materials Article
Structural Coloration of Polyester Fabrics Coated with Al/TiO2 Composite Films and Their Anti-Ultraviolet Properties Xiaohong Yuan 1, * 1 2 3
*
ID
, Yuanjing Ye 2 , Min Lian 1 and Qufu Wei 3
Fujian Key Laboratory of Novel Functional Textile Fibers and Materials, Faculty of Clothing and Design, Minjiang University, Fuzhou 350108, China;
[email protected] Fujian Fibers Inspection Bureau, Fuzhou 350026, China;
[email protected] Key Laboratory of Eco-Textiles, Ministry of Education, Jiangnan University, Wuxi 214122, China;
[email protected] Correspondence:
[email protected]; Tel.: +86-186-5071-3490
Received: 22 May 2018; Accepted: 11 June 2018; Published: 14 June 2018
Abstract: Al/TiO2 composite film was successfully deposited on polyester fabrics by using magnetron sputtering techniques. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) were used to examine the deposited films on the fabrics, and the structural colors and anti-ultraviolet property of fabrics were also analyzed. The results indicated that polyester fabrics coated with Al/TiO2 composite films achieved structural colors. The reactive sputtering times of TiO2 films in Al/TiO2 composite films were 10 min, 12 min, 18 min, 20 min, 26 min, 27 min, 30 min and 45 min, respectively, the colors of corresponding fabrics were bluish violet, blue, cyan, green, yellow, yellowish red, orange and blue-green, which was consistent with the principle of the thin film interference. The structure of the TiO2 film in Al/TiO2 composite films was non-crystalline, though the fabrics were heated and maintained at the temperature of 200 ◦ C. The anti-ultraviolet property of the fabrics deposited with Al/TiO2 composite films were excellent because of the effect of Al/TiO2 composite films. Keywords: structural coloration; Al/TiO2 composite films; anti-ultraviolet property; magnetron sputtering
1. Introduction With the intensification of pollution problems in the traditional printing and dyeing industry and the strengthening of people’s awareness of environmental protection, structural coloration, as an ecological dyeing technique, has attracted increasing attention from researchers [1–5]. Structural coloration, differing from chemical dyeing, without water and chemicals, utilizes the dispersion, scattering, diffraction and interference of light to create colors [6]. Therefore, research interest in structurally-colored textiles has gradually increased and is currently mainly focused on photonic crystals materials. However, the preparation process of photonic crystal materials is rather complicated and the cost is high, so it is difficult to realize industrial production [7–10]. Our research group developed a simple and low cost method to prepare structurally-colored textile, that is, textiles coated with nano-metal/semiconductor composite films by magnetron sputtering technology, not only can achieve the structure colors on the textiles surface, but also obtain other functions [11]. In our previous study, the metal silver was chosen as the metal film material. In this paper, the metal aluminum (Al) was chosen as the metal film material. Metal aluminum is very common in nature, and its price is much cheaper than metal Ag. Aluminum has many excellent properties, such as conductivity, anti-ultraviolet, anti-electromagnetic shielding and other properties. The Al film is the only material in the metal film that has a high reflectance from the ultraviolet, visible to infrared, and has excellent optical properties [12,13].
