KR101160676B1 - Turbidity mesuring apparatus - Google Patents

Turbidity mesuring apparatus Download PDF

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KR101160676B1
KR101160676B1 KR1020100000293A KR20100000293A KR101160676B1 KR 101160676 B1 KR101160676 B1 KR 101160676B1 KR 1020100000293 A KR1020100000293 A KR 1020100000293A KR 20100000293 A KR20100000293 A KR 20100000293A KR 101160676 B1 KR101160676 B1 KR 101160676B1
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light
light emitting
housing
turbidity
window
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KR1020100000293A
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KR20110080188A (en
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김선용
형기우
형성훈
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(주)동양화학
동양하이테크산업주식회사
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Abstract

The present invention relates to a turbidity measuring device, comprising: a housing provided with a light emitting window and a light receiving window through which light is transmitted; a light emitting unit that is embedded in the housing and emits light to a sample number located outside the housing through the light emitting window; And a lock-in amplifier for multiplying a signal output from the photodetector with a reference signal and outputting a multiplication result signal through a low pass filter. According to the turbidity measuring device, it is possible to remove the noise contained in the signal output through the photodetector to increase the measurement accuracy.

Description

Ultra-low concentration turbidity measuring device {Turbidity mesuring apparatus}

The present invention relates to a turbidity measuring device, and more particularly to a turbidity measuring device that can accurately measure the turbidity of the sample water.

Due to serious environmental pollution, research on the measurement and removal of water quality and air pollution is indispensable and active.

Above all, the measurement and improvement of the pollution level of water, which is the source of humans and all living things, is the most important.In order to judge water pollution, biological characteristics of the water environment, chemical properties such as trace elements in suspended solids, and water color, smell, turbidity The physical characteristics of the should be considered.

Among them, especially turbidity is a quantitative indicator of the cloudiness of water and is expressed as scattering and absorption by light of particles suspended in water. This turbidity is caused by various suspended substances and the size of suspended particles in the water varies from colloidal dispersion to coarse dispersion. This includes nanoscale ultrafine particles.

Turbidity is caused by extremely fine dispersoids, such as colloidal dispersion, in water in relatively stagnant conditions, such as lakes, and by coarse dispersoids, mostly in flowing water, such as river water.

Particulates that form sediment or suspended solids are the main pollutants that affect the environment, such as water sources and lakes, and these particles flow into the water supply pipes and cause problems such as erosion or deposition inside the pipes. In addition, metal fine particles are generated by corrosion of the surface of a water pipe made of a metal pipe, causing erosion at the same time as corrosion inside the pipe, thereby causing damage to the pipe. Particles in the pipe form scales on the inner surface of the pipe, disrupting the flow of fluid inside the pipe, and particles smaller than 64 μm that cause turbidity can directly damage biological activity or cause harmful chemicals. It can also be a means of delivery.

And when the water quality is contaminated by colloids or dispersoids, the transparency of the water changes, so that the degree of contamination can be easily known.

These ultrafine particles include a variety of metals, organic substances, viruses, algae and mold, and carcinogenic substances such as polycyclic aromatic hydrocarbons (PAH). In particular, ultra-fine particles consist of metal elements such as heavy metals, so it is urgent to develop measurement methods and monitoring technologies.

In addition, organic matter is introduced into the water quality and the number of microorganisms increases, causing biological contamination. In this case, especially in drinking water management, monitoring of microorganisms is also a very important measurement variable. Therefore, when measuring turbidity to evaluate water quality, ultra-fine particles or microorganisms among suspended solids in water should be accurately detected.

However, conventional turbidity measuring devices are configured to detect turbidity using a tungsten filament lamp or an infrared LED as a light source. Such a conventional light source emits only light having a wavelength in the ultraviolet band and thus cannot selectively detect particles of various sizes in the water, and easily detects particles of 6 μm or less with a low energy beam such as an infrared LED. There is a problem that is not. In addition, the conventional turbidity measuring device has a problem that can not detect any microorganisms in the water at all.

In the conventional turbidity sensor as described above, when the microorganism or suspended matter is deposited on the detection unit, the detection performance of the device may be significantly reduced.

On the other hand, when using the signal output from the photodetector for detecting light in the turbidity measuring device as it is as a measurement signal, there is a problem that the measurement accuracy is lowered by the noise component.

