CN114324536B - Hydrogen probe device is decided to metal melt - Google Patents
Hydrogen probe device is decided to metal melt Download PDFInfo
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- CN114324536B CN114324536B CN202210016713.1A CN202210016713A CN114324536B CN 114324536 B CN114324536 B CN 114324536B CN 202210016713 A CN202210016713 A CN 202210016713A CN 114324536 B CN114324536 B CN 114324536B
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Abstract
A metal melt hydrogen determination probe device comprises an upper insulating connecting piece, a lower insulating connecting piece, a stainless steel pipe and a conductive protective cover; the stainless steel bar and the proton conductor are sequentially arranged inside the upper insulating connecting piece, the lower insulating connecting piece, the stainless steel pipe and the conductive protective cover from top to bottom; the proton conductor is a blind-end pipe, the lower part of the proton conductor is a hemispherical end enclosure, the top of the hemispherical end enclosure is connected with a cylindrical side wall to form an integral structure, and a high-temperature cement plate is fixed on the inner wall of the cylindrical side wall; the high-temperature cement plate divides the proton conductor into an upper space and a lower space; the upper surface of the high-temperature cement board is coated with a porous electrode coating; the outer surface and the inner surface of the proton conductor are coated with an outer porous electrode coating and an inner porous electrode coating, respectively. The device of the invention has simple assembly and disassembly, and can only replace the probe without replacing the main body part of the sensor after the sensor reaches the service life, thereby saving a large amount of cost.
Description
Technical Field
The invention relates to the technical field of sensors in the metallurgical industry, in particular to a metal melt hydrogen determination probe device.
Background
The proton conductor sensing hydrogen is a novel hydrogen measuring method, and the method can accurately, rapidly and real-timely measure the hydrogen in the metal melt and the gas, realizes on-line intelligent monitoring, and is a hydrogen measuring method with great prospect. When the sensing material used in the sensor is an ideal pure proton conductor, the galvanic reaction is shown in formula (1):
H 2 (reference electrode) = H 2 (metal electrode) (1);
the electromotive force generated by the primary cell in the ideal state is shown in equation (2):
the hydrogen content in the metal melt is shown in formula (3):
in the above formulae, R is a gas constant of 8.314J/(mol. K); t is temperature, in K; f is a Faraday constant of 96485C/mol; e is electromotive force, unit V; k is an alloy coefficient; s is the hydrogen content in the metal melt, and the unit ml/100g;
hydrogen partial pressure of the metal melt, in atm,
hydrogen partial pressure in atm is the reference side.
When the proton conductor is pure proton conductive, the hydrogen content in the metal melt of the electrode to be measured is calculated by controlling the hydrogen partial pressure of the reference electrode and utilizing the electromotive force generated by the primary battery.
EP0544281 TYK apparatus for measuring hydrogen content in metal melts below 1000 ℃ with SrCe 0.95 Yb 0.05 O 3-x 、CaZr 0.9 In 0.1 O 3-x 、BaCe 0.95 Y 0.05 O 3-x The proton conductor is used as a hydrogen sensitive material, the metal wires of Pt, ni and the like are used as electrode leads, and the proton conductor, the mullite tube, the air chamber and other parts are bonded into a whole by using a ceramic binder to ensure the connection; patent application with publication number CN105319253 discloses a sensor and a measuring method for measuring hydrogen content in molten metal, and CaZr is used 0.9 In 0.1 O 3-x The proton conductor is used as a hydrogen sensitive material, a metal wire such as platinum, gold, silver, nickel-chromium and the like is used as an electrode lead, and an insulating ceramic binder is used for bonding the proton conductor and the through pipe into a whole to ensure the connection of the proton conductor and the through pipe; US 2005/0252789 discloses a hydrogen sensing device and method using SrCe 0.95 Yb 0.05 O 3-δ 、CaZr 0.9 In 0.1 O 3-δ As the hydrogen sensitive material, alpha-Ti/beta-Ti, alpha-Zr/beta-Zr, beta-Zr/delta-Zr and alpha-Hf/delta-Hf are used as solid reference electrodes, and the device is sealed into a whole by an internal filling material and a glass sealant, but the patent only relates to a probe part and does not disclose a support and an electrode lead connecting part required by the sensor.
