CN104291813A - Method for preparing and forming solid electrolyte tube for hydrogen detection - Google Patents
Method for preparing and forming solid electrolyte tube for hydrogen detection Download PDFInfo
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- CN104291813A CN104291813A CN201410488165.8A CN201410488165A CN104291813A CN 104291813 A CN104291813 A CN 104291813A CN 201410488165 A CN201410488165 A CN 201410488165A CN 104291813 A CN104291813 A CN 104291813A
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Abstract
The invention discloses a method for preparing and forming a solid electrolyte tube for hydrogen detection. The method comprises the steps of: weighing the raw materials CaCO3, ZrO2 and In2O3 according to a molar ratio of CaCO3 to ZrO2 to In2O3 being 1 to (0.8-0.95) to (0.025-0.1), wet-grinding the raw materials, pressing the mixed powder into a wafer with a diameter of 20-30 mm and a thickness of 2-5 mm, calcining the wafer at 1000-1400 DEG C to obtain CaZr1-xInxO3-alpha (0.05 =< x <= 0.2, atomic ratio), then crushing the wafer into powder, adding the powder into a fused mixture of paraffin wax, oleic acid and beeswax, stirring by using an electromagnetic stirrer, forming the mixture to a tube shape by using a hot pressing injection method, discharging wax at a high temperature, and finally sintering at 1450-1550 DEG C to obtain a CaZr1-xInxO3-alpha (0.05 =< x <= 0.2) electrolyte tube. The electrolyte tube has a smooth surface, a compact structure, high chemical stability and thermal shock resistance, and can be applied to the continuous and accurate measurement of hydrogen content in fused masses of aluminum, magnesium alloys under a variable temperature environment.
Description
Technical field
The invention belongs to metallurgical quality detection field, relate to a kind of Al alloys andMg alloys liquation hydrogen sensor technology, be specifically related to preparation and the manufacturing process of wherein solid electrolyte tube.
Background technology
In the process of aluminium alloy, magnesium alloy smelting, the reaction of moisture of melt easily and in furnace gas and burner hearth refractory materials and inhale hydrogen.When Al alloys andMg alloys melt solidifying, a large amount of hydrogen is separated out with molecular form, makes foundry goods produce the defect such as pin hole, Micro shrinkage.Along with the consumption of Al alloys andMg alloys and the expanding day of range of application, people more and more pay close attention to for the measuring method of alloy melt hydrogen content, wish that the Accurate Determining of realization to Al alloys andMg alloys melt hydrogen richness is with Instructing manufacture.Current reality widely applies to the survey hydrogen methods (as first bubble method, Telegas method etc.) on producing to have length detection time, cannot realize the shortcomings such as on-line continuous measurement.Concentration cell method, as a kind of survey hydrogen methods newly, greatly overcomes these shortcomings, and this survey hydrogen methods almost can at the hydrogen richness of instantaneous measurement melt, therefore can realize online, continuous precision and measure.
Concentration cell method utilizes solid electrolyte that aluminium liquid to be measured and the material with constant hydrogen dividing potential drop are formed concentration cell, records electromotive force and the temperature of battery, obtained the hydrogen content in aluminium liquid by Nernst (this spy of energy) Solving Equations.Solid electrolyte is the key component of concentration cell method, and its specific conductivity, the quality of transference number of ions to concentration cell have material impact.Current solid electrolyte has sheet, cylindric and tubulose three kinds of structures, and wherein the solid electrolyte of tubular structure is the one of current comparative maturity, its excellent property and stable.
Domestic invention in concentration cell method hydrogen sensor at present mainly contains, and Chinese patent literature " a kind of reference electrode of hydrogen sensor and preparation method thereof " (publication number CN 1097508A) has invented a kind of yttrium-hydrogen system alloy that adopts as the solid electrolyte of hydrogen sensing reference electrode.This sensor adopts 1% hydrogen standard gas to carry as the sensor of reference electrode relative to Japan, it is convenient to change, and cost is lower.Chinese patent " a kind of method and device measuring hydrogen pressure in solid steel " (notification number CN101661016A) has invented one with BaCe
0.85 ~ 0.9y
0.1 ~ 0.15o
3-ɑor Ba
3ca
1.18nb
1.82o
9-δor ZrO
2middle doping Y
2o
3as solid electrolyte, adopt 1% standard hydrogen as the sensor of reference electrode.This sensor has low price, wield feature compared to traditional steel sample vacuum melting survey hydrogen methods of getting.Chinese patent " a kind of hydrogen sensor and method for preparing solid electrolyte " (notification number CN101071119A) has invented one with BaCeO
3doping Y
2o
3as solid electrolyte, make a kind of hydrogen sensor of reference electrode with yttrium-hydrogen alloy.It is high that this sensor has precision, and cost is low, easy to carry, the feature of easy handling.
The research of concentration cell hydrogen sensor in recent years achieves huge progress, but it is little to be applied in industrial environment at present.Domestic beginning in concentration cell hydrogen sensor develops SrCeO
3base and BaCeO
3the proton conductor of base and CaZrO
3base and BaZrO
3the proton conductor of base is the hydrogen sensor of solid electrolyte, although wherein SrCeO
3base and BaCeO
3the proton conductor of base is relative to CaZrO
3base and BaZrO
3the specific conductivity height point of the proton conductor of base, but chemical stability and physical strength lower, therefore actual production CaZrO
3base and BaZrO
3the proton conductor of base is better as the hydrogen sensor of solid electrolyte.Be applied to the CaZrO in experiment at present
3base and BaZrO
3the electrolytic tube of base all can not realize carrying out continuous print mensuration under varying temperature environment, and many and unrealized commercialization, be badly in need of the preparation method optimizing solid electrolyte tube material, and electrolyte is configured as part for the manufacture of sensor, for the measurement carrying out melt hydrogen content under alternating temperature.
