JP5237644B2 - Hydrogen amount measuring device - Google Patents

Description

  The present invention relates to a hydrogen amount measuring apparatus that measures the amount of hydrogen contained in a measurement object.

  A fuel tank storing a hydrogen storage product storing a predetermined amount of hydrogen, a hydrogen storage small block for releasing hydrogen stored by heating, a pressure container storing the hydrogen storage small block, and a heater for heating the pressure container And a hydrogen amount measuring device formed by a pressure gauge for measuring the internal pressure of the pressure vessel, a hydrogen flow path connected to the fuel tank and the pressure vessel, and an electromagnetic valve for opening and closing the hydrogen flow path (see Patent Document 1). ).

The procedure for measuring the amount of hydrogen in this hydrogen amount measuring apparatus is as follows. In this apparatus, the relationship between the pressure rise in the pressure vessel and the hydrogen amount is obtained in advance. By opening the hydrogen flow path with the solenoid valve opened, the internal pressure of the fuel tank and the internal pressure of the pressure vessel are balanced, and the amount of hydrogen stored in the fuel tank and the amount of hydrogen stored in the pressure vessel are stored. The amount of hydrogen in the small block is the same. In this state, the hydrogen valve is closed by closing the solenoid valve, the pressure vessel is heated by the heater to release hydrogen from the hydrogen storage small block, and the pressure gauge pressure rise due to the hydrogen released from the small block Determined by. Next, the amount of hydrogen corresponding to the pressure increase measured from the relationship between the pressure increase in the pressure vessel and the amount of hydrogen is obtained. After the measurement of the amount of hydrogen is completed, the hydrogen valve is opened from the closed state to the open state. When the water channel is opened, the internal pressure of the fuel tank and the internal pressure of the pressure vessel are balanced, the hydrogen amount of the hydrogen occlusion and the hydrogen amount of the hydrogen occlusion small block become the same, and the hydrogen amount can be measured again. . This hydrogen amount measuring apparatus measures the amount of hydrogen in the small block after storing the hydrogen in the hydrogen storage small block in an equilibrium state between the internal pressure in the fuel tank and the internal pressure in the pressure vessel. The amount of hydrogen can be accurately measured.
Japanese Patent Laid-Open No. 10-221332

  The hydrogen amount measuring device disclosed in Patent Document 1 heats a predetermined measurement object, gradually raises the temperature of the object from a low temperature to a high temperature, and releases the hydrogen from the object. Therefore, the amount of hydrogen released when the object to be measured is in a predetermined temperature range cannot be measured. This hydrogen amount measuring apparatus cannot determine the type of hydrogen contained in the object based on the temperature of the object to be measured.

  When the object to be measured is a steel material, it is necessary to measure diffusible hydrogen that causes delayed fracture of the steel material. The diffusible hydrogen gradually enters the steel material after the production of the steel material, and causes local deterioration in the steel material by floating inside the steel material at room temperature. Therefore, measuring the amount of diffusible hydrogen contained in a steel material is important in analyzing the current strength of the steel material and predicting the life and replacement time of the steel material. Since the hydrogen amount measuring device disclosed in Patent Document 1 cannot measure the diffusible hydrogen of a steel material, the current strength of the steel material cannot be analyzed using this device. The time cannot be predicted.

  An object of the present invention is to provide a hydrogen amount measuring device capable of quantifying the amount of hydrogen released from an object to be measured when the object to be measured is in a predetermined temperature range. Another object of the present invention is to be able to quantify the amount of diffusible hydrogen contained in the steel material, analyze the current strength of the steel material, and predict the life and replacement time of the steel material. It is to provide a quantity measuring device.

The hydrogen amount measuring apparatus of the present invention for solving the above-described problems is a vacuum chamber for storing a measurement object having a deformed and unusual mass, and gradually increasing the temperature of the measurement object stored in the vacuum chamber from a low temperature to a high temperature. A temperature raising mechanism , a standard hydrogen gas supply mechanism that supplies standard hydrogen gas to the vacuum chamber at a constant release rate, a temperature sensor that measures the temperature of the vacuum chamber, and a vacuum chamber connected to the vacuum chamber. Analyzes the hydrogen gas partial pressure of the hydrogen gas released from the measurement object as the temperature of the measurement object rises, and analyzes the partial pressure of the standard hydrogen gas supplied from the standard hydrogen gas supply mechanism to the vacuum chamber. and pressure the analyzer, and a controller for the partial pressure analyzer and temperature sensor are connected, the controller, the standard hydrogen gas output from the partial pressure analyzer A calibration curve setting means for setting the calibration curve by using the release rate corresponding to the partial pressure of the pressure and the standard hydrogen gas, the measurement object by fitting the hydrogen gas partial pressure outputted from the partial pressure analyzer calibration curve Hydrogen gas release rate determining means for determining the release rate of hydrogen gas released from the hydrogen, and hydrogen quantity quantifying means for integrating the release rate determined by the hydrogen gas release rate determining means to quantify the amount of hydrogen contained in the measurement object And correlation specifying means for specifying the correlation between the amount of hydrogen quantified by the hydrogen amount quantifying means and the measured temperature output from the temperature sensor.

As an example of the hydrogen amount measuring apparatus according to the present invention, a standard hydrogen gas supply mechanism is connected to a tank that stores standard hydrogen gas with a purity of 99.999% or more and a controller, and the standard hydrogen gas supply mechanism has a constant hydrogen gas release rate. And a hydrogen gas supply device for supplying gas from the tank to the vacuum chamber .

  As another example of the hydrogen amount measuring apparatus according to the present invention, the calibration curve setting means uses the partial pressure of at least three standard hydrogen gases and at least three discharge velocities corresponding to the partial pressures of the standard hydrogen gases. Set the line.

As another example of the hydrogen amount measuring apparatus of the present invention, in the calibration curve setting means, the standard hydrogen gas partial pressure and the release rate corresponding to the standard hydrogen gas partial pressure are written in the calibration curve prepared in advance, and the partial pressure The coordinate that is the intersection of the release rate and the point is specified, the line segment that passes through the coordinate is drawn from the origin of the calibration curve, the slope of the line segment is obtained, the function having that slope is calculated, and the calibration by that function A calibration curve storage means for displaying the calibration curve in which the curve is displayed on the calibration curve and the controller stores the partial pressure, the release rate, the slope, the function, and the calibration curve is included .

As another example of the hydrogen content measuring apparatus of the present invention, the time interval of the partial pressure analysis in the partial pressure analyzer is in the range of 0.01 to 5 seconds .

As another example of the hydrogen amount measuring apparatus of the present invention, a temperature increasing mechanism is connected to the controller, and the controller includes a temperature increasing rate adjusting means for increasing the temperature of the measuring object at a temperature increasing rate of 50 to 200 ° C./hr. The temperature rising range of the measurement object stored in the vacuum chamber is room temperature to 1000 ° C.

As another example of the hydrogen amount measuring apparatus of the present invention, the controller includes a background partial pressure analyzing means for causing the partial pressure analyzer to analyze the background partial pressure of the hydrogen gas remaining in the vacuum chamber, and releasing the hydrogen gas. The speed determining means subtracts the background partial pressure from the hydrogen gas partial pressure to calculate the substantial partial pressure, and applies the substantial partial pressure to the calibration curve to determine the release speed of the hydrogen gas released from the measurement object. .

As another example of the hydrogen content measuring apparatus of the present invention,
The ultimate vacuum of the vacuum chamber is in the range of 1 × 10 ⁻⁷ to 1 × 10 ⁻¹³ Pa, and the background partial pressure of hydrogen gas in the vacuum chamber is 1 × 10 ⁻⁹ Pa or less .

As another example of the hydrogen amount measuring apparatus of the present invention, the hydrogen amount quantifying means calibrates the hydrogen gas partial pressure of the hydrogen gas released from the measurement object when the measurement object is heated to room temperature to 300 ° C. Fit the line and quantify the amount of diffusible hydrogen contained in the measurement object . As another example of the hydrogen content measuring apparatus of the present invention, the measurement object is a steel material.