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However, there are few reports on the Al/TiO2 composite films deposited [14,15], especially on the fabric substrates. Metal Al materials and semiconductor TiO2 materials were selected in this paper, and nano-Al/TiO2 composite films were deposited on the fabric surface by magnetron sputtering technology. The structural colors and anti-ultraviolet property of fabrics coated with nano-Al/TiO2 composite films were analyzed. This research is intended to provide a theoretical and experimental basis for the development of multi-functional and structurally-colored textiles. 2. Experimental Section 2.1. Materials The substrate used was a white polyester plain weave fabric. The fabric was cut into a circular sample with a diameter of 5 cm, and then washed with the acetone solution, followed by drying and storing. The sputtering targets used were 99.99% Aluminum (Al) target and 99.99% titanium (Ti) target. 2.2. Preparation of Al/TiO2 Composite Films Al/TiO2 composite films were prepared by the sputtering unit (JPG-450 type, SKY Technology Development Co., Ltd., Shenyang, China). The working conditions were set as a base pressure of 1.5 × 10−3 Pa and a working gas pressure of 0.8 Pa. 99.99% Argon was used a working gas and the distance between the target and the fabric substrate was 70 cm. The revolving speed of samples was 10 r/min in order to achieve the even deposition on the fabric. The preparation process of Al/TiO2 composite films was as follows. Firstly, Al film was deposited by RF magnetron sputtering with an Argon (Ar) gas flow rate of 20 mL/min, a sputtering power of 120 W and for a sputtering time of 30 min. Then the titanium film was deposited by DC magnetron sputtering with an Ar gas flow rate of 50 mL/min, a sputtering power of 100 W and for a sputtering time of 10 min. Finally, the titanium dioxide film was deposited by RF reactive sputtering using titanium target with a sputtering power of 300 W, gas flow rates of Ar and O2 were set as 20 mL/min and 10 mL/min respectively. The sputtering time was set as 10 min, 12 min, 18 min, 20 min, 26 min, 27 min, 30 min and 45 min, respectively, and the corresponding sample numbers was marked as Nos. 1, 2, 3, 4, 5, 6, 7 and 8. 2.3. Microstructure and Composition of Al/TiO2 Composite Films The chemical composition and valence state of the deposited composite films on the textile substrate were analyzed by X-ray photoelectron spectroscopy (Escalab 250XiXPS, VG Instruments, UK) using Al Ka monochromator as X-ray source. The composite films deposited on the textile substrate also were examined by X-ray diffraction (D8XRD, Bruker-AXS, Karlsruhe, Germany) measurements on a Bruker-AXS X-ray diffractometer system with Cu Kα radiation. Scanning range was 2–90◦ . 2.4. Structural Color and Color Fastness Test The color photographs of all samples were taken with a Japanese Sony DCR-HC90E digital camera. The colors of the samples were analyzed using a spectrophotometer (Color-Eye 7000A, GretagMacbeth, USA). According to the 1976 norm of the Commission International de I’Eclairage (CIE), light source of D65, observation angle of 10◦ , L*, a*, b*, C* values and reflectance curves were tested respectively. Among them, the lightness L*, the chromaticity a* and b* refer to three mutually perpendicular coordinate axes in the color space, and C* is the chroma, which indicates the purity of the color. The reflectance curve also reflects the color of the sample.
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Materials 2018, 11, of x FOR PEER REVIEW of 11color The fastness composite films deposited on polyester fabrics could be expressed3 by fastness to washing, which was tested according to GB/T 3921-2008 [16] “textile test for color fastness The fastness of composite films deposited on polyester fabrics could be expressed by color to washing with soap or soap and soda”.
fastness to washing, which was tested according to GB/T 3921-2008 [16] “textile test for color fastness to washing withProperty soap or soap 2.5. Anti-Ultraviolet Test and soda”.
2.5. Anti-Ultraviolet Property Test According to GB/T18830-2009 [17], anti-ultraviolet properties of the samples were tested by ultraviolet transmittance analyzer (UV-1000F, Lapsphere, evaluation indexes According to GB/T18830-2009 [17], anti-ultraviolet propertiesUSA).The of the samples were tested by of anti-ultraviolet properties included solar ultraviolet transmittance T (UVA) and T (UVB) and ultraviolet ultraviolet transmittance analyzer (UV-1000F, Lapsphere, USA).The evaluation indexes of antiprotection factorproperties (UPF), solar UV-A spectral transmittance T (UVA), solar spectral transmittance ultraviolet included solar ultraviolet transmittance T (UVA) andUV-B T (UVB) and ultraviolet protection factor (UPF), solar factor UV-A (UPF). spectral transmittance (UVA), UV-B T (UVB) and ultraviolet protection Each sample wasTtested fivesolar times, and spectral the average T (UVB) and ultraviolet protection factor (UPF). Each sample was tested five times, valuestransmittance were reported. and the average values were reported.