Summary of the invention
The object of the invention is for above-mentioned present situation, aim to provide a kind of easy synthesis, be convenient to the preparation method of solid electrolyte tube that is shaped and manufacturing process.
To achieve these goals, the present invention includes the preparation of solid electrolyte material and shaping two part of solid electrolyte tube;
The preparation method of described solid electrolyte material comprises the steps:
(1.1) batch mixing:
By CaCO
3, ZrO
2and In
2o
3according to mol ratio be: CaCO
3: ZrO
2: In
2o
3wet ball grinding is carried out in=1:0.8 ~ 0.95:0.025 ~ 0.1, replaces ball milling 8 ~ 24 hours, ball milling post-drying with the speed rotating of 200 ~ 300r/min interval, then is sieved by the powder after drying, and obtains the mixed powder that granularity is less than 5 μm;
(1.2) solid phase synthesis:
Mixed powder after sieve powder is poured in mould, makes disk, the sheet pressed is put into high-temperature calcination stove, under normal pressure, air atmosphere, carry out high temperature solid state reaction synthesis, cool to room temperature with the furnace afterwards;
(1.3) pulverize:
Solid electrolyte sheet after being synthesized by high temperature solid state reaction carries out wet ball grinding after smashing to pieces, post-drying sieving obtain the ionogen powder that granularity is less than 5 μm;
The shaping of described solid electrolyte tube comprises the steps:
(2.1) shaping slurry preparation:
Slurry is mixed with together with the flowable mass that described ionogen powder body material and subsequent heat should be able to be removed;
(2.2) hot-injection molding:
Poured into by slurry in the slurry cylinder of hot-injection molding machine, controlling wax slurry temperature by heating oil bath is 70 ~ 90 DEG C, and in the middle of slurry cylinder with heating oil bath, be full of the liquid medium that conducts heat be beneficial to conduct heat and uniform temperature, controlling grouting port temperature is 40 ~ 50 DEG C; Afterwards mould is placed on hot-injection molding machine riser pipe mouth place, utilizes cylinder-pressing mould, control cylinder pressure is 0.3 ~ 0.5MPa, by pressure, the slurry in slurry cylinder is injected in mould, pressurize took out mould after 5 ~ 15 seconds, by mold releasability, obtained electrolytic tube;
(2.3) de-waxing:
The electrolytic tube of forming is heated de-waxing under normal pressure, air atmosphere, and de-waxing temperature increasing schedule is: room temperature to 100 ~ 150 DEG C, and temperature rise rate is 0.1 ~ 0.3 DEG C/min; 3 ~ 7h is incubated when 100 ~ 150 DEG C; 100 ~ 150 DEG C to 400 ~ 600 DEG C, temperature rise rate is 0.2 ~ 0.5 DEG C/min; 400 ~ 600 DEG C of insulation 1 ~ 3h; 400 ~ 600 DEG C to 950 ~ 1050 DEG C, temperature rise rate is 0.5 ~ 2 DEG C/min; 950 ~ 1050 DEG C of insulation 1 ~ 3h; Cool to room temperature with the furnace;
(2.4) sinter:
By the high temperature sintering under normal pressure, air atmosphere of the electrolytic tube after de-waxing, sintering temperature increasing schedule: room temperature to 900 ~ 1100 DEG C, temperature rise rate is 3 ~ 5 DEG C/min; 900 ~ 1100 DEG C of insulation 1 ~ 2h; 900 ~ 1100 DEG C to 1450 ~ 1550 DEG C, temperature rise rate is 1.5 ~ 2.5 DEG C/min; 1450 ~ 1550 DEG C of insulation 5 ~ 15h; Cool to room temperature with the furnace, finally obtain solid electrolyte tube.
The present invention has following characteristics:
(1) utilize high-temperature solid phase reaction method can obtain perovskite typed proton conductor solid electrolyte, method is simple, and it is high that material is prepared into power.Figure 1 shows that the X ray diffracting spectrum of high―temperature nuclei material, obtain the CaZr that purity is high
1-xin
xo
3-α(0.05≤x≤0.2, atomic ratio), is reacted into power close to a hundred per cent.
(2) the present invention adopts In doping CaZrO
3matrix is as proton conductor, and this material is substantially all pure proton conductor in use temperature scope (700 ~ 850 DEG C), its chemical stability and thermal shock resistance relatively good, can be used for manufacturing electrochemical measurement of hydrogen sensor element.
(3) in shaping slurry set-up procedure, adopt induction stirring (or mechanical stirring, or vacuum electromagnetic stirs, or vacuum machine stirs), obtain high CaZr
1-xin
xo
3-αthe slurry of (0.05≤x≤0.2) powder ratio, the electrolytic tube biscuit follow-up de-waxing time that of being shaped is short, and easily emptying.
(4) adopt the CaZr that hot-injection molding method obtains
1-xin
xo
3-αthe compact structure of (0.05≤x≤0.2) solid electrolyte body, tube wall is smooth.Figure 2 shows that and utilize present method to be shaped and CaZr after sintering
1-xin
xo
3-α(0.05≤x≤0.2) solid electrolyte tube.For the vitrified pipe (as shown in Figure 2) that one end open, one end are closed, the external diameter 5 ~ 10mm of pipe, internal diameter 3 ~ 8mm, length of tube is 15 ~ 30mm.
(5) the CaZr that obtains of the present invention
1-xin
xo
3-αthe density of (0.05≤x≤0.2) solid electrolyte tube is high, and chemical stability and thermal shock resistance by force, have certain mechanical property, can meet the hydrogen richness in continuous measuring high-temperature melt under varying temperature environment.
