Patent Publication Number: US-11022587-B2

Title: Electric conductivity detector and method for determining phase adjustment value

Description:
TECHNICAL FIELD 
     The present invention relates to an electrical conductivity detector used, for example, for detection of a sample component in ion chromatography, and a method for determining a phase adjustment value used for phase adjustment in the electrical conductivity detector. 
     BACKGROUND ART 
     An electrical conductivity detector (also referred to as a conductivity meter or a conductivity sensor) immerses a pair of electrodes in a sample liquid flowing through a cell, applies a voltage between these electrodes, and detects a change of the magnitude of a current flowing between the electrodes as a change in the electrical conductivity of the sample liquid. 
     In the electrical conductivity detector, the electrical conductivity is determined using an amplified signal obtained by amplifying a current value flowing between the electrodes by an amplification circuit. If the gain (amplification factor) of the amplification circuit is large, small changes in a current can be detected with high sensitivity so that resolution is improved, whereas the upper limit of detectable electrical conductivity is lowered, and the detection range is narrowed. On the contrary, when the gain of the amplification circuit is small, the detection sensitivity is lowered, but the upper limit of the detectable electrical conductivity is also increased, and the detection range is widened. 
     Thus, the detection sensitivity (or resolution) and the detection range are in a trade-off relationship. Therefore, in a case where the variation of the electric conductivity of the sample liquid is large, when the electric conductivity is detected by amplifying the current using only one gain in the amplification circuit, there is a problem that the electric conductivity of the sample liquid exceeds the upper limit of the detectable electric conductivity or the detection sensitivity is insufficient. 
     Therefore, if the gain of the amplification circuit is only one, it is impossible to achieve both measurement of the electric conductivity over a wide range and detection with high resolution. In view of such a problem, changing the gain of the amplification circuit as necessary has been conventionally performed (see, for example, Patent Document 1). 
     PRIOR ART DOCUMENT 
     Patent Document 
     Patent Document 1: Japanese Patent Application Laid-Open No. 11-281687 
     SUMMARY OF THE INVENTION 
     Problems to be Solved by the Invention 
     If the gain of the amplification circuit is changed during the measurement, the waveform of the electric conductivity may be disturbed and discontinuous before and after the switching of the gain. 
     An object of the present invention is to suppress disturbance of a waveform caused by switching of a gain of an amplification circuit in an electrical conductivity detector. 
     Solutions to the Problems 
     The present inventor has found that the cause of the disturbance of the waveform of the electric conductivity before and after the switching of the gain of the amplification circuit is that the phase delay amounts generated in the circuits constituting respective gains of the amplification circuit are different from each other, and therefore, the phase of the current amplified using the gain and the phase of the current amplified using another gain are shifted from each other. Then, the present inventor came to the idea that, if the phase delay amounts generated in the circuits constituting respective gains of the amplification circuit are examined in advance, the phases of the currents amplified using the respective gains can be adjusted to be the same using the delay amounts. The present invention has been made based on such a finding. 
     The electrical conductivity detector according to the present invention includes a cell, a pair of electrodes, a voltage application part, an amplification circuit, a phase adjustment value holding part, and a signal processing circuit. A sample liquid flows through the cell. The pair of electrodes are immersed in the liquid flowing through the cell, and a predetermined voltage is applied between the pair of electrodes by the voltage application part. The amplification circuit has a plurality of gains, and is configured to amplify a current flowing between the pair of electrodes using any one of the gains to obtain an amplified signal. The phase adjustment value holding part is configured to hold phase adjustment values determined in advance for each of the gains for canceling a phase difference between amplified signals obtained using each of the gains of the amplification circuit. The phase adjustment value is, for example, a phase delay amount generated in a circuit including each gain circuit of the amplification circuit. The phase adjustment value can be examined using the method of the present invention described later. The signal processing circuit is configured to calculate electrical conductivity of the liquid flowing through the cell using an amplified signal obtained by being amplified by the amplification circuit and the phase adjustment value which is for the gain used to obtain the amplified signal and is held in the phase adjustment value holding part. 
     In a preferred embodiment, the signal processing circuit is configured to adjust a phase of a reference signal multiplied by the amplification circuit obtained by the amplification circuit to determine the electric conductivity using the phase adjustment value for the gain used to obtain the amplified signal. 
     It is preferable that the electrical conductivity detector according to the present invention further includes a gain adjustment part configured to automatically adjust the gain of the amplification circuit according to a magnitude of the current flowing between the pair of electrodes. With this, the gain of the amplification circuit is automatically switched according to the magnitude of the current flowing between the pair of electrodes, so that a user can perform wide-range detection and high-resolution detection without manually adjusting the gain. 
     A method is provided for determining a phase adjustment value for canceling a phase difference between amplified signals obtained using gains of an amplification circuit of an electrical conductivity detector. The electrical conductivity detector comprises at least: a cell through which sample water flows; a pair of electrodes immersed in the sample water flowing through the cell; a voltage application part configured to apply a voltage between the pair of electrodes; the amplification circuit configured to amplify a current flowing between the pair of electrodes using any one of the gains to obtain the amplified signal; a signal processing circuit configured to calculate electrical conductivity of the sample water using the amplified signal obtained by the amplification circuit. The method includes, in the stated order: 
     a step of conducting between the pair of electrodes by a resistance having a resistance value with negligible capacitance; 
     a step of acquiring amplified signal waveforms for one cycle of the amplified signal, which is obtained by using each of the gains of the amplification circuit, of the current flowing between the pair of electrodes; and 
     a step of determining a phase difference between each of the amplified signals, obtained by using each of the gains, and the reference signal, as a phase adjustment value for each of the gains, by calculating a difference between a time when the amplified signal reaches a maximum value in each of the amplified signal waveforms and a time when the reference signal reaches a maximum value in one cycle of a waveform of the reference signal or by calculating a difference between a time when the amplified signal reaches a minimum value in each of the amplified signal waveforms and a time when the reference signal reaches a minimum value in one cycle of the waveform of the reference signal. 
     Effects of the Invention 
     In the electrical conductivity detector according to the present invention, the electric conductivity of the sample liquid is determined using the phase adjustment value determined in advance for each of the gains for eliminating the phase difference between the amplified signals obtained using each of the gains of the amplification circuit together with the amplified signal obtained by amplification by the amplification circuit, so that the disturbance of the electrical conductivity waveform due to the switching of the gain of the amplification circuit is suppressed, and the electrical conductivity waveform in a continuous shape can be obtained. 
     According to the method of the present invention, the phase adjustment value used in the electrical conductivity detector can be acquired. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is a configuration diagram schematically showing one embodiment of an electrical conductivity detector. 
         FIG. 2  is a principle diagram for explaining the principle of electrical conductivity measurement of the same embodiment. 
         FIG. 3  is a principle diagram of a configuration for examining a phase difference adjustment value used in the electrical conductivity detector of the same embodiment. 
         FIG. 4  is a flowchart showing an example of a method for acquiring a phase difference adjustment value for each gain. 
         FIG. 5A  is a diagram showing an example of an electrical conductivity waveform when a phase of a reference signal is not adjusted. 
         FIG. 5B  is a diagram showing an example of an electrical conductivity waveform when the phase of the reference signal is adjusted. 
     