According to the hydrogen amount measuring apparatus of the present invention, a predetermined measurement object is heated in a vacuum, and the temperature of the object is gradually raised from a low temperature to a high temperature, whereby hydrogen gas released from the object is obtained. The partial pressure analyzer analyzes the partial pressure of hydrogen gas and applies the partial pressure of hydrogen gas output from the partial pressure analyzer to the calibration curve to determine the release rate of the hydrogen gas released from the measurement object. Since the determined release rate is integrated to quantify the amount of hydrogen contained in the measurement object, the amount of hydrogen released when the measurement object is in a predetermined temperature range can be reliably measured. Since this hydrogen amount measuring device identifies the correlation between the quantified amount of hydrogen and the temperature of the measurement object, the hydrogen amount corresponding to each temperature of the measurement object can be confirmed. Based on this, the type of hydrogen contained in the object can be determined. When the object to be measured is a steel material, it is necessary to measure diffusible hydrogen that causes delayed fracture, but the hydrogen content measuring device uses hydrogen released when the object to be measured is in a predetermined temperature range. Therefore, the amount of diffusible hydrogen contained in the steel material can be measured. This hydrogen amount measuring apparatus can analyze the current strength of steel materials and can predict the life and replacement time of steel materials.

The hydrogen amount measuring apparatus sets a calibration curve using the partial pressure of the standard hydrogen gas output from the partial pressure analyzer and the release rate corresponding to the partial pressure of the standard hydrogen gas. The hydrogen amount measurement device supplies standard hydrogen gas at a constant release rate from the hydrogen gas supply mechanism into the vacuum chamber, sets a calibration curve based on the partial pressure and release rate of the standard hydrogen gas, and Since the hydrogen gas partial pressure of the released hydrogen gas is applied to the calibration curve to determine the amount of hydrogen contained in the measurement object, the amount of hydrogen contained in the measurement object can be reliably quantified.

The hydrogen amount measuring apparatus sets a calibration curve using partial pressures of at least three standard hydrogen gases and at least three release rates corresponding to the partial pressures of the standard hydrogen gases. The hydrogen amount measuring apparatus can improve the reliability and certainty of the calibration curve by setting the calibration curve based on the partial pressure and release rate of at least three standard hydrogen gases. The hydrogen amount measuring apparatus applies the hydrogen gas partial pressure of the hydrogen gas released from the measurement object to a calibration curve set from the partial pressure and the release speed of at least three standard hydrogen gases, and the hydrogen amount of the object. Therefore, the amount of hydrogen contained in the measurement object can be measured with high reliability.

In the hydrogen amount measuring device, the time interval of partial pressure analysis in the partial pressure analyzer is in the range of 0.01 to 5 seconds, and the partial pressure analyzer releases hydrogen gas from the measurement object at the time interval. Since the partial pressure is analyzed, the amount of hydrogen contained in the object can be finely quantified while corresponding to the temperature of the object to be measured that changes from moment to moment, and when the measurement object is in a predetermined temperature range The amount of hydrogen released can be reliably measured with high reliability. The hydrogen amount measuring apparatus can confirm the hydrogen amount corresponding to each temperature of the measurement object, and can reliably determine the type of hydrogen contained in the object based on the temperature of the measurement object.

Since the hydrogen amount measuring device raises the temperature of the measurement object at a temperature increase rate of 50 to 200 ° C./hr , the measurement object can reach the maximum measurement temperature in a short time. The corresponding amount of hydrogen can be quantified in a short time. This hydrogen amount measuring device can set the heating rate of the measurement object freely within the above range, so select the heating rate that matches the measurement object according to the type, physical properties, and properties of the measurement object. can do.

The amount of hydrogen measurement device has an ultimate vacuum of the vacuum chamber in the range of 1 × 10 ⁻⁷ to 1 × 10 ⁻¹³ Pa, and by making the inside of the vacuum chamber an ultra-high vacuum, substances other than hydrogen can be obtained. It does not remain in the chamber, and the amount of hydrogen contained in the measurement object can be reliably measured with high reliability. Since the hydrogen gas background partial pressure of the hydrogen gas in the vacuum chamber is 1 × 10 ⁻⁹ Pa or less, the hydrogen amount measuring apparatus has a very low concentration of hydrogen remaining in the vacuum chamber. There is no error in quantifying the amount, and the amount of hydrogen contained in the measurement object can be reliably measured with high reliability.

The hydrogen amount measuring device calculates the actual partial pressure by subtracting the background partial pressure from the hydrogen gas partial pressure output from the partial pressure analyzer, and quantifies the hydrogen amount by fitting the partial partial pressure to the calibration curve. Even if hydrogen remains in the vacuum chamber, the residual hydrogen is subtracted to quantify the amount of hydrogen so that the residual hydrogen does not cause an error in quantifying the amount of hydrogen in the measurement object. The amount of hydrogen contained in the object can be reliably measured with high reliability.

The hydrogen amount measuring device applies a hydrogen gas partial pressure of hydrogen gas released from a measurement object when the temperature of the measurement object is raised to room temperature to 300 ° C. to a calibration curve, so that diffusivity contained in the measurement object is obtained. Since the amount of hydrogen is quantified , if the object to be measured is, for example, steel, the amount of diffusible hydrogen that causes delayed fracture can be reliably quantified, and the current strength of the steel can be analyzed. At the same time, it is possible to reliably predict the life and replacement time of the steel material.

  The details of the hydrogen amount measuring apparatus according to the present invention will be described below with reference to the accompanying drawings. FIG. 1 is a configuration diagram of a hydrogen amount measuring apparatus 10 shown as an example, and FIG. 2 is an end view taken along line AA of FIG. In FIG. 1, the front-rear direction is indicated by an arrow X, and the up-down direction is indicated by an arrow Y. In FIG. 2, the surrounding direction is indicated by an arrow Z. In FIG. 1, the electric furnace 13 (temperature raising mechanism) is shown as a cross-sectional view, and a part of the transport mechanism 12 that transports the steel sample 20 (measurement object) to the inside 19 of the vacuum chamber 11 is omitted. . The hydrogen amount measuring apparatus 10 includes a vacuum chamber 11, a transport mechanism 12, an electric furnace 13, a temperature sensor 14, a partial pressure analyzer 15, a standard gas supply mechanism 16, and a controller 17 as main components. And The transport mechanism 12, the electric furnace 13, the temperature sensor 14, the partial pressure analyzer 15, and the standard hydrogen gas supply mechanism 16 are connected to the controller 17 via an interface 18 (wired or wireless).

  The vacuum chamber 11 is made of quartz glass, tempered glass, or heat-resistant glass formed in a cylindrical shape, and extends in the front-rear direction. The chamber 11 can store a steel material sample 20 of a predetermined size in the interior 19 thereof. The steel material sample 20 may be a steel material product itself manufactured as a product having a predetermined shape or a part of the steel material product. Therefore, the steel material sample 20 measured in this measuring apparatus 10 is intended for those of irregular and irregular masses whose shapes, weights, and volumes are not uniform. In addition, the measuring object in this measuring apparatus 10 is not limited to the steel material sample 20, In addition to the steel material sample 20, all organic substances and inorganic substances are contained as a measuring object.

  In the vacuum chamber 11, the steel material sample 20 is placed on the center portion 21 in the front-rear direction. A vacuum valve 23 and a vacuum pump 24 are connected to one end 22 of the chamber 11. The valve 23 and the pump 24 are connected via a cylindrical pipe 25 and are connected to the controller 17 via the interface 18. A vacuum gauge (not shown) is installed in the pipe line 25. The vacuum gauge is connected to the controller 17 via an interface. The transport mechanism 12 is connected to the other end portion 26 of the chamber 11.

  The transport mechanism 12 is attached to a cylindrical casing 27 extending in the front-rear direction, a transport bar 28 installed inside the casing 27 and extending in the front-rear direction, and one end 29 of the transport bar 28 to attach the steel material sample 20. A support member (not shown) that is detachably supported and an induction magnet (not shown) arranged on the outer peripheral surface of the casing 27 are formed. The casing 27 is provided with a vacuum gauge (not shown). The vacuum gauge is connected to the controller 17 via an interface.