Accompanying drawing explanation
Fig. 1 is the CaZr of 1400 DEG C of solid state reaction kinetics
1-xin
xo
3-αthe XRD figure of (0.05≤x≤0.2);
Fig. 2 is the CaZr that the present invention is shaped
1-xin
xo
3-α(0.05≤x≤0.2) solid electrolyte tube;
Fig. 3 is that hot pressing forms shape schematic diagram;
In figure: 1-heater strip; 2-riser pipe; 3-slurry; 4-cylinder; 5-mould; 6-slurry cylinder; 7-heating oil bath; 8-water.
Embodiment
First the present invention is prepared by high-temperature solid phase reaction method and surveys hydrogen solid electrolyte material---the CaZrO of In doping
3, i.e. CaZr
1-xin
xo
3-α(0.05≤x≤0.2), wherein relates to starting material and selects and proportioning, and solid state reaction calcining process; Then utilize hot-injection molding method figuration manufacture to go out solid electrolyte tube, wherein relate to the Controlling principle of the forming parameters such as slurry preparation, forming temperature, compacting pressure; The body de-waxing finally being shaped also sinters out CaZr
1-xin
xo
3-α(0.05≤x≤0.2) solid electrolyte tube, wherein relates to de-waxing temperature increasing schedule and sintering temperature increasing schedule.
The inventive method comprises the preparation of solid electrolyte material and shaping two part of solid electrolyte tube, is described as follows:
1, the preparation method of solid electrolyte material
Raw material adopts CaCO
3, ZrO
2, In
2o
3powder, proportioning raw materials is:
According to mol ratio: CaCO
3: ZrO
2: In
2o
3=1:0.8 ~ 0.95:0.025 ~ 0.1
Material preparation process step is as follows.
(1.1) batch mixing
By CaCO
3, ZrO
2and In
2o
3ball grinder is put into according to proportioning raw materials, add appropriate dehydrated alcohol or acetone, wet ball grinding in ball mill, with the speed rotating of 200 ~ 300r/min interval alternately ball milling, each ball milling intermittent time is 10 ~ 30 minutes accumulative ball millings 8 ~ 24 hours, sieve after powder after ball milling is dried, obtain mixed powder granularity and be less than 5 μm.
(1.2) high temperature process heat
After sieving, mixed powder uses hydropress tabletted in a mold, is calcined by the sheet pressed under normal pressure, air atmosphere.Calcining temperature increasing schedule: room temperature to 700 ~ 900 DEG C, temperature rise rate is 5 ~ 10 DEG C/min; 700 ~ 900 DEG C of insulation 0.5 ~ 2h; 700 ~ 900 DEG C to 1000 ~ 1400 DEG C, temperature rise rate is 1.5 ~ 5 DEG C/min; 1000 ~ 1400 DEG C of insulation 5 ~ 15h; Cool to room temperature with the furnace.
Mixed powder disk diameter can be 20 ~ 30mm, and thickness can be 2 ~ 5mm.
(1.3) dispersion and fining
The CaZr obtained by high temperature solid state reaction
1-xin
xo
3-α(0.05≤x≤0.2) lamellar body is put into ball mill and is added appropriate dehydrated alcohol or acetone wet ball grinding after smashing to pieces.Ball milling code: with the speed rotating of 200 ~ 300r/min interval alternately ball milling, each ball milling intermittent time is 10 ~ 30 minutes, accumulative ball milling 8 ~ 24 hours.Dry after sieving and obtain the CaZr that granularity is 1 ~ 5 μm
1-xin
xo
3-α(0.05≤x≤0.2) powder.
2, the manufacturing process of solid electrolyte tube
(2.1) shaping slurry preparation
Go out electrolytic tube for ease of electrolyte powder body heat injection-compression molding, above-mentioned ionogen powder body material is mixed with slurry together with flowable mass (subsequent heat should be removed).Flowable mass selects paraffin, beeswax and oleic acid.
The concrete quality ratio of powder, paraffin, beeswax and oleic acid is as follows:
Powder: paraffin: beeswax: oleic acid
80～95％：16～4％：3.0～0.5％：1.0～0.1％
Paraffin and beeswax are heated to melt completely in 70 ~ 90 DEG C of waters bath with thermostatic control (or constant temperature oil bath), stir with glass stick after then adding oleic acid, after paraffin, beeswax and oleic acid mix, add CaZr
1-xin
xo
3-α(0.05≤x≤0.2) powder, makes CaZr
1-xin
xo
3-α(0.05≤x≤0.2) powder stirs, and continues afterwards to stir to remove gas in slurry, and regulates slurry viscosity.
As preferred mode, a certain amount of paraffin and beeswax can be taken put into flask and be heated to melt completely 70 ~ 90 DEG C of waters bath with thermostatic control (or constant temperature oil bath), then stir with glass stick after adding a certain amount of oleic acid, after oleic acid mixes, add CaZr several times
1-xin
xo
3-α(0.05≤x≤0.2) powder, makes CaZr
1-xin
xo
3-α(0.05≤x≤0.2) powder stirs, and adds a small amount of oleic acid, paraffin and beeswax again to improve slurry viscosity after powder adds, and stirs abundant degasification in 2-7 days afterwards and makes slurry full and uniform.
(2.2) hot-injection molding
Utilize hot-injection molding machine to carry out hot-injection molding, control slurry temperature 70 ~ 90 DEG C, grouting port temperature 40 ~ 50 DEG C, forming pressure 0.3 ~ 0.5MPa, dwell time 10 ~ 20s.Obtained by molding solid electrolyte tube biscuit external diameter is 7-10mm, and internal diameter is 3-6mm, and length is 15-30mm.