    
    
     EMBODIMENTS OF THE INVENTION 
     In the following, one embodiment of each of an electrical conductivity detector and a method for acquiring a phase adjustment value used in the electrical conductivity detector according to the present invention will be described with reference to the drawings. 
     First, the configuration of one embodiment of the electrical conductivity detector will be described with reference to  FIG. 1 . 
     The electrical conductivity detector includes a cell  2 , a pair of electrodes  4   a  and  4   b , a voltage application part  6 , an amplification circuit  8 , a gain adjustment part  10 , a signal processing circuit  12 , and a phase adjustment value holding part  14 . 
     A sample liquid flows through the cell  2 , and the pair of electrodes  4   a  and  4   b  are immersed in the sample liquid flowing through the cell  2 . The voltage application part  6  is configured to apply a predetermined voltage between the electrodes  4   a  and  4   b . The amplification circuit  8  is configured to amplify a current flowing between the electrodes  4   a  and  4   b  when the predetermined voltage is applied by the voltage application part  6  to generate an amplified signal. The amplification circuit  8  has a plurality of gains, and amplifies the current flowing between the electrodes  4   a  and  4   b  using any one of the gains. 
     The gain adjustment part  10  is configured to associate the current level flowing between the electrodes  4   a  and  4   b  with the gain used to amplify the current in advance, read the magnitude of the current flowing between the electrodes  4   a  and  4   b , and select a gain according to the size. As a result, when the electrical conductivity of the sample liquid flowing through the cell  2  exceeds a certain value, the gain of the amplification circuit  8  is automatically switched, and the amplification factor of the current is reduced. The gain adjustment part  10  is a function realized by hardware or software. 
     The amplified signal generated by the amplification circuit  8  is taken into the signal processing circuit  12 . The signal processing circuit  12  is configured to determine the electrical conductivity of the sample water flowing through the cell  2  using the amplified signal from the amplification circuit  8 . When determining the electrical conductivity using the amplified signal, the signal processing circuit  12  is configured to eliminate the influence due to the phase delay specific to the gain using the phase adjustment value for the gain used to generate the amplified signal. The phase adjustment value for each gain is held in the phase adjustment value holding part  14 . The phase adjustment value holding part  14  is realized by a partial area of a storage device. 
     The measurement principle of the electrical conductivity detector will be described with reference to  FIG. 2 . In the following description, the voltage (input voltage) V in  applied between the electrodes  4   a  and  4   b  will be described as sin θ for convenience. 
     As shown in the figure, the cell  2  can be approximated by a parallel circuit of a capacitance C cell  between the electrodes  4   a  and  4   b  and a resistance value R cell . The capacitance C cell  and the resistance value R cell  between the electrodes  4   a  and  4   b  are variables whose values change depending on the electric conductivity of the sample liquid. 
     The amplification circuit  8  changes the gain by changing a resistance value of an operational amplifier. Here, the amplification circuit  8  is described as having two gains (high and medium) realized by two resistance values R gainH  and R gainM , but the amplification circuit  8  may have three or more gains. Amplified signals S gainH  and S gainM  obtained by amplifying the current flowing between the electrodes  4   a  and  4   b  using gains are expressed by Equations (1) and (2) below, respectively. In Equations (1) and (2), α H  and α M  are phase delay amounts generated in a circuit including each gain, and w is an angular frequency. 
     
