CN104250095A - High-sensitivity thermosensitive ferrite material and preparation method thereof - Google Patents
High-sensitivity thermosensitive ferrite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-sensitivity thermosensitive ferrite material with the molecular formula of CuxZnyTizFe1.97O4, wherein x, y and z represent the adding proportion of each main metal element, the value range of x:y is 2:3-1:1, and x + y = 1; 0.03 <= z <= 0.05; the change rate of the high-sensitivity thermosensitive ferrite material near the Curie temperature is as high as 1400 / DEG C, the temperature sensitivity of the high-sensitivity thermosensitive ferrite material is corresponding higher, so that the high-sensitivity thermosensitive ferrite material creates a basis for preparation of a high precision thermosensitive device. At the same time, a preparation method of the high-sensitivity thermosensitive ferrite material is also disclosed, the method comprises the steps of proportioning, first ball milling, pre sintering, second ball milling, molding and sintering, wherein the pre sintering temperature is 800 to 1000 DEG C, the sintering temperature is 1070 to 1090 DEG C; and by the preparation method of the high-sensitivity thermosensitive ferrite material, the thermosensitive ferrite material with good performance can be prepared at lower sintering temperature.
Description
Technical field
The present invention relates to soft magnetic ferrite technical field, particularly relate to a kind of high-sensitivity thermosensitive Ferrite Material and preparation method thereof.
Background technology
Soft magnetic materials magnetic permeability or saturation induction density when envrionment temperature exceedes Curie temperature can decline rapidly until magnetic disappears, utilize this characteristic that soft magnetic materials is had very long history as thermo-sensitive material, the temp-sensitive sensor that is magnetic of current application, temperature-sensitive solid-state relay, overheated watch-dog etc.
The mass-producing application of magnetic temp-sensitive sensor starts from the eighties in last century, and various countries have carried out a large amount of research work to heat sensitive ferrite magneticsubstance, wherein especially outstanding with Japan.Sony company of Japan just discussed the preparation method of heat sensitive ferrite material in the Japanese Patent JP48099698 of its application in 1972.This material is primarily of ferric oxide, manganous carbonate and zinc oxide composition, and different according to component concentration, the Curie temperature scope of its Ferrite Material is 40 ~ 200 DEG C.
The application of soft magnetic materials in the said products forms seriation at present, such as, seriation in the scope of-40 ~ 150 DEG C abroad, and the precision of a lot of product generally reaches within 2 DEG C, and some special types even reach within 1 DEG C; And the precision of the product of domestic a lot of manufacturers can only control at 5 ~ 10 DEG C.
Further, along with the development of technology, soft magnetic ferrite is used to have again a lot of new application as thermo-sensitive material.Such as in magneto-optical drive element as photo-sensitive cell, in ultrasound hyperthermia system as mediation material, realize heating and temperature automatically controlled function.
These new application are had higher requirement for the characteristic of magneticsubstance, especially higher to the requirement of its sensitivity.And the height of sensitivity has very large relation with magneticsubstance at the fall off rate of near Curie temperature magnetic permeability.
The magneticsubstance that current magnetic temperature sensor adopts is generally MnZn, NiZn ferrite, wherein the adopted ferritic magnetic permeability of MnZn series is about 2000, at the fall off rate of near Curie temperature magnetic permeability at about 200/ DEG C, whole downcomer span has 10 DEG C, brings very large difficulty to the making of high precision device.
Therefore, be necessary to study high-sensitivity thermosensitive Ferrite Material.
Summary of the invention
The object of the present invention is to provide a kind of high-sensitivity thermosensitive Ferrite Material and preparation method thereof, to improve the sensitivity of heat sensitive ferrite material.
For solving the problem, the present invention proposes a kind of high-sensitivity thermosensitive Ferrite Material, and the molecular formula of this high-sensitivity thermosensitive Ferrite Material is: Cu
xzn
yti
zfe
1.97o
4, wherein, x, y, z represent the adding proportion of each main metal element, and the span of x:y is 2:3 ~ 1:1, and x+y=1; 0.03≤z≤0.05.