In the existing hydrogen measuring device, proton conductor sensing hydrogen probes are all integrated, so that the sensors are difficult to inspect and maintain after problems occur, and the sensors must be integrally replaced after the sensors reach the service life, and the problems increase the use cost of the sensors; therefore, there is a need for a split sensor probe that is easy to remove, repair, and replace.
Disclosure of Invention
In order to solve the problems, the invention provides a metal melt hydrogen determination probe device, which is based on a proton conductor concentration cell hydrogen measurement method, uses solid metal hydride as a reference electrode, outputs concentration cell electromotive force by a proton conductor probe, and uses metal hydride and an inner porous electrode and the like as a positive electrode together; the outer porous electrode and the protective cover are jointly used as the negative electrode, the assembly and the disassembly are simple, and when the sensor reaches the service life, only the probe is replaced without replacing the main body part of the sensor.
The metal melt hydrogen determination probe device comprises an upper insulating connecting piece 4, a lower insulating connecting piece 8, a stainless steel pipe 6 and a conductive protective cover 7; the upper insulating connecting piece 4 is an integrated structure consisting of a top plate, a side wall and a hollow pipe, wherein the top plate is provided with a middle through hole, an electrode hole and a galvanic couple hole; the top end of the hollow tube is connected with the bottom surface of the top plate, the upper part of the side wall is sleeved outside the side surface of the top plate, internal threads are arranged in the side wall, the hollow tube is coaxial with the through hole, and the inner diameter of the hollow tube is larger than that of the through hole; the electrode hole and the galvanic couple hole are positioned between the outer wall of the hollow pipe and the inner wall of the side wall; the lower insulating connecting piece 8 is cylindrical, and external threads are arranged on the outer wall surface; the stainless steel pipe 6 is cylindrical, and the upper part and the lower part of the outer wall are respectively provided with an upper external thread and a lower external thread; the conductive protective cover 7 is in a cylindrical shape, internal threads are arranged on the upper part of the inner wall surface of the side wall of the conductive protective cover, and a vent hole 14 is arranged on the bottom plate; the upper insulating connecting piece 4 is in threaded sealing connection with the upper external thread of the stainless steel pipe 6, and the lower external thread of the stainless steel pipe 6 is in threaded sealing connection with the conductive protective cover 7 and the lower insulating connecting piece 8 simultaneously; the stainless steel bar 2 and the proton conductor 15 are sequentially arranged inside the upper insulating connecting piece 4, the lower insulating connecting piece 8, the stainless steel pipe 6 and the conductive protective cover 7 from top to bottom; the proton conductor 15 is a blind-end pipe, the lower part of the proton conductor is a hemispherical end enclosure, the top of the hemispherical end enclosure is connected with a cylindrical side wall to form an integral structure, and a high-temperature cement plate 11 is fixed on the inner wall of the cylindrical side wall; the high temperature cement plate 11 divides the proton conductor 15 into an upper space and a lower space, and the lower space is used for placing the reference electrode 13; the upper surface of the high-temperature cement board 11 is coated with a porous electrode coating; the outer surface and the inner surface of the proton conductor 15 are coated with the outer porous electrode coating 12 and the inner porous electrode coating 10, respectively.
In the device, the stainless steel bar 2 is an integrated structure consisting of a bar body and a single-step pagoda joint at the upper part of the bar body; the stainless steel rod 2 passes through a through hole and a hollow pipe on the top plate of the upper insulating connecting piece 4; the bottom end of the stainless steel rod 2 is connected with the porous electrode coating of the high-temperature cement board 11; the spring 3 is placed on the single-step pagoda joint, and the top end of the spring 3 is tightly pressed and connected with the bottom surface of the top plate of the upper connecting piece 4.
