February 2011

Research & Development

A new dynamic method for measuring hydrogen partial pressure in molten aluminum alloy
Sun Qian, *Li Dayong, Wang Lihua and Zhang Jianlei (Harbin University of Science & Technology, Harbin 150080, China)

Abstract: Hydrogen partial pressure is an important parameter to calculate hydrogen concentration levels in molten aluminum alloy. A new dynamic method for measuring hydrogen partial pressure in molten aluminum alloy is studied. Dynamic and rapid measurement is realized through changing the volume of the vacuum chamber and calculating the pressure difference P between the theoretical and measured pressures in the vacuum chamber. Positive P indicates hydrogen transmits from melt to vacuum chamber and negative P means the reverse. When P is equal to zero, hydrogen transmitted from both sides reached a state of dynamical equilibrium and the pressure in the vacuum chamber is equal to the hydrogen partial pressure in the molten aluminum alloy. Compared with other existing measuring methods, the new method can significantly shorten the testing time and reduce measuring cost. Key words: molten aluminum alloy; hydrogen partial pressure; dynamic measurement; rapid measurement CLC number: TG 146.2+1 Document code: A Article ID: 1672-6421(2011)01-001-04

he hydrogen in aluminum alloy has a great effect on its mechanical properties, such as plasticity, toughness, fatigue life and stress corrosion resistance, etc[1-3]. In aluminum alloy castings, the reduction of hydrogen content in the melt is a vital procedure in obtaining high quality aluminum castings [4]. Therefore, accurate measurement of hydrogen concentration in molten aluminum alloy is very important in controlling the casting quality and also in the evaluation of the degassing efficiency. Nowadays, in foundry production, methods such as decompression solidification method, first bubble appearance method, inert gas carrying hydrogen method, concentration cell method, direct manometry method and CHAPEL method, etc, are used to measure the hydrogen content in molten aluminum alloy [5-6]. The decompression method is classified as qualitative analysis method; while, almost all the others are quantitative methods. The concentration cell method has the highest measuring speed among all these methods, but its measuring cost is much higher than that of others. Except for the concentration cell method, almost all of these methods need decompression as the basic measuring condition to measure hydrogen partial pressure in molten aluminum alloy,
*Li Dayong
Male, born in 1958, professor, Ph. D. Research direction: online test, automatic control technology;NDE tech. of material property. Sun Qian (Male, born in 1980, doctoral candidate) is one of Ph.D students supervised by him. E-mail: dyli@hrbust.edu.cn

then followed by calculating the hydrogen content of the molten alloy. In order to measure hydrogen partial pressure accurately, plenty of time must be needed to make sure that the hydrogen in the molten aluminum can diffuse out completely. Since hydrogen diffusion power declines with the decrease of hydrogen content in the melt, the time for reaching equilibrium will be lengthen [7-8]. So, shortening the testing time in the melt is a pivotal process to reduce the measuring time. As pointed out in literature [9] that the gas of 80% to 90% that dissolved in aluminum alloy is hydrogen, therefore, in the present study, the hydrogen content in aluminum melt was approximated by the total gas content.

1 Basic principle of the dynamic measurement of hydrogen partial pressure

For an airtight thermostatic gas chamber, when the gas volume changes, the gas pressure will change accordingly. The relationship between gas pressure and volume should satisfy the ideal gas state equation: (1)

P = nRT / V

Received: 2010-03-22;

Accepted: 2010-09-20

where, P The gas pressure inside the container; n The number of gas molecules; R The gas constant; T The absolute temperature and V The gas volume. Assumed that the airtight thermostatic gas chamber is a cylinder-shaped container with cross-sectional area S, when
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the diaphragm of the gas chamber move with a linear speed v, at a given time t, the gas volume V = Svt will also change at a given rate. Therefore, the changing rate of the gas pressure can be obtained by the time derivative of Equation (1): dp nRT 1 (2) = 2 dt S v t or dP 1 = k 2 dt t where,
(3)