Preferably, the span of x, y is: 0.4<x<0.5,0.5<y<0.6, and x+y=1.
Preferably, the size of the Curie temperature of this high-sensitivity thermosensitive Ferrite Material changes within the scope of 20 ~ 100 DEG C.
Preferably, the magnetic permeability of this high-sensitivity thermosensitive Ferrite Material at the rate of change of near Curie temperature up to 1400/ DEG C.
Preferably, the raw material of this high-sensitivity thermosensitive Ferrite Material is: the Fe that purity is greater than 99%
2o
3, the CuO that purity is greater than 99%, ZnO and the purity TiO that is greater than 99% that purity is greater than 99%
2; And the weight ratio of each composition is:
Fe
2O
3：62～66%，CuO：13.3～16.7%，ZnO：16.7～20.5%，TiO
2：1.0～1.7%。
Preferably, by regulating TiO
2content regulate the size of the Curie temperature of this high-sensitivity thermosensitive Ferrite Material.
Meanwhile, for solving the problem, the present invention also proposes a kind of preparation method of above-mentioned high-sensitivity thermosensitive Ferrite Material, comprises the steps:
Batching: purity is greater than the Fe of 99%
2o
3, CuO, ZnO and TiO
2by molecular formula Cu
xzn
yti
zfe
1.97o
4composition requirement preparation major ingredient powder, and be mixed into material powder;
A ball milling: material powder is put into ball mill, the deionized water quality such as adding carries out ball milling, and Ball-milling Time is 1 ~ 4 hour, makes it mix;
Pre-burning: the material mixed is sieved, precipitates, dry after put into stove pre-burning, calcined temperature is: 800 ~ 1000 DEG C, and soaking time is 1 ~ 4 hour;
Secondary ball milling: Preburning material is put into ball mill, the deionized water weight such as adding carries out ball milling, and Ball-milling Time is 1 ~ 4 hour, sieves, precipitates post-drying;
Shaping: in the powder of drying, to add the polyvinyl alcohol solution that concentration is 5%, solution weight is 10 ~ 12% of the weight of the powder of drying, compression moulding after stirring;
Sintering: the sample after compression moulding is put into stove and sinters, sintering temperature is: 1070 ~ 1090 DEG C, and soaking time is 1.5 ~ 2.5 hours.
Preferably, Fe
2o
3, CuO, ZnO and TiO
2weight ratio be:
Fe
2O
3：62～66%，CuO：13.3～16.7%，ZnO：16.7～20.5%，TiO
2：1.0～1.7%。
Preferably, by regulating TiO
2content regulate the size of the Curie temperature of this high-sensitivity thermosensitive Ferrite Material.
Preferably, the span of x, y is: 0.4<x<0.5,0.5<y<0.6, and x+y=1.
The present invention, owing to adopting above technical scheme, makes it compared with prior art, has following advantage and positively effect:
1) high-sensitivity thermosensitive Ferrite Material provided by the invention uses Fe
2o
3, CuO, ZnO and TiO
2as raw material, the NiZn ferrite that its raw material ratio used is traditional is cheap;
2) high-sensitivity thermosensitive Ferrite Material provided by the invention just can sinter in atmosphere, and its technique is simpler than traditional MnZn ferrite;
3) magnetic permeability of high-sensitivity thermosensitive Ferrite Material provided by the invention at the rate of change of near Curie temperature up to 1400/ DEG C, therefore its to the traditional NiZn ferrite of the remolding sensitivity of temperature and MnZn ferrite high;
4) high-sensitivity thermosensitive Ferrite Material provided by the invention, the size of its Curie temperature is by regulating TiO
2content regulate, thus simple and convenient, various Curie temperature requirement can be met, for the design of high precision device is with very large convenience.