(2.3) de-waxing
The body of forming is heated de-waxing under normal pressure, air atmosphere.De-waxing temperature increasing schedule: room temperature to 100 ~ 150 DEG C, temperature rise rate is 0.1 ~ 0.3 DEG C/min; 3 ~ 7h is incubated when 100 ~ 150 DEG C; 100 ~ 150 DEG C to 400 ~ 600 DEG C, temperature rise rate is 0.2 ~ 0.5 DEG C/min; 400 ~ 600 DEG C of insulation 1 ~ 3h; 400 ~ 600 DEG C to 950 ~ 1050 DEG C, temperature rise rate is 0.5 ~ 2 DEG C/min; 950 ~ 1050 DEG C of insulation 1 ~ 3h; Cool to room temperature with the furnace.
(2.4) sinter
By the high temperature sintering under normal pressure, air atmosphere of the body after de-waxing.Sintering temperature increasing schedule: room temperature to 900 ~ 1100 DEG C, temperature rise rate is 3 ~ 5 DEG C/min; 900 ~ 1100 DEG C of insulation 1 ~ 2h; 900 ~ 1100 DEG C to 1450 ~ 1550 DEG C, temperature rise rate is 1.5 ~ 2.5 DEG C/min; 1450 ~ 1550 DEG C of insulation 5 ~ 15h; Cool to room temperature with the furnace, obtain CaZr
1-xin
xo
3-α(0.05≤x≤0.2) ceramiic solid electrolyte pipe.
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described further.It should be noted that at this, the explanation for these embodiments understands the present invention for helping, but does not form limitation of the invention.In addition, if below in described each embodiment of the present invention involved technical characteristic do not form conflict each other and just can mutually combine.
Embodiment 1
Figure 1 shows that detecting proof by X-ray diffraction obtains CaZr
1-xin
xo
3-αthe building-up process of (0.05≤x≤0.2) material is as follows.
Raw material adopts CaCO
3, ZrO
2, In
2o
3, prepare burden by following mol ratio:
CaCO
3：ZrO
2：In
2O
3＝1：0.9：0.05
By CaCO
3, ZrO
2and In
2o
3put into ball grinder according to the above ratio, add appropriate dehydrated alcohol and be used as ball-milling medium, in ball mill, carry out wet ball grinding, with the speed rotating of 250r/min interval alternately ball milling, each ball milling intermittent time is 25 minutes accumulative ball millings 16 hours.Powder after ball milling is dried and sieves.Mixed powder hydropress after sieve is made diameter 25mm, and thickness is the disk of 3mm, disk is put into high-temperature calcination stove, calcines under normal pressure, air atmosphere.Calcining temperature increasing schedule: room temperature to 800 DEG C, temperature rise rate is 5 DEG C/min; 800 DEG C of insulation 2h; 800 DEG C to 1400 DEG C, temperature rise rate is 3 DEG C/min; 1400 DEG C of insulation 10h; Cool to room temperature with the furnace.Figure 1 shows that the XRD figure of high―temperature nuclei material, show to obtain the high CaZr of purity
1-xin
xo
3-α(0.05≤x≤0.2).
The CaZr obtained by high temperature solid state reaction
1-xin
xo
3-α(0.05≤x≤0.2) lamellar body is put into ball mill and is added appropriate dehydrated alcohol wet ball grinding after smashing to pieces.Ball milling code: with the speed rotating of 250r/min interval alternately ball milling, each ball milling intermittent time is 20 minutes, accumulative ball milling 16 hours.Oven dry obtains the CaZr that granularity is less than 5 μm after sieving
1-xin
xo
3-α(0.05≤x≤0.2) powder.
By the CaZr of gained
1-xin
xo
3-α(0.05≤x≤0.2) powder is prepared for hot-injection molding slurry according to the ratio of following powder, paraffin, beeswax and oleic acid:
Powder: paraffin: beeswax: oleic acid
85％：12％：2.9％：0.1％
Detailed process is: take a certain amount of paraffin and beeswax and put into flask and be heated to melt completely in constant temperature 80 DEG C of water-baths, then add a certain amount of oleic acid and stir with glass stick, after oleic acid mixes, adding CaZr several times
1-xin
xo
3-α(0.05≤x≤0.2) powder, adds remaining oleic acid, paraffin and beeswax again to improve slurry viscosity after powder adds, and carrys out degasification afterwards and make slurry full and uniform with the stirring that induction stirring is carried out 7 days.
The slurry be stirred is put into hot-injection molding machine, as shown in Figure 3, the slurry 3 be stirred is poured in the slurry cylinder 6 of hot-injection molding machine, controlling wax slurry temperature by heating oil bath 7 is 70 DEG C, in the middle of slurry cylinder 6 with heating oil bath 7, be full of water 8 be beneficial to conduct heat and uniform temperature, controlling grouting port temperature by heater strip 1 is 45 DEG C.Mould 5 is placed on hot-injection molding machine riser pipe 2 mouthfuls place afterwards, utilize cylinder 4 compaction mold 5, control cylinder pressure is 0.4MPa, by pressure, the slurry 3 in slurry cylinder is injected in mould 5 by riser pipe 2, takes out mould 5 after pressurize 15s, the demoulding, obtain one end open, one end close solid electrolyte tube biscuit, the external diameter of pipe is 8mm, and internal diameter is 5mm, and length is 20mm.
The body of forming is heated de-waxing under normal pressure, air atmosphere.De-waxing temperature increasing schedule: room temperature to 120 DEG C, temperature rise rate is 0.2 DEG C/min; 5h is incubated when 120 DEG C; 120 DEG C to 500 DEG C, temperature rise rate is 0.3 DEG C/min; 500 DEG C of insulation 2h; 500 DEG C to 1000 DEG C, temperature rise rate is 1 DEG C/min; 1000 DEG C of insulation 2h; Cool to room temperature with the furnace.
