TWI506266B - True and adulterate liquor recognizable color-changing chip and method making the same - Google Patents

Description

Color-changing wafer for identifying true and false wine and its preparation method

The invention relates to a color changing wafer for identifying true and false wine and a preparation method thereof, in particular to an electromagnetic simulation software according to a finite difference time domain method and a full three-dimensional structure analysis, which calculates a microsphere in a three-dimensional photonic crystal array required for identifying an alcohol concentration. Particle size, the desired nano-sized microspheres are prepared by soap-free emulsion polymerization, and the micro-sphere arrays are arranged in a self-assembled manner, and the PS three-dimensional photonic crystal array is conveniently observed by a human eye at a specific inclination angle. The method is placed in a transparent wafer outer case having a liquid injection port, and becomes a simple technique for recognizing a color-changing wafer of true and false wine.

At present, most methods for detecting whether or not alcohol is contained in alcohol on the market are spectrophotometry, electrochemical detection, gas chromatography, liquid chromatography, and sensors. Although there is a certain degree of accuracy, the biggest problem is that the operation process is cumbersome, time-consuming, and costly. Therefore, if the polystyrene (PS) opal array is used as the methyl alcohol identification and distinguishing the type sensing wafer of the distilled liquor and the brewed wine according to the technology provided by the present invention, the user does not need to have the identification time quickly. Operate complex equipment and precise chemical operation procedures. For example, I282854 is a method for detecting methanol by near-infrared ray, in order to prepare a plurality of methanol-containing sample liquids, and irradiating several sample liquids with a near-infrared light source to obtain an absorption spectrum thereof, and obtaining a relationship between the spectral values and the methanol concentration. The calibration curve is finally irradiated with an infrared light source to obtain an absorption spectrum, and then compared with the calibration curve to calculate the methanol concentration contained therein. Such as I249030 The method for detecting methanol and the method for preparing a methanol detection carrier are to provide a methanol detection carrier for the methanol reaction reagent, and to insert the carrier into the sample to be tested, and then observe the carrier when the carrier is taken out from the object to be tested. Whether the carrier produces a color change, and if there is a color change, it means that the analyte contains methanol.

The object of the present invention is to provide a method for preparing a color-changing wafer which is easy to manufacture, low in cost, light in weight, non-polluting, portable, and capable of fully utilizing the physical optical characteristics of a photonic crystal to have an effect of identifying an alcohol type. The technical means for achieving this purpose is to use the electromagnetic simulation software EM explorer calculated by the finite difference time domain method to calculate the incident angle and wavelength of the light, the refractive index and arrangement structure of the microspheres, and the medium between the ball joints to calculate the specificity. The size of polystyrene (PS) nanospheres to be prepared when reflecting the wavelength of light. The PS nanospheres were synthesized by soap-free emulsion polymerization, and the required PS nanosphere diameters were prepared by using parameters such as monomer addition amount, starting dose, polymerization temperature and stirring rate. The PS nanospheres were arranged in a neat array by solution evaporation to form a photonic color recognition wafer comprising a PS opal structure.

The object of the present invention is to provide a color-changing wafer for identifying authentic wines which is simple in manufacture, low in cost, light in weight, non-polluting, portable, and capable of fully utilizing the physical optical characteristics of photonic crystals to achieve the effect of identifying alcohols. The color of the structure reflected by the PS opal structure prepared according to the method of the previous paragraph is green because the gap between the PS nanospheres is air (refractive index n = 1). When we use a micropipette (Pipet) to take 2μl of the alcohol liquid to be tested (methanol refractive index n=1.329; ethanol refractive index n=1.362) into the gap of the PS nanosphere array, due to the refraction of the alcohol liquid to be tested The rate is different, when the light is arranged through the order between the microspheres and the microspheres Different color changes are reflected, which in turn produces a function recognizable by the human eye. We use this color change method as a recognition chip for quickly discriminating between true and false wines.