Accompanying drawing explanation
The schema of the preparation method of the high-sensitivity thermosensitive Ferrite Material that Fig. 1 provides for the embodiment of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, high-sensitivity thermosensitive Ferrite Material that the present invention proposes and preparation method thereof is described in further detail.According to the following describes and claims, advantages and features of the invention will be clearer.It should be noted that, accompanying drawing all adopts the form that simplifies very much and all uses non-ratio accurately, only for object that is convenient, the aid illustration embodiment of the present invention lucidly.
The high-sensitivity thermosensitive Ferrite Material that the present invention proposes, its molecular formula is: Cu
xzn
yti
zfe
1.97o
4, wherein, x, y, z represent the adding proportion of each main metal element, and the span of x:y is 2:3 ~ 1:1, and x+y=1; 0.03≤z≤0.05.
As preferably, the span of x, y is: 0.4<x<0.5,0.5<y<0.6, and x+y=1.
Preparing the raw material that this high-sensitivity thermosensitive Ferrite Material uses is: the Fe that purity is greater than 99%
2o
3, the CuO that purity is greater than 99%, ZnO and the purity TiO that is greater than 99% that purity is greater than 99%
2; And the weight ratio of each composition is: Fe
2o
3: 62 ~ 66%, CuO:13.3 ~ 16.7%, ZnO:16.7 ~ 20.5%, TiO
2: 1.0 ~ 1.7%.The NiZn ferrite that the raw material ratio that high-sensitivity thermosensitive Ferrite Material provided by the invention uses is traditional is cheap, does not need to use Ni, has thus greatly saved cost.
At above-mentioned compositing range, if Fe
2o
3less than 62%, then can occur initial permeability on the low side be not suitable for situation, and if Fe
2o
3more than 66%, then quality factor can occur and reduce, what be difficult to cook is not suitable for situation.If CuO is less than 13.3%, then can occur initial permeability on the low side be not suitable for situation, and if CuO more than 16.7%, then can occur quality factor reduce be not suitable for situation.If ZnO is less than 16.7%, then can occur initial permeability on the low side be not suitable for situation, and if ZnO more than 20.5%, then can produce unfavorable tendency that Curie temperature is on the low side.If TiO
2less than 1.0%, then can occur initial permeability on the low side be not suitable for situation, and if TiO
2more than 1.7%, then can produce unfavorable tendency that Curie temperature is on the low side.
Large quantifier elimination shows both at home and abroad, and material basic recipe determines the intrinsic performance of material, as saturation induction density B
s, magnetic permeability μ and Curie temperature T
cdeng.Therefore, raw-material to choose or the adjustment of content of raw material all can produce various different impact to the performance of last obtained heat sensitive ferrite material, the present invention has considered various properties of materials and have chosen above-mentioned starting material, and obtains above-mentioned suitable content range by the impact of the raw-material content of research on the performance of heat sensitive ferrite material.
Below provide the formula of several specific embodiment to high-sensitivity thermosensitive Ferrite Material of the present invention to be described.Problem for convenience of explanation, the preparation technology of the high-sensitivity thermosensitive Ferrite Material in following embodiment is all consistent, and its difference is only the formula of raw material.
Embodiment 1
The high-sensitivity thermosensitive Ferrite Material that the present embodiment provides, its formula is: Fe
2o
3: 65.45%, CuO:13.57%, ZnO:19.98%, TiO
2: 1.00%, its molecular formula is: Cu
xzn
yti
0.03fe
1.97o
4, wherein, the value of x is the value of 0.41, y is 0.59, and the molecular formula of high-sensitivity thermosensitive Ferrite Material that namely the present embodiment provides is Cu
0.41zn
0.59ti
0.03fe
1.97o
4.