An object of the present invention is to provide a turbidity measuring apparatus that can be improved to remove turbidity measurement accuracy by removing noise included in a signal output from a photodetector.

In order to achieve the above object, a turbidity measuring device according to the present invention includes a housing provided with a light emitting window and a light receiving window through which light is transmitted; A light emitting unit embedded in the housing and emitting light to the sample water located outside the housing through the light emitting window; A photo detector embedded in the housing and detecting light incident through the light receiving window; And a lock-in amplifier for multiplying a signal output from the photodetector with a reference signal and outputting the multiplication result signal through a low pass filter.

Preferably, the light emitting window and the polymer film is formed on the surface of the light receiving window, respectively, to prevent the deposition of microorganisms or suspended solids contained in the sample water;

In addition, the polymer film is formed by coating a sol-gel formed by the sol-gel method on the light emitting window and the light receiving window using dimethoxydimethylsilane and tetramethylorthosilicate as precursors.

The light emitting part emits an infrared light to detect a general turbidity, a first lamp that emits ultraviolet light to detect microorganisms contained in the sample water, a second lamp that emits laser light to detect fine particles, and general turbidity. It is preferable to have a third lamp.

In addition, the optical fiber for transmitting the light emitted from the first, second and third lamps to the light emitting window, respectively; And a light receiving optical fiber for transferring the light incident through the light receiving window to the photodetector.

According to the turbidity measuring device according to the present invention, the measurement accuracy can be increased by removing the noise component included in the signal detected by the photodetector after irradiating the sample water.

1 is a cross-sectional view showing the inside of a probe applied to the turbidity measuring device according to the present invention,
FIG. 2 is a block diagram illustrating a signal processor that processes a signal output from the photodetector of the probe of FIG. 1.
Figure 3 is a SEM photograph showing the E.coil JM109 deposited on the surface of the test and control and a graph showing it quantitatively,
4 is a SEM photograph showing the B. cereus 318 deposited on the surface of the test and control and a graph showing it quantitatively,
5 is a graph showing the output value according to the concentration in the formazin standard solution using the turbidity measuring apparatus of the present invention,
Figure 6 is a graph showing the output value according to the concentration of microorganisms using the turbidity measuring device according to the present invention,
Figure 7 is a graph showing the output value for the turbidity samples for each concentration prepared with a formazin standard solution for the application of lock-in amplifier and non-application.

Hereinafter, the turbidity measuring device according to a preferred embodiment of the present invention with reference to the accompanying drawings will be described in more detail.

1 is a cross-sectional view illustrating the inside of a probe applied to a turbidity measuring apparatus according to the present invention, and FIG. 2 is a block diagram illustrating a signal processor that processes a signal output from the photodetector of the probe of FIG. 1.

1 and 2, the turbidity measuring device according to the present invention includes a housing 20, a light emitting part 30 embedded in the housing 20, and a light detector 40 detecting light. , The light emitting optical fiber 50 for transmitting the light of the light emitting unit 30 to the sample water located in the lower portion of the housing 20, and the light receiving unit for transmitting the light or fluorescence scattered from the sample water to the photodetector 40 The lock-in amplifier 120 processes a signal output from the optical fiber 60 and the photodetector 40.

The housing 20 has a cylindrical shape as a whole so as to function as a probe, and the lower part is submerged in or in contact with the sample water for turbidity measurement. The housing 20 has a structure in which the upper housing 21 and the lower housing 23 are screwed together, and an annular pad 24 for maintaining airtightness is provided between the upper housing 21 and the lower housing 23. Is mounted. The upper and lower coupling structures of the housing 20 facilitate replacement and maintenance of components in the housing 20.

The light emitting unit 30, the photodetector 40, and the light emitting and receiving optical fibers 50 and 60 are installed in the housing 20. And the light irradiation surface for irradiating light with the sample water to measure the turbidity, that is, the bottom surface of the housing 20 is formed in a concave conical shape drawn inward. At this time, the bottom of the housing 20 is formed so that the left and right sides face each other at a 90 ° angle as shown.

Through-holes are formed at one side and the other side of the bottom of the housing 20 facing each other, and the light-emitting window 25 and the light-receiving window 27 through which light is transmitted are respectively provided in the through-holes. The light emitting window 25 and the light receiving window 27 are made of glass or transparent acrylic.

