CN107140976A - A kind of oxygen sensor used in vehicle Zirconia electrolytic powder composition - Google Patents
A kind of oxygen sensor used in vehicle Zirconia electrolytic powder composition Download PDFInfo
- Publication number
- CN107140976A CN107140976A CN201710335832.2A CN201710335832A CN107140976A CN 107140976 A CN107140976 A CN 107140976A CN 201710335832 A CN201710335832 A CN 201710335832A CN 107140976 A CN107140976 A CN 107140976A
- Authority
- CN
- China
- Prior art keywords
- micron
- powder
- zirconium oxide
- diameter
- particle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Composite Materials (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention relates to a kind of oxygen sensor used in vehicle Zirconia electrolytic powder composition, including 70~90wt% zirconium oxide one-levels powder, 0.1~25wt% zirconium oxide second patent flour bodies and 4~15wt% sintering aids；Wherein, the meso-position radius of the zirconium oxide one-level powder are 0.1~0.4 micron, and particle diameter distribution is at 0.05~5 micron；The meso-position radius of the zirconium oxide second patent flour body are 0.5~2.5 micron, and particle diameter distribution is 0.05~100 micron.The present invention is for the aluminum oxide sintering shrinkage characteristic different from zirconium oxide, by matching the Zirconium powder that different-grain diameter is distributed, and reaches the purpose matched during co-sintering with aluminum oxide contraction.
Description
Technical field
The present invention relates to a kind of Zirconia electrolytic powder composition for automotive oxygen sensor field, belong to material neck
Domain.
Background technology
Due to environmental pressure, energy-saving and emission-reduction turn into the development topic of fuel vehicle, and lambda sensor realizes energy-saving and emission-reduction
One of critical component.The core component of lambda sensor is exactly the ceramic chip that zirconium oxide is sensitive electrolyte, at present, most of factories
Business uses all-zirconium oxide chip, but it has notable defect in terms of high-temperature insulation resistance, anti-thermal shock, therefore, must not
More complicated structure and technique is not taken to reduce the negative effect of insulation and thermal shock.If the other parts outside electrolyte are using exhausted
The aluminum oxide that edge excellent performance, thermal coefficient of expansion are low, thermal conductivity factor is high, then can simplify structure and technique, and avoid to the full extent
The risk that insulation and thermal shock are brought.But, due to aluminum oxide and difference of the zirconia ceramics in terms of sintering shrinkage, obtain two
The ceramics of person's good combination are a big difficult points.
The content of the invention
The problem of for zirconium oxide and difficult aluminum oxide co-sintering, can altogether it be burnt with alumina substrate the invention provides one kind
The Zirconium powder formula tied and be well combined, the standby vapour being made up of Zirconia electrolytic and alumina substrate is fired available for common
Car lambda sensor.
On the one hand, a kind of oxygen sensor used in vehicle Zirconia electrolytic powder composition of the invention, including 70~90wt% oxidations
Zirconium one-level powder, 0.1~25wt% zirconium oxide second patent flour bodies and 4~15wt% sintering aids；Wherein, the zirconium oxide one-level powder
Meso-position radius be 0.1~0.4 micron, particle diameter distribution is at 0.05~5 micron；The meso-position radius of the zirconium oxide second patent flour body are 0.5
~2.5 microns, particle diameter distribution is 0.05~100 micron.
Relative to the zirconia material of same particle diameter distribution, alumina sintering shrinks typically small.The present invention by using
The bigger zirconium oxide second patent flour body of particle diameter, reduction zirconium oxide shrinks, and zirconium oxide is reached contraction during common burning with aluminum oxide
Consistent purpose.Sintering aid is added, by the formation of solid phase reaction and glass phase, the consistency of Zirconia electrolytic is improved.
It is preferred that including 80~90wt% zirconium oxide one-levels powder, 0.1~10wt% zirconium oxide second patent flour bodies and 4~
15wt% sintering aids.
It is preferred that the zirconium oxide one-level powder or/and zirconium oxide second patent flour body are pure zirconia or yttrium stable zirconium oxide,
Wherein in yttrium stable zirconium oxide, the doping of yttrium is below 8mol%, preferably below 5mol%.