Embodiment 2
The high-sensitivity thermosensitive Ferrite Material that the present embodiment provides, its formula is: Fe
2o
3: 65.46%, CuO:14.23%, ZnO:19.31%, TiO
2: 1.00%, its molecular formula is: Cu
xzn
yti
0.03fe
1.97o
4, wherein, the value of x is the value of 0.43, y is 0.57, and the molecular formula of high-sensitivity thermosensitive Ferrite Material that namely the present embodiment provides is Cu
0.43zn
0.57ti
0.03fe
1.97o
4.
Embodiment 3
The high-sensitivity thermosensitive Ferrite Material that the present embodiment provides, its formula is: Fe
2o
3: 65.47%, CuO:14.90%, ZnO:18.63%, TiO
2: 1.00%, its molecular formula is: Cu
xzn
yti
0.03fe
1.97o
4, wherein, the value of x is the value of 0.45, y is 0.55, and the molecular formula of high-sensitivity thermosensitive Ferrite Material that namely the present embodiment provides is Cu
0.45zn
0.55ti
0.03fe
1.97o
4.
Embodiment 4
The high-sensitivity thermosensitive Ferrite Material that the present embodiment provides, its formula is: Fe
2o
3: 65.48%, CuO:15.56%, ZnO:17.96%, TiO
2: 1.00%, its molecular formula is: Cu
xzn
yti
0.03fe
1.97o
4, wherein, the value of x is the value of 0.47, y is 0.53, and the molecular formula of high-sensitivity thermosensitive Ferrite Material that namely the present embodiment provides is Cu
0.47zn
0.53ti
0.03fe
1.97o
4.
Embodiment 5
High-sensitivity thermosensitive 0.43 Ferrite Material that the present embodiment provides, its formula is: Fe
2o
3: 65.49%, CuO:16.23%, ZnO:17.28%, TiO
2: 1.00%, its molecular formula is: Cu
xzn
yti
0.03fe
1.97o
4, wherein, the value of x is the value of 0.49, y is 0.51, and the molecular formula of high-sensitivity thermosensitive Ferrite Material that namely the present embodiment provides is Cu
0.49zn
0.51ti
0.03fe
1.97o
4.
Embodiment 6
The high-sensitivity thermosensitive Ferrite Material that the present embodiment provides, its formula is: Fe
2o
3: 65.12%, CuO:13.57%, ZnO:19.98%, TiO
2: 1.33%, its molecular formula is: Cu
xzn
yti
0.04fe
1.96o
4, wherein, the value of x is the value of 0.41, y is 0.59, and the molecular formula of high-sensitivity thermosensitive Ferrite Material that namely the present embodiment provides is Cu
0.41zn
0.59ti
0.04fe
1.96o
4.
Embodiment 7
The high-sensitivity thermosensitive Ferrite Material that the present embodiment provides, its formula is: Fe
2o
3: 64.79%, CuO:13.57%, ZnO:19.98%, TiO
2: 1.66%, its molecular formula is: Cu
xzn
yti
0.05fe
1.95o
4, wherein, the value of x is the value of 0.41, y is 0.59, and the molecular formula of high-sensitivity thermosensitive Ferrite Material that namely the present embodiment provides is Cu
0.41zn
0.59ti
0.05fe
1.95o
4.
And prepare a large amount of samples in above-mentioned each embodiment.
By randomly drawing measurement to a large amount of sample, the size obtaining the Curie temperature of the high-sensitivity thermosensitive Ferrite Material that the embodiment of the present invention provides changes within the scope of 20 ~ 100 DEG C.
And randomly draw 10 samples to measure its performance, particularly, Curie temperature T
c, 30 DEG C of places measure obtain magnetic permeability μ, magnetic permeability is at the rate of change a of near Curie temperature
μrefer to table 1:
Table 1: the performance test table of sample
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | |
| T C(℃) | 30 | 38 | 46 | 54 | 62 | 20 | 10 |
| μ (0 DEG C of place) | 980 | 860 | 740 | 620 | 500 | 871 | 757 |
| a μ(/℃) | 751 | 607 | 712 | 659 | 644 | 804 | 860 |
As can be seen from Table 1, the high-sensitivity thermosensitive Ferrite Material that the embodiment of the present invention provides measures the magnetic permeability μ that obtains all more than 500 at 0 DEG C of place, have even close to 1000, and the magnetic permeability of this high-sensitivity thermosensitive Ferrite Material at the rate of change of near Curie temperature up to 751/ DEG C.The excellent combination property of heat sensitive ferrite material provided by the invention as can be seen here, its magnetic permeability is higher at the rate of change of near Curie temperature, and thus it is also corresponding higher to the sensitivity of temperature, thus creates basis for the preparation of high precision temperature-sensitive device.
