CN114324536B - Hydrogen probe device is decided to metal melt - Google Patents

Hydrogen probe device is decided to metal melt Download PDF

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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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metal melt
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厉英
黄文龙
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Northeastern University China
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Abstract

一种金属熔体定氢探头装置,包括上绝缘连接件、下绝缘连接件、不锈钢管和导电保护罩;上绝缘连接件、下绝缘连接件、不锈钢管和导电保护罩的内部从上至下依次设有不锈钢棒和质子导体;质子导体为盲端管,其下部为半球型封头,半球型封头的顶部连接圆筒状侧壁构成一体结构,圆筒状侧壁的内壁上固定有高温水泥板;高温水泥板将质子导体分隔为上部空间和下部空间;高温水泥板的上表面涂敷有多孔电极涂层;质子导体的外表面和内表面分别涂敷外多孔电极涂层和内多孔电极涂层。本发明的装置的装配及拆卸简单,当传感器达到使用寿命后,可只更换探头,而无需更换传感器主体部分,可节约大量成本。

Figure 202210016713

A metal melt hydrogen determination probe device, including an upper insulating connector, a lower insulating connector, a stainless steel tube and a conductive protective cover; the interior of the upper insulating connector, the lower insulating connector, the stainless steel tube and the conductive protective cover is from top to bottom There are stainless steel rods and proton conductors in turn; the proton conductor is a blind-end tube, the lower part of which is a hemispherical head, the top of the hemispherical head is connected to the cylindrical side wall to form an integrated structure, and the inner wall of the cylindrical side wall is fixed with High-temperature cement board; the high-temperature cement board separates 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 inner surface of the proton conductor are respectively coated with an outer porous electrode coating and an inner Porous Electrode Coating. The device of the present invention is easy to assemble and disassemble, and when the sensor reaches the service life, only the probe can be replaced without replacing the main part of the sensor, which can save a lot of cost.

Figure 202210016713

Description

一种金属熔体定氢探头装置A metal melt hydrogen determination probe device

技术领域technical field

本发明涉及冶金行业中传感器技术领域,具体涉及一种金属熔体定氢探头装置。The invention relates to the technical field of sensors in the metallurgical industry, in particular to a metal melt hydrogen determination probe device.

背景技术Background technique

质子导体传感测氢是一种新型测氢方法,该方法可以准确、迅速、实时的对金属熔体及气体中的氢进行测量,实现在线的智能监控,是一种极具前景的测氢方法。当传感器所使用的传感材料为理想的纯质子导体时,其原电池反应如公式(1)所示:Hydrogen measurement by proton conductor sensing is a new method of hydrogen measurement. This method can accurately, rapidly and real-time measure hydrogen in metal melts and gases, and realize online intelligent monitoring. It is a promising hydrogen measurement method. method. When the sensing material used in the sensor is an ideal pure proton conductor, its galvanic battery reaction is shown in formula (1):

H2(参比极)=H2(金属极) (1);H 2 (reference pole) = H 2 (metal pole) (1);

理想状态下原电池产生的电动势如公式(2)所示:The electromotive force generated by the primary battery under ideal conditions is shown in formula (2):

Figure BDA0003456325640000011
Figure BDA0003456325640000011

金属熔体中的氢含量如公式(3)所示:The hydrogen content in the metal melt is shown in formula (3):

Figure BDA0003456325640000012
Figure BDA0003456325640000012

以上各式中,R为气体常数8.314J/(mol·K);T为温度,单位K;F为法拉第常数96485C/mol;E为电动势,单位V;k为合金系数;S为金属熔体中的氢含量,单位ml/100g;

Figure BDA0003456325640000013
Figure BDA0003456325640000014
为金属熔体的氢分压,单位atm,
Figure BDA0003456325640000015
为参比侧的氢分压,单位atm。In the above formulas, R is the gas constant 8.314J/(mol K); T is the temperature, unit K; F is the Faraday constant 96485C/mol; E is the electromotive force, unit V; k is the alloy coefficient; S is the metal melt Hydrogen content in hydrogen, unit ml/100g;
Figure BDA0003456325640000013
Figure BDA0003456325640000014
is the hydrogen partial pressure of the metal melt, in atm,
Figure BDA0003456325640000015
is the partial pressure of hydrogen on the reference side, in atm.

当质子导体为纯质子导电时,通过控制参比极的氢分压,利用原电池产生的电动势计算出待测极金属熔体中的氢含量。When the proton conductor is pure proton conduction, by controlling the hydrogen partial pressure of the reference electrode, the hydrogen content in the metal melt of the electrode to be measured is calculated by using the electromotive force generated by the primary battery.

EP0544281 TYK公司的测量1000℃以下金属熔体中氢含量的装置,以SrCe0.95Yb0.05O3-x、CaZr0.9In0.1O3-x、BaCe0.95Y0.05O3-x等质子导体作为氢敏材料,Pt、Ni等金属丝作为电极引线,使用陶瓷粘结剂将质子导体、莫来石管、气室等部件粘结为一体以保证其连接;公开号为CN105319253的专利申请公布了一种测量熔融金属中氢含量的传感器及测量方法,使用CaZr0.9In0.1O3-x质子导体作为氢敏材料,以铂、金、银、镍铬等金属丝作为电极引线,以绝缘陶瓷粘结剂,将质子导体与通管粘结为一体以保证其连接;专利US 2005/0252789公布了一种氢传感装置及方法,以SrCe0.95Yb0.05O3-δ、CaZr0.9In0.1O3-δ作为氢敏材料,α-Ti/β-Ti、α-Zr/β-Zr、β-Zr/δ-Zr、α-Hf/δ-Hf作为固态参比电极,以内部填充材料及玻璃密封剂将装置密封为一体,但该专利只涉及探头部分,未公开传感器所需的支撑及电极引线连接部分。EP0544281 TYK company's device for measuring hydrogen content in molten metal below 1000 ℃, using proton conductors such as 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 as hydrogen sensors Materials, metal wires such as Pt and Ni are used as electrode leads, and ceramic binders are used to bond parts such as proton conductors, mullite tubes, and gas chambers to ensure their connection; the patent application with publication number CN105319253 has announced a A sensor and measurement method for measuring hydrogen content in molten metal, using CaZr 0.9 In 0.1 O 3-x proton conductors as hydrogen sensitive materials, platinum, gold, silver, nickel chromium and other metal wires as electrode leads, and insulating ceramic binders , the proton conductor and the through pipe are bonded together to ensure their connection; patent 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 a hydrogen sensitive material, α-Ti/β-Ti, α-Zr/β-Zr, β-Zr/δ-Zr, α-Hf/δ-Hf are used as solid reference electrodes, and internal filling materials and glass sealants The device is sealed as a whole, but the patent only involves the probe part, and the support and electrode lead connection part required by the sensor are not disclosed.

目前的测氢装置中,质子导体传感测氢探头均为一体式,当传感器出现问题后较难进行检查与维修,且当传感器达到使用寿命后,必须整体进行更换,这些问题增加了传感器的使用成本;因此,需要一种易于拆卸、维修及更换的分体式传感器探头。In the current hydrogen measuring device, the proton conductor sensing hydrogen measuring probes are all integrated. When the sensor has a problem, it is difficult to check and maintain, and when the sensor reaches the end of its service life, it must be replaced as a whole. These problems increase the sensor’s cost of use; therefore, a split sensor probe that is easy to disassemble, repair and replace is required.

发明内容Contents of the invention

为了解决上述问题,本发明提供一种金属熔体定氢探头装置,基于质子导体浓差电池测氢法,使用固态金属氢化物作为参比极,质子导体探头输出浓差电池电动势,金属氢化物与内侧多孔电极等共同作为正极;外侧多孔电极与保护罩等共同作为负极,具有装配及拆卸简单,当传感器达到使用寿命后只更换探头,无需更换传感器主体部分。In order to solve the above problems, the present invention provides a metal melt hydrogen determination probe device, based on the proton conductor concentration cell hydrogen measurement method, using solid metal hydride as a reference electrode, the proton conductor probe outputs the electromotive force of the concentration cell, and the metal hydride Together with the inner porous electrode as the positive electrode; the outer porous electrode and the protective cover as the negative electrode, it is easy to assemble and disassemble. When the sensor reaches the end of its service life, only the probe needs to be replaced without replacing the main part of the sensor.

本发明的金属熔体定氢探头装置包括上绝缘连接件4、下绝缘连接件8、不锈钢管6和导电保护罩7;上绝缘连接件4是由顶板、侧壁和中空管组成的一体结构,其中顶板上设有中通孔、电极孔和电偶孔;中空管顶端与顶板底面连接,侧壁上部套在顶板侧面外,侧壁内设有内螺纹,中空管与中通孔同轴,且中空管内径大于中通孔内径;电极孔和电偶孔位于中空管外壁和侧壁内壁之间;下绝缘连接件8为圆筒状,外壁面上设有外螺纹;不锈钢管6为圆筒状,外壁的上部和下部分别设有上外螺纹和下外螺纹;导电保护罩7为圆桶状,其侧壁内壁面上部设有内螺纹,底板上设有通气孔14;上绝缘连接件4与不锈钢管6的上外螺纹通过螺纹密封连接,不锈钢管6的下外螺纹与导电保护罩7和下绝缘连接件8同时通过螺纹密封连接;上绝缘连接件4、下绝缘连接件8、不锈钢管6和导电保护罩7的内部从上至下依次设有不锈钢棒2和质子导体15;质子导体15为盲端管,其下部为半球型封头,半球型封头的顶部连接圆筒状侧壁构成一体结构,圆筒状侧壁的内壁上固定有高温水泥板11;高温水泥板11将质子导体15分隔为上部空间和下部空间,下部空间用于放置参比电极13;高温水泥板11的上表面涂敷有多孔电极涂层;质子导体15的外表面和内表面分别涂敷外多孔电极涂层12和内多孔电极涂层10。The metal melt hydrogen determination probe device of the present invention includes an upper insulating connector 4, a lower insulating connector 8, a stainless steel tube 6 and a conductive protective cover 7; the upper insulating connector 4 is an integral body composed of a top plate, a side wall and a hollow tube structure, wherein the top plate is provided with a through hole, an electrode hole and a galvanic hole; the top of the hollow tube is connected to the bottom of the top plate, the upper part of the side wall is sleeved outside the side of the top plate, and an internal thread is provided in the side wall, and the hollow tube is connected to the middle through The holes are coaxial, and the inner diameter of the hollow tube is larger than the inner diameter of the through hole; the electrode hole and the galvanic hole are located between the outer wall of the hollow tube and the inner wall of the side wall; the lower insulating connector 8 is cylindrical, and the outer wall is provided with external threads ; The stainless steel pipe 6 is cylindrical, and the upper and lower parts of the outer wall are respectively provided with an upper external thread and a lower external thread; The air hole 14; the upper insulating connector 4 and the upper external thread of the stainless steel pipe 6 are connected by thread sealing, and the lower external thread of the stainless steel pipe 6 is connected with the conductive protective cover 7 and the lower insulating connector 8 by thread sealing at the same time; the upper insulating connector 4 , the lower insulating connector 8, the stainless steel pipe 6 and the conductive protective cover 7 are provided with a stainless steel rod 2 and a proton conductor 15 from top to bottom; The top of the head is connected to the cylindrical side wall to form an integrated structure, and a high-temperature cement board 11 is fixed on the inner wall of the cylindrical side wall; the high-temperature cement board 11 divides the proton conductor 15 into an upper space and a lower space, and the lower space is used to place The reference electrode 13; the upper surface of the high-temperature cement board 11 is coated with a porous electrode coating; the outer and inner surfaces of the proton conductor 15 are coated with an outer porous electrode coating 12 and an inner porous electrode coating 10, respectively.

上述装置中,不锈钢棒2由棒体及其上部的单阶宝塔接头构成一体结构;不锈钢棒2穿过上绝缘连接件4顶板上的通孔和中空管;不锈钢棒2的底端与高温水泥板11的多孔电极涂层连接;单阶宝塔接头上放置弹簧3,弹簧3的顶端与上连接件4的顶板底面压紧连接。In the above device, the stainless steel rod 2 is composed of a rod body and a single-stage pagoda joint on its upper part to form an integrated structure; the stainless steel rod 2 passes through the through hole and the hollow tube on the top plate of the upper insulating connector 4; the bottom end of the stainless steel rod 2 is connected to the high temperature The porous electrode coating of the cement board 11 is connected; the spring 3 is placed on the single-stage pagoda joint, and the top of the spring 3 is pressed and connected with the bottom surface of the top plate of the upper connector 4 .

上述装置中,质子导体15的圆筒状侧壁外表面的上部通过高温粘结剂9与下绝缘连接件8的内壁粘接固定;质子导体15内设置参比电极13,并通过高温水泥板11密封在质子导体15的下部空间;所述的参比电极13为金属氢化物CaHx或YHx;质子导体15、高温水泥板11和参比电极13构成探头部分。In the above-mentioned device, the upper part of the outer surface of the cylindrical side wall of the proton conductor 15 is bonded and fixed with the inner wall of the lower insulating connector 8 by a high-temperature adhesive 9; 11 is sealed in the lower space of the proton conductor 15; the reference electrode 13 is metal hydride CaH x or YH x ; the proton conductor 15, the high temperature cement plate 11 and the reference electrode 13 constitute the probe part.

上述装置中,质子导体15的半球型封头与通气孔14相对,质子导体15的半球型封头与导电保护罩7底板之间压紧连接。In the above device, the hemispherical head of the proton conductor 15 is opposite to the air hole 14 , and the hemispherical head of the proton conductor 15 is tightly connected to the bottom plate of the conductive protective cover 7 .

上述装置中,上绝缘连接件4的电偶孔内安装有热电偶5,热电偶5底端位于质子导体15的上部空间内,热电偶5底端与高温水泥板11之间有间隙;热电偶5为双孔刚玉管,内部双孔分别为K型热电偶丝的正负极,下部侧壁上设有开槽,位于开槽处的热电偶丝的正负极底端通过焊接连接,正负极顶端连接的导线与外部的测温装置连接。In the above-mentioned device, a thermocouple 5 is installed in the couple hole of the upper insulating connector 4, the bottom end of the thermocouple 5 is located in the upper space of the proton conductor 15, and there is a gap between the bottom end of the thermocouple 5 and the high-temperature cement plate 11; Couple 5 is a double-hole corundum tube, and the inner double holes are the positive and negative poles of the K-type thermocouple wire respectively. There is a slot on the lower side wall, and the bottom ends of the positive and negative poles of the thermocouple wire located at the slot are connected by welding. The wires connected to the top of the positive and negative poles are connected to the external temperature measuring device.

上述装置中,上绝缘连接件4的电极孔内设置不锈钢电极1;不锈钢电极1为倒置的T型结构,不锈钢电极1的竖杆部分穿过电极孔,不锈钢电极1的横杆部分与不锈钢管6顶端压紧连接。In the above device, a stainless steel electrode 1 is arranged in the electrode hole of the upper insulating connector 4; the stainless steel electrode 1 is an inverted T-shaped structure, the vertical bar part of the stainless steel electrode 1 passes through the electrode hole, and the horizontal bar part of the stainless steel electrode 1 is connected to the stainless steel tube 6 top compression connection.

上述装置中,导电保护罩7的材质为石墨。In the above device, the conductive protective cover 7 is made of graphite.

上述装置中,上绝缘连接件4的材质为聚四氟乙烯。In the above device, the material of the upper insulating connector 4 is polytetrafluoroethylene.

上述装置中,下绝缘连接件8的材质为陶瓷;所述的陶瓷为macor陶瓷。In the above device, the material of the lower insulating connector 8 is ceramic; the ceramic is macor ceramic.

上述装置中,各多孔电极涂层的为多孔Pt电极。In the above device, each porous electrode is coated with a porous Pt electrode.

上述装置中,高温水泥板11的材质为Aremco 503高温水泥。In the above device, the high temperature cement board 11 is made of Aremco 503 high temperature cement.

本发明的金属熔体定氢探头装置的使用方法为:The using method of the metal melt hydrogen determination probe device of the present invention is:

(1)将金属熔体定氢探头装置浸入金属熔体中,此时金属熔体中的氢通过通气孔14扩散,并与参比电极13建立氢浓度差;质子导体15的内外侧之间产生电动势;(1) Immerse the metal melt hydrogen determination probe device in the metal melt. At this time, the hydrogen in the metal melt diffuses through the vent hole 14, and establishes a hydrogen concentration difference with the reference electrode 13; between the inner and outer sides of the proton conductor 15 generate electromotive force;

(2)以内多孔电极涂层10和不锈钢棒2作为正极,以外多孔电极涂层11、导电保护罩7、不锈钢管6和不锈钢电极1作为负极;通过电压表测量两极之间的电压;通过热电偶5测量不锈钢管6内的温度;(2) With the porous electrode coating 10 and the stainless steel rod 2 as the positive pole, the outer porous electrode coating 11, the conductive protective cover 7, the stainless steel tube 6 and the stainless steel electrode 1 are used as the negative pole; measure the voltage between the two poles by a voltmeter; Even 5 measures the temperature in the stainless steel pipe 6;

(3)当温度和电压值均在稳定状态时,将测得电压值带入公式(2)和(3)计算出金属熔体中的氢含量。(3) When the temperature and voltage values are in a steady state, the measured voltage value is brought into formulas (2) and (3) to calculate the hydrogen content in the metal melt.

上述方法中,电压值在稳定状态是指每秒测量电压值,当连续10秒的电压值的标准差≤0.3mV时,即为稳定状态。In the above method, the voltage value in a steady state means that the voltage value is measured every second, and when the standard deviation of the voltage value for 10 consecutive seconds is ≤0.3mV, it is a steady state.

上述方法中,电压值的稳定状态在开始测量后的2~4min,温度的稳定状态在开始测量后的1~1.5min;即当电压值处于稳定状态时,温度也在稳定状态。In the above method, the stable state of the voltage value is 2-4 minutes after the start of the measurement, and the stable state of the temperature is 1-1.5 minutes after the start of the measurement; that is, when the voltage value is in a stable state, the temperature is also in a stable state.

上述方法中,金属熔体为铝熔体、镁熔体、锌熔体、镍熔体、铜熔体、铁熔体或钢熔体。In the above method, the metal melt is aluminum melt, magnesium melt, zinc melt, nickel melt, copper melt, iron melt or steel melt.

本发明采用金属氢化物、质子导体内多孔电极、不锈钢棒共同作为正极;质子导体外多孔电极和不锈钢管等作为负极;质子导体通过螺纹与其他部件相连,易于拆卸;氢敏材料为晶格缺陷型高温质子导体,利用质子导体的浓差电池电动势及希瓦特定律进行测氢;两个电极均为不锈钢,在温度变化区域不会产生热电势。The invention adopts metal hydride, porous electrode inside the proton conductor, and stainless steel rod as the positive electrode; the porous electrode outside the proton conductor and stainless steel pipe are used as the negative electrode; the proton conductor is connected with other components through threads, which is easy to disassemble; the hydrogen-sensitive material is a lattice defect Type high-temperature proton conductor, using the electromotive force of the concentration cell of the proton conductor and Schwart's law to measure hydrogen; the two electrodes are stainless steel, and no thermoelectric potential will be generated in the temperature change area.

本发明的装置的装配及拆卸简单,当传感器达到使用寿命后,可只更换探头,而无需更换传感器主体部分,可节约大量成本。The device of the present invention is easy to assemble and disassemble, and when the sensor reaches the service life, only the probe can be replaced without replacing the main part of the sensor, which can save a lot of cost.

附图说明Description of drawings

图1为本发明的金属熔体定氢探头装置结构示意图;Fig. 1 is the structural representation of the metal melt hydrogen determination probe device of the present invention;

图2为图1中各部件结构示意图;Fig. 2 is the structural representation of each part in Fig. 1;

图中,1、不锈钢电极,2、不锈钢棒,3、弹簧,4、上绝缘连接件,5、热电偶,6、不锈钢管,7、导电保护罩,8、下绝缘连接件,9、高温粘结剂,10、内多孔电极涂层,11、高温水泥板,12、外多孔电极涂层,13、参比电极,14、通气孔,15、质子导体;In the figure, 1. Stainless steel electrode, 2. Stainless steel rod, 3. Spring, 4. Upper insulating connector, 5. Thermocouple, 6. Stainless steel tube, 7. Conductive protective cover, 8. Lower insulating connector, 9. High temperature Binder, 10. Inner porous electrode coating, 11. High temperature cement board, 12. Outer porous electrode coating, 13. Reference electrode, 14. Air vent, 15. Proton conductor;

图3为本发明实施例1中测得的时间-温度/电压曲线图;Fig. 3 is the time-temperature/voltage curve chart that records in the embodiment of the present invention 1;

图4为本发明实施例2中测得的时间-温度/电压曲线图;Fig. 4 is the time-temperature/voltage curve chart that records in the embodiment of the present invention 2;

图5为本发明实施例3中测得的时间-温度/电压曲线图;Fig. 5 is the time-temperature/voltage graph that records in the embodiment of the present invention 3;

图6为本发明实施例4中测得的时间-温度/电压曲线图;Fig. 6 is the time-temperature/voltage graph measured in the embodiment of the present invention 4;

图7为本发明实施例5中测得的时间-温度/电压曲线图;Fig. 7 is the time-temperature/voltage graph measured in the embodiment of the present invention 5;

图8为本发明实施例6中测得的时间-温度/电压曲线图;Fig. 8 is the time-temperature/voltage graph measured in embodiment 6 of the present invention;

图9为本发明实施例7中测得的时间-温度/电压曲线图。Fig. 9 is a graph of time-temperature/voltage measured in Example 7 of the present invention.

具体实施方式Detailed ways

以下为本发明优选实施例,基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。The following are the preferred embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

本发明实施例中导电保护罩7的材质为石墨;上绝缘连接件4的材质为聚四氟乙烯;下绝缘连接件8的材质为陶瓷;所述的陶瓷为macor陶瓷;各多孔电极涂层的为多孔Pt电极;,高温水泥板11的材质为Aremco 503高温水泥。In the embodiment of the present invention, the material of the conductive protective cover 7 is graphite; the material of the upper insulating connector 4 is polytetrafluoroethylene; the material of the lower insulating connector 8 is ceramic; the ceramic is 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.

本发明实施例中通气孔14的孔径为1~3mm,通气孔数量为1~20个。In the embodiment of the present invention, the diameter of the ventilation holes 14 is 1-3 mm, and the number of ventilation holes is 1-20.

本发明实施例中导电保护罩7的高度大于比质子导体15的高度大5~50mm。In the embodiment of the present invention, the height of the conductive protective cover 7 is 5-50 mm greater than the height of the proton conductor 15 .

本发明实施例中,不锈钢管6和导电保护罩7的外壁上喷涂耐金属熔体腐蚀涂层,用于防护金属熔体的腐蚀。In the embodiment of the present invention, the outer walls of the stainless steel pipe 6 and the conductive protective cover 7 are sprayed with a metal melt corrosion-resistant coating to protect the metal melt from corrosion.

本发明实施例中,热电偶5外套有耐高温绝缘套管,以防止热电偶5接触内多孔电极涂层10。In the embodiment of the present invention, the thermocouple 5 is covered with a high temperature resistant insulating sleeve to prevent the thermocouple 5 from contacting the inner porous electrode coating 10 .

本发明实施例中的高温粘结剂为Aremco 503高温水泥。The high temperature binder in the embodiment of the present invention is Aremco 503 high temperature cement.

本发明的金属熔体定氢探头装置更换探头的步骤为:将金属熔体定氢探头装置倒置,即导电保护罩7位于上方,不锈钢棒2位于下方;旋转拆除导电保护罩7,此时导电保护罩及探头部分也被拆下;旋转分离导电保护罩7与探头部分;将新的探头部分旋转安装进导电保护罩9中,再将导电保护罩9旋转安装于不锈钢管6。The steps for replacing the probe device of the metal melt hydrogen determination probe device of the present invention are as follows: the metal melt hydrogen determination probe device is inverted, that is, the conductive protective cover 7 is located at the top, and the stainless steel rod 2 is located at the bottom; The protective cover and the probe part are also removed; the conductive protective cover 7 and the probe part are rotated and separated;

本发明实施例中的

Figure BDA0003456325640000051
为参比电极的氢分压所参考的文献为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.和R.W.Curtis,P.Chiotti,Thermodynamic properties of calcium hydride[J],1963,67,5,1061–1065.。In the embodiment of the present invention
Figure BDA0003456325640000051
The referenced literature for the hydrogen partial pressure of the reference electrode is LNYannopoulos, RK Edwards, PG Wahlbeck, The Thermodynamics of the Yttrium-Hydrogen System [J], The Journal of Physical Chemistry, 1965,69 (8): 2510-2515. and RW Curtis , P. Chiotti, Thermodynamic properties of calcium hydride [J], 1963, 67, 5, 1061–1065.

本发明实施例中的参比电极为YHx+YH2-δThe reference electrode in the embodiment of the present invention is YH x +YH 2-δ .

实施例1Example 1

金属熔体定氢探头装置结构如图1所示,包括上绝缘连接件4、下绝缘连接件8、不锈钢管6和导电保护罩7;The structure of the metal melt hydrogen determination probe device is shown in Figure 1, including an upper insulating connector 4, a lower insulating connector 8, a stainless steel tube 6 and a conductive protective cover 7;

各部件结构如图2所示;The structure of each part is shown in Figure 2;

上绝缘连接件4是由顶板、侧壁和中空管组成的一体结构,其中顶板上设有中通孔、电极孔和电偶孔;中空管顶端与顶板底面连接,侧壁上部套在顶板侧面外,侧壁内设有内螺纹,中空管与中通孔同轴,且中空管内径大于中通孔内径;电极孔和电偶孔位于中空管外壁和侧壁内壁之间;The upper insulating connector 4 is an integrated structure composed of a top plate, a side wall and a hollow tube, wherein the top plate is provided with a through hole, an electrode hole and a galvanic couple hole; the top of the hollow tube is connected with the bottom surface of the top plate, and the upper part of the side wall is sleeved on Outside the side of the top plate, the side wall is provided with internal threads, the hollow tube is coaxial with the through hole, and the inner diameter of the hollow tube is larger than the inner diameter of the through hole; the electrode hole and the galvanic hole are located between the outer wall of the hollow tube and the inner wall of the side wall ;

下绝缘连接件8为圆筒状,外壁面上设有外螺纹;The lower insulating connector 8 is cylindrical, and the outer wall is provided with external threads;

不锈钢管6为圆筒状,外壁的上部和下部分别设有上外螺纹和下外螺纹;The stainless steel pipe 6 is cylindrical, and the upper and lower parts of the outer wall are respectively provided with an upper external thread and a lower external thread;

导电保护罩7为圆桶状,其侧壁内壁面上部设有内螺纹,底板上设有通气孔14;The conductive protective cover 7 is barrel-shaped, and the upper part of the inner wall surface of the side wall is provided with an internal thread, and the bottom plate is provided with a ventilation hole 14;

上绝缘连接件4与不锈钢管6的上外螺纹通过螺纹密封连接,不锈钢管6的下外螺纹与导电保护罩7和下绝缘连接件8同时通过螺纹密封连接;The upper insulating connecting piece 4 is connected with the upper external thread of the stainless steel pipe 6 through thread sealing, and the lower external thread of the stainless steel pipe 6 is connected with the conductive protective cover 7 and the lower insulating connecting piece 8 through thread sealing at the same time;

上绝缘连接件4、下绝缘连接件8、不锈钢管6和导电保护罩7的内部从上至下依次设有不锈钢棒2和质子导体15;Stainless steel rods 2 and proton conductors 15 are sequentially arranged inside the upper insulating connector 4, the lower insulating connector 8, the stainless steel tube 6 and the conductive protective cover 7 from top to bottom;

质子导体15为盲端管,其下部为半球型封头,半球型封头的顶部连接圆筒状侧壁构成一体结构,圆筒状侧壁的内壁上固定有高温水泥板11;高温水泥板11将质子导体15分隔为上部空间和下部空间,下部空间用于放置参比电极13;高温水泥板11的上表面涂敷有多孔电极涂层;质子导体15的外表面和内表面分别涂敷外多孔电极涂层12和内多孔电极涂层10;The proton conductor 15 is a blind-end tube, and its lower part is a hemispherical head. The top of the hemispherical head is connected to a cylindrical side wall to form an integrated structure. A high-temperature cement board 11 is fixed on the inner wall of the cylindrical side wall; the high-temperature cement board 11 The proton conductor 15 is divided into an upper space and a lower space, and the lower space is used to place 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 respectively coated with Outer porous electrode coating 12 and inner porous electrode coating 10;

不锈钢棒2由棒体及其上部的单阶宝塔接头构成一体结构;不锈钢棒2穿过上绝缘连接件4顶板上的通孔和中空管;不锈钢棒2的底端与高温水泥板11的多孔电极涂层连接;单阶宝塔接头上放置弹簧3,弹簧3的顶端与上连接件4的顶板底面压紧连接;The stainless steel rod 2 is composed of the rod body and the single-stage pagoda joint on the upper part to form an integrated structure; the stainless steel rod 2 passes through the through hole and the hollow tube on the top plate of the upper insulating connector 4; the bottom end of the stainless steel rod 2 and the high temperature cement plate 11 The porous electrode coating is connected; the spring 3 is placed on the single-stage pagoda joint, and the top of the spring 3 is pressed and connected with the bottom surface of the top plate of the upper connector 4;

质子导体15的圆筒状侧壁外表面的上部通过高温粘结剂9与下绝缘连接件8的内壁粘接固定;质子导体15内设置参比电极13,并通过高温水泥板11密封在质子导体15的下部空间;所述的参比电极13为金属氢化物CaHx或YHx;质子导体15、高温水泥板11和参比电极13构成探头部分;The upper part of the outer surface of the cylindrical side wall of the proton conductor 15 is bonded and fixed to the inner wall of the lower insulating connector 8 by a high-temperature adhesive 9; The lower space of the conductor 15; the reference electrode 13 is a metal hydride CaH x or YH x ; the proton conductor 15, the high temperature cement plate 11 and the reference electrode 13 constitute the probe part;

质子导体15的半球型封头与通气孔14相对,质子导体15的半球型封头与导电保护罩7底板之间压紧连接;The hemispherical head of the proton conductor 15 is opposite to the air hole 14, and the hemispherical head of the proton conductor 15 is tightly connected to the bottom plate of the conductive protective cover 7;

上绝缘连接件4的电偶孔内安装有热电偶5,热电偶5底端位于质子导体15的上部空间内,热电偶5底端与高温水泥板11之间有间隙;热电偶5为双孔刚玉管,内部双孔分别为K型热电偶丝的正负极,下部侧壁上设有开槽,位于开槽处的热电偶丝的正负极底端通过焊接连接,正负极顶端连接的导线与外部的测温装置连接;A thermocouple 5 is installed in the couple hole of the upper insulating connector 4, the bottom end of the thermocouple 5 is located in the upper space of the proton conductor 15, and there is a gap between the bottom end of the thermocouple 5 and the high-temperature cement board 11; Hole corundum tube, the inner double holes are the positive and negative poles of the K-type thermocouple wire respectively, the lower side wall is provided with a slot, the bottom end of the positive and negative poles of the thermocouple wire located at the slot is connected by welding, the top of the positive and negative poles The connecting wire is connected with the external temperature measuring device;

上绝缘连接件4的电极孔内设置不锈钢电极1;不锈钢电极1为倒置的T型结构,不锈钢电极1的竖杆部分穿过电极孔,不锈钢电极1的横杆部分与不锈钢管6顶端压紧连接;A stainless steel electrode 1 is set in the electrode hole of the upper insulating connector 4; the stainless steel electrode 1 is an inverted T-shaped structure, the vertical rod part of the stainless steel electrode 1 passes through the electrode hole, and the horizontal rod part of the stainless steel electrode 1 is pressed against the top of the stainless steel tube 6 connect;

使用方法为:The method of use is:

将金属熔体定氢探头装置浸入金属熔体中,此时金属熔体中的氢通过通气孔14扩散,并与参比电极13建立氢浓度差;质子导体15的内外侧之间产生电动势;Immerse the metal melt hydrogen determination probe device into the metal melt, at this time, the hydrogen in the metal melt diffuses through the vent hole 14, and establishes a hydrogen concentration difference with the reference electrode 13; an electromotive force is generated between the inner and outer sides of the proton conductor 15;

以内多孔电极涂层10和不锈钢棒2作为正极,以外多孔电极涂层11、导电保护罩7、不锈钢管6和不锈钢电极1作为负极;通过电压表测量两极之间的电压;通过热电偶5测量不锈钢管6内的温度;The inner porous electrode coating 10 and the stainless steel rod 2 are used as the positive pole, and the outer porous electrode coating 11, the conductive protective cover 7, the stainless steel tube 6 and the stainless steel electrode 1 are used as the negative pole; the voltage between the two poles is measured by a voltmeter; measured by a thermocouple 5 The temperature in the stainless steel pipe 6;

当温度和电压值均在稳定状态时,将测得电压值带入公式(3)计算出金属熔体中的氢含量;When the temperature and the voltage value are all in a steady state, the measured voltage value is brought into formula (3) to calculate the hydrogen content in the metal melt;

电压值在稳定状态是指每秒测量电压值,当连续10秒的电压值的标准差≤0.3mV时,即为稳定状态。The voltage value in a stable state refers to measuring the voltage value every second. When the standard deviation of the voltage value for 10 consecutive seconds is less than or equal to 0.3mV, it is a stable state.

电压值的稳定状态在开始测量后的2~4min,温度的稳定状态在开始测量后的1~1.5min;即当电压值处于稳定状态时,温度也在稳定状态;The stable state of the voltage value is 2 to 4 minutes after the start of the measurement, and the stable state of the temperature is 1 to 1.5 minutes after the start of the measurement; that is, when the voltage value is in a stable state, the temperature is also in a stable state;

金属熔体为纯铝熔体;测得的时间-温度/电压曲线如图3所示;稳定状态的E=213.6×10-3V,T=988K,则有

Figure BDA0003456325640000061
取纯铝的合金的系数k为1.0057,则
Figure BDA0003456325640000062
含氢量
Figure BDA0003456325640000063
The metal melt is pure aluminum melt; the measured time-temperature/voltage curve is shown in Figure 3; E=213.6×10 -3 V and T=988K in the steady state, then there is
Figure BDA0003456325640000061
Taking the coefficient k of the alloy of pure aluminum as 1.0057, then
Figure BDA0003456325640000062
Hydrogen content
Figure BDA0003456325640000063

实施例2Example 2

金属熔体定氢探头装置结构同实施例1;The structure of the metal melt hydrogen determination probe device is the same as in Embodiment 1;

使用方法同实施例1,不同点在于:Using method is the same as embodiment 1, and difference is:

金属熔体为ZL108铝合金熔体;测得的时间-温度/电压曲线如图4所示;稳定状态的E=267.2×10-3V,T=955K,则有

Figure BDA0003456325640000064
取ZL108铝合金的系数k为0.543,则
Figure BDA0003456325640000071
The metal melt is a ZL108 aluminum alloy melt; the measured time-temperature/voltage curve is shown in Figure 4; E=267.2×10 -3 V and T=955K in the steady state, then there is
Figure BDA0003456325640000064
Taking the coefficient k of ZL108 aluminum alloy as 0.543, then
Figure BDA0003456325640000071

根据计算有含氢量

Figure BDA0003456325640000072
Hydrogen content according to the calculation
Figure BDA0003456325640000072

实施例3Example 3

金属熔体定氢探头装置结构同实施例1;The structure of the metal melt hydrogen determination probe device is the same as in Embodiment 1;

使用方法同实施例1,不同点在于:Using method is the same as embodiment 1, and difference is:

金属熔体为A356铝合金熔体;测得的时间-温度/电压曲线如图5所示;稳定状态的E=196.1×10-3V,T=986K,则有

Figure BDA0003456325640000073
取A356铝合金的系数k为0.8309,则
Figure BDA0003456325640000074
The metal melt is A356 aluminum alloy melt; the measured time-temperature/voltage curve is shown in Figure 5; E=196.1×10 -3 V and T=986K in the steady state, then there is
Figure BDA0003456325640000073
Taking the coefficient k of A356 aluminum alloy as 0.8309, then
Figure BDA0003456325640000074

根据计算有含氢量

Figure BDA0003456325640000075
Hydrogen content according to the calculation
Figure BDA0003456325640000075

实施例4Example 4

金属熔体定氢探头装置结构同实施例1;The structure of the metal melt hydrogen determination probe device is the same as in Embodiment 1;

使用方法同实施例1,不同点在于:Using method is the same as embodiment 1, and difference is:

金属熔体为纯镁熔体;测得的时间-温度/电压曲线如图6所示;稳定状态的E=216.0×10-3V,T=1021K,则有

Figure BDA0003456325640000076
取纯镁的系数k为36.423,则
Figure BDA0003456325640000077
The metal melt is pure magnesium melt; the measured time-temperature/voltage curve is shown in Figure 6; E=216.0×10 -3 V and T=1021K in the steady state, then there is
Figure BDA0003456325640000076
Taking the coefficient k of pure magnesium as 36.423, then
Figure BDA0003456325640000077

根据计算有含氢量

Figure BDA0003456325640000078
Hydrogen content according to the calculation
Figure BDA0003456325640000078

实施例5Example 5

金属熔体定氢探头装置结构同实施例1;The structure of the metal melt hydrogen determination probe device is the same as in Embodiment 1;

使用方法同实施例1,不同点在于:Using method is the same as embodiment 1, and difference is:

金属熔体为AZ91E镁合金熔体;测得的时间-温度/电压曲线如图7所示;稳定状态的E=220.5×10-3V,T=1025K,则有

Figure BDA0003456325640000079
取AZ91E镁合金的系数k为33.920,则
Figure BDA00034563256400000710
The metal melt is an AZ91E magnesium alloy melt; the measured time-temperature/voltage curve is shown in Figure 7; the steady state E=220.5×10 -3 V, T=1025K, then
Figure BDA0003456325640000079
Taking the coefficient k of AZ91E magnesium alloy as 33.920, then
Figure BDA00034563256400000710

根据计算有含氢量

Figure BDA00034563256400000711
Hydrogen content according to the calculation
Figure BDA00034563256400000711

实施例6Example 6

金属熔体定氢探头装置结构同实施例1;The structure of the metal melt hydrogen determination probe device is the same as in Embodiment 1;

使用方法同实施例1,不同点在于:Using method is the same as embodiment 1, and difference is:

金属熔体为ZL101铝合金熔体;测得的时间-温度/电压曲线如图8所示;稳定状态的E=97.6×10-3V,T=973K,则有

Figure BDA00034563256400000712
取ZL101铝合金的系数k为0.762,则
Figure BDA00034563256400000713
The metal melt is ZL101 aluminum alloy melt; the measured time-temperature/voltage curve is shown in Figure 8; E=97.6×10 -3 V and T=973K in the steady state, then there is
Figure BDA00034563256400000712
Taking the coefficient k of ZL101 aluminum alloy as 0.762, then
Figure BDA00034563256400000713

根据计算有含氢量

Figure BDA00034563256400000714
Hydrogen content according to the calculation
Figure BDA00034563256400000714

实施例7Example 7

金属熔体定氢探头装置结构同实施例1;The structure of the metal melt hydrogen determination probe device is the same as in Embodiment 1;

使用方法同实施例1,不同点在于:Using method is the same as embodiment 1, and difference is:

金属熔体为ZM5镁合金熔体;测得的时间-温度/电压曲线如图9所示;稳定状态的E=122.7×10-3V,T=1019K,则有

Figure BDA0003456325640000081
取ZM5镁合金的系数k为32.461,则
Figure BDA0003456325640000082
The metal melt is a ZM5 magnesium alloy melt; the measured time-temperature/voltage curve is shown in Figure 9; E=122.7×10 -3 V and T=1019K in the steady state, then there is
Figure BDA0003456325640000081
Taking the coefficient k of ZM5 magnesium alloy as 32.461, then
Figure BDA0003456325640000082

根据计算有含氢量

Figure BDA0003456325640000083
Hydrogen content according to the calculation
Figure BDA0003456325640000083

Claims (9)

1.一种金属熔体定氢探头装置,其特征在于包括上绝缘连接件、下绝缘连接件、不锈钢管和导电保护罩;上绝缘连接件是由顶板、侧壁和中空管组成的一体结构,其中顶板上设有中通孔、电极孔和电偶孔;中空管顶端与顶板底面连接,侧壁上部套在顶板侧面外,侧壁内设有内螺纹,中空管与中通孔同轴,且中空管内径大于中通孔内径;电极孔和电偶孔位于中空管外壁和侧壁内壁之间;下绝缘连接件为圆筒状,外壁面上设有外螺纹;不锈钢管为圆筒状,外壁的上部和下部分别设有上外螺纹和下外螺纹;导电保护罩为圆桶状,其侧壁内壁面上部设有内螺纹,底板上设有通气孔;上绝缘连接件与不锈钢管的上外螺纹通过螺纹密封连接,不锈钢管的下外螺纹与导电保护罩和下绝缘连接件同时通过螺纹密封连接;上绝缘连接件、下绝缘连接件、不锈钢管和导电保护罩的内部从上至下依次设有不锈钢棒和质子导体;质子导体为盲端管,其下部为半球型封头,半球型封头的顶部连接圆筒状侧壁构成一体结构,圆筒状侧壁的内壁上固定有高温水泥板;高温水泥板将质子导体分隔为上部空间和下部空间,下部空间用于放置参比电极;高温水泥板的上表面涂敷有多孔电极涂层;质子导体的外表面和内表面分别涂敷外多孔电极涂层和内多孔电极涂层;1. A metal melt hydrogen determination probe device is characterized in that it includes an upper insulating connector, a lower insulating connector, a stainless steel tube and a conductive protective cover; the upper insulating connector is an integral body composed of a top plate, a side wall and a hollow tube structure, wherein the top plate is provided with a through hole, an electrode hole and a galvanic hole; the top of the hollow tube is connected to the bottom of the top plate, the upper part of the side wall is sleeved outside the side of the top plate, and an internal thread is provided in the side wall, and the hollow tube is connected to the middle through The holes are coaxial, and the inner diameter of the hollow tube is larger than the inner diameter of the through hole; the electrode hole and the galvanic hole are located between the outer wall of the hollow tube and the inner wall of the side wall; the lower insulating connector is cylindrical, and an external thread is provided on the outer wall; The stainless steel tube is cylindrical, and the upper and lower parts of the outer wall are respectively provided with upper and lower external threads; the conductive protective cover is in the shape of a barrel, and the upper part of the inner wall of the side wall is provided with internal threads, and the bottom plate is provided with ventilation holes; The insulating connecting piece is connected with the upper external thread of the stainless steel pipe through thread sealing, and the lower external thread of the stainless steel pipe is connected with the conductive protective cover and the lower insulating connecting piece through thread sealing at the same time; the upper insulating connecting piece, the lower insulating connecting piece, the stainless steel pipe and the conductive The interior of the protective cover is provided with stainless steel rods and proton conductors in turn from top to bottom; the proton conductor is a blind-end tube, the lower part of which is a hemispherical head, and the top of the hemispherical head is connected to the cylindrical side wall to form an integrated structure. A high-temperature cement board is fixed on the inner wall of the shaped side wall; the high-temperature cement board divides the proton conductor into an upper space and a lower space, and the lower space is used to place 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 conductor are respectively coated with an outer porous electrode coating and an inner porous electrode coating; 所述的不锈钢棒由棒体及其上部的单阶宝塔接头构成一体结构;不锈钢棒穿过上绝缘连接件顶板上的通孔和中空管;不锈钢棒的底端与高温水泥板的多孔电极涂层连接;单阶宝塔接头上放置弹簧,弹簧的顶端与上连接件的顶板底面压紧连接。The stainless steel rod is composed of a rod body and a single-stage pagoda joint on its upper part to form an integrated structure; the stainless steel rod passes through the through hole and the hollow tube on the top plate of the upper insulating connector; the bottom end of the stainless steel rod and the porous electrode of the high temperature cement board Coating connection; a spring is placed on the single-stage pagoda joint, and the top of the spring is pressed and connected with the bottom surface of the top plate of the upper connector. 2.根据权利要求1所述的一种金属熔体定氢探头装置,其特征在于所述的质子导体的圆筒状侧壁外表面的上部通过高温粘结剂与下绝缘连接件的内壁粘接固定;质子导体内设置参比电极,并通过高温水泥板密封在质子导体的下部空间;所述的参比电极为金属氢化物CaHx或YHx;质子导体、高温水泥板和参比电极构成探头部分。2. A metal melt hydrogen determination probe device according to claim 1, characterized in that the upper part of the outer surface of the cylindrical side wall of the proton conductor is bonded to the inner wall of the lower insulating connector by a high-temperature adhesive connected and fixed; the reference electrode is set in the proton conductor, and is sealed in the lower space of the proton conductor by a high-temperature cement board; the reference electrode is a metal hydride CaH x or YH x ; the proton conductor, the high-temperature cement board and the reference electrode constitute the probe part. 3.根据权利要求1所述的一种金属熔体定氢探头装置,其特征在于所述的质子导体的半球型封头与通气孔相对,质子导体的半球型封头与导电保护罩底板之间压紧连接。3. A metal melt hydrogen determination probe device according to claim 1, characterized in that the hemispherical head of the proton conductor is opposite to the air hole, and the hemispherical head of the proton conductor and the bottom plate of the conductive protective cover Compression connection between. 4.根据权利要求1所述的一种金属熔体定氢探头装置,其特征在于所述的上绝缘连接件的电偶孔内安装有热电偶,热电偶底端位于质子导体的上部空间内,热电偶底端与高温水泥板之间有间隙;热电偶为双孔刚玉管,内部双孔分别为K型热电偶丝的正负极,下部侧壁上设有开槽,位于开槽处的热电偶丝的正负极底端通过焊接连接,正负极顶端连接的导线与外部的测温装置连接。4. A metal melt hydrogen determination probe device according to claim 1, characterized in that a thermocouple is installed in the galvanic couple hole of the upper insulating connector, and the bottom end of the thermocouple is located in the upper space of the proton conductor , there is a gap between the bottom end of the thermocouple and the high-temperature cement board; the thermocouple is a double-hole corundum tube, and the inner double holes are the positive and negative poles of the K-type thermocouple wire, and there is a slot on the lower side wall, which is located at the slot The positive and negative bottom ends of the thermocouple wires are connected by welding, and the wires connected to the top of the positive and negative electrodes are connected to the external temperature measuring device. 5.根据权利要求1所述的一种金属熔体定氢探头装置,其特征在于所述的上绝缘连接件的电极孔内设置不锈钢电极;不锈钢电极为倒置的T型结构,不锈钢电极的竖杆部分穿过电极孔,不锈钢电极的横杆部分与不锈钢管顶端压紧连接。5. A metal melt hydrogen determination probe device according to claim 1, characterized in that a stainless steel electrode is arranged in the electrode hole of the upper insulating connector; the stainless steel electrode is an inverted T-shaped structure, and the vertical position of the stainless steel electrode is The rod part passes through the electrode hole, and the cross rod part of the stainless steel electrode is pressed and connected with the top of the stainless steel tube. 6.根据权利要求1所述的一种金属熔体定氢探头装置,其特征在于所述的导电保护罩的材质为石墨。6. A metal melt hydrogen determination probe device according to claim 1, characterized in that the material of the conductive protective cover is graphite. 7.根据权利要求1所述的一种金属熔体定氢探头装置,其特征在于所述的上绝缘连接件的材质为聚四氟乙烯。7. A metal melt hydrogen determination probe device according to claim 1, characterized in that the material of the upper insulating connector is polytetrafluoroethylene. 8.根据权利要求1所述的一种金属熔体定氢探头装置,其特征在于所述的下绝缘连接件的材质为陶瓷;所述的陶瓷为macor陶瓷。8. A metal melt hydrogen determination probe device according to claim 1, characterized in that the material of the lower insulating connector is ceramic; the ceramic is macor ceramic. 9.一种权利要求1所述的一种金属熔体定氢探头装置的使用方法,其特征在于按以下步骤进行:9. A method for using a metal melt hydrogen determination probe device according to claim 1, characterized in that the following steps are performed: (1)将金属熔体定氢探头装置浸入金属熔体中,此时金属熔体中的氢通过通气孔扩散,并与参比电极建立氢浓度差;质子导体的内外侧之间产生电动势;(1) Immerse the metal melt hydrogen determination probe device into the metal melt. At this time, the hydrogen in the metal melt diffuses through the vent hole, and establishes a hydrogen concentration difference with the reference electrode; an electromotive force is generated between the inner and outer sides of the proton conductor; (2)以内多孔电极涂层和不锈钢棒作为正极,以外多孔电极涂层、导电保护罩、不锈钢管和不锈钢电极作为负极;通过电压表测量两极之间的电压;通过热电偶测量不锈钢管内的温度;(2) The inner porous electrode coating and stainless steel rod are used as positive electrodes, and the outer porous electrode coating, conductive protective cover, stainless steel tube and stainless steel electrode are used as negative electrodes; the voltage between the two electrodes is measured by a voltmeter; the temperature inside the stainless steel tube is measured by a thermocouple ; (3)当温度和电压值均在稳定状态时,通过测得电压值计算出金属熔体中的氢含量。(3) When the temperature and voltage values are in a stable state, the hydrogen content in the metal melt is calculated by the measured voltage value.
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