CN108133659B - Cold chain storage and transportation monitoring label based on nanometer temperature-sensitive color-changing material - Google Patents
Cold chain storage and transportation monitoring label based on nanometer temperature-sensitive color-changing material Download PDFInfo
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- CN108133659B CN108133659B CN201711422840.7A CN201711422840A CN108133659B CN 108133659 B CN108133659 B CN 108133659B CN 201711422840 A CN201711422840 A CN 201711422840A CN 108133659 B CN108133659 B CN 108133659B
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- 238000003860 storage Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 title claims abstract description 8
- 238000012544 monitoring process Methods 0.000 title claims abstract description 8
- 239000004038 photonic crystal Substances 0.000 claims abstract description 24
- 230000008859 change Effects 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 230000004044 response Effects 0.000 claims abstract description 9
- 229920006254 polymer film Polymers 0.000 claims abstract description 3
- 238000007789 sealing Methods 0.000 claims abstract description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000003086 colorant Substances 0.000 claims 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000010354 integration Effects 0.000 abstract description 2
- 230000002427 irreversible effect Effects 0.000 abstract description 2
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 229960005486 vaccine Drugs 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000000875 corresponding effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
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- 239000002390 adhesive tape Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
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- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000275 quality assurance Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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Images
Classifications
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/02—Forms or constructions
- G09F3/0291—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Measuring Temperature Or Quantity Of Heat (AREA)
Abstract
The invention discloses a method for manufacturing a cold chain storage and transportation monitoring label based on a nano temperature-sensitive color-changing material. Which comprises the following steps: 1) preparing a magnetic response type photonic crystal; 2) ultrasonically dispersing the magnetic response photonic crystal prepared in the step 1) in temperature-sensitive dispersion liquid; 3) sealing the dispersion liquid in the step 2) in a thin container or a polymer film; 4) under the condition of an external special magnetic field, the temperature-sensitive liquid film presents a pattern and a color; 5) and placing the label in a refrigerator to fix the pattern and the color to obtain the cold chain temperature label. The label can not generate color change in the sensitive temperature, and the color and the pattern change beyond the sensitive temperature and are irreversible. The invention has the advantages that: high sensitivity, high reliability, high anti-counterfeiting performance and high integration.
Description
Technical Field
The invention relates to the field of new materials and indicating products.
Background
The vaccine needs strict cold chain storage and transportation in the circulation process, otherwise deterioration and invalidation can be caused, and the first risk is ineffective immunity when the vaccine which is not stored and transported at the temperature of 2-8 ℃ is inoculated. Similar events have led to widespread concern as to whether foods or pharmaceuticals that require freezing or refrigeration are compounded in the supply chain segment with relevant standards (DB 31/T388-2007). If the consumer can know whether the single-piece goods to be frozen or refrigerated are stored out of specification like reading the production date and the shelf life, the confidence of the consumer on the quality assurance of the goods can be undoubtedly enhanced, and meanwhile, accidents caused by uneven temperature inside the refrigerating box and the cabinet can be avoided. Therefore, it is necessary to develop a new technology capable of detecting the storage and transportation environment of the tag, and fundamentally solve the supervision problem of cold chain storage.
The existing technologies in the market can be divided into electronic technologies and non-electronic technologies, the electronic technologies (such as RFID technologies) can record temperature changes, but the electronic technologies are large in size, expensive and only suitable for whole boxes and whole cabinets of articles due to the need of a power supply, and cannot be used for single articles. The conventional non-electronic temperature labels generally indicate temperature by reacting a chemical substance mixed in a substrate with a dye to change color after the substrate is heated and melted. Its main disadvantages include: 1) the price is high; 2) the dyes or chemicals used are toxic; 3) only specific temperature can be displayed, and the application range is narrow; 4) poor mechanical property and easy damage. While the patent (200420078916.0 cold chain label) also has its disadvantages: 1) the label is filled with liquid and can only be vertically placed, and if the label is inclined, whether the label is separated from a cold chain cannot be distinguished; 2) the temperature sensing material is ethanol, the temperature response property is single, and whether a certain temperature point is exceeded or not can be judged only.
In summary, the conventional non-electronic small-sized cold chain temperature tag still has many defects. The market has raised urgent needs for labels that can safely, cheaply, accurately show whether a single item of merchandise is over-temperature. The invention uses the metastable state temperature-sensitive type photonic crystal nano material to sense the change of the storage and transportation environment temperature, and technically realizes the visual indication.
Disclosure of Invention
Aiming at the defects of the existing goods of the cold chain label, the application provides the design and preparation of the cold chain storage and transportation monitoring label by adopting the metastable state temperature-sensitive photonic crystal as a core material. By forming a metastable photonic crystal structure under special conditions, unique structural color is presented. In a low-temperature environment, the photonic crystal structure can exist stably, and the color is kept all the time. When the ambient temperature rises, the structure is destructively changed, so that the color is lost, the sample is put into a low-temperature environment again, the original photonic crystal structure cannot be formed again, and the color of the sample cannot be recovered (as shown in figure 1). Thus, the technique can achieve temperature-sensitive irreversible color change indication. In addition, the performance can be adjusted by optimizing parameters of the photonic crystal, such as the shape of the nano-particles, the size of the nano-particles, the surface property modification of the nano-particles, the formula of the stabilizing solution and the like, so that the photonic crystal can meet different application requirements: the cold chain storage color-changing indicator has different color-changing ranges (such as blue, green to red), response rates (such as seconds, minutes and hours), response intervals (such as-50-20 ℃ and the like).
The application has the advantages that:
1. high sensitivity, when the environmental temperature changes for a certain time, for example, from below 8 ℃ (the preservation temperature range of most vaccines) to above 8 ℃, the indicator material can sensitively change color to indicate whether the vaccine is separated from the cold chain.
2. High reliability: when the ambient temperature is below the indicated temperature, the color of the label does not change. The higher the environmental temperature is, the faster the medicine and food deteriorate, the corresponding acceleration of the color change of the label can be realized, and the label can be suitable for different environmental temperature changes. The color change of the label is particularly well correlated with the quality of the goods to be refrigerated.
3. High anti-counterfeiting performance: on one hand, under the environment above the transition point, the color of the label is irreversibly changed, the label is placed again to the environment below the transition point, and the color of the label cannot be recovered, so that whether any link from factory leaving to use is separated from a cold chain or not can be effectively judged. On the other hand, the color generation mechanism of the label is based on a novel intelligent nano optical material, belongs to the international research frontier, has high technical threshold and is difficult to be simulated by lawbreakers.
4. High integration: the indicator can be designed into different forms such as liquid, polymer film and the like, is conveniently pasted or sprayed on the surface of a commodity, and does not influence the production, transportation and storage of the commodity.
Drawings
FIG. 1 is a schematic diagram of a temperature-sensitive intelligent color-changing indicator
In the example of FIG. 2, the fading change of the sample at room temperature (time corresponding to a to f is 0, 3, 12, 20, 30, 60 minutes, respectively, and one centimeter is shown on the scale.)
FIG. 3 is a transmission electron micrograph of photonic crystal particles in example
Detailed Description
Examples
This example shows an implementation of one of the metastable photonic crystals for use in a tag. The temperature-sensitive label consists of 10% of photonic crystal nanoparticles by volume, 50% of water by volume and 40% of diethylene glycol by volume. Forming a pattern under the conditions of an external special magnetic field and low temperature (3-5 ℃), as shown in a process a of FIG. 1; placing the label with the pattern in a refrigerator at 5 ℃ and no obvious color change is observed in the experimental period (fig. 1, process b); when the proportion of the temperature-sensitive material exceeds 8 ℃, the liquid fluidity is improved due to the temperature rise, the original photonic crystal structure cannot be maintained, so that the color and the pattern gradually change until the color and the pattern disappear (the process c in figure 1), wherein the label is taken out and placed in the normal temperature (20 ℃), the color of the label is sequentially changed from blue, to cyan, to green, to yellow and to orange as shown in figure 2, and the corresponding time is 0, 3, 12, 20, 30 and 60 minutes of exposure to the normal temperature respectively. The label is placed in the refrigerator at any point in time and the color does not return to blue (fig. 1 process d). The time for separating from the cold chain can be judged from the color, and in addition, the higher the exposure temperature is, the faster the color change is, and the larger the deterioration risk of the marked commodity is also indicated.
The temperature-sensitive label is prepared by the following specific steps:
1. preparation of Fe3O4Photonic crystal particles: 20 ml of ethylene glycol was added to a 50 ml reactor at room temperature, and 0.5 mg of PSSMA (3: 1) was slowly added under vigorous magnetic stirring to form a homogeneous clear solution, then 0.54 g of ferric chloride hexahydrate (FeCl) was added to the solution3·6H2O) and 1.5 g of sodium acetate, stirring for 30 minutes, removing the magnetic stirring, filling the mixture into a reaction kettle, and placing the reaction kettle in a 200-DEG oven for reaction for 10 hours. After the reaction is finished, the temperature is reduced to room temperature, the sample is collected by centrifugation (the rotating speed is 11000 r/min, the time is 5 min), the sample is washed with water and ethanol for three times respectively, and then the sample is dispersed in 15 ml of water, and then the sample is separated by a magnet for further washing. The transmission electron microscope picture of the photonic crystal particles is shown in figure 3, and the photonic crystal particles are uniform spherical ferroferric oxide particles with the particle size of 120 +/-10 nanometers.
2. And taking out 200 microliters of samples, drying in an 80-DEG oven, and weighing the mass of the samples to obtain the mass of the photonic crystal particles contained in the samples with single volume. A200. mu.l sample was taken out, 11000 rpm was conducted, and the supernatant was removed by centrifugation for 5 minutes, and 200. mu.l of a total dispersion composed of water and diethylene glycol (water and diethylene glycol were added in a volume ratio of 5: 4) was added. Ultrasonically treating until the solution is uniformly dispersed, sucking the solution by using a flat capillary tube, and sealing two ends of the capillary tube by using ultraviolet curing adhesive and ultraviolet light.
3. And placing the mesostable magnetic temperature-sensitive photonic crystals packaged with the mesostable magnetic temperature-sensitive photonic crystals on a magnetic adhesive tape for 5-10 minutes, arranging the photonic crystals into an ordered structure under the action of a magnetic field, displaying structural color, removing the magnetic field, placing the state in a refrigerator for storage, and keeping the formed color unchanged within a detection time range, wherein the indicator packaged with the mesostable magnetic temperature-sensitive photonic crystals is a cold chain label.
4. The label is attached to the commodity to be refrigerated, and whether the commodity is separated from the cold chain can be judged through whether the color changes.
Finally, it must be said here that: the above embodiments are only used for further detailed description of the technical solutions of the present invention, and should not be understood as limiting the scope of the present invention, and the insubstantial modifications and adaptations by those skilled in the art according to the above descriptions of the present invention are within the scope of the present invention.
Claims (3)
1. A cold chain storage and transportation monitoring label based on a nanometer temperature-sensitive color-changing material is characterized in that: the preparation method of the label comprises the following steps:
1) preparing magnetic response type photonic crystal particles;
2) ultrasonically dispersing the magnetic response photonic crystal particles prepared in the step 1) in a dispersion liquid to form a temperature-sensitive dispersion liquid, wherein the dispersion liquid consists of water and diethylene glycol;
3) sealing the temperature-sensitive dispersion liquid in the step 2) in a thin container or a polymer film;
4) under the condition of an external magnetic field, the temperature-sensitive dispersion liquid integrally presents patterns and colors;
5) placing the label in a refrigerator to fix patterns and colors to obtain a cold chain storage and transportation monitoring label; the temperature-sensitive dispersion comprises the following components:
firstly, photonic crystal particles account for 5-20% of the volume fraction;
water accounts for 10-90% of the volume fraction;
and the diethylene glycol accounts for 5-85% of the volume fraction.
