Facile and Effective Coloration of Dye-Inert Carbon Fiber Fabrics with

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Facile and Effective Coloration of Dye-Inert Carbon Fiber Fabrics with Tunable Colours and Excellent Laundering Durability Fengxiang Chen, Huiyu Yang, Ke Li, Bo Deng, Qingsong Li, Xin Liu, Binghai Dong, Xingfang Xiao, Dong Wang, Yong Qin, Shi-Min Wang, Ke-Qin Zhang, and Weilin Xu ACS Nano, Just Accepted Manuscript • DOI: 10.1021/acsnano.7b05139 • Publication Date (Web): 21 Sep 2017 Downloaded from http://pubs.acs.org on September 21, 2017

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Facile and Effective Coloration of Dye-Inert Carbon Fiber Fabrics with Tunable Colours and Excellent Laundering Durability

Fengxiang Chen,

†,‡,⊥

Huiyu Yang, †,

⊥

⊥

⊥

⊥

Ke Li, †, Bo Deng, †, Qingsong Li,§, Xin Liu, †,

Binhai Dong, ‡,⊥ Xingfang Xiao, † Dong Wang, † Yong Qin,

#,

⊥

* Shi-Min Wang, ‡,* Ke-Qin

Zhang,§,* & Weilin Xu† ,* ⊥

†

State Key Laboratory of New Textile Materials & Advanced Processing Technologies and

Hubei Key Laboratory of Advanced Textile Materials & Application, Wuhan Textile University, Wuhan, Hubei 430200, China ‡

Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials and

Ministry of Education Key Laboratory for the Green Preparation and Application of Functional Materials, Hubei University, Wuhan, Hubei, 430062, China §

National Engineering Laboratory for Modern Silk, College for Textile and Clothing

Engineering, Soochow University, Suzhou, Jiangsu 215123, China #

State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of

Sciences, Taiyuan 030001, China

KEYWORDS: Carbon fiber fabrics, Coloring, Atomic layer deposition, Titanium oxide, Laundering durability

1 Environment ACS Paragon Plus

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ABSTRACT: Carbon fiber is a good candidate in various applications, including military, structural, sports equipment, energy storage, and infrastructure. Coloring of carbon fiber has been a big challenge for decades due to their high degrees of crystallization and insufficient chemical affinity to dyes. Here, multicolored carbon fiber fabrics (CFFs) are fabricated using a feasible, effective atomic layer deposition (ALD) technique. The vibrant and uniform structural colors originate from thin film interference is simply regulated by controlling the thickness of comformal TiO2 coatings on the surface of black carbon fibers (CFs). Impressively, the colorful coatings show excellent laundering durability, which can endure 50 cycles of domestic launderings. Moreover, the mechanical properties only drop off slightly after coloring. Overall, these results open a alternative avenue for development of TiO2 nanostructured films with multifunctional features grown using ALD technologies. This technology is speculated to have potential applications in various fields such as color engineering and radiation-proof fabrics, and will further guide material design for future innovations in functional optical and color-display devices. More importantly, this research demonstrates a route for the coloring of black carbon fiber-based materials with vibrant colors.


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Carbon fiber, produced from polymeric precursors or carbon allotrope building blocks through pyrolysis and carbonization in an inert environment, is defined as the fibrous carbonbased material with a graphite crystal structure consisting of at least 92.0 wt% carbon content.1,

2

Excellent mechanical properties, good biological compatibility, high thermal

resistance, electrical conductivity and chemical inertness of carbon fiber make it a top candidate in various fields including aerospace, sports, automotive, chemical industry, infrastructure, military, energy, textile.3-6 Carbon fiber fabrics have been trapped inside a mono-chromatic black cage for decades both due to their high degrees of crystallization and insufficient chemical affinity to dyes.2 Very few information could be digged out about colored carbon fabrics except for the products via hybrid weaves with around 50% dyeable yarns such as glass, polyester, copper and aramid, which will weak its mechanical properties.7 In addition to the hybrid colored carbon fiber fabrics, Patents EP0420655 A2 describe a colored carbon fiber fabric achieved using a polymer resin of a flaky colorant. Apple also patented a method (US7790637 B2) to color carbon fiber’s look by using an additional “scrim” layer to mask the carbon fibers and impart a color other than black. All in a word, nowadays it is still a big challenge for scientist to color the carbon fiber fabrics with lasting full-colors directly while maintaining its high mechanical properties.8 Even though projected use of carbon fiber continues to soar, real colored carbon fiber fabrics are still wistful by markets. Structural color is a valuable gift the nature granted to us,

