CN106045482B - Rare earth oxide doped aluminium base high-performance metal bath determines the preparation method of HydroNit sensor material - Google Patents
Rare earth oxide doped aluminium base high-performance metal bath determines the preparation method of HydroNit sensor material Download PDFInfo
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Abstract
The present invention relates to the preparation method that a kind of rare earth oxide doped aluminium base high-performance metal bath determines HydroNit sensor material, this method is sanded the method combined by general milling and high-performance and prepares powder, using optimization solid-phase synthesis, prepares Al through double sintering2‑x RE x O3‑α Proton conducting solid electrolyte.Specifically to analyze pure Al2O3、RE2O3For raw material, through baking material, ingredient, pre-grinding, it is preforming, be pre-sintered, it is broken, eventually mill, final shaping unit, proton conducting solid electrolyte is prepared in the technical solution that is sintered eventually, the electrolyte has fine and close structure, higher proton conductive, higher high-temperature stability and chemical stability, preferable mechanical strength and resistance to corrosion, and raw material is relatively inexpensive, as the continuous on-line determination probe material of metal bath hydrogen content, it is able to solve the problem that existing probe material at high temperature stability is poor, can not measure applied to more dystectic copper liquid and molten steel hydrogen content.
Description
Technical field
The present invention relates to the preparations that a kind of rare earth oxide doped aluminium base high-performance metal bath determines HydroNit sensor material
Method belongs to electrochemistry and analysis detection field.
Background technique
The traditional metal materials such as copper, iron, aluminium have good mechanical, mechanics and electric property, are widely used in national warp
Ji construction, national defense construction field.The machinery such as intensity, hardness, plasticity and toughness of these metal materials and mechanical property and material itself
Smelting process it is closely bound up, hydrogen must be strictly controlled in the smelting process of above-mentioned metal material as a kind of harmful element.
Hydrogen in metal material is usually in smelting process by the vapor in furnace gas, the raw material containing moisture and refractory material band
Enter.Hydrogen can both be dissolved in liquid metal or be dissolved in solid metallic.Due to hydrogen in solid metallic solubility very little, such as
Hydrogen content in fruit metal bath is too high, will be precipitated in gaseous form in its cooling and process of setting, cause subcutaneous gas
Bubble, central pipe, shrinkage porosite and crackle significantly reduce the mechanical mechanics properties such as the intensity, plasticity and impact flexibility of metal product.Cause
This carries out effective be monitored and controlled for improving metal material quality extremely to the hydrogen content in metal bath in smelting process
It closes important.
Traditional metal bath hydrogen content measuring method mainly has first bubble method, Decompressing Solidification Method, Telegas method, DPM
Method, Chapel method, sampling chemical analysis etc., the above method is long, complicated for operation there is analysis time, control difficulty is big, takes
With inconvenient for use, measurement accuracy be low and many disadvantages such as cannot achieve continuous on-line measurement.With electrochemistry and solid electrolytic
There is a kind of brand-new metal bath survey hydrogen technology, the i.e. legal hydrogen of concentration cell at present in the development of matter theory.This method is mainly sharp
The measurement of hydrogen content is realized with the principle that proton conducting solid electrolyte constitutes electrochemical hydrogen concentration cell.Utilize concentration cell method
When measuring metal bath hydrogen content, solid electrolyte side is connected with the hydrogen centainly dividedP 2, and in the molten aluminum of the electrolyte other side
There is also certain gaseous phase partial pressures for molten hydrogenP 1, since solid electrolyte allows proton to pass through, and two sides hydrogen partial pressure difference is to structure
At concentration cell, wherein being passed through the side partial pressure of hydrogenP 2Usually it is known that according to Nernst equationE=RTln(P 1/P 2) /
(2F), wherein F is Faraday constant, as long as therefore measuring the electromotive force of solid electrolyte two sidesEWith the temperature in molten aluminum to be measuredT, the partial pressure of the molten hydrogen in molten aluminum can be acquired according to Nernst equationP 1, and according to Sievert law [%H]=KP 1^ (1/2),
WhereinKFor the equilibrium constant, when the dissolution of hydrogen in molten aluminum reaches balance, in molten aluminum hydrogen concentration [%H] and molten hydrogen gaseous phase partial pressureP 1Square root it is directly proportional, therefore the concentration of molten hydrogen in molten aluminum can be calculated according to above-mentioned theory.It is dense for metal bath
For difference battery determines hydrogen, core technology is the research and development of high-performance proton conducting solid electrolyte, therefore for matter
The research and probe of subconductivity solid electrolyte material is the research hotspot of institute, colleges and universities and enterprise always.It is all both at home and abroad
Multi-expert scholar has carried out a large amount of significant research work in this field, and the proton conductor researched and developed at present is solid
Body electrolyte system mainly has: BaCeO3、CaZrO3、SrCeO3、BaZrO3、SrTiO3System etc..
BaCeO3System, by the element dopings such as Y, Nd, Sm, Yb, Gd BaCeO3It is formed, is the Ca-Ti ore type having now been found that
The higher material of conductivity in proton conductor, for activation energy in 0.5 ~ 0.6 eV, the system ionic Effective Conductivity is complex, belongs to
Ion mixed conductor, at 800 DEG C or more, ionic conduction is occupied an leading position, and is occupied an leading position in 800 DEG C or less proton conductives.