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k=

nRT Sv

When the chamber reached the required vacuum that contain high purity hydrogen, the airtight thermostatic gas chamber is connected with the molten alloy by the measuring probe and formed channels for hydrogen diffusion, the gas pressure change will not follow Equation (3), but controlled by the hydrogen partial pressure in the molten alloy. If the hydrogen partial pressure is higher than the gas pressure in the chamber, the hydrogen will transmit from the molten alloy to the gas chamber through the probe. This will lead to the actual pressure of the gas chamber become higher than the theoretical value. Contrarily, if the hydrogen partial pressure in the molten alloy is lower than the gas pressure in the chamber, the hydrogen in the gas chamber will transmit to the molten alloy, which will make the actual pressure of the gas chamber lower than its theoretical value. Only when the hydrogen partial pressure of the molten alloy equals to the gas pressure of the chamber, the hydrogen diffusion is in dynamic equilibrium. This gas pressure of the chamber can be regarded as the hydrogen partial pressure of the molten alloy. So, by continuously changing the pressure in the gas chamber and monitoring the real-time value, we can calculate the pressure difference P between the theoretical and the practical values. From P it can be judged whether the hydrogen diffusion reaches dynamic equilibrium. Diffusion takes time; the dynamic measurement method presented in this study is no exception. But the dynamic equilibrium state is not controlled by the hydrogen diffusion power, but the gas volume changes. This method transforms the measurement from the "passive waiting" to "active approximation". Accordingly, it can greatly shorten the measuring time and achieve the purpose of rapidly measurement. The specific implementation procedures are as follows. Firstly, pure hydrogen was used to "flush" the vacuum chamber and make it retain a pre-determined vacuum value (this value is determined by the specific alloy) by vacuum pump. Secondly, the vacuum chamber is connected with the molten alloy through a probe in order to form hydrogen diffusion channel. Then, with the uniform decrease of the vacuum chamber volume, the vacuum pressure increases continuously. If the pressure of vacuum chamber is lower than the hydrogen partial pressure, the hydrogen can transmit to the vacuum chamber, which is called "breathe in hydrogen". If the gas pressure of vacuum chamber is higher, the hydrogen can transmit to the molten alloy, which is called
2

"breathe out hydrogen". In other words, during the process of changing the volume, there are two factors that determine the vacuum chamber pressure. On one hand, the volume decrease leads to the pressure increase; On the other hand, "breathe out hydrogen" leads to the pressure decrease (or "breathe in hydrogen" leads to the pressure increase). During the gradual increase of the vacuum chamber pressure, if the real-time pressure value P 1 of the chamber is monitored, the corresponding theoretical pressure P 2 can be calculated easily according to the Clapyron equation and thus the pressure difference P between them can also be obtained. Therefore, it can be judged accurately that the vacuum chamber is either in "breathe in hydrogen" or "breathe out hydrogen" stage. Positive P means the practical pressure becomes higher than the theoretical pressure, and it is the "breathe in hydrogen" stage. Negative P means the practical pressure becomes lower than the theoretical pressure, and it is "breathe out hydrogen" stage. When P is equal to zero, the practical pressure equals to the theoretical pressure and the hydrogen diffusion reaches dynamic equilibrium stage. As a result, the pressure of the vacuum chamber is the hydrogen partial pressure of the molten alloy [10]. Figure 1 shows the practical measured curve of the pressure difference P . Measurement accuracy depends on the leakage ratio of the vacuum system and also on the accuracy of data acquisition. When the sampling point is not the point where P equals to zero, it can be solved by interpolation.