11‧‧‧ glass substrate

12‧‧ ‧ polystyrene microspheres

13‧‧‧ incident light

21‧‧‧ glass substrate

22‧‧‧Oxygen plasma modification

23‧‧‧Polystyrene microsphere array

30‧‧‧ Identify true and false wine color changing chips

31‧‧‧Liquid injection port

32‧‧‧Polystyrene microsphere array

33‧‧‧Black PC reflector

34‧‧‧ wafer cassette

The first diagram is a schematic diagram of the electric field operation of the imitation opal structure of the present invention; the second diagram is a schematic diagram of the self-assembly alignment process of the polystyrene microsphere of the present invention; the third diagram is a schematic diagram of the simple identification of the true and false wine discoloration wafer of the present invention; The figure is an array of polystyrene opal structures photographed by an electron microscope; the fifth figure is a reflection spectrum of an array of polystyrene opal structures of the present invention with an analog value (blue line) and an experimental value (orange line); -1 is a reflection spectrum of the PS microsphere array of the present invention after actual testing with anhydrous methanol; the sixth a-2 is a CIE chromaticity diagram of the PS microsphere array of the present invention after actual testing with anhydrous methanol; 1 is a reflection spectrum of the PS microsphere array of the present invention after actual testing with anhydrous ethanol; the sixth b-2 is a CIE chromaticity diagram of the PS microsphere array of the present invention after actual testing with anhydrous ethanol; The PS microsphere array was invented to test the substrate pattern with anhydrous methanol and absolute ethanol. Figure a is a test for anhydrous methanol, and obvious ablation phenomenon can be found therefrom. Figure b is a test for anhydrous ethanol, and the substrate is still intact; eighth a-1 Picture book Inventive PS microsphere array after high-alcoholic actual test after reflection spectrum; eighth a-2 diagram of the present invention PS microsphere array after high-alcoholic actual test CIE chromaticity diagram; eighth b-1 diagram of the present invention The reflectance spectrum of the PS microsphere array after actual testing of white wine; The eighth b-2 is a CIE chromaticity diagram of the PS microsphere array of the present invention after actual testing of white wine; and Annex 1 is a photograph of a sample for identifying a true and false wine color changing wafer of the present invention.

The technical feature of the present invention is an embodiment of the present invention, which uses a finite difference time domain calculus and an electromagnetic simulation software (simulator) for full three-dimensional structural analysis to determine a desired polystyrene (PS) nanometer. Ball size. Since the structural color is caused by the reflection of the incident light through the three-dimensional photonic crystal periodically arranged in the microspheres, the full spectrum color of visible light can be reflected by preparing polystyrene (PS) nanospheres of different sizes. Therefore, the present invention must first calculate an ideal value that can be recognized by the naked eye before performing color optical sensing discrimination. From the optical point of view, it is found that the higher the reflectance, the more likely the human eye is to produce a glare phenomenon. Because the human eye has a better discrimination against green light. Therefore, the finite difference time domain method (Bragg-Snell's Law) is first used to infer the required particle size of the PS microspheres when producing a photonic crystal microsphere array capable of reflecting green light. The relevant calculation formula is as shown in the following formulas (1) and (2), formula (1): λ = 2 (2 / 3) ^1⁄2 D (n _{2 -} sin ² θ) ^1⁄2 ; formula (2): n = [(0.74 *n _sphere ² )+(0.26*n _air ² )] ^1⁄2 .

In the various researches of the analog photonic crystal, the EM explorer software of the finite difference time domain calculation mode is combined with the incident angle and wavelength of the light, the refractive index of the microsphere, and the medium between the spherical joints to calculate the desire. The size of the PS nanospheres to be prepared when a particular reflected light wavelength is obtained. Here, we assume that the incident angle of the incident light 13 is θ=10°~60°, the reflected green light wavelength λ=495nm~570nm, and the refractive index of the polystyrene (PS)12 on the glass substrate _{11n sphere} = 1.6, n _air = 1.0 According to the calculation (please refer to the first figure), it can be seen that when the particle size D of the polystyrene (PS) microspheres is approximately in the range of 223 nm to 273 nm, it is possible to produce a naphthalene with a higher green reflection value. An array of meters of polystyrene (PS) microspheres.

