CN104446455B - For the Determining oxygen probe solid electrolyte and preparation method under high temperature and hypoxia condition - Google Patents
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- CN104446455B CN104446455B CN201410604879.0A CN201410604879A CN104446455B CN 104446455 B CN104446455 B CN 104446455B CN 201410604879 A CN201410604879 A CN 201410604879A CN 104446455 B CN104446455 B CN 104446455B
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Abstract
The invention discloses a kind of Determining oxygen probe solid electrolyte being used under high temperature and hypoxia condition and preparation method, belong to Determining oxygen probe preparing technical field.The Determining oxygen probe solid electrolyte of the present invention being used under high temperature and hypoxia condition is (ZrO2)1‑x‑y‑z‑w(Yb2O3)x(Al2O3)y(MgO)z(CaO)wQuinary system solid electrolyte；Wherein 0.04≤x≤0.055,0.003≤y≤0.01,0.01≤z≤0.02,0.008≤w≤0.015.The preparation method of the present invention is by converting the compositely proportional of raw material and adjusting corresponding heat treating regime come the phase composition ratio in controllable adjustment material, preparation technology greatly reduces sintering energy consumption and cost, the solid electrolyte of acquisition can realize temporal evolution of the room temperature texture to high temperature microstructure, and can realize and be used for multiple times in the case where not destroying its structure.
Description
Technical field
It is more particularly to a kind of for determining oxygen under high temperature and hypoxia condition the invention belongs to Determining oxygen probe preparing technical field
Probe solid electrolyte and preparation method.
Background technology
In metallurgical process, Determining oxygen probe is in blast furnace, blast furnace pig bed, converter, electric furnace, double refining, continuous casting production
It has been widely used etc. process.Required in particularly super clean steel production process molten steel include micro- S+P+O+H+N≤
50ppm, wherein O≤10ppm, S≤2ppm, N≤11ppm, P≤10ppm, H≤0.6ppm.Existing domestic Determining oxygen probe is weighed
Now determine oxygen ability and typically disclosure satisfy that requirement in O >=more than 100ppm.Low oxygen content O≤10ppm measurement, no matter finally determining oxygen
The form of probe is sheet, tubulose or needle-like, its high-temperature conductivity to Determining oxygen probe solid electrolyte, thermal conductivity, heat resistanceheat resistant
Shock stability has high requirement.ZrO of the Determining oxygen probe solid electrolyte from early stage2- CaO oxygen concentration cells, SiO2- (FeO) electricity
Xie Zhi, ZrO2- MgO solid electrolytes, Mg-PSZ solid electrolytes, Mg-PSZ coating YSZ electrolyte, ZrO2- MgO-CaO,
ZrO2-MgO-Al2O3, ZrO2-CaO-Al2O3Etc. ternary system electrolyte, ZrO is progressively developed into2-Y2O3-Al2O3- MgO quaternary bodies
System.In the meantime, people attempt to use various means, such as using high pure raw material, adjustment material preparation process or change material composition
Etc., constantly improve ZrO2The electrical conductivity of based solid electrolyte material.These effort achieve certain effect, but its electricity
It is limited that conductance, which improves amplitude, and it will be extremely difficult to want to be greatly improved in existing level.
Solid electrolyte enough thermal conductivity, good anti-thermal shock fracture property, high is led under hypoxemia-hot conditions
The organic unity of electrical property three could obtain measurement signal within the effective time.It is single in three kinds of phase structures of zirconium oxide
Monoclinic phase (m-ZrO2) thermal conductivity it is maximum, Tetragonal (t-ZrO2) there is obvious thermal shock resistance, and cubic phase content is to determine
One of principal element of electrical property and measurement accuracy.Therefore, the solid electrolyte of specific room temperature Phase Proportion is obtained, is solved in height
Under the conditions of temperature between solid electrolyte thermal shock resistance and electrical property matching problem key.
The content of the invention
To overcome the deficiencies in the prior art, primary and foremost purpose of the invention is to provide a kind of for high temperature and hypoxemia
Under the conditions of Determining oxygen probe solid electrolyte.Determining oxygen probe solid electrolyte of the present invention has higher conductance special to be a kind of
The compound electrolyte material of property and enough mechanical properties.