  Between the end portion 26 of the vacuum chamber 11 and the end portion 30 of the casing 27, a gate valve 31 that can be opened and closed is installed. An openable / closable hatch (not shown) is attached to the other end of the casing 27. A nitrogen gas injection device (not shown) for injecting nitrogen gas into the casing 27 is installed at a substantially central portion of the casing 27. A first position sensor (not shown) is installed on the outer peripheral surface of the vacuum chamber 11 in the vicinity of the gate valve 31. A second position sensor (not shown) is installed on the outer peripheral surface of the casing 17 in the vicinity of the gate valve 31. The gate valve 31 is connected to the controller 17 via the interface 18. The nitrogen gas injection device and the first and second position sensors are connected to the controller 17 via an interface.

  A vacuum valve (not shown) and a vacuum pump 32 are connected to the end 30 of the casing 27. The valve and the pump 32 are connected via a cylindrical pipe line 33 and are connected to the controller 17 via the interface 18. A vacuum gauge (not shown) is installed in the pipe line 33. The vacuum gauge is connected to the controller 17 via an interface. The transport rod 28 is movable in the front-rear direction inside the casing 27. The induction magnet is capable of moving the outer peripheral surface of the casing 27 in the front-rear direction and sliding the outer peripheral surface of the casing 27 in the surrounding direction while sliding on the outer peripheral surface of the casing 27. The transport mechanism 12 transports the steel material sample 20 from the end portion 26 of the chamber 11 to the central portion 21 using the transport rod 28, and places the steel material sample 20 in the central portion 21 of the chamber 11.

  The electric furnace 13 is formed of a control unit (not shown) and a heating unit 34 that generates heat to a predetermined temperature by a temperature control function of the control unit. The control unit is connected to the controller 17 via the interface 18. The heating unit 34 is made of a heating element 35 and a heat insulating material 36 surrounding the heating element 35. The heat insulating material 36 keeps the heating element 35 warm. As the electric furnace 13, a resistance heating furnace, an induction heating furnace, or a direct current type electric furnace can be used. The heating unit 34 of the electric furnace 13 can be swung in the vertical direction of the vacuum chamber 11 via a hinge 37, and surrounds the outer peripheral surface of the chamber 11 from the surrounding direction by swiveling toward the chamber 11. The electric furnace 13 gradually raises the temperature of the steel material sample 20 located in the interior 19 of the chamber 11 from low temperature to high temperature.

  The temperature sensor 14 is attached to the electric furnace 13, penetrates the heating part 34 of the electric furnace 13 in the vertical direction, and the measurement part 38 is located in the vicinity of the outer peripheral surface of the vacuum chamber 11. Although the thermocouple type is used for the temperature sensor 14, a resistance temperature sensor, a thermistor, an IC temperature sensor, and a magnetic temperature sensor can also be used. The temperature sensor 14 measures the temperature of the chamber 11 in time series and outputs the measured temperature to the controller 17.

  The partial pressure analyzer 15 is connected to a conduit 25 extending between the valve 23 and the pump 24 via a cylindrical conduit 39. The analyzer 15 uses a quadrupole mass separator (not shown). The quadrupole mass separator is formed of an ion source that ionizes hydrogen molecules, a filter unit that performs mass separation, and a detection unit that detects ions that have passed through the filter unit. In addition to the quadrupole mass separator, a double-focusing mass separator or a time-of-flight mass separator can be used. The analyzer 15 analyzes the hydrogen gas partial pressure of the hydrogen gas released from the steel sample 20 and diffusing in the interior 19 of the chamber 11 in time series, and outputs the analysis result (hydrogen gas partial pressure) to the controller 17. Further, the partial pressure of the standard hydrogen gas supplied from the standard hydrogen gas supply mechanism 16 and diffusing inside the chamber 11 is analyzed, and the analysis result (standard hydrogen gas partial pressure) is output to the controller 17.

  The standard hydrogen gas supply mechanism 16 includes a tank 40 that stores standard hydrogen gas having a purity of 99.999% or more, a hydrogen gas supply device 41 that supplies the standard hydrogen gas to the vacuum chamber 11 at a constant hydrogen gas release rate, A cylindrical first supply pipe 42 extending between the tank 40 and the supply apparatus 41 and a cylindrical second supply pipe 43 extending between the chamber 11 and the supply apparatus 41 are formed. A vacuum gauge (not shown) is attached to the supply device 41. Vacuum valves 44 and 45 are attached to the first supply pipe 42 and the second supply pipe 43. The supply device 41, the vacuum valves 44 and 45, and the vacuum gauge are connected to the controller 17 via the interface 18. The supply device 41 supplies a standard hydrogen gas with a constant pressure and a constant amount to the chamber 11 through the second supply pipe 43 at a constant time.

  The controller 17 is a computer having a central processing unit (CPU or MPU) and a memory, and incorporates a large-capacity hard disk. An input device such as a keyboard 46 and a mouse and an output device such as a display 47 and a printer are connected to the controller 17 via an interface. On the hard disk, the heating rate of the steel material sample 20, the time interval of the partial pressure analysis in the partial pressure analyzer 15, a calibration diagram showing the calibration curve (see FIG. 3), the background of hydrogen gas in the interior 19 of the chamber 11 The partial pressure is stored. The rate of temperature increase, the time interval of partial pressure analysis, and the background partial pressure can be input and changed at any time via an input device. The central processing unit of the controller 17 activates the application stored in the memory based on the control by the operating system, and executes the following means according to the activated application.

  The central processing unit of the controller 17 executes background partial pressure analysis means for causing the partial pressure analyzer 15 to analyze the background partial pressure of the hydrogen gas remaining in the interior 19 of the vacuum chamber 11, and is output from the analyzer 15. A background partial pressure storing means for storing the background partial pressure in the hard disk is executed. The central processing unit executes a calibration curve setting means for setting a calibration curve using the partial pressure of the standard hydrogen gas output from the analyzer 15 and the hydrogen release rate corresponding to the partial pressure of the standard hydrogen gas. A calibration curve storage means for storing the calibration curve thus stored in the hard disk is executed. Furthermore, when the calibration curve is changed, a calibration curve update unit is executed to rewrite the calibration curve before the change to the calibration curve after the change.

  The central processing unit of the controller 17 executes a temperature increase rate adjusting means for adjusting the temperature increase rate for the steel material sample 20 and applies the hydrogen gas partial pressure output from the partial pressure analyzer 15 to the calibration curve to fit the steel material sample 20. A hydrogen gas release rate determining means for determining a hydrogen gas release rate of the hydrogen gas released from is executed. The central processing unit executes a hydrogen amount quantifying unit that quantifies the amount of hydrogen contained in the steel material sample 20 from the hydrogen gas releasing rate, and stores the hydrogen gas releasing rate determined by the hydrogen gas releasing rate determining unit in the hard disk in time series. The hydrogen gas release rate storage means is executed. The central processing unit executes hydrogen amount storage means for storing the hydrogen amount quantified by the hydrogen amount quantification means in time series on the hard disk, and specifies the correlation between the hydrogen release rate and the measured temperature output from the temperature sensor 14. The correlation first specifying means is executed. Furthermore, a correlation second specifying means (correlation specifying means) for specifying the correlation between the hydrogen amount quantified by the hydrogen amount quantifying means and the measured temperature output from the temperature sensor 14 is executed.

  The central processing unit of the controller 17 executes correlation first storage means for storing the correlation between the hydrogen gas release rate and the measured temperature on the hard disk, and stores the correlation between the hydrogen amount and the measured temperature on the hard disk. The second storage means is executed. Further, a correlation first output means for outputting the correlation between the hydrogen gas release rate and the measured temperature is executed, and a correlation second output means for outputting the correlation between the hydrogen amount and the measured temperature is executed. The measuring procedure in the measuring apparatus 10 is as follows. First, after measuring the background partial pressure of the residual hydrogen gas inside the vacuum chamber 11, a calibration curve is set with standard hydrogen gas, and then the steel material sample 20 is transported. From 12 to the inside 19 of the chamber 11, various hydrogen amounts contained in the steel material sample 20 are measured.

