CN111536950B - Method for removing temperature influence of profile marine measuring instrument - Google Patents

Abstract

The invention relates to the technical field of ocean detection, in particular to a method for removing temperature influence of a profile ocean measuring instrument, which comprises the following steps: 1) carrying out temperature correction on an LED light source of the detection module; 2) correcting the data corrected in the step 1) for the chemical reaction rate. The invention aims at the system-level correction of the temperature influence of the profile ocean instrument; each independent influence factor is independently processed during correction; the coverage is wide, and the application adaptability is good.

Description

Method for removing temperature influence of profile marine measuring instrument

Technical Field

The invention relates to the technical field of ocean detection, in particular to a method for removing temperature influence of a profile ocean measuring instrument.

Background

The marine measuring instrument based on the spectrophotometer method is an important component of the marine instrument, and at the present stage, the application of the instrument is concentrated on in-situ measurement and is widely applied in the market. With the progressive market and application, more users want to be able to make profile measurements and cruise measurements. In order to meet the requirement, optimization needs to be carried out on the basis of the original instrument.

Among the various factors, temperature is a non-negligible factor of the profiler. Because the liquid injection mode and the reaction mode are different, the influence of the temperature on the in-situ measuring instrument and the profile measuring instrument is completely different, and the influence of the temperature change on the instruments must be reduced in order to improve the measuring precision of the profile measuring instrument.

In both in-situ and profiling instruments, the instrument is sensitive to temperature changes in several ways: in the first aspect, the light source LED in the measuring module generally has a light-emitting intensity that decreases with increasing temperature; the second aspect is the efficiency of the chemical reaction, which generally increases with increasing temperature.

Therefore, the influence change trends of the temperature on the LED light sources are different, and the influence is analyzed and summarized under the situation with higher requirements on precision due to different chemical methods adopted by considering the manufacturer difference, batch difference and individual difference of the LED light sources with different light sources.

The profile measuring instrument adopts different chemical reaction methods, mainly uses a flow injection method to continuously extract seawater and reagents, has no specific reaction part, and can continuously sample after a fixed reaction delay.

Therefore, if the influence of the temperature is not controlled, the instrument measurement value is inevitably influenced, which is shown in the following aspects.

The first is to produce a change in chemical reactivity. The chemical reaction rate increases with the increase of the liquid temperature, so that, when other factors are unchanged, the seawater with different concentrations may show the same measured value at different temperatures, and the accuracy is lost.

The second is to change the luminous intensity of the light source LED. The luminous intensity of the LED generally decreases with the increase of temperature, and when other factors are not changed, the luminous intensity of the same LED changes at different temperatures, resulting in changes of the color rendering value and the blank value, and when the color rendering value and the blank value are measured by two LEDs respectively, the deviation of the final calculated value is inestimable due to the individual difference of the LEDs.

The third is to mask the light decay of the LED. The typical LED luminous intensity varies with time and can be roughly divided into three stages. In the first stage, the luminous intensity of the LED is attenuated more quickly, the curve graph is obvious, but the maintaining time is relatively short; in the second stage, the light attenuation of the LED is very gentle, and the better LED can be attenuated by about 1% in one year; in the third stage, the LED passes through a remarkable inflection point, the light intensity is sharply reduced, and the LED basically fails. In applications, the LED is typically tuned to the second stage before it is used. The light attenuation is determined by the using time and conditions, and the temperature rise can shorten the stabilization time of the LED, thereby indirectly influencing the light attenuation. Different application conditions and different LED individuals can influence the actual light intensity of the instrument, and the LED stability time cannot be accurately evaluated. Moreover, the influence of light attenuation and temperature on the light intensity of the LED changes in the same direction, and the influence of the light attenuation can be ignored.

Generally, the chemical reactivity and the light intensity of the LED are sensitive to temperature and vary relatively stably, while the light decay is insensitive to temperature and varies drastically. In general application, only the chemical reaction rate and the light intensity of the LED can be processed in terms of hardware and methods, and only basic LED service life judgment is needed for light attenuation.

Disclosure of Invention

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a method for removing the temperature influence of a profile ocean measuring instrument, and provides an effective temperature correction method for eliminating the influence of temperature on a light source LED and the influence of temperature on the chemical reaction rate.

(II) technical scheme

The invention provides the following technical scheme:

a method of removing temperature effects of a profile marine measurement instrument, comprising the steps of:

1) carrying out temperature correction on the LED light source of the detection module by adopting a reference method or a constant temperature method;

2) correcting the data corrected in the step 1) for the chemical reaction rate.