The system proton conductor alkalinity is stronger, but mechanical strength and chemical stability are poor, meets CO when such as 700 DEG C2Equal sour gas hold
Easily react.
CaZrO3System, by the element dopings such as In, Ga, Sc CaZrO3It is formed, is almost that pure proton is led in its use scope
Body, for proton transfer number up to 0.99 or more, the system chemical stability and thermal shock resistance are preferable, but it is in synthesis in solid state process
The sintering temperature of middle requirement is higher, and proton conductivity is usually than CaCeO3Low 2 orders of magnitude of system.
SrCeO3System, by the element dopings such as Yb, Tm, Y, Ga, Sc, Sm, Dy, In SrCeO3It is formed, conductivity activation energy is
0.6 eV or so inhibits oxonium ion to migrate electric conductivity, therefore has higher because the lattice of its orthohormbic structure is by larger distortion
Proton transfer number, under the high temperature conditions in hydrogen atmosphere be almost pure proton conductor.The system and BaCeO3System is similar,
CO2Etc. be easy to happen reaction in acid atmospheres, chemical stability is poor.
SrZrO3System, by the element dopings such as Yb, Y, Ga, In SrZrO3Formed, the system have preferable mechanical strength and
Chemical stability, especially at high temperature and CO2Etc. stability in acid atmospheres be much higher than SrCeO3 Furthermore system is being higher than
Still proton transfer number with higher at a temperature of 900 DEG C, but the series proton conductor proton transfer activation energy is compared with SrCeO3
System is high, and conductivity is compared with SrCeO3It is the low 1-2 order of magnitude.
BaZrO3System, the system is by the element dopings such as In, Sc, Y, Sc BaZrO3It is formed, lattice structure is stablized, chemistry
Stability and high mechanical strength, resistance to reduction is good, to CO2Etc. acid atmospheres tolerances it is high, fusing point is high, and the coefficient of expansion is small, but burns
Junction temperature is higher, with SrZrO3Similar, conductive capability is lower than SrCeO3Be the 1-2 order of magnitude, proton transfer activation energy also compared with
SrCeO3It is high.
In conclusion certain development is had been achieved in terms of proton conducting solid electrolyte exploitation and preparation at present,
And the domestic and international acquired representative patents in the field mainly have: U.S. patent Nos (US2009016995), Germany's invention are special
Sharp (DE19535922), Chinese invention patent (CN101119A), Chinese invention patent (CN102442818A), Chinese invention are special
Sharp (CN101215644A), Chinese invention patent (CN104968632A), Chinese invention patent (CN1491420A) etc..
Although there has been the development of certain scale in terms of proton conducting solid electrolyte research and development at present, at present
Many proton conducting solid electrolyte systems through developing are lower since there are conductivity, sinterability is poor, expensive, high
Temperature stability difference or the various disadvantages such as poor chemical stability and high-temperature metal melt hydrogen content measurement probe can not be applied to
Material.The probe material for being now widely used for aluminium and aluminum alloy melt hydrogen assay is mainly In2O3The CaZrO of doping3System
Proton conducting solid electrolyte, such as 1992, the metal bath hydrogen content of entitled " NOTORP " of Japanese TYK company research and development
Measurement probe, the probe is with CaZr0.9In0.1O3-α Proton conductor solid electrolyte is probe material, with Ar+1%H2As reference
, it can be achieved that molten aluminum continuously surveys hydrogen 20h, longest has been able to meet substantially the aluminum melt hydrogen under industrial environment and contains electrode up to 50h
Measure the demand of on-line continuous detection.However the dopant In as used by synthesis probe material2O3It is unstable, hold at high temperature
It easily decomposes, In2O3 (s)→In2O(g) + O2(g), therefore the hydrogen content measurement assembled using the proton conducting solid electrolyte is visited
Head obviously can not be applied to the copper liquid under more operation at high temperature and the hydrogen content measurement in molten steel.
Summary of the invention
Determine technical problem to be solved by the invention is to provide a kind of proton conducting solid electrolyte and as metal bath
The purposes of HydroNit sensor material.
Proton conducting solid electrolyte of the invention, with rare earth oxide RE2O3For dopant, Al2O3For matrix, doping
Ratio is 0.0005-0.025.Chemical composition is expressed as Al2-x RE x O3-α , whereinx=0.001-0.05。
The rare earth RE is one or more of in Yb, Pr, Sm, Dy, Er.
Show α-A1 according to team's early-stage study where inventor2O3Itself hardly embodies proton conductive, but if will
The biggish rare earth oxide of a small amount of atomic radius is doped to α-A12O3Solid solution is formed in matrix, will destroy matrix α-
A12O3Original atom period potential field, and distortion of lattice is generated, the crystal structure after making doping is conducive to proton in biography wherein
It passs, so that rare earth oxide doped alpha-A12O3As proton conducting solid electrolyte.
Material of the present invention proton conductive, higher high-temperature stability and chemical stability with higher, preferable machine
Tool intensity and resistance to corrosion, and raw material is relatively inexpensive, is the ideal material for making high-temperature metal melt hydrogen content measurement probe,
Solve under existing high-temperature metal melt hydrogen content measurement probe material at high temperature it is unstable, can not be applied to more dystectic copper liquid and
The problem of molten steel hydrogen content continuous on-line determination.