It is preferred that the particle diameter of the zirconium oxide one-level powder is between 0.05~5 micron, wherein 10% diameter of particle is less than
0.1 micron, 90% diameter of particle is less than 1.5 microns, and powder meso-position radius are 0.1~0.4 micron.
It is preferred that the particle diameter of the zirconium oxide second patent flour body is between 0.05~100 micron, wherein 10% diameter of particle is less than
0.1 micron, 90% diameter of particle is less than 15 microns, and powder meso-position radius are 0.5~2.5 micron.
It is preferred that the sintering aid is nano magnesia, nano calcium oxide, nano yttrium oxide, nano aluminium oxide, boron oxide
At least one of.
Also, it is preferred that the sintering aid particle diameter is between 0.05~5 micron, wherein 10% diameter of particle is less than 0.15
Micron, 90% diameter of particle is less than 1 micron, and meso-position radius are 0.2~0.3 micron.
On the other hand, present invention also offers a kind of with above-mentioned oxygen sensor used in vehicle Zirconia electrolytic powder composition phase
The alumina powder matched somebody with somebody, the particle diameter of the alumina powder is between 0.05~10 micron, wherein 10% diameter of particle is micro- less than 0.1
Rice, 90% diameter of particle is less than 1.5 microns, and meso-position radius are between 0.1~0.4 micron.
Another further aspect, burns altogether the invention provides a kind of oxygen sensor used in vehicle Zirconia electrolytic powder and alumina powder
Method, it is characterised in that including：
By alumina powder precompressed under low pressure 50MPa, aluminum oxide base substrate is obtained,
By above-mentioned oxygen sensor used in vehicle Zirconia electrolytic powder, high pressure is pressed into ceramics after aluminum oxide billet surface is paved
Piece；
Gained potsherd is sintered 1~3 hour at 1400~1600 DEG C, obtains described burning body altogether.
It is preferred that the high pressure is 100MPa.
The present invention is for the aluminum oxide sintering shrinkage characteristic different from zirconium oxide, it is difficult to prepare what the two was well combined
The problem of ceramic co-fired body, a kind of Zirconium powder formula is provided, by matching the Zirconium powder that different-grain diameter is distributed, reached
During co-sintering the purpose matched is shunk with aluminum oxide.It is primarily applicable for automotive oxygen sensor field.
Brief description of the drawings
Fig. 1 is respectively Zirconia-alumina common burning porcelain body prepared by comparative example 1 (left side) and the embodiment of the present invention 1 (right side)
Picture；
Fig. 2 is the SEM figures that the Zirconia-alumina prepared using Zirconium powder formula in the embodiment of the present invention 2 burns body altogether；
Fig. 3 is the SEM figures that the Zirconia-alumina prepared using Zirconium powder formula in the embodiment of the present invention 3 burns body altogether；
Fig. 4 is the SEM figures that the Zirconia-alumina prepared using Zirconium powder formula in the embodiment of the present invention 4 burns body altogether；
Fig. 5 is the SEM figures that the Zirconia-alumina prepared using Zirconium powder formula in the embodiment of the present invention 5 burns body altogether；
Fig. 6 is the SEM figures that the Zirconia-alumina prepared using Zirconium powder formula in comparative example 2 of the present invention burns body altogether.
Embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
The present invention is by matching zirconia particles particle diameter distribution, and reduction zirconium oxide shrinks, reached during co-sintering with
Aluminum oxide shrinks the purpose of matching.
Illustrate to following exemplary oxygen sensor used in vehicle Zirconia electrolytic powder and alumina substrate that the present invention is provided
Common burning body preparation method.