  An example of background partial pressure measurement in the hydrogen amount measuring apparatus 10 will be described as follows. When the apparatus 10 is activated, the controller 17 operates and an initial screen (not shown) is displayed on the display 47 connected to the controller 17. When the background partial pressure measurement is selected from the various items on the initial screen, the condition setting screen is displayed on the display 47. On the condition setting screen, a partial pressure analysis time interval input area and a setting button in the partial pressure analyzer 15 are displayed. The time interval of the partial pressure analysis can be set in the range of 0.01 to 5 seconds. When a setting button is pressed after inputting time (seconds) in the time interval input area, a condition confirmation button and a cancel button are displayed on the display 47. Press the cancel button to return to the initial screen.

When the condition confirmation button is pressed, the measurement of the background partial pressure is started after the set time interval is stored in the hard disk. In the measurement of the background partial pressure, the controller 17 opens the vacuum valve 23 and also opens the vacuum valve of the pipe line 33 and operates the vacuum pumps 24 and 32. The gate valve 31 is closed. It is assumed that the time interval of the partial pressure analysis is set to 3 seconds. The degree of vacuum in the inside 19 of the vacuum chamber 11, the partial pressure analyzer 15, the pipes 25 and 39, the casing 27, and the pipe 33 is set to a range of 1 × 10 ⁻⁷ to 1 × 10 ⁻¹³ Pa by the pumps 24 and 32. Retained.

  The controller 17 monitors the degree of vacuum output from the vacuum gauge, and the inside 19 of the vacuum chamber 11, the partial pressure analyzer 15, the pipes 25 and 39, the casing 27, and the pipe line 33 have reached a predetermined degree of vacuum. When the determination is made, a partial pressure analysis command for the residual hydrogen gas remaining in the interior 19 of the vacuum chamber 11 is output to the partial pressure analyzer 15. The partial pressure analyzer 15 analyzes the partial pressure of the remaining hydrogen gas inside the chamber 11 at intervals of 3 seconds in accordance with the analysis command, and outputs the analysis result (background partial pressure) to the controller 17 (background partial pressure). Analytical means). The controller 17 stores the background partial pressure output from the analyzer 15 in the hard disk (background partial pressure storage means). The background partial pressure is measured every time the amount of hydrogen in the new steel material sample 20 is measured.

In this hydrogen amount measuring apparatus 10, since the degree of vacuum in the interior 19 of the vacuum chamber 11 is maintained in the range of 1 × 10 ⁻⁷ to 1 × 10 ⁻¹³ Pa by the vacuum pump 24, substances other than hydrogen can be contained in the chamber. The hydrogen amount contained in the steel material sample 20 can be reliably measured with high reliability. Further, the concentration of hydrogen remaining in the interior 19 of the chamber 11 is extremely low, and the background partial pressure of the residual hydrogen gas in the interior 19 of the chamber 11 is 1 × 10 ⁻⁹ Pa or less. Therefore, in this measuring apparatus 10, the residual hydrogen does not cause an error in the quantification of the amount of hydrogen in the steel material sample 20, and the amount of hydrogen contained in the steel material sample 20 can be reliably measured with high reliability. In addition, when the degree of vacuum inside the chamber 11 is less than 1 × 10 ⁻⁷ Pa, substances other than hydrogen may remain in the inside 19 of the chamber 11, and the amount of hydrogen contained in the steel material sample 20 should be accurately measured. May not be possible.

  FIG. 3 is a calibration curve diagram showing a calibration curve 51 shown as an example. An example of calibration curve setting in the measuring apparatus 10 will be described as follows. A calibration curve setting is selected from various items on the initial screen displayed on the display 47. When the calibration curve setting is selected, a condition confirmation screen is displayed on the display 47. In the condition confirmation screen, the time (3 seconds) set in the background partial pressure measurement is displayed in the time interval display area of the partial pressure analysis, and further, a condition confirmation button and a condition change button are displayed. When changing the time interval of the partial pressure analysis, the condition change button is pressed, the changed time interval is input in the time interval input area displayed on the display 47, and the condition setting is performed again.

  If there is no change in the conditions, press the condition confirmation button. When the condition confirmation button is pressed, a condition setting screen for setting a calibration curve is displayed on the display 47. On the condition setting screen, a standard hydrogen gas supply frequency input area and a setting button are displayed. After inputting the number of times of supply in the number of times of supply input area, when a setting button is pressed, a condition confirmation button and a cancel button are displayed on the display 47. Press the cancel button to return to the initial screen.

When the condition confirmation button is pressed, the calibration curve setting is started after the set number of times of supply is stored in the hard disk. In the calibration curve setting, the controller 17 opens the vacuum valves 44 and 45 to make the tank 40 and the supply device 41 communicate with each other, and makes the supply device 41 and the vacuum chamber 11 communicate with each other. The vacuum valve 23 is in an open state, and the vacuum pump 24 is in an operating state. In addition, the supply frequency shall be set to 3 times. The degree of vacuum in the interior 19 of the vacuum chamber 11, the partial pressure analyzer 15, the pipes 25 and 39, the supply device 41 and the supply pipes 42 and 43 is in the range of 1 × 10 ⁻⁷ to 1 × 10 ⁻¹³ Pa by the pump 24. Is held in.

  The controller 17 outputs a first standard hydrogen gas supply command to the gas supply device 41, and outputs a first standard hydrogen gas partial pressure analysis command released to the interior 19 of the vacuum chamber 11 to the partial pressure analyzer 15. To do. As the tank 40 and the supply device 41 communicate with each other, the first standard hydrogen gas flows from the tank 40 through the first supply pipe 42 into the supply device 41. In accordance with the supply command, the supply device 41 supplies a constant pressure and a constant amount of the first standard hydrogen gas to the second supply pipe 43 at a constant time, and supplies the controller 17 with the hydrogen gas release rate of the supplied first standard hydrogen gas. Output. The first standard hydrogen gas is released into the interior 19 of the vacuum chamber 11 through the second supply pipe 43, diffuses in the interior 19 of the chamber 11, and reaches the partial pressure analyzer 15. The partial pressure analyzer 15 analyzes the partial pressure of the first standard hydrogen gas and outputs the analysis result (first standard hydrogen gas partial pressure) to the controller 17. The controller 17 correlates the discharge speed of the first standard hydrogen gas output from the supply device 41 and the partial pressure of the first standard hydrogen gas output from the analyzer 15 with each other, and the discharge speed and the partial pressure thereof. Are stored on the hard disk.

After storing the release speed and partial pressure of the first standard hydrogen gas, the controller 17 closes the vacuum valve 44 to shut off the tank 40 and the hydrogen gas supply device 41, and connects the supply pipes 42, 43 and the supply device 41. The process waits until the first standard hydrogen gas remaining in the interior, the interior 19 of the vacuum chamber 11, the pipelines 25 and 39, and the partial pressure analyzer 15 is discharged to the outside via the vacuum pump 24. The waiting time is set in advance and stored in the hard disk. When the standby time elapses, the controller 17 opens the vacuum valve 44 to allow the tank 40 and the gas supply device 41 to communicate with each other. The degree of vacuum in the interior 19 of the vacuum chamber 11, the partial pressure analyzer 15, the pipes 25 and 39, the supply device 41 and the supply pipes 42 and 43 is in the range of 1 × 10 ⁻⁷ to 1 × 10 ⁻¹³ Pa by the pump 24. Is held in. The controller 17 outputs a supply command for the second standard hydrogen gas to the supply device 41, and outputs an analysis command for the partial pressure of the second standard hydrogen gas released into the interior 19 of the chamber 11 to the partial pressure analyzer 15.

  The second standard hydrogen gas flows from the tank 40 through the first supply pipe 42 into the hydrogen gas supply device 41. In accordance with the supply command, the supply device 41 supplies the second standard hydrogen gas with a constant pressure and a constant amount to the second supply pipe 43 at a constant time and supplies the controller 17 with the hydrogen gas release rate of the second standard hydrogen gas to be supplied Output. The second standard hydrogen gas is released into the interior 19 of the vacuum chamber 11 through the second supply pipe 43, diffuses in the interior 19 of the chamber 11, and reaches the partial pressure analyzer 15. The partial pressure analyzer 15 analyzes the partial pressure of the second standard hydrogen gas and outputs the analysis result (second standard hydrogen gas partial pressure) to the controller 17. The controller 17 associates the release speed of the second standard hydrogen gas output from the supply device 41 and the partial pressure of the second standard hydrogen gas output from the analyzer 15 with each other, and the release speed and the partial pressure thereof. Are stored on the hard disk.