Further, the step 1) of performing temperature correction on the LED light source of the detection module by using a reference method includes the following steps:

a. the LED requires an aging process before use;

b. monitoring the temperature of the LED;

c. Collecting a main signal of the LED light passing through the seawater to be detected and a reference signal of the LED light passing through the air;

d. calibrating a curve of the light intensity and the temperature of the LED;

e. and (4) correcting the light intensity of the LED by applying the Law of Laobbier, and adjusting the concentration of the substance to be detected to the same temperature point.

Further, the step d comprises the following steps:

d1. determining the number of calibration points required by calibration, at least 5 points;

d2. determining the temperature of each calibration point within a preset temperature range;

d3. calibrating the relation between blank channel background noise and temperature, turning off the LED, only keeping air in the detection channel, keeping the temperature at each calibration point for at least one hour, respectively recording the background noise of the main channel and the reference channel at each calibration point, and fitting a curve to obtain B_{Ginseng, electricity}、B_{Electricity and main}The curve of (d);

d4. calibrating the relation between the blank value channel sampling value and the temperature: opening the LED, only reserving air in the detection channel, keeping the temperature of each calibration point for at least one hour, respectively recording signal values of the main channel and the reference channel at each calibration point, and fitting a curve to obtain B_{Ginseng radix (Panax ginseng C.A. Meyer)}、B_{Master and slave}The curve of (d);

d5. according to B_{Ginseng radix (Panax ginseng C.A. Meyer)}＝B_{Ginseng, electricity}+B_{Ginseng, light}And B_{Master and slave}＝B_{Electricity and main}+B_{Water, main part}+B_{Light and main}Relation, respectively calculating the LED light intensity B of the blank value channel _{Ginseng, light}And B_{Light and main}Curve as a function of temperature, wherein B_{Water, main part}Calculating according to a zero value;

d6. according to

Calculation of R_BThe variation curve of the light intensity ratio of the main light path and the reference light path on the blank value channel along with the temperature;

d7. calibrating the relation between the background noise of the color rendering value channel and the temperature, turning off the LED, only keeping air in the detection channel, keeping the temperature of each calibration point for at least one hour, respectively recording the background noise of the main channel and the reference channel at each calibration point, and fitting a curve to obtain C_{Ginseng, electricity}、C_{Electricity and main}The curve of (d);

d8. calibrating the relation between the sampling value of the color rendering value channel and the temperature, turning on the LED, only reserving air in the detection channel, keeping the temperature of each calibration point constant for at least one hour, respectively recording the signal values of the main channel and the reference channel at each calibration point, and fitting a curve to obtain a curve;

d9. according to C_{Ginseng radix (Panax ginseng C.A. Meyer)}＝C_{Ginseng, electricity}+C_{Ginseng, light}And C_{Master and slave}＝C_{Electricity and main}+C_{Water, main part}+C_{Light and main}*ρ_TransformingRelation, respectively calculating color rendering value channel LED light intensity C_{Ginseng, light}And C_{Light and main}Curve as a function of temperature, in which C_{Water, main part}Calculating according to a zero value;

d10. according to

Calculation of R_CI.e. the variation curve of the light intensity ratio of the main light path and the reference light path on the color rendering value channel along with the temperature.

Further, the step d2 determines the temperature of each calibration point, which is distributed evenly within the preset temperature range.

Further, the step 1) of performing temperature correction on the LED light source of the detection module by using a constant temperature method includes the following steps:

the LED needs aging treatment before use;

b. the method comprises the following steps that an aluminum substrate emitting plate is adopted, the temperature of the aluminum substrate is controlled by adjusting the power of a power resistor arranged at the emitting plate, and then the temperature of an LED is controlled to be constant;

c. according to blank value ═ B_{Light (A)}＝B-B_{Electric power}-B_{Water (W)}And color rendering value ═ C_{Light (es)}*ρ_Transforming＝C-C_{Electric power}-C_{Water (W)}Calibrating the curve of LED intensity and temperature, i.e. for B_{Electric power}+B_{Water (W)}And C_{Electric power}+C_{Water (W)}And calibrating the two sums by a curve.

