CN101661016B - Method for measuring hydrogen pressure in solid steel and device - Google Patents

Abstract

The invention relates to a method for measuring hydrogen pressure in solid steel and a device; the device is composed of a ceramic solid electrolyte pipe, an alundum tube, an air inlet pipe, an electrode lead wire, an air exhaust pipe and a high-resistance digital voltmeter; a sample to be measured is contacted with the close end of the ceramic solid electrolyte pipe, one end of the electrode lead wire is contacted with the sample to be measured, the other end thereof is stretched in the air inlet pipe and is contacted with the inner wall of the ceramic solid electrolyte pipe, the temperature of the sample to be measured can be controlled at 0-50 DEG C or 200-800 DEG C, standard hydrogen passes through the air inlet pipe, the measuring time is controlled for 5-30 minutes, electrodynamic force value is read by the high-resistance digital voltmeter, and then the pressure of the hydrogen to be measured is calculated. The method realizes to measure hydrogen pressure in solid steel at a range of from 0 to 50 DEG C or from 200 to 800 DEG C in an on-line way, so as to find defect sites of solid steel and aluminium alloy in a real-time manner and carry out dehydrogenation in advance.

Description

A kind of method and device of measuring hydrogen pressure in the solid-state steel

Technical field

The invention belongs to solid electrolyte and chemical sensor technical field, be specifically related to the technology that solid ceramic electrolyte sensing method is measured hydrogen pressure in the solid-state steel.

Background technology

Chinese scholar in 1940 is to the steel axle research of rupturing voluntarily of Britain's wrecked aircraft; The fracture that has proved steel is first caused that by hydrogen the accidents such as transgranular fracture, motor vehicle axle fracture and chemical plant cracking of U.S.'s Properties of Heavy Rail Steel By fracture and power station, China Ge Zhou Ba stainless steel blade all are because hydrogen-induced fracture.So-called " white point ", " hairline ", " flake " are all same hydrogen and split reason in various degree reaction under different condition.

Hydrogen in the molten steel is mainly derived from the hydrogen that the water vapor decomposition produces in the smelting process.The vibration frequency of gap hydrogen atom is 10 ¹³/ S has very big random STOCHASTIC DIFFUSION speed.The solubility with temperature of hydrogen in metal reduces and descends.When hydrogen atom moves to the metal inside fault location, the hydrogen atom that falls into defective is combined into hydrogen molecule, is spread to all directions by source point, and motion becomes the cradle of lattice fatigue crack repeatedly.The pressure of molecular hydrogen accumulation often surpasses hundreds of MPa, causes the steel cracking when surpassing the fracture strength of steel.So hydrogen embrittlement is the result who presses combined action in distortion reduction and the fault location height.

Traditional analytical approach of getting hydrogen such as steel appearance vacuum fusion, troublesome poeration, equipment is expensive, and is lag information.There is research (to contain H with the NAFION polymer membrane ⁺Or H ₂O) as solid electrolyte, Fe ²⁺/ Fe ³⁺Sulfate hydrate is measured the hydrogen in the room temperature steel appearance as contrast electrode, has obtained sensing electromotive force and the relation of response time.There is in the recent period report to adopt the hydrogen of a minicollector from steel appearance surface collection steel appearance again, analyzes then, the method trouble.The NAFION polymer membrane costs an arm and a leg, and cannot say for sure to deposit, and is yielding, is inconvenient to use.

Summary of the invention

To the problem that above-mentioned analytical approach exists, the present invention provides a kind of solid ceramic electrolyte sensing method to measure the method for hydrogen pressure in the solid-state steel, reaches the purpose of hydrogen pressure in on-line determination room temperature or the high-temperature solid steel.

The present invention utilizes the solid ceramic electrolyte, the pressure of hydrogen in the solid-state steel of online detection, or the solid-state steel heat treatment process of online detection hydrogen separate out pressure.The inventive method can 0～50 ℃ of temperature range steel of online detection in hydrogen pressure, or the liberation of hydrogen pressure of 200～800 ℃ of steel heat processing procedures of online detection.

Device of the present invention is made up of solid ceramic electrolytic tube, alundum tube, draft tube, contact conductor, gas outlet and high resistant digital voltmeter; Alundum tube one end is connected with solid ceramic electrolytic tube openend, and alundum tube and the socket of solid ceramic electrolytic tube soon also bonds together.Cementing agent is selected commercially available epoxy adhesive commonly used, acrylic resin binder, dried cementing agent of wink (like 502 glue) or high temperature resistant cement etc. for use; Dried cementing agent was selected for use and was solidified getting final product of 0～50 ℃ of temperature of back ability epoxy adhesive, acrylic resin binder or wink, and high temperature resistant cement is selected for use and solidified getting final product of back 200～800 ℃ of temperature of ability.Draft tube is passed the blind end of alundum tube, stretches in the alundum tube and near solid ceramic electrolytic tube bottom interior wall, leaves the slit between draft tube outer wall, end face and solid ceramic electrolytic tube bottom interior wall, and this slit can get final product through standard hydrogen.On the sidewall of alundum tube, gas outlet is set.One end of contact conductor stretches in the draft tube and with solid ceramic electrolytic tube bottom interior wall and contacts, and contact conductor connects high resistant digital voltmeter, high resistant digital voltmeter internal resistance>=10 ⁹Ohm.

The solid ceramic electrolytic tube is the ceramic pipe of an end opening, end sealing, and the diameter of pipe is: external diameter 4～8mm, and pipe thickness is 0.8～1mm, length of tube is 8～16mm.The material of solid ceramic electrolytic tube is BaCe _0.85～0.9Y _0.1～0.15O _3-α, or Ba ₃Ca _1.18Nb _1.82O _9-δ, or ZrO ₂(Y ₂O ₃), i.e. ZrO ₂Middle doping Y ₂O ₃, by mass percentage, Y ₂O ₃Content 8～9%, ZrO ₂Content 91%～92%.

The ZrO that is selected for use ₂(Y ₂O ₃) the solid ceramic electrolytic tube is existing commercially available prod.

The BaCe that is selected for use _0.85～0.9Y _0.1～0.15O _3-αThe preparation method is following for the solid ceramic electrolytic tube.

Raw material adopts BaCO ₃, CeO ₂And Y ₂O ₃, according to molar ratio computing, proportioning raw materials is:

BaCO ₃∶CeO ₂∶Y ₂O ₃＝1∶(0.85～0.9)∶(0.1～0.15)

Processing step is following.

(1) batch mixing

With BaCO ₃, CeO ₂And Y ₂O ₃Putting into the agate jar, adopt bowl mill, is that medium carries out wet ball grinding with the absolute ethyl alcohol, and with 200～500 rev/mins speed ball millings 5～10 hours, air dry then, the granularity of mixed powder reaches 1～2 μ m.

