Photonic Watermark on Banknotes
Journal: Journal of Materials Chemistry C
Manuscript ID: TC-ART-11-2013-032228.R1 Article Type: Paper
Date Submitted by the Author: 06-Jan-2014
Complete List of Authors: hu, haibo; University of Science and Technology of China,
Zhong, Hao; University of science and technology of China,
Chen, Changle; University of Science and Technology of China, CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering
Chen, Qianwang; University of science and technology of China,
Journal of Materials Chemistry C
6.10
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UNIVERSITY OF SCIENCE AND TECHNOLOGY OF CHINA https://www.doczj.com/doc/c317009410.html,
Dear Editor Frey:
Thank you for your and the two Reviewers’ efforts in the review of our manuscript entitled “Photonic Watermark on Banknotes ” (Manuscript ID TC-ART-11-2013-032228) for consideration as a paper in Journal of Materials Chemistry C . We are very grateful that the two reviewers have raised some valuable comments leading to the improvements of the paper. We have carefully read the reviewers’ comments and revised our manuscript according to their suggestions. The detailed responses to the comments from the Reviewers are listed as follows. We are now submitting our revised manuscript to you. We hope that you and the reviewers will satisfy our revisions.
The purpose of Journal of Materials Chemistry C to publish the original and meaningful research rapidly has been accepted extensively. Here we promise that the article is original and unpublished elsewhere. I would be grateful if the manuscript could be considered for publication in Journal of Materials Chemistry C . Thank you very much for your more attention to our paper. If any questions arise, please feel free to inform us by e-mail.
Best wishes, Sincerely,
Dr. Haibo Hu Jan. 6, 2014
Haibo Hu
Hefei National Laboratory for Physical Science at Microscale
University of Science & Technology of China Hefei 230026, P. R. China
E-mail: haibohu@https://www.doczj.com/doc/c317009410.html, Tel: +86-551-63607251 Jan. 6, 2014
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Answer to the comments made by the reviewer:
Referee: 1
Comments:
The authors demonstrated anti-counterfeiting on banknotes using magnetic-responsive photonic watermark. This work gives us a vivid example and can promote the application of magnetic-responsive photonic crystals in the field of anti-counterfeiting. I would recommend the publication of this manuscript pending a few minor revisions:
Answer: Thanks for the reviewer’s helpful comments. Your valuable opinions deserve our great attentions and will help us to significantly improve our paper. According to your opinions, the manuscript has been revised and the modified part was marked by red in the revised manuscript. We hope that you will satisfy our revisions. Finally, thank you again for your helpful comments on our paper.
Issue (1) Materials are suggested to be included in the title.
Answer: Thanks for the reviewer’s helpful comments. According to your opinion, materials have been included in the title, which has been changed to “Magnetically Responsive Photonic Watermark on Banknotes”.
Issue (2) As we know, banknotes will be used many times by different people during long-period circulation. I am wondering how long and how many times the photonic watermark can be used.
Could the authors give an assessment?
Answer:Thanks for the reviewer’s very professional comments. Indeed, as the reviewer say, banknotes will be used many times by different people during long-period circulation and the durability of anti-counterfeiting devices is important for their potentially practical applications. First of all, the P-watermark has good stability during a short period of time. Please see the Figure 8 and page 12. As shown the Figure 8,
a P-watermark containing invisible photonic prints was orderly folded, twisted, pressed and thermally treated
under 70℃ for one hour (The normal temperature of the environment, at which the banknotes are used, does
not exceed 70 degrees Celsius), and then was applied to a magnetic field. We can clearly see that the invisible photonic prints can still be released by a magnet immediately (Figure 8d, f, h, i). The results further clearly demonstrated the stability of the P-watermark. In addition, the results indirectly indicate that the glycol micro-droplets cannot leak in severe environment such as high temperature or mechanical force (folding, pressing or twisting) and only the UV light can induce chain scission of the PDMS macromolecules, resulting in the shrinkage and rapture of PDMS networks.
However, the long-time durability of the magnetically responsive photonic watermark is not very good, and the activity of the magnetically responsive photonic watermark can maintain for about one week. We think the reason is that ethylene glycol slowly evaporates through the PDMS layer that is a gas-permeable membrane and eventually, the magnetic particles will lose the liquid environment and cannot assemble anymore. We have two methods to circumvent this problem. First, if we seal the banknote in 0.17mm thin glasses (the glasses were sealed together with PDMS), the P-watermark is stable for more than 6 months. Second, we are currently working with high boiling point solvent to substitute ethylene glycol, so that the solvent will not evaporates easily.
The magnetically responsive photonic watermark is still in the proof-of-concept stage and a lot of work is still needed for devising appropriate encapsulation layers to make the P-watermark more stable and commercially viable. However, these results indicate that the fabrication of responsive photonic crystals based anti-counterfeiting devices on banknotes is possible. We will make a further detailed study to improve the durability of the magnetically responsive photonic watermark in the subsequent research.
Issue (3) Could the author give us the meaning of “crypticity” in the last paragraph?
Answer: Thanks for the reviewer’s helpful comments. The word “crypticity” in the last paragraph has been replaced by the word “security”. The modified part was marked by red in the revised manuscript.
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Issue (4) Figures are not well organized. Authors should pay more attention to the annotations, for example, (a), (b), and (c) should appear for the three figures. Also, figures captions should be double checked carefully.
Answer: Thanks for the reviewer’s helpful comments. Your valuable opinions deserve our great attentions and will help us to significantly improve our paper. According to your opinions, the Figures in the manuscript have been reorganized and the figures captions also have been checked carefully. The modified part was marked by red in the revised manuscript. We hope that you will be satisfied with our revisions.
Finally, thank you again for all of your comments on our paper.
Referee: 2 Comments:
The manuscript demonstrated a method of fabricating photonic-crystals-based anti-counterfeiting patterns on banknotes. These photonic crystals patterns are lithographically printable, magnetically responsive and can be easily perceived by naked eyes. However, Ref. 34 published in Sci. Rep.(DOI:10.1038/srep01484) and other papers from the same group have introduced this fabrication method (this technique has been named as “invisible photonic printing”). They have already investigated the mechanism and demonstrated its use in constructing structure color patterns. The authors showed an application of these photonic-crystals-based anti-counterfeiting patterns on banknotes. Some other works about photonic crystals for security materials are also need to be noticed, particular applications towards banknotes anti-counterfeiting (such as Chem. Mater., 2013, 25, 2684). Therefore, the reviewer suggests the authors should better highlight some scientific novelty or technique improvements in this paper, particularly compared with their previous published works. Answer: Thanks for the reviewer’s helpful comments. Your valuable opinions deserve our great attentions and will help us to significantly improve our paper. According to your opinions, the manuscript has been revised and the modified part was marked by red in the revised manuscript (Please see the Page 2-4). We hope that you will be satisfied with our revisions. Finally, thank you again for your helpful comments on our paper.
Moreover, the pattern mechanism is that the photonic-display-layer can be easily destructed under UV irradiation. UV light induce chain scission of the PDMS macromolecules, resulting in the shrinkage and rapture of PDMS networks, therefore causing the leakage of the glycol solution in the micro-droplets among the solidified PDMS polymer matrix. Are there any other factors that can also induce the shrinkage of PDMS? For example, high temperature, oxygen in air or mechanical force (folding,
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pressing or tearing…)? Some related experiment is missing to ensure the glycol micro-droplets cannot leak in severe environment.
Answer: Thanks for the reviewer’s very professional comments. According to your opinions, some related experiments had been carried out and added in the revised manuscript. The modified part was marked by red in the revised manuscript. Please see the Figure 8 and page 12. As shown in the Figure 8, a P-watermark containing invisible photonic prints was orderly folded, twisted, pressed and thermally treated under 70℃ for one hour (The normal temperature of the environment, at which the banknotes are used, does not exceed 70 degrees Celsius), and then was applied to a magnetic field. We can clearly see that the invisible photonic prints can still be released by a magnet immediately (Figure 8d, f, h, i). The results further clearly show the stability of the P-watermark. In addition, the results indirectly indicate that the glycol micro-droplets can not leak in severe environment such as high temperature or mechanical force (folding, pressing or twisting) and only the UV light can induce chain scission of the PDMS macromolecules, resulting in the shrinkage and
rapture of PDMS networks.