Another object of the present invention is to provide the above-mentioned Determining oxygen probe solid electrolytic being used under high temperature and hypoxia condition
The preparation method of matter.The present invention is with ZrO2-Yb2O3-Al2O3Based on-MgO-CaO Quinary systems, specific material supplier is taken
Skill flow, a kind of probe solid electrolyte that oxygen content is measured under the conditions of pyrometallurgy being prepared from.
The purpose of the present invention is achieved through the following technical solutions：A kind of Determining oxygen probe being used under high temperature and hypoxia condition is consolidated
Body electrolyte, is (ZrO2)1-x-y-z-w(Yb2O3)x(Al2O3)y(MgO)z(CaO)wQuinary system solid electrolyte；Wherein 0.04≤
X≤0.055,0.003≤y≤0.01,0.01≤z≤0.02,0.008≤w≤0.015.
The above-mentioned Determining oxygen probe method for preparing solid electrolyte being used under high temperature and hypoxia condition, is concretely comprised the following steps：
Take 4~5.5 mass parts Yb2O3Powder, 0.3~1 mass parts Al2O3Powder, 1~2 mass parts MgO powders, 0.8~
1.5 mass parts CaO powders and 90~93.9 mass parts ZrO2Powder, adds 1~3 mass parts binding agent, equal using mechanical mixture
Dry-pressing formed after even, briquetting pressure is 100~400Mpa, and 1575 DEG C~1650 are warming up to 3~10 DEG C/min of heating rate
DEG C, in 1575 DEG C~1650 DEG C temperature sintering 2h~4h, 2h~3h is then heat-treated in 1150 DEG C~1300 DEG C, cooling is used
In the Determining oxygen probe solid electrolyte under high temperature and hypoxia condition.
Described Yb2O3Powder is 1 μm of the Yb that central diameter is2O3Powder；
Described Al2O3Powder is 1 μm of the Al that central diameter is2O3Powder；
Described MgO powders are 5 μm of the MgO powders that central diameter is；
Described CaO powders are 3 μm of the CaO powders that central diameter is；
Described ZrO2Powder is 3 μm of the ZrO that central diameter is2Powder.
Described binding agent is the 10vol%PVA aqueous solution.
The present invention has the following advantages and effect relative to prior art：
The present invention is by converting the compositely proportional of raw material and adjusting corresponding heat treating regime come in controllable adjustment material
Phase composition ratio, its Chemical Characteristics are (ZrO2)0.9-0.939-(Yb2O3)0.04-0.055-(Al2O3)0.003-0.01-
(MgO)0.01-0.02-(CaO)0.008-0.015。Al2O3Presence have beneficial to crystal grain refinement, and the abnormal long of particle can be suppressed
Greatly.Sample sinters 2-4h and in 1150 DEG C of -1300 DEG C of heat treatment 2-4h through 1575 DEG C of -1650 DEG C of temperature, is being not required to extra guarantor
Sintering degree is can reach in the case of shield atmosphere, and the heat treatment time of five yuan of compound system powders is not required to oversize, the later stage
Property indices can be controlled well, greatly reduce sintering energy consumption and cost.
Monoclinic phase can reduce the modulus of elasticity and thermal coefficient of expansion of solid electrolyte material, increase the anti-thermal shock of material
Property.Suitable room temperature Phase Proportion can make thermal shock resistance optimal, but it cannot be guaranteed that the maximum of measurement process intermediate ion electrical conductivity
Change.Therefore, the phase constitution under room temperature condition quick at high temperature must be converted under the conditions of guarantee high-temperature low-oxygen to Emission in Cubic
High ionic conductivity.The solid electrolyte prepared by the special process in the present invention can realize room temperature texture to high temperature
The temporal evolution of tissue, and can realize and be used for multiple times in the case where not destroying its structure.
The five yuan of material systems taken in the present invention, the mixed proportion of reasonable feed change could have higher conductance
Rate, its electrical property is together decided on by the content of a variety of doped chemicals, a kind of shadow of dopant content by another dopant content
Ring.A certain stabiliser content is individually finely tuned, the decline of electrical property can be caused on the contrary, the micro fluctuation of a certain composition is enough to be formed
Substantial amounts of substandard products.One of key technical feature of the present invention is exactly the linkage adjustment of raw material proportioning.Meet Determining oxygen probe solid electricity
The most important condition for solving material is high consistency.Major influence factors include：Sintering temperature, heating rate, powder characteristics, into
Type pressure, additive capacity etc..On the basis of diameter of particle distribution level is matched somebody with somebody, composition is suitably adjusted, Post isothermal treatment can
To eliminate the density variation caused by different sintering temperatures.