(2) compression moulding

The material that mixes is adopted hydropress, be pressed into the disk that thickness is 10～15mm, diameter 10～20mm with the pressure of 15～20MPa.

(3) solid phase synthesis

The disk that presses is placed the molybdenum disilicide stove, under normal pressure, air atmosphere, be warming up to 1300～1500 ℃, be incubated 8～12 hours, naturally cool to room temperature with 1～3 ℃/minute heating rate.

(4) isostatic compaction

Mixture behind the solid phase synthesis being ground to form the powder that granularity is 1～2 μ m, powder is put into mould, mould is put into the isostatic pressing machine working cylinder, is pressure transmitting medium with static pressure oil, pressure 180～220MPa, and pressurize 1～2 hour is pressed into body.

(5) sintering

With the body that presses, place the molybdenum disilicide stove, under normal pressure, air atmosphere; Be warming up to 900～1100 ℃ with 1～1.5 ℃/minute heating rate; Be incubated 1～3 hour, be warming up to 1500～1600 ℃ with 1～1.5 ℃/minute heating rate again, be incubated 8～12 hours; Naturally cool to room temperature, obtain BaCe _0.85～0.9Y _0.1～0.15O _3-αThe solid ceramic electrolytic tube.

The Ba that is selected for use ₃Ca _1.18Nb _1.82O _9-δThe preparation method is following for the solid ceramic electrolytic tube.

Raw material adopts BaCO ₃, CaCO ₃And Nb ₂O ₅, according to molar ratio computing, proportioning raw materials is:

BaCO ₃∶CaCO ₃∶Nb ₂O ₅＝3∶1.18∶1.82

Processing step is following.

(1) batch mixing

With BaCO ₃, CaCO ₃And Nb ₂O ₅Putting into the agate jar, adopt bowl mill, is that medium carries out wet ball grinding with the absolute ethyl alcohol, and with 200～500 rev/mins speed ball millings 5～10 hours, air dry then, the granularity of mixed powder reaches 1～2 μ m.

(2) compression moulding

The material that mixes is adopted hydropress, be pressed into the disk that thickness is 10～15mm, diameter 10～20mm with the pressure of 15～20MPa.

(3) solid phase synthesis

The disk that presses is placed the molybdenum disilicide stove, under normal pressure, air atmosphere, be warming up to 1300～1500 ℃, be incubated 8～12 hours, naturally cool to room temperature with 1～3 ℃/minute heating rate.

(4) isostatic compaction

Mixture behind the solid phase synthesis being ground to form the powder that granularity is 1～2 μ m, powder is put into mould, mould is put into the isostatic pressing machine working cylinder, is pressure transmitting medium with static pressure oil, pressure 180～220MPa, and pressurize 1～2 hour is pressed into body.

(5) sintering

With the body that presses, place the molybdenum disilicide stove, under normal pressure, air atmosphere; Be warming up to 900～1100 ℃ with 1～1.5 ℃/minute heating rate; Be incubated 1～3 hour, be warming up to 1500～1600 ℃ with 1～1.5 ℃/minute heating rate again, be incubated 8～12 hours; Naturally cool to room temperature, obtain Ba ₃Ca _1.18Nb _1.82O _9-δThe solid ceramic electrolytic tube.

To adopt standard hydrogen be high-purity argon gas (purity >=99.999%) with high-purity hydrogen (purity >=99.999%) mixed gas as contrast electrode, number percent meter by volume, hydrogen 0.5%～2%, argon gas 98%～99.5%.

Contact conductor adopts stainless steel wire, nickel wire, iron wire or copper wire.

When adopting device of the present invention to measure in the solid-state steel hydrogen pressure; The blind end of sample to be tested with the solid ceramic electrolytic tube contacted, an end of contact conductor is contacted (other end of contact conductor has stretched in the draft tube and with solid ceramic electrolytic tube inwall and contacted) with sample to be tested.The thermometric end of thermopair contacts with sample to be tested.

The temperature of control sample to be tested is 0～50 ℃, in draft tube, feeds standard hydrogen, and the flow of control criterion hydrogen is 0.01～0.1Nm ³/ h, pressure are that (hydrogen partial pressure is 500～2000Pa) to normal pressure, 5～30 minutes control survey time, reads the electromotive force value through the high resistant digital voltmeter, the pressure of calculating sample to be tested hydrogen.

Adopt device of the present invention to measure when hydrogen is separated out pressure in the solid-state steel heat treatment process; The solid ceramic electrolytic tube of apparatus of the present invention and the part of alundum tube are placed in the resistance furnace, and the length that is placed on the alundum tube in the resistance furnace is 1/5～4/5 of alundum tube length overall.The blind end of sample to be tested with the solid ceramic electrolytic tube contacted, an end of contact conductor is contacted (other end of contact conductor has stretched in the draft tube and with solid ceramic electrolytic tube inwall and contacted) with sample to be tested.The thermometric end of thermopair contacts with sample to be tested.

The temperature of control sample to be tested is 200～800 ℃, in draft tube, feeds standard hydrogen, and the flow of control criterion hydrogen is 0.01～0.1Nm ³/ h, pressure are that (hydrogen partial pressure is 500～2000Pa) to normal pressure, 5～30 minutes control survey time, reads the electromotive force value through the high resistant digital voltmeter, the pressure of calculating sample to be tested hydrogen.

Computing formula (Nernst equation) is:

$E=\frac{\mathrm{RT}}{2F}\mathrm{Ln}\frac{P_{H_2}^I}{P_{H_2}^{\mathrm{II}}}$

In the formula: E-electromotive force, V;

The R-gas law constant, 8.314J.mol ^-1K ^-1

The F-Faraday constant, 96485C/mol;

T-absolute temperature, K;

is respectively the Hydrogen Vapor Pressure value of contrast electrode and sample to be tested, Pa;

The principle of this method foundation is following.

Apparatus of the present invention and sample to be tested constitute concentration cell, and form is:

(-) utmost point M,

| the solid ceramic electrolyte |

M (+) utmost point (is established $P_{H_2}^I>P_{H_2}^{\mathrm{II}}$ )

Wherein M represents sample to be tested.

Cell reaction is:

(-) utmost point:

(+) utmost point: 2H ⁺(solid ceramic electrolyte)+2e → 2H,

Overall reaction is:

If electromotive force E negative value, expression $P_{H_2}^I<P_{H_2}^{\mathrm{II}},$ Do not influence result of calculation.

According to nernst equation; of known contrast electrode is worth, and can calculate value of sample to be tested.