Figure 8
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The reviewer doubted the endurance of this P-watermark, which will hinder their general application on banknote.
Answer: Thanks for the reviewer’s very professional comments. Indeed, as the reviewer say, banknotes will be used many times by different people during long-period circulation and the durability of anti-counterfeiting devices is important for their potentially practical applications. First of all, the P-watermark has good stability during a short period of time. Please see the Figure 8 and page 12. As shown the Figure 8, a P-watermark containing invisible photonic prints was orderly folded, twisted, pressed and thermally treated under 70℃ for one hour (The normal temperature of the environment, at which the banknotes are used, does not exceed 70 degrees Celsius), and then was applied to a magnetic field. We can clearly see that the invisible photonic prints can still be released by a magnet immediately (Figure 8d, f, h, i). The results further clearly demonstrated the stability of the P-watermark. In addition, the results indirectly indicate that the glycol micro-droplets cannot leak in severe environment such as high temperature or mechanical force (folding, pressing or twisting) and only the UV light can induce chain scission of the PDMS macromolecules, resulting in the shrinkage and rapture of PDMS networks.
However, the long-time durability of the magnetically responsive photonic watermark is not very good, and the activity of the magnetically responsive photonic watermark can maintain for about one week. We think the reason is that ethylene glycol slowly evaporates through the PDMS layer that is gas-permeable membrane and eventually, the magnetic particles will lose the liquid environment and cannot assemble anymore. We have two methods to circumvent this problem. First, if we seal the banknote in 0.17mm thin glasses (the glasses were sealed together with PDMS), the P-watermark is stable for more than 6 months. Second, we are currently working with high boiling point solvent to substitute ethylene glycol, so that the solvent will not evaporates easily.
The magnetically responsive photonic watermark is still in the proof-of-concept stage and a lot of work is still needed for devising appropriate encapsulation layers to make the P-watermark more stable and commercially viable. However, these results indicate that the fabrication of responsive photonic crystals
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based anti-counterfeiting devices on banknotes is possible. We will make a further detailed study to improve the durability of the magnetically responsive photonic watermark in the subsequent research. Finally, thank you again for your comments on our paper.
Magnetically Responsive Photonic Watermark on Banknotes
1
Haibo Hu,a Hao Zhong,b Changle Chen,*c Qianwang Chen,*a
2
3
High performance photonic anti-counterfeiting watermark that can be incorporated 4
into banknotes has been developed by combining a novel invisible photonic printing 5
with flexible, translucent and ultra-thin magnetic-responsive photonic display film. 6
The photonic anti-counterfeiting watermark has latent colourful patterns that are 7
lithographically printable and magnetically responsive, and can be easily perceived by 8
naked eyes under magnetic fields. In addition, the distinct differences of the spectral 9
characteristics between the invisible-form and visible-form of the patters can be 10
accurately detected by special optical instrument, which makes the photonic 11
anti-counterfeiting watermark provide double security information to identify the 12
authenticity of banknotes. Moreover, the strategy allows accurate control of the 13
optical diffraction colour and the structural design of the latent patterns. The 14
fabrication process does not damage the banknotes and allows fast, convenient and 15
scalable production at low-costs. The present work demonstrates that the fabrication 16
of high performance photonic-crystals-based anti-counterfeiting devices on banknotes 17
is possible.
18
19
20
21
22
23
24
25
26
a Hefei National Laboratory for Physical Sciences at Microscale and Department of Materials
Science & Engineering, University of Science and Technology of China, Hefei, 230026, China.
E-mail: cqw@https://www.doczj.com/doc/c317009410.html,; Fax: +86-551-63603005; Tel: +86-551-63607251
b Department of Materials of Science and Engineering, University of Science and Technology of
China, Hefei, 230026, China
c CAS Key Laboratory of Soft Matter Chemistry an
d Department of Polymer Scienc
e and
Engineering, University of Science and Technology of China, Hefei, 230026, China.E-mail: changle@https://www.doczj.com/doc/c317009410.html, Page 10 of 26
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1. Introduction
1
To prevent forgery, modern banknotes utilize more than 50 different 2
anti-counterfeiting measures, including watermarks, holograms, raised printing, 3
fluorescent ink and embedded foil strips. However, banknote counterfeiting still 4
remains a serious global problem. The fast development and generalization of 5
high-resolution equipment, such as digital cameras, scanners, and printers, 6
continuously enhance counterfeiting technologies and make anti-counterfeiting 7
process more and more difficult. As such, scientists and engineers have been 8
dedicated to developing new anti-counterfeiting materials and innovative technologies 9
to be incorporated in the banknotes.1-5
10
Photonic crystals (PCs),6,7artificial materials with periodic modulation in
11
refractive index, can be used to manipulate and control light because their photonic
12
band gap forbids the propagation of electromagnetic waves in a certain frequency
13
range.Since their inception, they have been envisioned for a range of applications
14
such as optical filters, switches, cavities, waveguides, design of low-threshold lasers
15
and highly efficient light emitting diodes.8PCs with a tunable photonic band gap in
16
the visible and near infrared regions can display exceptionally bright and brilliant
17
re?ected colours arising from coherent Bragg optical diffraction,9 which can be easily
18
perceived by the naked eye or detected by special photoelectric devices. Moreover,
19
the optical signals of these responsive PCs can be easily tuned by external stimuli,
20
making them highly useful for a wide range of practical applications including color
21
displays,10-14 bio- and chemical sensors,15-19security devices,20,21photonic printing
22
systems22-26and photonic paper and ink.27-29Since optical feature could be an
23
effective security device that the general public could easily recognize, responsive
24
PCs are very promising banknote anti-counterfeiting materials due to their unique
25
optical properties.
26
However, integration of responsive PCs on banknotes to realize the photonic
27
anti-counterfeiting still faces great challenges due to the following difficulties. First,
28
to be incorporated into the banknotes, the anti-counterfeiting materials should have
29
access to ultra-thin and homogeneous oriented film with excellent flexibility, adhesion
30
to paper substrate and impermeability to water or organic solvents. In addition, the
31
anti-counterfeiting materials should not affect human health during the production and
32
circulation processes. Finally, an essential element for realizing photonic
33
anti-counterfeiting on banknotes is a reliable invisible identifying information input
34
technology that can effectively load latent patterns and text messages to provide the
35
prerequisite identification information, which can be easily recognized by general
36
public with convenient and non-toxic means and also detected by professionals with
37
portable instrument.
38
Recently, Shin-Hyun Kim et. al. demonstrated a novel colloidal photonic crystals 1
anti-counterfeiting device on banknotes, which are fabricated through shear-induced 2
crystallization of repulsive colloids, and UV-induced photopolymerization enabled the 3
rapid solidi?cation and micropatterning of the crystal structure through 4
photolithography.30The multiple photolithography steps produced multicolored 5
photonic crystal micropatterns, which provide high selectivity in optical identi?cation, 6
thereby being potentially useful for preventing counterfeiting on banknotes.
7
This technique elegantly realized the photonic anti-counterfeiting on banknotes. 8
However, to our knowledge, no reports exists on responsive photonic crystals 9
anti-counterfeiting devices, in which the previously invisible photonic crystal patterns 10
can be conveniently released by simple and non-toxic means and be easily recognized 11
by general public. Therefore, there is still a need to develop a practical technique to 12
produce responsive photonic crystals anti-counterfeiting devices on banknotes.
13
In this respect, we have been engaged in ongoing efforts at developing practical 14
responsive photonic anti-counterfeiting device. We recently reported the synthesis of a 15
novel photonic anti-counterfeiting device using structural colors derived from 16
magnetic-responsive photonic crystals with double photonic bandgap 17
heterostructures.21 Although the fabricated photonic crystal patterns can be 18
transformed between the invisible state and visible state by application or withdrawal 19
of a magnet, it is difficult to prepare freestanding films that can firmly stick on the 20
paper and realize the optionally input of anti-counterfeiting information due to the 21
complicated fabrication procedures and the required block template of fabricating 22
photonic crystal patterns. These drawbacks severely limit the practical utility of such 23
photonic anti-counterfeiting device on banknotes. Then we further developed a novel 24
invisible photonic printing which can optionally and simply load magnetically 25
responsive photonic patterns in a photonic paper. The previously loaded latent 26
photonic patterns can be immediately released by a magnet, which can be easily 27
perceived by naked eyes and detected by special instrument. However, an obvious 28
flaw remains. The used photonic paper is too thick (more than 1000 μm) to be 29
integrated into the banknote. In addition, the flexibility of the photonic paper is not 30
very ideal for banknote anti-counterfeiting.