Proton conducting solid electrolyte material of the invention is prepared by high-temperature solid phase reaction method, especially by following technology
Scheme is realized.
1) baking material weighs a certain amount of analytically pure Al2O3With rare earth oxide RE2O3, it is respectively placed in zirconium oxide with cover
In crucible, the moisture that is put into Muffle furnace in drying material；
2) ingredient, the raw material that will be dried in step 1), according to the proton conducting solid electrolyte Al to be synthesized2- x RE x O3-α Composition, weigh and appropriate carry out ingredient；
3) raw material load weighted in step 2 is mixed and is packed into ball grinder by pre-grinding, using dehydrated alcohol as medium, carries out ball
Mill obtains the mixed powder of 200 mesh through dry and sieving；
4) preforming, it is carried out in normal pressure and air atmosphere, certainly using fluid pressure type by mixed powder obtained in step 3)
Dynamic tablet press machine is pressed into disk, and is waited press with 200-300MPa's using cold with the pressure of 8-12MPa, pressure maintaining 60s -100s
Pressure, pressure maintaining 10-50min are further compacted；
5) it is pre-sintered, the disk suppressed in step 4) is kept the temperature into 1-3h at 1200-1400 DEG C, is then heated to
1450-1550 DEG C of heat preservation 10-20h is pre-sintered (specific pre-sintering system is as shown in Figure 1)；
6) be crushed, the circular disc test specimen being pre-sintered in step 5) is crushed, prevent in shattering process introducing other
Impurity；
7) it grinds, raw material broken in step 6) is roughly ground using agate mortar, and use sand mill, with anhydrous eventually
Ethyl alcohol is that medium is sanded, and drying obtains nanoscale mixed powder；
8) nanometer grade powder obtained in step 7) is utilized fluid pressure type automatic tableting press in 6-10MPa by final shaping unit again
Under, pressure maintaining 60-100s is pressed into disk, and using cold isostatic press with 200-300MPa pressure, pressure maintaining 10-50min is further
Compacting；
9) sintering eventually, carries out in normal pressure and air atmosphere, and the circular disc test specimen suppressed in step 8) is placed in high temperature and is burnt
In freezing of a furnace, 1400-1550 DEG C of heat preservation 2-4h then heats to 1600 DEG C -1650 DEG C, keeps the temperature 10-20h, cools to the furnace later
Room temperature (specific end sintering schedule is as shown in Figure 2), obtains Al2-x RE x O3-α Proton conducting solid electrolyte.
In above scheme, in step 1), the baking material temperature schedule of use are as follows: 3-8 DEG C of heating rate/min, 500-900 DEG C
At a temperature of keep the temperature 4-8h, furnace cooling later.
In step 2, Al2O3: RE2O3=(2-x):x,x=0.001-0.05, with used rare earth oxide and preparation work
The difference of skill is adjusted, no matter using which kind of oxidexValue is no more than it in α-Al2O3In solid solubility limit.
In step 3), the ball milling parameter of pre-grinding powder are as follows: dehydrated alcohol additional amount is 70-80wt%, and ball material mass ratio is 2:
1, big ball, middle ball and pellet quality ratio 3:4:3, revolving speed 200-500r/min, ball milling 24-96h.
In step 4), the circular disc test specimen diameter 50-100mm suppressed, thickness 5-20mm, specimen size according to powder amount and
Other technological parameters are adjusted, and according to the needs of technique, can also be pressed into other shapes and size.
In step 5), pre-sintering carries out in normal pressure and air atmosphere, temperature schedule are as follows: 3-6 DEG C of heating rate/min rises
Temperature is warming up to 1450-1550 DEG C of heat preservation 10-20h then with 4-8 DEG C/min heating rate to 1200-1400 DEG C of heat preservation 1-3h,
Cool to room temperature with the furnace later.
In step 7), parameter is sanded are as follows: 3-6h is sanded in revolving speed 2000-3000r/min.
In step 8), circular disc test specimen diameter 10-25mm, the thickness 1-10mm suppressed, can also be pressed into other shapes and
Size, concrete foundation technique and the needs for determining HydroNit sensor assembling adjust.
In step 9), sintering carries out in normal pressure and air atmosphere eventually, temperature schedule are as follows: 3-6 DEG C of heating rate/min rises
Temperature keeps the temperature 2-4h to 1400-1550 DEG C, then with 4-8 DEG C/min heating rate, is warming up to 1600-1650 DEG C, keeps the temperature 10-
20h cools to room temperature with the furnace later,
The present invention is with α-A12O3It is prepared for proton conducting solid electrolyte for basis material, due to α-A12O3Basis material
For corundum material, (crystal structure is as shown in Figure 3), itself is the structural ceramics of high comprehensive performance, therefore prepared
Proton conducting solid electrolyte inherits the advantages of basis material, equally has high-melting-point, high intensity, good chemical stability
And many advantages, such as thermal stability, it can adapt to the extreme operating conditions of high-temperature metal melt hydrogen content measurement probe.
