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Article
Mechanochromic Micro-fibers Stabilized by Polymer Blending
Ruchira Colaco, Sindu Shree, Leonard Siebert, Clement Appiah,
Mathias Dowds, Sven Schultzke, Rainer Adelung, and Anne Staubitz
ACS Appl. Polym. Mater., Just Accepted Manuscript • DOI: 10.1021/acsapm.0c00213 • Publication Date (Web): 10 Apr 2020
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Mechanochromic Micro-fibers Stabilized by Polymer
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Blending
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13 Ruchira Colaco,§, ¥ Sindu Shree,§, † Leonard Siebert,† Clement Appiah,§, ¥ Mathias Dowds,‡ Sven
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15 Schultzke,‡ Rainer Adelung,† and Anne Staubitz§,¥,†
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18 § Institute for Organic and Analytical Chemistry, University of Bremen, Leobener Str. 7, 28359
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21 Bremen, Germany
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24 ¥ MAPEX Center for Materials and Process, University of Bremen, Bibliothekstr. 1, 28359
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26 Bremen, Germany
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† Institute for Materials Science, Functional Nanomaterials, Kiel University, Kaiserstr. 2, 24143
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32 Kiel, Germany
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35 ‡ Otto-Diels-Institute for Organic Chemistry, University of Kiel, Otto-Hahn-Platz 4, 24098 Kiel,
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Germany
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3 ABSTRACT
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6 Stimuli responsive polymers processed into micro-fibers bear the potential to be fabricated as
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systems detecting stress-induced failures. Micro-fiber processing of spiropyran (SP)
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11 functionalized polymer poly(methyl acrylate) (PMA), in pristine form and as a blend with
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13 poly(methyl methacrylate) (PMMA) was studied. Material in-homogenities such as bead
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15 formation and fiber-fiber fusion affected the durability of the micro-fibers which were aimed to be
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18 applied as self-reporting materials. The present study investigates the effect of polymer blending
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20 to improve the structural stability, i.e. the shape of the fibers compared to the non-blended PMA
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22 fibers (NBF). Blended micro-fibers (BF) with less than 4 wt% PMMA could overcome the
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structural malfunctions observed in NBF. Rheological analyses confirmed that there were no
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27 drastic alterations in the mechanical properties due to blending with a low amount of PMMA. We
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29 report the mechano-activation in the structurally stable and durable BF, processed via centrifugal
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force spinning (CFS). These fibers detected high strain deformations and retained the
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34 mechanochromic response after unloading. The color change in the BF confirms strain induced
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36 isomerization of SP which will further assist in the visual inspection of damage before failure. The
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38 micro-fibers also showed reversible photochromism upon irradiation with ultraviolet (UV) light
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41 (360-370 nm) and green light (520-530 nm). The outstanding benefit of processing micro-fibers
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43 from polymer blends is the ease of obtaining structurally stable, self-reporting material with longer
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45 durability.
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KEYWORDS: blended micro-fibers (BF), centrifugal force spinning (CFS), mechanochromic,
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50 non-blended micro-fibers (NBF), poly(methyl acrylate) (PMA), poly(methyl methacrylate)
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52 (PMMA), spiropyran (SP).