Ionic conductivity of the Determining oxygen probe solid electrolyte that the present invention is obtained at 1000 DEG C is 4-8 × 10-2Scm-1,
Ten times are circulated without obvious crackle through the shake of -1000 DEG C-hydro-thermal of room temperature, and remaining bending strength still has 35-55%.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
For the Determining oxygen probe solid electrolyte (ZrO under high temperature and hypoxia condition2)0.927(Yb2O3)0.04(Al2O3)0.003
(MgO)0.015(CaO)0.015Preparation, comprise the following steps that：
It is (ZrO by Chemical Characteristics2)0.927-(Yb2O3)0.04-(Al2O3)0.003-(MgO)0.015-(CaO)0.015Weigh 4
The Yb that 1 μm of mass parts central diameter2O3Powder, the Al of 0.3 1 μm of mass parts central diameter2O3Powder, the MgO powder of 1.5 5 μm of mass parts central diameters
Body, the CaO powders of 1.5 3 μm of mass parts central diameters and the ZrO of 3 μm of 92.7 mass parts central diameters2Powder, adds 10vol%PVA water-soluble
Liquid binding agent (addition of binding agent be 1 mass parts), using mechanical mixture it is uniform after, dry-pressing formed, briquetting pressure is
100Mpa, 1600 DEG C are warming up to 3 DEG C/min of heating rate, in 1600 DEG C of temperature sintering 3h, are then heat-treated 2h in 1200 DEG C,
Cooling obtains the Determining oxygen probe solid electrolyte (ZrO being used under high temperature and hypoxia condition2)0.927(Yb2O3)0.04(Al2O3)0.003
(MgO)0.015(CaO)0.015。
Embodiment 2
For the Determining oxygen probe solid electrolyte (ZrO under high temperature and hypoxia condition2)0.903(Yb2O3)0.055(Al2O3)0.01
(MgO)0.02(CaO)0.012Preparation, comprise the following steps that：
It is (ZrO by Chemical Characteristics2)0.903-(Yb2O3)0.055-(Al2O3)0.01-(MgO)0.02-(CaO)0.012Weigh
The Yb of 5.5 1 μm of mass parts central diameters2O3Powder, the Al of 11 μm of mass parts central diameter2O3Powder, the MgO powders of 25 μm of mass parts central diameters,
The CaO powders of 1.2 3 μm of mass parts central diameters and the ZrO of 3 μm of 90.3 mass parts central diameters2Powder, adds the 10vol%PVA aqueous solution and glues
Tie agent (addition of binding agent be 3 mass parts), using mechanical mixture it is uniform after, dry-pressing formed, briquetting pressure is 300Mpa, with
6 DEG C/min of heating rate is warming up to 1650 DEG C, in 1650 DEG C of temperature sintering 2h, 2h is then heat-treated in 1150 DEG C, cooling is obtained
For the Determining oxygen probe solid electrolyte (ZrO under high temperature and hypoxia condition2)0.903(Yb2O3)0.055(Al2O3)0.01(MgO)0.02
(CaO)0.012。
Embodiment 3
For the Determining oxygen probe solid electrolyte (ZrO under high temperature and hypoxia condition2)0.925(Yb2O3)0.05(Al2O3)0.007
(MgO)0.01(CaO)0.008Preparation, comprise the following steps that：
It is (ZrO by Chemical Characteristics2)0.925-(Yb2O3)0.05-(Al2O3)0.007-(MgO)0.01-(CaO)0.008Weigh 5
The Yb that 1 μm of mass parts central diameter2O3Powder, the Al of 0.7 1 μm of mass parts central diameter2O3Powder, the MgO powders of 15 μm of mass parts central diameter,
The CaO powders of 0.8 3 μm of mass parts central diameter and the ZrO of 3 μm of 92.5 mass parts central diameters2Powder, adds the 10vol%PVA aqueous solution and glues
Tie agent (addition of binding agent be 2 mass parts), using mechanical mixture it is uniform after, dry-pressing formed, briquetting pressure is 400Mpa, with
10 DEG C/min of heating rate is warming up to 1575 DEG C, in 1575 DEG C of temperature sintering 4h, 3h is then heat-treated in 1300 DEG C, cooling is obtained
For the Determining oxygen probe solid electrolyte (ZrO under high temperature and hypoxia condition2)0.925(Yb2O3)0.05(Al2O3)0.007(MgO)0.01