Principle of design of the present invention is: adopt CuZnTi iron series oxysome as thermo-sensitive material, suitable adjustment formula and sintering process make the ratio of the Cu ion in material and Zn ion be 2: 3 ~ 1: 1, permeability can up to 1400/ DEG C at the rate of change of near Curie temperature in this case, far above MnZn ferrite, the ferritic level of NiZn, and the Curie temperature size of material can by regulating TiO
2content change within the scope of 20 ~ 100 DEG C, this material is that the design of high precision device is with very large convenience.
Although the basic recipe of material determines the intrinsic performance of material, as saturation induction density B
s, magnetic permeability μ and Curie temperature T
cdeng, but preparation technology, as calcined temperature and sintering temperature etc., microstructure, grain size, the B of material can be changed significantly
scrystal boundary forms, and then the Macroscopic physical characteristic affecting material is as initial permeability μ
i, electricalresistivityρ, disaccommodation DF, magnetic permeability temperature factor a
μetc..Therefore, in the preparation process of soft magnetic materials, the formula of necessary strict control of material and preparation technology, just can obtain the heat sensitive ferrite material of excellent performance.The present invention has considered the impact of preparation technology on heat sensitive ferrite material on the basis of above-mentioned formula, obtains the preparation technology of the heat sensitive ferrite material of applicable above-mentioned formula.
Please refer to Fig. 1, the schema of the preparation method of the high-sensitivity thermosensitive Ferrite Material that Fig. 1 provides for the embodiment of the present invention, as shown in Figure 1, the preparation method of high-sensitivity thermosensitive Ferrite Material provided by the invention, comprises the steps:
S1, batching step
Purity is greater than the Fe of 99%
2o
3, CuO, ZnO and TiO
2by molecular formula Cu
xzn
yti
zfe
1.97o
4composition requirement preparation major ingredient powder, and be mixed into material powder; Wherein, the span of x, y is: 0.4<x<0.5,0.5<y<0.6, and x+y=1; 0.03≤z≤0.05.Particularly, Fe
2o
3, CuO, ZnO and TiO
2weight ratio be: Fe
2o
3: 62 ~ 66%, CuO:13.3 ~ 16.7%, ZnO:16.7 ~ 20.5%, TiO
2: 1.0 ~ 1.7%.
S2, a ball milling step
Material powder is put into ball mill, and the deionized water quality such as adding carries out ball milling, and Ball-milling Time is 1 ~ 4 hour, makes it mix.
S3, burn in step
The material mixed is sieved, precipitates, dry after put into stove pre-burning, calcined temperature is: 800 ~ 1000 DEG C, and soaking time is 1 ~ 4 hour.
S4, secondary ball milling step
Preburning material is put into ball mill, and the deionized water weight such as adding carries out ball milling, and Ball-milling Time is 1 ~ 4 hour, sieves, precipitates post-drying.
S5, forming step
In the powder of drying, add the polyvinyl alcohol solution that concentration is 5%, solution weight is 10 ~ 12% of the weight of the powder of drying, compression moulding after stirring.
S6, sintering step
Sample after compression moulding is put into stove sinter, sintering temperature is: 1070 ~ 1090 DEG C, and soaking time is 1.5 ~ 2.5 hours.
Below provide the preparation method of several specific embodiment to high-sensitivity thermosensitive Ferrite Material of the present invention to be described.