Body after de-waxing is put into high temperature sintering furnace, high temperature sintering under normal pressure, air atmosphere.Sintering temperature increasing schedule is: room temperature to 1000 DEG C, and temperature rise rate is 4 DEG C/min; 1000 DEG C of insulation 1.5h; 1000 DEG C to 1500 DEG C, temperature rise rate is 2 DEG C/min; 1500 DEG C of insulation 10h; Naturally room temperature is cooled to the furnace.Finally obtain CaZr
1-xin
xo
3-α(0.05≤x≤0.2) ceramiic solid electrolyte pipe.
Embodiment 2
Raw material adopts CaCO
3, ZrO
2, In
2o
3, prepare burden by following mol ratio:
CaCO
3：ZrO
2：In
2O
3＝1：0.8：0.1
By CaCO
3, ZrO
2and In
2o
3put into ball grinder according to the above ratio, add appropriate dehydrated alcohol and be used as ball-milling medium, in ball mill, carry out wet ball grinding, with the speed rotating of 200r/min interval alternately ball milling, each ball milling intermittent time is 10 minutes accumulative ball millings 8 hours.Powder after ball milling is dried and sieves.Mixed powder hydropress after sieve is made diameter 30mm, and thickness is the disk of 2mm, disk is put into high-temperature calcination stove, calcines under normal pressure, air atmosphere.Calcining temperature increasing schedule: room temperature to 700 DEG C, temperature rise rate is 10 DEG C/min; 700 DEG C of insulation 0.5h; 700 DEG C to 1000 DEG C, temperature rise rate is 1.5 DEG C/min; 1000 DEG C of insulation 15h; Cool to room temperature with the furnace.
The CaZr obtained by high temperature solid state reaction
1-xin
xo
3-α(0.05≤x≤0.2) lamellar body is put into ball mill and is added appropriate dehydrated alcohol wet ball grinding after smashing to pieces.Ball milling code: with the speed rotating of 200r/min interval alternately ball milling, each ball milling intermittent time is 10 minutes, accumulative ball milling 8 hours.Oven dry obtains the CaZr that granularity is less than 5 μm after sieving
1-xin
xo
3-α(0.05≤x≤0.2) powder.
By the CaZr of gained
1-xin
xo
3-α(0.05≤x≤0.2) powder is prepared for hot-injection molding slurry according to the ratio of following powder, paraffin, beeswax and oleic acid:
Powder: paraffin: beeswax: oleic acid
80％：16％：3％：1％
Detailed process is: take a certain amount of paraffin and beeswax and put into flask and be heated to melt completely in constant temperature 70 DEG C of water-baths, then add a certain amount of oleic acid and stir with glass stick, after oleic acid mixes, adding CaZr several times
1-xin
xo
3-α(0.05≤x≤0.2) powder, adds remaining oleic acid, paraffin and beeswax again to improve slurry viscosity after powder adds, and stirs the stirring carried out 2 days afterwards carry out degasification and make slurry full and uniform with vacuum electromagnetic.
The slurry be stirred is put into hot-injection molding machine, as shown in Figure 3, the slurry 3 be stirred is poured in the slurry cylinder 6 of hot-injection molding machine, controlling wax slurry temperature by heating oil bath 7 is 70 DEG C, in the middle of slurry cylinder 6 with heating oil bath 7, be full of water 8 be beneficial to conduct heat and uniform temperature, controlling grouting port temperature by heater strip 1 is 40 DEG C.Mould 5 is placed on hot-injection molding machine riser pipe 2 mouthfuls place afterwards, utilize cylinder 4 compaction mold 5, control cylinder pressure is 0.5MPa, by pressure, the slurry 3 in slurry cylinder is injected in mould 5 by riser pipe 2, takes out mould 5 after pressurize 10s, the demoulding, obtain one end open, one end close solid electrolyte tube biscuit, the external diameter of pipe is 5mm, and internal diameter is 3mm, and length is 15mm.
The body of forming is heated de-waxing under normal pressure, air atmosphere.De-waxing temperature increasing schedule: room temperature to 100 DEG C, temperature rise rate is 0.1 DEG C/min; 3h is incubated when 100 DEG C; 100 DEG C to 400 DEG C, temperature rise rate is 0.2 DEG C/min; 400 DEG C of insulation 1h; 400 DEG C to 950 DEG C, temperature rise rate is 0.5 DEG C/min; 950 DEG C of insulation 1h; Cool to room temperature with the furnace.
Body after de-waxing is put into high temperature sintering furnace, high temperature sintering under normal pressure, air atmosphere.Sintering temperature increasing schedule is: room temperature to 900 DEG C, and temperature rise rate is 5 DEG C/min; 900 DEG C of insulation 2h; 900 DEG C to 1450 DEG C, temperature rise rate is 1.5 DEG C/min; 1450 DEG C of insulation 15h; Naturally room temperature is cooled to the furnace.Finally obtain CaZr
1-xin
xo
3-α(0.05≤x≤0.2) ceramiic solid electrolyte pipe.
Embodiment 3
Raw material adopts CaCO
3, ZrO
2, In
2o
3, prepare burden by following mol ratio:
CaCO
3：ZrO
2：In
2O
3＝1：0.95：0.025
By CaCO
3, ZrO
2and In
2o
3put into ball grinder according to the above ratio, add proper amount of acetone and be used as ball-milling medium, in ball mill, carry out wet ball grinding, with the speed rotating of 300r/min interval alternately ball milling, each ball milling intermittent time is 30 minutes accumulative ball millings 24 hours.Powder after ball milling is dried and sieves.Mixed powder hydropress after sieve is made diameter 20mm, and thickness is the disk of 5mm, disk is put into high-temperature calcination stove, calcines under normal pressure, air atmosphere.Calcining temperature increasing schedule: room temperature to 900 DEG C, temperature rise rate is 5 DEG C/min; 900 DEG C of insulation 2h; 900 DEG C to 1400 DEG C, temperature rise rate is 5 DEG C/min; 1400 DEG C of insulation 5h; Cool to room temperature with the furnace.