3. Results and Discussion 3. Results and Discussion
3.1. XPS Analysis
3.1. XPS Analysis
All samples coated with Al/TiO2 composite films differ only in the thickness of TiO2 film. All samples coated with Al/TiO2 composite films differ only in the thickness of TiO2 film. Therefore, the XPS test results should be similar, and No. 4 sample was selected as a representative to Therefore, the XPS test results should be similar, and No. 4 sample was selected as a representative analyze chemical composition and valence Figure photoelectron spectroscopy to its analyze its chemical composition and state. valence state.1 presents Figure 1 the presents the photoelectron of No.spectroscopy 4 sample. of No. 4 sample. 6,000
O1s
(a) 400,000
(b)
Al2p
Counts/ s
Ti2p
200,000
5,000
4,500
C1s
Counts/ s
300,000
Ti2s
Ti(LMM)
5,500
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100,000
0 1200
1000
800
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82
Binding Energy / eV 80,000
100,000
76
74
72
70
68
O1s
(d)
70,000
90,000
60,000
80,000 70,000
50,000 40,000
Counts/ s
Counts/ s
78
Binding Energy / eV
Ti2p3/2
(c)
80
Ti2p1/2
30,000
60,000 50,000 40,000
20,000
30,000
10,000
20,000 10,000
0 475
470
465
460
Binding Energy / eV
455
545
540
535
530
525
Binding Energy / eV
Figure 1. X-ray photoelectron spectroscopy of No. 4 sample: (a) Full spectrum; (b) Al2p peak; (c) Ti2p
Figure 1. X-ray photoelectron spectroscopy of No. 4 sample: (a) Full spectrum; (b) Al2p peak; (c) Ti2p peak; peak; (d) O1s peak. (d) O1s peak.
In Figure 1a, only the characteristic peaks of Al, Ti, and O elements are presented in the XPS full spectrum No. 4 sample, and there was peaks also a handful which is mainly derived from the carbon In Figureof1a, only the characteristic of Al, of Ti,C,and O elements are presented in the XPS in the ultra-high vacuum chamber in the XPS equipment. Figure 1b shows the Al2p peak of Al, and the full spectrum of No. 4 sample, and there was also a handful of C, which is mainly derived from it can be seen that the position of Al2p peak was 73.74 eV, which is approximately the same as thepeak carbon in the ultra-high vacuum chamber in the XPS equipment. Figure 1b shows the Al2p binding energy of metal Al, suggesting that Al was present in the composite films in the form of the of Al, and it can be seen that the position of Al2p peak was 73.74 eV, which is approximately metallic aluminum [18,19]. As can be seen from Figure 1c, the positions of Ti2p1/2 and Ti2p3/2 peak same as the binding energy of metal Al, suggesting that Al was present in the composite films in the form of metallic aluminum [18,19]. As can be seen from Figure 1c, the positions of Ti2p1/2 and
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Ti2p3/2 peak were 464.00 eV and 458.28 eV, respectively, and the results were consistent with the TiO2 were 464.00 It eVindicates and 458.28 eV,Tirespectively, and the results were consistent with the TiO22 form binding binding energy. that was completely oxidized, and was presented in TiO [20,21]. energy. It indicates that Ti was completely oxidized, and was presented in TiO 2 form [20,21]. Figure Figure 1d shows the O1s peak of the O element. It can be seen from Figure 1d that the O1s peak 1d shows the O1s peak of the O at element. canand be seen from Figure 1d that the O1s peak position of of position of O element was located 530.07IteV, the result is consistent with the binding energy O element was located at 530.07 eV, and the result is consistent with the binding energy of O in TiO2 O in TiO2 [22,23]. It also indicates that Ti existed in the composite film in the form of TiO2 . [22,23]. It also indicates that Ti existed in the composite film in the form of TiO2. Consequently, the XPS analysis indicates that the composite films deposited on the polyester Consequently, the XPS analysis indicates that the composite films deposited on the polyester fabricfabric surface werewere Al/TiO films. 2 composite surface Al/TiO 2 composite films. 3.2. XRD Analysis 3.2. XRD Analysis Due Due to Al/TiO films bymagnetron magnetron sputtering at room temperature, 2 composite to Al/TiO 2 composite filmswere were prepared prepared by sputtering at room temperature, the TiO film2 film in the composite films was crystalstructure. structure. general, the2 TiO in the composite films wasdifficult difficult to to form form aacrystal In In general, TiO2TiO film2 film was was crystallized by sputtering at high temperatureor or calcination calcination after [24]. crystallized by sputtering at high temperature aftersputtering sputtering [24]. Without affecting the properties the textile substrate, the temperature the textile Without affecting the properties of theoftextile substrate, the temperature of theoftextile fabricfabric substrate substrate was reactive raised during reactive sputtering so as the to crystallize films in composite the Al/TiO2films. was raised during sputtering so as to crystallize TiO2 filmsthe in TiO the 2Al/TiO 2 films. Since the experimental substrate was polyester fabrics, too high a temperature Sincecomposite the experimental substrate was polyester fabrics, too high a temperature would affect the fabric would affect the fabric dimensional stability and performance. Therefore, the fabric substrate was dimensional stability and performance. Therefore, the fabric substrate was heated and maintained the heated and maintained the temperature at 100 °C and 200 °C respectively during RF reactive temperature at 100 ◦ C and 200 ◦ C respectively during RF reactive sputtering. Taking No. 7 as an example, sputtering. Taking No. 7 as an example, the XRD test was performed when the temperature of the the XRD test was performed when the temperature of200 the°C, textile substrate was normal temperature, textile substrate was normal temperature, 100 °C, and respectively. The experimental results ◦ C, respectively. The experimental results are shown in Figure 2. 100 ◦ C, and 200 are shown in Figure 2.