Further, the step 2) adopts a constant temperature method to correct the influence of the temperature on the chemical reaction rate, and comprises the following steps:

a. keeping the LED at room temperature, turning off the LED light source of the blank value and color value detection channels, and respectively measuring B_{Electric power}+B_{Water (W)}And C_{Electric power}+C_{Water (W)}；

b. Keeping the LED at room temperature, opening an LED light source of the blank value detection channel, and measuring B;

c. obtaining a blank value B_{Light (es)}＝B-B_{Electric power}-B_{Water (W)}The components are not influenced by chemical reaction rate, so that the blank value of two temperature points is the same, namely the blank value _{Value of}Blank value_Than＝B_{Light (A)}＝B-B_{Electric power}-B_{Water (W)}；

d. Finding T_{Constant temperature}Point color value, regulating the temperature of the mixture of seawater and reagent to T_{Constant temperature}Can measure C_{Constant temperature}Color rendering value_{Constant temperature}＝C_{Constant temperature}-C_{Electric power}-C_{Water (W)}；

e. Finding T_{Ratio of}Point color value, regulating the temperature of the mixture of seawater and reagent to T_{Ratio of}Can measure C_{Ratio of}Color rendering value_{Ratio of}＝C_{Ratio of}-C_{Electric power}-C_{Water (W)}；

f. Finding T_{Constant temperature}Point sum T_{Ratio of}The color rendering value at the point temperature is related, the proportionality coefficient R is

g. When curve correction is performed, the color rendering value is used_{Ratio of}Color rendering value of R_{Constant temperature}Applied to the whole curve to obtain T_{Ratio of}Time color rendering value curve;

h. applying Laobbier's law to correct data,

wherein the temperature at the constant temperature point is assumed to be T_{Constant temperature}Temperature at the temperature point to be compared is T_{Ratio of}。

Further, the step 2) adopts a calibration method to correct the influence of the temperature on the chemical reaction rate, and comprises the following steps:

a. determining the number of fixed points, 5 points or 7 points according to the application condition;

b. determining the temperature of the calibration points, generally evenly distributing in a temperature range, and recommending that the distance between the temperature points is not less than 5 ℃;

c. selecting a certain concentration standard solution, wherein the test values of the standard solution at the highest temperature point and the lowest temperature point do not exceed the linear interval of the measurement range of the instrument;

d. Heating the standard solution to the temperature of each calibration point in sequence, keeping the temperature for one hour, and measuring and recording numerical values;

e. fitting the obtained data to obtain a curve formula;

f. and correcting the data according to the temperature and curve formula.

(III) advantageous effects

Compared with the prior art, the invention provides a novel anti-counterfeiting method, which has the following beneficial effects:

1. system level correction for temperature effects of profiled marine instruments;

2. each independent influence factor is independently processed during correction;

3. the coverage is wide, and the application adaptability is good.

Description of the drawings:

FIG. 1 is a schematic diagram of the fluid path of a single channel configuration of a measurement module having a reference channel;

FIG. 2 is a schematic diagram of an optical channel of a single channel configuration of a measurement module having a reference channel;

FIG. 3 is a schematic diagram of the fluid path of a single channel configuration of a measurement module without a reference channel;

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The first embodiment is as follows:

1) carrying out temperature correction on an LED light source of the detection module;

in view of the influence of temperature, generally, the concentration of the substance to be measured is converted to a specific temperature, so as to facilitate the later data analysis processing. This specified temperature is generally room temperature, i.e. 25 ℃ or 300K.

The first method comprises the following steps: reference method

Single-channel structure

The concentration of each substance to be measured needs to be measured, and generally, the blank value and the color value are measured by an independent channel respectively, and the measurement channels of the blank value and the color value are completely the same except that the liquid circulating in the channel is different. The following description is given with reference to a common measurement channel, and is applicable to both blank value and color value measurement channels.

As shown in fig. 1, a single channel configuration of a measurement module is shown, with the direction of the arrows indicating the flow path and direction of the liquid within the channel.

As shown in fig. 2, a single channel optical path is exhibited. The light emitted by the light source LED has two transmission paths, one of which passes through a section of liquid of a specified length and the other of which passes through a section of air. Both can be received by the photoelectric tube and sent to the circuit for sampling processing. The information of the measured substance of the seawater can be reflected through the signal of the measured seawater, and can be called as a main signal; the signal through the air can be used to monitor the status of the LED, which can be referred to as a reference signal.

In the invention, the light source LED is positioned on the transmitting plate, the main signal is sampled by the main receiving plate, and the reference signal is sampled by the reference receiving plate.

In the present invention, the temperature of the LED needs to be monitored, and there are several ways.

First, the thermometric component is placed on the emitter plate. The temperature measurement part is close to the LED at the moment, the measured temperature is closest to the temperature of the LED, but the signal quantity between PCBs can be increased, meanwhile, the working current and the temperature signal of the LED are easy to interfere, and the stability of the luminous intensity of the LED is influenced. The method can be used in the occasions with stronger layout capability of the whole machine, better PCB design process and higher requirement on temperature.