The light emitting unit 30 is a light source for irradiating light to the sample water, the first lamp 31 for emitting ultraviolet light to detect microorganisms present in the sample water, and the laser light for emitting fine particles A second lamp 33 and a third lamp 35 for emitting near infrared light to detect general turbidity.

The microparticles mean suspended solids having a size of less than 6 μm, and include ultra-fine particles having nanoscale sizes. In addition, the general turbidity refers to suspended solids that can be detected by a conventional turbidity detector, and means suspended solids from particles having a size of 6 μm or more to coarse dispersoids.

Preferably, the first lamp 31 is an ultraviolet diode emitting light having a wavelength of 330 to 350 nm, the second lamp 33 is a laser diode emitting light having a wavelength of 810 to 830 nm, and the third lamp 35 Uses an infrared diode that emits light of a wavelength of 840 to 900nm.

Small particles scatter more strongly in shorter wavelength bands than longer wavelength bands, and larger particles scatter more strongly in wider wavelength bands.

In the wavelength range of 840 to 900nm, it is easy to detect particles having a size of 6 µm or more. However, for particles having a size smaller than that, when the light is irradiated to the particles, the amount of reflected light increases and the scattered light at the 90 degree position required for turbidity detection is reduced. In order to detect ultra-fine particles of 6 μm or less, a light source having strong energy such as a laser light source is required. In particular, a laser having a wavelength band of 830 nm can detect nanoparticles having a diameter of 10 nm or less.

The first, second and third lamps 31, 33 and 35 are installed on the printed circuit board 17 which is electrically connected to the main body provided with the signal processing unit together with the photodetector 40. At this time, each lamp is inserted and installed by each cylindrical lamp insertion tube 71 so that mutual light does not interfere with each other, the end of the lamp insertion tube 71 so that light can be transmitted to the light emitting optical fiber 30. One end of the light emitting optical fiber 30 is connected. In this case, the lens 73 may be inserted into the lamp insertion tube 71 between the lamp 31 and the light emitting optical fiber 51 so that light emitted from the lamp 31 may be transmitted in parallel.

The turbidity measuring device 10 may provide accurate water analysis data by detecting microorganisms, microparticles, and general suspended solids having relatively large particles by using three light sources having different wavelengths.

Ultraviolet light of the first lamp 31 is used to detect microorganisms.

The second lamp 33 and the third lamp 35 are for detecting suspended solids from ultrafine particles to coarse dispersoids present in the sample water in addition to the microorganisms. The lamps are scattered by the particles in the sample water at 90 ° angle. It is to detect the amount of particles by measuring at.

The light emitting optical fiber 50 is a means for transmitting the light emitted from the first, second and third lamps to the light emitting window 25 formed on the bottom of the housing. It is composed of the first, second and third light emitting optical fibers 51, 53, 55 to transmit the light source. One end of the light emitting optical fiber 50 is connected to the lamp insertion tube 71 of the light emitting part 30 and extends to the light emitting window 25.

Therefore, the light emitted from the light emitting part 25 is transmitted through the light emitting optical fiber 50 to the light emitting window 25 and is incident on the sample water located outside the bottom of the housing 20, and a part of the light incident on the sample water. Is scattered by suspended solids contained in the sample water. The light scattered at an angle of 90 ° is incident on the light receiving window 27 and transmitted to the photodetector 40 through the light receiving optical fiber 60.

As the light emitting and light receiving optical fibers 50 and 60, glass optical fibers or plastic optical fibers may be used.

As described above, the light emitted from the light emitting unit 30 may be transmitted through the optical fibers 50 and 60 to reduce the volume of the device 10 and minimize interference of the light.

The photo detector 40 uses a photo-multiplication tube (PMT) to detect the amount of light scattered from the sample water. The optical multiplier converts an input optical signal into an electrical signal and outputs the electrical signal. In addition, a photodiode can be used as the photodetector 40. The photodetector 40 is inserted into the cylindrical insertion tube 75 and installed on the printed circuit board 17 in order to prevent the light emitted from the light emitting portion from directly entering. A lens may be installed at the end 77 of the insertion tube 75.

