Biopolymer-based composites enable to combine different functionalities using renewable materials and cost-effective routes. Here we fabricate novel thermoresponsive photonic films combining cellulose nanocrystals (CNCs) with a polydiolcitrate elastomer exhibiting shape memory properties, known as hydroxyl-dominant poly(dodecanediol-co-citrate) (PDDC-HD). Iridescent films of CNCs are first made by evaporation-induced self-assembly, then embedded in the PDDC-HD prepolymer, and finally cured to obtain a cross-linked composite with shape memory properties. The fabricated samples are characterized by polarized optical microscopy, scanning electron microscopy, and thermomechanical cycling. The obtained hybrid material combines both intense structural coloration and shape memory effect. The association of stiff cellulose nanocrystals and soft polydiolcitrate elastomer enhances the overall mechanical properties (increased modulus and reduced brittleness). This hybrid nanocomposite takes advantage of two promising materials and expands their possibilities to cover a wide range of potential applications as multiresponsive devices and sensors. As they perform from room to body temperatures, they could be also good candidates for biomedical applications.EU FP7 NoE Nanophotonics4Energy Grant No. 248855, the Spanish MINECO project MAT2015-68075 (SIFE), and Comunidad de Madrid S2013/MIT-2740 (PHAMA_2.0) program. All the authors acknowledge the Royal Society (2014/R2-IE140719). A.E. was supported by the FPI PhD program from the MICINN. S.V., B.F.P., and A.G.P. are funded by the BBSRC David Phillips fellowship [BB/K014617/1] and the ERC-2014-STG H2020 639088. G.G. acknowledges the EPSRC [1525292]. M.C.S. acknowledges the Instituto de Salud Carlos III of Spain for a Miguel Servet I contract (MS13/00060)

Blanco, Á

Dumanli, AG

Espinha, A

Frka-Petesic, B

Guidetti, G

Hamad, WY

López, C

Serrano, MC

Vignolini, S

Apollo (Cambridge)