9-13

which could be found in

natural opal, butterfly wings, squid skin, peacock feathers, and sea mice spines, has inspired a great deal of research devoted to mimick this natural phenomenon.14, 15 Structural color is caused by complex light interactions like thin-film interference, diffraction, coherent scattering, and spatially confined absorption from regular/irregular micro- and nano-


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structures. 10, 16, 17 Generally, structural colors do not fade and are environmentally friendly, which advantages over coloring by traditional dying methods. 8,13 Many

construction

techniques

including

sol-gel

methods,18

self-assemble,19,20

holographic lithography,21 ink-jet printing,22 anodization,23-25 electrophoretic deposition,8, 26 electro-spinning,27 and atomic layer deposition (ALD)28-30 have been utilized to create structural color. Among these, ALD has been recognized as one of the most efficient and promising approaches due to its high efficiency, precise and simple thickness control, excellence conformability to the sophisticate surfaces.31-35 Moreover, the ALD process consumes few chemicals and little water, thusly minimizing environmental pollution,8 making ALD a promising alternative to traditional dyeing techniques. Furthermore, the oxygen-free characteristics of ALD make it particularly suitable to fabricate of multicolored carbon fibers (CFs) and CFs-based fabrics (CFFs), which are thermally labile to oxygen. Building structural color via ALD gives us a torch to both light up the black cage of CFFs, with various colors, while maintaining the inherently excellent color brightness, color fastness of structural color and exploiting the environmental friendliness of ALD. Here, a strategy based on ALD, is proposed to fabricate conformal TiO2 coatings on CFFs, to endow them with vibrant multiple colors. The reflective spectra are highly dependent on the thickness of the TiO2 layers, which are regulated by the number of ALD cycles. (The CFFs samples treated by different ALD cycles are denoted by CFFs-ALD-n, where n is the number of cycles).


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Figure 1. Schematic illustrations of fabrication procedure of multicolored CFFs using the ALD method and the chemical reaction mechanism for deposition of TiO2 layer on CFFs.

Notably, the surface of CFFs is dominated by the chemically inert sp2-bonding, in contrast with the surface of silk fibers, which has the abundant out-of-plane functional groups. 36-38

Thus, initiating the ALD reaction on CFFs is difficult.39 However, there is still some

defects and oxygen-containing functional groups (such as -OH and -COOH) on the surface of the CFFs, which is confirmed by the following X-ray photoelectron spectroscope (XPS) analysis (Figure S5 a1 and a2). The defects and oxygen-containing functional groups were reported to be effective to initiate the growth of TiO2 via ALD.

31, 36, 40

The reaction

mechanism shown in Figure 1 illustrates the deposition of TiO2 on the surface of CFFs via ALD. A detailed growth mechanism illustrating the ALD TiO2 on the CFFs is given in Figure S2. First, TIP was introduced onto the surface of the CFFs via self-limit chemical reaction with the active groups of the CFs, the -OH or -COOH, to form -OCH(CH3)2. Then, a monolayer TiO2 thin film with outmost exposed -OH formed by reacting secondly-introduced H2O with the -OCH(CH3)2.40-41 Remaining species were removed by a nitrogen gas purge 5 Environment ACS Paragon Plus

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after each step. By repeating above mentioned ALD cycle to definite numbers, the desired thickness of TiO2 layers could be precisely regulated.