The CaZr obtained by high temperature solid state reaction
1-xin
xo
3-α(0.05≤x≤0.2) lamellar body is put into ball mill after smashing to pieces and is added proper amount of acetone wet ball grinding.Ball milling code: with the speed rotating of 300r/min interval alternately ball milling, each ball milling intermittent time is 30 minutes, accumulative ball milling 24 hours.Oven dry obtains the CaZr that granularity is less than 5 μm after sieving
1-xin
xo
3-α(0.05≤x≤0.2) powder.
By the CaZr of gained
1-xin
xo
3-α(0.05≤x≤0.2) powder is prepared for hot-injection molding slurry according to the ratio of following powder, paraffin, beeswax and oleic acid:
Powder: paraffin: beeswax: oleic acid
95％：4％：0.5％：0.5％
Detailed process is: take a certain amount of paraffin and beeswax and put into flask and be heated to melt completely in constant temperature 90 DEG C of water-baths, then add a certain amount of oleic acid and stir with glass stick, after oleic acid mixes, adding CaZr several times
1-xin
xo
3-α(0.05≤x≤0.2) powder, adds remaining oleic acid, paraffin and beeswax again to improve slurry viscosity after powder adds, and carrys out degasification afterwards and make slurry full and uniform with the stirring that mechanical stirring is carried out 7 days.
The slurry be stirred is put into hot-injection molding machine, as shown in Figure 3, the slurry 3 be stirred is poured in the slurry cylinder 6 of hot-injection molding machine, controlling wax slurry temperature by heating oil bath 7 is 90 DEG C, in the middle of slurry cylinder 6 with heating oil bath 7, be full of water 8 be beneficial to conduct heat and uniform temperature, controlling grouting port temperature by heater strip 1 is 50 DEG C.Mould 5 is placed on hot-injection molding machine riser pipe 2 mouthfuls place afterwards, utilize cylinder 4 compaction mold 5, control cylinder pressure is 0.3MPa, by pressure, the slurry 3 in slurry cylinder is injected in mould 5 by riser pipe 2, takes out mould 5 after pressurize 5s, the demoulding, obtain one end open, one end close solid electrolyte tube biscuit, the external diameter of pipe is 10mm, and internal diameter is 7mm, and length is 30mm.
The body of forming is heated de-waxing under normal pressure, air atmosphere.De-waxing temperature increasing schedule: room temperature to 150 DEG C, temperature rise rate is 0.3 DEG C/min; 7h is incubated when 150 DEG C; 150 DEG C to 600 DEG C, temperature rise rate is 0.5 DEG C/min; 600 DEG C of insulation 3h; 600 DEG C to 1050 DEG C, temperature rise rate is 2 DEG C/min; 1050 DEG C of insulation 3h; Cool to room temperature with the furnace.
Body after de-waxing is put into high temperature sintering furnace, high temperature sintering under normal pressure, air atmosphere.Sintering temperature increasing schedule is: room temperature to 1100 DEG C, and temperature rise rate is 3 DEG C/min; 1100 DEG C of insulation 1h; 1100 DEG C to 1550 DEG C, temperature rise rate is 2.5 DEG C/min; 1550 DEG C of insulation 5h; Naturally room temperature is cooled to the furnace.Finally obtain CaZr
1-xin
xo
3-α(0.05≤x≤0.2) ceramiic solid electrolyte pipe.
The above is preferred embodiment of the present invention, but the present invention should not be confined to the content disclosed in this embodiment and accompanying drawing.The equivalence completed under not departing from spirit disclosed in this invention so every or amendment, all fall into the scope of protection of the invention.
Claims (10)
1. survey a preparation method for hydrogen solid electrolyte material, the raw material that the method adopts is CaCO
3, ZrO
2and In
2o
3powder, the mol ratio of raw material is: CaCO
3: ZrO
2: In
2o
3=1:0.8 ~ 0.95:0.025 ~ 0.1, step of preparation process is as follows:
(1.1) batch mixing:
By CaCO
3, ZrO
2and In
2o
3proportionally carry out wet ball grinding, replace ball milling 8 ~ 24 hours, ball milling post-drying with the speed rotating of 200 ~ 300r/min interval, then the powder after drying is sieved, obtain the mixed powder that granularity is less than 5 μm;
(1.2) solid phase synthesis:
Mixed powder after sieve powder is poured in mould, makes disk, the sheet pressed is put into high-temperature calcination stove, under normal pressure, air atmosphere, carry out high temperature solid state reaction synthesis, cool to room temperature with the furnace afterwards;
(1.3) pulverize:
Solid electrolyte sheet after being synthesized by high temperature solid state reaction carries out wet ball grinding after smashing to pieces, post-drying sieving obtain the ionogen powder that granularity is less than 5 μm.
2. survey the preparation method of hydrogen solid electrolyte material according to claim 1, it is characterized in that, in step (1.2), the processing parameter of described high temperature solid state reaction is:
First room temperature to 700 ~ 900 DEG C, temperature rise rate is 5 ~ 10 DEG C/min; 700 ~ 900 DEG C of insulation 0.5 ~ 2h again; Then from 700 ~ 900 DEG C to intensification 1000 ~ 1400 DEG C, temperature rise rate is 1.5 ~ 5 DEG C/min, 1000 ~ 1400 DEG C of insulation 5 ~ 15h; Cool to room temperature with the furnace.
3. survey the preparation method of hydrogen solid electrolyte material according to claim 1, it is characterized in that, in step (1.3), the detailed process of wet ball grinding is: put into ball mill after being smashed to pieces by the lamellar body that high temperature solid state reaction is obtained and add appropriate dehydrated alcohol or acetone wet ball grinding, with the speed rotating of 200 ~ 300r/min interval alternately ball milling, each ball milling intermittent time is 10 ~ 30 minutes, accumulative ball milling 8 ~ 24 hours.