The present invention is with rare earth oxide doped alpha-A12O3The high temperature proton conducting solid electrolyte electricity with higher of preparation
Conductance, (Fig. 4 show made using embodiment 4 for proton conductive with higher especially in vapor and hydrogen atmosphere
The conductivity of standby obtained proton conductor at different conditions), proton transfer number with higher, the metal bath assembled with it
Hydrogen content measurement probe can export more stable electromotive force signal at different temperatures, and (Fig. 5 is shown to be prepared using embodiment 2
Proton conductor assembled determine HydroNit sensor measurement copper liquid in the obtained electromotive force signal of hydrogen content), can satisfy preparation
The needs of high-temperature metal melt hydrogen content measurement probe material.
The present invention uses pre-sintering and whole sintering under different temperatures system to combine, and the method for twice firing prepares high temperature
Proton conducting solid electrolyte, prepared high temperature proton conducting solid electrolyte has very high consistency, and (Fig. 6 is shown
Using the relative density of 3 preparation-obtained 3 groups of samples of embodiment, 97% or more), therefore prepared proton conductive
Solid electrolyte has the corrosive power of good high temperature resistant metal melt and slag.
The present invention mainly uses general milling and high-performance that the abrasive material mode combined is sanded and completes powder preparation, prepared
Powder be uniformly mixed, granularity reaches nano-scale, large specific surface area, reactivity are high, can guarantee solid phase reaction and burning
The abundant progress of knot process, prepared proton conducting solid electrolyte crystallinity is good, performance is stable, defect rate is low, repeats
Property is good.
The present invention prepares rare earth oxide doped aluminium base proton conducting solid electricity using the solid reaction process after optimization
Xie Zhi has carried out a large amount of experimental study to the temperature schedule of sintering process using the method for orthogonal experiment and has explored, as a result early period
Show that pre-sintering proposed in the present invention and whole sintering temperature system being capable of the excellent Al of processability2-x RE x O3-α Matrix
Conducting solid electrolyte, strictly in accordance with the temperature schedule proposed in the present invention both can guarantee solid solution and sintering process it is abundant into
Row, and it is able to suppress the Mechanics of Machinery intensity and resistance to corrosion for excessively growing up and reducing material of crystal grain in insulating process.
The present invention makes full use of China's alumina abundant and rare earth resources, and the high-temperature metal melt of function admirable is prepared
Hydrogen content measurement probe material, compared with existing high-temperature metal melt hydrogen content measures probe material, relatively inexpensive with raw material,
The features such as being easy to get, and can be utilized for the comprehensive high-efficiency of China's rare earth resources abundant open up new approach to a certain extent.
Detailed description of the invention
Fig. 1 pre-sintering temperature system schematic diagram.
Fig. 2 end sintering temperature system schematic diagram.
Fig. 3 α-Al2O3Crystal structure schematic diagram.
The conductivity of the preparation-obtained proton conductor of Fig. 4 embodiment 4 at different conditions.
Fig. 5 determines HydroNit sensor electromotive force variation with temperature curve graph with what proton conductor prepared by embodiment 2 was assembled.
The relative density of 3 preparation-obtained 3 groups of samples of Fig. 6 embodiment.
Proton conducting solid electrolyte XRD material phase analysis result prepared by Fig. 7 embodiment 1.
Specific embodiment
Embodiment 1
The pure Al of analysis of certain mass is weighed roughly2O3And Yb2O3, it is respectively placed in clean oxidation zirconium crucible, covers earthenware
Crucible lid, is put into Muffle furnace, and 5 DEG C/min of heating rate is arranged, 8h is dried at 500 DEG C, dries drug.
It is Al according to molar ratio2O3: Yb2O3The ratio of=1.999:0.001 takes the powder dried in right amount respectively, loads in mixture
In ball grinder, dehydrated alcohol is added, the slurry that solid content is 20-30wt% is modulated into, using aluminum oxide abrading-ball, ball material matter
For amount than being 2:1, the mass ratio of big ball, middle ball and bead takes 3:4:3, and using planetary ball mill, setting revolving speed is 300r/min,
Ball milling 96h, is transferred to evaporating dish for slurry later, is placed in explosion-proof constant temperature oven after drying at 200 DEG C and obtains blocky powder, passes through
After agate mortar corase grinding, it is sieved using 200 the polished standard screens, obtains pre-grinding powder.
Powder after above-mentioned pre-grinding is utilized into fluid pressure type automatic tableting press, with the pressure of 8MPa, pressure maintaining 100s is pressed into Φ
The disk of 80 × 10mm is several, and the disk of compression moulding is utilized cold isostatic press, with the pressure of 250MPa, pressure maintaining 50min, into
The compacting of one step.
The circular disc test specimen being pressed into is placed in oxidation zirconium crucible, crucible cover is covered, is placed in high temperature sintering furnace, normal pressure
And under air atmosphere, 3 DEG C/min of heating rate is set, 1200 DEG C of heat preservation 3h are warming up to, then with the heating rate of 5 DEG C/min,
1450 DEG C of heat preservation 20h are warming up to, cool to room temperature with the furnace later, obtain being pre-sintered sample.