The PS nanospheres of the present invention are synthesized by the soap-free emulsion polymerization method to prepare uniform particle size PS microspheres (polys tyrene spheres), styrene St, deionized water DI.Water, sodium styrene sulfonate NaSS , that is, the ratio of St:DI.Water:NaSS=10:90:45 is uniformly stirred in the reaction flask, and the polymerization reaction is started by adding 0.09 g of the initiator KPS under a nitrogen atmosphere at a temperature of 70 ° C for 24 hours. Then, a PS microsphere suspension can be synthesized. Since the particle size of the PS microspheres we need can reflect the green light band, we use the formulas (1) and (2) of the first two paragraphs to calculate the NaSS content of 45 mg to polymerize the desired particle size. PS microspheres.

In the preparation technique of the polystyrene (PS) microsphere array of the present invention, since the glass substrate 21 itself is not hydrophilic, the surface of the glass substrate 21 is surface-modified by an oxygen plasma cleaner (Plasma Cleaner). The glass substrate 21 has a hydrophilic property. Thereafter, the glass substrate 21 subjected to the oxygen plasma modification 22 is vertically immersed in a PS suspension having a concentration of 10%, and the PS suspension of the immersed glass substrate 21 is covered with aluminum foil paper, and then the surface is drawn. A small hole was opened and finally the water in the solution was evaporated at a temperature of 60 ° C to obtain a highly ordered polystyrene (PS) microsphere array 23 as shown in the second figure.

The simple identification of the true and false wine color changing wafer 30 of the present invention is performed by first placing the opal structure of the PS microsphere array on the black PC reflecting plate 33 and then placing it in an inclined manner outside the glass wafer having the liquid injection port 31. The box 34 is conveniently viewed by the human eye, that is, a simple type of alcohol identification wafer (ie, identifying the true and false wine color changing wafer 30), as shown in the third figure and the sample photograph shown in the attached one.

The present invention performs PS nanosphere array analysis, that is, performs (1) analysis of the influence of structural color; (2) microsphere structure analysis; and (3) optical analysis (reflection spectrum).

In the analysis of the influence on the color of the structure, the present invention synthesizes a 242 nm particle size microsphere, which can reflect the green structural color by its particle size, and the average particle size of the PS microsphere when the NaSS content is between 40 and 45 mg. The diameter is around 223nm to 273nm to show the color of green light. If the wine is dropped into the color-changing wafer of the present invention, when the wine is completely volatilized, the wine is liquid because the structure of the PS nanosphere array remains intact and can continuously reflect green light. The judgment is true (ie, the alcohol in the liquor is ethanol); and if the structure of the PS microspheres is ablated after the test, the reflected light deviates from the original green light due to the collapse of the structure of the partial nanosphere array. Then, it is judged that the liquor is false (that is, the alcohol in the liquor is methanol or contains methanol).

In the analysis of the structure of the microspheres, the present invention utilizes the solution evaporation method in the self-assembly method to fabricate a microsphere array of a three-dimensional photonic crystal, which is controlled by temperature control by the charge of the PS microsphere itself and the effect of van der Waals attraction. The microspheres are self-assembled into an ordered periodic structure. We prepared a PS microsphere array by solution evaporation at an ambient temperature of 60oC, and observed the microstructure of the microsphere array alignment with a scanning electron microscope (SEM) (see Figure 4). It can be clearly seen from the fourth figure that the PS microsphere array exhibits a closely packed structural arrangement.

Among optical analysis (reflection spectroscopy), the present invention uses a UV-Vis spectrometer to observe the PS structure. This work is to confirm whether the experimental value can approach the analog value, so that the fabricated PS microsphere structure can reflect green light, and Non-other bands (see Figure 5). It can be confirmed from the figure that the experimental value is close to the theoretical value and the reflection wavelength is similar. Although the reflection peak of the experimental value is slightly lower, the trend is consistent with the theoretical value and does not affect the judgment criterion.