Second, the thermometric component is placed on the main receiving plate. The measured temperature of the LED is not very accurate, but the temperature of the measuring point can be used for representing the temperature of the LED because the temperature in the instrument does not change drastically and the measured value and the temperature of the LED keep a basically stable difference. The change in temperature has a greater effect on the luminous intensity of the LED than the accuracy of the temperature. The method can be used under the conditions that the whole structure is complex, the space is small, the application condition is harsh, and certain requirements are met on the temperature accuracy of the LED.

Thirdly, the temperature measuring component is placed on the main control panel. Because the main control board is complex, and a plurality of ICs such as MCU and the like are internally integrated with a temperature measuring function, certain cost can be saved, the complexity among PCBs is reduced, and the accuracy of temperature measuring values can be further reduced. The method can be used under the conditions of sensitive cost, high modularization degree required by the PCB and low temperature requirement on the LED.

In addition, in both the second and third methods, correction can be made by using a constant temperature environment.

LED aging

In the present invention, the LED needs an aging process before use in order to allow the LED to pass through the first stage as soon as possible and enter a plateau. Generally, the aging process uses up a short amount of time without damaging the LEDs and can maximize the troubleshooting of failed LEDs.

Specifically, the following points are observed:

the aging constant temperature cannot exceed the limit temperature of the LED, and is recommended to be reduced by 5 ℃ compared with the limit temperature;

the aging humidity cannot be too high and is close to the actual application environment as much as possible;

the aging time of a single time is not suitable to be too long, the aging time is recommended to be controlled within 12 hours, and if the aging effect is not obvious, the aging can be carried out for several times;

If unqualified LEDs cannot be well selected, temperature impact can be carried out, but the frequency is not too high, otherwise qualified LEDs can be damaged

Influence factor of sampling value

In the invention, the light source receiving end receives the photoelectric signal and samples the photoelectric signal to be expressed in the form of digital quantity, all variables are digital quantity without unit, and if necessary, the relation between the required unit and the digital quantity can be derived automatically.

The following relationship is satisfied at the main light path of the blank value channel:

B_{master and slave}＝B_{Electricity and main}+B_{Water, main part}+B_{Light and main}

Wherein, B_{Master and slave}Is the sampling value of the main light path of the blank value channel; b is_{Electricity and main}The background noise of the circuit of the main light path of the blank value channel is the sampling value at the receiving end after the LED is turned off; b is_{Water, main part}The background influence of the water body of the main light path of the blank value channel mainly reflects the influence of factors such as turbidity, fluorescence and the like of the water body, and the value of the background influence is far smaller than that of B in the application of a spectrophotometer method_{Light and main}Generally, the noise can be ignored, and when the influence is large and cannot be ignored, the noise can be used as a fixed value for calculation and is merged into circuit noise during calculation; b is_{Light and main}The response of the luminous intensity of the light source LED at the receiving end is shown, and when the LED is in a stable period, the natural light attenuation of the LED is negligible, namely, the natural light attenuation only changes along with the temperature of the LED.

Similarly, the following relationship is satisfied at the main light path of the color rendering value channel:

C_{master and slave}＝C_{Electricity and main}+C_{Water, main part}+C_{Light and main}*ρ_Transforming

Wherein, C_{Master and slave}Is the sampling value of the main light path of the color rendering value channel; c_{Electricity and main}Is the background noise of the circuit of the main light path of the color rendering channel; c_{Water, main part}The background influence of the water body of the main light path of the color rendering value channel; c_{Light and main}The response of the luminous intensity of the light source LED at the receiving end; rho_TransformingThe influence is generated after the substance to be detected in the sample reacts with the chemical reagent, the intensity of the light beam can be reduced, and the higher the concentration is, the more remarkable the reduction is.

The following relationship is satisfied at the reference light path of the blank value channel:

B_{ginseng radix (Panax ginseng C.A. Meyer)}＝B_{Ginseng, electricity}+B_{Ginseng, light}

Wherein, B_{Ginseng radix (Panax ginseng C.A. Meyer)}The sampling value of the reference light path of the blank value channel; b is_{Ginseng, electricity}Is the background noise of the circuit of the blank value channel reference light path; b is_{Ginseng, light}The luminous intensity of the LED of the light source is receivedThe response of the terminal. The influence of the medium included in the reference optical path is not included here, because the medium of the reference optical path is air, and the influence is small and negligible compared with air.

Similarly, the following relationship is satisfied at the reference light path of the color rendering value channel:

C_{ginseng radix (Panax ginseng C.A. Meyer)}＝C_{Ginseng, electricity}+C_{Ginseng, light}

Wherein, C_{Ginseng radix (Panax ginseng C.A. Meyer)}Is a sampling value of a color rendering value channel reference light path; c _{Ginseng, Electricity}Is the background noise of the circuit of the color rendering channel reference optical path; c_{Ginseng, light}Is the response of the luminous intensity of the light source LED at the receiving end.