Embodiment 8
The present embodiment is mainly described calcined temperature, problem for convenience of explanation, the preparation method of the high-sensitivity thermosensitive Ferrite Material in the present embodiment only changes calcined temperature, and other step and processing condition are all consistent, and has prepared a large amount of samples based on different calcined temperatures.Particularly, the Parameter Conditions of each step is as follows:
Purity is selected to be greater than the Fe of 99% in batching step
2o
3, CuO, ZnO and TiO
2as raw material, wherein the ratio of each component is: Fe
2o
3: 64.8%, CuO:14.9%, ZnO:18.6%, TiO
2: 1.7%, these raw materials are mixed into material powder;
In a ball milling step, Ball-milling Time controls is 2 hours, and material powder is mixed; It should be noted that, in the present embodiment, Ball-milling Time is 2 hours, but can select Ball-milling Time as the case may be actually, and the present invention is not as limit;
Arranging calcined temperature in burn in step is respectively: 800 DEG C, 850 DEG C, 900 DEG C, 950 DEG C, 1000 DEG C, soaking time is 2 hours; And in order to compare, also at calcined temperature is 600 DEG C, 700 DEG C, 1100 DEG C, 1200 DEG C, prepare comparative sample;
In secondary ball milling step, Ball-milling Time is 2 hours, sieves, precipitates post-drying; It should be noted that, in the present embodiment, the time of secondary ball milling is 2 hours, but can select the time of secondary ball milling as the case may be actually, and the present invention is not as limit;
To add concentration in forming step be the weight of the polyvinyl alcohol solution of 5% is 15% of the weight of the powder of drying, compression moulding after stirring; It should be noted that, in the present embodiment, the weight of polyvinyl alcohol solution is 15% of the weight of the powder of drying, but can select the weight of polyvinyl alcohol solution actually as the case may be, and the present invention is not as limit; As a rule the weight of polyvinyl alcohol solution is 10 ~ 12% of the weight of the powder of drying;
Arranging sintering temperature in sintering step is 1080 DEG C, and soaking time is 2 hours.It should be noted that, on the basis of formula of the present invention, sintering temperature is within the scope of 1070 ~ 1090 DEG C, and the present invention is not as limit, and soaking time also all meets the demands in 1.5 ~ 2.5 hours window.
Randomly draw sample prepared by the present embodiment to measure its performance, particularly, 30 DEG C of places measure obtain magnetic permeability μ, magnetic permeability is at the rate of change a of near Curie temperature
μrefer to table 2:
Table 2: the performance test table of sample prepared by different calcined temperature
As can be seen from Table 2, on the basis of formula provided by the invention, calcined temperature to be arranged within the scope of 800 ~ 1000 DEG C obtained sample and to measure the magnetic permeability μ that obtains at 30 DEG C of places all more than 1000, what have even reaches 1400, and the magnetic permeability of this high-sensitivity thermosensitive Ferrite Material at the rate of change of near Curie temperature up to 1400/ DEG C.But calcined temperature be arranged on lower than 800 DEG C or decline all to some extent higher than the performance of material when 1000 DEG C.
