CN102442705A

CN102442705A - Preparation method of iron oxide

Info

Publication number: CN102442705A
Application number: CN2011102895027A
Authority: CN
Inventors: 张学; 司松海; 司乃潮; 李晓薇; 张志敏; 陈振华
Original assignee: Zhenjiang Yinuowei Shape Memory Alloys Co Ltd
Current assignee: Zhenjiang Yinuowei Shape Memory Alloys Co Ltd
Priority date: 2011-09-21
Filing date: 2011-09-21
Publication date: 2012-05-09

Abstract

A preparation method of iron oxide belongs to the technical field of the iron oxide preparation. The preparation method is characterized by comprising the following steps of: pouring 50 ml of high-purity water into a beaker, putting the beaker on a stirrer, introducing N2 to remove O2 in the water, weighing potassium ferrocyanide by using an electronic balance, pouring the potassium ferrocyanide into a solution, and then pouring potassium hydroxide and hydrazine hydrate, discontinuously introducing N2 during the process, and adding the prepared solution into a high-pressure kettle for fixing; putting the high-pressure kettle into a constant-temperature box to preserve heat at 200 degrees centigrade, taking out the high-pressure kettle after the heat preservation time ends, pouring out supernate, and then adding an appropriate amount of water into the high-pressure kettle, pouring a sample into the beaker after implementing ultrasound for a moment, and then implementing the ultrasound for a moment again, putting the beaker on a magnet, standing for about 2 min, pouring out the supernate, washing the obtained iron oxide with ethanol, and then pouring the washed iron oxide into a sample tube for sealing; and observing changes of shapes and sizes of the iron oxide by a scanning electron microscope, and then using an SQUID MPMS-5XL superconducting quantum magnetic measurement system to measure the magnetic performances of each sample.

Description

A kind of preparation method of red stone

Technical field

The invention belongs to the red stone preparing technical field, refer in particular to a kind of preparation method of red stone.

Background technology

Along with the fast development of Iron And Steel Industry, continuous 9 years iron and steel outputs of China occupy the first in the world, and still, in environmental consciousness more and more stronger today, the low status with the first in the world big steel country of the utilization ratio of steel industry solid waste is extremely unbecoming.Change slag hearth as the by product in the convertor steelmaking process, if can utilize the ferro element that changes in the slag hearth to prepare nano-sized iron oxide, not only can efficent use of resources, and can also expand the raw material range of nano-sized iron oxide.Nano-sized iron oxide has good weathering resistance, photostabilization, magnetic and ultraviolet ray is had good absorption and shielding effect; Can be widely used in aspects such as luster coating, printing ink, plastics, leather, automobile finish, electronics, high magnetic material, catalyzer and biological medicine process; Many investigators pay attention to studying its appearance structure, matrix material and surface-treated, thereby have synthesized like Fe ₃O ₄Nanometer rod, nanotube, nano belt, mesoporous Fee ₃O ₄Deng material with unique appearance structure, and like Fe ₃O ₄/ PS, Fe ₃O ₄/ BaSO4, Fe ₃O ₄/ γ-Fe ₂O ₃In matrix material.These materials are owing to the change of appearance structure, and some character also is improved to a certain extent.The present invention develops a kind of preparation method of red stone, and through the pattern of change red stone, thereby the saturation magnetization of making and coercive force change.This uses red stone widely and the use of frontier has had prior realistic meaning.

Summary of the invention

The objective of the invention is to develop a kind of preparation method of red stone, it is characterized by: in beaker, pour the 50mL high purity water into, be put on the whisking appliance, feed N ₂The O in the water ₂Ex-all takes by weighing yellow prussiate of potash with electronic balance, pours in the solution, pours Pottasium Hydroxide and Hydrazine Hydrate 80 again into, in this process, constantly feeds N ₂, with fixing in the joining solution adding autoclave.Autoclave is put into thermostat container 200 ℃ of insulations, after insulation finishes, take out autoclave; Pour out supernatant liquid, in autoclave, add suitable quantity of water then, moments later ultrasonic; Sample is poured in the beaker, in ultrasonic again a moment, beaker is put on the magnet; Leave standstill about 2min, pour out supernatant liquid, the red stone of gained is poured in the sample hose with alcohol flushing sealed.With sem observation red stone morphology change, and then survey the magnetic property of each sample with SQUID MPMS-5XL superconduction quantum magneticmeasurement system.Table 1, table 2, table 3 are respectively the variable quantity of KOH, soaking time, Hydrazine Hydrate 80.