Above-mentioned pre-sintering sample is crushed, and is roughly ground with agate mortar, utilizes high-performance sand grinder later, with
Dehydrated alcohol is medium, and revolving speed 2000r/min is sanded 6h, then the slurry after sand milling is transferred in evaporating dish, is placed in anti-
In quick-fried thermostatic drying chamber, 200 DEG C of drying are sieved after agate mortar is ground, obtain nanoscale mixed powder.
By above-mentioned mixed powder, using fluid pressure type automatic tableting press, at 6MPa, pressure maintaining 100s is pressed into 16 × 2mm of Φ
Circular disc test specimen, and the disk obtained after compacting is utilized into cold isostatic press, with 200MPa pressure, pressure maintaining 50min is further pressed
It is real.
By the sample of compression moulding be placed on oxidation zirconium crucible in, cover crucible cover, be placed in high temperature sintering furnace, normal pressure and
Under air atmosphere, 3 DEG C/min of heating rate is set, is warming up to 1400 DEG C, keeps the temperature 4h, then with the heating rate of 5 DEG C/min, is risen
Temperature keeps the temperature 20h, cools to room temperature with the furnace later, obtain the Al with higher-density to 1600 DEG C1.999Yb0.001O3-α Proton
Conducting solid electrolyte material (synthesized proton conductor XRD material phase analysis result is as shown in Figure 7).
Embodiment 2
The pure Al of analysis of certain mass is weighed roughly2O3And Pr2O3, it is respectively placed in clean oxidation zirconium crucible, covers earthenware
Crucible lid, is put into Muffle furnace, and 5 DEG C/min of heating rate is arranged, 7h is dried at 600 DEG C, dries drug.
It is Al according to molar ratio2O3: Pr2O3The ratio of=1.997:0.003 takes the powder of suitable above-mentioned drying respectively
Body loads in mixture in ball grinder, and a certain amount of dehydrated alcohol is added, and is modulated into the slurry that solid content is 20-30 wt %, uses
Aluminum oxide abrading-ball, ball material mass ratio are 2:1, and the mass ratio of big ball, middle ball and bead takes 3:4:3, using planetary ball mill,
Setting revolving speed is 350r/min, and slurry is transferred to evaporating dish later, is placed in explosion-proof constant temperature oven and dries at 200 DEG C by ball milling 72h
Blocky powder is obtained after dry, after agate mortar is roughly ground, is sieved using 200 the polished standard screens, obtains pre-grinding powder.
Powder after above-mentioned pre-grinding is utilized into fluid pressure type automatic tableting press, with the pressure of 9MPa, pressure maintaining 100s is pressed into Φ
The disk of 80 × 10mm is several, and the disk of compression moulding is utilized cold isostatic press, with the pressure of 250MPa, pressure maintaining 40min, into
The compacting of one step.
The circular disc test specimen being pressed into is placed in oxidation zirconium crucible, crucible cover is covered, is placed in high temperature sintering furnace, is arranged
3 DEG C/min of heating rate is warming up to 1300 DEG C of heat preservation 2h, then with the heating rate of 5 DEG C/min, is warming up to 1500 DEG C of heat preservations
15h obtains being pre-sintered sample.
Above-mentioned pre-sintering sample is crushed, and is roughly ground with agate mortar, utilizes high-performance sand grinder later, with
Dehydrated alcohol is medium, and revolving speed 2500r/min is sanded 5h, then the slurry after sand milling is transferred in evaporating dish, is placed in anti-
In quick-fried thermostatic drying chamber, 200 DEG C of drying are sieved after agate mortar is roughly ground, obtain nanoscale mixed powder.
By above-mentioned mixed powder, using fluid pressure type automatic tableting press, at 7MPa, pressure maintaining 100s is pressed into 16 × 2mm of Φ
Circular disc test specimen, and the circular disc test specimen obtained after compacting is utilized into cold isostatic press, with 200MPa pressure, pressure maintaining 40min, further
Compacting.
The sample of compression moulding is placed in oxidation zirconium crucible, crucible cover is covered, is placed in high temperature sintering furnace, setting rises
Warm 3 DEG C/min of speed is warming up to 1450 DEG C, keeps the temperature 3h, then with the heating rate of 5 DEG C/min, is warming up to 1650 DEG C, heat preservation
15h cools to room temperature with the furnace later, obtains the Al with higher-density1.997Pr0.003O3-α Proton conducting solid electrolyte material
Material.It is probe material with proton conductor prepared by embodiment 2, a platinum filament is welded into the side of above-mentioned proton conductor piece and is drawn
As conducting wire, proton conductor piece is then welded with conducting wire side using high-temperature cement and is sealed with alundum tube one end, wherein platinum
Silk passes through alundum tube and draws, and is then provided with a certain amount of metal hydride in alundum tube to provide stable hydrogen partial pressure, in addition,
Equipped with a certain amount of Al2O3Then powder filler seals the other end of alundum tube with high-temperature cement, wherein platinum filament is by height
Warm water mud sealed end is pierced by, and so far probe electrode is completed, and a root surface is separately taken to be cased with the platinum filament of thin alundum tube as circuit
Electrode constitutes the platinum filament lead of probe electrode with the two poles of the earth that loop electrode is coupled with the digital voltmeter being connected with computer
Determine hydrogen production device.Enough copper billets are placed in corundum crucible, then crucible is packed into after being melted in high temperature test furnace and keeps certain
Temperature immerses above-mentioned hydrogen content measuring device and thermocouple in copper liquid, records the temperature of copper liquid by computer and determines HydroNit sensor
The electromotive force value surveyed, obtained electromotive force variation with temperature curve graph are as shown in Figure 5.