31
Herein, we present a novel “photonic anti-counterfeiting watermark 32
(P-watermark)” technique for integration of responsive PCs on banknotes to realize 33
the responsive photonic anti-counterfeiting based on our previous reports. The 34
P-watermark is an ultra-thin and translucent polymer film containing latent photonic 35
prints, which has good flexibility and can firmly adhere to the banknotes. The 36
P-watermark technique enables optional input of invisible photonic prints contained in 37
the P-watermark utilizing UV printing and simple pattern design software on a 38
personal computer. The showing of the pre-hidden latent photonic prints is 39 Page 12 of 26
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instantaneous, and the only required instrument is a magnet, which is easy to obtain 1
and harmless to human body. Under magnetic fields, the immediately released 2
photonic prints can be easily perceived by naked-eyes, which allows ordinary people 3
to quickly identify the authenticity of banknotes. Meanwhile, the distinct differences 4
of the spectral characteristics between the invisible-form and visible-form can be 5
accurately detected by special optical instrument, which allows professionals to 6
further verify the authenticity of banknotes. In this way, the P-watermark itself can 7
provide double security information. Finally, the P-watermark fabrication process 8
does not damage the banknotes and offer the potential for fast, convenient and 9
scalable production at low-costs. With these superior features, the P-watermark will
10
attract a wide range of research interests from both academia and industry, and find
11
broad applications in many fields including banknotes anti-counterfeiting.
12
2. Experimental section
13
2.1 Materials
14
Ferrocene (Fe(C5H5)2,≥98%), hydrogen peroxide (H2O2, 30%), and acetone(C3H6O,
15
≥99%), ethylene glycol(C2H6O2, ≥99%) were of analytic grade from the Shanghai
16
Chemical Factory, China. PDMS (Sylgard 184) was purchased as a two-component
17
kit that contained the vinyl-terminated base and curing agent from Dow Corning. All
18
chemicals were used as received without further purification.
19
2.2 Synthesis of monodisperse carbon-encapsulated superparamagnetic colloidal
20
nanoparticles with different average particle size
21
In a typical synthesis,21ferrocene (0.30 g) was dissolved in acetone (30 ml). After
22
intense sonication for 30 min, hydrogen peroxide (1.00, 1.50, and 2.00 ml) was slowly
23
added into the above mixture solution, which then was vigorously stirred for 30 min
24
with a magnetic stirring apparatus. After that, the precursor solution was transferred to
25
the Teflon lined stainless autoclave with a total volume of 50.0 ml and then heated to
26
and maintained at 210°C. After 72 h, the carbon-capped superparamagnetic colloidal
27
nanoparticles with average particle size 190 nm, 135 nm, 115 nm were obtained
28
respectively as shown in the Figure 1. Synthesized superparamagnetic colloidal
29
nanoparticles were initially dispersed in acetone. Then these superparamagnetic
30
colloidal nanoparticles were collected by magnetic separation, and re-dispersed in
31
glycol solution (10 mg/ml) respectively for further use.
32
33
34
35
1
Figure 1.Representative TEM images of the obtained uniform carbon-capped 2
superparamagnetic colloidals nanoparticles at the same magnification. The average 3
diameters of these nanoparticles, obtained by measuring about 100 clusters for each 4
sample, are (a), (d) 190 nm; (b), (e) 135 nm and (c), (f) 115 nm.
5
6
2.3 Fabrication of photonic anti-counterfeiting watermark
7
Prior to photonic anti-counterfeiting watermark fabrication, the banknote was cleaned 8
with acetone and deionized water and dried at 80° C for 5 min. Blank PDMS (Dow 9
Corning Sylgard 184) prepolymer was mixed in a10:1 ratio with the curing agent and 10
then spun onto a planar, transparent PET foil (2 cm×2 cm×100 μm) at 1000 rpm for 11
20 s to get the first 80 μm thick protective layer. It was left to cure at room 12
temperature for 1 h to minimize bubbles or pinholes formation, and was annealed at 13
60° C for 2 h. Then 0.5 ml glycol containing 5 mg of carbon-encapsulated 14
superparamagnetic colloidal nanoparticles (CNPs) was mixed with 2.0 g Sylgard 184 15
and 0.4 g curing agent. After intense mechanical agitation for 5 min, the viscous 16
mixture was spun onto above obtained first protective layer with a spin rate varying 17
between 500 and 1000 rpm and with two spin times, 10 and 15 s to get a 80 μm thick 18
second photonic display layer, which was left to cure at 60°for 2 h. Once cured, 19
based on our previously reported invisible photonic printing technique, a two-step 20
process was used to generate the invisible photonic prints on the obtained photonic 21
display layer to form the latent magnetic-responsive photonic watermark. First, 22
graphics designed on a personal computer were printed on a transparent slide with 23
common office laser printer. Then, as a photomask, the printed slides were sealed to 24
the second photonic display layer under the UV-irradiation for 30 minutes and peeled 25
off after the irradiation. Finally, the second photonic display layer was coated with a 26
layer of blank PDMS prepolymer by spin coating method again. It was transferred 27
onto the target area of the banknote substrate and left to cure at 60°for 2 h to 28 Page 14 of 26
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complete the whole process. The fabrication steps of photonic anti-counterfeiting 1 watermark on banknote are illustrated in Figure 2. An NdFeB permanent magnet with 2 center magnetic field of 0.05 T was used to generate a magnetic field, which was 3 attached to the back of the P-watermark to reveal the latent photonic prints.
4
5 Figure 2. Schematic illustration of the procedure to fabricate photonic watermark on
6 banknote 7
8 2.4 Characterizations
9 Field emission scanning electron microanalysis (FESEM) was taken on a JEOL 10 JSM-6700F Field emission scanning electron microanalyser. Transmission electron 11 microscopy (TEM) images were obtained on Hitachi H-800 transmission electron 12 microscope, using an accelerating voltage of 200 kV . A Panasonic DMC-FX3 digital 13 camera was used to capture the photos of photonic prints illuminated by ordinary 14 electric light. The Fourier transform infrared spectrum (FT-IR) was obtained using a 15 Magna-IR 750 spectrometer in the range of 700-1400 cm -1 with a resolution of 4 cm -1. 16 The transmittance spectra were measured using a DUV-3700 spectrometer in the 17 range of 300-800 nm with a resolution of 0.10 nm. The photos were taken without 18 ?ash light to present the actual visual image. The reflection spectra were all measured 19 by using a fiber optic spectrometer (Ava Spec-2048, Avantes) with incident and 20 reflection angles of 0 °.
21 3. Results and discussion
22 As is illustrated in Figure 3a, the P-watermark has a three-layer structure and the 23 first layer is the blank polydimethylsiloxane (PDMS) elastomeric polymer film (~80 24 microns thick) served as an inactive protective layer that is transparent. The second 25 layer called photonic-display-layer is fabricated by depositing liquid PDMS 26 prepolymer containing uniformly dispersed micro-droplets of the glycol solution of 27 carbon-encapsulated superparamagnetic colloidal nanoparticles (CNPs) on the first 28 layer with spinning coating method followed by thermal curing of the composite 29 polymer film. Because it contains a large number of CNPs, this layer is pale brown 30 (the intrinsic color of the CNPs) and translucent (Figure S1a, S1c, S1e). Under an
31
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external magnetic ?eld, this layer can immediately display brilliant color (Figure S1b, 1
S1d, S1f) as the CNPs dispersed in each glycol micro-droplets are assembled into 2
one-dimensional photonic crystal structures along the magnetic field lines and 3
strongly diffract different visible light depending on the average particle size (Figure 4
1).31-33 Control experiment showed that the thickness of the second 5
photonic-display-layer has very little effect on its reflectivity when the thickness 6
increases from 81 to 343 microns. As the thickness of the photonic-display-layer 7
increases, the reflectance does not greatly increase (Figure 4a). However, there is an 8
obvious decrease in the light transmittance in the visible range with increasing 9
thickness (Figure 4b). This is mainly due to the increasingly intense light scattering 10
induced by the more and more CNPs in the second photonic-display-layer as the 11
thickness increases. As a result, even if the thickness of the second 12
photonic-display-layer increases, deeper part of the photonic-display-layer can not 13
participate in the reflection of visible range of light wavelength because the visible 14
light cannot reach the deeper part of the photonic display layer. So it is very difficult 15
to obtain a photonic-display-layer possessing both high transmittance and reflectivity.