Embodiment 9
The present embodiment is mainly described sintering temperature, problem for convenience of explanation, the preparation method of the high-sensitivity thermosensitive Ferrite Material in the present embodiment only changes sintering temperature, and other step and processing condition are all consistent, and has prepared a large amount of samples based on different sintering temperatures.Particularly, the Parameter Conditions of each step is as follows:
Purity is selected to be greater than the Fe of 99% in batching step
2o
3, CuO, ZnO and TiO
2as raw material, wherein the ratio of each component is: Fe
2o
3: 64.8%, CuO:14.9%, ZnO:18.6%, TiO
2: 1.7%, these raw materials are mixed into material powder;
In a ball milling step, Ball-milling Time controls is 2 hours, and material powder is mixed; It should be noted that, in the present embodiment, Ball-milling Time is 2 hours, but can select Ball-milling Time as the case may be actually, and the present invention is not as limit;
Arranging calcined temperature in burn in step is: 900 DEG C, and soaking time is 2 hours;
In secondary ball milling step, Ball-milling Time is 2 hours, sieves, precipitates post-drying; It should be noted that, in the present embodiment, the time of secondary ball milling is 2 hours, but can select the time of secondary ball milling as the case may be actually, and the present invention is not as limit;
To add concentration in forming step be the weight of the polyvinyl alcohol solution of 5% is 15% of the weight of the powder of drying, compression moulding after stirring; It should be noted that, in the present embodiment, the weight of polyvinyl alcohol solution is 15% of the weight of the powder of drying, but can select the weight of polyvinyl alcohol solution actually as the case may be, and the present invention is not as limit; As a rule the weight of polyvinyl alcohol solution is 10 ~ 12% of the weight of the powder of drying;
Arranging sintering temperature in sintering step is respectively 1070 DEG C, 1075 DEG C, 1080 DEG C, 1085 DEG C, 1090 DEG C, and soaking time is 2 hours; And in order to compare, also at sintering temperature is 900 DEG C, 1000 DEG C, 1100 DEG C, 1200 DEG C, prepare comparative sample.
Randomly draw sample prepared by the present embodiment to measure its performance, particularly, 30 DEG C of places measure obtain magnetic permeability μ, magnetic permeability is at the rate of change a of near Curie temperature
μrefer to table 3:
Table 3: the performance test table of sample prepared by different sintering temperature
As can be seen from Table 3, on the basis of formula provided by the invention, sintering temperature to be arranged within the scope of 1070 ~ 1090 DEG C obtained sample and to measure the magnetic permeability μ that obtains at 30 DEG C of places all more than 1200, what have even reaches 1441, and the magnetic permeability of this high-sensitivity thermosensitive Ferrite Material at the rate of change of near Curie temperature up to 1425/ DEG C.But sintering temperature be arranged on lower than 1070 DEG C or decline all to some extent higher than the performance of material when 1090 DEG C.Therefore high-sensitivity thermosensitive Ferrite Material provided by the invention can reach good over-all properties at a relatively low sintering temperature.
Certainly, it should be noted that, the setting of calcined temperature of the present invention and sintering temperature carries out on the basis of formula provided by the invention, consider the characteristic of each composition of formula Raw and temperature to the impact of the over-all properties of obtained sample, obtain preferably calcined temperature of the present invention and sintering temperature.
In sum, the invention provides a kind of high-sensitivity thermosensitive Ferrite Material, its molecular formula is: Cu
xzn
yti
zfe
1.97o
4, wherein, x, y, z represent the adding proportion of each main metal element, and the span of x:y is 2:3 ~ 1:1, and x+y=1; 0.03≤z≤0.05.High-sensitivity thermosensitive Ferrite Material provided by the invention is at the rate of change of near Curie temperature up to 1400/ DEG C, and thus it is also corresponding higher to the sensitivity of temperature, thus creates basis for the preparation of high precision temperature-sensitive device.Additionally provide a kind of preparation method of high-sensitivity thermosensitive Ferrite Material simultaneously, the party comprises batching step, ball milling step, burn in step, secondary ball milling step, forming step and a sintering step, wherein, calcined temperature is 800 ~ 1000 DEG C, and sintering temperature is 1070 ~ 1090 DEG C; The preparation method of high-sensitivity thermosensitive Ferrite Material provided by the invention can processability is good at a relatively low sintering temperature heat sensitive ferrite material.
Obviously, those skilled in the art can carry out various change and modification to invention and not depart from the spirit and scope of the present invention.Like this, if these amendments of the present invention and modification belong within the scope of the claims in the present invention and equivalent technologies thereof, then the present invention is also intended to comprise these change and modification.