Embodiment 3
The pure Al of analysis of certain mass is weighed roughly2O3And Sm2O3, it is respectively placed in clean oxidation zirconium crucible, covers earthenware
Crucible lid, is put into Muffle furnace, and 5 DEG C/min of heating rate is arranged, 6h is dried at 700 DEG C, dries drug.
It is Al according to molar ratio2O3: Sm2O3The ratio of=1.99:0.01 takes the powder of suitable above-mentioned drying respectively,
It loads in mixture in ball grinder, a certain amount of dehydrated alcohol is added, the slurry that solid content is 20-30 wt % is modulated into, using oxidation
Aluminum abrading-ball, ball material mass ratio are 2:1, and the mass ratio of big ball, middle ball and bead takes 3:4:3, using planetary ball mill, setting
Revolving speed is 400r/min, and slurry is transferred to evaporating dish later by ball milling 48h, is placed in explosion-proof constant temperature oven after drying at 200 DEG C
Blocky powder is obtained, after agate mortar is roughly ground, is sieved using 200 the polished standard screens, obtains pre-grinding powder.
Powder after above-mentioned pre-grinding is utilized into fluid pressure type automatic tableting press, with the pressure of 10MPa, pressure maintaining 100s is pressed into
The disk of 80 × 10mm of Φ is several, and the disk of compression moulding is utilized cold isostatic press, with the pressure of 250MPa, pressure maintaining 30min,
Further it is compacted sample.
The circular disc test specimen being pressed into is placed in oxidation zirconium crucible, crucible cover is covered, is placed in high temperature sintering furnace, is arranged
3 DEG C/min of heating rate is warming up to 1400 DEG C of heat preservation 1h, then with the heating rate of 5 DEG C/min, is warming up to 1550 DEG C of heat preservations
10h cools to room temperature with the furnace later, obtains being pre-sintered sample.
Above-mentioned pre-sintering sample is crushed, and is roughly ground with agate mortar, utilizes high-performance sand grinder later, with
Dehydrated alcohol is medium, and revolving speed 3000r/min is sanded 4h, then the slurry after sand milling is transferred in evaporating dish, is placed in anti-
In quick-fried thermostatic drying chamber, 200 DEG C of drying are sieved after agate mortar is roughly ground, obtain nanoscale mixed powder.
By above-mentioned mixed powder, using fluid pressure type automatic tableting press, at 8MPa, pressure maintaining 100s is pressed into 16 × 2mm of Φ
Circular disc test specimen, and the disk obtained after compacting is utilized into cold isostatic press, with 200MPa pressure, pressure maintaining 30min is further pressed
It is real.
The sample of compression moulding is placed in oxidation zirconium crucible, crucible cover is covered, is placed in high temperature sintering furnace, setting rises
Warm 3 DEG C/min of speed is warming up to 1500 DEG C, keeps the temperature 2h, then with the heating rate of 5 DEG C/min, is warming up to 1600 DEG C, heat preservation
10h cools to room temperature with the furnace later, obtains the Al with higher-density1.99Sm0.01O3-α Proton conducting solid electrolyte material
Material.Using the bulk density for 3 groups of samples that Archimedes method measurement technique according to embodiment 3 is prepared, then divide
Not divided by its theoretical density, the relative density that each sample is calculated is as shown in Figure 6.
Embodiment 4
The pure Al of analysis of certain mass is weighed roughly2O3And Dy2O3, it is respectively placed in clean oxidation zirconium crucible, covers earthenware
Crucible lid, is put into Muffle furnace, and 5 DEG C/min of heating rate is arranged, 5h is dried at 800 DEG C, dries drug.
It is Al according to molar ratio2O3: Dy2O3The ratio of=1.985:0.015 takes the powder of suitable above-mentioned drying respectively
Body loads in mixture in ball grinder, and a certain amount of dehydrated alcohol is added, and is modulated into the slurry that solid content is 20-30 wt %, uses
Aluminum oxide abrading-ball, ball material mass ratio are 2:1, and the mass ratio of big ball, middle ball and bead takes 3:4:3, using planetary ball mill,
Setting revolving speed is 450r/min, and slurry is transferred to evaporating dish later, is placed in explosion-proof constant temperature oven and dries at 200 DEG C by ball milling 36h
Blocky powder is obtained after dry, after agate mortar is roughly ground, is sieved using 200 the polished standard screens, obtains pre-grinding powder.
Powder after above-mentioned pre-grinding is utilized into fluid pressure type automatic tableting press, with the pressure of 11MPa, pressure maintaining 100s is pressed into
The disk of 80 × 10mm of Φ is several, and the disk of compression moulding is utilized cold isostatic press, with the pressure of 250MPa, pressure maintaining 20min,
Further it is compacted sample.
The circular disc test specimen being pressed into is placed in oxidation zirconium crucible, crucible cover is covered, is placed in high temperature sintering furnace, is arranged
3 DEG C/min of heating rate is warming up to 1400 DEG C of heat preservation 2h, then with the heating rate of 5 DEG C/min, is warming up to 1550 DEG C of heat preservations
15h cools to room temperature with the furnace later, obtains being pre-sintered sample.