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3 INTRODUCTION
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6 Self-reporting polymers have garnered a growing interest in the last decade due to their ability
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8 to signal material failures.1–5 The polymers are functionalized with chemical species known as
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10 mechanochromes, which impart a stress sensing ability by altering their optical properties in
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response to the induced force.6–8 Spiropyran (SP), which is yellow to colorless, is the best
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15 researched stimuli-responsive specie that reversibly isomerizes to the highly colored, purple
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17 merocyanine (MC) form.9–12 SP is the primary choice for syntheses of a wide range of functional
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polymers as the switching properties are retained both, when incorporated covalently or non-
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22 covalently.1,3,8,13,14,15,16 SP has been reported to respond to light and impact force in polymeric
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24 materials when dispersed in an amount as low as 0.5 wt %.16,17 Additionally, a wide range of SP
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26 doped polymers such as poly(L-lactic acid) (PLLA),18 poly(methyl methacrylate) (PMMA),19
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29 poly(methacrylic acid) PMAA20 have been fabricated into micro-fibers. Due to the random
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31 distribution of mechanochromes in the material, the above studies focused mainly on the
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33 fabrication processes and the photochromic sensitivity of the micro-fibers. For effective force
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translation from polymer chains to the molecular switch, covalent functionalization in the
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38 elastomeric poly(methyl acrylate) PMA polymer showed effective mechano-activation.2 Optimum
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40 macroscopic force should align the polymer chains as well as sufficient number of SP in the
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direction of the applied force, which can be further isomerized to MC.14,17
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45 Further processing of functional polymers into nano- or micro-fibers, adds unique structural
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47 characteristics such as high surface to volume ratio and porosity in the materials.19,22 The synergy
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49 of the mechanochromic and structural properties has the potential to enhance the exisiting
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52 applications of fibers, which are widely used in textiles,19 membranes,23 scaffolds in tissue
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54 engineering,24–26 and as reinforcements in composite materials.27 Only a limited number of SP-
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3 functionalized polymeric micro-fibers have been assessed for their mechanochromic activity. One
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6 such study reported the low-strain mechano-activation in nano-fibers with SP in the repeating unit
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8 of a brittle polymer.28 The efficient color change was due to the high amount of SP, in-turn making
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10 it a highly expensive method. For the large scale applications of mechanochromic materials for
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damage identification, cost effectivity is integral.17
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15 The focus of the research presented here was placed on mechanochromic sensitivity in blended
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17 micro-fibers. The functionalized PMA polymer had a single SP in the long polymer chain. The
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high-throughput processing of fibers was carried out using a self-designed centrifugal force
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22 spinning (CFS) machine. The method of polymer blending with PMMA was used to overcome
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24 structural in-homogenities in the PMA fiborous network due to it’s low glass transition
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26 temperature (Tg). An easy, low cost method was developed to fabricate structurally stable micro-
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29 fibers with longer durability. Finally, the response of the fibers to mechanical force and UV
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31 irradiation was studied to demonstrate their use as self-reporting fibers (SRF).
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6 RESULTS AND DISCUSSION
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8 Polymer blending for structurally stable micro-fibers
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10 The micro-fibers obtained from pure SP functionalized PMA are labelled as non-blended fibers
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(NBF) and from the blend of PMA with PMMA as blended fibers (BF). The detailed fabrication
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15 process is reported in the materials and methods section. All fibers were examined under a
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17 scanning electron microscope (SEM). The outcome of the centrifugal force-spinning (CFS)
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process has been observed to produce either beads-only, fused-fibers or the desired bead-free
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22 fibers.29,30 The NBF processed from PMA were either beads-only at low concentration (< 20 wt%,
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24 see SI, Figure S1) or deformed due to fiber-fiber fusion at higher concentraction (20-33 wt%)
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26 Figure 1 (top).
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29 Additional increase in the concentration above 33 wt % limited the laminar volumetric flow at
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31 the smallest nozzle diameter (0.15 mm) due to the Hagen-Poiseuille law, whereas the larger sized
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33 nozzle (0.20 mm) gave thicker fibers (see SI, Figure S2).31 Therefore, the solution optimization
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shows reduced bead formation but increased fiber fusion. Such deformations in fibers may be due
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38 to the incomplete solvent evaporation, which is crucial for high quality fibers and takes place in
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40 two stages. Firstly, the mass transfer of the solvent takes place at the surface of the jet in-flight,
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before reaching the collectors. Secondly, the remaining solvent diffuses into the polymer matrix
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45 and evaporates post fiber formation.32 However, the thermogravimetric analyses (TGA) of the
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47 NBF fibers (see SI, Figure S3), showed no sign of residual solvent in the fibers.
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21 Figure 1. Top: SEM images of the non-blended fibers (NBF) of PMA in 22 wt%, 25 wt% and
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33 wt % concentration (left to right). Bottom: Bead free SEM images of blended fibers (BF)
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26 having 3 wt% of PMMA with increasing magnification (Inset: histogram plot indicating fiber
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28 diameter distribution of BF). The fibers were spun at 5000 rpm from a 0.20 mm diameter nozzle.
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The regions marked (red) show the fused NBF and (yellow) point out a single fiber diameter of
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33 the BF.
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36 Therefore, we suspected that the low glass transition temperature (Tg) of the elastomeric PMA
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38 (14 °C-17 °C)31 might be a reason for the structural degradation in the fibers (see SI, Figure S4).