Figure 2. XRD patterns of the sample coated with Al/TiO2 composite films for reaction sputtering TiO2
Figure 2. XRD patterns of the sample coated with Al/TiO2 composite films for reaction sputtering film at different temperature. TiO2 film at different temperature.
It can be seen from Figure 2 that the XRD patterns of the Al/TiO2 composite films deposited on polyester fabrics prepared TiO2 film at room temperature, 100films °C and 200 °C on It can be seen from Figureby2 reactive that thesputtered XRD patterns of the Al/TiO deposited 2 composite ◦ ◦ C look look similar. There were only the characteristic peaks of polyester fabric substrate, without polyester fabrics prepared by reactive sputtered TiO2 film at room temperature, 100 C and 200 the characteristic peaks of the crystalline structures of Al and TiO 2, indicating that the structures of Al similar. There were only the characteristic peaks of polyester fabric substrate, without the characteristic and TiO2 all were amorphous structures. peaks of the crystalline structures of Al and TiO2 , indicating that the structures of Al and TiO2 all were Normally, the metal element was easy to form a crystal structure, but the Al film in the Al/TiO2 amorphous structures. composite film was not crystallized here. The main reason was that the preparation of the Al film Normally, the metaland element was easy towas form a crystal structure, butthe the Al film in the Al/TiO2 used RF sputtering, the deposition rate very low, which affected ordered arrangement composite filmresulting was notincrystallized here. The main reason wasThe that theofpreparation of of theTiO Al2 film of atoms, the amorphous structures structure of Al. type anatase crystal used film RF sputtering, andobtained the deposition rate was very low, which theand ordered arrangement was generally for at temperatures between 350 °C affected and 500 °C, the type of rutile of crystal was formed when the temperature exceeded 500 °C The [25,26]. Considering influence atoms, resulting in the amorphous structures structure of Al. type of anatasethe crystal of TiOof2 film ◦ ◦ polyester fabric substrate, the temperature was only added to 200 °C, resulting in a non-crystalline was generally obtained for at temperatures between 350 C and 500 C, and the type of rutile crystal structurewhen of TiOthe 2 film. was formed temperature exceeded 500 ◦ C [25,26]. Considering the influence of polyester fabric substrate, the temperature was only added to 200 ◦ C, resulting in a non-crystalline structure of TiO2 film.
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To summarize, the XRD patterns of Al/TiO2 composite films deposited on polyester fabrics ◦ C and 200 ◦ C indicated that prepared To bysummarize, reactive sputtering of TiOof2 Al/TiO film at2 composite room temperature, 100on the XRD patterns films deposited polyester fabrics prepared both Al and TiOsputtering films had non-crystalline TiO cannot by reactive of TiO2 film at room temperature, 100 °C and 200 °Cstructures. indicated that both Al and TiO2 form 2 in the Al/TiO 2 composite 2 film a crystal structure at the temperature of 200 ◦ C, but 200 ◦ CTiO was thecannot limit temperature for heating in the Al/TiO2 composite films had non-crystalline structures. 2 film form a crystal structure at the the temperature of 200 °C,performance but 200 °C was limit temperature for heating theby polyester while polyester fabrics, while the ofthe polyester fabrics were affected furtherfabrics, heating. the performance of polyester fabrics were affected by further heating.