RESULTS AND DISCUSSION The field emission scanning electron microscope (FESEM) micrographs reveal that a bundle of CFFs-ALD-4000 consists of many monofilament CFs with diameters of 7-8 µm. A few small irregular protuberances were identified as aggregates of TiO2 nanoparticles in the inset of Figure 2(a).41 The FESEM micrographs in Figures 2a and 2b indicates that the monofilament CFs was fully covered by the uniform, compact TiO2 layers, which exhibit grooves that significantly resemble those of the pristine CFs (Figure S1), thus proving the conformability of ALD. To further investigate the interface between TiO2 layer and CFs, the TEM image of the fresh cross-section of the CFs-ALD-2000 monofilament treated by focused ion beam (FIB) was shown in Figure S3 a and b. It can be clearly seen from Figure S3 a that the TiO2 coating shows a uniform thickness. The vague interface (indicated by the red circle) between the CFs core and the TiO2 shell, particular at the high magnification (Figure S3 b), revealing the excellent interfacial adhesion between the CFs and the TiO2 coating. The complementary contours of energy dispersive X-ray spectroscopy mapping of C, O and Ti (Figure S3 c-g) focusing on the TiO2/CFs interface furtherly convince that the TiO2 was coated firmly and conformally onto CFs. This good comformality of TiO2 coating is further proved by Figure S4. The thickness of the TiO2 layer on CFs-ALD-4000 was measured from the corresponding TEM images of ultra-thin samples prepared with the FIB. The actual average thickness of TiO2 coating of CFs-ALD-4000 was 350 ± 6.5 nm (averaged from twenty different positions) as shown in Figure 2c. Furthermore, a compact but unclear interface between the TiO2 coating and the CF was observed in the inset of the enlarged TEM micrograph. Figure 2d shows a hollow TiO2 coating, which was obtained by removing the


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CFs in an air atmosphere at 550 °C for 240 min. This proves that interfacial chemical reactions occur on the surface of the CFs form a conformal TiO2 coating through the ALD process. An elemental analysis energy dispersive X-ray spectroscopy (EDS) mapping (Figure S4) was performed using energy dispersive X-ray spectroscope, which demonstrates that the TiO2 coating was unequivocally formed on the surface of the CFFs (insets of Figure 2d).

Figure 2 FESEM and TEM images of the TiO2-coated CFs. (a) FESEM images of CFFsALD-4000, shown at different magnifications; (b) FESEM images of a ruptured sample of CF-ALD-4000. The central part is the CF, while the surrounding portion is the TiO2 coating; (c) TEM images of a cross-sectional view of the interfacial region of a CF coated with TiO2, shown at different magnifications; (d) SEM images of TiO2 coating by removing the CFs under the air-annealing at 550 °C for 240 min. The inserted is Energy dispersive X-ray spectroscopy (EDS) of Ti and O of the isolated TiO2 shell. (e) XRD spectra of CFFs, CFFsALD-4000 and an individual TiO2 shell isolated from the CFFs-ALD-4000, where the CFFs


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were removed by air-annealing at 550 °C for 240 min, the corresponding insets show the enlarged XRD patterns. (f) XPS spectra of the CFFs and CFFs-ALD-4000.

Figure 2e shows the X-ray diffraction (XRD) spectra of CFFs and CFFs-ALD-4000. Both spectra exhibit peaks at 25.2° and 43.8°, which indicate the (002) and (004) crystallographic planes in turbostratic carbonaceous substances.42 The relatively lower intensity of the spectra of CFFs-ALD-4000 compared with that of the CFFs could be attributed to the screening effects of the TiO2 coating, which limited the detection depth of the XRD. Annealing at 550 °C for 240 min transformed the amorphous TiO2 coatings into tetragonal rutile TiO2 , which exhibited identical XRD peaks, indicating the (101), (004), (200), (105) and (204) planes. However, before annealing, the coated TiO2 layers on the CFFs-ALD-4000 exhibited the amorphous structure, as shown in the inset spectra of Figure 2e. The chemical composition and stoichiometry of the CFFs and CFFs-ALD-4000 were compared using a wide-scanning XPS spectrum, as shown in Figure 2f. For the CFFs, only C 1s and O 1s peaks appeared (Figure S5 a1-a2). The presence of O 1s reveals the existence of oxygen-containing functional groups on the surface of CFFs. However, the Ti peak of CFFs-ALD-4000 indicates that TiO2 was successful constructed on the surface of the CFFs. The CFFs-ALD-4000 exhibited three carbon peaks (Figure S5 b1), with binding energies at 284.35, 286.00, and 288.70 eV, which could be assigned to C-C, C-O, and COO- bonding, respectively.43 In addition, the CFFs-ALD-4000 exhibited three deconvoluted oxygen peaks with binding energies at 530.19, 531.26 and 532.61 eV (Figure S5 b2), which are associated with the lattice oxygen of TiO2, –OH and C-O groups, respectively.44 Ti 2p1/2 and Ti 2p3/2 peaks with binding energies of 464.42 and 458.71 eV respectively, can be clearly observed in the Ti spectrum of the CFFs-ALD-4000 (Figure S5 b3). The difference between the binding