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Because of this, even at a higher polymer concentration (33 wt%), fiber-fiber fusion (Figure 1,
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43 bottom) could not be avoided due to the intrinsic property (low Tg) of PMA. In order to enhance
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45 the durability and impart structural stability, the PMA was blended with PMMA. Atactic PMMA
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47 has a Tg of 106 °C to 114 °C,31 which should stabilize the structural integrity of the fibers at
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50 ambient temperatures. The Tg of the commercially purchased PMMA was measured to be 110 °C
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52 (see SI, Figure S5). The SEM analyses of the BF clearly revealed a bead-free fiber matrix (Figure
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54 1, bottom and see SI, Figure S6). They were structurally stable and showed no fiber-fiber
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3 deformation in comparison to the NBF. Addition of PMMA upto merely 3 wt %, reduced the
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6 skeletal deformities compared to fibers from pure PMA solutions. For further applications of the
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10 essential, which according to our knowledge has not been investigated. A comparison between the
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fiber matrix of NBF and BF, immediately after the spinning process and after a year is shown in
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15 Figure 2. The NBF matrix coalesced into bulk, in contrast to the well retained fibourous network
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deterioration of the entire microscopic structure over time. The optical images after day 400 of
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22 NBF showed only a reminiscent thick fiber strand at the sample border. Coalesence of the NBF
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29 limits the utilization of the material as self-reporting fibers, although the polymer is
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31 functionalizable SP and also processable into micro-fibers. On the other hand, the BF shows
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mechanochromic effect as they retain the micro-scopic fiber network in contrast to the NBF
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(a), (b) Digital images after spinning (day 0); (c),(d) after day 400; (e),(f) optical images after day
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38 Mechanochromism of blended-fibers
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40 To examine the mechanochromic-activation in polymers, the orientation of mechanophores in
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43 the direction of the applied force is pivotal.14 Aligned molecular chains are ideal to mechanically
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45 induce isomerization of SP covalently incorporated in the polymer backbone.14 Force translation
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47 to the mechanophore was induced by uniaxial tensile force, applied parallel to the aligned BF
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(Figure 3). The fibers (l0 = 25 mm) were stretched in the tensile test apparatus using a 10 kN load
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52 cell at the rate of 1 mm/s. Several methods of sample preparation had to be optimized in order to
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3 every cycle, the elongation was increased by 20 mm and the sample was cycled between the
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6 extended position and the reference position. With increasing strain, necking was observed in the
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8 fibers (see SI, Figure S9, Figure S10). Consequently, the micro-fibers underwent excessive
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10 thinning, rendering the detection of color change with bare eyes. After an elongation of 145 mm,
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i.e., 480% strain, the first appearance of color change from yellow to light pink could be visually
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15 identified in the relaxed sample (see the marked area in Figure 3a). The mechanochromic response
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17 suggests sufficient alignment of polymer chains in the direction of the applied force. As the
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polymer was amorphous, the initial chain alignment may be correlated to the yielding strength of
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22 the fibers. Beyond the yielding point, plastic deformation sets in and the fibers donot re-coil to the
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29 165 mm i.e., 560%. The relaxed sample showed enhanced color change in the bottom half of the
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31 sample (see marked area in Figure 3a). The elongation cycles were continued until 185 mm i.e.,
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33 640% (Figure 3a), withstanding cyclic loading upto five times before failure. The fibers were
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further stretched until breaking point, where even the fragments had switched and retained the
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38 color visible to the bare eye, postrupture (see SI, Figure S9). Thus, we conclude that BF makes an
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40 ideal stress indicator, over a wide range of elongations. Such a system has the potential to be
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applied as a self-reporting material before failure.
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45 For comparison and analyses of the mechanochromic response, the relaxed sample after 560%
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47 elongation was divided into four zones (Figure 3b). Visually, the indication of color change to
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49 deep pink is most prominent in the zones three and four of the sample relaxed after 560%
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52 elongation. The mechanochromic analyses of a polymeric matrix reported the sensitivity of the
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3 to pink.17 Considering this, the mechano-activation in the BF was also investigated in relation to
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6 the mean intensity of the green channel (Ig) using the ImageJ software (for details see SI). A plot
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8 of the change in the Ig values across the four zones of 560% relaxed sample were traced and
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10 provided with a standardized green color bar for reference (Figure 3b). The Ig values across the
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zones (one to four) demonstrated a gradual decrease in the mean intensity which related to greater
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17 change in zone four of the sample (Figure 3b). The extent of damage at higher deformations in
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the BF was thus clearly evident by the change in the Ig values and by visual inspection of the fibers.