The lock-in amp 120 is applied to remove noise other than the signal component to be measured among the signals output from the photodetector 40 through the cable 15. The multiplier 122 and the reference signal generator 124 and a low pass filter (LPF) 126.

Preferably, the reference signal generator 124 is constructed so that the frequency of the output signal can be changed in correspondence to the driven lamp. That is, when the first lamp 31 is driven, a reference signal having a frequency corresponding to the center frequency of the first lamp 31 is output, and when the second lamp 33 is driven, the reference signal is driven at the center frequency of the second lamp 33. A reference signal of a corresponding frequency is output, and when the third lamp 35 is driven, a reference signal of a frequency corresponding to the center frequency of the third lamp 35 is output.

In this case, the selective driving of the first to third lamps 31, 33, 35 is constructed so that the user can select using the operation unit 170, and the control unit 150 instructs the lamp selection driving of the operation unit 170. The reference signal generator 124 is controlled to correspond to the frequency of the reference signal output from the reference signal generator 124 so as to output the center frequency signal of the driving target lamp.

The lock-in amplifier 120 multiplies the signal output from the photodetector 40 by the reference signal output from the reference signal generator 124 by the multiplier 122, and a low pass filter (i) for the output signal of the multiplier 122. 126).

Therefore, only the signal corresponding to the reference signal frequency corresponding to the signal to be measured can be output through the low pass filter 126 to detect the ultra low concentration turbidity.

Reference numeral 130 is an amplifier for amplifying the signal output from the lock-in amplifier 120, reference numeral 140 is an A / D converter for converting the output signal of the amplifier 130 to a digital signal and output to the controller 150, Reference numeral 160 is a display unit for displaying the turbidity value calculated by the controller 150.

On the other hand, the polymer film 80 for preventing the deposition of microorganisms or suspended solids contained in the sample water is formed on the surface of the light emitting window and the light receiving window. Deposition here means that microorganisms or various suspended substances in the sample water adhere to the surface.

The polymer film 80 using a hydrophobic sol-gel is formed using a dimethoxydimethylsilane (DiMe- DMOS) and tetramethyl-orthosilicate (TMOS) as a precursor material (Precursor).

The sol-gel solution obtained by mixing so that the volume ratio of TMSO: DiMe-DMOS: distilled water: 0.1 M HCl is 1: 2.45: 1.70: 1.1, respectively, is stirred for hydrolysis and condensation reaction for 3.5 hours.

Figure 112010000278440-pat00001

Centrifuge for 5 min at 7500 rpm to obtain hydrophobic sol (Sol) precipitated in the stirred sol-gel solution. To 1 ml of the precipitated sol obtained by centrifugation, about 50 ul of 0.1 M phosphate buffer solution (0.1 M Potassium phosphate buffer, pH 7) is added.

Since the hydrophobic sol-gel made as described above does not have a hydroxyl group (-OH) capable of binding to water, it is possible to prevent deposition by reducing the mutual binding force with microorganisms or suspended solids contained in the sample water.

The sol-gel is injected into the surface of the light-receiving window and the light-emitting window and evenly applied to the surface by spin coating, and then dried at room temperature for 4-5 days to prevent cracking of the film surface. The polymer film 80 is formed. In addition to spin coating, sol-gel may be applied to the surface of the light receiving window and the light emitting window by using dip coating or spray coating.

On the other hand, the light emitting unit 30 applied to the turbidity measuring device 10 may be configured as a first lamp alone for detecting microorganisms, or a second lamp alone for detecting fine particles, unlike shown. In addition, the light emitting unit may be configured by combining two lamps among the first lamp and the second and third lamps, and of course, a conventional lamp may be used in addition to the first, second and third lamps. to be.

Hereinafter, the deposition characteristics of the polymer film 80 will be described.

<Experimental Example 1; Microbial Deposition Characteristics of Polymer Membranes>

The volume ratio of TMSO: DiMe-DMOS: distilled water: 0.1M HCl was 1: 2.45: 1.70: 1.1, respectively, and the mixture was stirred for hydrolysis and condensation for 3.5 hours. Centrifugation (condition: 7500 rpm, 5 min) was performed to obtain the hydrophobic sol precipitated in the stirred sol-gel solution. 50 ul / mL (sol) of 0.1 M phosphate buffer solution (0.1 M Potassium phosphate buffer, pH 7) was added to the precipitated sol obtained by centrifugation to obtain a hydrophobic sol-gel. The sol-gel is injected onto a glass surface with a diameter of 12 mm, followed by a spin coating technique (condition: 1 step 400 rpm, 10 sec, 2 steps 1200 rpm, 20 sec) evenly applied to the surface, followed by room temperature (20 Dried to form a transparent thin polymer film.