3.3. Structural Color Analysis 3.3. Structural Color Analysis
The color photos of the original fabric and the polyester fabrics coated with Al/TiO2 composite The color photos of the original fabric and the polyester fabrics coated with Al/TiO2 composite film are shown in Figure 3. These photos were formed by selecting 2 cm from the central of samples film are shown in Figure 3. These photos were formed by selecting 2 cm from the central of samples and then enlarging. and then enlarging.
(a)
(b)
(c)
(d)
(e)
(f) Figure 3. Cont.
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(g)
(h)
(i) Figure 3. Color photographs of the original sample and the samples with different sputtering time of
Figure 3. Color photographs of the original sample and the samples with different sputtering time of TiO2 film: (a) Original sample; (b) 10 min; (c) 12 min; (d) 18 min; (e) 20 min; (f) 26 min; (g) 27 min; (h) TiO2 film: (a) Original sample; (b) 10 min; (c) 12 min; (d) 18 min; (e) 20 min; (f) 26 min; (g) 27 min; 30 min; (i) 45 min. (h) 30 min; (i) 45 min.
It can be clearly seen from Figure 3 that the thickness of the TiO2 film in Al/TiO2 composite films was different andseen the colors the samples also different. The original white fabric presented a It can be clearly fromof Figure 3 that were the thickness of the TiO 2 film in Al/TiO2 composite films variety of structural colors because their surfaces were coated with Al/TiO 2 composite films. As the was different and the colors of the samples were also different. The original white fabric presented thickness of TiO2 films in Al/TiO2 composite films increased, the structural colors changed from a variety of structural colors because their surfaces were coated with Al/TiO2 composite films. As the purple, blue, cyan, green, yellow, orange to red, respectively. In this experiment, the thickness of the thickness of TiO2 films in Al/TiO2 composite films increased, the structural colors changed from TiO2 film was mainly controlled by the reactive sputtering time. The reactive sputtering times of TiO2 purple, blue, cyan, yellow, orange red,18respectively. Inmin, this27 experiment, of films for Nos. 1–8green, samples were 10 min, 12tomin, min, 20 min, 26 min, 30 min the and thickness 45 min, the TiO film was mainly controlled by the reactive sputtering time. The reactive sputtering times 2 respectively, and the corresponding fabric colors were bluish violet, blue, cyan, green, yellow, of TiO 1–8and samples were The 10 min, 12 indicated min, 18 min, 20 min, 26 min, 27 min, 30 min 2 films for yellowish red,Nos. orange blue-green. results that the corresponding wavelength of and 45 min, and the corresponding fabric blue, cyan, yellow, the respectively, samples was proportional to the thickness of colors the TiOwere 2 film,bluish which violet, was consistent withgreen, the thin film interference yellowish red, orangetheory. and blue-green. The results indicated that the corresponding wavelength of the Figure 4 reveals theto corresponding reflection spectra of samples coated with different thickness samples was proportional the thickness of the TiO 2 film, which was consistent with the thin film of TiO 2 thin films in Al/TiO2 composite film. interference theory. Figure 4 reveals the corresponding reflection spectra of samples coated with different thickness of TiO2 thin films in Al/TiO2 composite film.
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No.3
No.5
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14
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No.8
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8 6 4
No.1 No.2
2 0 400
450
500
550
600
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Wavelength / nm Figure 4. Reflection spectra of the samples coated with Al/TiO2 composite films. Figure 4. Reflection spectra of the samples coated with Al/TiO2 composite films.