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26 isomerization, the Ig values of zone four were tracked and plotted in relation to the induced
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29 elongation from 0% to 480% respectively (Figure 3c).
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37 Figure 3. (a) Mechanochromic response of BF visible to the bare eye after an elongation of 480%,
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39 560% and 640%; (b) Mean intensity of green channel (Ig) by ImageJ analysis of 560% relaxed
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41 sample divided in four zones; (c) Ig values from zone four of fibers stretched from 0% until 480%
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(for the images of periodic elongation of the fibers of see SI, Figure S8) and of the relaxed sample
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49 For the initial extentions from 0% to 160%, the Ig values recored were constant, suggesting that
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54 (Figure 3c). The effect can be attributed to the role of chain entanglement, which is a dominant
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3 to 320%, a step wise drop in the Ig value was observed, illustrating further orientation of the
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6 polymer chains in the direction of the applied stress.17 Similarly, with increase in the induced
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8 strain, the intensity profile display a gradual drop until 480% in the stretched sample. This
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elongation which was difficult to observe in the stretched state due to excessive thinning of the
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Rheology of micro-fibers
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22 To study the influence of PMMA blending on the mechanical properties of the functional PMA
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24 polymer, room temperature rheological measurements were investigated. The frequency-
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26 dependent storage (G') and loss (G'') moduli were compared between the NBF (33 wt%) and BF
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29 consisting PMMA (3 wt%) respectively (Figure 4). All other BF (1 to 5 wt %) showed the same
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31 viscoelastic behavior (see SI, Figure S11). It was found that the mechanical response of the blends
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33 was dominated by G´ at low angular frequency (elastic part, G'>>) and by G'' at higher angular
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frequency (viscous part, G'' >> G') presenting them as viscoelastic systems. A viscoelastic
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38 transition regime (G'  G'') was identified between angular frequencies of 0.1-1 rad/s. The
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40 viscoelastic transition regime (crossover point) increases slightly from 1 wt% PMMA to 5 wt%
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43 PMMA incorporation (see SI, Figure S11). It is worth mentioning that the blends showed no
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45 Newtonian flow at low frequencies. A plateau was not clearly observed at low frequencies for the
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47 complex viscosity (see SI, Figure S11), however, an ever increasing viscosity as the frequency
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approaches zero was observed. This implies the blends do not flow, but are rather solid-
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the NBF and BF (Inset: plot of error bar for the crossover point of NBF and BF respectively).
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30 As previously investigated by Callies et al.,33 increasing the concentration of a material within the
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34 a stronger cohesion at large deformations (general theory of rubber elasticity).33 Thus if the
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introduction of the different PMMA had significant influence on the concentration of the blends,
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39 then an expected change in the elastic modulus (G') of the blends at lower frequencies with the
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41 increasing wt% of the PMMA fraction should be noticeable in (Figure 4). However, according to
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43 (see SI, Figure S11), no significant change in the modulus of the blends were observed with
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46 increasing PMMA wt%. This implies that the fraction of the PMMA from 1 wt% to 5 wt% was
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48 very less to cause any significant difference in the modulus of elasticity of the polymer blends.
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50 The absolute values of and G' for all the blends are within the orders of magnitude of 10 kPa. This
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Photochromism in micro-fibers
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10 The photochemical studies of the BF fiber-mat were carried out by UV illumination to isomerize
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12 the closed SP moieties and convert them to their open MC isomer.1 The transformation of SP to
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14 MC is due to the cleavage of the heterolytic C-O bond,10 giving rise to an intense color change
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form light yellow to purple in the fibers (Figure 5). The isomerization is also plausible from the
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19 fluorescence of the MC form observed during UV irradiation.10 The highly colored MC form
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21 (Figure 5c) switches back to light yellow coloration upon irradiation with green light (Figure 5d).
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30 Figure 5. Digital image of BF indicating reviersible switching between SP to MC (a) before
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irradiation; (b) during UV irradiation; (c) after UV for 5 min on each side; (d) after green
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35 irradiation for 3 min on each side (white scale bar = 3mm).