The microbial deposition power of the polymer membrane was tested to verify the performance of the polymer membrane. The glass on which the polymer film was formed was used as a test sphere, and the glass to which the polymer membrane was not formed was used as a control.

Escherichia coli JIM109 and Bacillus cereus 318 strains were used for the test of microbial deposition. In this test, LB complex medium (Yeast extract: 5 g / L, Tryptone: 10 g / L, NaCl: 10 g / L) for the culture of Escherichia coli , Bacillus medium (Glucose: 5 g) for the culture of Bacillus cereus / L, Peptone: 5 g / L, Yeast extract: 5 g / L, NaHCO 3 : 3 g / L). Meanwhile, in order to prevent contamination by foreign substances before the culture experiment, the test and control groups were sterilized for 24 hours by irradiating with ultraviolet light. Test and control were added to Escherichia coli and Bacillus cereus cultures, respectively, and cultured for 24 hours using shaking culture (KoBiotech Co., Korea) at 37 ° C and 80rpm. The test and control groups collected at regular time intervals during the cultivation were washed once with the distilled water, the surface to be measured for deposition of microorganisms, and then placed in a beaker containing distilled water and washed for 3 minutes at 150 rpm in a stirrer. Surface to which the suspended cells were removed was dried for 10 minutes at 60 ° C. for gram staining, and flame sterilization was performed to fix the microorganisms deposited on the surface to be deposited. After flame sterilization, staining was performed for 1 minute using 0.2 mL of crystal violet solution for gram dyeing. The surface to be washed with distilled water was again stained with 0.2 mL of iodine solution for 1 minute, decolorized with 95% ethanol, and then restained with 0.2 mL of Safranin O for 1 minute. . Finally, the test and control groups washed with distilled water were dried at 70 ℃ for 10 minutes to remove moisture. Scanning electron microscope (SEM) photographing of the test target surface and the test target surface of the above-described staining process was performed to quantitatively measure the number of deposited microorganisms, and the results are shown in FIGS. 3 and 4, respectively.

Figure 3 shows the deposition characteristics of Escherichia coli , one of the most used microorganisms for the production of various medicines and biological products. 3 is a sample collected at regular time intervals (6, 12, 18, 24 hours) and the microorganisms deposited on the surface of the test and control per unit area (mm 2 ) based on SEM images of microorganisms deposited on each surface It is a quantitative representation of the number of. In Figure 3 sol-gel coated surface means a test sphere, glass means a control.

Referring to FIG. 3, Escherichia coli was deposited on the surface of the control at about 7.7 × 10 4 cells / mm 2 at 6 hours after incubation, but after 6 hours of incubation, it was deposited on the glass surface because it enters the stop and die phases in the cell growth cycle. The number of microorganisms lost gradually decreased.

In comparison, the number of Escherichia coli deposited per unit area was reduced by more than 97% at 18 hours after incubation compared to the maximum number of microorganisms deposited on the control. In other words, it can be seen that the hydrophobic sol-gel constituting the polymer membrane prevents the deposition of microorganisms by reducing the physical interaction between the microorganisms that are Gram-negative bacteria and the surface of the membrane.

Figure 4 shows the deposition characteristics of Bacillus cereus . 4 shows samples collected at regular time intervals (3, 6, 12, 18, 24 hours) and deposited on the surface of test and control per unit area (mm 2 ) based on SEM photographs of microorganisms deposited on each surface. It shows quantitatively the population of microorganisms. In Figure 4, sol-gel coated surface means a test sphere, glass means a control.

Looking at Figure 4, Bacillus cereus in the control was deposited about 3.2 × 10 4 cells / mm 2 at 12 hours after incubation, and after 12 hours the number of microorganisms deposited was greatly reduced. In comparison, Bacillus cereus deposited on the test plots had a maximum number of deposited cells of 6.2 × 10 2 cells / mm 2 after 3 hours of incubation, which was reduced by more than 98%. Therefore, it can be seen that the polymer membrane can prevent the deposition of the Gram-positive bacteria Bacillus cereus microorganism.