Table 1 adds the amount of KOH

The variation of table 2 soaking time

The content of table 3 Hydrazine Hydrate 80

As can be seen from Figure 1: when not adding KOH, the pattern of the red stone of gained is to be petal-like top plektron (Fig. 1 a), after adding 0.5mLKOH; The pattern of red stone still is a spindle-type; Different is a few place branch (Fig. 1 b) to have occurred, after the amount that adds KOH reaches 1.5mL, octahedra (Fig. 1 c) on the basis of spindle-type red stone, occurred; Show increase, the oriented octahedra trend that transforms of red stone along with KOH; When add-on was 2.5mL, red stone became the octahedron of standard, and the spindle-type octahedron has not almost had (Fig. 1 d), and when KOH content reached 5mL, it was octahedra flat-top to have occurred, had destroyed octahedral integrity (Fig. 1 e) this moment again.

As can beappreciated from fig. 2, under the situation that does not add KOH, behind the insulation 1h, the pattern of red stone demonstrate the hexahedron type (Fig. 2 a), behind the insulation 6h, the pattern of red stone irregular (Fig. 2 b), behind the insulation 12h, red stone demonstrates spindle shape (Fig. 2 c).This explanation, not having under the condition of KOH, along with the growth of soaking time, the pattern of red stone has the trend that changes to the spindle shape through hexahedron gradually.

Can be found out that by Fig. 3 behind the adding 2.5mL KOH, soaking time almost is octahedra from 1 hour to 12 hours variation always, this explanation is after adding 2.5mL KOH, and soaking time does not almost influence the shape of red stone.

Can know that by Fig. 4 when not adding Hydrazine Hydrate 80, the red stone pattern is relatively more chaotic, and (Fig. 4 a); When adding the 2.5mL Hydrazine Hydrate 80, two rib flat-tops octahedra (Fig. 4 b) have appearred, after Hydrazine Hydrate 80 content increases to 5mL; Octahedron is comparison rule; But also having a little is flat-top octahedra (Fig. 4 c), when Hydrazine Hydrate 80 content is 10mL, and octahedral pattern not only rule but also complete (Fig. 4 d).Therefore can know, when Hydrazine Hydrate 80 content by 0mL when 10mL increases, the pattern of red stone is grown to octahedron gradually.

Fig. 5 a has shown that the red stone saturation magnetization is with the change curve of soaking time when adding the KOH of 2.5mL.In Fig. 5 b, when insulation 1h, saturation magnetization is 69emu/g, and during insulation 6h, saturation magnetization is 92emu/g, and after soaking time reached 12h, saturation magnetization reached 93emu/g.Hence one can see that, and along with the growth of soaking time, the red stone saturation magnetization increases gradually.In Fig. 5 c, during insulation 1h, coercivity H is 550e; During insulation 6h, coercive force is 140e; When soaking time was 12h, coercive force was 40e.Know that by above along with the increase of soaking time, the red stone coercive force reduces gradually.

Above-mentioned red stone prepares in the process, and in the 50mL high purity water, adding KOH is 2.5mL, and soaking time is 1 to 12 hour; The Hydrazine Hydrate 80 add-on is 10mL; The pattern of red stone is rule and complete octahedron, and this moment, saturation magnetization increased, and coercive force reduces gradually.

Description of drawings

Fig. 1 adds the pattern photo of the captured red stone of SEM behind the KOH of different amounts

(a) do not add KOH; (b) add KOH amount 0.5mL; (c) add KOH amount 1.5ml; (d) add KOH amount 2.5mL; (e) add KOH amount 5mL

Fig. 2 different captured red stone pattern photo of soaking time SEM when not adding KOH

(a) insulation 1h; (b) insulation 6h; (c) insulation 12h

The different captured red stone pattern photo of soaking time SEM when Fig. 3 adds 2.5mlKOH

(a) insulation 1h; (b) insulation 6h; (c) insulation 12h

Fig. 4 adds the captured red stone pattern photo of different content Hydrazine Hydrate 80 SEM

(a) 0ml Hydrazine Hydrate 80; (b) 2.5ml Hydrazine Hydrate 80; (c) 5ml Hydrazine Hydrate 80; (d) 10ml Hydrazine Hydrate 80