After storing the release speed and partial pressure of the second standard hydrogen gas, the controller 17 closes the vacuum valve 44 to shut off the tank 40 and the hydrogen gas supply device 41, and connects the supply pipes 42, 43 and the supply device 41. The process waits until the second standard hydrogen gas remaining in the inside, the inside 19 of the vacuum chamber 11, the pipe lines 25 and 39, and the partial pressure analyzer 15 is discharged to the outside through the vacuum pump 24. When the standby time elapses, the controller 17 opens the vacuum valve 44 to allow the tank 40 and the supply device 41 to communicate with each other. The degree of vacuum in the interior 19 of the chamber 11, the partial pressure analyzer 15, the pipes 25 and 39, the supply device 41, and the supply pipes 42 and 43 is set to a range of 1 × 10 ⁻⁷ to 1 × 10 ⁻¹³ Pa by the pump 24. Is retained. The controller 17 outputs a supply command for the third standard hydrogen gas to the supply device 41, and outputs an analysis command for the partial pressure of the third standard hydrogen gas discharged into the interior 19 of the chamber 11 to the partial pressure analyzer 15.

  The third standard hydrogen gas flows from the tank 40 through the first supply pipe 42 into the hydrogen gas supply device 41. In accordance with the supply command, the supply device 41 supplies a constant pressure and a constant amount of the third standard hydrogen gas to the second supply pipe 43 at a constant time, and supplies the controller 17 with a hydrogen gas release rate of the supplied third standard hydrogen gas. Output. The third standard hydrogen gas is released into the interior 19 of the vacuum chamber 11 through the second supply pipe 43, diffuses in the interior 19 of the chamber 11, and reaches the partial pressure analyzer 15. The partial pressure analyzer 15 analyzes the partial pressure of the third standard hydrogen gas and outputs the analysis result (third standard hydrogen gas partial pressure) to the controller 17.

  The controller 17 associates the release rate of the third standard hydrogen gas output from the hydrogen gas supply device 41 and the partial pressure of the third standard hydrogen gas output from the analyzer 15 with each other. Store the partial pressure on the hard disk. After storing the release speed and partial pressure of the third standard hydrogen gas, the controller 17 closes the vacuum valve 44 to shut off the tank 40 and the supply device 41, and supplies the inside of the supply pipes 42 and 43 and the supply device 41. The process waits until the third standard hydrogen gas remaining in the inside 19 of the vacuum chamber 11, the pipe lines 25 and 39, and the partial pressure analyzer 15 is discharged to the outside through the vacuum pump 24. When the standby time has elapsed, the controller 19 closes the vacuum valve 45 and shuts off the vacuum chamber 11 and the supply mechanism 16.

When the release speed and partial pressure of the first to third standard hydrogen gases are stored, the controller 17 takes out a calibration curve prepared in advance from the hard disk. In the calibration curve, as shown in FIG. 3, the horizontal pressure represents the partial pressure of standard hydrogen gas, and the vertical axis represents the hydrogen gas release rate of standard hydrogen gas. The controller 17 enters the partial pressures of the first to third standard hydrogen gases and the gas release rates of the standard hydrogen gases in the calibration curve. When the controller 17 enters the partial pressures and the release rates in the calibration curve, the controller 17 specifies the first to third coordinates 48, 49, and 50, which are the intersection points of the partial pressures and the release rates. For example, when the release rate of the first standard hydrogen gas is 2.9 × 10 ⁻⁵ atm · cc / s and the partial pressure at that time is 1 × 10 ⁻⁹ Pa, the release rate and the partial pressure thereof When the first coordinate is 48 and the second standard hydrogen gas release rate is 3.9 × 10 ⁻⁵ atm · cc / s, and the partial pressure is 1 × 10 ⁻⁷ Pa The intersection of the discharge speed and the partial pressure is defined as a second coordinate 49. Furthermore, when the release rate of the third standard hydrogen gas is 5.9 × 10 ⁻⁵ atm · cc / s and the partial pressure at that time is 1 × 10 ⁻⁵ Pa, the release rate and the partial pressure thereof Let the third coordinate 50 be the intersection point with.

  When the controller enters the first to third coordinates 48, 49, 50 in the calibration diagram, the controller draws a line segment passing through the coordinates 48, 49, 50 from the origin of the calibration diagram, and obtains the inclination of the line segment. After that, a function having the slope is calculated, and as shown in FIG. 3, a calibration curve 51 based on the function is displayed on the calibration curve (calibration curve setting means). The controller 17 stores a calibration curve in which each partial pressure, each release speed, slope, function, and calibration curve 51 are written in the hard disk (calibration curve storage means).

  In order to change the calibration curve 51, calibration curve resetting is selected from various items on the initial screen displayed on the display 47. When the calibration curve resetting is selected, a condition confirmation screen for the calibration curve resetting is displayed on the display 47. On the condition confirmation screen, the time set for background partial pressure measurement (3 seconds) is displayed in the time interval display area for partial pressure analysis, and the number of supplies (3 times) is displayed in the standard hydrogen gas supply frequency display area. The In addition, a condition confirmation button, a condition change button, and a cancel button are displayed.

  When canceling the resetting of the calibration curve 51, the cancel button is pressed, and when the condition is not changed, the condition confirmation button is pressed. In order to change these conditions, the condition change button is pressed, the changed time interval or supply frequency is input in the time interval input area or supply frequency input area displayed on the display 47, and the setting button is pressed. When the setting button is pressed, a condition confirmation button, a condition change button, and a cancel button are further displayed. If there is no condition change again, the condition confirmation button is pressed.

When the condition confirmation button is pressed, the controller 17 newly sets a calibration curve 51 in accordance with the conditions displayed on the condition confirmation screen. The vacuum valves 23 and 45 are in an open state, and the vacuum pump 24 is in an operating state. The degree of vacuum in the interior 19 of the vacuum chamber 11, the partial pressure analyzer 15, the pipes 25 and 39, the hydrogen gas supply device 41, and the supply pipes 42 and 43 is 1 × 10 ⁻⁷ to 1 × 10 ⁻¹³ by the vacuum pump 24. It is held in the range of Pa. The setting procedure of the calibration curve 51 in the calibration curve resetting is the same as that of the calibration curve 51 in the calibration curve setting, and therefore the description thereof is omitted. When the calibration curve 51 stored in the hard disk is changed, the controller 17 rewrites the calibration curve 51 before the change to the calibration curve 51 after the change (calibration curve update means), and the calibration curve into which the calibration curve 51 after the change is written. The figure (including each partial pressure, each release rate, slope, and function) is stored on the hard disk.

  In the hydrogen amount measuring apparatus 10, the calibration curve 51 is set from the partial pressures of the three standard hydrogen gases and the three release rates of the standard hydrogen gases, thereby improving the reliability and certainty of the calibration curve 51. Can do. In the calibration curve setting, the calibration curve 51 is obtained using the partial pressures and the release rates of the first to third standard hydrogen gases, but one or two standard hydrogen gas partial pressures and one. Alternatively, the calibration curve 51 can be obtained using two release rates, and the calibration curve 51 can be obtained using partial pressures of four or more standard hydrogen gases and four or more release rates.

  An example of the conveyance of the steel material sample 20 to the inside 19 of the chamber 11 by the conveyance mechanism 12 will be described as follows. From various items on the initial screen displayed on the display 47, the sample transport is selected. When the sample transport is selected, a condition confirmation screen is displayed on the display 47. On the condition confirmation screen, the time interval (3 seconds) set in the background partial pressure measurement is displayed in the time interval display area for partial pressure analysis, and a condition confirmation button, a condition change button, and a cancel button are displayed.