       
         
           
             
               
                 
                   
                     S 
                     gainH 
                   
                   = 
                   
                     
                       [ 
                       
                         
                           
                             1 
                             
                               R 
                               cell 
                             
                           
                           ⁢ 
                           
                             sin 
                             ⁡ 
                             
                               ( 
                               
                                 θ 
                                 - 
                                 
                                   α 
                                   H 
                                 
                               
                               ) 
                             
                           
                         
                         + 
                         
                           ω 
                           ⁢ 
                           
                               
                           
                           ⁢ 
                           
                             C 
                             cell 
                           
                           ⁢ 
                           
                             cos 
                             ⁡ 
                             
                               ( 
                               
                                 θ 
                                 - 
                                 
                                   α 
                                   H 
                                 
                               
                               ) 
                             
                           
                         
                       
                       ] 
                     
                     × 
                     
                       R 
                       gainH 
                     
                   
                 
               
               
                 
                   ( 
                   1 
                   ) 
                 
               
             
             
               
                 
                   
                     S 
                     gainM 
                   
                   = 
                   
                     
                       [ 
                       
                         
                           
                             1 
                             
                               R 
                               cell 
                             
                           
                           ⁢ 
                           
                             sin 
                             ⁡ 
                             
                               ( 
                               
                                 θ 
                                 - 
                                 
                                   α 
                                   M 
                                 
                               
                               ) 
                             
                           
                         
                         + 
                         
                           ω 
                           ⁢ 
                           
                               
                           
                           ⁢ 
                           
                             C 
                             cell 
                           
                           ⁢ 
                           
                             cos 
                             ⁡ 
                             
                               ( 
                               
                                 θ 
                                 - 
                                 
                                   α 
                                   M 
                                 
                               
                               ) 
                             
                           
                         
                       
                       ] 
                     
                     × 
                     
                       R 
                       gainM 
                     
                   
                 
               
               
                 
                   ( 
                   2 
                   ) 
                 
               
             
           
         
       
     
     The signal processing circuit  12  includes a multiplier that multiplies the amplified signals S gainH  and S gainM  by a reference signal, and a filter that accumulates the multiplied value for one period. The reference signal is the same sin θ as the input signal. The electrical conductivity detector of the embodiment is configured to adjust the phase of this reference signal using the phase adjustment value held in the phase adjustment value holding part  14 , but here the description is continued as the reference signal being sin θ. 
     The values obtained by multiplying the amplified signals S gainH  and S gainM  by the reference signal sin θ, accumulating these for one period, and dividing the accumulated values by the resistance values R gainH  and R gainM  are expressed by Equations (3) and (4) below. 
     