The spectral reflectance curves of Nos. 1 and 2 samples were close to each other, but they were
The spectral curves of Nos. 1 and 2 was samples were close to each other, butpurple they were slightly offset. reflectance The maximum reflection wavelength approximate 400 nm, which is in the andoffset. blue wavelength range.reflection Therefore,wavelength the colors ofwas Nos.approximate 1 and 2 samples werewhich determined to be slightly The maximum 400 nm, is in the purple bluish violet and blue, consistent with the fabric colors presented in Figure 3b,c. The center and blue wavelength range. Therefore, the colors of Nos. 1 and 2 samples were determined to be bluish of the reflectivity curve of the No. presented 3 sample was located3b,c. at 420The nm,center whichwavelength is in the blueof the violetwavelength and blue, consistent with the fabric colors in Figure wavelength range. Therefore, the No. 3 sample color was cyan, which is also consistent with the fabricrange. reflectivity curve of the No. 3 sample was located at 420 nm, which is in the blue wavelength color in Figure 3d. The maximum reflection wavelength of No. 4 sample was 510 nm, which is in the Therefore, the No. 3 sample color was cyan, which is also consistent with the fabric color in Figure 3d. green wavelength range, and was therefore consistent with the fabric color in Figure 3e. The The maximum reflection wavelength of No. 4 sample was 510 nm, which is in the green wavelength maximum reflection wavelengths of No. 5 sample, No. 6 sample and No. 7 sample were 600 nm, 650 range, and consistent with the tofabric color in Figure The maximum reflection nm, andwas 690 therefore nm, respectively corresponding yellow, yellowish red, 3e. orange color, and consistent wavelengths of No. 5 sample, No. 6 sample and No. 7 sample were 600 nm, 650 nm, and 690 nm, with the results in Figure 3f,g,h. The maximum reflection wavelength of No. 8 sample was 480 nm, respectively corresponding to yellow, yellowish red, orange color, and consistent with the results in corresponding to blue-green color, and consistent with the result in Figure 3i. L*, a*,The b* and C* valuesreflection for samples are shown inofTable Figure 3f,g,h. maximum wavelength No. 1.8 sample was 480 nm, corresponding to blue-green color, and consistent with the result in Figure 3i. 1. L*, a*, b*, C* scale of the samples coated with Al/TiO2 composite films. L*, a*, b* and Table C* values for samples are shown in Table 1. Samples L* a* b* C* Table 1. No. L*, a*, scale of the samples Al/TiO2 composite films. 1 b*, C* 19.781 1.681 coated with −23.979 24.038 No. 2 15.710 7.106 −25.764 26.726 Samples L* a* b* C* No. 3 37.515 −7.281 −15.323 16.965 No. 4 32.794 −5.054 −1.578 5.294 No. 1 19.781 1.681 −23.979 24.038 No. 5 2 43.093 −1.776 20.878 No. 15.710 7.106 −20.803 25.764 26.726 No. 6 3 39.357 8.058 19.646 No. 37.515 −7.281 −17.917 15.323 16.965 No. 32.794 −5.054 −0.494 1.578 5.294 No. 7 4 34.164 17.240 17.247 No. 43.093 −1.776 20.803 20.878 No. 8 5 34.174 −13.992 −9.235 16.764 No. 6 39.357 8.058 17.917 19.646 No.be 7 seen that 34.164 17.240 From Table 1, it can the L* values of Nos. 1–8 0.494 samples were17.247 quite different, indicating No. 8 34.174 − 13.992 − that the lightness of the samples was significantly distinct. The9.235 chroma C* 16.764 values of Nos. 1–8 samples differed greatly, with the minimum chroma value of No.4 and the maximum chroma value of No. 2 sample,Table also manifesting thatseen the color of the of samples different. Thewere a* and b* values From 1, it can be that and the purity L* values Nos. are 1–8 samples quite different, of Nos. 1–8 samples were different, indicating that the samples colors were in different positions in indicating that the lightness of the samples was significantly distinct. The chroma C* values of the color space. Nos. 1–8 samples differed greatly, with the minimum chroma value of No.4 and the maximum chroma Figure 5 represents the distribution of chromaticity indices, a* and b*, for all the samples coated value of No. 2 sample, also manifesting that the color and purity of the samples are different. The a* with Al/TiO2 composite films.
and b* values of Nos. 1–8 samples were different, indicating that the samples colors were in different positions in the color space. Figure 5 represents the distribution of chromaticity indices, a* and b*, for all the samples coated with Al/TiO2 composite films.
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No.5
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No.4 White No.8 No.3
0
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No.1 -25
No.2
-50 -50
-25
0
25
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a*(D65) Figure the samples samples coated coated with with Al/TiO Al/TiO22 Figure 5. 5. Distribution Distribution of of chromaticity chromaticity indices, indices, a* a* and and b*, b*, for for the composite composite films. films.