The change curve of Fig. 5 magnetic and soaking time

Embodiment

Embodiment 1

In beaker, pour the 50mL high purity water into, be put on the whisking appliance, feed N ₂The O in the water ₂Ex-all takes by weighing yellow prussiate of potash 2.1110g with electronic balance, pours in the solution, pours Pottasium Hydroxide 2.5ml and Hydrazine Hydrate 80 10ml again into, in this process, constantly feeds N ₂, with fixing in the joining solution adding autoclave.Autoclave is put into thermostat container 200 ℃ of insulations, be incubated 1 hour, take out autoclave; Pour out supernatant liquid, in autoclave, add suitable quantity of water then, moments later ultrasonic; Sample is poured in the beaker, in ultrasonic again a moment, beaker is put on the magnet; Leave standstill about 2min, pour out supernatant liquid, the red stone of gained is poured in the sample hose with alcohol flushing sealed.With sem observation red stone morphology change, and then survey the magnetic property of each sample with SQUID MPMS-5XL superconduction quantum magneticmeasurement system.At this moment, the red stone pattern is that the octahedron of standard is full, saturation magnetization is that 69emu/g, coercivity H are 550e;

Embodiment 2

In beaker, pour the 50mL high purity water into, be put on the whisking appliance, feed N ₂The O in the water ₂Ex-all takes by weighing yellow prussiate of potash 2.1110g with electronic balance, pours in the solution, pours Pottasium Hydroxide 2.5ml and Hydrazine Hydrate 80 10ml again into, in this process, constantly feeds N ₂, with fixing in the joining solution adding autoclave.Autoclave is put into thermostat container 200 ℃ of insulations, be incubated 6 hours, take out autoclave; Pour out supernatant liquid, in autoclave, add suitable quantity of water then, moments later ultrasonic; Sample is poured in the beaker, in ultrasonic again a moment, beaker is put on the magnet; Leave standstill about 2min, pour out supernatant liquid, the red stone of gained is poured in the sample hose with alcohol flushing sealed.With sem observation red stone morphology change, and then survey the magnetic property of each sample with SQUID MPMS-5XL superconduction quantum magneticmeasurement system.At this moment, the red stone pattern is that the octahedron of standard is full, saturation magnetization is that 92emu/g, coercivity H are 140e.

Embodiment 3

In beaker, pour the 50mL high purity water into, be put on the whisking appliance, feed N ₂The O in the water ₂Ex-all takes by weighing yellow prussiate of potash 2.1110g with electronic balance, pours in the solution, pours Pottasium Hydroxide 2.5ml and Hydrazine Hydrate 80 10ml again into, in this process, constantly feeds N ₂, with fixing in the joining solution adding autoclave.Autoclave is put into thermostat container 200 ℃ of insulations, be incubated 12 hours, take out autoclave; Pour out supernatant liquid, in autoclave, add suitable quantity of water then, moments later ultrasonic; Sample is poured in the beaker, in ultrasonic again a moment, beaker is put on the magnet; Leave standstill about 2min, pour out supernatant liquid, the red stone of gained is poured in the sample hose with alcohol flushing sealed.With sem observation red stone morphology change, and then survey the magnetic property of each sample with SQUID MPMS-5XL superconduction quantum magneticmeasurement system.At this moment, the red stone pattern is that the octahedron of standard is full, saturation magnetization is that 93emu/g, coercivity H are 40.

Claims

1. the preparation method of a red stone is characterized by: in beaker, pour the 50mL high purity water into, be put on the whisking appliance, feed N ₂The O in the water ₂Ex-all takes by weighing yellow prussiate of potash with electronic balance, pours in the solution, pours hydroxide clock and Hydrazine Hydrate 80 again into, in this process, constantly feeds N ₂, with joining solution add in the autoclave fixingly, autoclave is put into thermostat container 200 ℃ of insulations, treat that soaking time finishes after; Take out autoclave, pour out supernatant liquid, in autoclave, add suitable quantity of water then, moments later ultrasonic; Sample is poured in the beaker, in ultrasonic again a moment, beaker is put on the magnet; Leave standstill about 2min, pour out supernatant liquid, the red stone of gained is poured in the sample hose with alcohol flushing sealed; With sem observation red stone morphology change, and then survey the magnetic property of each sample with SQUID MPMS-5XL superconduction quantum magneticmeasurement system.

2. according to the preparation method of the said a kind of red stone of claim 1, in the 50mL high purity water, add yellow prussiate of potash 2.1147g, Pottasium Hydroxide 2.5ml and Hydrazine Hydrate 80 10ml, in this process, constantly feed N ₂, with fixing in the joining solution adding autoclave, autoclave is put into thermostat container 200 ℃ of insulations, be incubated 12 hours.At this moment, the red stone pattern is that the octahedron of standard is full, the specific magnetising moment is 93emu/g, and coercivity H is 40.