CN106483104A - Alcohol concentration measurement apparatus and method using PVDF Terahertz plasma resonance effect - Google Patents

Alcohol concentration measurement apparatus and method using PVDF Terahertz plasma resonance effect Download PDF

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CN106483104A
CN106483104A CN201611125163.8A CN201611125163A CN106483104A CN 106483104 A CN106483104 A CN 106483104A CN 201611125163 A CN201611125163 A CN 201611125163A CN 106483104 A CN106483104 A CN 106483104A
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silica membrane
turntable
thin film
lens
pvdf
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李向军
郭风雷
胡建荣
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China Jiliang University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/55Specular reflectivity
    • G01N21/552Attenuated total reflection
    • G01N21/553Attenuated total reflection and using surface plasmons

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Abstract

The invention discloses a kind of alcohol concentration measurement apparatus of utilization PVDF Terahertz plasma resonance effect and method.Single-frequency Terahertz (THz) ripple being sent by backward wave oscillator reaches schottky diode detector after silicon prismatic reflection.When the turntable that silicon prism is located rotates to an angle and detector place turntable rotates corresponding twice angle, and the anglec of rotation is in particular range during scan variations, and detector can get angle reflection coefficient curve.Resonance peak in this reflection coefficient curve changes movement with alcohol concentration.Because the power of backward wave oscillator is larger, make the radius of detector place turntable larger, anglec of rotation resolution is allow to be less than one point, when in this measurement apparatus, solution to be measured changes from pure water to absolute alcohol, the resonance peak of angle reflection coefficient curve is mobile is more than 18 degree so that the precision that this measurement apparatus measures alcohol concentration reaches more than one thousandth.