Fig.1: Practical measured curve of the different pressure

2 Experimental setup of dynamically measuring hydrogen partial pressure

The experimental setup is shown schematically in Fig.2. It composed of vacuum pump, variable-volume chamber, variable-volume drive unit, vacuum valve group, probe, isolation unit, hydrogen storage container, pressure sensor, temperature sensor, isothermal bath, data acquisition and processing unit, etc. The vacuum pump is used to evacuate the vacuum chamber to the pre-determined value that the alloy required. The

February 2011

Research & Development

3 Experiment and result analysis

Experiment was carried out according to the following procedures. Firstly, set the variable-volume chamber as the maximum volume, then the probe is entirely immersed in the molten aluminum alloy, and the valves controlling the vacuum pump and the probe are opened while the others are closed. Under the control of computer, vacuum pump starts to evacuate and simultaneously the pressure sensor monitores the pressure. When the pressure reaches the pre-determined value, the pump is turned off. The valve between the vacuum chamber and the hydrogen storage container is then opened, and after moderate amount of pure hydrogen is transmitted to the chamber the valve is closed. Secondly, start the vacuum pump again, and when the vacuum reachs the pre-determined value, the bump is turned off. Lastly, start the variablevolume drive unit, and thus the volume of the chamber will be changed. During this course, the real-time volume increment and the theoretical pressure are automatically calculated by the computer according to the time of the volume change. Meanwhile, the real-time pressure of the vacuum chamber can be obtained by the pressure sensors. So the pressure difference P between theoretical and practical values at any given time can be obtained. From P , the hydrogen partial pressure can also be concluded easily, and it is the practical pressure where P equals to zero. Experiments on pure aluminum and various aluminum alloys have been performed by using the newly designed device. Figure 3 shows the pressure change of the variable-volume chamber and the P curves of pure aluminum melt. The right-hand-side is the measured pressure change curve of the chamber and the left one is the P curve. The items at the top right corner are the melt temperature, the real-time pressure difference value between theoretical pressure and the practical pressure and the measured hydrogen partial pressure. It can be seen from Fig.3 that as the chamber volume changes, the pressure increases continuously and thus the pressure difference P gradually approaches to the "zero-axis" and finally it goes across the "zero-axis" and entered into P < 0 region where the "breath out hydrogen" will occur. The practical pressure value of the point where the P curve and the zero-axis intersects (intersection point of the Line 1 and Line 2 on the right-hand-side graph) is the hydrogen partial pressure of the molten alloy. Table 1 shows the measurement results of the hydrogen partial pressure for various aluminum alloys. In Table 1 the original pressure of the vacuum chamber, the melt temperature, the hydrogen partial pressure and the time of achieving the hydrogen partial pressure are also given. In order to evaluate the reliability and accuracy of the newly designed setup, comparative experiments on various aluminum alloys were performed by using the self-constructed measuring device and the KZCH-1 type hydrogen tester that imported from Japan. Results show that the new method spends 0.250.45 minutes while the KZCH-1 type tester spends more than 6 minutes to obtain results with same precision.
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1-vacuum pump; 2-variable-volume chamber; 3-variable-volume drive unit; 4-1, 4-2 and 4-3- vacuum valve group; 5-probe; 6-isolation unit; 7-hydrogen storage container; 8-pressure sensors; 9-temperature sensors; 10-isothermal bath; 11-data acquisition and processing unit

Fig.2: Schematical of experimental setup

volume of the variable-volume chamber can be altered by the drive unit and, therefore, its internal pressure can be changed continuously at uniform speeds. Because the probe is used as diffusion channel between vacuum chamber and aluminum melt, it must meet the requirements of high thermal stability, high temperature mechanical strength and appropriate permeability in order to ensure that there are no decomposition, gas generation and liquid infiltration except for gas infiltration when heated. The isolation unit is used to prevent the molten aluminum alloys from the vacuum chamber when the probe is damaged. The hydrogen storage container is used to provide pure hydrogen for the vacuum chamber before measurement in order to enhance the purity of gas medium in the vacuum chamber. Vacuum valves that used to control the gas loop are installed between the probe, the hydrogen storage container and the vacuum chamber. The pressure sensor directly connected to the vacuum chamber is used to monitor the real-time change of interior pressure, and the temperature sensor is used to monitor the real-time temperature of the melt. The output signals of these two sensors are sent to the data acquisition and processing unit which consists of signal pre-processing circuit, A/D converter module, serial communication interface and industrial control computer. The signal pre-processing circuit will amplify the mV-level signal of the thermocouple output in order to meet the requirements of data acquisition modules. Data acquisition module transmits the temperature and pressure signals to computer through the serial mode and computer carries out the calculation and evaluation. The isothermal bath has two functions, first, to keep the gas that imported from the probe cool down, second, ensure that the gas in the vacuum chamber maintained at constant temperature and, therefore, the measurement accuracy can be improved. All actions of the variable-volume drive unit, the vacuum pump and the vacuum valve group are automatically controlled by computer.