Use the pressure of hydrogen to characterize hydrogen richness and characterize as substance, the present invention has realized hydrogen pressure in 0～50 ℃ of on-line determination or 200～800 ℃ of temperature range internal solid steel first, can find the defective locations of solid-state steel in real time, carries out dehydrogenation in advance and handles.The solid ceramic electrolyte that is adopted all has certain conductivity (1 * 10 in 0～800 ℃ of scope ^-9～1 * 10 ^-3S.cm ^-1), all can operate as normal in 0～800 ℃ of scope.The solid ceramic electrolyte is a defect sturcture, has catalytic activity, though conductivity is lower in 0～50 ℃ of temperature range, can in this temperature range, measure hydrogen pressure in the solid-state steel.The inventive method is equally applicable to the detection of other metallic hydrogen pressure such as magnesium alloy, titanium alloy, nickel alloy, aldary and aluminium alloy, is applicable to the detection of hydrogen pressure of sheet material, tubing and the container of these metals.

Description of drawings

Fig. 1 is an apparatus structure synoptic diagram of the present invention.

Fig. 2 separates out the apparatus structure synoptic diagram of hydrogen pressure for solid-state steel in 200～800 ℃ of thermal treatments of mensuration of the present invention.

Among the figure: 1 solid ceramic electrolytic tube, 2 alundum tubes, 3 draft tube, 4 contact conductors, 5 gas outlets, 6 high resistant digital voltmeters, 7 cementing agents, 8 thermopairs, 9 samples to be tested, 10 resistance furnaces.

Embodiment

Below further specify method of the present invention through embodiment.

Embodiment 1

Device of the present invention is made up of solid ceramic electrolytic tube 1, alundum tube 2, draft tube 3, contact conductor 4, gas outlet 5 and high resistant digital voltmeter 6; Alundum tube 2 one ends are connected with solid ceramic electrolytic tube 1 openend, and alundum tube 2 and 1 socket of solid ceramic electrolytic tube soon also bonds together.Cementing agent 7 is selected commercially available epoxy adhesive commonly used for use.Draft tube 3 is passed the blind end of alundum tube 2, stretches in the alundum tube 2 and near solid ceramic electrolytic tube 1 bottom interior wall, leaves the slit between draft tube 3 outer walls, end face and solid ceramic electrolytic tube 1 bottom interior wall, and this slit can get final product through standard hydrogen.Gas outlet 5 is set on the sidewall of alundum tube 2.One end of contact conductor 4 stretches in the draft tube 3 and with solid ceramic electrolytic tube 1 bottom interior wall and contacts, and contact conductor 4 connects high resistant digital voltmeter 6, high resistant digital voltmeter 6 internal resistances>=10 ⁹Ohm.

The solid ceramic electrolytic tube is the ceramic pipe of an end opening, end sealing, and the diameter of pipe is: external diameter 6mm, and pipe thickness is 0.9mm, length of tube is 12mm.The material of ceramic pipe is BaCe _0.88Y _0.12O _3-α

The BaCe that is selected for use _0.88Y _0.12O _3-αThe preparation method is following for the solid ceramic electrolytic tube.

Raw material adopts BaCO ₃, CeO ₂And Y ₂O ₃, according to molar ratio computing, proportioning raw materials is:

BaCO ₃∶CeO ₂∶Y ₂O ₃＝1∶0.88∶0.12

Processing step is following.

(1) batch mixing

With BaCO ₃, CeO ₂And Y ₂O ₃Putting into the agate jar, adopt bowl mill, is that medium carries out wet ball grinding with the absolute ethyl alcohol, and with 350 rev/mins speed ball millings 8 hours, air dry then, the granularity of mixed powder reaches 2 μ m.

(2) compression moulding

The material that mixes is adopted hydropress, be pressed into the disk that thickness is 12mm, diameter 15mm with the pressure of 18MPa.

(3) solid phase synthesis

The disk that presses is placed the molybdenum disilicide stove, under normal pressure, air atmosphere, be warming up to 1400 ℃, be incubated 10 hours, naturally cool to room temperature with 2 ℃/minute heating rates.

(4) isostatic compaction

Mixture behind the solid phase synthesis being ground to form the powder that granularity is 2 μ m, powder is put into mould, mould is put into the isostatic pressing machine working cylinder, is pressure transmitting medium with static pressure oil, pressure 200MPa, and pressurize 1.5 hours is pressed into body.

(5) sintering

With the body that presses, place the molybdenum disilicide stove, under normal pressure, air atmosphere; Be warming up to 1000 ℃ with 1.5 ℃/minute heating rates, be incubated 2 hours, be warming up to 1550 ℃ with 1.5 ℃/minute heating rate again; Be incubated 10 hours, naturally cool to room temperature, obtain BaCe _0.88Y _0.12O _3-αThe solid ceramic electrolytic tube.

To adopt standard hydrogen be high-purity argon gas (purity >=99.999%) with high-purity hydrogen (purity >=99.999%) mixed gas as contrast electrode, number percent meter by volume, hydrogen 1%, argon gas 99%.

Contact conductor adopts stainless steel wire.

When adopting device of the present invention to measure in the solid-state steel hydrogen pressure; The blind end of sample to be tested 9 with solid ceramic electrolytic tube 1 contacted, an end of contact conductor 4 is contacted (other end of contact conductor 4 has stretched in the draft tube 3 and with solid ceramic electrolytic tube 1 inwall and contacted) with sample to be tested 9.The thermometric end of thermopair 8 contacts with sample to be tested 9.

The temperature of control sample to be tested SPCC steel is 25 ℃, in draft tube, feeds standard hydrogen, and the flow of control criterion hydrogen is 0.05Nm ³/ h, pressure are normal pressure (hydrogen partial pressure is 1000Pa), 20 minutes control survey time, read the electromotive force value through the high resistant digital voltmeter, and calculate the pressure of sample to be tested hydrogen, computing formula (Nernst equation) is:

$E=\frac{\mathrm{RT}}{2F}\mathrm{Ln}\frac{P_{H_2}^I}{P_{H_2}^{\mathrm{II}}}$

In the formula: E-electromotive force, V;

The R-gas law constant, 8.314J.mol ^-1K ^-1

The F-Faraday constant, 96485C/mol;

T-absolute temperature, K;

is respectively the Hydrogen Vapor Pressure value of contrast electrode and sample to be tested, Pa;

Record electromotive force E=0.23815V,

Try to achieve the pressure of hydrogen in the sample to be tested SPCC steel $P_{H_2}^{\mathrm{II}}=8.875\&times;{10}^{-6}\mathrm{Pa}.$

Embodiment 2

Device of the present invention is made up of solid ceramic electrolytic tube 1, alundum tube 2, draft tube 3, contact conductor 4, gas outlet 5 and high resistant digital voltmeter 6; Alundum tube 2 one ends are connected with solid ceramic electrolytic tube 1 openend, and alundum tube 2 and 1 socket of solid ceramic electrolytic tube soon also bonds together.Cementing agent 7 is selected commercially available acrylic resin binder commonly used for use.Draft tube 3 is passed the blind end of alundum tube 2, stretches in the alundum tube 2 and near solid ceramic electrolytic tube 1 bottom interior wall, leaves the slit between draft tube 3 outer walls, end face and solid ceramic electrolytic tube 1 bottom interior wall, and this slit can get final product through standard hydrogen.Gas outlet 5 is set on the sidewall of alundum tube 2.One end of contact conductor 4 stretches in the draft tube 3 and with solid ceramic electrolytic tube 1 bottom interior wall and contacts, and contact conductor 4 connects high resistant digital voltmeter 6, high resistant digital voltmeter 6 internal resistances>=10 ⁹Ohm.