Calibration curve of light intensity and temperature of LED

In the invention, the relation between the LED luminous intensity and the temperature needs to be calibrated before the instrument is used, so that a basis is provided for later data correction.

The specific operation is as follows:

according to application requirements, determining the number of calibration points required by calibration, and generally proposing 7 points or 9 points in a laboratory, wherein the minimum number is 5 points;

determining the temperature of each calibration point according to the applied temperature range, and generally, suggesting the temperature to be evenly distributed in the temperature range;

calibrating the relation between blank channel background noise and temperature: turning off the LED, only reserving air in the detection channel, keeping the temperature of each calibration point constant for at least one hour, recording the background noise of the main channel and the reference channel at each calibration point, and fitting a curve to obtain B_{Ginseng, electricity}，B_{Electricity and main}The curve of (d);

calibrating the relation between the blank value channel LED and the temperature: opening the LED, only reserving air in the detection channel, keeping the temperature of each calibration point for at least one hour, respectively recording signal values of the main channel and the reference channel at each calibration point, and fitting a curve to obtain B _{Ginseng radix}、B_{Master and slave}The curve of (d);

according to formula B_{Ginseng radix (Panax ginseng C.A. Meyer)}＝B_{Ginseng, electricity}+B_{Ginseng, light}And B_{Master and slave}＝B_{Electricity and main}+B_{Water, main part}+B_{Light and main}Relationship, scoreSeparately obtain B_{Ginseng, light}And B_{Light and main}Curve as a function of temperature, in which B_{Water, main part}Calculating according to a zero value;

according to the formula

Calculation of R_BThe variation curve of the light intensity ratio of the main light path and the reference light path on the blank value channel along with time;

similarly, C of color rendering value channel is calibrated_{Ginseng, electricity}，C_{Electricity and main}，C_{Ginseng, light}And

curve as a function of temperature.

LED light intensity correction

Before applying the Lao Bo Bill law, the factors need to be combed, the influence of various irrelevant factors is eliminated, and only the parameters required by the law are reserved. According to the law requirement, B_{Light and main}As a blank value, C_{Light and main}*ρ_TransformingThe result is used as color rendering value, for which the unnecessary circuit background noise and water body background influence need to be removed, and according to B_{Light and main}And C_{Light and main}And adjusting the concentration of the substance to be detected to the same temperature point according to the relation with the temperature.

In the application, assuming that the actual temperature t has been achieved, the calibration method is as follows.

Reading the current temperatures t, and B_{Ginseng radix (Panax ginseng C.A. Meyer)}，B_{Master and slave}，C_{Ginseng radix (Panax ginseng C.A. Meyer)}，C_{Master and slave}。

A blank value is calculated. According to B_{Ginseng, electricity}Curve, calculate B_{Ginseng, electricity} (ii) a According to B_{Ginseng, light}＝B_{Ginseng radix (Panax ginseng C.A. Meyer)}-B_{Ginseng, electricity}To find B_{Ginseng, light}(ii) a Then B is_{Light and main}＝R_B*B_{Ginseng, light}I.e. blank value ═ B_{Light and main}。

And calculating a color rendering value. Generally, to meet the needs of industrialization, the white value channel and the color value channel are made to be identical, so C_{Water, main part}＝B_{Water, main part}＝B_{Master and slave}-B_{Electricity and main}-B_{Light and main}(ii) a According to C_{Ginseng, electricity}Curve, calculate C_{Ginseng, electricity}(ii) a According to C_{Ginseng, light}＝C_{Ginseng radix (Panax ginseng C.A. Meyer)}-C_{Ginseng, electricity}Calculating C_{Ginseng, light}(ii) a Then C is_{Light and main}＝R_C*C_{Ginseng, light}(ii) a According to C_{Electricity and main}Curve, calculate C_{Electricity and main}. At this time, the color rendering value is C_{Light and main}*ρ_Transforming＝C_{Master and slave}-C_{Electricity and main}-C_{Water, main part}。

At this time, the blank value and the color rendering value are substituted into the Lab Law to obtain the concentration of the substance to be measured at the current temperature t.

When the unified temperature set point is T, according to C_{Light and main}、B_{Light and main}The temperature curve of (2) is obtained by calculating the value at the point T and then substituting the value into a law formula for calculation.

The second method comprises the following steps: constant temperature method

In the present invention, another method may be used to perform temperature correction on the detection module. The present invention uses no reference channel, but only general channels, as shown in fig. 3, in which arrows indicate the flowing path of liquid.