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Vol.8 No.1

Fig.3: Pressure change curve and P curve of pure aluminum melt in the variable-volume Table1: Experimental results on the hydrogen partial pressure of different aluminum alloys
Alloy type
7B50 7A04 5A06 LD11 3A21 Initial pressure (kPa) 1.5 1.5 1.5 2.0 2.0 Temp. () 810 800 808 805 803 Measured H2 partial pressure by new method (kPa) 2.9533 3.6140 3.4918 3.4012 3.1437 Measured H2 content by new method (mL/100g) 0.085 0.076 0.078 0.106 0.098 Measured H2 content by KZCH-1 (mL/100g) 0.083 0.075 0.074 0.107 0.096 Measuring time by new method (min) 0.32 0.43 0.45 0.30 0.25 Measuring time by KZCH-1 (min) 7 9 10 6 6

4 Conclusions
(1) The hydrogen partial pressure in the molten aluminum alloy can be measured dynamically by continuously changing the volume of the vacuum chamber, calculating the theoretical pressure, monitoring the real-time pressure and calculating the real-time pressure difference between the theoretical and the practical values. (2) A measurement system which mainly consists of variablevolume chamber, hydrogen storage container, variablevolume drive unit, vacuum pump, pressure sensor, probe, data acquisition and processing unit etc. has been constructed. By this system low cost high-precision rapid measurement of the hydrogen partial pressure of molten Al alloy can be realized. (3) With further experimental study and improvement in mathematical modeling, this new method can be used for the fast measurement of hydrogen content in molten aluminum alloy.

References
Lunarska E, Chernyaeva O. Effect of precipitates on hydrogen transport and hydrogen embrittlement of aluminum alloys. Materials Science, 2004, 40(3): 399-407. [2] Jones R H. The influence of hydrogen on the stress-corrosion cracking of low-strength Al-Mg alloys. JOM, 2003, 55(2): 42-46. [1]

Spivak L V and Lunarska E A. The effect of hydrogen on the shear modulus of polycrystalline aluminums. Technical Physics Letters, 2006, 32(1): 55-57. [4] Yan Hongtao, Xiao Gang. Research of hydrogen-removal refinement process in aluminum alloy melt. Hot Working Technology, 2007, 36(1): 73-74. (in Chinese) [5] Wu Shusen, Mao Youwu, Xu Sixiang, et al. The quantitative measurement method and measuring device for hydrogen content in molten aluminum alloy. China patent: CN1699957, 11/23/2005. (in Chinese) [6] Wang Yingjie. Hydrogen Analysis Technology of Cast Aluminum Alloy. In: The Proceedings of the Eleventh China Foundry Annual Conference, Foundry Institution of Chinese Mechanical Engineering Society, 2006: 611-615. (in Chinese) [7] Wu Ruizhi, Shu Da, Wang Jun, Sun Baode. Application of continuous online hydrogen tester in study of aluminum melt hydrogen absorption. Light Alloy Fabrication Technology, 2006, 9(1): 27-30. (in Chinese) [8] Gan Wukui, Long Guorong, Zeng Jianmin. Law of hydrogen content change in molten aluminium alloy during casting under adjusted pressure. Aeronautical Manufacturing Technology, 2004 (6): 103104. (in Chinese) [9] Li Jiehua, Hao Qitang. The current situation and the tendency of the purification technology of molten aluminum alloy. China Foundry Machinery & Technology, 2005.6(1): 32-34. (in Chinese) [10] Li Dayong, Sun Qian, Wang Lihua, Zhang Jianlei. The method of dynamic measurement of hydrogen partial pressure in molten aluminum alloy. China patent: 200810064302x, 10/21/2009.

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