  Press the cancel button to stop the sample transport, and press the condition confirmation button if there is no change in the conditions. When changing these conditions, the condition change button is pressed, the changed time interval is input in the time interval input area displayed on the display 47, and the setting button is pressed. When the setting button is pressed, a condition confirmation button, a condition change button, and a cancel button are further displayed. If there is no condition change again, the condition confirmation button is pressed.

When the condition confirmation button is pressed, the controller 17 closes the vacuum valve of the pipe line 33, injects nitrogen gas into the casing 27 through the nitrogen gas injection device, and fills the inside of the casing 27 with nitrogen gas. Set the inside to atmospheric pressure. At this time, the gate valve 31 is in a closed state, and the vacuum pump 24 is in an operating state. The degree of vacuum in the interior 19 of the vacuum chamber 11, the pipe lines 25 and 39, and the partial pressure analyzer 15 is maintained in the range of 1 × 10 ⁻⁷ to 1 × 10 ⁻¹³ Pa by the pump 24. When the controller 17 monitors the degree of vacuum output from the vacuum gauge and determines that the inside of the casing 27 has returned to the atmospheric pressure, the controller 17 stops injecting nitrogen gas, and displays a hatch opening / closing message and a hatch closing completion button on the display 47. Is displayed. By filling the casing 27 with nitrogen gas, it is possible to prevent other types of gas from remaining inside the casing 27.

  Next, the steel material sample 20 is supported on the support member, the hatch is opened, and the conveying rod 28 is installed inside the casing 27. At this time, the support member faces the gate valve 31. After the steel material sample 20 and the conveying rod 28 are installed inside the casing 27, the hatch is closed to seal the casing, and a hatch closing completion button displayed on the display 47 is pressed. When the closing completion button is pressed, the controller 17 opens the valve of the pipe line 33 and discharges nitrogen gas from the casing 27 to the outside via the vacuum pump 32. When the controller 17 monitors the degree of vacuum output from the vacuum gauge and determines that the inside of the casing 27 has reached a predetermined degree of vacuum, the controller 17 displays a transportable message on the display 47.

  After the transportable message is displayed, the induction magnet moves the outer peripheral surface of the casing 27 in the front-rear direction toward the vacuum chamber 11. The magnetic force of the magnet acts on the transport rod 28, and the steel material sample 20 and the transport rod 27 supported by the support member together with the magnet move in the front-rear direction toward the gate valve 31. When the support member reaches the vicinity of the gate valve 31, an ON signal is output from the second position sensor to the controller 17. The controller 17 that has received the ON signal from the second position sensor opens the gate valve 31.

  After the gate valve 31 is opened, the induction magnet is moved further back and forth toward the vacuum chamber 11. The steel material sample 20 and the transport rod 28 supported by the support member by the magnetic force of the magnet pass through the gate valve 31 and move in the front-rear direction toward the central portion 21 of the chamber 11. When the support member passes through the gate valve 31, an OFF signal is output from the second position sensor to the controller 17, and an ON signal is output from the first position sensor to the controller 17. When the controller 17 receives the OFF signal from the second position sensor and the ON signal from the first position sensor, the controller 17 determines that the support member has passed through the gate valve 31 from the transport mechanism 12 toward the chamber 11. Further, when the conveying rod 28 is moved through the magnet and the support member reaches the central portion 21 of the chamber 11, the magnet is moved in the direction around the casing 27 and the conveying rod 28 is rotated. When the transport rod 28 is rotated, the support member is rotated and the steel material sample 20 is directed downward of the chamber 11. In this state, the support of the support member is released, and the steel material sample 20 is placed on the central portion 21 of the chamber 11.

  After the steel material sample 20 is placed on the central portion 21 of the vacuum chamber 11, the induction magnet is moved away from the chamber 11, and the conveying rod 27 is removed from the chamber 11 together with the support member. When the support member is removed from the chamber 11 and the support member is positioned in the vicinity of the gate valve 31 inside the casing 27, an OFF signal is output from the first position sensor to the controller 17, and an ON signal is output from the second position sensor to the controller 17. Is output. When the controller 17 receives the OFF signal from the first position sensor and the ON signal from the second position sensor, the controller 17 determines that the support member has passed through the gate valve 31 from the chamber 11 toward the casing 27, and the gate valve 31. Close.

  An example of measuring the hydrogen amount of the steel material sample 20 in the hydrogen amount measuring apparatus 10 will be described as follows. When the steel sample 20 is placed on the central portion 21 of the chamber 11 and the gate valve 31 is closed, a measurement start button and a cancel button are displayed on the display 47. Press the cancel button to stop the measurement. When the measurement start button is pressed, a condition confirmation area is displayed on the display 47. In the condition confirmation area, the time interval (3 seconds) set in the background partial pressure measurement is displayed in the time interval display area for partial pressure analysis, and further, a condition confirmation button, a condition change button, and a cancel button are displayed. If there is no condition change, press the condition confirmation button. When the cancel button is pressed, the controller 17 stops the hydrogen amount measurement.

When the condition confirmation button is pressed, a condition setting area, a setting button, and a cancel button are displayed on the display 47. In the condition setting area, a temperature rise speed input area and a maximum temperature input area are displayed. When the temperature rise rate (° C./hr) is entered in the temperature rise rate input area, the maximum attained temperature (° C.) is entered in the maximum reached temperature input area, and the setting button is pressed. A condition change button and a cancel button are displayed. If there is no condition change, press the condition confirmation button. When the condition confirmation button is pressed, the controller 17 outputs the temperature rise rate and the highest temperature to the controller of the electric furnace 13 and outputs a temperature measurement command for the vacuum chamber 11 to the temperature sensor 14. Further, a partial pressure analysis command for hydrogen gas released from the steel material sample 20 is output to the partial pressure analyzer 15. The rate of temperature rise can be set in the range of 50 to 200 ° C./hr, and the maximum temperature reached can be set in the range of room temperature to 1000 ° C. It is assumed that the temperature rise rate is set to 100 ° C./hr, and the maximum temperature reached is set to 800 ° C. The measuring device 10 can freely select a temperature increase rate and a maximum temperature that match the sample 20 according to the type, physical properties, and properties of the steel sample 20. The degree of vacuum in the interior 19 of the chamber 11, the pipelines 25 and 39, and the partial pressure analyzer 15 is maintained in the range of 1 × 10 ⁻⁷ to 1 × 10 ⁻¹³ Pa by the vacuum pump 24.

  Since this hydrogen amount measuring apparatus 10 raises the temperature of the steel material sample 20 at a temperature increase rate of 50 to 200 ° C./hr, the steel material sample 20 can reach the maximum measurement temperature in a short time. The amount of hydrogen corresponding to the temperature can be quantified in a short time. Since this measuring device 10 can freely set the temperature rise rate of the measurement object within the above range, the temperature rise rate that matches the object is selected according to the type, physical properties, and properties of the measurement object. be able to. If the rate of temperature rise is less than 50 ° C./hr, it takes a long time to measure the amount of hydrogen. When the rate of temperature rise exceeds 200 ° C./hr, it is difficult to accurately determine the amount of hydrogen, and the measurement reliability is lowered.

  The control unit of the electric furnace 13 causes the heating unit 34 to generate heat from the room temperature to the maximum temperature at a specified temperature increase rate according to the temperature increase rate and the maximum temperature that are output from the controller 17. The temperature increase rate is set to 100 ° C./hr, and the temperature rises by 100 ° C. per hour, so it takes 8 hours to reach the maximum temperature of 800 ° C. The controller 17 calculates the actual temperature increase rate from the measured temperature output from the temperature sensor 14, and determines whether the actual temperature increase rate matches the set temperature increase rate. When the actual temperature rise rate and the set temperature rise rate do not match, the controller 17 executes feedback control for matching the actual temperature rise rate with the set temperature rise rate (temperature rise rate adjusting means).

  In the feedback control, the controller 17 converts the set temperature rise rate into a reference input signal, calculates the actual temperature rise rate, converts it to the same feedback amount as the reference input signal, and feeds back the feedback amount. The deviation is obtained by comparing with the reference input signal. The controller 17 creates a control signal so that the controlled object (electric furnace 13) performs a predetermined operation based on the deviation, converts the control signal into an operation signal (operation amount) necessary for operation, and converts the operation signal to Output to the controller of the electric furnace 13. The control unit of the electric furnace 13 adjusts the heat generation in the heating unit 34 based on the operation signal output from the controller 17 and matches the actual temperature increase rate with the set temperature increase rate. The deviation is a difference between the set temperature rise rate and the feedback amount, and is an operation signal that corrects the actual temperature rise rate. The control operation of feedback control is PID control.