In the device, the upper part of the outer surface of the cylindrical side wall of the proton conductor 15 is fixedly adhered to the inner wall of the lower insulating connector 8 through the high-temperature adhesive 9; a reference electrode 13 is arranged in the proton conductor 15, and the space below the proton conductor 15 is sealed by a high-temperature cement plate 11; the reference electrode 13 is metal hydride CaH x Or YH x (ii) a The proton conductor 15, the high-temperature cement plate 11, and the reference electrode 13 constitute a probe portion.
In the device, the hemispherical head of the proton conductor 15 is opposite to the vent hole 14, and the hemispherical head of the proton conductor 15 is tightly connected with the bottom plate of the conductive protective cover 7.
In the device, a thermocouple 5 is arranged in a thermocouple hole of an upper insulating connecting piece 4, the bottom end of the thermocouple 5 is positioned in the upper space of a proton conductor 15, and a gap is reserved between the bottom end of the thermocouple 5 and a high-temperature cement plate 11; the thermocouple 5 is a double-hole corundum tube, the inner double holes are respectively the positive and negative electrodes of the K-shaped thermocouple wire, the side wall of the lower part is provided with a notch, the bottom ends of the positive and negative electrodes of the thermocouple wire positioned at the notch are connected through welding, and a lead connected with the top ends of the positive and negative electrodes is connected with an external temperature measuring device.
In the device, a stainless steel electrode 1 is arranged in an electrode hole of an upper insulating connecting piece 4; the stainless steel electrode 1 is of an inverted T-shaped structure, the vertical rod part of the stainless steel electrode 1 penetrates through the electrode hole, and the horizontal rod part of the stainless steel electrode 1 is tightly connected with the top end of the stainless steel tube 6 in a pressing mode.
In the above device, the conductive cover 7 is made of graphite.
In the above device, the upper insulating connector 4 is made of teflon.
In the device, the lower insulating connecting piece 8 is made of ceramic; the ceramic is a macor ceramic.
In the above device, each porous electrode coating is a porous Pt electrode.
In the above apparatus, the material of the high temperature cement board 11 is Aremco 503 high temperature cement.
The use method of the metal melt hydrogen determination probe device comprises the following steps:
(1) Immersing the metal melt hydrogen determination probe device into the metal melt, wherein hydrogen in the metal melt diffuses through the vent hole 14 and establishes a hydrogen concentration difference with the reference electrode 13; electromotive force is generated between the inside and outside of the proton conductor 15;
(2) The inner porous electrode coating 10 and the stainless steel bar 2 are used as positive electrodes, and the outer porous electrode coating 11, the conductive protective cover 7, the stainless steel pipe 6 and the stainless steel electrode 1 are used as negative electrodes; measuring the voltage between the two poles through a voltmeter; measuring the temperature in the stainless steel tube 6 by the thermocouple 5;
(3) And (3) substituting the measured voltage value into the formulas (2) and (3) to calculate the hydrogen content in the metal melt when the temperature and the voltage value are both in a stable state.
In the method, the voltage value in the stable state means that the voltage value is measured every second, and when the standard deviation of the voltage value for continuous 10 seconds is less than or equal to 0.3mV, the voltage value is in the stable state.
In the method, the stable state of the voltage value is 2-4 min after the start of measurement, and the stable state of the temperature is 1-1.5 min after the start of measurement; i.e. when the voltage value is in a steady state, the temperature is also in a steady state.
In the above method, the metal melt is an aluminum melt, a magnesium melt, a zinc melt, a nickel melt, a copper melt, an iron melt or a steel melt.
The invention adopts metal hydride, a proton conductor inner porous electrode and a stainless steel bar as the anode; a proton conductor outer porous electrode, a stainless steel pipe and the like are used as a negative electrode; the proton conductor is connected with other parts through threads, so that the proton conductor is easy to disassemble; the hydrogen sensitive material is a lattice defect type high-temperature proton conductor, and hydrogen measurement is carried out by utilizing the concentration cell electromotive force of the proton conductor and the Shewa specific law; the two electrodes are made of stainless steel, and thermoelectric force cannot be generated in a temperature change area.
The device of the invention has simple assembly and disassembly, and can only replace the probe without replacing the main body part of the sensor after the sensor reaches the service life, thereby saving a large amount of cost.
Drawings
FIG. 1 is a schematic structural view of a hydrogen determination probe device for a metal melt according to the present invention;
FIG. 2 is a schematic view of the components of FIG. 1;
in the figure, 1, a stainless steel electrode, 2, a stainless steel rod, 3, a spring, 4, an upper insulating connecting piece, 5, a thermocouple, 6, a stainless steel pipe, 7, a conductive protective cover, 8, a lower insulating connecting piece, 9, a high-temperature adhesive, 10, an inner porous electrode coating, 11, a high-temperature cement plate, 12, an outer porous electrode coating, 13, a reference electrode, 14, a vent hole, 15 and a proton conductor;
FIG. 3 is a graph of time-temperature/voltage curves measured in example 1 of the present invention;
FIG. 4 is a graph of time-temperature/voltage curves measured in example 2 of the present invention;
FIG. 5 is a graph of time-temperature/voltage curves measured in example 3 of the present invention;
FIG. 6 is a graph of time-temperature/voltage measured in example 4 of the present invention;
FIG. 7 is a time-temperature/voltage graph measured in example 5 of the present invention;
FIG. 8 is a graph of time-temperature/voltage curves measured in example 6 of the present invention;
FIG. 9 is a time-temperature/voltage graph measured in example 7 of the present invention.
Detailed Description
The following is a preferred embodiment of the present invention, and all other embodiments obtained by those skilled in the art without any inventive work are within the scope of the present invention.
In the embodiment of the invention, the conductive protective cover 7 is made of graphite; the upper insulating connecting piece 4 is made of polytetrafluoroethylene; the lower insulating connecting piece 8 is made of ceramic; the ceramic is a macor ceramic; each porous electrode coating is a porous Pt electrode; the high-temperature cement board 11 is made of Aremco 503 high-temperature cement.
In the embodiment of the invention, the aperture of the vent holes 14 is 1-3 mm, and the number of the vent holes is 1-20.
In the embodiment of the invention, the height of the conductive protection cover 7 is 5-50 mm greater than that of the proton conductor 15.
In the embodiment of the invention, the outer walls of the stainless steel pipe 6 and the conductive protective cover 7 are sprayed with the metal melt corrosion resistant coating for preventing the corrosion of the metal melt.
In the embodiment of the present invention, the thermocouple 5 is externally sleeved with a high temperature resistant insulating sleeve to prevent the thermocouple 5 from contacting the inner porous electrode coating 10.
The high-temperature binder in the embodiment of the invention is Aremco 503 high-temperature cement.
The method for replacing the probe of the metal melt hydrogen determination probe device comprises the following steps: the metal melt hydrogen determination probe device is inverted, namely the conductive protective cover 7 is positioned above the metal melt hydrogen determination probe device, and the stainless steel rod 2 is positioned below the metal melt hydrogen determination probe device; the conductive protective cover 7 is removed in a rotating mode, and the conductive protective cover and the probe part are also removed at the moment; rotationally separating the conductive protective cover 7 from the probe part; a new probe part is rotatably installed in the conductive protective cover 9, and then the conductive protective cover 9 is rotatably installed on the stainless steel tube 6.
In the embodiment of the invention
References to The partial pressure of Hydrogen for The reference electrode are L.N. Yannopoulos, R.K. Edwards, P.G. Wahlbeck, the Thermodynamics of The Yttrium-Hydrogen System [ J.]The Journal of Physical Chemistry,1965,69 (8): 2510-2515. And R.W.Curtis, P.Chiotti, thermodynamic properties of calcium hydride [ J ]],1963,67,5,1061–1065.。
Reference electrode in the present example was YH x +YH 2-δ 。
Example 1
The structure of the metal melt hydrogen determination probe device is shown in figure 1 and comprises an upper insulating connecting piece 4, a lower insulating connecting piece 8, a stainless steel pipe 6 and a conductive protective cover 7;
the structure of each part is shown in FIG. 2;
the upper insulating connecting piece 4 is an integrated structure consisting of a top plate, a side wall and a hollow pipe, wherein the top plate is provided with a middle through hole, an electrode hole and a galvanic couple hole; the top end of the hollow tube is connected with the bottom surface of the top plate, the upper part of the side wall is sleeved outside the side surface of the top plate, internal threads are arranged in the side wall, the hollow tube is coaxial with the middle through hole, and the inner diameter of the hollow tube is larger than that of the middle through hole; the electrode hole and the galvanic couple hole are positioned between the outer wall of the hollow pipe and the inner wall of the side wall;
the lower insulating connecting piece 8 is cylindrical, and external threads are arranged on the outer wall surface;
the stainless steel pipe 6 is cylindrical, and the upper part and the lower part of the outer wall are respectively provided with an upper external thread and a lower external thread;
the conductive protective cover 7 is in a cylindrical shape, internal threads are arranged on the upper part of the inner wall surface of the side wall of the conductive protective cover, and a vent hole 14 is arranged on the bottom plate;
the upper insulating connecting piece 4 is in threaded sealing connection with the upper external thread of the stainless steel pipe 6, and the lower external thread of the stainless steel pipe 6 is in threaded sealing connection with the conductive protective cover 7 and the lower insulating connecting piece 8 simultaneously;
the stainless steel bar 2 and the proton conductor 15 are sequentially arranged inside the upper insulating connecting piece 4, the lower insulating connecting piece 8, the stainless steel pipe 6 and the conductive protective cover 7 from top to bottom;
the proton conductor 15 is a blind-end pipe, the lower part of the proton conductor is a hemispherical end enclosure, the top of the hemispherical end enclosure is connected with a cylindrical side wall to form an integral structure, and a high-temperature cement plate 11 is fixed on the inner wall of the cylindrical side wall; the high temperature cement plate 11 divides the proton conductor 15 into an upper space and a lower space, and the lower space is used for placing the reference electrode 13; the upper surface of the high-temperature cement board 11 is coated with a porous electrode coating; the outer surface and the inner surface of the proton conductor 15 are coated with the outer porous electrode coating 12 and the inner porous electrode coating 10, respectively;
the stainless steel bar 2 is an integrated structure consisting of a bar body and a single-stage pagoda joint at the upper part of the bar body; the stainless steel rod 2 passes through a through hole and a hollow pipe on the top plate of the upper insulating connecting piece 4; the bottom end of the stainless steel rod 2 is connected with the porous electrode coating of the high-temperature cement board 11; a spring 3 is arranged on the single-step pagoda joint, and the top end of the spring 3 is tightly pressed and connected with the bottom surface of the top plate of the upper connecting piece 4;
the upper part of the outer surface of the cylindrical side wall of the proton conductor 15 is fixedly bonded with the inner wall of the lower insulating connecting piece 8 through a high-temperature adhesive 9; a reference electrode 13 is arranged in the proton conductor 15, and the space below the proton conductor 15 is sealed by a high-temperature cement plate 11; the reference electrode 13 is metal hydride CaH x Or YH x (ii) a The proton conductor 15, the high-temperature cement plate 11 and the reference electrode 13 form a probe part;
the hemispherical head of the proton conductor 15 is opposite to the vent hole 14, and the hemispherical head of the proton conductor 15 is tightly connected with the bottom plate of the conductive protective cover 7;
a thermocouple 5 is arranged in a thermocouple hole of the upper insulating connecting piece 4, the bottom end of the thermocouple 5 is positioned in the upper space of the proton conductor 15, and a gap is reserved between the bottom end of the thermocouple 5 and the high-temperature cement plate 11; the thermocouple 5 is a double-hole corundum tube, the inner double holes are respectively the positive and negative electrodes of the K-type thermocouple wire, a notch is arranged on the side wall of the lower part, the bottom ends of the positive and negative electrodes of the thermocouple wire positioned at the notch are connected through welding, and a lead connected with the top ends of the positive and negative electrodes is connected with an external temperature measuring device;
a stainless steel electrode 1 is arranged in an electrode hole of the upper insulating connecting piece 4; the stainless steel electrode 1 is of an inverted T-shaped structure, a vertical rod part of the stainless steel electrode 1 penetrates through an electrode hole, and a transverse rod part of the stainless steel electrode 1 is tightly connected with the top end of the stainless steel pipe 6 in a pressing mode;
the using method comprises the following steps:
immersing the metal melt hydrogen determination probe device into the metal melt, wherein hydrogen in the metal melt diffuses through the vent hole 14 and establishes a hydrogen concentration difference with the reference electrode 13; electromotive force is generated between the inside and outside of the proton conductor 15;
the inner porous electrode coating 10 and the stainless steel bar 2 are used as positive electrodes, and the outer porous electrode coating 11, the conductive protective cover 7, the stainless steel pipe 6 and the stainless steel electrode 1 are used as negative electrodes; measuring the voltage between the two poles through a voltmeter; measuring the temperature in the stainless steel tube 6 by the thermocouple 5;
when the temperature and the voltage value are both in a stable state, substituting the measured voltage value into a formula (3) to calculate the hydrogen content in the metal melt;
the voltage value in the steady state means that the voltage value is measured every second, and when the standard deviation of the voltage value for continuous 10 seconds is less than or equal to 0.3mV, the steady state is obtained.
The stable state of the voltage value is 2-4 min after the measurement is started, and the stable state of the temperature is 1-1.5 min after the measurement is started; namely, when the voltage value is in a stable state, the temperature is also in the stable state;
the metal melt is pure aluminum melt; the measured time-temperature/voltage curve is shown in fig. 3; steady state E =213.6 × 10 -3 V, T =988K, then
The coefficient k of the pure aluminum alloy is 1.0057, then
Hydrogen content
Example 2
The structure of the metal melt hydrogen determination probe device is the same as that of the embodiment 1;
the method of use is the same as in example 1, except that:
the metal melt is ZL108 aluminum alloy melt; the measured time-temperature/voltage curve is shown in fig. 4; steady state E =267.2 × 10 -3 V, T =955K, then
Taking the coefficient k of ZL108 aluminum alloy as 0.543, then
According to the calculated hydrogen content
Example 3
The structure of the metal melt hydrogen determination probe device is the same as that of the embodiment 1;
the using method is different from that of the embodiment 1 in that:
the metal melt is A356 aluminum alloy melt; the measured time-temperature/voltage curve is shown in fig. 5; steady state E =196.1 × 10 -3 V, T =986K, then there are
Taking the coefficient k of the A356 aluminum alloy as 0.8309
According to calculation of the hydrogen content
Example 4
The structure of the metal melt hydrogen determination probe device is the same as that of the embodiment 1;
the using method is different from that of the embodiment 1 in that:
the metal melt is pure magnesium melt; the measured time-temperature/voltage curve is shown in fig. 6; steady state E =216.0 × 10 -3 V, T =1021K, then
If the coefficient k of the pure magnesium is 36.423, the
According to the calculated hydrogen content
Example 5
The structure of the metal melt hydrogen determination probe device is the same as that of the embodiment 1;
the using method is different from that of the embodiment 1 in that:
the metal melt is AZ91E magnesium alloy melt; the measured time-temperature/voltage curve is shown in fig. 7; steady state E =220.5 × 10 -3 V，T＝1025K, then there are
Taking the coefficient k of AZ91E magnesium alloy as 33.920
According to calculation of the hydrogen content
Example 6
The structure of the metal melt hydrogen determination probe device is the same as that of the embodiment 1;
the method of use is the same as in example 1, except that:
the metal melt is ZL101 aluminum alloy melt; the measured time-temperature/voltage curve is shown in fig. 8; steady state E =97.6 × 10 -3 V, T =973K, then
Taking the coefficient k of ZL101 aluminum alloy as 0.762
According to calculation of the hydrogen content
Example 7
The structure of the metal melt hydrogen determination probe device is the same as that of the embodiment 1;
the method of use is the same as in example 1, except that:
the metal melt is ZM5 magnesium alloy melt; the measured time-temperature/voltage curve is shown in fig. 9; steady state E =122.7 × 10 -3 V, T =1019K, then
When the coefficient k of the ZM5 magnesium alloy is 32.461, the
According to calculation of the hydrogen content
Claims (9)
1. A metal melt hydrogen determination probe device is characterized by comprising an upper insulating connecting piece, a lower insulating connecting piece, a stainless steel pipe and a conductive protective cover; the upper insulating connecting piece is an integrated structure consisting of a top plate, a side wall and a hollow pipe, wherein the top plate is provided with a middle through hole, an electrode hole and a galvanic couple hole; the top end of the hollow tube is connected with the bottom surface of the top plate, the upper part of the side wall is sleeved outside the side surface of the top plate, internal threads are arranged in the side wall, the hollow tube is coaxial with the middle through hole, and the inner diameter of the hollow tube is larger than that of the middle through hole; the electrode hole and the galvanic couple hole are positioned between the outer wall of the hollow pipe and the inner wall of the side wall; the lower insulating connecting piece is cylindrical, and external threads are arranged on the outer wall surface of the lower insulating connecting piece; the stainless steel pipe is cylindrical, and the upper part and the lower part of the outer wall are respectively provided with an upper external thread and a lower external thread; the conductive protective cover is in a barrel shape, internal threads are arranged on the upper part of the inner wall surface of the side wall of the conductive protective cover, and a vent hole is arranged on the bottom plate; the upper insulating connecting piece is connected with the upper external thread of the stainless steel pipe in a sealing way through threads, and the lower external thread of the stainless steel pipe is simultaneously connected with the conductive protective cover and the lower insulating connecting piece in a sealing way through threads; the stainless steel bar and the proton conductor are sequentially arranged inside the upper insulating connecting piece, the lower insulating connecting piece, the stainless steel pipe and the conductive protective cover from top to bottom; the proton conductor is a blind end pipe, the lower part of the proton conductor is a hemispherical end enclosure, the top of the hemispherical end enclosure is connected with a cylindrical side wall to form an integral structure, and a high-temperature cement plate is fixed on the inner wall of the cylindrical side wall; the high-temperature cement plate divides the proton conductor into an upper space and a lower space, and the lower space is used for placing a reference electrode; the upper surface of the high-temperature cement board is coated with a porous electrode coating; the outer surface and the inner surface of the proton conductor are respectively coated with an outer porous electrode coating and an inner porous electrode coating;
the stainless steel bar is of an integrated structure consisting of a bar body and a single-step pagoda joint on the upper part of the bar body; the stainless steel rod penetrates through a through hole and a hollow pipe on the top plate of the upper insulating connecting piece; the bottom end of the stainless steel bar is connected with the porous electrode coating of the high-temperature cement board; and a spring is placed on the single-step pagoda joint, and the top end of the spring is tightly pressed and connected with the bottom surface of the top plate of the upper connecting piece.
2. The metal melt hydrogen determination probe device according to claim 1, wherein the upper part of the outer surface of the cylindrical side wall of the proton conductor is fixedly bonded with the inner wall of the lower insulating connecting piece through a high-temperature adhesive; a reference electrode is arranged in the proton conductor and is sealed in the lower space of the proton conductor through a high-temperature cement board; the reference electrode is metal hydride CaH x Or YH x (ii) a The proton conductor, the high-temperature cement plate and the reference electrode constitute a probe portion.
3. The metal melt hydrogen determination probe device according to claim 1, wherein the hemispherical head of the proton conductor is opposite to the vent hole, and the hemispherical head of the proton conductor is connected with the bottom plate of the conductive protective cover in a compression manner.
4. The metal melt hydrogen determination probe device according to claim 1, wherein a thermocouple is installed in a thermocouple hole of the upper insulating connecting piece, the bottom end of the thermocouple is located in the upper space of the proton conductor, and a gap is formed between the bottom end of the thermocouple and the high-temperature cement plate; the thermocouple is a double-hole corundum tube, the inner double holes are respectively the positive and negative electrodes of the K-type thermocouple wire, a notch is formed in the side wall of the lower portion of the thermocouple wire, the bottom ends of the positive and negative electrodes of the thermocouple wire located in the notch are connected through welding, and a lead connected with the top ends of the positive and negative electrodes is connected with an external temperature measuring device.
5. The metal melt hydrogen determination probe device according to claim 1, wherein a stainless steel electrode is arranged in an electrode hole of the upper insulating connecting piece; the stainless steel electrode is of an inverted T-shaped structure, the vertical rod part of the stainless steel electrode penetrates through the electrode hole, and the horizontal rod part of the stainless steel electrode is connected with the top end of the stainless steel tube in a pressing mode.
6. The metal melt hydrogen determination probe device according to claim 1, wherein the conductive shield is made of graphite.
7. The metal melt hydrogen determination probe device according to claim 1, wherein the upper insulating connector is made of polytetrafluoroethylene.
8. The metal melt hydrogen determination probe device according to claim 1, wherein the lower insulating connecting member is made of ceramic; the ceramic is a macor ceramic.
9. The use method of the metal melt hydrogen determination probe device of claim 1, which is characterized by comprising the following steps:
(1) Immersing the metal melt hydrogen determination probe device into the metal melt, wherein hydrogen in the metal melt diffuses through the vent hole and establishes a hydrogen concentration difference with the reference electrode; electromotive force is generated between the inside and outside of the proton conductor;
(2) The inner porous electrode coating and the stainless steel bar are used as a positive electrode, and the outer porous electrode coating, the conductive protective cover, the stainless steel pipe and the stainless steel electrode are used as a negative electrode; measuring the voltage between the two poles through a voltmeter; measuring the temperature in the stainless steel tube by a thermocouple;
(3) And when the temperature and the voltage value are both in a stable state, calculating the hydrogen content in the metal melt by measuring the voltage value.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1278509A (en) * | 1968-10-28 | 1972-06-21 | Asea Ab | Means for measuring the oxygen content of a metallic melt |
| US4882032A (en) * | 1988-06-27 | 1989-11-21 | General Motors Corporation | Hydrogen probe |
| JPH0829375A (en) * | 1994-07-12 | 1996-02-02 | Tokyo Yogyo Co Ltd | Sensor for measuring quantity of hydrogen dissolved in molten metal |
| JPH0829379A (en) * | 1994-07-15 | 1996-02-02 | Tokyo Yogyo Co Ltd | Sensor for measuring quantity of hydrogen dissolved in molten metal |
| CN112129824A (en) * | 2020-09-24 | 2020-12-25 | 东北大学 | Device and method for nondestructively measuring hydrogen content in solid steel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0421868D0 (en) * | 2004-10-01 | 2004-11-03 | Environmental Monitoring And C | Apparatus and method for measuring hydrogen concentration |
| EP2929338A1 (en) * | 2012-12-07 | 2015-10-14 | Environmental Monitoring And Control Limited | Method and apparatus for monitoring gas concentration |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1278509A (en) * | 1968-10-28 | 1972-06-21 | Asea Ab | Means for measuring the oxygen content of a metallic melt |
| US4882032A (en) * | 1988-06-27 | 1989-11-21 | General Motors Corporation | Hydrogen probe |
| JPH0829375A (en) * | 1994-07-12 | 1996-02-02 | Tokyo Yogyo Co Ltd | Sensor for measuring quantity of hydrogen dissolved in molten metal |
| JPH0829379A (en) * | 1994-07-15 | 1996-02-02 | Tokyo Yogyo Co Ltd | Sensor for measuring quantity of hydrogen dissolved in molten metal |
| CN112129824A (en) * | 2020-09-24 | 2020-12-25 | 东北大学 | Device and method for nondestructively measuring hydrogen content in solid steel |
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