Description

Using PVDF Terahertz plasma resonance effect alcohol concentration measurement apparatus and Method
Technical field
The invention belongs to THz wave technology field, it is related to one kind and utilizes Kynoar (PVDF) thin film Terahertz surface The alcohol concentration measurement apparatus of plasma resonance effect.
Background technology
Terahertz (Terahertz or THz) ripple typically refers to frequency in the interval electromagnetic wave of 0.1~10THz, its photon Energy be about 1~10meV, just the energy of transition is roughly the same and molecular vibration and rotational energy level between.Most of polarity Molecule such as hydrone, amino molecule etc. have strong absorption, the vibration of many organic macromolecules (DNA, protein etc.) to THz radiation Transition between energy level and rotational energy level is also just in THz wavelength band.Therefore, the THz spectrum of material (includes transmitting, reflection And transmitted spectrum) including abundant physics matter and chemical information, it absorbs and dispersion characteristics can be used to do explosive, medicine Deng detection and the identification of chemistry and biological sample, in physicss, chemistry, biomedicine, astronomy, material science and environmental science Etc. aspect there is important using value.
PVDF is the copolymer of fluorine-containing vinyl monomer, and it has the characteristic of fluororesin and resins for universal use concurrently, good except having Chemical resistance, heat-resisting quantity, oxidative resistance, weatherability, outside resistance to x radiation x performance, also have piezoelectricity, ferroelectricity, The properties such as pyroelectricity.PVDF has four kinds of polymorphic structures:α, β, γ, δ phase, wherein β phase are electric polarity forms, have higher Piezoelectric property.Particularly the THz dielectric properties of the PVDF of β phase can be located at THz with the description of Drude model, its plasma frequency Frequency range, so that can excite THz surface plasmons at medium PVDF interface, has important application in sensory field.
Solution concentration is an important physical amount, in chemical industry, metallurgy, papermaking, wine brewing, sugaring, environmental protection industry (epi) and scientific research etc. Field all usually needs solution concentration is measured.Wherein particularly alcoholic beverages are state control products, to therein There are strict requirements for ethanol content.Rapidly and accurately measure ethanol content in beverage particularly significant in food industry quality control. Therefore pass through to measure the light of solution because the refractive index of solution is directly related with its concentration and temperature with optical parametrics such as absorbances Learn parameter to measure solution concentration be one of conventional method, for example Fibre Optical Sensor, infrared and Raman spectrometry etc..With Membrance separation is compared with reference to the electrochemistry method such as enzyme process, and this kind of have measuring speed soon, and high precision is especially suitable for inflammable and explosive etc. Place measures.Near-infrared, mid-infrared and Raman spectrum have been applied to the measurement of ethanol content in beverage, but build in measuring method At the vertical initial stage, need to complete in high volume to test to set up chemometric model.And how model is with light intensity signal or and intensity Measured perception is realized in the change of directly related amount, and the stability requirement to light source is high, and calculates complexity.
Content of the invention
The present invention seeks to overcoming the shortcomings of alcohol concentration in existing electrochemical process and spectroscopy measurements beverage, provide one kind Alcohol concentration measurement apparatus and its method using Terahertz anisotropic media resonance effect.
The alcohol concentration measurement apparatus of the utilization PVDF Terahertz plasma resonance effect of the present invention include semicircle silicon Prism (1), the first silica membrane (2), PVDF thin film (3), the second silica membrane (4), alcoholic solution to be measured (5), HR-Si substrate (6), the first turntable (7), backward wave oscillator (8), the first politef lens (9), the second polytetrafluoroethyl-ne Alkene lens (10), the 3rd politef lens (11);4th politef lens (12);Schottky diode detector (13), the second turntable (14);
Semicircle silicon prism (1) lower surface be close to successively to arrange the first silica membrane (2), PVDF thin film (3), second Silica membrane (4), alcoholic solution to be measured (5) and HR-Si substrate (6), are passed through by the THz ripple that backward wave oscillator (8) sends First politef lens (9), the second politef lens (10) focus on semicircle silicon prism (1), then through semicircle Shape silicon prism (1) and the first silica membrane (2), PVDF thin film (3), the second silica membrane (4), are close to be placed in height Outgoing semicircle silicon prism (1) after alcoholic solution to be measured (5) reflection in resistance silicon substrate (6), then pass through the 3rd politef Lens (11), the 4th politef lens (12) reach schottky diode detector (13);
Semicircle silicon prism (1), the first silica membrane (2), PVDF thin film (3), the second silica membrane (4), Alcoholic solution (5) to be measured, HR-Si substrate (6) are arranged on the first turntable (7);Schottky diode detector (13) is installed On the second turntable (14).
The thickness of the first silica membrane (2) and the second silica membrane (4) is 10 microns, the thickness of PVDF thin film Spend for 30 microns, the thickness of alcoholic solution is 200 microns.
Alcohol concentration measuring process to be measured is as follows:
1) place alcoholic solution to be measured respectively between HR-Si substrate (6) and the second silica membrane (4) first;
2) THz wave that backward wave oscillator (8) sends is operated in 0.65THz, through semicircle silicon prism (1) and the One silica membrane (2), PVDF thin film (3), the second silica membrane (4), are close to be placed on HR-Si substrate (6) Schottky diode detector (13) is reached, the first turntable (7) angle of rotation that prism is located after alcoholic solution (5) reflection to be measured Degree θ, the second turntable (14) that schottky diode detector (13) is located rotates 2 θ;θ in 20 to 80 degree scanning, sweep by angle The step-length retouched is less than 1 point, angulation reflection coefficient curve.
3) the angle reflection coefficient being recorded according to the alcoholic solution to be measured of unknown concentration, calculates resonance peak position;And generation Enter standard solubility-resonance peak and measure the Exact concentrations that calibration trace obtains alcoholic solution to be measured.
Standard solubility-resonance peak measurement calibration trace obtains as follows:
1) place respectively between HR-Si substrate (6) and the second silica membrane (4) first pure water, 5%, 10%, 15%th, 20%, 25%, 30%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%th, 90%, 95%, 100% proof-spirit solution;