2. The cold chain warehousing and transportation monitoring label of claim 1, the polymeric film being PDMS or PEGDA.
3. The cold chain warehousing and transportation monitoring tag of claim 1, wherein the tag performance characteristics are:
1) the color change range is as follows: blue to green to red;
2) the response rate is: second, minute and hour;
3) the response interval is: -50-20 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711422840.7A CN108133659B (en) | 2017-12-25 | 2017-12-25 | Cold chain storage and transportation monitoring label based on nanometer temperature-sensitive color-changing material |
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| CN201711422840.7A CN108133659B (en) | 2017-12-25 | 2017-12-25 | Cold chain storage and transportation monitoring label based on nanometer temperature-sensitive color-changing material |
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| CN108133659A CN108133659A (en) | 2018-06-08 |
| CN108133659B true CN108133659B (en) | 2021-04-09 |
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| CN109377860A (en) * | 2018-12-06 | 2019-02-22 | 陕西科技大学 | A kind of cold chain storage and transportation surveillance tag and preparation method thereof being irreversibly changed |
| WO2021031063A1 (en) * | 2019-08-19 | 2021-02-25 | 苏州科技大学 | Photonic crystal structure-based visualized heat accumulation indicator, manufacturing of same, and applications thereof |
| CN111816053A (en) * | 2020-07-21 | 2020-10-23 | 苏州善恩纳米功能材料科技有限公司 | Solid-state temperature-sensitive color-changing label |
| CN111816054A (en) * | 2020-07-21 | 2020-10-23 | 苏州善恩纳米功能材料科技有限公司 | Solid-state temperature-sensitive color-changing label |
| CN114664173B (en) * | 2022-03-14 | 2024-01-16 | 复旦大学 | Cold chain transportation visual photonic crystal time-temperature joint monitoring tag, preparation method and application |
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| GB2419401B (en) * | 2004-10-20 | 2009-04-22 | Sensor Highway Ltd | Differential optical fibre sensor |
| KR100953578B1 (en) * | 2009-08-05 | 2010-04-21 | 주식회사 나노브릭 | Printing medium, printing method and printing apparatus using photonic crystal characteristics |
| CN102504801A (en) * | 2011-10-20 | 2012-06-20 | 厦门浩添冷链科技有限公司 | Irreversible (37 DEG C) thermochromic developer and preparation method thereof |
| CN103354057B (en) * | 2013-08-08 | 2016-01-27 | 东南大学 | Responsibility mesoporous colloidal photon crystal anti-fake mark of gas and preparation method thereof |
| CN203772447U (en) * | 2013-12-16 | 2014-08-13 | 中国船舶重工集团公司第七二四研究所 | Discoloration detection label for cold chain |
| CN105424217B (en) * | 2015-11-23 | 2019-03-12 | 卢安迪 | The cryogenic temperature monitoring method and cryogenic temperature monitoring agent of Cold Chain Logistics |
| CN105601951B (en) * | 2015-12-28 | 2018-03-02 | 上海第二工业大学 | A kind of fast preparation method of gel photonic crystal |
| CN106408048B (en) * | 2016-09-06 | 2019-10-22 | 上海理工大学 | A kind of novel intelligent label and monitoring method for cold chain monitoring |
| CN106448438A (en) * | 2016-09-28 | 2017-02-22 | 同济大学 | Production method and application method of cold chain logistics temperature monitoring mark patches |
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