As shown in Figure 5, a* and b* values of Nos. 1–8 samples coated with Al/TiO2 composite films As shown in Figure 5, a* and b* values of Nos. 1–8 samples coated with Al/TiO2 composite were different in the color space. According to the CIE 1976 chromaticity diagram, the colors of these films were different in the color space. According to the CIE 1976 chromaticity diagram, the colors samples were bluish violet, blue, cyan, green, yellow, yellowish red, orange and blue-green. The of these samples were bluish violet, blue, cyan, green, yellow, yellowish red, orange and blue-green. results are consistent with the experimental results shown in Figures 3 and 4. The results are consistent with the experimental results shown in Figures 3 and 4. As a consequence, polyester fabrics coated with Al/TiO2 composite films presented structural As a consequence, polyester fabrics coated with Al/TiO2 composite films presented structural colors resulted from the effect of nano-composite films, and the colors varied along with the change colors resulted from the effect of nano-composite films, and the colors varied along with the change of of the TiO2 film thickness. With the increase of the TiO2 film thickness, the colors of fabrics changed the TiO2 film thickness. With the increase of the TiO2 film thickness, the colors of fabrics changed from from purple, blue, cyan, green, yellow, orange to red. When the thicknesses of the TiO2 films purple, blue, cyan, green, yellow, orange to red. When the thicknesses of the TiO2 films continued to continued to increase, the colors of the fabrics changed regularly followed by these seven colors, and increase, the colors of the fabrics changed regularly followed by these seven colors, and the results the results were consistent with the rules of thin film interference. In this experiment, the reactive were consistent with the rules of thin film interference. In this experiment, the reactive sputtering sputtering times of TiO2 films for the samples were 10 min, 12 min, 18 min, 20 min, 26 min, 27 min, times of TiO2 films for the samples were 10 min, 12 min, 18 min, 20 min, 26 min, 27 min, 30 min and 30 min and 45 min, respectively, and the corresponding fabric colors were bluish violet, blue, cyan, 45 min, respectively, and the corresponding fabric colors were bluish violet, blue, cyan, green, yellow, green, yellow, yellowish red, orange and blue-green. yellowish red, orange and blue-green. Compared with the polyester fabrics coated with Ag/TiO2 composite film samples, the color Compared with the polyester fabrics coated with Ag/TiO2 composite film samples, the color rules rules of fabrics coated with nano-composite films were the same, though the underlying metal in of fabrics coated with nano-composite films were the same, though the underlying metal in composite composite films was different. The corresponding wavelength of colors was linearly proportional to films was different. The corresponding wavelength of colors was linearly proportional to the thickness the thickness of TiO2 films [27]. of TiO2 films [27]. Due to the different refractive indexes of metallic Ag and Al, the sputtering efficiency of the TiO2 Due to the different refractive indexes of metallic Ag and Al, the sputtering efficiency of the film was affected, resulting in the difference between the sputtering time and the corresponding TiO2 film was affected, resulting in the difference between the sputtering time and the corresponding wavelength of the fabric color. For example, the reactive sputtering times of the TiO2 films in Ag/TiO2 wavelength of the fabric color. For example, the reactive sputtering times of the TiO2 films in Ag/TiO2 composite films deposited on polyester fabrics were 1 min, 3 min, and 4 min, correspondingly, the composite films deposited on polyester fabrics were 1 min, 3 min, and 4 min, correspondingly, reactive sputtering times of the TiO2 films in Al/TiO2 composite films deposited on polyester fabrics the reactive sputtering times of the TiO2 films in Al/TiO2 composite films deposited on polyester were 12 min, 20 min, and 26 min, respectively, the corresponding fabrics colors were blue, green, and fabrics were 12 min, 20 min, and 26 min, respectively, the corresponding fabrics colors were blue, yellow [25]. As a result, the deposition efficiency of the TiO2 films in Al/TiO2 composite films was green, and yellow [25]. As a result, the deposition efficiency of the TiO2 films in Al/TiO2 composite lower than that in Ag/TiO2 composite films. films was lower than that in Ag/TiO2 composite films. According to the experimental results, the color fastness to washing of polyester fabrics coated According to the experimental results, the color fastness to washing of polyester fabrics coated with Al/TiO2 composite films was 5, so the color fastness to washing of samples was very good. It with Al/TiO2 composite films was 5, so the color fastness to washing of samples was very good. indicated that Al/TiO2 composite films and polyester fabrics were combined strongly, and the It indicated that Al/TiO2 composite films and polyester fabrics were combined strongly, and the composite films were firm, and not easy to fall off. composite films were firm, and not easy to fall off.