Claims (10)
1. a high-sensitivity thermosensitive Ferrite Material, is characterized in that, the molecular formula of this high-sensitivity thermosensitive Ferrite Material is: Cu
xzn
yti
zfe
1.97o
4, wherein, x, y, z represent the adding proportion of each main metal element, and the span of x:y is 2:3 ~ 1:1, and x+y=1; 0.03≤z≤0.05.
2. high-sensitivity thermosensitive Ferrite Material as claimed in claim 1, it is characterized in that, the span of x, y is: 0.4<x<0.5,0.5<y<0.6, and x+y=1.
3. high-sensitivity thermosensitive Ferrite Material as claimed in claim 2, it is characterized in that, the size of the Curie temperature of this high-sensitivity thermosensitive Ferrite Material changes within the scope of 20 ~ 100 DEG C.
4. high-sensitivity thermosensitive Ferrite Material as claimed in claim 3, is characterized in that, the magnetic permeability of this high-sensitivity thermosensitive Ferrite Material at the rate of change of near Curie temperature up to 1400/ DEG C.
5. high-sensitivity thermosensitive Ferrite Material as claimed in claim 4, it is characterized in that, the raw material of this high-sensitivity thermosensitive Ferrite Material is: the Fe that purity is greater than 99%
2o
3, the CuO that purity is greater than 99%, ZnO and the purity TiO that is greater than 99% that purity is greater than 99%
2; And the weight ratio of each composition is:
Fe
2O
3：62～66%，CuO：13.3～16.7%，ZnO：16.7～20.5%，TiO
2：1.0～1.7%。
6. high-sensitivity thermosensitive Ferrite Material as claimed in claim 5, is characterized in that, by regulating TiO
2content regulate the size of the Curie temperature of this high-sensitivity thermosensitive Ferrite Material.
7. a preparation method for high-sensitivity thermosensitive Ferrite Material as claimed in claim 1, is characterized in that, comprise the steps:
Batching: purity is greater than the Fe of 99%
2o
3, CuO, ZnO and TiO
2by molecular formula Cu
xzn
yti
zfe
1.97o
4composition requirement preparation major ingredient powder, and be mixed into material powder;
A ball milling: material powder is put into ball mill, the deionized water quality such as adding carries out ball milling, and Ball-milling Time is 1 ~ 4 hour, makes it mix;
Pre-burning: the material mixed is sieved, precipitates, dry after put into stove pre-burning, calcined temperature is: 800 ~ 1000 DEG C, and soaking time is 1 ~ 4 hour;
Secondary ball milling: Preburning material is put into ball mill, the deionized water weight such as adding carries out ball milling, and Ball-milling Time is 1 ~ 4 hour, sieves, precipitates post-drying;
Shaping: in the powder of drying, to add the polyvinyl alcohol solution that concentration is 5%, solution weight is 10 ~ 12% of the weight of the powder of drying, compression moulding after stirring;
Sintering: the sample after compression moulding is put into stove and sinters, sintering temperature is: 1070 ~ 1090 DEG C, and soaking time is 1.5 ~ 2.5 hours.
8. the preparation method of high-sensitivity thermosensitive Ferrite Material as claimed in claim 7, is characterized in that, Fe
2o
3, CuO, ZnO and TiO
2weight ratio be:
Fe
2O
3：62～66%，CuO：13.3～16.7%，ZnO：16.7～20.5%，TiO
2：1.0～1.7%。
9. the preparation method of high-sensitivity thermosensitive Ferrite Material as claimed in claim 8, is characterized in that, by regulating TiO
2content regulate the size of the Curie temperature of this high-sensitivity thermosensitive Ferrite Material.
10. the preparation method of high-sensitivity thermosensitive Ferrite Material as claimed in claim 7, it is characterized in that, the span of x, y is: 0.4<x<0.5,0.5<y<0.6, and x+y=1.
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|---|---|---|---|---|
| CN111943659A (en) * | 2020-07-06 | 2020-11-17 | 南昌大学 | Preparation process of high-frequency low-loss high-resistivity nickel-zinc ferrite material |
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