Experimental Example 2 Detection Performance of Polymer Membrane

This test was conducted to investigate the effect of polymer membranes on the performance of suspended solids and microorganisms.

As a common experimental condition, a housing equipped with a light emitting window and a light receiving window in which a polymer film was formed, and a housing equipped with a light emitting window and a light receiving window in which a polymer film was not formed were left in water for 10 days for accurate experiments.

Introduced into 0.0, 0.2, 0.4, 0.6, 0.8, 1.0 NTU samples prepared with a formazin standard solution using each apparatus (Coating and Non-coating) left in water for 10 days to investigate the output value according to the concentration. Shown in

And the turbidity sensor (Coating and Non-coating) left in water for 10 days is introduced into the microbial samples of 0.00, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30 CFU (cells / mL), respectively, Investigation was shown in FIG.

As shown in FIGS. 5 and 6, when the polymer film-coated light emitting window and the light receiving window probe are used, the output value increases linearly in proportion to the concentration of suspended substances or microorganisms, and the light emitting window and the number of the uncoated polymer film are not shown. The output value is more accurate than the result using the device with the light window. As a result, it can be seen that the performance of the device in which the polymer film is formed is greatly improved.

On the other hand, the results of the experiment to confirm the measurement performance according to the concentration of the turbidity sample prepared with the formazin standard solution for the case of applying the lock-in amplifier 120 and not applied is shown in FIG.

As can be seen from FIG. 7, detection of a turbidity concentration of 0.2 NTU or less is not possible when the lock-in amplifier is not applied, and detection of turbidity concentration of 0.2 NTU or less is possible when the lock-in amplifier is applied. By applying the lock-in amplifier 120 as described above, turbidity of low concentration can be detected, thereby improving turbidity detection performance.

10: turbidity measuring device 20: housing
25: light emitting window 27: light receiving window
30: light emitting unit 31: first lamp
33: second lamp 35: third lamp
40: photodetector 50: light emitting optical fiber
60: light receiving optical fiber 80: polymer film
120: lock-in amplifier

Claims (3)

delete A housing provided with a light emitting window and a light receiving window through which light is transmitted;
A light emitting unit embedded in the housing and emitting light to the sample water located outside the housing through the light emitting window;
A photo detector embedded in the housing and detecting light incident through the light receiving window;
A lock-in amplifier configured to multiply the signal output from the photodetector with a reference signal and output the multiplication result signal through a low pass filter; And
And a polymer film formed on surfaces of the light emitting window and the light receiving window, respectively, for preventing the deposition of microorganisms or suspended solids contained in the sample water.
The turbidity measuring apparatus of claim 2, wherein the polymer film is formed by coating a sol-gel formed by a sol-gel method on the light emitting window and the light receiving window using dimethoxydimethylsilane and tetramethylorthosilicate as precursors. .
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5716338A (en) 1980-07-02 1982-01-27 Seiko Epson Corp Light absorption measuring equipment with locked-in amplifier
JPH07140043A (en) * 1993-11-15 1995-06-02 Oki Electric Ind Co Ltd Optical fiber sensor unit
KR20090082060A (en) * 2008-01-30 2009-07-29 동양하이테크산업주식회사 Turbidity mesuring probe and turbidity mesuring apparatus thereof
KR20100089319A (en) * 2009-02-03 2010-08-12 동양하이테크산업주식회사 Turbidity mesuring probe with macromolecule membrane modified by hydrophobic sol-gels

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5716338A (en) 1980-07-02 1982-01-27 Seiko Epson Corp Light absorption measuring equipment with locked-in amplifier
JPH07140043A (en) * 1993-11-15 1995-06-02 Oki Electric Ind Co Ltd Optical fiber sensor unit
KR20090082060A (en) * 2008-01-30 2009-07-29 동양하이테크산업주식회사 Turbidity mesuring probe and turbidity mesuring apparatus thereof
KR20100089319A (en) * 2009-02-03 2010-08-12 동양하이테크산업주식회사 Turbidity mesuring probe with macromolecule membrane modified by hydrophobic sol-gels

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