16
Based on these considerations, 80 microns thickness was chosen, with which the 17
reflectivity is easy (more than ten per cent) to be perceived by naked-eyes and 18
detected by a fiber optic spectrometer (Ava Spec-2048, Avantes). In addition, the light 19
transmittance with this thickness can reach 18% at a wavelength of 550 nm (Figure 20
4b), which is translucent and allows us to clearly see the patterns under the photonic 21
display layer. (Figure S1). This is very valuable for the purpose of anti-counterfeiting.
22
Due to the strong adhesion at PDMS–PDMS interface, the second 23
photonic-display-layer can firmly adhere to the first inactive protective layer when it 24
is cured. The third layer is also blank PDMS elastomeric polymer film, which is 25
served as a “glue” layer to bond the double-layer flexible photonic display film to the 26
paper substrate which is un-flat. A key feature of the PDMS pre-polymer is that it 27
penetrates deep into the ?bers of substrates such as papers, providing strong adhesion 28
without chemical bonding after curing.4,34
29
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1 Figure 3. (a) Cross-sectional scanning electron microscopy image of a paper with a
2 completed P-watermark, (b) Obtained optical microscopy image of a cross-section
3 of a paper with a completed P-watermark under a vertically aligned external
4 magnetic field. (c), (d), (e), (f) Photographs of a 20-Euro banknote with a completed
5 P-watermark; (e) latent graphics on photonic watermark without an external
6 magnetic field and (f) latent graphics revealed by an external magnetic field 7
8
9 Figure 4. (a) Plot of reflectance versus wavelength for the second 10 photonic-display-layer with different thickness, (b) Plot of transmittance versus 11 wavelength for the second photonic-display-layer with different thickness. 12
13
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Figure 3c-f demonstrated the incorporation of a completed P-watermark into the 1 banknotes without any damage. The pictures of the completed P-watermark on a 2 20-Euro banknote, under no external magnetic field (Figure 3e), and 0.05T external 3 magnetic field (Figure 3f) are shown to demonstrate its superior features. The 4 P-watermark was translucent (Figure 3e) and we can clearly see the patterns of the 5 banknote (Figure 3f), covered under the P-watermark. Under a vertical magnetic field, 6 the prior-printed colorful mark (20) is revealed due to the vastly different re?ection 7 wavelength contrast between the background and the prints (Figure 5). This process is 8 instantaneous and requires only a magnet that is easy to obtain and harmless to human 9 body. The technology-intensive preparation methods of the P-watermark make it more 10 difficult, time-consuming, and costly for the counterfeiter.
11
12 Figure 5. Representative reflection spectra taken from latent photonic watermark, 13 revealed photonic watermark and background of the P-watermark containing 14 carbon-capped superparamagnetic colloidals nanoparticles with average particle size 15 (a) 190 nm, (b) 135 nm and (c) 115 nm. 16
17 The key point of this work is the fabrication of latent, multi-colored and 18 magnetic-responsive photonic watermark that can be easily recognized by general 19 public and also detected by professionals with portable instrument on the second 20 photonic-display-layer using our recently developed invisible photonic printing 21 technique.35 According to our previous report, intense UV-irradiation will induce 22 chain scission of the PDMS macromolecules in the irradiated surface region, 23 involving both the main chain backbone and the side groups, leading to the formation 24 of new Si-O-Si bonds on the exposed areas. This silica-like structure is denser and 25 more compact, resulting in the shrinkage and rapture of PDMS networks. This process 26 eventually induced the irreversible breakage of the glycol micro-droplets in the 27 solidified PDMS matrix, and led to the destruction of the magnetically responsive 28 photonic activities of the irradiated area of the second photonic-display-layer due to 29 the loss of glycol liquid medium that is required for the dynamic assembly of the 30 CNPs. Figure 3b is an optical microscopy image of the cross-section of a P-watermark 31 on a paper under a vertical magnetic field. Clearly, the UV-irradiated region no longer 32 produced a color change under external magnetic field. In contrast, the shielded 33 regions can still strongly diffract brilliant optical colors and the magnetic-responsive
34