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38 The formation of the highly colored, open-ring MC form is a result of the extended conjugation
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40 of the π-system, shifting the characteristic absorption into the visible region (λ = 550 to 570 nm)
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(Figure 6a). On illumination with green light, the MC signal (λmax = 564 nm) disappeared, which
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45 confirmed MC to SP back switching behavior in the fibers (Figure 6a).
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47 Spiropyrans undergo photodegradation when subjected to multiple back and forth UV and green
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49 light irradiations.10,34 In order to examine the cyclic photochemical activity of SP in fibers, the BF
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52 fibers were illuminated with alternating UV and green light for six cycles and the corresponding
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54 spectra were measured after each irradiation (Figure 6b). The inset in Figure 6b represents
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3 absorption intensities recorded at 564 nm to verify the photochemical stability of the molecular
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6 switch in the fibers. There was no substantial photodegradation detected in the fibers for 12
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8 irradiations. The reversible ring-closing reaction from MC to SP can also occur via spontaneous
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10 thermal relaxation over time (Figure 6c).34 The thermal back conversion of MC to SP was
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monitored for 17 h after irradiating the fibers with UV light for 5 min on each side. At an interval
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15 of every 17 minutes, absorption spectra were recorded at 20 °C (Figure 6c). The study revealed a
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intensity of absorption was reduced by 20 % from that measured at 0 h, indicating slow
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22 transformation of the specimen towards the photostationary equilibrium. The exponential decay
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24 revealed a half-life time of τ =15 h 12 min ± 3 h. As a result, this system was well-suited to retain
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38 Figure 6. (a) UV-vis absorption spectra of the BF fibers for the open MC form (red line) and the
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40 closed SP form (black line) on irradiating with UV light and green light on each side for 5 min and
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43 3 min respectively. (b) SP and MC absorption UV-vis absorption spectra peaks for six cycles. Inset
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45 is the absorption intensity (at λmax = 564 nm) form the cyclic measurements. (c) Thermal relaxation
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47 of MC-SP was monitored for 17 h after irradiating the sample with UV light for 5 min on each
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side. The absorption values (λmax = 564 nm) are fitted exponentially (red line with blue spots) to
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52 procure the half-life time of the fibers.
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3 MATERIALS AND METHODS
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6 If not stated otherwise, all chemicals were commercially available, of analytical grade and used
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8 without further purification. The monomer methyl acrylate (MA, 99%, inhibitor MEHQ
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10 (100 ppm)) was purchased from Sigma-Aldrich Ltd. and the poly(methyl methacrylate) PMMA
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(Mn : 100 kDa, a colorless coarse powder), was purchased from Kunststoff- und
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15 Farbengesellschaft mbH. The list of chemicals with purity and supplier (Table S1 and Table S2)
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17 see SI, section.
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The covalent incorporation of SP into the polymer backbone of PMA was carried out with the
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22 spiropyran functionalized α-bromoester 1 (Scheme 1), as an initiator . Using methyl acrylate (MA)
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24 as the monomer (2), elemental copper as transition metal catalyst Cu(0), and the ligand tris[2-
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26 (dimethylamino)ethyl]amine (Me6TREN) (3), the atom transfer radical polymerization (ATRP)
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29 was carried out in dimethyl sulfoxide (DMSO) as the solvent at 30 °C.2 The synthetic route1,3 of
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31 the precursors molecules to 1 is shown in (see SI, Scheme S1). For the details of all the analytical
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33 instruments used for characterization see SI, section 3. All experimental procedures with the
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corresponding chemical characterizations (1H NMR, 13C {1H }NMR, IR, HRMS (EI-TOF)) and
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38 the melting points from DSC measurements are given in the section 9 of the SI. The corresponding
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40 DSC plots, GPC plots and 1H NMR, 13C {1H }NMR plots of the synthesized products are given in
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sections 10-12 of the SI respectively.
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3 Scheme 1. Synthesis of the mechanophore linked polymer PMA via the ATRP method.3
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24 Micro-fiber processing
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In CFS (Figure 7), a concentrated polymer solution is rapidly ejected through a rotating nozzle
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29 and the fibers are collected on the radially placed rods. During the spinning process, both the
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31 centrifugal force and the air frictional force act on the solution.27 However, only when the rotating
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33 speed exceeds a critical value, the centrifugal force overcomes the surface tension of the solution
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36 and the liquid jet is ejected from the nozzle tip. The solvent evaporates in-flight and the polymer
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38 fiber is finally caught on the collector rods.29 The fiber characteristics such as fiber diameter and
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40 morphology depend on the fluid properties such as viscosity and solution concentration as well on
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the operating parameters, namely nozzle-collector distance, nozzle diameter and rotating speed.35
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3 The non-blended polymer solutions were processed into fibers using a self-designed centrifugal
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6 spinning machine at 5000 rpm equipped with a 0.15 mm or a 0.20 mm diameter nozzle respectively
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8 (Figure 7).