  The vacuum chamber 11 is gradually heated by the electric furnace 13 and gradually increases in temperature from a low temperature (room temperature) toward a maximum temperature. The steel material sample 20 stored in the interior 19 of the chamber 11 is heated as the chamber 11 is heated, and the temperature is increased from a low temperature (room temperature) toward the highest temperature at a temperature increase rate of 100 ° C./hr. The temperature of the steel material sample 20 gradually increases, and when the steel material sample 20 enters a specific temperature range, hydrogen gas contained in the steel material sample 20 is gradually released from the sample 20. The hydrogen gas released from the steel material sample 20 diffuses inside the chamber 11 and reaches the partial pressure analyzer 15. The analyzer 15 analyzes the hydrogen gas partial pressure of the hydrogen gas released from the steel material sample 20 every 3 seconds, and outputs the analysis result (hydrogen gas partial pressure) to the controller 17 in time series.

FIG. 4 is a view of a display screen showing an example of a correlation chart between the hydrogen release rate and temperature, and FIG. 5 is a view of the same display screen as FIG. 4 showing in the temperature range from 40 to 300 ° C. . FIG. 6 is a diagram of a display screen showing an example of various correlation data. 4 and 5, the horizontal axis represents temperature (° C.) and the vertical axis represents hydrogen gas release rate (PPb.sec ⁻¹ , PPm / s). 4 to 6, a save button 52, a data range designation area 53, a background partial pressure display area 54, a sample weight display area 55, and a chart area 56 are displayed. In the data range designation area 53, a temperature range designation button 57 and an entire display button 58 are displayed. The background partial pressure display area 54 displays the background partial pressure (Pa) at the time of measuring the hydrogen amount, and the sample weight display area 55 displays the weight (g) of the measured steel material sample. .

  The controller 17 subtracts the background partial pressure from the hydrogen gas partial pressure output from the partial pressure analyzer 15 to calculate a substantial partial pressure. The controller 17 takes out the calibration curve stored in the hard disk, applies the calculated partial pressure to the calibration curve 51 displayed in the calibration curve, and determines the release rate of the hydrogen gas released from the steel material sample 20 ( Hydrogen gas release rate determining means). Specifically, the actual partial pressure is substituted into the partial pressure (horizontal axis) of the calibration curve, and a vertical line is drawn from the substitution position toward the calibration curve 51. When the vertical line intersects with the calibration curve 51, a horizontal line is drawn from there. , The release rate when the horizontal line intersects the vertical axis (hydrogen release rate) is read, and the hydrogen gas release rate corresponding to the partial pressure into which the read release rate is substituted is obtained.

  The controller 17 associates the hydrogen gas release rate with the partial pressure and stores them in time series on the hard disk (hydrogen gas release rate storage means). The controller 17 specifies the correlation between the hydrogen gas release rate and the measured temperature output from the temperature sensor 14 (correlation first specifying means). Specifically, the measurement temperature at the time of measuring the partial pressure measured every 3 seconds is determined, the hydrogen gas release rate with respect to the measurement temperature is determined, and the determined measurement temperature is associated with the hydrogen gas release rate. . The controller 17 stores the correlation between the hydrogen gas release rate and the measured temperature in the hard disk (correlation first storage means).

  When the correlation chart display is selected from the items on the initial screen, the controller 17 displays a correlation chart between the hydrogen release rate and the measured temperature in the entire temperature range on the display 47 as shown in FIG. Relation first output means). The correlation chart of FIG. 4 can be output via a printer (correlation first output means). In the correlation diagram of FIG. 4, a first peak of hydrogen release appears in the temperature range of 40 ° C. to 300 ° C., and a second peak of hydrogen release appears in the temperature range of 300 ° C. to 600 ° C. Here, diffusible hydrogen that causes delayed fracture of steel is hydrogen (first peak) released in a temperature range of 40 ° C. to 300 ° C. where the trapping action is small, and gradually enters after the production of the steel. This causes local deterioration in the steel material by floating inside the steel material. Note that hydrogen (second peak) released in the temperature range of 300 ° C. to 600 ° C. where the trapping action is large has entered during the production of the steel material and does not cause delayed fracture of the steel material.

  The display screen of FIG. 5 partially shows the correlation chart of FIG. 4, and the correlation chart in the temperature range of 40 ° C. (room temperature) to 300 ° C. is displayed. In the display screen of FIG. 4, when the temperature range designation button 57 is pressed in the data range designation area 53, a temperature range input area, a display button, and a cancel button are displayed on the display 47 (not shown). When a temperature range is designated in the temperature range input area and the display button is pressed, a correlation chart in the designated temperature range is displayed on the display 47 as shown in FIG.

  The controller 17 quantifies the amount of hydrogen contained in the steel material sample 20 by integrating the hydrogen gas release rate (hydrogen amount quantification means), and stores the quantified hydrogen amount in time series on the hard disk (hydrogen amount storage means). The controller 17 specifies the correlation between the quantified hydrogen amount and the measured temperature output from the temperature sensor 14 (correlation second specifying means), and stores the correlation between the specified hydrogen amount and the measured temperature in the hard disk. (Correlation second storage means). When the correlation data display is selected from the initial screen, the controller 17 displays the correlation data in the entire temperature range on the display 47 (correlation second output means). The correlation data can be output via a printer (correlation second output means).

  When the temperature range designation button 57 in the data range designation area 53 is pressed on the correlation data display screen in the entire temperature range, a temperature range input area, a display button, and a cancel button are displayed on the display 47 (FIG. Not shown). When the temperature range is designated in the temperature range input area and the display button is pressed, the correlation data in the designated temperature range is displayed on the display 47 as shown in FIG. 6 (correlation second output means). The correlation data in FIG. 6 can be output via a printer (correlation second output means). In the output correlation data, as shown in FIG. 6, temperature (° C.), hydrogen partial pressure (Pa), analysis interval (s), hydrogen partial pressure-background partial pressure (BG), hydrogen release rate (ppm) / S), the amount of hydrogen (ppm) within the analysis interval, and the cumulative amount of hydrogen (ppm) are displayed.

  The hydrogen amount measuring apparatus 10 heats the steel material sample 20 in the vacuum chamber 11 and gradually raises the temperature of the steel material sample 20 from a low temperature (room temperature) to a high temperature, thereby reducing the hydrogen gas partial pressure released from the sample 20. The hydrogen gas partial pressure is applied to the calibration curve 51 to identify the hydrogen gas release rate, and the amount of hydrogen contained in the steel sample 20 is quantified from the hydrogen gas release rate. It is possible to reliably measure the amount of hydrogen released when it is in the range. Since the hydrogen amount measuring apparatus 10 specifies the correlation between the quantified amount of hydrogen and the temperature of the steel material sample 20, the hydrogen amount corresponding to each temperature of the steel material sample 20 can be confirmed. Based on this, the type of hydrogen contained in the sample 20 can be determined. Since this hydrogen amount measuring apparatus 10 can measure the amount of diffusible hydrogen contained in the steel material sample 20, it can analyze the current strength of the steel material corresponding to the sample 20, and the life and replacement of the steel material. The time can be predicted.

  The hydrogen amount measuring apparatus 10 supplies standard hydrogen gas from the hydrogen gas supply mechanism 16 to the inside 19 of the vacuum chamber 11 at a constant release rate, and sets a calibration curve 51 based on the partial pressure and release rate of the standard hydrogen gas. The hydrogen gas partial pressure released from the steel material sample 20 is applied to the calibration curve 51 to specify the hydrogen gas release speed, and the amount of hydrogen contained in the steel material sample 20 is determined from the hydrogen gas release speed. The amount of hydrogen contained in the steel material sample 20 can be reliably quantified with high reliability. In the hydrogen amount measuring apparatus 10, since the time interval of the partial pressure analysis in the partial pressure analyzer 15 is in the range of 0.01 to 5 seconds, the sample 20 corresponds to the temperature of the steel sample 20 that changes every moment. The amount of hydrogen contained in can be precisely quantified, and the amount of hydrogen released when the steel sample 20 is in a predetermined temperature range can be reliably measured with high reliability. When the time interval of the partial pressure analysis exceeds 5 seconds, it is not possible to perform fine measurement in accordance with the temperature rise of the steel material sample 20, and the reliability of various correlation data decreases.