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photonic activity is maintained. Figure 6a and 6c are scanning electron microscopy 1 (SEM) images of the irradiated surface region of the second photonic-display-layer. 2 After UV-irradiation, the PDMS polymer matrix in the irradiated surface region was 3 wrinkled and tended to rupture. However, the PDMS polymer matrix in the shielded 4 surface region was relatively smooth with no obvious cracks (Figure 6b and 6d). 5 Figure S2 is the Fourier transform infrared spectrum (FTIR) of the second 6 photonic-display-layer with different UV-irradiation time, which clearly indicate a 7 noticeable decrease in the –CH 3 signals with increasing exposure time. 8 Simultaneously, the shape of Si–O bond absorption peak was changed, indicating the 9 structure transformation from CH 3–Si–O– fragments to –O–Si–O– network.36,37 All of 10 the above results are fully consistent with our previous reports and clearly illustrate 11 that intense UV-irradiation can effectively destroy the magnetic-responsive photonic 12 activity of the exposed region.
13
14 Figure 6. Scanning-electron micrographs of surface of the second
15 photonic-display-layer, (a, c): irradiated region; (b, d): unirradiated region
16
17 In the preparation process, a common transparent slide with printed-graphics 18 designed on a computer was used as a photo-mask to partially block the 19 UV-irradiation. At the end of irradiation (Spectroline SB-100P, 365 nm, 4800 20 μW/cm -2), the exposed regions underwent a permanent change and lose the 21 magnetic-responsive photonic activity as a consequence of the irreversible breakage 22 of the ethylene glycol droplets. In contrast, the shielded regions still possess the 23 magnetic-responsive photonic activity and can display a colorful pattern under 24 magnetic field. Since the patterns printed on the slide can be easily designed with 25 simple computer software, this system offers great control over the latent patterns 26 printed on the second photonic-display-layer. In addition, the optical diffraction color
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in，on，at的时间用法和地点用法 一、in, on, at的时间用法 ①固定短语： in the morning/afternoon/evening在早晨/下午/傍晚, at noon/night在中午/夜晚, （不强调范围，强调的话用during the night） early in the morning=in the early morning在大清早， late at night在深夜 on the weekend在周末（英式用at the weekend在周末，at weekends每逢周末） on weekdays/weekends在工作日/周末， on school days/nights在上学日/上学的当天晚上， ②不加介词 this, that, last, next, every, one, yesterday, today, tomorrow, tonight，all，most等之前一般不加介词。如， this morning 今天早晨 （on）that day在那天（that day更常用些） last week上周 next year明年 the next month第二个月（以过去为起点的第二个月，next month以现在为起点的下个月） every day每天 one morning一天早晨 yesterday afternoon昨天下午 tomorrow morning明天早晨 all day/morning/night整天/整个早晨/整晚（等于the whole day/morning/night） most of the time （在）大多数时间 ③一般规则 除了前两点特殊用法之外，其他≤一天，用on，＞一天用in，在具体时刻或在某时用at（不强调时间范围） 关于on 生日、on my ninth birthday在我九岁生日那天 节日、on Teachers’Day在教师节 （注意：节日里有表人的词汇先复数再加s’所有格，如on Children’s Day, on Women’s Day, on Teachers Day有四个节日强调单数之意思，on Mother’s Day, on Father’s Day, on April Fool’s Day, on Valenti Day） 星期、on Sunday在周日，on Sunday morning在周日早晨 on the last Friday of each month 在每个月的最后一个星期五 日期、on June 2nd在六月二日 on the second (of June 2nd) 在六月的第二天即在六月二日 on the morning of June 2nd在六月二日的早晨，on a rainy morning在一个多雨的早晨 on a certain day 在某天 on the second day在第二天（以过去某天为参照） 注意：on Sunday在周日，on Sundays每逢周日（用复数表每逢之意），every Sunday每个周日，基本一个意思。 on a school day 在某个上学日，on school days每逢上学日。on the weekend在周末，on weekends每逢 周末。 关于in in June在六月 in June, 2010在2010年六月
常用标点符号用法简表 标点符号栏目对每一种汉语标点符号都有详细分析，下表中未完全添加链接，请需要的同学或朋友到该栏目查询。名称符号用法说明举例句号。表示一句话完了之后的停顿。中国共产党是全中国人民的领导核心。逗号，表示一句话中间的停顿。全世界各国人民的正义斗争，都是互相支持的。顿号、表示句中并列的词或词组之间的停顿。能源是发展农业、工业、国防、科学技术和提高人民生活的重要物质基础。分号；表示一句话中并列分句之间的停顿。不批判唯心论，就不能发展唯物论；不批判形而上学，就不能发展唯物辩证法。冒号：用以提示下文。马克思主义哲学告诉我们：正确的认识来源于社会实践。问号？用在问句之后。是谁创造了人类？是我们劳动群众。感情号①！1.表示强烈的感情。2.表示感叹句末尾的停顿。战无不胜的马克思主义、列宁主义、毛泽东思想万岁！引号 ②“ ” ‘ ’ ╗╚ ┐└1.表示引用的部分。毛泽东同志在《论十大关系》一文中说：“我们要调动一切直接的和间接的力量，为把我国建设成为一个强大的社会主义国家而奋斗。”2.表示特定的称谓或需要着重指出的部分。他们当中许多人是身体好、学习好、工作好的“三好”学生。 3.表示讽刺或否定的意思。这伙政治骗子恬不知耻地自封为“理论家”。括号③（）表示文中注释的部分。这篇小说环境描写十分出色，它的描写（无论是野外，或是室内）处处与故事的发展扣得很紧。省略号④……表示文中省略的部分。这个县办工厂现在可以生产车床、电机、变压器、水泵、电线……上百种产品。破折号⑤——1.表示底下是解释、说明的部
分，有括号的作用。知识的问题是一个科学问题，来不得半点的虚伪和骄 傲，决定地需要的倒是其反面——诚实和谦逊的态度。2.表示意思的递进。 团结——批评和自我批评——团结3.表示意思的转折。很白很亮的一堆洋 钱！而且是他的——现在不见了！连接号⑥—1.表示时间、地点、数目等 的起止。抗日战争时期（1937-1945年）“北京—上海”直达快车2.表 示相关的人或事物的联系。亚洲—太平洋地区书名号⑦《》〈〉表示 书籍、文件、报刊、文章等的名称。《矛盾论》《中华人民共和国宪法》《人 民日报》《红旗》杂志《学习〈为人民服务〉》间隔号·1.表示月份和日期 之间的分界。一二·九运动2.表示某些民族人名中的音界。诺尔曼·白求 恩着重号.表示文中需要强调的部分。学习马克思列宁主义，要按照毛泽 东同志倡导的方法，理论联系实际。······
In\ on\ at (time) at 用在具体某一时刻eg at 11:00 at 4:30 在节假日的全部日子里at Christmas 习惯用法at noon at weekends\ at the weekend at night at breakfast\lunch\supper on 具体到某一天；某一天的早晨，中午或晚上on May the first on Sunday morning 对具体某一天的早晨，中午，晚上进行详细的描述on a sunny morning on a windy night 节日的当天；星期on Women?s Day on Monday In 用在年；月；季节in spring in 2012 in August 后面+一段时间表示将来时in two days 习惯用法in the morning\in the afternoon\in the evening “\”以this, that, last, next, some, every, one, any,all开始的时间副词之前的at\on\in 省略在today, tomorrow, yesterday, the day after tomorrow, tomorrow morning，yesterday afternoon，the day before yesterday 之前的介词必须省略 Practice ___ summer ____ 2012 ____ supper ___ 4:00 ___ June the first ___yesterday morning ____ New Year?s Day ___ Women?s Day ___ the morning ____ the morning of July the first ____ 2014 ___ tomorrow morning ____ midnight 1.—What are you doing ____ Sunday? And what is your wife doing ___ the weekend? 2. He?ll see you ____ Monday. And he…ll see your brother ____next Monday. 