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energy of the Ti 2p1/2 and Ti 2p3/2 peaks is 5.71 eV, which is in good agreement with asreported. [34, 36] The relationship between the color and thickness of the TiO2 coatings, which was regulated by the number of ALD cycles (n), is plotted linearly as shown in Figure 3a. According to the calculation, the experimental growth rate of ~0.086 nm/cycle is lower than the theoretical value of 0.1 nm/cycle.45 Many factors, such as the deposition temperature, surface properties of the substrate, density of active sites, pulse length, and deposition pressure, could have cause this discrepancy.46-48 Meanwhile, a series of colors, such as blue, blue-white, gold, brown, green, and purple, was observed under natural light after various ALD cycles. Notably, a significant difference between the hue of the warp yarns (convex part) and weft yarns (concave part) of CFFs-ALD can be distinguished by the naked eyes. Interestingly, the color brightness varied with the direction of incident light and observation. We speculated that this difference mainly originated from the smooth structures of fibers and their highly-oriented arrangements in the CFFs.

As depicted in Figure S6a, when the

direction of incident light is parallel to the fiber axis, very litter mirror-like reflected lights could be detected at the certain viewing angles. Meanwhile, when the incident light is come perpendicular to the fiber axis, the light could be reflected in various directions by the curved surface, and thus, diffusely reflected light could be easily detected at various viewing angles. To demonstrate these differences, photos of CFFs-ALD-3500 carbon fabrics under various illumination and viewing angles are presented in Figure S6b. The fibers that are perpendicular to the incident light can be seen from all viewing angles, while the fibers parallel to the incident light can be seen only in the directions when the combination of viewing and illuminating angles exhibits mirror symmetry. Thus, less reflected lights resulted in a dark purple appearance for warp yarns, and more reflected light led to brighter purple for


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weft yarns, which may present the specific color effects on the various fabric structures even with the conformal coating on the fibers, which coincides with the above results.

Figure 3. Optical properties of CFFs and CFFs-ALD-n. (a) The thickness of TiO2 coatings on the CFFs as a function of ALD cycles. The insets show the corresponding optical images of multicolored CFFs. (b) Reflective spectra of CFFs-ALD-0, CFFs-ALD-2000, CFFs-ALD4000 and CFFs-ALD-6000. (c) The angle-resolved reflection spectra of CFFs-ALD-6000. (d) Series

photographs

of

patterned

WTU

(Wuhan

Textile

University)

LOGO

(http://english.wtu.edu.cn/) with different colors on the CFFs taken at the normal angle by the digital camera, and their corresponding colors in CIE chromaticity.

The reflective spectra of CFFs-ALD with 2000, 4000, and 6000 cycles were measured with an optical spectrometer, as shown in Figure 3b. All spectra display multiple peaks of constructive thin-film interference over the entire spectra of incident light, which are similar to those of the spin-coated polymer films on smooth, highly reflective surfaces.49 For CFFs-


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ALD-2000, the reflective peak at 419 nm is associated with a blue-white color. In contrast, the two reflective peaks at 374 nm and 763 nm of CFFs-ALD-4000 together form the hue that the human eyes interpret as brown. In the curve of CFFs-ALD-6000, two peaks at 374 nm and 546 nm represent green and gold colors respectively, which are interpreted by human eyes, as purple when mixed together. The angle-resolved reflective spectra of CFFs-ALD6000 with the incident angles of 0, 5, 10, 15, 20, 25, 30° are shown in Figure 3c. The nearly angle-independent purple color of CFFs-ALD-6000 can be demonstrated by negligible shifts around the reflective peak of 546 nm. This is because the tubular CFs in the bundles are only 7-8 µm in diameter. Thus, the incident light shifted minimally from the axis, and the light was averaged by adjacent fibers. Therefore, there are almost no peak shifts in the reflective spectra. Figure 3d demonstrates the structural colored CFFs with the logo of our university via a mask. Four colors, ranging from dark blue to purple, were realized by varying the ALD cycles. To straightforwardly sense the color variations with different ALD cycles, the reflective spectra were converted into Commission Internationale de l’Eclairage (CIE) chromaticity value as shown in Figure 3d.