(CaO)0.008。
Ionic conductivity of the Determining oxygen probe solid electrolyte at 1000 DEG C that above-described embodiment 1~3 is obtained for 4-8 ×
10-2Scm-1, ten times are circulated without obvious crackle through -1000 DEG C of thermal shocks of room temperature, and remaining bending strength still has 35-55%.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (3)
1. a kind of Determining oxygen probe solid electrolyte being used under high temperature and hypoxia condition, it is characterised in that：The Determining oxygen probe is consolidated
Body electrolyte is to contain ZrO2、Yb2O3、Al2O3, MgO, CaO Quinary system solid electrolyte, wherein, the quality of each oxide
Part it is：4 ~ 5.5 mass parts Yb2O3, 0.3 ~ 1 mass parts Al2O3, 1 ~ 2 mass parts MgO, 0.8 ~ 1.5 mass parts CaO and 90 ~ 93.9
Mass parts ZrO2。
2. a kind of preparation side of Determining oxygen probe solid electrolyte being used under high temperature and hypoxia condition according to claim 1
Method, it is characterised in that：Take 4 ~ 5.5 mass parts Yb2O3Powder, 0.3 ~ 1 mass parts Al2O3Powder, 1 ~ 2 mass parts MgO powders, 0.8
~ 1.5 mass parts CaO powders and 90 ~ 93.9 mass parts ZrO2Powder, adds 1 ~ 3 mass parts binding agent, uniform using mechanical mixture
Afterwards, dry-pressing formed, briquetting pressure is 100 ~ 400MPa, and 1575 DEG C ~ 1650 DEG C insulations are warming up to 3 ~ 10 DEG C/min of heating rate
2h ~ 4h, is then heat-treated 2h ~ 3h in 1150 DEG C ~ 1300 DEG C, and cooling obtains the Determining oxygen probe being used under high temperature and hypoxia condition and consolidated
Body electrolyte.
3. a kind of preparation side of Determining oxygen probe solid electrolyte being used under high temperature and hypoxia condition according to claim 2
Method, it is characterised in that：Described Yb2O3For 1 μm of powder of central diameter, described Al2O3For 1 μm of powder of central diameter, described MgO
For 5 μm of powder of central diameter, described CaO is the powder of 3 μm of central diameter, described ZrO2For 3 μm of powder of central diameter.
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| CN104829226B (en) * | 2015-03-27 | 2017-04-12 | 山东中厦电子科技有限公司 | A sensitive functional material used for a planar oxygen sensor and a preparing method thereof |
| CN106053577B (en) * | 2016-05-17 | 2018-12-28 | 东北大学 | Determine HydroNit sensor solid electrolyte and preparation method |
| CN106045482B (en) * | 2016-05-27 | 2019-05-10 | 内蒙古科技大学 | Rare earth oxide doped aluminium base high-performance metal bath determines the preparation method of HydroNit sensor material |
| CN106810249B (en) * | 2017-02-13 | 2020-10-02 | 湖南镭目科技有限公司 | Solid electrolyte for oxygen battery sensor and preparation method thereof |
| CN109409367B (en) * | 2018-11-02 | 2021-09-21 | 四川大学 | Infrared image grading identification method based on rock temperature rise characteristics |
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| CN1646901A (en) * | 2002-04-25 | 2005-07-27 | 日本科学技术社 | Detecting electrode and nitrogen oxide sensor using the same |
| CN102109485A (en) * | 2009-12-29 | 2011-06-29 | 比亚迪股份有限公司 | Oxygen sensor electrode slurry and oxygen sensor sensing layer and preparation methods thereof |
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|---|---|---|---|---|
| CN1646901A (en) * | 2002-04-25 | 2005-07-27 | 日本科学技术社 | Detecting electrode and nitrogen oxide sensor using the same |
| CN102109485A (en) * | 2009-12-29 | 2011-06-29 | 比亚迪股份有限公司 | Oxygen sensor electrode slurry and oxygen sensor sensing layer and preparation methods thereof |
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