In the invention, the LED light source positioned on the transmitting plate emits light beams, and after passing through the horizontal path, the light beams are received by the photodiode positioned on the receiving plate, and are subjected to circuit processing acquisition and the like.

In the invention, the aluminum substrate is used as the plate material of the emitting plate instead of the conventional FR4 material, and a controlled power resistor and a thermistor are also added on the emitting plate. By utilizing the excellent heat-conducting property of the aluminum substrate, the temperature of the aluminum substrate is increased by applying high-power consumption on the power resistor, and further, the temperature of the LED is increased. The thermistor is used for monitoring the temperature of the aluminum substrate. Therefore, the temperature of the aluminum substrate can be controlled by adjusting the power of the power resistor, and the temperature of the LED can be further controlled.

Generally, in order to achieve good effects, the following points are required:

the aluminum substrate surrounds the LEDs as comprehensively as possible, so that the surface mounted LEDs are selected as possible, and the bonding range of the surface mounted LEDs and the aluminum substrate is enlarged;

a proper heat-insulating layer is added outside the aluminum substrate;

after the aluminum substrate is debugged, the three-proofing paint is smeared to prevent seawater from eroding the circuit board after atomization;

the power resistor is a patch type metal film resistor;

the set constant temperature point is slightly higher than the highest point of the application temperature so as to ensure that all the test points are corrected to the same temperature point;

the LED also needs to be aged before it is used, the same procedure as described before.

The following relationship is satisfied at the blank value channel:

B＝B_{electric power}+B_{Water (W)}+B_{Light (es)}

Wherein, B is a sampling value of a blank value channel; b is_{Electric power}The background noise of the circuit that is the blank value channel; b is_{Water (W)}The background influence of the water body of the blank value channel mainly reflects the influence of factors such as turbidity, fluorescence and the like of the water body, and the value of the background influence is far smaller than that of B in the application of a spectrophotometer method_{Light (es)}Generally, the noise can be ignored, and when the influence is large and cannot be ignored, the noise can be used as a fixed value for calculation and is merged into circuit noise during calculation; b is_{Light (es)}Is the response of the luminous intensity of the light source LED at the receiving end.

Similarly, the following relationship is satisfied at the color value channel:

C＝C_{electric power}+C_{Water (W)}+C_{Light (es)}*ρ_Transforming

Wherein, C is a sampling value of a main optical path of a color rendering value channel; c_{Electric power}Is the background noise of the circuit of the main light path of the color rendering channel; c_{Water (W)}The background influence of the water body of the main light path of the color rendering value channel; c_{Light (es)}The response of the luminous intensity of the light source LED at the receiving end; rho_TransformingThe influence is generated after the substance to be detected in the sample reacts with the chemical reagent, the intensity of the light beam is reduced, and the higher the concentration is, the more remarkable the reduction is.

When calibrating, only need to B_{Electric power}+B_{Water (W)}And C_{Electric power}+C_{Water (W)}The two sums may be calibrated as a curve, which may be calibrated as described above.

So that in the calculation of the time of the calculation,

blank value of B_{Light (es)}＝B-B_{Electric power}-B_{Water (W)}

Color rendering value of C_{Light (es)}*ρ_Transforming＝C-C_{Electric power}-C_{Water (W)}

Because the temperature of the LED light source is fixed, generally, a constant temperature point can be directly used as a comparison point, and temperature correction is not needed. Generally, when instruments of the same measurement method and different manufacturers are used for comparison, whether the trends of data curves of the instruments are the same or not and whether the difference between the curves is stable or not can be compared.

2) And correcting the corrected data for the chemical reaction rate.

The first method comprises the following steps: constant temperature method

In the present invention, in order to correct the influence of the temperature on the chemical reaction rate, the correction may be performed by a constant temperature method. Because the temperature of the mixed solution is fixed, the chemical reaction rate can be taken as a constant value, and the same reaction rate can occur to various mixed solutions with different concentrations. Generally, the chemical reaction rate at the constant temperature point can be directly used as a base point, and temperature correction is not required. The special condition needs to be corrected, and the correction can be carried out by adopting the following steps:

a. keeping the LED at room temperature, turning off the LED light source of the blank value and color value detection channels, and respectively measuring B_{Electric power}+B_{Water (W)}And C_{Electric power}+C_{Water (W)}；

b. Keeping the LED at room temperature, opening an LED light source of the blank value detection channel, and measuring B;

c. Obtaining a blank value B_{Light (A)}＝B-B_Electricity-B_{Water (I)}The components of the material are not influenced by chemical reaction rate, so that the blank values of the two temperature points are the same, namely the blank value_{Constant temperature}Blank value_{Ratio of}＝B_{Light (es)}＝B-B_{Electric power}-B_{Water (W)}；