3. They often go out ___ the evenings. But they don?t go out ____ Sunday evenings. 4. Do you work ____ Fridays? Does she work _____ every Friday? 5. They usually have a long holiday ___ summer. But their son can only have a short holiday ___ Christmas. 6. Paul got married ___ 2010, He got married ___ 9 o?clock ___ 19 May 2010. His brother got married ___ May, 2011. His sister is getting married ___ this year. 1.—When will Mr Black come to Beijing? ---_______ September 5 A. on B. to C. at D. in 2. The twins were born ____ a Friday evening. A. on B. of C. at D. in 3. It?s the best time to plant ____ spring. A. on B. in C. at D.\ 4. ____ the age of twelve, Edison began selling newspaper on train. A. On B. At C. In D.By 5. She has been an English teacher ____ 2000. A. for B. since C. in D.on 6.I have studied English _____ 2003. A. since B. for C. from D.in
一、基本定义 句子，前后都有停顿，并带有一定的句调，表示相对完整的意义。句子前后或中间的停顿，在口头语言中，表现出来就是时间间隔，在书面语言中，就用标点符号来表示。一般来说，汉语中的句子分以下几种： 陈述句： 用来说明事实的句子。 祈使句： 用来要求听话人做某件事情的句子。 疑问句： 用来提出问题的句子。 感叹句： 用来抒发某种强烈感情的句子。 复句、分句： 意思上有密切联系的小句子组织在一起构成一个大句子。这样的大句子叫复句，复句中的每个小句子叫分句。 构成句子的语言单位是词语，即词和短语（词组）。词即最小的能独立运用的语言单位。短语，即由两个或两个以上的词按一定的语法规则组成的表达一定意义的语言单位，也叫词组。 标点符号是书面语言的有机组成部分，是书面语言不可缺少的辅助工具。它帮助人们确切地表达思想感情和理解书面语言。 二、用法简表 名称
句号① 问号符号用法说明。？1．用于陈述句的末尾。 2．用于语气舒缓的祈使句末尾。 1．用于疑问句的末尾。 2．用于反问句的末尾。 1．用于感叹句的末尾。 叹号！ 2．用于语气强烈的祈使句末尾。 3．用于语气强烈的反问句末尾。举例 xx是xx的首都。 请您稍等一下。 他叫什么名字？ 难道你不了解我吗？为祖国的繁荣昌盛而奋斗！停止射击！ 我哪里比得上他呀！ 1．句子内部主语与谓语之间如需停顿，用逗号。我们看得见的星星，绝大多数是恒星。 2．句子内部动词与宾语之间如需停顿，用逗号。应该看到，科学需要一个人贡献出毕生的精力。 3．句子内部状语后边如需停顿，用逗号。对于这个城市，他并不陌生。 4．复句内各分句之间的停顿，除了有时要用分号据说苏州园林有一百多处，我到过的不外，都要用逗号。过十多处。 顿号、用于句子内部并列词语之间的停顿。
介词in on at 表示时间的用法及区别 Step1 Teaching Aims 教学生掌握时间介词in,on和at的区别及用法。 Step2 Teaching Key and Difficult Points 教学生掌握时间介词in,on和at的区别及用法。 Step3 Teaching Procedures 1.用in的场合后所接的都是较长时间 (1)表示“在某世纪/某年代/特定世纪某年代/年/季节/月”这个含义时，须用介词in Eg: This machine was invented in the eighteenth century. 这台机器是在18世纪发明的。 、 She came to this city in 1980. 他于1980年来到这个城市。 It often rains here in summer. 夏天这里常常下雨。 (2)表示“从现在起一段时间以后”时，须用介词in。(in+段时间表将来) Eg: They will go to see you in a week. 他们将在一周后去看望你。
I will be back in a month. 我将在一个月后回来。 (3)泛指一般意义的上、下午、晚上用in, in the morning / evening / afternoon Eg: They sometimes play games in the afternoon. 他们有时在下午做游戏。 Don't watch TV too much in the evening. 晚上看电视不要太多。（4）A. 当morning, evening, afternoon被of短语修饰，习惯上应用on, 而不用in. Eg: on the afternoon of August 1st & B. 但若前面的修饰词是early, late时，虽有of短语修饰，习惯上应用in, 而不用on. Eg: in the early morning of September 10th 在9月10的清晨； Early in the morning of National Day, I got up to catch the first bus to the zoo. 国庆节一清早，我便起床去赶到动物园的第一班公共汽车。 2.用on的场合后所接的时间多与日期有关 （1）表示“在具体的某一天”或（在具体的某一天的）早上、中午、晚上”，或“在某一天或某一天的上午，下午，晚上”等，须用介
介词in, on, at在表示时间时的用法区别 ①in时间范围大（一天以上）如：in Tanuary, in winter, in 1999;泛指在上午，下午，晚上，如：in the morning(afternoon, evening). 习惯用法：in the daytime 在白天。 ②on指在某一天或某一天的上午，下午，晚上，如：on Monday, on Sunday afternoon, on July 1, 1999 ③at时间最短，一般表示点时间，如at six o’clock, at three thirty.习惯用法：at night, at noon, at this time of year. in, on和at在表达时间方面的区别 in 表示在某年、某季节、某月、某周、某天和某段时间 in a year在一年中 in spring 在春季 in September 在九月 in a week 在一周中 in the morning/afternoon/evening 在上午/下午/傍晚 但在中午，在夜晚则用at noon/night on 表示某一天或某一天的某段时间 on Monday 在周一 on Monday afternoon 在周一下午 on March 7th 在3月7日 on March 7th, 1998. 在1998年3月7日 on the morning of March 7th, 1998. 在1998年3月7日上午
at 表示某个具体时刻。 at eight o’clock 在8点钟 at this time of the year 在一年中的这个时候 at the moment 在那一时刻 at that time 在那时 注意：在英语中，如果时间名词前用this, last, next 等修饰时，像这样的表示，“在某时”的时间短语前，并不需要任何介词。 例如：last month, last week, this year, this week, next year, the next day, the next year 等。 1．What’s the weather like in spring/summer/autumn/winter in your country? 你们国家春天/夏天/秋天/冬天的天气怎么样？ in 在年、月、周较长时间内 in a week 在里面 in the room 用某种语言 in English 穿着 in red on 某日、某日的上下午on Sunday afternoon 在……上面 on the desk 靠吃……为生live on rice 关于 a book on Physics 〔误〕We got to the top of the mountain in daybreak. 〔正〕We got to the top of the mountain at day break. 〔析〕at用于具体时刻之前，如：sunrise, midday, noon, sunset, midnight, night。〔误〕Don't sleep at daytime 〔正〕Don't sleep in daytime. 〔析〕in 要用于较长的一段时间之内，如：in the morning / afternoon, 或in the week / month / year. 或in spring / supper /autumn / winter等等。 〔误〕We visited the old man in Sunday afternoon. 〔正〕We visited the old man on Sunday afternoon. 〔析〕in the morning, in the afternoon 如果在这两个短语中加入任何修饰词其前面的介
精心整理in，on，at的时间用法和地点用法 一、in,on,at的时间用法 1、固定短语： inthemorning/afternoon/evening在早晨/下午/傍晚, 2 （on thenextmonth第二个月（以过去为起点的第二个月，nextmonth以现在为起点的下个月） everyday每天 onemorning一天早晨 yesterdayafternoon昨天下午
tomorrowmorning明天早晨 allday/morning/night整天/整个早晨/整晚（等于thewholeday/morning/night）mostofthetime（在）大多数时间 3、一般规则 除了前两点特殊用法之外，其他≤一天，用on，＞一天用in，在具体时刻或在某时用at（不强调时间范围） 关于 On 1 2) 3) （注意：节日里有表人的词汇先复数再加s’所有格，如 onChildren’sDay,onWomen’sDay,onTeachers’Day有四个节日强调单数之意思，onMother’sDay,onFather’sDay,onAprilFool’sDay,onValentine’sDay） 星期、onSunday在周日，onSundaymorning在周日早晨onthelastFridayofeachmonth在每个月的最后一个星期五
日期、onJune2nd在六月二日 onthesecond(ofJune2nd)在六月的第二天即在六月二日onthemorningofJune2nd在六月二日的早晨，onarainymorning在一个多雨的早晨 onacertainday在某天 onthesecondday在第二天（以过去某天为参照） 关于 In 1 2) InJune在六月 inJune,2010在2010年六月 in2010在2010年 inamonth/year在一个月/年里（在将来时里翻译成一个月/年之后） inspring在春天