Figure 4. (a) Laundering durability of CFFs-ALD-2500. Washing of CFFs-ALD-2500 was performed according to American Association of Textile Chemists and Colorists 61-2006


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methods (AATCC 61-2006), tested with WOB detergent (0.15%, w/w) and 100 stainless steel balls in the water bath of 71°C. (b) Stress-strain curves of CFFs-ALD.

Particularly when multi-colored CFFs are used as clothing or personal protective equipment (PPE), their laundering durability and liquid repellency are important factors should be considered. Here, the laundering durability of CFFs-ALD-2500 was evaluated according to the American Association of Textile Chemists and Colorists test method 612006 (AATCC TM61-2006). The excellent laundering durability of the TiO2 coating on CFFs-ALD-2500, was demonstrated by the K/S values (Table S1) and un-offset reflective peaks in Figure 4a, which both remained the same after 10 accelerated laundering cycles (equivalent to 50 commercial or domestic launderings). In addition to the laundering durability, liquid repellency is another factor that should be considered for textile. The repellent effects of CFFs-ALD-2500 against an aqueous solution of methylene blue (MB), oil red/ethanol solution, coffee, milk, and ink are shown in Figure S7. All liquid droplets exhibit spherical shapes with high contact angles (CAs), thus confirming the excellent water-based liquid repellency of the CFFs-ALD-2500. As we known, the excellent mechanical properties of carbon fibers make it a star materials in many fields. The surface modification and other additional treatments will largely sacrifice its mechanical properties. Therefore, the mechanical properties of CFs-ALDn should be evaluated. Figure 4b and Table S2 show the mechanical properties of the CFsALD-n with different ALD cycles. The bare carbon fiber exhibits a tensile strength of 5.24±1.28 GPa, modulus of 303.40±26.09 GPa and strain at break of 1.69±0.32%, respectively. Corresponding values of CFs-ALD-n drop off slightly after ALD treatment. This may be due to the weak oxidation resistance of CFFs under the synergy effects of temperature and residual oxygen as reported in literature.44


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CONSLUSION In conclusion, a feasible, environmentally-friendly TiO2 coating by ALD for producing color on dye-inert CFFs is proposed. Conformal coatings with vibrant colors are obtained by building up TiO2 coating to the appropriate thickness on the surface of CFFs. Structural colors spanning different color categories with vibrant and uniform hues can be precisely regulated simply by varying the thickness of the TiO2 coatings. Moreover, the chemically bonded TiO2 demonstrated excellent laundering durability, which could endure machine washing 50 times without significant color fading. Applications of the colorful CFFs may extend into the consumer electronics and automobile industries. Furthermore, their excellent water repellency is another advantage, which may be applicable in water-proof fabrics.

METHODS Materials. 3K plain weave PAN-based CFFs (1.72g/cm3) were purchased from Toray group, Japan. The CFFs are cut into approximately 5×5 cm piece and air-dried for further use after ultrasonic cleaned in the ethanol for 30 min. Titanium (IV) isopropoxide (TIP, 99.999% metals basis, analytical grade) was directly used as received from Aladdin Industrial Co., Ltd. Preparation of Multicolored Carbon Fiber Fabrics. ALD reaction was performed in a self-made hot-wall closed ALD reactor as previously reported.36-38 High-purity nitrogen (N2, 99.999%) was used as both purging and carrying gas at a steady flow rate of 50 sccm (standard cubic centimeters per minute) throughout the ALD process. Multi-layer TiO2 were fabricated in following procedure. Firstly, the cleaned CFFs were placed into the ALD reactor and kept at 150 ºC for 30 min in a vacuum (~0.5 Torr) to reach an equilibrium. Second, H2O and TIP were alternatingly introduced into the ALD reactor. To provide sufficient vapor pressures for the ALD TiO2 process, the TIP was heated to 80 °C, while water was maintained at room temperature. One complete cycle of the ALD cycle proceeded


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in the following order: H2O pulse/ exposure/N2 purge/TIP pulse/exposure/N2 purge, with a duration of 0.05/8/20/0.2/8/20 seconds, respectively. Finally, sample sets were thus prepared by varying the ALD cycle numbers were systematically set up and performed. All other reaction conditions are kept same without further noting. Morphologies,