       
         
           
             
               
                 
                   
                     
                       ∫ 
                       0 
                       
                         2 
                         ⁢ 
                         π 
                       
                     
                     ⁢ 
                     
                       
                         [ 
                         
                           
                             
                               1 
                               
                                 R 
                                 cell 
                               
                             
                             ⁢ 
                             
                               sin 
                               ⁡ 
                               
                                 ( 
                                 
                                   θ 
                                   - 
                                   
                                     α 
                                     H 
                                   
                                 
                                 ) 
                               
                             
                           
                           + 
                           
                             ω 
                             ⁢ 
                             
                                 
                             
                             ⁢ 
                             
                               C 
                               cell 
                             
                             ⁢ 
                             
                               cos 
                               ⁡ 
                               
                                 ( 
                                 
                                   θ 
                                   - 
                                   
                                     α 
                                     H 
                                   
                                 
                                 ) 
                               
                             
                           
                         
                         ] 
                       
                       × 
                       sin 
                       ⁢ 
                       
                           
                       
                       ⁢ 
                       θ 
                     
                   
                   = 
                   
                     
                       
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                             ⁢ 
                             cell 
                           
                         
                       
                       ⁢ 
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                       ⁢ 
                       
                           
                       
                       ⁢ 
                       
                         α 
                         H 
                       
                     
                     + 
                     
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                       ⁢ 
                       
                           
                       
                       ⁢ 
                       
                         C 
                         cell 
                       
                       ⁢ 
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                       ⁢ 
                       
                           
                       
                       ⁢ 
                       sin 
                       ⁢ 
                       
                           
                       
                       ⁢ 
                       
                         α 
                         H 
                       
                     
                   
                 
               
               
                 
                   ( 
                   3 
                   ) 
                 
               
             
             
               
                 
                   
                     
                       ∫ 
                       0 
                       
                         2 
                         ⁢ 
                         π 
                       
                     
                     ⁢ 
                     
                       
                         [ 
                         
                           
                             
                               1 
                               
                                 R 
                                 cell 
                               
                             
                             ⁢ 
                             
                               sin 
                               ⁡ 
                               
                                 ( 
                                 
                                   θ 
                                   - 
                                   
                                     α 
                                     M 
                                   
                                 
                                 ) 
                               
                             
                           
                           + 
                           
                             ω 
                             ⁢ 
                             
                                 
                             
                             ⁢ 
                             
                               C 
                               cell 
                             
                             ⁢ 
                             
                               cos 
                               ⁡ 
                               
                                 ( 
                                 
                                   θ 
                                   - 
                                   
                                     α 
                                     M 
                                   
                                 
                                 ) 
                               
                             
                           
                         
                         ] 
                       
                       × 
                       sin 
                       ⁢ 
                       
                           
                       
                       ⁢ 
                       θ 
                     
                   
                   = 
                   
                     
                       
                         π 
                         
                           R 
                           cell 
                         
                       
                       ⁢ 
                       cos 
                       ⁢ 
                       
                           
                       
                       ⁢ 
                       
                         α 
                         M 
                       
                     
                     + 
                     
                       ω 
                       ⁢ 
                       
                           
                       
                       ⁢ 
                       
                         C 
                         cell 
                       
                       ⁢ 
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                       ⁢ 
                       
                           
                       
                       ⁢ 
                       
                         α 
                         M 
                       
                     
                   
                 
               
               
                 
                   ( 
                   4 
                   ) 
                 
               
             
           
         
       
     
     When Equations (3) and (4) above are divided by n, the electrical conductivities G H  and G M  are obtained. That is, G H  and G M  are expressed by Equations (5) and (6) below, respectively. 
     
       
         
           
             
               
                 
                   
                     G 
                     H 
                   
                   = 
                   
                     
                       
                         1 
                         
                           R 
                           cell 
                         
                       
                       ⁢ 
                       cos 
                       ⁢ 
                       
                           
                       
                       ⁢ 
                       
                         α 
                         H 
                       
                     
                     + 
                     
                       ω 
                       ⁢ 
                       
                           
                       
                       ⁢ 
                       
                         C 
                         cell 
                       
                       ⁢ 
                       sin 
                       ⁢ 
                       
                           
                       
                       ⁢ 
                       
                         α 
                         H 
                       
                     
                   
                 
               
               
                 
                   ( 
                   5 
                   ) 
                 
               
             
             
               
                 
                   
                     G 
                     M 
                   
                   = 
                   
                     
                       
                         1 
                         
                           R 
                           cell 
                         
                       
                       ⁢ 
                       cos 
                       ⁢ 
                       
                           
                       
                       ⁢ 
                       
                         α 
                         M 
                       
                     
                     + 
                     
                       ω 
                       ⁢ 
                       
                           
                       
                       ⁢ 
                       
                         C 
                         cell 
                       
                       ⁢ 
                       sin 
                       ⁢ 
                       
                           
                       