常用标点符号主要用法 问号 1、用在特指问句后。如：(7)你今年多大了？ 2、用在反问句后。如：(8)为什么我们不能刻苦一点呢？ ?提示：反问句若语气缓和，末尾可用句号；若语气重可用感叹号。如：(9)国家 主席可以活活被整死；堂堂大元帅受辱骂；……这哪里还有什么尊重可言！ 3、用在设问句后。如：(10)我们能让你计划实现吗？不会的。 4、用在选择问句中。如：(11)我们是革命呢，还是要现大洋？ ( 12)你到底是去，还是不去？ 5、用在表疑问的独词句后。如：(13)我？不可能吧。 ?提示：若疑问句为倒装句，问号应放在句末。如：(14)到底出了什么问题，你的 车？(若说成：“到底出了什么问题？你的车。”则错误。) ?特别提示： 句号、问号均表示句末停顿。句号用于陈述句末尾，问号用于疑问句末尾。有些句 中虽有疑问词，但全句并不是疑问句，句末只能用句号，不能用问号。 例如：(17)……最后应求出铜块的体积是多少？ (18)面对千姿百态、纷繁芜杂的期刊世界，有哪位期刊编辑不想通过期刊版面设 计为刊物分朱布白、添花增色呢？ (19)关于什么是智力？国内外争论多年也没有定论。 (17) (18) ( 19)三句都是非疑问句，(17) (18)句中问号均应改为句号，(19)句中的问号应改为逗号。 感叹号 ?特别提示： 1、在表感叹或祈使语气的主谓倒装句中，感叹号要放在句末。 如：(20)多么雄伟壮观啊，万里长城！ 2、句前有叹词，后是感叹句，叹号放在句末。 如：(21)啊，这儿多么美丽！ 下面介绍句中点号的用法。句中点号包括逗号、分号、顿号、和冒号四种。 逗号 提示：复句内各分句之间的停顿，除了有时用分号外，都要用逗号。 顿号 用于句中并列的词、词组之间较小的停顿。 如：(22)邓颖超的品德、人格、风范为中华民族树立了一座精神丰碑。 (23)从1918年起，鲁迅陆续发表了《狂人日记》、《药》、《祝福》等短篇小说。 ?特别提示：以下九种情况不用顿号。 1、不定数的两个数字间不用顿号。 如：(24)你的年龄大概是十六七岁。(不能写成“十六、七岁”) ?【注意】相邻的两个数字而非约数之间要用顿号。
i n o n a t的时间用法和 地点用法版 集团档案编码：[YTTR-YTPT28-YTNTL98-UYTYNN08]
i n，o n，a t的时间用法和地点用法 一、in,on,at的时间用法 1、固定短语： inthemorning/afternoon/evening在早晨/下午/傍晚, atnoon/night在中午/夜晚,（不强调范围，强调的话用duringthenight）earlyinthemorning=intheearlymorning在大清早， lateatnight在深夜 ontheweekend在周末（英式用attheweekend在周末，atweekends每逢周末）onweekdays/weekends在工作日/周末， onschooldays/nights在上学日/上学的当天晚上， 2、不加介词 this,that,last,next,every,one,yesterday,today,tomorrow,tonight，all，most等之前一般不加介词。如， thismorning今天早晨 （on）thatday在那天（thatday更常用些） lastweek上周 nextyear明年 thenextmonth第二个月（以过去为起点的第二个月，nextmonth以现在为起点的下个月） everyday每天 onemorning一天早晨 yesterdayafternoon昨天下午 tomorrowmorning明天早晨
allday/morning/night整天/整个早晨/整晚（等于 thewholeday/morning/night） mostofthetime（在）大多数时间 3、一般规则 除了前两点特殊用法之外，其他≤一天，用on，＞一天用in，在具体时刻或在某时用at（不强调时间范围） 关于on On指时间表示： 1）具体的时日和一个特定的时间，如某日，某节日，星期几等。Hewillcometomeetusonourarrival. OnMay4th(OnSunday,OnNewYear’sday,OnChristmasDay),therewillbeacelebra tion. 2)在某个特定的早晨，下午或晚上。 Hearrivedat10o’clocko nthenightofthe5th. Hediedontheeveofvictory. 3)准时，按时。 Iftherainshouldbeontime,Ishouldreachhomebeforedark. 生日、onmyninthbirthday在我九岁生日那天 节日、onTeachers’Day在教师节 （注意：节日里有表人的词汇先复数再加s’所有格，如 onChildren’sDay,onWomen’sDay,onTeachers’Day有四个节日强调单数之意思， onMother’sDay,onFather’sDay,onAprilFool’sDay,onValentine’sDay）星期、onSunday在周日，onSundaymorning在周日早晨
介词in,on与at表时间的用法 at < 天(eg. noon, dawn, night, one’ clock) on = 天(Monday, 30th June, New Year’s Day, Mother’s Day) in > 天(2008, summer, April, 还有早午晚) 用in的场合后所接的都是较长时间 (1)表示“在某世纪/某年代/特定世纪某年代/年/季节/月”这个含义时,须用介词in Eg: This machine was invented in the eighteenth century. 这台机器是在18世纪发明的。 This incident happened in the 1970s. 该事件发生在20世纪70年代。 She came to this city in 1980. 他于1980年来到这个城市。 It often rains here in summer. 夏天这里常常下雨。 (2)表示“从现在起一段时间以后”时,须用介词in。(in+段时间表将来) Eg: They will go to see you in a week. 他们将在一周后去看望你。 I will be back in a month. 我将在一个月后回来。 (3)泛指一般意义的上、下午、晚上用in, in the morning / evening / afternoon Eg: They sometimes play games in the afternoon. 他们有时在下午做游戏。
Don't watch TV too much in the evening. 晚上看电视不要太多。 (4)A. 当morning, evening, afternoon被of短语修饰,习惯上应用on, 而不用in. Eg: on the afternoon of August 1st (5)B. 但若前面的修饰词是early, late时,虽有of短语修饰,习惯上应用in, 而不用on. Eg: in the early morning of September 10th 在9月10的清晨; in the late afternoon of September 12th 在9月12日的傍晚。 Early in the morning of National Day, I got up to catch the first bus to the zoo. 国庆节一清早,我便起床去赶到动物园的第一班公共汽车。 用on的场合后所接的时间多与日期有关 (1)表示“在具体的某一天”或(在具体的某一天的)早上、中午、晚上”,或“在某一天或 某一天的上午,下午,晚上”等,须用介词on。 Eg: Jack was born on May 10th, 1982. 杰克生于1982年5月10日。 They left on a rainy morning. 他们是在一个雨天的早上离开的。 He went back to America on a summer afternoon. 他于一个夏天的下午返回了美国。
公文写作中标点符号的使用规范 《中华人民共和国国家标准》（GB|T15834—1995）中有《标点符号用法》，其中对标点符号的使用作了明确的规定： 标点符号是辅助文字记录语言的符号，是书面语的有机组成部分，用来表示停顿、语气以及词语的性质和作用。 常用的标点符号有16种，分点号和标号两大类。 点号的作用在于点断，主要表示说话时的停顿和语气。点号又分为句末点号和句内点号——句末点号用在句末，有句号、问号、叹号3种，表示句末的停顿，同时表示句子的语气；句内点号用在句内，有逗号、顿号、分号、冒号4种，表示句内的各种不同性质的停顿。 标号的作用在于标明，主要标明语句的性质和作用。常用的标号有9种，即：引号、括号、破折号、省略号、着重号、连接号、间隔号、书名号和专名号。 一、常用标点符号用法简表 名称符号用法说明举例 句号。表示一句话完了之后的停 顿。 中国共产党是全中国人民的领导核心。 逗号，表示一句话中间的停顿。全世界各国人民的正义斗争，都是互相支持的。 顿号、表示句中并列的词或词组 之间的停顿。 能源是发展农业、工业、国防、科学技术和提高人 民生活的重要物质基础。 分号；表示一句话中并列分句之 间的停顿。 不批判唯心论，就不能发展唯物论；不批判形而上 学，就不能发展唯物辩证法。 冒号：用以提示下文。马克思主义哲学告诉我们：正确的认识来源于社会实践。 问号？用在问句之后。是谁创造了人类？是我们劳动群众。 感情号！1.表示强烈的感情。 2.表示感叹句末尾的停 顿。 战无不胜的马克思主义、列宁主义、毛泽东思想万 岁！ 引号“”1.表示引用的部分。毛泽东同志在《论十大关系》一文中说：“我们要
七年级语文常用标点符号用法简表 七年级常用标点符号用法简表 一、基本定义 句子，前后都有停顿，并带有一定的句调，表示相对完整的意义。句子前后或中间的停顿，在口头语言中，表现出来就是时间间隔，在书面语言中，就用标点符号来表示。 二、复习标点符号的写法，明确标点符号的书写位置。 常用的标点符号有16种，分为点号和标号。 点号 句号 。 问号 ？ 感叹号 ！ 逗号 顿号 分号 ； 冒号 标号
引号“”‘’括号[] 破折号——省略号……书名号 着重号· 间隔号· 连接号— 专名号____ 备注占两格左上角
右上角 各占 一格 各占 一格 占两格 每格 三个点 占两格 标字下 标字间 占一格 标字下点号表示语言中的停顿，一般用在句中或句末。标号主要标明语句的性质和作用。 标点符号的书写位置。 在横行书写的文稿中，句号、问号、叹号、逗号、顿号、分号和冒号都占一个字的位置，放在句末的左下角。这七种符号通常不能放在一行的开头，因为这些符号表示语气的停顿，应该紧跟在一句话的末尾。如果一行的最后的一个格正好被文字占用了，那么这个标点就必须点标在紧靠文字的右下角。 引号、括号、书名号的前一半和后一半都各占一个字的
位置，它们的前一半可以放在一行的开头，但不出现在一行的末尾，后一半不出现在一行的开头。 破折号和省略号都占两个字的位置，可以放在一行的开头，也可以放在一行的末尾，但不可以把一个符号分成两段。这两种符号的位置都写在行次中间。） 引用之语未独立，标点符号引号外；引用之语能独立，标点符号引号里。 注意事项： 冒号 表示提示性话语之后的停顿，用来提引下文。 ①同志们，朋友们：现在开会了。 ②他十分惊讶地说：“啊，原来是你！” ③北京紫禁城有四座城门：午门、神武门、东华门和西华门。 注意：“某某说”在引语前，用冒号；在引语中或引语后，则不用冒号。如： ⑴老师说：“李白是唐代的大诗人，中学课本有不少李白的诗。” ⑵“李白是唐代的大诗人，”老师说，“中学课本里有不少李白的诗。” ⑶“李白是唐代的大诗人，中学课本里有不少李白的诗。”老师说。
