CN102608168B - Air-sensitive resistance material and preparation method thereof - Google Patents

Air-sensitive resistance material and preparation method thereof Download PDF

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CN102608168B
CN102608168B CN201210048461.7A CN201210048461A CN102608168B CN 102608168 B CN102608168 B CN 102608168B CN 201210048461 A CN201210048461 A CN 201210048461A CN 102608168 B CN102608168 B CN 102608168B
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resistance
atmosphere
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CN102608168A (en
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曹石
李俊
秦元斌
杨槐馨
李建奇
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Institute of Physics of CAS
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Abstract

The invention provides an air-sensitive resistance material and a preparation method thereof. The material is a compound with a general formula as follows: RFe2O4(RFeO3), wherein R is Y, Dy, Ho, Er, Tm, Yb, Lu or In, and n is equal to 0 or 1. According to the invention, the material is used as a detection resistance wire and has the advantages of corrosion resistance, high-temperature resistance, high response time (at the order of second), simple preparation process and very wide working temperature zone (-50DEG C-200DEG C).

Description

Air-sensitive resistance material and preparation method thereof
Technical field
The invention belongs to atmosphere field of detecting, particularly relate to a kind of air-sensitive resistance material and preparation method thereof.
Background technology
For some material, its resistance value changes with the change of residing ambient atmosphere.Resistance has different mechanism to atmosphere response, such as, in different atmosphere sample surfaces and atmosphere gas generation redox reaction, cause sample surfaces band structure to change thus affect the Electric transport properties of sample, or because gas with various temperature conductivity is different, thus cause the temperature detecting resistance wire in atmosphere different, by the size of measuring resistance, the gaseous environment residing for sample and its pressure just can be calculated.
A kind of element of common probe gas vacuum tightness is that skin draws buffer resistance to advise, and this Pirani gauge generally uses tinsel, and corrosion-resistant and high-temperature resistant is poor, therefore skin draws buffer resistance rule to have narrower operation temperature area, and only for detecting the vacuum tightness of given gas.Remaining air-sensitive detecting element, as SnO 2gas sensor can according to SnO 2in different atmosphere, resistance value is different and demarcate the composition of probe gas, but its work response temperature is higher, could occur chemical with atmosphere thus cause component resistance to change to reach the object detecting atmosphere under high temperature.
Summary of the invention
Therefore, the object of the invention is at least one problem solving above prior art, a kind of new gas sensing resistance detecting material is provided.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
According to an aspect of the present invention, provide a kind of air-sensitive resistance material, this material is the compound of following general formula: RFe 2o 4(RFeO 3) n, wherein R is Y, Dy, Ho, Er, Tm, Yb, Lu or In, and n equals 0 or 1.
In above-mentioned air-sensitive resistance material, wherein, described material is monocrystalline or polycrystalline.
According to a further aspect in the invention, one is provided to prepare air-sensitive resistance material RFe 2o 4method, comprise the following steps:
Step 1): by R 2o 3and Fe 2o 3fully mix, at CO according to mol ratio 1: 2 2and H 2atmosphere under sinter, temperature be 1000 DEG C to 1300 DEG C, be then cooled to room temperature, obtain RFe 2o 4powder; Wherein R is Y, Dy, Ho, Er, Tm, Yb, Lu or In;
Step 2): the polycrystal powder obtained is placed in platinum crucible and is heated to 1500 DEG C-1700 DEG C, solid is melted, and is then cooled to 900 DEG C.
In the above-mentioned methods, step 1) be included in 1200 DEG C at sintering, then cool to room temperature with the furnace.
In the above-mentioned methods, step 2) comprise and be heated to 1620 DEG C.
In the above-mentioned methods, step 2) comprise and be cooled to 900 DEG C with the speed of 1 DEG C/min.
According to another aspect of the invention, one is provided to prepare air-sensitive resistance material RFe 3o 7method, comprise the following steps:
Step 1): by R 2o 3and Fe 2o 3fully mix according to mol ratio 2: 3, mix rear tabletted, put into tubular furnace, at CO 2with H 2sinter under mixed atmosphere;
Step 2): when step 1) product temperatur that obtains is when being down to 900 DEG C, product is put into mixture of ice and water and quenches.
In the above-mentioned methods, step 1) in sintering time be 48 hours.
In the above-mentioned methods, step 1) in sintering temperature be 1200 DEG C.
Compared with prior art, the invention has the advantages that:
The present invention uses oxide ceramic material to serve as detection resistance wire, anticorrosive, high temperature resistant, and the response time fast (response time is the magnitude of second), preparation technology is simple, has very broad operation temperature area (-50 DEG C ~ 200 DEG C).To different atmosphere (comprising vacuum), resistive response can be produced, thus reaches the object of detection atmosphere in the warm area of room temperature range to 400K.Gas sensing resistance detecting material of the present invention not only may be used for detection vacuum tightness for the preparation of vacuum meter, and the character of the atmosphere sensitivity under normal temperature can also be utilized to be prepared into gas sensor.
Accompanying drawing explanation
Referring to accompanying drawing, embodiments of the present invention is further illustrated, wherein:
Fig. 1 shows LuFe 2o 4the current-voltage relation obtained under different atmosphere;
Fig. 2 shows LuFe 2o 4resistance responding range at different temperatures when gaseous environment changes gradually;
Fig. 3 shows LuFe 2o 4resistance periodically changes in oxygen and vacuum;
Fig. 4 shows YbFe 2o 4the change curve of resistance successively in vacuum, argon gas and oxygen;
Fig. 5 shows Yb 2fe 3o 7the change curve of resistance successively in vacuum, argon gas and oxygen;
Fig. 6 shows InFe 2o 4the change curve of resistance successively in vacuum, argon gas and oxygen.
Embodiment
Below by embodiment, specifically describe RFe of the present invention 2o 4(RFeO 3) nthe performance of several typical material and preparation method in (n=0,1) system.
Embodiment 1:LuFe 2o 4the preparation of sample
LuFe used in experiment 2o 4polycrystalline is synthesized by traditional solid-state sintering.By highly purified luteium oxide Lu 2o 3and Fe (99.99%) 2o 3(99.9%) fully mix than 1: 2 according to mole (mol), put into tubular furnace, use CO 2and H 2different volume ratios (such as 1.9 ~ 7) controls different redox conditions, sinters, then cool to room temperature with the furnace at 1200 DEG C.The polycrystalline LuFe obtained 2o 4powder to be placed in platinum crucible and to be heated to 1620 DEG C, and solid is melted, and is then cooled to 900 DEG C with the speed of 1 DEG C/min.Growing the monocrystalline typical sizes obtained is 1 × 2 × 0.5mm 3.
Fig. 1 shows LuFe 2o 4the current-voltage relation obtained under different atmosphere.As shown in Figure 1, under different probe current, sample LuFe in different atmosphere 2o 4pressure drop different, namely sample resistance is different in different atmosphere.As can be seen here, the corresponding relation of resistance and atmosphere is utilized can to make gas sensing resistance meter.
Fig. 2 shows LuFe 2o 4resistance when gaseous environment changes gradually responding range at different temperatures.As shown in the figure, as sample LuFe 2o 4when residing gaseous environment changes (changing to vacuum from argon gas), its electrical response scope is that room temperature arrives 350K.In other gas with various, also there is same character.
Fig. 3 shows LuFe 2o 4resistance periodically changes in oxygen and vacuum.As can be seen here, sample gas-sensitive property has well repeatable and sensitivity, and sample resistance reduces with the increase of vacuum tightness.
Embodiment 2:Lu 2fe 3o 7the preparation of sample
By highly purified luteium oxide Lu 2o 3and Fe (99.99%) 2o 3(99.9%) fully mix according to mol ratio 2: 3, mix rear tabletted, put into tubular furnace at CO 2with H 2partial pressure of oxygen is controlled, wherein CO under mixed atmosphere 2: H 2volume ratio adjustable (such as 1.9 ~ 7), sinters 48 hours, when sample temperature is down to about 900 DEG C, sample is put into mixture of ice and water and quench at 1200 DEG C, obtained Lu 2fe 3o 7polycrystalline.
Experiment records, as sample LuFe 2o 4when residing gaseous environment changes (changing to vacuum from argon gas), its electrical response scope is that room temperature arrives 370K, and also has same character in other gas with various.
Embodiment 3:YbFe 2o 4the preparation of sample
YbFe used in experiment 2o 4polycrystalline is synthesized by traditional solid-state sintering.By highly purified yttria Yb 2o 3and Fe (99.99%) 2o 3(99.9%) fully mix than 1: 2 according to mole (mol), put into tubular furnace, use CO 2and H 2different volume ratios (such as 1.9 ~ 7) controls different redox conditions, sinters, then cool to room temperature with the furnace at 1200 DEG C.The polycrystalline YbFe obtained 2o 4powder to be placed in platinum crucible and to be heated to 1620 DEG C, and solid is melted, and is then cooled to 900 DEG C with the speed of 1 DEG C/min.Mixed atmosphere CO in whole process 2: H 2volume ratio is adjustable.Growing the monocrystalline typical sizes obtained is 1 × 2 × 0.5mm 3.
Fig. 4 shows YbFe 2o 4the change curve of resistance successively in vacuum, argon gas and oxygen.As can be seen from the figure, in different atmosphere, sample resistance has larger difference.
Embodiment 4:Yb 2fe 3o 7the preparation of sample
By highly purified luteium oxide Yb 2o 3and Fe (99.99%) 2o 3(99.9%) fully mix according to mol ratio 2: 3, mix rear tabletted, put into tubular furnace at CO 2with H 2partial pressure of oxygen is controlled, wherein CO under mixed atmosphere 2: H 2volume ratio adjustable (such as 1.9 ~ 7), sinters 48 hours, when sample temperature is down to about 900 DEG C, sample is put into mixture of ice and water and quench at 1200 DEG C, obtained Yb 2fe 3o 7polycrystalline.