4. the solid electrolyte material obtained by preparation method described in claim 1.
5. a manufacturing process for solid electrolyte tube, specifically comprises the steps:
(2.1) shaping slurry preparation:
Slurry is mixed with together with the flowable mass that ionogen powder body material and subsequent heat should be able to be removed;
(2.2) hot-injection molding:
Poured into by slurry in the slurry cylinder of hot-injection molding machine, controlling wax slurry temperature by heating oil bath is 70 ~ 90 DEG C, and in the middle of slurry cylinder with heating oil bath, be full of the liquid medium that conducts heat be beneficial to conduct heat and uniform temperature, controlling grouting port temperature is 40 ~ 50 DEG C; Afterwards mould is placed on hot-injection molding machine riser pipe mouth place, utilizes cylinder-pressing mould, control cylinder pressure is 0.3 ~ 0.5MPa, by pressure, the slurry in slurry cylinder is injected in mould, pressurize took out mould after 5 ~ 15 seconds, by mold releasability, obtained electrolytic tube;
(2.3) de-waxing:
The electrolytic tube of forming is heated de-waxing under normal pressure, air atmosphere, and de-waxing temperature increasing schedule is: room temperature to 100 ~ 150 DEG C, and temperature rise rate is 0.1 ~ 0.3 DEG C/min; 3 ~ 7h is incubated when 100 ~ 150 DEG C; 100 ~ 150 DEG C to 400 ~ 600 DEG C, temperature rise rate is 0.2 ~ 0.5 DEG C/min; 400 ~ 600 DEG C of insulation 1 ~ 3h; 400 ~ 600 DEG C to 950 ~ 1050 DEG C, temperature rise rate is 0.5 ~ 2 DEG C/min; 950 ~ 1050 DEG C of insulation 1 ~ 3h; Cool to room temperature with the furnace;
(2.4) sinter:
By the high temperature sintering under normal pressure, air atmosphere of the electrolytic tube after de-waxing, sintering temperature increasing schedule: room temperature to 900 ~ 1100 DEG C, temperature rise rate is 3 ~ 5 DEG C/min; 900 ~ 1100 DEG C of insulation 1 ~ 2h; 900 ~ 1100 DEG C to 1450 ~ 1550 DEG C, temperature rise rate is 1.5 ~ 2.5 DEG C/min; 1450 ~ 1550 DEG C of insulation 5 ~ 15h; Cool to room temperature with the furnace, finally obtain solid electrolyte tube.
6. a manufacturing process for solid electrolyte tube described in claim 5, is characterized in that, described flowable mass is paraffin, beeswax and oleic acid, and its quality proportioning is:
Powder: paraffin: beeswax: oleic acid
80～95％：16～4％：3.0～0.5％：1.0～0.1％
Part paraffin and part beeswax are heated to melt completely in constant temperature 70 ~ 90 DEG C of water-baths, then add a part of oleic acid and stir, after oleic acid mixes, adding CaZr several times
1-xin
xo
3-αpowder, adding residue oleic acid, paraffin and beeswax again to improve slurry viscosity, afterwards with stirring to remove gas, and obtaining the slurry that mixes after powder adds.
7. a manufacturing process for solid electrolyte tube described in claim 5, is characterized in that, the one end open of the electrolytic tube that (2.2) obtain, one end are closed, the external diameter 7 ~ 10mm of pipe, internal diameter 3 ~ 6mm, and length of tube is 15 ~ 30mm.
8. the preparation of solid electrolyte tube and a manufacturing process, comprise the preparation of solid electrolyte material and shaping two processes of solid electrolyte tube;
The preparation process of described solid electrolyte material comprises the steps:
(1.1) batch mixing:
By CaCO
3, ZrO
2and In
2o
3according to mol ratio be: CaCO
3: ZrO
2: In
2o
3wet ball grinding is carried out in=1:0.8 ~ 0.95:0.025 ~ 0.1, replaces ball milling 8 ~ 24 hours, ball milling post-drying with the speed rotating of 200 ~ 300r/min interval, then is sieved by the powder after drying, and obtains the mixed powder that granularity is less than 5 μm;
(1.2) solid phase synthesis:
Mixed powder after sieve powder is poured in mould, makes disk, the sheet pressed is put into high-temperature calcination stove, under normal pressure, air atmosphere, carry out high temperature solid state reaction synthesis, cool to room temperature with the furnace afterwards;
(1.3) pulverize:
Solid electrolyte sheet after being synthesized by high temperature solid state reaction carries out wet ball grinding after smashing to pieces, post-drying sieving obtain the ionogen powder that granularity is less than 5 μm;
The forming process of described solid electrolyte tube comprises the steps:
(2.1) shaping slurry preparation:
Slurry is mixed with together with the flowable mass that described ionogen powder body material and subsequent heat should be able to be removed;
(2.2) hot-injection molding:
Poured into by slurry in the slurry cylinder of hot-injection molding machine, controlling wax slurry temperature by heating oil bath is 70 ~ 90 DEG C, and in the middle of slurry cylinder with heating oil bath, be full of the liquid medium that conducts heat be beneficial to conduct heat and uniform temperature, controlling grouting port temperature is 40 ~ 50 DEG C; Afterwards mould is placed on hot-injection molding machine riser pipe mouth place, utilizes cylinder-pressing mould, control cylinder pressure is 0.3 ~ 0.5MPa, by pressure, the slurry in slurry cylinder is injected in mould, pressurize took out mould after 5 ~ 15 seconds, by mold releasability, obtained electrolytic tube;
(2.3) de-waxing:
The electrolytic tube of forming is heated de-waxing under normal pressure, air atmosphere, and de-waxing temperature increasing schedule is: room temperature to 100 ~ 150 DEG C, and temperature rise rate is 0.1 ~ 0.3 DEG C/min; 3 ~ 7h is incubated when 100 ~ 150 DEG C; 100 ~ 150 DEG C to 400 ~ 600 DEG C, temperature rise rate is 0.2 ~ 0.5 DEG C/min; 400 ~ 600 DEG C of insulation 1 ~ 3h; 400 ~ 600 DEG C to 950 ~ 1050 DEG C, temperature rise rate is 0.5 ~ 2 DEG C/min; 950 ~ 1050 DEG C of insulation 1 ~ 3h; Cool to room temperature with the furnace;
(2.4) sinter:
By the high temperature sintering under normal pressure, air atmosphere of the electrolytic tube after de-waxing, sintering temperature increasing schedule: room temperature to 900 ~ 1100 DEG C, temperature rise rate is 3 ~ 5 DEG C/min; 900 ~ 1100 DEG C of insulation 1 ~ 2h; 900 ~ 1100 DEG C to 1450 ~ 1550 DEG C, temperature rise rate is 1.5 ~ 2.5 DEG C/min; 1450 ~ 1550 DEG C of insulation 5 ~ 15h; Cool to room temperature with the furnace, finally obtain solid electrolyte tube.