                       ⁢ 
                       
                         α 
                         M 
                       
                     
                   
                 
               
               
                 
                   ( 
                   6 
                   ) 
                 
               
             
           
         
       
     
     From Equations (5) and (6) above, it is found that the electrical conductivities G H  and G M  determined by calculation not only depend on R cell  and C cell , which vary depending on the actual electrical conductivity of the sample water, but also depend on the phase delay amounts α H  and α M  that occur in the respective circuits. Since the delay amounts α H  and α M  are values specific to the respective circuits including the gains, α H ≠α M . Therefore, G H ≠G M , and as shown in  FIG. 5A , the waveform of the electric conductivity does not continue before and after the gain switching. 
     Here, since α H  and α M  are phase differences from the reference signal multiplied by the amplified signals S gainH  and S gainM , if the phase differences between the amplified signals S gainH  and S gainM  and the reference signal multiplied thereby are set to 0, that is, if the reference signals multiplied by the amplified signals S gainH  and S gainM  are respectively sin (θ−α H ) and sin (θ−α M ), α H  and α M  in Equations (5) and (6) above will be 0, respectively, and the equation below is satisfied. 
     
       
         
           
             
               
                 
                   
                     G 
                     H 
                   
                   = 
                   
                     
                       G 
                       M 
                     
                     = 
                     
                       1 
                       
                         R 
                         cell 
                       
                     
                   
                 
               
               
                 
                   ( 
                   7 
                   ) 
                 
               
             
           
         
       
     
     Accordingly, as shown in  FIG. 5B , the waveform of the electric conductivity continues before and after the gain of the amplification circuit  8  is switched. In the phase adjustment value holding part  14  (see  FIG. 1 ), the phase delay amounts α H  and α M  generated in the circuits including the gains of the amplification circuit  8  are held as phase adjustment values. 
     A method for acquiring the phase adjustment values α H  and α M  will be described with reference to the principle diagram of  FIG. 3  and the flowchart of  FIG. 4 . 
     When the phase adjustment values α H  and α M  are acquired, as shown in  FIG. 3 , in place of the cell  2 , a resistor (resistance value R) small enough to ignore the capacitance is mounted between the electrodes  4   a  and  4   b . (Step S 1 ). In this state, any one gain of the amplification circuit  8  is selected (step S 2 ), the amplified signals obtained by amplifying the current flowing through the resistor by being applied with the voltage sin θ between the electrodes  4   a  and  4   b  using the gains and the reference sin θ are read for one circle by an arithmetic processing part  16  realized by, for example, a CPU (step S 3 ). 
     The amplified signals S gainH  and S gainM  obtained by amplifying the currents flowing through the electrodes  4   a  and  4   b  using the respective gains by the amplification circuit  8  are as follows. 
     
       
         
           
             
               
                 
                   
                     S 
                     gainH 
                   
                   = 
                   
                     
                       1 
                       R 
                     
                     ⁢ 
                     
                       sin 
                       ⁡ 
                       
                         ( 
                         
                           θ 
                           - 
                           
                             α 
                             H 
                           
                         
                         ) 
                       
                     
                     × 
                     
                       R 
                       gainH 
                     
                   
                 
               
               
                 
                   ( 
                   8 
                   ) 
                 
               
             
             
               
                 
                   
                     S 
                     gainM 
                   
                   = 
                   
                     
                       1 
                       R 
                     
                     ⁢ 
                     
                       sin 
                       ⁡ 
                       
                         ( 
                         
                           θ 
                           - 
                           
                             α 
                             M 
                           
                         
                         ) 
                       
                     
                     × 
                     
                       R 
                       gainM 
                     
                   
                 
               
               
                 
                   ( 
                   9 
                   ) 
                 
               
             
           
         
       
     
     The arithmetic processing part  16  determines the time at which the amplified signals and the reference signal sin θ each have the maximum value (or the minimum value), and determines the phase differences α H , α M  between the amplified signals and the reference signal from the differences between them (Step S 4 ). Then, the determined phase differences are stored in the phase adjustment value holding part  14  as phase adjustment values (step S 5 ). By performing this operation for all the gains provided in the amplification circuit  8 , the phase adjustment value for each gain can be determined. 
     DESCRIPTION OF REFERENCE SIGNS 
     
         
         
           
               2 : Cell 
               4   a ,  4   b : Electrode 
               6 : Voltage application part 
               8 : Amplification circuit 
               10 : Gain adjustment part 
               12 : Signal processing circuit 
               14 : Phase adjustment value holding part