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23 Figure 7. (a) Schematic and (b) the self-designed centrifugal spinning machine where 1) radially
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25 placed collector rods; 2) spinneret; 3) solution injection inlet and reservoir; 4) DC motor;
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28 5) junction for nozzle attachment; 6) fibers; 7) exhaust to remove the solvent vapors produced
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30 during spinning.
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33 Fluid properties such as solution viscosity, concentration, surface tension along with the rotational
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speed and the centrifugal force acting on the solution jet, predominantly influence the resulting
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38 fiber morphologies.29 The type of morphology obtained can be correlated to the polymer solution
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40 concentration spun at a constant rotational speed.30 Therefore, the concentrations (wt %) of the
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42 polymer solutions were controlled and optimized to yield uniform and bead-free micro-fibers at a
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45 rotational speed of 5000 rpm through the smallest nozzle diameter (0.15 mm) available. For the
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47 PMA solutions, it was observed that the low-concentrated solutions (11 wt %, 15 wt % and 18
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49 wt % respectively) spun into a beads-only network (see SI, Figure S1). It has been shown in the
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literature that a low polymer concentration and hence low viscosity is insufficient to achieve the
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54 critical chain entanglement, essential for spinning bead-free fibers.30 In order to reduce the bead
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56 formation, the viscosity and thereby the polymer chain entanglement was increased by using
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3 higher solution concentration. The increase in concentration to (22 wt %), changed the fiber
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6 morphology from beads-only to beaded-fibers, however multiple fibers fused together on contact
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8 with other fibers.
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10 CONCLUSIONS
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In conclusion, using the high production-rate technique of CFS, bead-free and aligned fiber mats
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15 from polymer blends were fabricated. The blend constituted of a mechanophore-linked polymer
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17 PMA imparting the switching functionality and PMMA to improve structural stability of the fibers.
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The method of polymer blending reduced the physical deformations in fibers of functional polymer
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22 PMA, by merely adding upto 3 wt% PMMA. Most importantly, the blended micro-fibers (BF)
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24 were structurally stable and durable over a year. Stimuli-responsive properties of SP were
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26 successfully imparted in the resulting blend and active mechanochemical and photochemical
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29 isomerization of SP to MC was observed. The BF withstand high pre-elongations of approx. 480%,
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31 after which uniform switching was observed with a color change ideal for visual inspection. The
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33 fibers reversibly respond to UV and green light for at least six cycles with negligible
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photodegradation, making it suitable for sensing history of light exposure. Such structurally stable
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38 BF may have exceptional applications as durable components in composite materials for active
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40 stress monitoring.
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45 SUPPORTING INFORMATION
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47 The Supporting Information is available free of charge on the ACS Publications website.
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49 Spectroscopic data, GPC data and thermal analyses of all compounds and polymers. Tensile
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52 sample preparation, SEM and Rheology data of microfibers.
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3 AUTHOR INFORMATION
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6 Corresponding Authors
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8 *Rainer Adelung: ra@tf.uni-kiel.de
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10 *Anne Staubitz: staubitz@uni-bremen.de; orcid.org/0000-0002-9040-3297
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15 ORCID-Id
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17 Ruchira Colaco: orcid.org/0000-0002-5317-9273
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Sindu Shree: orcid.org/0000-0003-2536-5631
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22 Leonard Seibert: 0000-0001-5316-7240
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24 Clement Appiah: orcid.org/0000-0002-3179-3205
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26 Mathias Dowds: orcid.org/0000-0001-6096-0490
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29 Sven Schultzke: orcid.org/0000-0002-4975-6218
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34 Notes
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36 The authors declare no competing financial interest.
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38
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40 ACKNOWLEDGMENT
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42 This work was funded by the German Research Foundation (DFG) in the context of the
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44 Collaborative Research Center 677 “Function by Switching”, Project C14.
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C. Appiah and A. Staubitz also thank the Volkswagen (VW) Foundation for their support with the
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49 Project 93416.
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