The invention tests the standard liquid with the color-changing wafer prepared to identify the real wine. The alcohol identification wafer of the present invention was tested with anhydrous methanol and absolute ethanol, respectively, and the test conditions were as shown in the sixth a-1 diagram and the sixth a-2 diagram in anhydrous methanol, in absolute ethanol. Aspects are shown in Figures 6-1 and 6-2. The sixth a-1 diagram and the sixth a-2 diagram show the test condition of the alcohol identification wafer of the present invention for anhydrous methanol. From the sixth a-2 diagram, we can find that the wavelength shift condition is tested for 30 seconds. At the time of 60 seconds, the final test point is close to the origin, but it does not completely return to the origin of the beginning. This can be confirmed by the sixth a-1 diagram. The sixth b-1 diagram and the sixth b-2 diagram show that the alcohol identification wafer of the present invention is tested for absolute ethanol. From the sixth b-2 diagram, we can find that the wavelength shifting state has a uniform regularity. In the 60 second test time, the last return to the origin of the beginning, this phenomenon can be confirmed by the sixth b-1 figure. It can be understood from the above two examples that during the one-minute test, the anhydrous ethanol can return to the original test origin, and the anhydrous methanol can not return to the original origin, and the methanol test condition even has a part. The phenomenon of ablation exists (as shown in Figure 7). Therefore, the characteristics of methanol and ethanol can be utilized for the identification of true and false wines.

The invention performs the actual test on the liquid to be tested with the color-changing wafer prepared by the authenticity wine. The alcohol identification wafer of the present invention is separately tested by using the distilled liquor and the brewed wine which are common in the market. Therefore, sorghum and white wine are used as the examples for testing. The test results are as follows in the detection of sorghum wine. As shown in Fig. 8a-1 and Fig. 8-2, the detection of white wine is as shown in the eighth b-1 and the eighth b-2. The eighth a-1 diagram and the eighth a-2 diagram show the test results of the alcohol identification wafer of the present invention for sorghum liquor. From the eighth a-2 diagram, we can find that the wavelength shifting state has a certain regularity. Sex. At first, the wavelength of the green light to be measured will directly drop to the wavelength of the yellow light, and will slowly move from the yellow light blue to the green light wavelength during the test time of three minutes, and finally return to the point close to the origin. The eighth a-1 chart is supported. The eighth b-1 diagram and the eighth b-2 diagram show the test results of the alcohol identification wafer for white wine of the present invention. From the eighth b-2 diagram, we can find the wavelength shifting condition. At first, it moves from the green band to the yellow band, and then slowly moves to the white band. Finally, there is no return to the origin. This phenomenon can be confirmed by the eighth b-1 chart.

Technical features and effects of the present invention: The alcohol identification technique of the present invention can recognize methanol and ethanol. Different from the identification restrictions on distilled spirits on the market, this wafer combines optical instruments to obtain more accurate results. The invention adopts the solution evaporation method to cause the PS microspheres to self-assemble and arrange into an ordered structure, and the PS material has the advantages of monodispersion in addition to itself, wherein the microspheres are more likely to exhibit obvious colors when arranged in an ordered structure array, which is helpful. It is identified by the naked eye. Compared with the current detection technology, the present invention does not require large-scale instrument operation and professional operators, and can be promoted to ordinary people's livelihood families under the consideration of saving time and money, and food safety.

The above is only a possible embodiment of the present invention, and is not intended to limit the scope of the patents of the present invention, and the equivalent implementations of other changes according to the contents, features and spirits of the following claims should be It is included in the patent of the present invention. The invention is specifically defined in the structural features of the request item, is not found in the same kind of articles, and has practicality, advancement and industrial utilization, has met the requirements of the invention patent, and has filed an application according to law, and requests the bureau to approve the patent according to law. To protect the legal rights of the applicant.