d. Finding T_{Constant temperature}Point color value, regulating the temperature of the mixture of seawater and reagentIs T_{Constant temperature}Can measure C_{Constant temperature}Color rendering value_{Constant temperature}＝C_{Constant temperature}-C_{Electric power}-C_{Water (W)}；

e. Finding T_{Ratio of}Point color value, regulating the temperature of the mixture of seawater and reagent to T_{Ratio of}Can measure C_{Ratio of}Color rendering value_{Ratio of}＝C_{Ratio of}-C_{Electric power}-C_{Water (W)}；

f. Finding T_{Constant temperature}Point sum T_{Ratio of}The color rendering value at the point temperature is related, the proportionality coefficient R is

g. When curve correction is performed, the color rendering value is used_{Ratio of}Color rendering value of R_{Constant temperature}Applied to the whole curve to obtain T_{Ratio of}Time color rendering value curve;

h. applying Laobbier's law to correct data,

wherein the temperature at the constant temperature point is assumed to be T_{Constant temperature}Temperature at the temperature point to be compared is T_{Ratio of}。

The second method comprises the following steps: calibration method

In the invention, the influence of temperature on the chemical reaction can also be corrected by a calibration method, and the specific flow is as follows:

determining the number of fixed points, 5 points or 7 points according to the application condition;

determining the temperature of the calibration points, generally evenly distributing in a temperature range, and recommending that the distance between the temperature points is not less than 5 ℃:

Selecting a certain concentration standard solution, wherein the test values of the certain concentration standard solution at the highest temperature point and the lowest temperature point do not exceed the linear interval of the measurement range of the instrument;

sequentially heating the standard solution to the temperature of each calibration point, keeping the temperature for one hour, and measuring and recording numerical values;

fitting the obtained data to obtain a curve formula;

in the present invention, a temperature sensor is added to measure the water temperature, and generally, the temperature sensor is placed in the liquid path before the inlet of the detection module.

When data correction is carried out, a result can be simply obtained according to the temperature and a curve formula.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (5)

1. A method of removing the effects of temperature of a cross-sectional marine measurement instrument, comprising the steps of:

1) carrying out temperature correction on the LED light source of the detection module by adopting a reference method or a constant temperature method;

2) correcting the data corrected in the step 1) according to the adopted chemical reaction rate;

The step 1) comprises the following steps when a reference method is adopted:

a. the LED requires an aging process before use;

b. monitoring the temperature of the LED;

c. collecting a main signal of LED light passing through detected seawater and a reference signal of LED light passing through air;

d. calibrating a curve of the light intensity and the temperature of the LED;

e. correcting the light intensity of the LED by applying the Law of Larber, and adjusting the concentration of the substance to be detected to the same temperature point;

the step 1) comprises the following steps when a constant temperature method is adopted:

the LED needs aging treatment before use;

b, adopting an aluminum substrate emitting plate, controlling the temperature of the aluminum substrate by adjusting the power of a power resistor arranged at the emitting plate, and further controlling the temperature of the LED to be constant;

cc. according to blank value ═ B_{Light (es)}＝B-B_{Electric power}-B_{Water (W)}And color rendering value ═ C_{Light (es)}*ρ_Transforming＝C-C_{Electric power}-C_{Water (W)}Calibrating the curve of LED intensity and temperature, i.e. for B_{Electric power}+B_{Water (W)}And C_{Electric power}+C_{Water (W)}And calibrating the two sums by a curve.

2. The method for removing temperature influence of a profile marine measurement instrument according to claim 1, wherein said step d comprises the steps of:

d1. determining the number of calibration points required by calibration, at least 5 points;

d2. determining the temperature of each calibration point within a preset temperature range;

d3. Calibrating the relation between blank channel background noise and temperature, turning off the LED, only keeping air in the detection channel, keeping the temperature at each calibration point for at least one hour, respectively recording the background noise of the main channel and the reference channel at each calibration point, and fitting a curve to obtain B_{Ginseng, electricity}、B_{Electricity and main}The curve of (d);

d4. calibrating the relation between the blank value channel sampling value and the temperature: opening the LED, only reserving air in the detection channel, keeping the temperature of each calibration point for at least one hour, respectively recording signal values of the main channel and the reference channel at each calibration point, and fitting a curve to obtain B_{Ginseng radix (Panax ginseng C.A. Meyer)}、B_{Master and slave}The curve of (d);