2) THz wave that backward wave oscillator (8) sends is operated in 0.65THz, through silicon prism (1) and the first dioxy SiClx thin film (2), PVDF thin film (3), the second silica membrane (4), are close to be placed in difference on HR-Si substrate (6) dense Schottky diode detector (13) is reached, the first turntable (7) that prism is located turns after proof-spirit solution (5) reflection of degree Dynamic angle, θ, the second turntable (14) that schottky diode detector (13) is located rotates 2 θ;θ 20 to 80 degree scanning when, angle The step-length of degree scanning is less than 1 point, angulation reflection coefficient curve.
3) after the angle reflection coefficient curve measuring all standard solution, resonance peak position and solution concentration are calculated Data Criterion solubility-resonance peak measurement calibration trace together, from pure water to absolute alcohol change procedure, reflection coefficient curve On mobile more than 18 degree of resonance peak, the step-length of angle scanning be less than 1 point so that measure alcohol concentration precision reach 0.1% with On.
Single-frequency Terahertz (THz) ripple being sent by backward wave oscillator reaches Schottky diode after silicon prismatic reflection Detector.When the turntable that silicon prism is located rotates to an angle and the detector place turntable corresponding twice angle of rotation, And in particular range during scan variations, detector can get angle reflection coefficient curve to the anglec of rotation.This reflection coefficient is bent Resonance peak on line changes movement with alcohol concentration.Due to the power of backward wave oscillator larger so that detector place turntable Radius larger so that anglec of rotation resolution can be less than one point, in this measurement apparatus, solution to be measured is from pure water to absolute alcohol During change, the resonance peak of angle reflection coefficient curve is mobile is more than 18 degree so that this measurement apparatus measures the precision of alcohol concentration Reach more than one thousandth.
Brief description
A kind of alcohol concentration using Kynoar (PVDF) thin film Terahertz surface plasma resonance effect of Fig. 1 is surveyed Amount apparatus structure schematic diagram;
Fig. 2 measures Terahertz reflection coefficient when pure water, 20%, 40%, 60%, 80%, 100% proof-spirit solution Curve;
Fig. 3. measurement pure water, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100% standard Resonance angle and its matched curve in reflection coefficient curve during alcoholic solution.
In figure:Semicircle silicon prism 1, the first silica membrane 2, PVDF thin film 3, the second silica membrane 4, to be measured Alcoholic solution 5, HR-Si substrate 6, the first turntable 7, backward wave oscillator 8, the first politef lens 9, the second polytetrafluoro Ethylene lens 10, the 3rd politef lens 11, the 4th politef lens 12, schottky diode detector 13, Two turntables 14.
Specific embodiment
As shown in figure 1, a kind of alcohol concentration measurement apparatus of utilization PVDF Terahertz plasma resonance effect, including half Circular silicon prism 1, the first silica membrane 2, PVDF thin film 3, the second silica membrane 4, alcoholic solution to be measured 5, high resistant Silicon substrate 6, the first turntable 7, backward wave oscillator 8, the first politef lens 9, the second politef lens the 10, the 3rd Politef lens 11;4th politef lens 12;Schottky diode detector 13, the second turntable 14;
Semicircle silicon prism 1 lower surface is close to arrange the first silica membrane 2, PVDF thin film 3, the second titanium dioxide successively Silicon thin film 4, alcoholic solution to be measured 5 and HR-Si substrate 6, the THz ripple being sent by backward wave oscillator 8 passes through the first politef Lens 9, the second politef lens 10 focus on semicircle silicon prism 1, then through semicircle silicon prism 1 and the first titanium dioxide Silicon thin film 2, PVDF thin film 3, the second silica membrane 4, are close to be placed in alcoholic solution to be measured 5 on HR-Si substrate 6 anti- Penetrate rear outgoing semicircle silicon prism 1, then reach Xiao Te through the 3rd politef lens 11, the 4th politef lens 12 Based diode detector 13;
Semicircle silicon prism 1, the first silica membrane 2, PVDF thin film 3, the second silica membrane 4, ethanol to be measured Solution 5, HR-Si substrate 6 are arranged on the first turntable 7;Schottky diode detector 13 is arranged on the second turntable 14 On.
The thickness of the first silica membrane 2 and the second silica membrane 4 is 10 microns, and the thickness of PVDF thin film is 30 microns, the thickness of alcoholic solution is 200 microns.
Measuring process is as follows:
1) place alcoholic solution to be measured respectively between HR-Si substrate 6 and the second silica membrane 4 first;
2) THz wave that backward wave oscillator 8 sends is operated in 0.65THz, through semicircle silicon prism 1 and the 1st Silicon oxide film 2, PVDF thin film 3, the second silica membrane 4, are close to be placed in alcoholic solution to be measured on HR-Si substrate 6 Schottky diode detector 13 is reached after 5 reflections, the first turntable 7 rotational angle θ that prism is located, Schottky diode is visited Survey the second turntable 14 rotation 2 θ that device 13 is located;In 20 to 80 degree scanning, the step-length of angle scanning is less than 1 point to θ, forms angle Degree reflection coefficient curve.
The 3 angle reflection coefficients being recorded according to the alcoholic solution to be measured of unknown concentration, calculate resonance peak position;And substitute into Standard solubility-resonance peak measures the Exact concentrations that calibration trace obtains alcoholic solution to be measured.
Standard solubility-resonance peak measurement calibration trace obtains as follows:
1) place respectively between HR-Si substrate 6 and the second silica membrane 4 first pure water, 5%, 10%, 15%, 20%th, 25%, 30%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%th, 95%, 100% proof-spirit solution;
2) THz wave that backward wave oscillator 8 sends is operated in 0.65THz, through silicon prism 1 and the first silicon dioxide Thin film 2, PVDF thin film 3, the second silica membrane 4, the proof-spirit of the variable concentrations being close to be placed on HR-Si substrate 6 Schottky diode detector 13 is reached after solution 5 reflection, the first turntable 7 rotational angle θ that prism is located, Schottky two pole The second turntable 14 that pipe detector 13 is located rotates 2 θ;In 20 to 80 degree scanning, the step-length of angle scanning is less than 1 point to θ, shape Angled reflection coefficient curve, as shown in Figure 2.
3) after the angle reflection coefficient curve measuring all standard solution, resonance peak position and solution concentration are calculated Data Criterion solubility-resonance peak measurement calibration trace (as shown in Figure 3) together, from pure water to absolute alcohol change procedure, Mobile more than 18 degree of resonance peak in reflection coefficient curve, the step-length of angle scanning is less than 1 point so that measuring alcohol concentration precision Reach more than 0.1%.