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3.4. Anti-Ultraviolet Property Analysis Table 2 shows the anti-ultraviolet properties of Nos. 1–8 samples coated with Al/TiO2 composite films. The smaller the values of T (UVA) and T (UVB), the anti-ultraviolet property is better. Conversely, the greater the ultraviolet protection factor (UPF), the anti-ultraviolet property is higher. Table 2. Anti-ultraviolet property of the samples coated with Al/TiO2 composite films. T (UVA)/% Samples No. No. No. No. No. No. No. No.
1 2 3 4 5 6 7 8
Average Value/% 3.65 3.05 3.75 3.61 3.49 3.47 3.82 3.49
Standard Deviation/% 0.44 0.75 0.12 0.11 0.08 0.15 0.05 0.10
T (UVB)/% Average Value/% 3.30 2.69 3.45 3.30 3.22 3.06 3.41 3.01
UPF
Standard Average Deviation/% Value 0.14 0.12 0.09 0.07 0.10 0.10 0.05 0.08
31.92 36.42 30.66 31.83 32.74 33.05 30.82 33.52
Standard Deviation 0.88 0.75 0.68 0.77 0.98 1.01 0.86 0.58
As can be seen from Table 2, the results of anti-ultraviolet property for Nos. 1–8 samples were similar, and T (UVA) and T (UVB) were less than 4%, and UPF was more than 30. According to the national standard GB/T18830-2002 [28], when UPF > 30 and T (UVA) < 5%, the samples can be called anti-UV textiles. It can be seen that all the polyester fabrics coated with Al/TiO2 composite films meet the requirements and belong to the UV protection product. The main reason was that the high reflectivity of the Al film reflects ultraviolet light, and the TiO2 film in the Al/TiO2 composite film also has the effect of UV protection. Duo to high refractive and high photoactivity, nano-TiO2 , as an excellent ultraviolet protection agent, can absorb ultraviolet ray, and reflect and scatter ultraviolet rays, and transmit visible light. In summary, the anti-ultraviolet property of polyester fabrics coated with Al/TiO2 composite films can be greatly improved resulting from the influence of Al/TiO2 composite films. 4. Conclusions Al/TiO2 composite film was successfully deposited on polyester fabrics using the magnetron sputtering technique. Due to the effect of nano-composite films, polyester fabrics coated with Al/TiO2 composite films achieves structure coloration. The reactive sputtering times of TiO2 films in Al/TiO2 composite films were 10 min, 12 min, 18 min, 20 min, 26 min, 27 min, 30 min and 45 min, respectively, the colors of corresponding fabrics were bluish violet, blue, cyan, green, yellow, yellowish red, orange and blue-green, which was consistent with the rules of the thin film interference. XPS analysis shows that the composited films deposited on the surface of the polyester fabrics substrate were Al/TiO2 composite films. The XRD patterns of Al/TiO2 composite films deposited on polyester fabrics prepared by reactive sputtering of TiO2 film at room temperature, 100 ◦ C and 200 ◦ C indicated that the structures of Al films and TiO2 films in Al/TiO2 composite films were non-crytalline structures. The anti-ultraviolet property of polyester fabrics coated with Al/TiO2 composite films were all excellent resulting from the influence of Al/TiO2 composite films. Author Contributions: Conceptualization, X.Y. and Q.W.; Methodology, X.Y.; Validation, Y.Y.; Formal Analysis, X.Y.; Investigation, M.L.; Data Curation, Y.Y.; Writing-Original Draft Preparation, X.Y.; Writing-Review & Editing, Q.W.; Project Administration, X.Y. Funding: This research was funded by Natural Science Foundation of Fujian Province (Grant No. 2018J01543), and Technical Plan Project of Fuzhou City (Grant No. 2016-G-77). Acknowledgments: We were sincerely grateful to the financial support from National Natural Science Foundation of China (Grant No. 51403098), and National Natural Science Foundation of China (Grant No. 51706092).
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Conflicts of Interest: The authors declare no conflict of interest.
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