Weighed according to oxygen sensor used in vehicle Zirconia electrolytic powder composition and automobile-used oxygen biography is obtained after each raw material components, mixing
Sensor Zirconia electrolytic powder.The formula may include 70~90wt% zirconium oxide one-levels powder, 0.1~25wt% zirconium oxides
Second patent flour body and 4~15wt% sintering aids.Wherein feed components by the zirconia particles of different-grain diameter grade (for example, yttrium is steady
Determine zirconia particles etc.) and sintering aid composition.Further, mainly by zirconium oxide one-level powder (for example, one-level yttrium Stable Oxygen
Change zirconium powder body etc.) and zirconium oxide second patent flour body (for example, two grades yttrium stable zirconium oxide powder etc.) and sintering aid constitute.The original
The mass percent of material each component includes：70~90wt% (be preferably 80~90wt%) zirconium oxide one-level powder, 0.1~
25wt% (being preferably 0.1~10wt%) zirconium oxide second patent flour bodies and 4~15wt% sintering aids.The quality percentage of the sintering aid
Than being preferably 4~15wt%.The present invention in zirconium oxide one-level powder by adding two grades of (0.1~25wt%) zirconium oxide in part
Powder is used for the particle diameter for adjusting Zirconium powder.If being added without the zirconium oxide second patent flour body, compared to aluminum oxide, zirconium oxide electricity
Solve matter and shrink excessive, lamination occurs in gained ceramics；If it is too many (such as larger than to add the zirconium oxide second patent flour body
25wt%), then Zirconia electrolytic is difficult to densification, is difficult to reach high voltage (such as in fuel-rich (oxygen deprivation) atmosphere lower sensor
0.9V).As a preferred example, one-level powder (the zirconium oxide one-level powder) accounting is 70~90wt%, second patent flour
Body (zirconium oxide second patent flour body) accounting is 0.1~25wt%, and sintering aid accounting is 4~15wt%.It is used as a preferred side
In case, one-level powder accounting be 80~90wt%, second patent flour body accounting be 0.1~10wt%, sintering aid accounting be 5~
15wt%.
By alumina powder precompressed under low pressure (for example, 50MPa), aluminum oxide base substrate is obtained.The alumina powder grain
Footpath is between 0.05~10 micron, wherein 10% diameter of particle is less than 0.1 micron, 90% diameter of particle is less than 1.5 microns, meso-position radius
Between 0.1~0.4 micron.
By above-mentioned oxygen sensor used in vehicle Zirconia electrolytic powder, high pressure is pressed into pottery after aluminum oxide billet surface is paved
After ceramics, sintered 1~3 hour at 1400~1600 DEG C, obtain described burning body altogether.The high pressure can be 100MPa.In addition, this
Oxygen sensor used in vehicle Zirconia electrolytic powder can be also laid in aluminum oxide base substrate table by invention by the tape casting, injection etc.
Face.
In the present invention, the Zirconium powder (zirconium oxide one-level powder or/and zirconium oxide second patent flour body) can be zirconium oxide
Or yttrium stable zirconium oxide, the wherein doping of yttrium is 0~8mol%, in preferred scheme, the doping of yttrium for 0~
The yittrium oxide for proper proportion of being adulterated in 5mol%, zirconium oxide, is conducive to increasing zirconium oxide electrical conductivity, reduces sensor internal resistance.
In the present invention, the Zirconium powder of described different-grain diameter grade includes the powder of two kinds of grades：Wherein zirconium oxide
The particle diameter of one-level powder can be between 0.05~5 micron, wherein 10% diameter of particle is less than 0.1 micron, 90% diameter of particle is less than
1.5 microns, powder meso-position radius are 0.1~0.4 micron..The particle diameter of zirconium oxide second patent flour body can be between 0.05~100 micron, its
In 10% diameter of particle be less than 0.1 micron, 90% diameter of particle be less than 15 microns, powder meso-position radius be 0.5~2.5 micron.
In the present invention, described sintering aid can for nano magnesia, nano calcium oxide, nano yttrium oxide, nano aluminium oxide,
One or several kinds in boron oxide, the sintering aid particle diameter is between 0.05~5 micron, wherein 10% diameter of particle is less than
0.15 micron, 90% diameter of particle is less than 1 micron, and meso-position radius are 0.2~0.3 micron.Using nanoscale sintering aid, it passes through
The formation of solid phase reaction and glass phase, improves the consistency of Zirconia electrolytic.
Meaning of the present invention is particle diameter and ratio by regulating and controlling Zirconium powder and sintering aid, obtains and alumina powder
Body co-sintering and the Zirconia electrolytic being well combined.The particle diameter of the alumina powder can between 0.05~10 micron, wherein
10% diameter of particle is less than 0.1 micron, and 90% diameter of particle is less than 1.5 microns, and meso-position radius are between 0.1~0.4 micron.