d5. according to B_{Ginseng radix (Panax ginseng C.A. Meyer)}＝B_{Ginseng, electricity}+B_{Ginseng, light}And B_{Master and slave}＝B_{Electricity and main}+B_{Water, main part}+B_{Light and main}Relation, respectively calculating the LED light intensity B of the blank value channel_{Ginseng, light}And B_{Light and main}Curve as a function of temperature, in which B_{Water, main part}Calculating according to a zero value;

d6. according to

Calculation of R_BThe variation curve of the light intensity ratio of the main light path and the reference light path on the blank value channel along with the temperature;

d7. calibrating the relation between the background noise of the color rendering value channel and the temperature, turning off the LED, only keeping air in the detection channel, keeping the temperature of each calibration point for at least one hour, respectively recording the background noise of the main channel and the reference channel at each calibration point, and fitting a curve to obtain C _{The sea cucumber is obtained by the steps of,electricity}、C_{Main, electricity}The curve of (c);

d8. calibrating the relation between the sampling value of the color rendering value channel and the temperature, turning on the LED, only reserving air in the detection channel, keeping the temperature of each calibration point constant for at least one hour, respectively recording the signal values of the main channel and the reference channel at each calibration point, and fitting a curve;

d9. according to C_{Ginseng radix (Panax ginseng C.A. Meyer)}＝C_{Ginseng, electricity}+C_{Ginseng, light}And C_{Master and slave}＝C_{Electricity and main}+C_{Water, main part}+C_{Light and main}*ρ_TransformingRelation, respectively calculating color rendering value channel LED light intensity C_{Ginseng, light}And C_{Light and main}Curve as a function of temperature, in which C_{Water, main part}Calculating according to a zero value;

d10. according to

Calculation of R_CI.e. the variation curve of the light intensity ratio of the main light path and the reference light path on the color rendering value channel along with the temperature.

3. The method for removing temperature influence of a profile marine measurement instrument according to claim 2, wherein the temperature of each calibration point is determined in step d2 and is equally distributed within a preset temperature range.

4. The method for removing the influence of the temperature of the profile marine measuring instrument according to claim 1, wherein the step 2) of correcting the influence of the temperature on the chemical reaction rate by using a constant temperature method comprises the steps of:

a. keeping the LED at room temperature, turning off the LED light source of the blank value and color value detection channels, and respectively measuring B _Electricity+B_{Water (I)}And C_Electricity+C_{Water (I)}；

b. Keeping the LED at room temperature, opening an LED light source of the blank value detection channel, and measuring B;

c. obtaining a blank value B_{Light (es)}＝B-B_{Electric power}-B_{Water (W)}The components are not influenced by chemical reaction rate, so that the blank values of two temperature points are the same,i.e. blank value_{Constant temperature}Blank value_{Ratio of}＝B_{Light (es)}＝B-B_{Electric power}-B_{Water (W)}；

d. Finding T_{Constant temperature}Point color value, regulating the temperature of the mixture of seawater and reagent to T_{Constant temperature}Can measure C_{Constant temperature}Color rendering value_{Constant temperature}＝C_{Constant temperature}-C_{Electric power}-C_{Water (W)}；

e. Finding T_{Ratio of}Point color value, regulating the temperature of the mixture of seawater and reagent to T_{Ratio of}Can measure C_{Ratio of}Color rendering value_{Ratio of}＝C_{Ratio of}-C_{Electric power}-C_{Water (W)}；

f. Finding T_{Constant temperature}Point sum T_{Ratio of}The color rendering value at the point temperature is related, the proportionality coefficient R is

g. When curve correction is performed, the color rendering value is used_{Ratio of}Color rendering value of R_{Constant temperature}Applied to the whole curve to obtain T_{Ratio of}Time color rendering value curve;

h. correcting the data by applying Larobert's law;

wherein the temperature at the constant temperature point is assumed to be T_{Constant temperature}Temperature at the temperature point to be compared is T_{Ratio of}。

5. The method for removing the influence of temperature of the profile marine measuring instrument according to claim 1, wherein the step 2) corrects the influence of temperature on the chemical reaction rate by using a calibration method, comprising the steps of:

a. Determining the number of fixed points, 5 points or 7 points according to the application condition;

b. determining the temperature of the calibration points, and evenly distributing the temperature within the temperature range, wherein the distance between the temperature points is not less than 5 ℃;

c. selecting a certain concentration standard solution, wherein the test values of the standard solution at the highest temperature point and the lowest temperature point do not exceed the linear interval of the measurement range of the instrument;

d. heating the standard solution to the temperature of each calibration point in sequence, keeping the temperature for one hour, and measuring and recording numerical values;

e. fitting the obtained data to obtain a curve formula;

f. and correcting the data according to the temperature and curve formula.

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