The solid ceramic electrolytic tube is the ceramic pipe of an end opening, end sealing, and the diameter of pipe is: external diameter 8mm, and pipe thickness is 1mm, length of tube is 16mm.The material of ceramic pipe is BaCe _0.9Y _0.1O _3-α

The BaCe that is selected for use _0.9Y _0.1O _3-αThe preparation method is following for the solid ceramic electrolytic tube.

Raw material adopts BaCO ₃, CeO ₂And Y ₂O ₃, according to molar ratio computing, proportioning raw materials is:

BaCO ₃∶CeO ₂∶Y ₂O ₃＝1∶0.9∶0.1

Processing step is following.

(1) batch mixing

With BaCO ₃, CeO ₂And Y ₂O ₃Putting into the agate jar, adopt bowl mill, is that medium carries out wet ball grinding with the absolute ethyl alcohol, and with 500 rev/mins speed ball millings 5 hours, air dry then, the granularity of mixed powder reaches 1.5 μ m.

(2) compression moulding

The material that mixes is adopted hydropress, be pressed into the disk that thickness is 15mm, diameter 20mm with the pressure of 20MPa.

(3) solid phase synthesis

The disk that presses is placed the molybdenum disilicide stove, under normal pressure, air atmosphere, be warming up to 1500 ℃, be incubated 8 hours, naturally cool to room temperature with 3 ℃/minute heating rates.

(4) isostatic compaction

Mixture behind the solid phase synthesis being ground to form the powder that granularity is 1.5 μ m, powder is put into mould, mould is put into the isostatic pressing machine working cylinder, is pressure transmitting medium with static pressure oil, pressure 220MPa, and pressurize 1 hour is pressed into body.

(5) sintering

With the body that presses, place the molybdenum disilicide stove, under normal pressure, air atmosphere; Be warming up to 1100 ℃ with 1.2 ℃/minute heating rates, be incubated 1 hour, be warming up to 1600 ℃ with 1.2 ℃/minute heating rate again; Be incubated 8 hours, naturally cool to room temperature, obtain BaCe _0.9Y _0.1O _3-αThe solid ceramic electrolytic tube.

To adopt standard hydrogen be high-purity argon gas (purity >=99.999%) with high-purity hydrogen (purity >=99.999%) mixed gas as contrast electrode, number percent meter by volume, hydrogen 2%, argon gas 98%.

Contact conductor adopts nickel wire.

When adopting device of the present invention to measure in the solid-state steel hydrogen pressure; The blind end of sample to be tested 9 with solid ceramic electrolytic tube 1 contacted, an end of contact conductor 4 is contacted (other end of contact conductor 4 has stretched in the draft tube 3 and with solid ceramic electrolytic tube 1 inwall and contacted) with sample to be tested 9.The thermometric end of thermopair 8 contacts with sample to be tested 9.

The temperature of control sample to be tested is 50 ℃, in draft tube, feeds standard hydrogen, and the flow of control criterion hydrogen is 0.1Nm ³/ h, pressure are normal pressure (hydrogen partial pressure is 2000Pa), 30 minutes control survey time, read the electromotive force value through the high resistant digital voltmeter, and calculate the pressure of sample to be tested hydrogen, computing formula (Nernst equation) is:

$E=\frac{\mathrm{RT}}{2F}\mathrm{Ln}\frac{P_{H_2}^I}{P_{H_2}^{\mathrm{II}}}$

In the formula: E-electromotive force, V;

The R-gas law constant, 8.314J.mol ^-1K ^-1

The F-Faraday constant, 96485C/mol;

T-absolute temperature, K;

is respectively the Hydrogen Vapor Pressure value of contrast electrode and sample to be tested, Pa;

Record electromotive force E=0.24106V

Try to achieve $P_{H_2}^{\mathrm{II}}=6.037\&times;{10}^{-6}\mathrm{Pa}.$

Embodiment 3

Device of the present invention is made up of solid ceramic electrolytic tube 1, alundum tube 2, draft tube 3, contact conductor 4, gas outlet 5 and high resistant digital voltmeter 6; Alundum tube 2 one ends are connected with solid ceramic electrolytic tube 1 openend, and alundum tube 2 and 1 socket of solid ceramic electrolytic tube soon also bonds together.Cementing agent 7 is selected dried cementing agent of commercially available wink commonly used (502 glue) for use.Draft tube 3 is passed the blind end of alundum tube 2, stretches in the alundum tube 2 and near solid ceramic electrolytic tube 1 bottom interior wall, leaves the slit between draft tube 3 outer walls, end face and solid ceramic electrolytic tube 1 bottom interior wall, and this slit can get final product through standard hydrogen.Gas outlet 5 is set on the sidewall of alundum tube 2.One end of contact conductor 4 stretches in the draft tube 3 and with solid ceramic electrolytic tube 1 bottom interior wall and contacts, and contact conductor 4 connects high resistant digital voltmeter 6, high resistant digital voltmeter 6 internal resistances>=10 ⁹Ohm.

The solid ceramic electrolytic tube is the ceramic pipe of an end opening, end sealing, and the diameter of pipe is: external diameter 4mm, and pipe thickness is 0.8mm, length of tube is 8mm.The material of ceramic pipe is BaCe _0.85Y _0.15O _3-α

The BaCe that is selected for use _0.85Y _0.15O _3-αThe preparation method is following for the solid ceramic electrolytic tube.

Raw material adopts BaCO ₃, CeO ₂And Y ₂O ₃, according to molar ratio computing, proportioning raw materials is:

BaCO ₃∶CeO ₂∶Y ₂O ₃＝1∶0.85∶0.15

Processing step is following.