Embodiment is enumerated further below to describe the present invention in detail.It will similarly be understood that following examples are served only for this
Invention is further described, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright the above is made belong to protection scope of the present invention.Following examples are specific
Technological parameter etc. is also only that an example in OK range, i.e. those skilled in the art can be done properly by this paper explanation
In the range of select, and do not really want to be defined in the concrete numerical value of hereafter example.
Embodiment 1
Doped yttrium amount is 5mol% in yttrium stable zirconium oxide described in this embodiment in one-level powder and second patent flour body；By 5g oxygen
Change aluminium powder body (D10=0.15 μm, D50=0.23 μm, D90=0.37 μm) is pressed into a diameter of in advance under room temperature 50MPa pressure
20mm disk base substrate；By 1.6g one-level powder (D10=0.1 μm, D50=0.4 μm, D90=0.9 μm), two grades of 0.32g
Powder (D10=0.23 μm, D50=0.64 μm, D90=3.04 μm), 0.08g it is nano alumina powder jointed (D10=0.11 μm,
D50=0.19 μm, D90=0.31 μm) after ground and mixed is uniform, paved at the top of aluminum oxide base substrate, in room temperature 100MPa pressure
Under be pressed into potsherd；Base substrate is sintered 2 hours at 1470 DEG C.In ceramics after sintering, aluminum oxide is well combined with zirconium oxide,
Without lamination, the ceramic body after sintering is shown in right figure potsherd in Fig. 1, wherein the consistency of Zirconia electrolytic be more than
90%.
Embodiment 2
Doped yttrium amount is 0.5mol% in yttrium stable zirconium oxide described in this embodiment in one-level powder and second patent flour body；By 5g
Alumina powder (D10=0.15 μm, D50=0.23 μm, D90=0.37 μm) is pressed into a diameter of in advance under room temperature 50MPa pressure
20mm disk；By 1.58g stair oxidation zirconium powder body (D10=0.1 μm, D50=0.4 μm, D90=0.9 μm), 0.32g
Second patent flour body (D10=0.23 μm, D50=0.64 μm, D90=3.04 μm), 0.1g boron oxides powder (D10=0.1 μm, D50=
0.3 μm, D90=0.9 μm) after ground and mixed is uniform, paves, be pressed under room temperature 100MPa pressure at the top of aluminum oxide base substrate
Potsherd；Base substrate is sintered 2 hours at 1500 DEG C.In ceramics after sintering, aluminum oxide is well combined with zirconium oxide, and no layering is existing
As SEM photograph is shown in accompanying drawing 2, and the wherein consistency of Zirconia electrolytic is more than 90%.
Embodiment 3
Doped yttrium amount is 0.5mol% in yttrium stable zirconium oxide described in this embodiment in one-level powder and second patent flour body；By 5g
Alumina powder (D10=0.15 μm, D50=0.23 μm, D90=0.37 μm) is pressed into a diameter of in advance under room temperature 50MPa pressure
20mm disk；By 1.74g one-levels powder (D10=0.1 μm, D50=0.4 μm, D90=0.9 μm), 0.01g second patent flour bodies
(D10=0.23 μm, D50=0.64 μm, D90=3.04 μm), 0.09g nano alumina powder jointed (D10=0.11 μm, D50=
0.19 μm, D90=0.31 μm), 0.16g yttrium oxide powders (D10=0.1 μm, D50=0.3 μm, D90=0.9 μm) ground and mixed
After uniform, paved at the top of aluminum oxide base substrate, potsherd is pressed under room temperature 100MPa pressure；Base substrate is sintered at 1450 DEG C
2 hours.In ceramics after sintering, aluminum oxide is well combined with zirconium oxide, and no lamination, SEM photograph is shown in accompanying drawing 3, wherein oxygen
The consistency for changing zirconium electrolyte is more than 90%.
