive force 1113 Oe.NiZnFe ₂o ₄be 49 emu/g, coercive force 75 Oe.NiFe under differing temps prepared by embodiment 4 ₂o ₄, its result is as can be seen from SEM (g) (h) (i) (j) and Figure 10 (b) VSM of XRD, Fig. 7 and Fig. 8 of Fig. 3, and sintering at different temperatures all can obtain the uniform NiFe of spinel structure ₂o ₄nano particle, along with rising NiFe after temperature is more than 800 DEG C of temperature ₂o ₄the small reunion of appearance of nano particle.

Claims

1. prepare the method for ferrospinel nano particle, it is characterized in that be M:Fe=1:2 proportioning by one or more metal M salt dissolving in DMF and the molysite that dissolves in DMF in atomic molar ratio, be that the DMF of M salt and Fe salt quality and 1 ~ 10 times mixes by M salt and Fe salt and quality, again solution is sintered 1 ~ 6 hour at 600 DEG C ~ 1100 DEG C after being stirred for transparent solution, obtain ferrospinel MFe ₂o ₄nano particle.

2. the method preparing ferrospinel nano particle according to claim 1, is characterized in that sintering temperature is 650 DEG C ~ 750 DEG C, sintering time 2 ~ 4 hours.

3. what the method described in claim 1 or 2 prepared prepares ferrospinel nano particle.