(1) batch mixing

With BaCO ₃, CeO ₂And Y ₂O ₃Putting into the agate jar, adopt bowl mill, is that medium carries out wet ball grinding with the absolute ethyl alcohol, and with 200 rev/mins speed ball millings 10 hours, air dry then, the granularity of mixed powder reaches 1 μ m.

(2) compression moulding

The material that mixes is adopted hydropress, be pressed into the disk that thickness is 10mm, diameter 10mm with the pressure of 15MPa.

(3) solid phase synthesis

The disk that presses is placed the molybdenum disilicide stove, under normal pressure, air atmosphere, be warming up to 1300 ℃, be incubated 12 hours, naturally cool to room temperature with 1 ℃/minute heating rate.

(4) isostatic compaction

Mixture behind the solid phase synthesis being ground to form the powder that granularity is 1 μ m, powder is put into mould, mould is put into the isostatic pressing machine working cylinder, is pressure transmitting medium with static pressure oil, pressure 180MPa, and pressurize 2 hours is pressed into body.

(5) sintering

With the body that presses, place the molybdenum disilicide stove, under normal pressure, air atmosphere; Be warming up to 900 ℃ with 1 ℃/minute heating rate, be incubated 3 hours, be warming up to 1500 ℃ with 1 ℃/minute heating rate again; Be incubated 12 hours, naturally cool to room temperature, obtain BaCe _0.85Y _0.15O _3-αThe solid ceramic electrolytic tube.

To adopt standard hydrogen be high-purity argon gas (purity >=99.999%) with high-purity hydrogen (purity >=99.999%) mixed gas as contrast electrode, number percent meter by volume, hydrogen 0.5%, argon gas 99.5%.

Contact conductor adopts iron wire.

When adopting device of the present invention to measure in the solid-state steel hydrogen pressure; The blind end of sample to be tested 9 with solid ceramic electrolytic tube 1 contacted, an end of contact conductor 4 is contacted (other end of contact conductor 4 has stretched in the draft tube 3 and with solid ceramic electrolytic tube 1 inwall and contacted) with sample to be tested 9.The thermometric end of thermopair 8 contacts with sample to be tested 9.

The temperature of control sample to be tested is 0 ℃, in draft tube, feeds standard hydrogen, and the flow of control criterion hydrogen is 0.01Nm ³/ h, pressure are normal pressure (hydrogen partial pressure is 500Pa), 5 minutes control survey time, read the electromotive force value through the high resistant digital voltmeter, and calculate the pressure of sample to be tested hydrogen, computing formula (Nernst equation) is:

$E=\frac{\mathrm{RT}}{2F}\mathrm{Ln}\frac{P_{H_2}^I}{P_{H_2}^{\mathrm{II}}}$

In the formula: E-electromotive force, V;

The R-gas law constant, 8.314J.mol ^-1K ^-1

The F-Faraday constant, 96485C/mol;

T-absolute temperature, K;

is respectively the Hydrogen Vapor Pressure value of contrast electrode and sample to be tested, Pa;

Record electromotive force E=0.26177V

Try to achieve $P_{H_2}^{\mathrm{II}}=1.091\&times;{10}^{-7}\mathrm{Pa}.$

Embodiment 4

Device of the present invention is made up of solid ceramic electrolytic tube 1, alundum tube 2, draft tube 3, contact conductor 4, gas outlet 5 and high resistant digital voltmeter 6; Alundum tube 2 one ends are connected with solid ceramic electrolytic tube 1 openend, and alundum tube 2 and 1 socket of solid ceramic electrolytic tube soon also bonds together.Cementing agent 7 is selected commercially available high temperature resistant cement commonly used for use.Draft tube 3 is passed the blind end of alundum tube 2, stretches in the alundum tube 2 and near solid ceramic electrolytic tube 1 bottom interior wall, leaves the slit between draft tube 3 outer walls, end face and solid ceramic electrolytic tube 1 bottom interior wall, and this slit can get final product through standard hydrogen.Gas outlet 5 is set on the sidewall of alundum tube 2.One end of contact conductor 4 stretches in the draft tube 3 and with solid ceramic electrolytic tube 1 bottom interior wall and contacts, and contact conductor 4 connects high resistant digital voltmeter 6, high resistant digital voltmeter 6 internal resistances>=10 ⁹Ohm.

The solid ceramic electrolytic tube is the ceramic pipe of an end opening, end sealing, and the diameter of pipe is: external diameter 6mm, and pipe thickness is 0.9mm, length of tube is 12mm.The material of ceramic pipe is Ba ₃Ca _1.18Nb _1.82O _9-δ

The Ba that is selected for use ₃Ca _1.18Nb _1.82O _9-δThe preparation method is following for the solid ceramic electrolytic tube.

Raw material adopts BaCO ₃, CaCO ₃And Nb ₂O ₅, according to molar ratio computing, proportioning raw materials is:

BaCO ₃∶CaCO ₃∶Nb ₂O ₅＝3∶1.18∶1.82

Processing step is following.

(1) batch mixing

With BaCO ₃, CaCO ₃And Nb ₂O ₅Putting into the agate jar, adopt bowl mill, is that medium carries out wet ball grinding with the absolute ethyl alcohol, and with 350 rev/mins speed ball millings 8 hours, air dry then, the granularity of mixed powder reaches 2 μ m.

(2) compression moulding

The material that mixes is adopted hydropress, be pressed into the disk that thickness is 12mm, diameter 15mm with the pressure of 18MPa.

(3) solid phase synthesis

The disk that presses is placed the molybdenum disilicide stove, under normal pressure, air atmosphere, be warming up to 1400 ℃, be incubated 10 hours, naturally cool to room temperature with 2 ℃/minute heating rates.

(4) isostatic compaction

Mixture behind the solid phase synthesis being ground to form the powder that granularity is 2 μ m, powder is put into mould, mould is put into the isostatic pressing machine working cylinder, is pressure transmitting medium with static pressure oil, pressure 200MPa, and pressurize 1.5 hours is pressed into body.

(5) sintering

With the body that presses, place the molybdenum disilicide stove, under normal pressure, air atmosphere; Be warming up to 1000 ℃ with 1.5 ℃/minute heating rates, be incubated 2 hours, be warming up to 1550 ℃ with 1.5 ℃/minute heating rate again; Be incubated 10 hours, naturally cool to room temperature, obtain Ba ₃Ca _1.18Nb _1.82O _9-δThe solid ceramic electrolytic tube.

To adopt standard hydrogen be high-purity argon gas (purity >=99.999%) with high-purity hydrogen (purity >=99.999%) mixed gas as contrast electrode, number percent meter by volume, hydrogen 1%, argon gas 99%.

Contact conductor adopts copper wire.