Embodiment 4
Doped yttrium amount is 5mol% in yttrium stable zirconium oxide described in this embodiment in one-level powder and second patent flour body；By 5g oxygen
Change aluminium powder body (D10=0.15 μm, D50=0.23 μm, D90=0.37 μm) is pressed into a diameter of in advance under room temperature 50MPa pressure
20mm disk；By 1.72g one-level powder (D10=0.1 μm, D50=0.4 μm, D90=0.9 μm), 0.20g second patent flour
Nano alumina powder jointed (D10=0.11 μm, D50 of body (D10=0.23 μm, D50=0.64 μm, D90=3.04 μm), 0.08g
=0.19 μm, D90=0.31 μm) after ground and mixed is uniform, paves, pushed in room temperature 100MPa pressure at the top of aluminum oxide base substrate
Potsherd is made；Base substrate is sintered 2 hours at 1500 DEG C.In ceramics after sintering, aluminum oxide is well combined with zirconium oxide, nothing point
Layer phenomenon, the SEM photograph of common burning porcelain body is shown in Fig. 4, and the wherein consistency of Zirconia electrolytic is more than 90%.
Embodiment 5
Doped yttrium amount is 5mol% in yttrium stable zirconium oxide described in this embodiment in one-level powder and second patent flour body；By 5g oxygen
Change aluminium powder body (D10=0.15 μm, D50=0.23 μm, D90=0.37 μm) is pressed into a diameter of in advance under room temperature 50MPa pressure
20mm disk；By 1.42g one-level powder (D10=0.1 μm, D50=0.4 μm, D90=0.9 μm), 0.5g second patent flour body
(D10=0.23 μm, D50=0.64 μm, D90=3.04 μm), 0.08g nano alumina powder jointed (D10=0.11 μm, D50=
0.19 μm, D90=0.31 μm) after ground and mixed is uniform, paved at the top of aluminum oxide base substrate, suppressed under room temperature 100MPa pressure
Into potsherd；Base substrate is sintered 2 hours at 1500 DEG C.In ceramics after sintering, aluminum oxide is well combined with zirconium oxide, no layering
Phenomenon, the SEM photograph of common burning porcelain body is shown in Fig. 5, and the wherein consistency of Zirconia electrolytic is more than 90%.
Comparative example 1
All change the Zirconium powder in embodiment 1 into stair oxidation zirconium powder body, aluminum oxide and other process conditions are constant,
Then aluminum oxide is completely disengaged from zirconia layer, and the ceramic body after sintering is shown in left figure in Fig. 1.
Comparative example 2
Doped yttrium amount is 5mol% in yttrium stable zirconium oxide described in this embodiment in one-level powder and second patent flour body；By 5g oxygen
Change aluminium powder body (D10=0.15 μm, D50=0.23 μm, D90=0.37 μm) is pressed into a diameter of in advance under room temperature 50MPa pressure
20mm disk；By 1.22g one-level powder (D10=0.1 μm, D50=0.4 μm, D90=0.9 μm), 0.70g second patent flour
Body (D10=0.23 μm, D50=0.64 μm, D90=3.04 μm), 0.08g it is nano alumina powder jointed ((D10=0.11 μm,
D50=0.19 μm, D90=0.31 μm)) after ground and mixed is uniform, paved at the top of aluminum oxide base substrate, in room temperature 100MPa pressure
Under be pressed into potsherd；Base substrate is sintered 2 hours at 1500 DEG C.Ceramic body is shown in Fig. 6, wherein Zirconia electrolytic cause after sintering
Density is less than 80%.As can be seen here, the Zirconia electrolytic low density prepared by this comparative example, it is impossible to meet automobile-used sensing
The requirement of device electrolyte.
This formula powder is utilized into different forming methods, such as the tape casting, injection can also obtain similar effect.
It is to be understood that：Described above is only the preferred embodiment of the present invention, for the common of the art
For technical staff, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improve and moistened
Decorations also should be regarded as protection scope of the present invention.
Claims (8)
1. a kind of oxygen sensor used in vehicle Zirconia electrolytic powder composition, it is characterised in that including 70~90wt% zirconium oxides one
Level powder, 0.1~25wt% zirconium oxide second patent flour bodies and 4~15wt% sintering aids；Wherein, in the zirconium oxide one-level powder
Position footpath is 0.1~0.4 micron, and particle diameter distribution is at 0.05~5 micron；The meso-position radius of the zirconium oxide second patent flour body are 0.5~2.5
Micron, particle diameter distribution is 0.05~100 micron.