Claims (4)

1. a kind of alcohol concentration measurement apparatus of utilization PVDF Terahertz plasma resonance effect are it is characterised in that include semicircle Shape silicon prism (1), the first silica membrane (2), PVDF thin film (3), the second silica membrane (4), alcoholic solution to be measured (5), HR-Si substrate (6), the first turntable (7), backward wave oscillator (8), the first politef lens (9), second poly- four Fluorothene lens (10), the 3rd politef lens (11);4th politef lens (12);Schottky diode detects Device (13), the second turntable (14);
Semicircle silicon prism (1) lower surface is close to arrange the first silica membrane (2), PVDF thin film (3), the second dioxy successively SiClx thin film (4), alcoholic solution to be measured (5) and HR-Si substrate (6), pass through first by the THz ripple that backward wave oscillator (8) sends Politef lens (9), the second politef lens (10) focus on semicircle silicon prism (1), then through semicircle silicon Prism (1) and the first silica membrane (2), PVDF thin film (3), the second silica membrane (4), are close to be placed in High Resistivity Si Go out radiosilicon prism (1) after alcoholic solution to be measured (5) reflection on substrate (6), then through the 3rd politef lens (11), the Four politef lens (12) reach schottky diode detector (13);
Semicircle silicon prism (1), the first silica membrane (2), PVDF thin film (3), the second silica membrane (4), to be measured Alcoholic solution (5), HR-Si substrate (6) are arranged on the first turntable (7);Schottky diode detector (13) is arranged on On two turntables (14).
2. device according to claim 1 is it is characterised in that described the first silica membrane (2) and the second titanium dioxide The thickness of silicon thin film (4) is 10 microns, and the thickness of PVDF thin film is 30 microns, and the thickness of alcoholic solution is 200 microns.
3. a kind of wine utilizing PVDF Terahertz plasma resonance effect using device as claimed in claim 1 using Terahertz Smart concentration measuring method is it is characterised in that its measuring process is as follows:
1) place alcoholic solution to be measured respectively between HR-Si substrate (6) and the second silica membrane (4) first;
2) THz wave that backward wave oscillator (8) sends is operated in 0.65THz, through semicircle silicon prism (1) and the one or two Silicon oxide film (2), PVDF thin film (3), the second silica membrane (4), to be measured on HR-Si substrate (6) by being close to be placed in Schottky diode detector (13) is reached after alcoholic solution (5) reflection, the first turntable (7) the rotational angle θ that prism is located, The second turntable (14) that schottky diode detector (13) is located rotates 2 θ;θ 20 to 80 degree scanning when, angle scanning Step-length is less than 1 point, angulation reflection coefficient curve;
3) the angle reflection coefficient being recorded according to the alcoholic solution to be measured of unknown concentration, calculates resonance peak position;And substitute into mark Quasi- solubility-resonance peak measures the Exact concentrations that calibration trace obtains alcoholic solution to be measured.
4. method as claimed in claim 3 is it is characterised in that described standard solubility-resonance peak measurement calibration trace passes through such as Lower step obtains:
1) place respectively between HR-Si substrate (6) and the second silica membrane (4) first pure water, 5%, 10%, 15%, 20%th, 25%, 30%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%th, 95%, 100% proof-spirit solution;
2) THz wave that backward wave oscillator (8) sends is operated in 0.65THz, through semicircle silicon prism (1) and the one or two Silicon oxide film (2), PVDF thin film (3), the second silica membrane (4), are close to be placed in difference on HR-Si substrate (6) Schottky diode detector (13) is reached, the first turntable (7) that prism is located after proof-spirit solution (5) reflection of concentration Rotational angle θ, the second turntable (14) that schottky diode detector (13) is located rotates 2 θ;θ 20 to 80 degree scanning when, The step-length of angle scanning is less than 1 point, angulation reflection coefficient curve.
3) measure all standard solution angle reflection coefficient curve after, calculate resonance peak position and with solution concentration data Criterion solubility-resonance peak measurement calibration trace together, from pure water to absolute alcohol change procedure, in reflection coefficient curve Mobile more than 18 degree of resonance peak, the step-length of angle scanning is less than 1 point so that measurement alcohol concentration precision reaches more than 0.1%.
CN201611125163.8A 2016-12-08 2016-12-08 Alcohol concentration measurement apparatus and method using PVDF Terahertz plasma resonance effect Pending CN106483104A (en)

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Application publication date: 20170308