Adopt device of the present invention to measure when hydrogen is separated out pressure in the solid-state steel heat treatment process; The solid ceramic electrolytic tube 1 of apparatus of the present invention and the part of alundum tube 2 are placed in the resistance furnace 10, and the length that is placed on the alundum tube 2 in the resistance furnace 10 is 2/5 of alundum tube length overall.The blind end of sample to be tested 9 with solid ceramic electrolytic tube 1 contacted, an end of contact conductor 4 is contacted (other end of contact conductor 4 has stretched in the draft tube 3 and with solid ceramic electrolytic tube 1 inwall and contacted) with sample to be tested 9.The thermometric end of thermopair 8 contacts with sample to be tested 9.

The temperature of control sample to be tested (SPCC steel) is 500 ℃, in draft tube, feeds standard hydrogen, and the flow of control criterion hydrogen is 0.05Nm ³/ h, pressure are normal pressure (hydrogen partial pressure is 1000Pa), 20 minutes control survey time, read the electromotive force value through the high resistant digital voltmeter, and calculate the pressure of sample to be tested hydrogen.

Computing formula (Nernst equation) is:

$E=\frac{\mathrm{RT}}{2F}\mathrm{Ln}\frac{P_{H_2}^I}{P_{H_2}^{\mathrm{II}}}$

In the formula: E-electromotive force, V;

The R-gas law constant, 8.314J.mol ^-1K ^-1

The F-Faraday constant, 96485C/mol;

T-absolute temperature, K;

is respectively the Hydrogen Vapor Pressure value of contrast electrode and sample to be tested, Pa;

Record electromotive force E=0.26086V

Try to achieve $P_{H_2}^{\mathrm{II}}=0.3969\mathrm{Pa}$

Embodiment 5

Device of the present invention is made up of solid ceramic electrolytic tube 1, alundum tube 2, draft tube 3, contact conductor 4, gas outlet 5 and high resistant digital voltmeter 6; Alundum tube 2 one ends are connected with solid ceramic electrolytic tube 1 openend, and alundum tube 2 and 1 socket of solid ceramic electrolytic tube soon also bonds together.Cementing agent 7 is selected commercially available high temperature resistant cement commonly used for use.Draft tube 3 is passed the blind end of alundum tube 2, stretches in the alundum tube 2 and near solid ceramic electrolytic tube 1 bottom interior wall, leaves the slit between draft tube 3 outer walls, end face and solid ceramic electrolytic tube 1 bottom interior wall, and this slit can get final product through standard hydrogen.Gas outlet 5 is set on the sidewall of alundum tube 2.One end of contact conductor 4 stretches in the draft tube 3 and with solid ceramic electrolytic tube 1 bottom interior wall and contacts, and contact conductor 4 connects high resistant digital voltmeter 6, high resistant digital voltmeter 6 internal resistances>=10 ⁹Ohm.

The solid ceramic electrolytic tube is the ceramic pipe of an end opening, end sealing, and the diameter of pipe is: external diameter 8mm, and pipe thickness is 1mm, length of tube is 16mm.The material of ceramic pipe is Ba ₃Ca _1.18Nb _1.82O _9-δ

The Ba that is selected for use ₃Ca _1.18Nb _1.82O _9-δThe preparation method is following for the solid ceramic electrolytic tube.

Raw material adopts BaCO ₃, CaCO ₃And Nb ₂O ₅, according to molar ratio computing, proportioning raw materials is:

BaCO ₃∶CaCO ₃∶Nb ₂O ₅＝3∶1.18∶1.82

Processing step is following.

(1) batch mixing

With BaCO ₃, CaCO ₃And Nb ₂O ₅Putting into the agate jar, adopt bowl mill, is that medium carries out wet ball grinding with the absolute ethyl alcohol, and with 500 rev/mins speed ball millings 5 hours, air dry then, the granularity of mixed powder reaches 1.5 μ m.

(2) compression moulding

The material that mixes is adopted hydropress, be pressed into the disk that thickness is 15mm, diameter 20mm with the pressure of 20MPa.

(3) solid phase synthesis

The disk that presses is placed the molybdenum disilicide stove, under normal pressure, air atmosphere, be warming up to 1500 ℃, be incubated 8 hours, naturally cool to room temperature with 3 ℃/minute heating rates.

(4) isostatic compaction

Mixture behind the solid phase synthesis being ground to form the powder that granularity is 1.5 μ m, powder is put into mould, mould is put into the isostatic pressing machine working cylinder, is pressure transmitting medium with static pressure oil, pressure 220MPa, and pressurize 1 hour is pressed into body.

(5) sintering

With the body that presses, place the molybdenum disilicide stove, under normal pressure, air atmosphere; Be warming up to 1100 ℃ with 1.2 ℃/minute heating rates, be incubated 1 hour, be warming up to 1600 ℃ with 1.2 ℃/minute heating rate again; Be incubated 8 hours, naturally cool to room temperature, obtain Ba ₃Ca _1.18Nb _1.82O _9-δThe solid ceramic electrolytic tube.

To adopt standard hydrogen be high-purity argon gas (purity >=99.999%) with high-purity hydrogen (purity >=99.999%) mixed gas as contrast electrode, number percent meter by volume, hydrogen 2%, argon gas 98%.

Contact conductor adopts stainless steel wire.

Adopt device of the present invention to measure when hydrogen is separated out pressure in the solid-state steel heat treatment process; The solid ceramic electrolytic tube 1 of apparatus of the present invention and the part of alundum tube 2 are placed in the resistance furnace 10, and the length that is placed on the alundum tube 2 in the resistance furnace 10 is 4/5 of alundum tube length overall.The blind end of sample to be tested 9 with solid ceramic electrolytic tube 1 contacted, an end of contact conductor 4 is contacted (other end of contact conductor 4 has stretched in the draft tube 3 and with solid ceramic electrolytic tube 1 inwall and contacted) with sample to be tested 9.The thermometric end of thermopair 8 contacts with sample to be tested 9.

The temperature of control sample to be tested is 800 ℃, in draft tube, feeds standard hydrogen, and the flow of control criterion hydrogen is 0.1Nm ³/ h, pressure are normal pressure (hydrogen partial pressure is 2000Pa), 30 minutes control survey time, read the electromotive force value through the high resistant digital voltmeter, and calculate the pressure of sample to be tested hydrogen.