2. oxygen sensor used in vehicle Zirconia electrolytic powder composition according to claim 1, it is characterised in that including 80~
90wt% zirconium oxide one-levels powder, 0.1~10wt% zirconium oxide second patent flour bodies and 4~15wt% sintering aids.
3. oxygen sensor used in vehicle Zirconia electrolytic powder composition according to claim 1 or 2, it is characterised in that described
Zirconium oxide one-level powder or/and zirconium oxide second patent flour body are pure zirconia or yttrium stable zirconium oxide powder, and wherein yttrium is stable aoxidizes
The doping of yttrium is below 8mol%, preferably below 5mol% in zirconium.
4. the oxygen sensor used in vehicle Zirconia electrolytic powder composition according to any one of claim 1-3, its feature exists
In the particle diameter of the zirconium oxide one-level powder is between 0.05~5 micron, wherein 10% diameter of particle is less than 0.1 micron, 90% powder
Body particle diameter is less than 1.5 microns, and powder meso-position radius are 0.1~0.4 micron.
5. the oxygen sensor used in vehicle Zirconia electrolytic powder composition according to any one of claim 1-3, its feature exists
In the footpath of the zirconium oxide second patent flour body grain is between 0.05~100 micron, wherein 10% diameter of particle is less than 0.1 micron, 90% powder
Body particle diameter is less than 15 microns, and powder meso-position radius are 0.5~2.5 micron.
6. the oxygen sensor used in vehicle Zirconia electrolytic powder composition according to any one of claim 1-5, its feature exists
In the sintering aid is at least one in nano magnesia, nano calcium oxide, nano yttrium oxide, nano aluminium oxide, boron oxide
Kind.
7. oxygen sensor used in vehicle Zirconia electrolytic powder composition according to claim 6, it is characterised in that described to help burning
Agent particle diameter is between 0.05~5 micron, wherein 10% diameter of particle is less than 0.15 micron, 90% diameter of particle is less than 1 micron,
Meso-position radius are 0.2~0.3 micron.
8. a kind of oxygen matched with oxygen sensor used in vehicle Zirconia electrolytic powder composition any one of claim 1-7
Change aluminium powder body, it is characterised in that the particle diameter of the alumina powder is between 0.05~10 micron, wherein 10% diameter of particle is less than
0.1 micron, 90% diameter of particle is less than 1.5 microns, and meso-position radius are between 0.1~0.4 micron.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710335832.2A CN107140976B (en) | 2017-05-12 | 2017-05-12 | Formula of zirconia electrolyte powder for oxygen sensor for vehicle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710335832.2A CN107140976B (en) | 2017-05-12 | 2017-05-12 | Formula of zirconia electrolyte powder for oxygen sensor for vehicle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107140976A true CN107140976A (en) | 2017-09-08 |
| CN107140976B CN107140976B (en) | 2021-04-16 |
Family
ID=59777067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710335832.2A Active CN107140976B (en) | 2017-05-12 | 2017-05-12 | Formula of zirconia electrolyte powder for oxygen sensor for vehicle |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107140976B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109437890A (en) * | 2018-10-12 | 2019-03-08 | 东莞市煜田新材料有限公司 | A kind of zirconia ceramics sintering aid and its preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19524759A1 (en) * | 1995-07-07 | 1997-01-09 | Didier Werke Ag | Prodn. of aluminium titanate ceramic - by calcining moulded body contg. alumina, titania, and additives contg. lanthanum |
| CN1847195A (en) * | 2005-04-12 | 2006-10-18 | 中国矿业大学（北京校区） | Sub-micron zirconium oxide electrolyte film material and its prepn process |
| CN104891969A (en) * | 2015-05-26 | 2015-09-09 | 苏州工业园区传世汽车电子有限公司 | Preparation method of zirconium oxide ceramic for oxygen sensor |