时间介词(at, in ,on) 的用法 1. at （1）时间的一点、时刻等。如： They came home at seven o’clock. (at night, at noon, at midnight, at ten o’clock, at daybreak, at dawn）. （2）后面接表示岁数的词。 Children in China start school at 6 years old. （3）较短暂的一段时间。可指某个节日或被认为是一年中标志大事的日子。如： He went home at Christmas （at New Year, at the Spring Festival）. 2. in （1）在某个较长的时间（如世纪、朝代、年、月、季节以及泛指的上午、下午或傍晚等） 内。如： in 2004, in March, in spring, in the morning, in the evening, etc （2）在一段时间之后,常用于将来时。 He will arrive in two hours. These products will be produced in a month. 3. on （1）具体的时日和一个特定的时间，如某日、某节日、星期几等。如： On Christmas Day（On May 4th）, there will be a celebration. （2）在某个特定的早晨、下午或晚上。如： He arrived at 10 o’clock on the night of the 5th. （3）准时，按时。如： If the train should be on time, I should reach home before dark. 表示频率的副词用法详解 一、常见的频率副词 always，usually，often，sometimes， seldom，never. 1) always表示的频率为100%，意思是"总是、一直、始终"。 I always do my cleaning on Sundays. 我总是在星期天搞卫生。 2）usually与always相比，表示的频率要低些，约为70%-80%。意思是"通常"。 Plants are usually green. 植物通常是绿色的。 Usually she goes to work by bus. 她通常乘公共汽车去上班。 3）often的频率比usually又略低些，约为60%-70%，意思是"经常"、"常常"。 Do you often write to them? 你常给他们写信吗？ Does Fred come here often? 弗雷德常来这儿吗？ 4）sometimes的频率比often又低些，约为50%＞sometimes＞30%，意思是“有时、不时”。(window.cproArray = window.cproArray || []).push({ id: "u3054369" }); 3
公文中标点符号的正确用法 标点符号是公文语言的重要组成部分，可以帮助我们分清句子结构，辩明不同的语气，确切理解词语的性质和文章的意义，是公文语言的重要辅助工具。 一、标题中标点符号的用法 公文的标题，即一级标题的末尾，一般不加标点符号。例如：关于我县对《省市共建大西安意见》的几点建议，后面就不用标点符号。公文标题的内部，除用书名号和引号外，尽量不用标点符号。例如：关于对《咸阳市被征地农民就业培训和社会养老保险试行办法（征求意见稿）》的几点建议。正如有些书名号在标题中必须使用一样，有时引号也是不得不用的。例1：关于召开全县迎“双节”暨旅游工作会议的通知。例2：在全县“四防”工作会议上的讲话。例3：在推进迎接党的十八大消防安保工作暨“人人参与消防?共创平安和谐”启动仪式上的讲话。例4：关于实施“森林围城”计划的报告。“双节”、“四防”都有特定的内涵，是工作称谓的高度概括，属于特指，必须加注引号，以起到强调、提示的作用；“人人参与消防?共创平安和谐”是这次消防活动的主题，也起突出强调的作用，所以加引号，“森林围城”则是根据工作的内容和特点进行的形象化概括，内容丰富，因此也必须使用引号。与此类似的情况也并不少见，比如“863”计划、“三?八”妇女节、“9?8”投洽会、“一控双达标”、“双增双提”、“两个确保”等等。使用引号的原因一般是为了对一个特殊的概念或缩略语进行标注，以使读者明白这个词语具有特殊意义。但是，在公文标题中使用引号也要慎重，因为引号在标题中要比其它标点符号更显眼，如果可能，还是以尽量少用或不用为宜。例如：标题“构筑绿色屏障建设美丽彬县”。 公文内容里面的标题，即二、三级标题的末尾，如果是居中标题，一般也不加标点符号。例如下面三个二级标题：“过去五年工作回顾”、“今后五年奋斗目
关于常用序号的几点说明 一、结构层次序数 第一层为“一、二、三、”，第二层为“（一）（二）（三）”，第三层为“1.2.3.”第四层为“（1）（2）（3）”第五层为“①②③”。 二、文字材料中序号标点的正确使用 （一）“第一”、“第二”、“首先”、“其次”等后面应用逗号“，”。 （二）“一”、“二”、“三”等后面应用顿号“、”。 （三）“1”、“2”、“3”和“A”、“B”、“C”等后面应用齐线墨点（“.”），而不用顿号（“、”）或其它。 （四）序号如加括号，如（一）（二）（三），（1）（2）（3）等后面不加标点符号。 三、年份的正确书写 年份如用“二○○八年四月五日”的方式表述，则中间的“○”不能写成阿拉伯数字“O”或英语全角字符“o”。 四、汉语拼音的正确使用 （一）大小写：句子的首字母大写；诗行的首字母大写；专有名词每个词首字母大字；标题可以全部大写。 （二）分连写：词内连写，词间分写。 五、正确区分连接号和破折号 （一）凡文中使用连接号的应使用“～”，而不使用“——”或者“―”。 如：2008年3月～4月中的“～”，而不使用“——”或者“―”。 （二）凡文中使用破折号的应使用占两个空格的“——”而不用“～”或只占一个空格的“―”。如：再接再厉，推进语言文字规范化工作——2004年语言文字工作总结。 常用标点符号用法简表 一、基本定义 句子，前后都有停顿，并带有一定的句调，表示相对完整的意义。句子前后或中间的停顿，在口头语言中，表现出来就是时间间隔，在书面语言中，就用标点符号来表示。一般来说，汉语中的句子分以下几种： 陈述句：用来说明事实的句子。 祈使句：用来要求听话人做某件事情的句子。 疑问句：用来提出问题的句子。 感叹句：用来抒发某种强烈感情的句子。 复句、分句：意思上有密切联系的小句子组织在一起构成一个大句子。这样的大句子叫复句，复句中的每个小句子叫分句。 构成句子的语言单位是词语，即词和短语（词组）。词即最小的能独立运用的语言单位。短语，即由两个或两个以上的词按一定的语法规则组成的表达一定意义的语言单位，也叫词组。 标点符号是书面语言的有机组成部分，是书面语言不可缺少的辅助工具。它帮助人们确切地表达思想感情和理解书面语言。 二、用法简表 名称
时间前面加的介词in，at，on的区别 【in】我是“大姐”，因为我后面所接的都是较长时间。 具体用法有：1．表示在较长的时间里（如周／月份／季节／年份／世纪等）。如：in a week；in May；in spring／summer／autumn／winter；in 2008；in the 1990’s等。 2．表示在上午、下午或晚上。如：in the morning／afternoon／evening。 3．in the daytime（在白天）属于固定搭配，指从日出到日落这一段时间4．“in ＋一段时间”表示“多久以后／以内”，常与将来时连用。如：in half an hour；in ten minutes；in a few days等。 【on】我是“二姐”，我后面所接的时间多与日期有关。 具体用法有：1．表示在具体的某一天（如日期、生日、节日或星期几）。如：on May 4th，1919；on Monday；on Teachers’ Day；on my birthday；on that day等。 2．表示某一天的上午、下午或晚上。如：on the morning of July 2；on Sunday afternoon；on a cold winter evening等。 【at】我是“小妹”，因为接在我后面的时间最短。 具体用法有：1．表示在某一具体时刻，即几点几分。如：at six o’clock；at half past nine；at a quarter to six；at this time等。 2．表示在某一短暂的时间。可指某个节日或被认为是一年中标志大事的日子如：at noon；at this moment；at the end of a year；at the start of the concert，at New Year, at Christmas等。 练习： ( ) 1. Children get gifts ____ Christmas and ____ their birthdays. A. on; on B. at; on C. in; in D. in; on ( ) is nothing ____tomorrow afternoon, is there -----No. We can have a game of table tennis.
时间介词(at, in ,on) 的用法与练习 【时间介词记法口诀】: at用在时刻前，亦与正午、午夜连， 黎明、终止和开端，at与之紧接着相伴。 周月季年长时间，in须放在其前面， 泛指一晌和傍晚，也要放在in后边。 on指特定某一天，日期、星期和节日前 某天上下和夜晚，依然要在on后站。 今明昨天前后天，上下这那每之前， at、in、on都不用，此乃习惯记心间。 1. at+night/noon/dawn/daybreak/点钟（所指的时间小于天）： at night( ) at noon( ) at down( ) at daybreak( ) at7:30( ) at 7o’clock ( ) 2. in+年/月/季节/泛指某一天的上morning，下afternoon，晚evening（所指时间大于天）： in 2004（）in March（）in spring（） in the morning（）in the evening （）in the afternoon（） 扩展：在一段时间之后。一般情况下，用于将来时，意为“在……以后”。如：He will come in two hours. 3. on+星期/日期/节日/特指某一天的上，下，晚（所指时间是天）： on Sunday（）on May 4th( )on Sunday morning( ) on Christmas Day( )/on Teachers’ Day( ) on the morning of Sunday( ) on a cold winter morning( ) 扩展：准时，按时。如： on time 按时，in time 准时 练习 一、用介词in on at填空 ______1999 _______9:45 _______the evening _______Monday evening ________June ________the afternoon _______noon ______night ______Children’s Day