  In the hydrogen amount measuring device 10, the background partial pressure is subtracted from the partial pressure of the hydrogen gas output from the partial pressure analyzer 15 to calculate the substantial partial pressure, and the substantial partial pressure is applied to the calibration curve 51 to generate hydrogen. Although the amount is quantified, the measurement of the background partial pressure can be omitted. In this case, the partial pressure of the hydrogen gas output from the partial pressure analyzer 15 is applied to the calibration curve 51 to quantify the amount of hydrogen.

  When the measurement of the hydrogen amount of the steel material sample 20 is completed, the controller 17 displays a measurement completion message and a sample carry-out button on the display 47. When the sample unloading button is pressed, the controller 17 opens the gate valve 31 and displays a sample unloadable message on the display 47. After the sample unloadable message is displayed on the display 47, the transfer rod 28 is inserted into the vacuum chamber 11 using an induction magnet, and the steel material sample 20 is supported by the support member. Next, the conveying rod 28 is pulled out from the chamber 11 using an induction magnet, and the steel material sample 20 is moved from the vacuum chamber 11 to the casing 27.

  When the controller 17 determines that the support member has moved from the chamber 11 to the casing 27 based on the ON / OFF signals from the first and second position sensors, the controller 17 closes the gate valve 31 and closes the vacuum valve in the conduit 33. Next, the controller 17 injects nitrogen gas into the casing 27 via the nitrogen gas injection device, fills the inside of the casing 27 with nitrogen gas, and brings the inside of the casing 27 to atmospheric pressure. When the controller 17 monitors the degree of vacuum output from the vacuum gauge and determines that the inside of the casing 27 has returned to atmospheric pressure, the controller 17 stops the injection of nitrogen gas and displays a hatch opening / closing message on the display 47. After the hatch opening / closing possible message is displayed, the hatch is opened, the conveying rod 28 is taken out of the casing 27, and the steel material sample 20 is removed from the support member. When the hatch is closed again after the conveying rod 28 is taken out of the casing 27, the controller 17 opens the valve of the pipe line 33 to return the casing 27 and the pipe line 33 to a predetermined degree of vacuum.

The block diagram of the hydrogen amount measuring apparatus shown as an example. FIG. 2 is an end view taken along line AA in FIG. 1. The calibration curve diagram which displayed the calibration curve shown as an example. The figure of the display screen which shows an example of the correlation diagram of hydrogen discharge | release rate and temperature. The figure of the display screen similar to FIG. 4 shown in the temperature range to 40-300 degreeC. The figure of the display screen which shows an example of various correlation data.

DESCRIPTION OF SYMBOLS 10 Hydrogen measuring device 11 Vacuum chamber 12 Conveyance mechanism 13 Electric furnace (temperature raising mechanism)
14 Temperature Sensor 15 Partial Pressure Analyzer 16 Hydrogen Gas Supply Mechanism 17 Controller 20 Steel Sample (Measurement Object)
23 Vacuum valve 24 Vacuum pump 27 Casing 28 Transport rod 31 Gate valve 32 Vacuum pump 34 Heating unit 40 Tank 41 Hydrogen gas supply device 44 Vacuum valve 45 Vacuum valve 51 Calibration curve

Claims (10)

A vacuum chamber for storing a measurement object having a deformed and different mass, a temperature raising mechanism for gradually increasing the temperature of the measurement object stored in the vacuum chamber from a low temperature to a high temperature, and a standard hydrogen gas in the vacuum chamber A standard hydrogen gas supply mechanism for supplying at a discharge rate, a temperature sensor for measuring the temperature of the vacuum chamber, and the measurement as the temperature of a measurement object connected to the vacuum chamber and stored in the vacuum chamber increases. A partial pressure analyzer for analyzing the partial pressure of the standard hydrogen gas supplied from the standard hydrogen gas supply mechanism to the vacuum chamber while analyzing the partial pressure of the hydrogen gas released from the object, and the temperature sensor And a controller connected to the partial pressure analyzer,
A calibration curve setting means for setting a calibration curve using the partial pressure of the standard hydrogen gas output from the partial pressure analyzer and a release rate corresponding to the partial pressure of the standard hydrogen gas; a hydrogen gas release rate determining means for determining the release rate of the released hydrogen gas output hydrogen gas partial pressure from the measurement object by fitting the calibration curve analyzer, by the hydrogen gas release rate determining means A hydrogen amount quantifying means for integrating the determined release rate to determine the amount of hydrogen contained in the measurement object, and a correlation between the hydrogen amount quantified by the hydrogen amount quantifying means and the measured temperature output from the temperature sensor A hydrogen amount measuring device having correlation specifying means for specifying The standard hydrogen gas supply mechanism is connected to the tank for storing standard hydrogen gas having a purity of 99.999% or more and the controller, and supplies the standard hydrogen gas from the tank to the vacuum chamber at a constant hydrogen gas release rate. The hydrogen amount measuring device according to claim 1, wherein the hydrogen amount measuring device is formed from a hydrogen gas supplying device. Wherein in the calibration line setting means, according to claim 1 or claim sets the calibration curve using at least three release rate corresponding to the partial pressure and the partial pressure of their standard hydrogen gas of at least three of the standard hydrogen gas 2 hydrogen amount measuring apparatus according to. In the calibration curve setting means, the partial pressure of the standard hydrogen gas and the release rate corresponding to the partial pressure of the standard hydrogen gas are written in a calibration curve prepared in advance, and is the intersection of the partial pressure and the release rate. Specify the coordinates, draw a line segment that passes through the coordinates from the origin of the calibration diagram, obtain the slope of the line segment, calculate a function having the slope, and convert the calibration curve based on the function to the calibration diagram 4. The hydrogen amount measuring apparatus according to claim 3 , wherein the controller includes a calibration curve storage means for storing a calibration curve diagram in which the partial pressure, the release rate, the slope, the function, and the calibration curve are written . 5. The hydrogen amount measuring apparatus according to claim 1, wherein a time interval of partial pressure analysis in the partial pressure analyzer is in a range of 0.01 to 5 seconds . The temperature raising mechanism is connected to the controller, and the controller includes temperature raising rate adjusting means for raising the temperature of the measurement object at a temperature raising rate of 50 to 200 ° C./hr, and is stored in the vacuum chamber. The hydrogen amount measuring apparatus according to any one of claims 1 to 5 , wherein a temperature rising range of the measurement object is room temperature to 1000 ° C. The controller includes background partial pressure analysis means for causing the partial pressure analyzer to analyze a background partial pressure of hydrogen gas remaining in the vacuum chamber, and the hydrogen gas release rate determination means includes The background partial pressure is subtracted from the pressure to calculate a substantial partial pressure, and the substantial partial pressure is applied to the calibration curve to determine the release rate of hydrogen gas released from the measurement object. The hydrogen amount measuring apparatus according to claim 6. The ultimate vacuum of the vacuum chamber is in the range of 1 × 10 ⁻⁷ to 1 × 10 ⁻¹³ Pa, and the background partial pressure of hydrogen gas in the vacuum chamber is 1 × 10 ⁻⁹ Pa or less. The hydrogen content measuring apparatus according to any one of claims 1 to 7. In the hydrogen amount quantifying means, a hydrogen gas partial pressure of hydrogen gas released from the measurement object when the measurement object is heated to room temperature to 300 ° C. is applied to the calibration curve, and the measurement object The hydrogen amount measuring apparatus according to claim 1 , wherein the amount of hydrogen of diffusible hydrogen contained in the gas is quantified . The hydrogen amount measuring apparatus according to claim 1, wherein the measurement object is a steel material.

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