| CN104891542A (en) * | 2015-06-24 | 2015-09-09 | 山东大学 | Preparation method of ultrafine alpha-Al2O3 powder |
-
2017
- 2017-05-12 CN CN201710335832.2A patent/CN107140976B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19524759A1 (en) * | 1995-07-07 | 1997-01-09 | Didier Werke Ag | Prodn. of aluminium titanate ceramic - by calcining moulded body contg. alumina, titania, and additives contg. lanthanum |
| CN1847195A (en) * | 2005-04-12 | 2006-10-18 | 中国矿业大学（北京校区） | Sub-micron zirconium oxide electrolyte film material and its prepn process |
| CN104891969A (en) * | 2015-05-26 | 2015-09-09 | 苏州工业园区传世汽车电子有限公司 | Preparation method of zirconium oxide ceramic for oxygen sensor |
| CN104891542A (en) * | 2015-06-24 | 2015-09-09 | 山东大学 | Preparation method of ultrafine alpha-Al2O3 powder |
Non-Patent Citations (1)
| Title |
|---|
| 任继文等: "钇稳定氧化锆纳米粉体烧结工艺的研究", 《材料工程》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109437890A (en) * | 2018-10-12 | 2019-03-08 | 东莞市煜田新材料有限公司 | A kind of zirconia ceramics sintering aid and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107140976B (en) | 2021-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xue et al. | Low‐temperature sintering of alumina with liquid‐forming additives | |
| Clemmer et al. | Influence of porous composite microstructure on the processing and properties of solid oxide fuel cell anodes | |
| Sun et al. | Fabrication of transparent Y2O3 ceramics via aqueous gelcasting | |
| JP3887413B2 (en) | Sintered solid electrolyte with high oxygen ion conductivity | |
| JP5405591B2 (en) | Co-doped YSZ electrolyte for solid oxide fuel cell stack | |
| KR20100087338A (en) | Low-creep zircon material with nano-additives and method of making same | |
| Suárez et al. | Effect of alumina addition on initial sintering of cubic ZrO2 (8YSZ) | |
| KR102517378B1 (en) | Improved performance of technical ceramics | |
| JP6655122B2 (en) | Method for producing proton conductive oxide fuel cell | |
| Laarz et al. | Colloidal processing of Al2O3-based composites reinforced with TiN and TiC particulates, whiskers and nanoparticles | |
| CN105732008A (en) | Co-firing method and application of laminated type zirconium oxide and aluminium oxide ceramic | |
| JPWO2015080065A1 (en) | Porous material and heat insulating film | |
| ATE281003T1 (en) | METHOD FOR PRODUCING AN ELECTRODE WITH TEMPERATURE-RESISTANT CONDUCTIVITY | |
| CN107140976A (en) | A kind of oxygen sensor used in vehicle Zirconia electrolytic powder composition | |
| Hanifi et al. | Development of monolithic YSZ porous and dense layers through multiple slip casting for ceramic fuel cell applications | |
| JP2793148B2 (en) | Method for producing porous ceramic laminate | |
| JP2003173801A (en) | Solid electrolyte fuel cell and its manufacturing method | |
| El‐Amir et al. | Effect of waste‐derived MA spinel on sintering and stabilization behavior of partially stabilized double phase zirconia | |
| Tsukuma et al. | Thermal and Mechanical Properties of Y 2 O 3-Partially Stabilized Zirconia | |
| CN109456059A (en) | A kind of preparation method of lanthanum manganate and the negative temperature coefficient heat-sensitive composite ceramic material of yttrium oxide double-layer structure | |
| JP3667112B2 (en) | Method for producing LaGaO3-based powder and method for producing LaGaO3-based sintered body | |
| Moskovits et al. | Sintering of bimodal Y2O3-stabilized zirconia powder mixtures with a nanocrystalline component | |
| JP2004164878A (en) | Manufacturing method of solid electrolyte type fuel cell | |
| WO2022193611A1 (en) | Basic porous ceramic matrix and preparation method therefor, electronic cigarette atomization core and electronic cigarette | |
| Burgos-Montes et al. | Mullite compacts obtained by colloidal filtration of alumina powders dispersed in colloidal silica suspensions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |