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Long-Lasting and Easy-to-Use Rewritable Paper Fabricated by Printing Technology Luzhuo Chen,*,†,‡,§ Mingcen Weng,†,‡,§ Feng Huang,†,‡,§ and Wei Zhang†,‡,§
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†
Fujian Provincial Key Laboratory of Quantum Manipulation and New Energy Materials, College of Physics and Energy, Fujian Normal University, Fuzhou 350117, China ‡ Fujian Provincial Collaborative Innovation Center for Optoelectronic Semiconductors and Efficient Devices, Xiamen 361005, China § Fujian Provincial Engineering Technology Research Center of Solar Energy Conversion and Energy Storage, Fuzhou 350117, China S Supporting Information *
ABSTRACT: Nowadays, urged by the high demand to reduce paper consumption, rewritable paper receives more and more attention. However, it is a great challenge to conveniently fabricate the rewritable paper which has long legible time of information and is easy to use simultaneously. Here, we report a new type of long-lasting rewritable paper based on color-memorizing thermochromic dye and photothermal-converting toner, which is fabricated by a two-step printing process. The rewritable paper demonstrates excellent rewriting performances (legible time > 6 months and reversibility > 100 times). The thermochromic effect is based on a temperature-driven phase change mechanism, accompanied by a lactone ring tautomerism of crystal violet lactone. The color of the rewritable paper rapidly changes from blue to colorlessness when the temperature is higher than 65 °C, and the colorless state can be maintained at room temperature. The color returns to blue when the temperature is lower than −10 °C. By using an electrothermal pen, a thermal printer, and near infrared (NIR) light, characters and images with high resolution can be handwritten, thermal-printed, and photoprinted on the rewritable paper. The written/printed information can be cleaned under lower temperature or can be quickly erased by NIR light. This rewritable paper is easy for large-scale production and will have promising opportunities in practical applications, such as long-lasting information recording and reading, rewritable label, reprintable displays, and so on. KEYWORDS: rewritable paper, thermochromic, printing technology, long-lasting, easy-to-use
1. INTRODUCTION
printed by ultraviolet light and can be erased when heated or exposed to oxygen in air. The erasure time can be 10 days in ambient conditions. Wang and co-workers fabricated a series of rewritable paper based on TiO2 nanoparticles.6−9 For example, they presented a new class of solid-state photoreversible color switching system by coupling the redox-driven color switching property of Prussian blue and its analogues nanoparticles with photocatalytic activity of TiO2 nanoparticles.7 The novel system has good rewriting performances (legible time > 5 days, reversibility > 80 times, and resolution > 5 μm). In a word, the reported rewritable systems represent new platforms for many practical applications involving temporary information recording and reading,4,7−9,20 various rewritable labels,5,8,21 security technology,22,23 and display.23,24 However, some problems need to be improved. First, the fabrication methods of
Although we live in a digital age, there is still a huge need for traditional printing materials. Unfortunately, most of the printing materials (e.g., posters) are only used for one-time reading before being disposed of, which leads to a huge environmental problem, such as solid waste and chemical pollution. Therefore, ink-free display and rewritable media are alternative approaches to solve the above problem. To date, there is some progress in this promising area, such as rewritable paper,1−9 thermochromic displays,10−13 photonic crystal materials,14−17 and shape memory polymers.18,19 Among them, the rewritable paper attracts intense interests of many researchers. Sun and co-workers designed a kind of rewritable paper based on the reversible discoloration reactions of polyoxometalates.4 The rewritable paper can keep handwritten and H2O2-jet printed letters with high resolution in ambient conditions for more than 3 months. Wei and coworkers reported a hybrid film by mixing tungsten oxide with polyvinylpyrrolidone.5 The rewritable media can be photo© XXXX American Chemical Society
Received: August 24, 2018 Accepted: October 25, 2018
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DOI: 10.1021/acsami.8b14625 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
Research Article
ACS Applied Materials & Interfaces
Figure 1. (a) Illustrations of reversible color-switching process of the thermochromic dye. (b) Schematic of the fabrication steps of the rewritable paper. (c) Optical images of the rewritable paper: thermochromic surface (left panel), toner surface (upper part of right panel), and thermochromic surface after being heated (>65 °C, lower part of right panel). (d) Cross-sectional SEM image of rewritable paper.
colored state exists in the ordinary temperature region, whereas the discolored (colorless) state merely maintains in a case that the material is exposed to the temperature higher than the color-switching temperature. Whitesides and co-workers proposed paper-based thermochromic displays. The thermochromic dye can change from colored state to translucent state, so as to show the paper underneath the dye.13 However, the thermochromic displays were not rewritable, which can only display predesigned information. Moreover, a continuous power was required to be applied to the device, in order to keep the information visible, which is energy-intensive. The rewritable paper proposed in this work is based on a kind of temperature-sensitive color-memorizing thermochromic dye (AKR67K01), purchased from Shanghai M&G Stationery Inc. It has been used in erasable pens. This kind of thermochromic dye is usually composed of a color former, a color developer, and a solvent. In this work, crystal violet lactone (CVL) is used as the color former. Phenolic compound (e.g., bisphenol A) is used as the developer, and aliphatic esters or aliphatic carboxylic acids are used as the solvent. The exact chemical compositions of the developer and solvent could not be obtained because they are trade secrets. However, the thermochromic mechanism is likely similar to other studies reported in the literature.28−34 The thermochromic effect is based on a temperature-driven phase change mechanism, accompanied by a molecular structure change of CVL. As shown in the left panel of Figure 1a, the thermochromic dye is in the colored state (blue color) at room temperature. When the thermochromic dye is heated over 65 °C, which is higher than the melting point of the solvent, the CVL and the developer are dissolved and separated in the solvent. At this time, the interaction between the CVL (electron donor) and the developer (electron acceptor) is blocked by the solvent molecule and the CVL turns to the ring-closed structure (Figure S1). Therefore, the color of the thermochromic dye changes from blue to colorlessness in 5 s, as shown in the right panel of Figure 1a. Furthermore, because the CVL and the developer are dissolved in the solvent, the solidification point of the mixture decreases. Hence, the thermochromic dye can keep the colorless state when the temperature returns back to
previously reported rewritable systems are relatively complicated and time-consuming.20,25−27 Second, the writing/ printing method of rewritable paper in many previous research studies is using ultraviolet light,4,5,7−9,21 which may not be convenient for users. Finally, many color-switching materials cannot maintain the colored/discolored state for a long time in ambient conditions. The legible time of information on the rewritable systems only lasts from several days5,7,9 to as long as 3 months,4 which is not long enough for information storage. Therefore, the rewritable system which can keep the information with long-lasting legible time is still a challenge. Here, we use a simple and low-cost printing technology to fabricate a new type of rewritable paper. It has a sandwich structure, consisting of a thermochromic layer, a photothermal layer, and a paper substrate. A layer of temperature-sensitive color-memorizing thermochromic dye is on one surface of the paper substrate, serving as the color-switching layer, whereas a layer of black toner is on the other surface of the paper substrate, serving as the heating layer to provide heat source for the thermochromic layer. After more than 100 colorswitching cycles, the thermochromic dye does not have observable color fading, which exhibits high durability. The rewritable paper can be handwritten with characters by using an electrothermal pen. It can also be directly printed with highresolution images by using a thermal printer. Moreover, it is able to be photoprinted by photomasks with near infrared (NIR) light irradiation. We also make a reprintable mobile phone shell as a demonstration of applications. The information can remain legible with very high resolution in ambient conditions for more than 6 months. This newly designed rewritable paper shows promising potentials for practical applications, such as long-lasting rewritable information recording and reading, rewritable label, reprintable displays, and so on.
2. RESULTS AND DISCUSSION Conventional thermochromic dye discolors when the temperature is higher than the color-switching temperature, and the color recovers to the original color when the temperature is lower than the color-switching temperature. Hence, only the B
DOI: 10.1021/acsami.8b14625 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
Research Article
ACS Applied Materials & Interfaces room temperature. When the thermochromic dye is cooled down to −10 °C, the CVL and the developer are recrystallized into the solid state and the interaction between them is recovered. The ring-closed structure of CVL returns to the ring-opening structure (Figure S1). Therefore, the color of the thermochromic dye returns back to blue color in 5 min (Figure 1a). In a word, the thermochromic dye used in this work can remain in the colored/colorless state at room temperature without being continuously applied with heat or any other power. Therefore, no energy is required to keep the written information on the rewritable paper, which is energy-saving. Herein, we fabricate the rewritable paper by using a fast and simple two-step printing method. Figure 1b schematically depicts the fabrication steps of the rewritable paper. First, the thermochromic layer with a thickness of 25 μm was printed on one surface of a piece of paper through a screen-printing method. Second, a laser printer was employed to directly print black toner on the other surface of the paper. Then, the photothermal layer with a thickness of 20 μm was formed. Finally, the rewritable paper with a total thickness of 105 μm was obtained. Experimental details are shown in the Experimental Section. The appearances of thermochromic layer (blue color or colorless) and photothermal layer (black color) are shown in Figure 1c. When the rewritable paper is heated over 65 °C, its color quickly turns to colorlessness. When the rewritable paper is cooled down to −10 °C, its color returns back to blue color. The fabricated rewritable paper shows great flexibility, as shown in Figure S2. The cross-sectional structure of the rewritable paper was observed by using a scanning electron microscope (SEM). As shown in Figure 1d, three layers in the rewritable paper are combined together tightly without delamination. The color-switching property of rewritable paper is attributed to the thermochromic layer, whereas the photothermal layer is served as an energy conversion layer which converts light power to heat. Hence, we mainly focus on the color-switching properties of the thermochromic layer. After fabrication step 1, a bilayer structure of thermochromic layer on the paper substrate was obtained. As shown in Figure 2a, the thermochromic layer (black line) had a strong absorption peak at ca. 610 nm, so it shows blue color. When it was heated over 65 °C, the strong absorption peak disappeared and its color changed from blue to colorlessness (red line of Figure 2a). When it was cooled down to −10 °C, the blue color appeared again together with the absorption peak (blue line in Figure 2a). The absorption spectrum of the plain paper is also shown in Figure 2a (magenta line) for comparison. The color-switching property based on the hysteresis characteristic of thermochromic dye was further studied. The paper with thermochromic layer was heated from room temperature (20 °C) to 80 °C and then cooled down to −20 °C. Finally, it returned to room temperature (20 °C). The measurement details are described in the Experimental Section. The temperature change progress is indicated by arrows in Figure 2b. The absorption intensities (wavelength of 550 nm) at each temperature are also shown in Figure 2b. It can be seen that when the temperature was higher than 65 °C, the thermochromic layer could keep the colorless state. During the temperature decreasing process, it still maintained a colorless state. Only after the temperature was lower than −10 °C, the thermochromic layer returned back to the colored state (blue color). Then, it kept the colored state (blue color) during the
Figure 2. (a) Absorption spectra of the thermochromic layer (black line), heated thermochromic layer (80 °C, red line), cooled thermochromic layer (−10 °C, blue line), and plain paper (magenta line). (b) Absorption spectrum showing the hysteresis characteristic of the thermochromic layer. (c) Absorption spectrum of the thermochromic layer during 100 heating/cooling cycles. (d) Temperature of the rewritable paper as a function of light power density.
temperature increasing process, until the temperature reached 65 °C. Hence, the thermochromic layer exhibits a wide hysteresis range caused by temperature changes, so that it can maintain the colored/colorless state at room temperature, which is the design fundamental of our rewritable paper. In order to study the repeatability of the thermochromic layer, its absorption intensity (at a wavelength of 550 nm) was measured over 100 cycles of heating and cooling processes. It shows no obvious decline (Figure 2c). Hence, the thermochromic process shows excellent reversibility and repeatability, which indicates that the thermochromic dye is suitable to be used as a color-switching component of the rewritable paper. Black toner is a daily-used printing material in laser printing. According to previous studies, the black toner is a complex mixture, generally including iron oxide, carbon black, charge control agents, polymers, resin, and inorganic/organic additives.35−37 When the black toner is printed on paper, the toner-coated paper strongly absorbs light ranging from visible to NIR wavelength (Figure S3). When the toner surface is irradiated by NIR light, the rewritable paper can be quickly heated, based on the photothermal effect. The temperature change of the rewritable paper was studied by irradiating NIR light (500 mW cm−2) on the toner surface of the rewritable paper. As shown in Figure S4, with the temperature increasing from room temperature (20 °C) to over 80 °C in 30 s, the photothermal layer was able to convert light power to heat. When the light was turned off, the temperature quickly decreased to 30 °C in 15 s. After that, the temperature slowly returned to room temperature (20 °C) in 75 s. The temperature stability during the heating and cooling cycling is important, as the color switching of rewritable paper is based on the thermochromic effect. Therefore, the temperature change of the rewritable paper was measured over 100 cycles. As shown in Figure S4, the temperature change tendency during the heating and cooling cycles C
DOI: 10.1021/acsami.8b14625 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
Research Article
ACS Applied Materials & Interfaces
tion, the writing/printing temperature must be higher than 65 °C. The thermal distributions of the rewritable paper were studied synchronously during NIR light irradiation. The infrared thermal images were captured by an infrared camera after NIR light irradiation for 30 s (Figure 3b). The thermal distribution is quite uniform on the surface of rewritable paper. The maximum temperature is higher than 80 °C, which satisfies the temperature threshold (>65 °C) to keep the colorless state. It can also be seen from Figure 3b that the temperature of the rewritable paper increases with the increase of input light power, which is in accordance with the results shown in Figure 2d. Considering the excellent color-switching performance of rewritable paper, a piece of rewritable paper (70 mm × 70 mm) was prepared to demonstrate the rewritable performances. As shown in Figure 4a, an electrothermal pen was used to handwrite English words and Chinese characters on the rewritable paper. The tip of the electrothermal pen can be heated up to a maximum temperature of 80 °C by an electrical
remained almost the same after 100 cycles, indicating excellent stability and repeatability. Moreover, the temperature control of the rewritable paper was studied by irradiating the toner surface with different intensities of light power. Figure 2d shows that higher light power results in higher temperature of the rewritable paper. It can be explained as follows. Higher light power leads to more light energy converting to thermal energy by the photothermal layer, resulting in higher temperature of the rewritable paper. The maximum temperature was 28.5 °C after the irradiation of low light power (50 mW cm−2), whereas the maximum temperature was up to 82.7 °C with the irradiation of high light power (500 mW cm−2). The obvious correlation between the light power and the temperature provides the possibility to obtain the desired temperature of the rewritable paper by adjusting the input light power. Therefore, Figure 2d also shows the temperature controllability of the rewritable paper. Finally, the thermochromic response of the rewritable paper to NIR light irradiation was investigated. The toner surface of rewritable paper was irradiated by different intensities of light power for 30 s. As the photothermal layer converts the light energy to thermal energy, the entire rewritable paper is heated, which leads to the color switching of the thermochromic layer, as presented in Figure 3a. When the rewritable paper was
Figure 3. (a) Thermochromic responses of rewritable paper (40 mm × 40 mm) irradiated by different intensities of light power for 30 s. (b) Infrared thermal images of the rewritable paper (40 mm × 40 mm) irradiated by different intensities of light power for 30 s.
irradiated by low power of light (50 mW cm−2) for 30 s, the rewritable paper showed a slight color switching (blue to colorlessness). The color-switching process was much obvious with the increase of light power. When the light power was increased to 500 mW cm−2, the rewritable paper completely changed to the colorless state. It should be noted that the color switching of the rewritable paper irradiated by low power of light (65 °C) is high enough to change the color of the thermochromic layer from blue to colorlessness. The colorless state can be maintained on the rewritable paper, even when the hot pen tip leaves the paper surface, which is defined as the “writing” process. On the other hand, the temperature of 80 °C is not too high to damage the rewritable paper. Hence, it is very easy to write information on the rewritable paper without using any chemical reagents. As shown in Figure 4b, we first handwrote characters on the rewritable paper by using the electrothermal pen. The written characters can keep for at least 6 months, as shown in Figure S5. Therefore, the rewritable paper also satisfies the need for long-lasting legible information storage. Two methods can be used to “clean” the written information on the rewritable paper. One method is called initializing, in which the rewritable paper is placed in a refrigerator with temperature lower than −10 °C. It takes about 5 min for the thermochromic layer to return to the initial blue color. Then, the users can rewrite information on the rewritable paper by using the electrothermal pen and initialize it under low temperature again (Figure 4b). The rewritable cycle can be up to more than 100 times. However, such a cleaning information method may be inconvenient for users, as the low-temperature environment (−10 °C) is not always convenient to be obtained and the cleaning time is a bit long. Therefore, the other cleaning method is provided, which is called the erasing method. As shown in Figure 4b, after the characters were written on the rewritable paper, the toner surface was irritated by NIR light (500 mW cm−2). The color of entire thermochromic layer turns from blue to colorlessness within 10 s, so that the written information can be erased quickly. Such a quick erasing process provides an alternative and fast cleaning way to improve the information privacy. If the users want to rewrite information on the rewritable paper, they can go through the initializing process again. Furthermore, taking advantage of thermal printing techniques, we can even print a paragraph of English words with excellent resolution on the rewritable paper by using a thermal printer (Figure 4c). In addition, a two-dimensional code (Figure 4d) and other complex images (Figure 4e−h) with very high resolution can also be printed on rewritable paper by using the thermal printer. Similarly, the printed images can be quickly erased by irradiating NIR light on the toner surface of the rewritable paper. After being initialized under low temperature, the rewritable paper is able to be printed repeatedly as well. In this way, the rewritable paper can be easily used in labels, express list, and temporary reading information. It is worth mentioning that in addition to thermal handwriting or printing letters and images on the rewritable paper, various images can also be photoprinted on it by NIR light irradiation through photomasks, which provides a contactless printing method. As a demonstration, a reprintable mobile phone shell is designed. The rewritable paper was fixed on a transparent mobile phone shell to form a reprintable mobile phone shell. The reprint process is schematically illustrated in Figure 5a. A photomask was placed upon the toner surface of the rewritable paper. When the NIR light was turned on for 30 s, the exposed regions of the photothermal layer were heated. Then, the corresponding regions of the thermochromic layer were also heated and the color turned
Figure 5. (a) Schematic illustration of photoprinting an image on a reprintable mobile phone shell by NIR light irradiation with a photomask. (b) Optical images of the mobile phone shell with different images. (c) Optical image of a photoprinted mobile phone shell setting on a mobile phone for practical usage.
from blue to colorlessness. In this way, the image on the photomask was photoprinted and transferred onto the rewritable paper. By using this method, clear images including patterns, characters, and numbers can be obtained, as shown in Figure 5b. Figure 5c shows that a photoprinted mobile phone shell is set on a mobile phone for practical usage. It should be noted that the printed images will not be self-erased in ambient conditions for at least 6 months, providing enough long time for daily use. After been initialized under low temperature, the reprintable mobile phone shell can be photoprinted with new images by NIR light for more than 100 times without losing in resolution. Hence, various customized products with personaldesigned patterns can be easily obtained by using our rewritable paper as a platform, which also provides fun for users.
3. CONCLUSIONS In summary, we report a new type of rewritable paper based on the color-memorizing thermochromic dye and photothermalconverting toner, which is fabricated by the printing technology. There are lots of advantages of our rewritable paper, compared with previously reported rewritable media. First of all, the proposed rewritable paper provides long legible time of information (>6 months), excellent reversibility (>100 times), and high resolution. Second, the writing/printing method is very easy. The characters and images can be written/printed by using an electrothermal pen, a thermal printer, and NIR light. These methods are all convenient to users in daily life, preventing the use of any chemical reagents. Third, the written/printed information can maintain over 6 months without color fading in ambient conditions, which is long enough for many practical applications involving information reading and storage. Finally, the simple fabrication method makes it possible for large-scale production. In addition, the rewritable paper can be further developed to have other colors by using different thermochromic dyes. For example, two kinds of rewritable paper with red color and black color are successfully fabricated (Figure S6). In a word, E
DOI: 10.1021/acsami.8b14625 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
Research Article
ACS Applied Materials & Interfaces Author Contributions
our rewritable paper overcomes several problems reported previously, such as short legible time, high toxicity and expensive price caused by complex synthesis of reversible color-switching materials, and so on. This new type of rewritable paper will show great potentials in many fields involving information recording and reading, various rewritable labels, reprintable displays, and so on.
L.C. contributed to all aspects of this study. M.W. contributed to the fabrication and characterization of the materials. F.H. and W.Z. contribute to part of characterization of the materials. The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes
The authors declare no competing financial interest.
4. EXPERIMENTAL SECTION
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4.1. Materials. Paper was commercial A4 print paper. The thermochromic dyes (blue: AKR67K01, red: AKR66231, black: AKR67K10) were purchased from Shanghai M&G Stationery Inc. Black toner (CE278A) was purchased from Hewlett-Packard Development Company, L.P. All materials were used without further pretreatment. 4.2. Fabrication of Rewritable Paper. The rewritable paper was fabricated by a two-step printing method. First, the thermochromic layer was fabricated through a screen-printing method. The thermochromic dye was directly cast onto the A4 paper with a paintbrush. In screen-printing, a nylon sheet (∼0.1 mm) was served as a shadow mask. By back-and-forth printing, the thermochromic layer was printed on the paper. After drying in ambient conditions for 1 h, a homogeneous thermochromic layer was obtained. Second, the photothermal layer was fabricated by using a laser printer (HP LaserJet 1536dnf MFP) to directly print black toner on the other surface of the paper. Finally, the rewritable paper was obtained. The rewritable paper can resist temperature over 180 °C. 4.3. Characterization and Measurement. SEM images were captured by a field emission SEM (Hitachi SU8010). In the hysteresis characteristic test, the sample was placed on a hot plate to obtain temperature higher than room temperature (20 °C). It was placed in a refrigerator to obtain temperature lower than room temperature (20 °C). The sample was placed at each temperature for 5 min. Then, it was placed in ambient environment at room temperature for another 5 min. After that, the absorption spectrum of the thermochromic layer was measured. The absorption spectra were measured by a UV/vis/ NIR spectrometer (PerkinElmer LAMBDA 950). All optical images were captured by a digital camera (SONY ILCE 6000). A NIR light source (Philips BR125) was used for light irradiation. The light power density was measured by an infrared power meter (Linshang LS122A). The temperature was recorded by a laser sight infrared thermometer (Optris LS) with a temperature resolution of 0.1 °C. The temperature data were obtained from the thermochromic surface of the paper. An infrared thermal imager (Fluke Ti10) was used to characterize the thermal distribution of the rewritable paper.
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ACKNOWLEDGMENTS This work was jointly supported by National Natural Science Foundation of China (51773039 and 11504051), Natural Science Foundation of Fujian Province for Distinguished Young Scientists (2017J06014 and 2018J06001), and Projects for Young Scientists in University Funded by the Education Department of Fujian Province (JZ160428).
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ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.8b14625.
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REFERENCES
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Structure change of the CVL; optical image showing the flexibility of the rewritable paper; absorption spectra of the toner-coated paper and the plain paper; temperature of the rewritable paper as a function of time when irradiated by NIR light (500 mW cm−2); optical images of the rewritable paper after different times; and optical images of the rewritable paper with other colors (red and black) (PDF)
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Luzhuo Chen: 0000-0003-4823-0748 F
DOI: 10.1021/acsami.8b14625 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
Research Article
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DOI: 10.1021/acsami.8b14625 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