Above-mentioned pre-sintering sample is crushed, and is roughly ground with agate mortar, utilizes high-performance sand grinder later, with
Dehydrated alcohol is medium, and revolving speed 3000r/min is sanded 3h, then the slurry after sand milling is transferred in evaporating dish, is placed in anti-
In quick-fried thermostatic drying chamber, 200 DEG C of drying are sieved after agate mortar is roughly ground, obtain nanoscale mixed powder.
By above-mentioned mixed powder, using fluid pressure type automatic tableting press, at 9MPa, pressure maintaining 100s is pressed into 16 × 2mm of Φ
Circular disc test specimen, and the disk obtained after compacting is utilized into cold isostatic press, with 200MPa pressure, pressure maintaining 20min is further compacted
Sample.
The sample of compression moulding is placed in oxidation zirconium crucible, crucible cover is covered, is placed in high temperature sintering furnace, setting rises
Warm 3 DEG C/min of speed is warming up to 1550 DEG C, keeps the temperature 2h, then with the heating rate of 5 DEG C/min, is warming up to 1650 DEG C, heat preservation
20h cools to room temperature with the furnace later, obtains the Al with higher-density1.985Dy0.015O3-α Proton conducting solid electrolyte material
Material.It will be polished flat according to circular disc test specimen surface prepared by embodiment 4 using sand paper, external coating platinum slurry and drying and roasting
Burning processing, said sample is placed in high temperature test furnace, certain temperature is warming up to, and is passed through certain atmosphere into furnace, is utilized
Electrochemical workstation surveys its ac impedance spectroscopy, then the resistance of sample is obtained using certain Equivalent Circuit Fitting, then by trying
It is as shown in Figure 4 that its conductivity is calculated in the data such as the thickness and diameter of sample.
Embodiment 5
The pure Al of analysis of certain mass is weighed roughly2O3And Er2O3, it is respectively placed in clean oxidation zirconium crucible, covers earthenware
Crucible lid, is put into Muffle furnace, and 5 DEG C/min of heating rate is arranged, 4h is dried at 900 DEG C, dries drug.
It is Al according to molar ratio2O3: Er2O3The ratio of=1.95:0.05 takes the powder of suitable above-mentioned drying respectively,
It loads in mixture in ball grinder, a certain amount of dehydrated alcohol is added, the slurry that solid content is 20-30 wt % is modulated into, using oxidation
Aluminum abrading-ball, ball material mass ratio are 2:1, and the mass ratio of big ball, middle ball and bead takes 3:4:3, using planetary ball mill, setting
Revolving speed is 450r/min, and slurry for 24 hours, is transferred to evaporating dish later by ball milling, is placed in explosion-proof constant temperature oven after drying at 200 DEG C
Blocky powder is obtained, after agate mortar is ground, is sieved using 200 the polished standard screens, obtains pre-grinding powder.
Powder after above-mentioned pre-grinding is utilized into fluid pressure type automatic tableting press, with the pressure of 12MPa, pressure maintaining 100s is pressed into
The disk of 80 × 10mm of Φ is several, and the disk of compression moulding is utilized cold isostatic press, with the pressure of 250MPa, pressure maintaining 10min,
Further it is compacted sample.
The circular disc test specimen being pressed into is placed in oxidation zirconium crucible, crucible cover is covered, is placed in high temperature sintering furnace, is arranged
3 DEG C/min of heating rate is warming up to 1400 DEG C of heat preservation 3h, then with the heating rate of 5 DEG C/min, is warming up to 1500 DEG C of heat preservations
20h cools to room temperature with the furnace later, obtains being pre-sintered sample.
Above-mentioned pre-sintering sample is crushed, and is roughly ground with agate mortar, utilizes high-performance sand grinder later, with
Dehydrated alcohol is medium, and revolving speed 3000r/min is sanded 5h, then the slurry after sand milling is transferred in evaporating dish, is placed in anti-
In quick-fried thermostatic drying chamber, 200 DEG C of drying are sieved after agate mortar is roughly ground, obtain nanoscale mixed powder.
By above-mentioned mixed powder, using fluid pressure type automatic tableting press, at 10MPa, pressure maintaining 100s, be pressed into Φ 16 ×
2mm circular disc test specimen, and the disk obtained after compacting is utilized into cold isostatic press, with 200MPa pressure, pressure maintaining 10min, further
It is compacted sample.
The sample of compression moulding is placed in oxidation zirconium crucible, crucible cover is covered, is placed in high temperature sintering furnace, setting rises
Warm 3 DEG C/min of speed is warming up to 1550 DEG C, keeps the temperature 3h, then with the heating rate of 5 DEG C/min, is warming up to 1600 DEG C, heat preservation
15h cools to room temperature with the furnace later, obtains the Al with higher-density1.95Er0.05O3-α Proton conducting solid electrolyte material
Material.
The embodiment of the present invention is illustrated above, but the present invention is not limited to the above embodiments, it can also basis
The purpose of innovation and creation of the invention makes a variety of variations, does under the Spirit Essence and principle of all technical solutions according to the present invention
Changes, modifications, substitutions, combinations, simplifications should be equivalent substitute mode, as long as meeting goal of the invention of the invention, as long as not
Away from technical principle and inventive concept of the invention, protection scope of the present invention is belonged to.