Computing formula (Nernst equation) is:

$E=\frac{\mathrm{RT}}{2F}\mathrm{Ln}\frac{P_{H_2}^I}{P_{H_2}^{\mathrm{II}}}$

In the formula: E-electromotive force, V;

The R-gas law constant, 8.314J.mol ^-1K ^-1

The F-Faraday constant, 96485C/mol;

T-absolute temperature, K;

is respectively the Hydrogen Vapor Pressure value of contrast electrode and sample to be tested, Pa;

Record electromotive force E=0.36059V

Try to achieve $P_{H_2}^{\mathrm{II}}=0.8197\mathrm{Pa}$

Embodiment 6

Device of the present invention is made up of solid ceramic electrolytic tube 1, alundum tube 2, draft tube 3, contact conductor 4, gas outlet 5 and high resistant digital voltmeter 6; Alundum tube 2 one ends are connected with solid ceramic electrolytic tube 1 openend, and alundum tube 2 and 1 socket of solid ceramic electrolytic tube soon also bonds together.Cementing agent 7 is selected commercially available high temperature resistant cement commonly used for use.Draft tube 3 is passed the blind end of alundum tube 2, stretches in the alundum tube 2 and near solid ceramic electrolytic tube 1 bottom interior wall, leaves the slit between draft tube 3 outer walls, end face and solid ceramic electrolytic tube 1 bottom interior wall, and this slit can get final product through standard hydrogen.Gas outlet 5 is set on the sidewall of alundum tube 2.One end of contact conductor 4 stretches in the draft tube 3 and with solid ceramic electrolytic tube 1 bottom interior wall and contacts, and contact conductor 4 connects high resistant digital voltmeter 6, high resistant digital voltmeter 6 internal resistances>=10 ⁹Ohm.

The solid ceramic electrolytic tube is the ceramic pipe of an end opening, end sealing, and the diameter of pipe is: external diameter 8mm, and pipe thickness is 1mm, length of tube is 16mm.The material of ceramic pipe is Ba ₃Ca _1.18Nb _1.82O _9-δ

The Ba that is selected for use ₃Ca _1.18Nb _1.82O _9-δThe preparation method is following for the solid ceramic electrolytic tube.

Raw material adopts BaCO ₃, CaCO ₃And Nb ₂O ₅, according to molar ratio computing, proportioning raw materials is:

BaCO ₃∶CaCO ₃∶Nb ₂O ₅＝3∶1.18∶1.82

Processing step is following.

(1) batch mixing

With BaCO ₃, CaCO ₃And Nb ₂O ₅Putting into the agate jar, adopt bowl mill, is that medium carries out wet ball grinding with the absolute ethyl alcohol, and with 200 rev/mins speed ball millings 10 hours, air dry then, the granularity of mixed powder reaches 1 μ m.

(2) compression moulding

The material that mixes is adopted hydropress, be pressed into the disk that thickness is 10mm, diameter 10mm with the pressure of 15MPa.

(3) solid phase synthesis

The disk that presses is placed the molybdenum disilicide stove, under normal pressure, air atmosphere, be warming up to 1300 ℃, be incubated 12 hours, naturally cool to room temperature with 1 ℃/minute heating rate.

(4) isostatic compaction

Mixture behind the solid phase synthesis being ground to form the powder that granularity is 1 μ m, powder is put into mould, mould is put into the isostatic pressing machine working cylinder, is pressure transmitting medium with static pressure oil, pressure 180MPa, and pressurize 2 hours is pressed into body.

(5) sintering

With the body that presses, place the molybdenum disilicide stove, under normal pressure, air atmosphere, be warming up to 900 ℃ with 1 ℃/minute heating rate, be incubated 3 hours, be warming up to 1500 ℃ with 1 ℃/minute heating rate again, be incubated 12 hours, naturally cool to room temperature, obtain Ba ₃Ca _1.18Nb _1.82O _9-δThe solid ceramic electrolytic tube.

To adopt standard hydrogen be high-purity argon gas (purity >=99.999%) with high-purity hydrogen (purity >=99.999%) mixed gas as contrast electrode, number percent meter by volume, hydrogen 2%, argon gas 98%.

Contact conductor adopts stainless steel wire.

Adopt device of the present invention to measure when hydrogen is separated out pressure in the solid-state steel heat treatment process; The solid ceramic electrolytic tube 1 of apparatus of the present invention and the part of alundum tube 2 are placed in the resistance furnace 10, and the length that is placed on the alundum tube 2 in the resistance furnace 10 is 4/5 of alundum tube length overall.The blind end of sample to be tested 9 with solid ceramic electrolytic tube 1 contacted, an end of contact conductor 4 is contacted (other end of contact conductor 4 has stretched in the draft tube 3 and with solid ceramic electrolytic tube 1 inwall and contacted) with sample to be tested 9.The thermometric end of thermopair 8 contacts with sample to be tested 9.

The temperature of control sample to be tested is 200 ℃, in draft tube, feeds standard hydrogen, and the flow of control criterion hydrogen is 0.01Nm ³/ h, pressure are normal pressure (hydrogen partial pressure is 500Pa), 5 minutes control survey time, read the electromotive force value through the high resistant digital voltmeter, and calculate the pressure of sample to be tested hydrogen.

Computing formula (Nernst equation) is:

$E=\frac{\mathrm{RT}}{2F}\mathrm{Ln}\frac{P_{H_2}^I}{P_{H_2}^{\mathrm{II}}}$

In the formula: E-electromotive force, V;

The R-gas law constant, 8.314J.mol ^-1K ^-1

The F-Faraday constant, 96485C/mol;

T-absolute temperature, K;

is respectively the Hydrogen Vapor Pressure value of contrast electrode and sample to be tested, Pa;

Record electromotive force E=0.20056V

Try to achieve $P_{H_2}^{\mathrm{II}}=0.0267\mathrm{Pa}.$

Embodiment 7

Device of the present invention is made up of solid ceramic electrolytic tube 1, alundum tube 2, draft tube 3, contact conductor 4, gas outlet 5 and high resistant digital voltmeter 6; Alundum tube 2 one ends are connected with solid ceramic electrolytic tube 1 openend, and alundum tube 2 and 1 socket of solid ceramic electrolytic tube soon also bonds together.Cementing agent 7 is selected commercially available high temperature resistant cement commonly used for use.Draft tube 3 is passed the blind end of alundum tube 2, stretches in the alundum tube 2 and near solid ceramic electrolytic tube 1 bottom interior wall, leaves the slit between draft tube 3 outer walls, end face and solid ceramic electrolytic tube 1 bottom interior wall, and this slit can get final product through standard hydrogen.Gas outlet 5 is set on the sidewall of alundum tube 2.One end of contact conductor 4 stretches in the draft tube 3 and with solid ceramic electrolytic tube 1 bottom interior wall and contacts, and contact conductor 4 connects high resistant digital voltmeter 6, high resistant digital voltmeter 6 internal resistances>=10 ⁹Ohm.