30‧‧‧ Identify true and false wine color changing chips

31‧‧‧Liquid injection hole

32‧‧‧Polystyrene microsphere array

33‧‧‧reflector

34‧‧‧ wafer cassette

Claims (10)

The invention relates to a method for identifying a color changing wafer of true and false wine, comprising the following steps: (1) calculating a particle size of a microsphere in a three-dimensional photonic crystal array required for identifying a liquor according to a finite difference time domain calculus and an electromagnetic simulation software; 2) using a soap-free emulsion polymerization method to prepare a desired nano-scale three-dimensional photonic crystal microsphere suspension; (3) using the three-dimensional photonic crystal microsphere suspension to self-assemble a three-dimensional photonic crystal with periodic alignment The microsphere array; and (4) placing the three-dimensional photonic crystal microsphere array in a transparent wafer outer casing having a liquid injection port to become a color-changing wafer for identifying true and false wine. The method of claim 1, wherein the finite difference time domain method of the step (1) and the electromagnetic simulation software are Bragg-Snell's Law and EM explorer software, with the formula λ=2(2/3) ^1⁄2 D(n ₂ - sin ² θ) ^1⁄2 and the formula n = [(0.74 * n _sphere ² ) + (0.26 * n _air ² )] ^1⁄2 , to estimate the size of the nano-scale microspheres to be prepared in order to obtain a specific reflected light wavelength. The method of claim 2, wherein the microspheres are polystyrene (PS) microspheres having a particle diameter ranging from 223 nm to 273 nm, the wavelength of the reflected light being a green wavelength, and the green wavelength band being blue. Both the shift and the red shift can clearly observe the change in wavelength. The method of claim 1, wherein the step (2) is uniformly stirred in a reaction flask at a ratio of St: ionized water DI. Water: NaSS = 10:90:45, at a temperature of about 70 ° C under a nitrogen atmosphere. The polymerization reaction was started by adding 0.09 g of the initiator KPS, and after about 24 hours, a polystyrene (PS) microsphere suspension was synthesized. The method of claim 4, wherein the NaSS content is between 40 and 45 mg. The method according to claim 1, wherein in the step (3), a glass substrate is surface-modified by an oxygen plasma reformer to have a hydrophilic property, and the glass substrate is immersed in a concentration of 10%. The three-dimensional photonic crystal microsphere suspension is obtained by a solution evaporation method at 60 ° C to obtain a highly ordered array of the microspheres. The method of claim 1, wherein the finite difference time domain method in step (1) is calculated And the electromagnetic simulation software EM explorer cooperates with the incident angle and wavelength of the light, the refractive index and arrangement structure of the microsphere, and the medium between the spherical slits to estimate the size of the nanosphere to be prepared when the wavelength of the specific reflected light is to be obtained. . A color-changing wafer for identifying authentic wine made by the method of claim 1, comprising the wafer outer casing, a reflecting plate and the three-dimensional photonic crystal microsphere array, wherein the three-dimensional photonic crystal microsphere array is distributed In the outer casing of the wafer, the reflector is located on the back of the three-dimensional photonic crystal microsphere array, and the outer casing has a chamber and an injection port for injecting the wine to be tested, through the reflector and the three-dimensional photonic crystal. The array of microspheres reflects the reflected light of the liquor, and the reflected light is used to judge whether the liquor is true or false. The color-changing wafer for identifying authentic wines according to claim 8, wherein the three-dimensional photonic crystal microspheres are polystyrene (PS) microspheres. The color-changing wafer for identifying authentic wines according to claim 8 or 9, wherein when the particle diameter of the microspheres is in the range of 223 nm to 273 nm, when the wine is dropped into the color-changing wafer, the wine is treated. If the green light is continuously reflected after complete volatilization, the wine is judged to be true; if the reflected light deviates from the original green light after the liquid is dropped, the wine is judged to be false.