9. preparation according to claim 8 and manufacturing process, it is characterized in that, in step (1.2), the processing parameter of described high temperature solid state reaction is:
First room temperature to 700 ~ 900 DEG C, temperature rise rate is 5 ~ 10 DEG C/min; 700 ~ 900 DEG C of insulation 0.5 ~ 2h again; Then from 700 ~ 900 DEG C to intensification 1000 ~ 1400 DEG C, temperature rise rate is 1.5 ~ 5 DEG C/min, 1000 ~ 1400 DEG C of insulation 5 ~ 15h; Cool to room temperature with the furnace; In step (1.3), the detailed process of wet ball grinding is: put into ball mill after being smashed to pieces by the lamellar body that high temperature solid state reaction is obtained and add appropriate dehydrated alcohol or acetone wet ball grinding, with the speed rotating of 200 ~ 300r/min interval alternately ball milling, each ball milling intermittent time is 10 ~ 30 minutes, accumulative ball milling 8 ~ 24 hours.
10. preparation according to claim 8 or claim 9 and manufacturing process, it is characterized in that, the flowable mass in described step (2.1) is paraffin, beeswax and oleic acid, and its quality proportioning is:
Powder: paraffin: beeswax: oleic acid
80～95％：16～4％：3.0～0.5％：1.0～0.1％
Part paraffin and part beeswax are heated to melt completely in constant temperature 70 ~ 90 DEG C of water-baths, then add a part of oleic acid and stir, after oleic acid mixes, adding CaZr several times
1-xin
xo
3-αpowder, adding residue oleic acid, paraffin and beeswax again to improve slurry viscosity, afterwards with stirring to remove gas, and obtaining the slurry that mixes after powder adds;
The one end open of the electrolytic tube that described step (2.2) obtains, one end are closed, the external diameter 7 ~ 10mm of pipe, internal diameter 3 ~ 6mm, and length of tube is 15 ~ 30mm.
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| CN106045480A (en) * | 2016-05-27 | 2016-10-26 | 内蒙古科技大学 | Method for preparing proton conductive electrolyte of molten metal hydrogen-determining sensor |
| CN106053577A (en) * | 2016-05-17 | 2016-10-26 | 东北大学 | Solid electrolyte for hydrogen probe and preparation method thereof |
| CN107121473A (en) * | 2017-03-31 | 2017-09-01 | 武汉泽科宁电子科技有限公司 | A kind of oxygen sensor ceramic piece and preparation method thereof |
| CN111517783A (en) * | 2020-04-30 | 2020-08-11 | 合肥学院 | Method for preparing calcium carbonate-YSZ composite solid electrolyte by ultrasonic microwave combination method |
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| CN101625336A (en) * | 2009-08-19 | 2010-01-13 | 河北理工大学 | Novel limited current hydrogen sensor and preparation method thereof |
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| CN101655475A (en) * | 2009-07-06 | 2010-02-24 | 河北理工大学 | Laminated limiting current type hydrogen sensor and preparation method thereof |
| CN101625335A (en) * | 2009-08-19 | 2010-01-13 | 河北理工大学 | Thick-film type limited current hydrogen sensor and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106053577A (en) * | 2016-05-17 | 2016-10-26 | 东北大学 | Solid electrolyte for hydrogen probe and preparation method thereof |
| CN106053577B (en) * | 2016-05-17 | 2018-12-28 | 东北大学 | Determine HydroNit sensor solid electrolyte and preparation method |
| CN106045480A (en) * | 2016-05-27 | 2016-10-26 | 内蒙古科技大学 | Method for preparing proton conductive electrolyte of molten metal hydrogen-determining sensor |
| CN106045480B (en) * | 2016-05-27 | 2021-03-16 | 内蒙古科技大学 | Preparation method of proton conductive electrolyte of molten metal hydrogen determination sensor |
| CN107121473A (en) * | 2017-03-31 | 2017-09-01 | 武汉泽科宁电子科技有限公司 | A kind of oxygen sensor ceramic piece and preparation method thereof |
| CN107121473B (en) * | 2017-03-31 | 2020-01-14 | 武汉泽科宁电子科技有限公司 | Oxygen sensor ceramic chip and preparation method thereof |
| CN111517783A (en) * | 2020-04-30 | 2020-08-11 | 合肥学院 | Method for preparing calcium carbonate-YSZ composite solid electrolyte by ultrasonic microwave combination method |
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