The solid ceramic electrolytic tube is the ceramic pipe of an end opening, end sealing, and the diameter of pipe is: external diameter 4mm, and pipe thickness is 0.8mm, length of tube is 8mm.The material of ceramic pipe is ZrO ₂(Y ₂O ₃), i.e. ZrO ₂Middle doping Y ₂O ₃, by mass percentage, Y ₂O ₃Content 8.5%, ZrO ₂Content 91.5%.

The ZrO that is selected for use ₂(Y ₂O ₃) the solid ceramic electrolytic tube is existing commercially available prod.

To adopt standard hydrogen be high-purity argon gas (purity >=99.999%) with high-purity hydrogen (purity >=99.999%) mixed gas as contrast electrode, number percent meter by volume, hydrogen 0.5%, argon gas 99.5%.

Contact conductor adopts nickel wire.

When adopting device of the present invention to measure in the solid-state steel (SPCC steel) hydrogen pressure; The solid ceramic electrolytic tube 1 of apparatus of the present invention and the part of alundum tube 2 are placed in the resistance furnace 10, and the length that is placed on the alundum tube 2 in the resistance furnace 10 is 1/5 of alundum tube length overall.The blind end of sample to be tested 9 with solid ceramic electrolytic tube 1 contacted, an end of contact conductor 4 is contacted (other end of contact conductor 4 has stretched in the draft tube 3 and with solid ceramic electrolytic tube 1 inwall and contacted) with sample to be tested 9.The thermometric end of thermopair 8 contacts with sample to be tested 9.

The temperature of control sample to be tested SPCC steel is 30 ℃, in draft tube, feeds standard hydrogen, and the flow of control criterion hydrogen is 0.03Nm ³/ h, pressure are normal pressure (hydrogen partial pressure is 1000Pa), 15 minutes control survey time, read the electromotive force value through the high resistant digital voltmeter, and calculate the pressure of sample to be tested hydrogen, computing formula (Nernst equation) is:

$E=\frac{\mathrm{RT}}{2F}\mathrm{Ln}\frac{P_{H_2}^I}{P_{H_2}^{\mathrm{II}}}$

In the formula: E-electromotive force, V;

The R-gas law constant, 8.314J.mol ^-1K ^-1

The F-Faraday constant, 96485C/mol;

T-absolute temperature, K;

is respectively the Hydrogen Vapor Pressure value of contrast electrode and sample to be tested, Pa;

Record electromotive force E=0.23794V,

Try to achieve the pressure of hydrogen in the sample to be tested SPCC steel $P_{H_2}^{\mathrm{II}}=1.223\&times;{10}^{-5}\mathrm{Pa}.$

Claims (8)

1. device of measuring hydrogen pressure in the solid-state steel; It is characterized in that being made up of solid ceramic electrolytic tube, alundum tube, draft tube, contact conductor, gas outlet and high resistant digital voltmeter, alundum tube one end is connected with solid ceramic electrolytic tube openend, and draft tube is passed the blind end of alundum tube; Stretch in the alundum tube and near solid ceramic electrolytic tube bottom interior wall; Leave the slit between draft tube outer wall, end face and solid ceramic electrolytic tube bottom interior wall, standard hydrogen can be passed through in this slit, feeds standard hydrogen through draft tube; Standard hydrogen is as contrast electrode; The sidewall of alundum tube is provided with gas outlet, and an end of contact conductor stretches in the draft tube and with solid ceramic electrolytic tube bottom interior wall and contacts, and contact conductor connects the high resistant digital voltmeter; Said standard hydrogen is the mixed gas of high-purity hydrogen of high-purity argon gas and purity >=99.999% of purity >=99.999%, number percent meter by volume, and hydrogen 0.5%～2%, argon gas 98%～99.5%, hydrogen partial pressure are 500～2000Pa.

2. according to the device of hydrogen pressure in the solid-state steel of the described mensuration of claim 1, it is characterized in that high resistant digital voltmeter internal resistance >=109 ohm.

3. according to the device of hydrogen pressure in the solid-state steel of the described mensuration of claim 1; It is characterized in that the solid ceramic electrolytic tube is the ceramic pipe of an end opening, end sealing; The diameter of pipe is: external diameter 4～8mm, and pipe thickness is 0.8～1mm, length of tube is 8～16mm.

4. according to the device of hydrogen pressure in claim 1 or the solid-state steel of 3 described mensuration, the material that it is characterized in that the solid ceramic electrolytic tube is BaCe _0.85～0.9Y _0.1～0.15O _3-α, or Ba ₃Ca _1.18Nb _1.82O _9-δ, or ZrO ₂Middle doping Y ₂O ₃, by mass percentage, Y ₂O ₃Content 8～9%, ZrO ₂Content 91%～92%.

5. according to the device of hydrogen pressure in the solid-state steel of the described mensuration of claim 1, it is characterized in that contact conductor adopts stainless steel wire, nickel wire, iron wire or copper wire.

6. adopt the device of hydrogen pressure in the solid-state steel of the described mensuration of claim 1 to measure the method for hydrogen pressure in the solid-state steel; It is characterized in that: the blind end of sample to be tested with the solid ceramic electrolytic tube contacted; One end of contact conductor is contacted with sample to be tested; The other end of contact conductor has stretched in the draft tube and with solid ceramic electrolytic tube inwall and has contacted, and the thermometric end of thermopair contacts with sample to be tested, and the temperature of control sample to be tested is 0～50 ℃; In draft tube, feed standard hydrogen, the flow of control criterion hydrogen is 0.01～0.1Nm ³/ h, pressure are normal pressure, 5～30 minutes control survey time, read the electromotive force value through the high resistant digital voltmeter, and calculate the pressure of sample to be tested hydrogen.

7. adopt the device of hydrogen pressure in the solid-state steel of the described mensuration of claim 1 to measure in the solid-state steel heat treatment process hydrogen and separate out the method for pressure; It is characterized in that the part of solid ceramic electrolytic tube and alundum tube is placed in the resistance furnace; The blind end of sample to be tested with the solid ceramic electrolytic tube contacted, an end of contact conductor is contacted with sample to be tested, the other end of contact conductor has stretched in the draft tube and with solid ceramic electrolytic tube inwall and has contacted; The thermometric end of thermopair contacts with sample to be tested; The temperature of control sample to be tested is 200～800 ℃, in draft tube, feeds standard hydrogen, and the flow of control criterion hydrogen is 0.01～0.1Nm ³/ h, pressure are normal pressure, 5～30 minutes control survey time, read the electromotive force value through the high resistant digital voltmeter, and calculate the pressure of sample to be tested hydrogen.

8. separate out the method for pressure according to hydrogen in the solid-state steel heat treatment process of the described mensuration of claim 7, it is characterized in that: the length that is placed on the alundum tube in the resistance furnace is 1/5～4/5 of alundum tube length overall.

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