Structural

and

Composition

Characterization. The surface

morphologies and microstructures of Multi-layer TiO2 coated CFFs were characterized by using field emission scanning electron microscopy (FESEM, S-4800, operated at 10 kV, Hitachi Ltd., Japan) aftersputtered with a platinum for 120s. The diameter of the carbon fiber and the thickness of the TiO2 were determined by the FESEM and TEM images using Image J software. High-resolution transmission electron microscopy (TEM) was performed using a JEOL JEM-2010 in bright-field mode. The cross-section of CFs bundle were obtained by using focused ion beam (FIB, FEI Helios Lab, operated at 30 kV, USA) technique. X-ray diffraction (XRD) patterns were characterized using an X'Pert PRO XRD spectrometer (PANalytical, Holland) at a scanning rate of 10° min−1 in the 2θ range from 20° to 70°. The reflection spectrum were collected by reflective spectrometer, equipped with a Cu-Kα radiation source (λ = 0.15405 nm) at generator voltage of 40 kV and current of 50 mA. X-ray photoelectron spectroscopy (XPS, SPM-9700, SHIMADZU, Co.) measurements equipped with a Al-Kα radiation source(1486.6 eV) were used in this study. Optical Measurement. Optical photographs of CFFs and CFFs-ALD were taken by a digital camera (Nikon DSLR D5100) under ordinary white light.The normal reflective spectra of the CFFs and CFFs-ALD with different ALD cycles were collected by PG2000-Pro spectrometer (Idea Optics Co., Ltd., China) equipped with a UV-VIS-NIR light source. Angle-resolved

reflective

spectra

were

measured

by

using

an

angle-resolved

microspectroscopy system (ARM160, Ideaoptics, PR China). Water repellency. The static water contact angles (WCAs) was measured by using a


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Dataphysics OCA 30 (Germany) with a 5 µL deionized water droplet at ambient temperature. Photos of all liquid spheres (methylene blue (MB) aqueous solution (100mg/L), oil red ethanol solution (75mg/L), coffee, milk, and ink) on the surface of CFFs-ALD were taken at 60 s after the dispensing needle detached from the droplet. Mechanical properties. Mechanical properties of the carbon fibers and multicolored carbon fiber were evaluated by using a XQ-1C tensile tester (Shanghai New Fiber Instrument Co., Ltd, China) at 25 °C and relative humidity of 63% at a gauge length 20 mm and strain rate of 0.1%/s. The samples were conducted at least 20 time and the average values were calculated.

ASSOCIATED CONTENT Supporting Information The Supportting Information is available free of charge on the ACS Publications website at DOI: XXX.. AUTHOR INFORMATION Corresponding Authors *

E-mail: [email protected].

*


*


*


Author Contributions Fengxiang Chen, Huiyu Yang, Ke Li, Bo Deng, Qingsong Li, Xin Liu, Binhai Dong contributed equally to this works.

The authors declare no competing financial interest.


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Funding This research was financial supported from the National Science Foundation for Distinguished Young Scholars (Grant No. 51325306), the National Natural Science Foundation of China (Grant No. 51203124, 51373110, 51773158, 51373110) and the Program for Middle-aged and Young Talents from Educational Commission of Hubei Province (Grant No. Q20120103). ACKNOWLEDGMENTS The authors are grateful to Dr. Ning Zhou, Wei Yuan (National Engineering Laboratory for Modern Silk, College for Textile and Clothing Engineering, Soochow University), Prof. Zhiguang Guo, Dr. Li Wan (School of Materials Science and Engineering, Hubei University) and Yaodong Liu (State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences) for their valuable advice.

REFERENCES 1. Frank, E.; Steudle, L. M.; Ingildeev, D.; Spörl, J. M.; Buchmeiser, M. R. Carbon Fibers: Precursor Systems, Processing, Structure, and Properties. Angew. Chem. Int. Ed. 2014, 53, 5262-5298. 2. Kim, J. W.; Lee, J. S. Preparation of Carbon Fibers from Linear Low Density Polyethylene. Carbon 2015, 94:524-530. 3. Frank, E.; Hermanutz, F.; Buchmeiser, M. R. Carbon Fibers: Precursors, Manufacturing, and Properties. Mater. Eng. 2012, 297, 493-501. 4. Feldhoff, A.; Pippel, E.; Wolterdorf, J. Interface Engineering of Carbon Fiber Reinforced Mg–Al Alloys. Adv. Eng. Mater. 2000, 2, 471-480.


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Facile and Effective Coloration of Dye-Inert Carbon Fiber Fabrics with

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