Fig. 5 shows Yb 2fe 3o 7the change curve of resistance successively in vacuum, argon gas and oxygen.As can be seen from the figure, in different atmosphere, sample resistance has larger difference.
Embodiment 5:InFe 2o 4the preparation of sample
InFe used in experiment 2o 4polycrystalline is synthesized by traditional solid-state sintering.By highly purified indium oxide In 2o 3and Fe (99.99%) 2o 3(99.9%) fully mix than 1: 2 according to mole (mol), put into tubular furnace, use CO 2and H 2different ratios controls different redox conditions, sinters, then cool to room temperature with the furnace at 1200 DEG C.The polycrystalline InFe obtained 2o 4powder to be placed in platinum crucible and to be heated to 1620 DEG C, and solid is melted, and is then cooled to 900 DEG C with the speed of 1 DEG C/min.Mixed atmosphere CO in whole process 2: H 2volume ratio is adjustable.Growing the monocrystalline typical sizes obtained is 1 × 2 × 0.5mm 3.
Fig. 6 shows InFe 2o 4the change curve of resistance successively in vacuum, argon gas and oxygen.As can be seen from the figure, in different atmosphere, sample resistance has larger difference.
Embodiment 6 ~ 10:
According to the processing step described in embodiment 1 and condition, high-purity mangesium oxide lutetium is wherein changed into yttria, dysprosia, holimium oxide, erbium oxide, thulium oxide, has prepared YFe respectively 2o 4, DyFe 2o 4, HoFe 2o 4, ErFe 2o 4and TmFe 2o 4.Show after tested, under different probe current, in different atmosphere, the pressure drop of sample is obviously different; (change to vacuum from argon gas) when gaseous environment changes residing for these products, electrical response scope is that room temperature arrives 400K.
Embodiment 11 ~ 15:
According to the processing step described in embodiment 2 and condition, high-purity mangesium oxide lutetium is wherein changed into yttria, dysprosia, holimium oxide, erbium oxide, thulium oxide, has prepared YFe respectively 3o 7, DyFe 3o 7, HoFe 3o 7, ErFe 3o 7and TmFe 3o 7.After tested, (change to vacuum from argon gas) when gaseous environment changes residing for these products, electrical response scope is that room temperature arrives 400K.
Can be found out by above embodiment, due at RFe 2o 4(RFeO 3) nfollowing phenomenon is found: at room temperature, material is (< 10 in different atmospheres and vacuum in the polycrystalline of (n=0 or 1, R=Yb, Lu, In, Y, Dy, Ho, Er or Tm) system or monocrystal material -2handkerchief), resistivity has obvious difference, and therefore the present invention uses RFe 2o 4(RFeO 3) nthe polycrystalline of (n=0,1) system or single crystal ceramic material, serve as gas sensing resistance detecting element.
RFe of the present invention 2o 4(RFeO 3) nin system, there is following characteristic: with the resistivity in air at room temperature for standard, at oxidizing atmosphere, as in oxygen, sample resistivity can increase (rate of change > 10%), in a vacuum (< 10 -2handkerchief), the resistivity of sample diminishes (rate of change > 10%).And along with by the increase of sample current density, the change of the resistivity that (comprises vacuum) under different atmosphere increases.As typical LuFe 2o 4sample, when current density is 2.5mA/cm 2time, under oxygen atmosphere, sample resistivity, relative to vacuum, changes 30%.When current density is 5.0mA/cm 2, this variable quantity is increased to 70%.In addition, to different atmosphere (comprising vacuum), resistive response can be produced, thus reaches the object of detection atmosphere in the warm area of room temperature range to 400K.
It should be noted that, above embodiment is only illustrative purpose, at preparation RFe of the present invention 2o 4other embodiments in, sintering temperature also can between 1000 DEG C to 1300 DEG C, and can adopt the modes such as cooling bath to cool.Obtaining RFe 2o 4heating-up temperature after powder can between 1500 DEG C-1700 DEG C, because if temperature is inadequate, material can not fully melt, the compound of needs can not be prepared, if but temperature is too high, can accelerate the volatilization of rare earth element, be therefore preferred process conditions between 1500 DEG C-1700 DEG C.In addition, cooling velocity can be different according to the concrete type of cooling, and those skilled in the art can decide according to cooling device and mode.At preparation RFe of the present invention 3o 7other embodiments in, sintering temperature also can between 1000 DEG C to 1300 DEG C, because in this temperature range, two kinds of compounds are mixed to get more abundant.
Although make specific descriptions with reference to the above embodiments for the present invention, but for the person of ordinary skill of the art, should be appreciated that and can modify based on content disclosed by the invention or improve, and these amendments and improvement be all within the spirit and scope of the present invention.

Claims (2)

1. a general formula is RFe 2o 4(RFeO 3) ncompound as the purposes of air-sensitive resistance material, wherein R is Y, Dy, Ho, Er, Tm, Yb, Lu or In, and n equals 0 or 1.
2. purposes according to claim 1, is characterized in that, described air-sensitive resistance material is monocrystalline or polycrystalline.
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