Claims (4)
1. a kind of preparation method of proton conducting solid electrolyte, the proton conducting solid electrolyte, with rare earth oxide
RE2O3For dopant, Al2O3For matrix, chemical composition is expressed as Al2-x RE x O3-α , whereinx= 0.001 -0.05；Its feature exists
In including the following steps:
1) baking material weighs a certain amount of analytically pure Al2O3With rare earth oxide RE2O3, it is respectively placed in oxidation zirconium crucible with cover
Moisture that is interior, being put into Muffle furnace in drying material；
2) ingredient, the raw material that will be dried in step 1), according to the proton conducting solid electrolyte Al to be synthesized2-x RE x O3-α Group
At weighing and appropriate carry out ingredient；
3) raw material load weighted in step 2 is mixed and is packed into ball grinder by pre-grinding, using dehydrated alcohol as medium, carries out ball milling,
The mixed powder of 200 mesh is obtained through dry and sieving；
4) preforming, by mixed powder obtained in step 3) using fluid pressure type automatic tableting press with the pressure of 8-12MPa, pressure maintaining
60s -100s is pressed into disk, and utilizes cold equal press with the pressure of 200-300MPa, and pressure maintaining 10-50min is further compacted；
5) it is pre-sintered, is carried out in normal pressure and air atmosphere, by the circular disc test specimen suppressed in step 4) at 1200-1400 DEG C
Lower heat preservation 1-3h then heats to 1450-1550 DEG C of heat preservation 10-20h and is pre-sintered；
6) it is crushed, the circular disc test specimen being pre-sintered in step 5) is crushed, prevents introducing other impurities in shattering process；
7) it grinds, raw material broken in step 6) is roughly ground using agate mortar, and use high-performance sand grinder, with nothing eventually
Water-ethanol is that medium is sanded, and drying obtains nanoscale mixed powder；
8) nanometer grade powder obtained in step 7) is utilized fluid pressure type automatic tableting press at 6-10MPa by final shaping unit again, is protected
Pressure 60-100s is pressed into disk, and using cold isostatic press with 200-300MPa pressure, pressure maintaining 10-50min is further compacted；
9) sintering eventually, carries out in normal pressure and air atmosphere, the circular disc test specimen suppressed in step 8) is placed in high temperature sintering furnace
Interior, 1400-1550 DEG C of heat preservation 2-4h then heats to 1600 DEG C -1650 DEG C, keeps the temperature 10-20h, cools to room with the furnace later
Temperature obtains proton conducting solid electrolyte.
2. preparation method according to claim 1, which is characterized in that in step 1), the baking material temperature schedule of use are as follows: rise
3-8 DEG C of warm speed/min keeps the temperature 4-8h at a temperature of 500-900 DEG C, furnace cooling later.
3. preparation method according to claim 1, which is characterized in that in step 3), the ball milling parameter of pre-grinding powder are as follows: nothing
Water-ethanol additional amount is 70-80wt%, and ball material mass ratio is 2:1, big ball, middle ball and pellet quality ratio 3:4:3, revolving speed 200-
500r/min, ball milling 24-96h.
4. preparation method according to claim 1, which is characterized in that in step 7), parameter is sanded are as follows: revolving speed 2000-
3-6h is sanded in 3000r/min.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085317A (en) * | 1992-09-30 | 1994-04-13 | 北京科技大学 | Proton conducting solid electrolyte solid-phase reference electrode hydrogen test probe |
| CN101215644A (en) * | 2007-12-27 | 2008-07-09 | 东北大学 | Dehydrogenation method for aluminum or aluminum alloy fused mass by using solid-state proton conductor and device thereof |
| JP2010038600A (en) * | 2008-08-01 | 2010-02-18 | Nippon Soken Inc | Gas sensor element |
| CN104446455A (en) * | 2014-11-03 | 2015-03-25 | 胡永刚 | Oxygen analysis probe solid electrolyte under high-temperature and low-oxygen condition and preparation method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070026285A1 (en) * | 2005-07-28 | 2007-02-01 | Wang Da Y | Proton conducting solid oxide electrolytes, electrochemical cells utilizing the proton conducting materials and methods of making the same |
-
2016
- 2016-05-27 CN CN201610367363.8A patent/CN106045482B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085317A (en) * | 1992-09-30 | 1994-04-13 | 北京科技大学 | Proton conducting solid electrolyte solid-phase reference electrode hydrogen test probe |
| CN101215644A (en) * | 2007-12-27 | 2008-07-09 | 东北大学 | Dehydrogenation method for aluminum or aluminum alloy fused mass by using solid-state proton conductor and device thereof |
| JP2010038600A (en) * | 2008-08-01 | 2010-02-18 | Nippon Soken Inc | Gas sensor element |
| CN104446455A (en) * | 2014-11-03 | 2015-03-25 | 胡永刚 | Oxygen analysis probe solid electrolyte under high-temperature and low-oxygen condition and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 包金小 等."金属液电解质制备及性能研究".《材料导报》.2015,第29卷(第10期), |
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