    1  Shape Memory Cellulose-based Photonic Reflectors André Espinha,† Giulia Guidetti,‡ María C. Serrano,§ Bruno Frka-Petesic,‡ Ahu Gumrah Parry,‡ Wadood Y. Hamad,∥ Álvaro Blanco,† Cefe López,*† Silvia Vignolini*‡ †Instituto de Ciencia de Materiales de Madrid, Consejo Superior de Investigaciones Científicas, Calle Sor Juana Inés de la Cruz, 3, Cantoblanco, 28049 Madrid, Spain ‡Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW UK §Hospital Nacional de Parapléjicos, Servicio de Salud de Castilla La Mancha, Finca La Peraleda s/n, 45071 Toledo, Spain ∥FPInnovations, 2665 East Mall, Vancouver, BC, Canada V6T 1Z4.     Supporting Information – PDF The supporting video can be found here: https://www.dropbox.com/s/t69wsja4ja6l0rn/00003s2.mpeg?dl=0 https://www.dropbox.com/s/08xzdo80z7twguo/00004s3.mpeg?dl=0  1) Experimental Section  Chemicals: Citric acid and 1,12-dodecanediol were purchased from Sigma-Aldrich and ethanol 99.5% from Panreac. All chemicals were used as received.  Fabrication of cellulose nanocrystals films: The cellulose nanocrystal suspension was provided by CelluForce. Films of cellulose nanocrystals were fabricated by EISA by pouring 2 mL of 1 wt% CNC suspension, at pH 5.5 into polystyrene Petri dishes of 3.6 cm diameter and allowed to     2  dry at ambient conditions. To obtain respectively red, green and blue films the ionic strength of the initial suspension was adjusted by subjecting it to heat treatment in a water bath at 60 °C for 12 h, 21 h and 30 h respectively. The dry films were then detached from the substrates and cut into individual flakes of similar shape, avoiding the edge region affected by a coffee-ring strain.1  Prepolymer synthesis: A prepolymer composed of citric acid and 1,12-dodecanediol (mol ratio of hydroxyl to carboxyl groups 4:3) was prepared following a previously reported protocolError! Bookmark not defined. and diluted in ethanol, at a concentration of 0.5 g.mL-1, with the help of mild heating and sonication. Preparation of SMP composites: Free-standing CNC flakes were immersed in the diluted prepolymer overnight, drained to remove the excess of prepolymer and finally left drying for ethanol evaporation. For further curing of the samples, they were held by three contact points, to prevent adhesion to a substrate, and thermally annealed at 80 ºC, in an oven for periods from 16 h to 20 h. Optical characterization: Optical characterization was performed in reflection mode on a customized Zeiss Axio microscope using a halogen lamp (Zeiss HAL100) as a light source with Koehler illumination. The light reflected off the sample passes through a quarter wave plate and a polarizing filter, specifically oriented to select either left-circularly-polarized or right-circularly-polarized light before being split between a CCD camera (UI-3580LE-C-HQ, IDS) and an optical fiber mounted in confocal configuration and connected to a spectrometer (AvaSpec-HS2048, Avantes). This setup allowed for the spectra acquisition from specific areas in the sample; all the spectra were normalized to the reflection of a silver mirror. Scanning Electron Microscopy: SEM images were acquired using a Leo Gemini 1530VP system, Zeiss, working in cross section at an angle of 90° with respect to the electron beam. The samples were placed on aluminum stubs using conductive carbon tape and sputter-coated with a     3  few nanometer thick layer to Au/Pd (Emitech K550) to minimize the charging effect. The acceleration voltage used was 4 kV and the working distance was 3- 4 mm.   2) Supplementary Figures  Figure S1. Fabrication procedure for the CNC/PDDC-HD hybrid structure and thermal activation steps.         4  Figure S2. SEM image showing the layered structure of the CNC/PDDC-HD hybrid material. The CNC thin film is sandwiched between two layers of PDDC-HD as a result of the impregnation process.  3) Estimation of the Young modulus of a simplified hybrid CNC/PDDC-HD layered material  The Young modulus of pure CNC films, noted Ecell, has been evaluated in the literature as being in the range of few GPa (1.5 GPa,2 5.8 GPa3).  The Young modulus of pure PDDC-HD bulk polymer has been estimated to 13.7 MPa at room temperature and decreasing to a plateau of 2 MPa above Ttrans = 30 °C.4 From the cross-section profile of the film displayed in Figure S2 and assuming that the Young modulus of the edge and the middle layers are given by the pure PDDC-HD and pure CNC ones, one can estimate an effective Young modulus of the overall material corresponding to the bending stress applied in a cantilever geometry using the following formula:5  𝐴1 =  𝑡1 ;  𝐴2 =  𝑡2 ∗ 𝐸𝐶𝑁𝐶/𝐸𝑃𝐷𝐷𝐶;  𝐴3 = 𝑡3; 𝐴𝑇 =  𝐴1 + 𝐴2 + 𝐴3;   𝑦1 =  𝑡1/2 ;  𝑦2 =  𝑡1 + 𝑡2/2;  𝑦3 = 𝑡1 + 𝑡2 + 𝑡3/2; 𝑦𝑇 = (𝑦1𝐴1 + 𝑦2𝐴2 + 𝑦3𝐴3)/𝐴𝑇 𝐼𝑖 =  𝐴𝑖[(𝑦𝑖 − 𝑦𝑇)2 + 𝑡𝑖2/12] ;  𝐼𝑇 =  ∑ 𝐼𝑖3𝑖=1 ; 𝐼𝑃𝐷𝐷𝐶 = (𝑡1 + 𝑡2 + 𝑡3)3/12; 𝐸ℎ𝑦𝑏𝑟𝑖𝑑 =  𝐸𝑃𝐷𝐷𝐶 ∗𝐼𝑇𝐼𝑃𝐷𝐷𝐶   From this simplified modeling, the effective Young modulus 𝐸ℎ𝑦𝑏𝑟𝑖𝑑  of the overall film is expected to increase by a factor ~2.7 as compared to pure PDDC-HD.   4) References     5                                                   (1) Mu, X.; Gray, D. Droplets of cellulose nanocrystal suspensions on drying give iridescent 3-D “coffee-stain” rings. Cellulose 2015, 22, 1103-1107.  (2) Cranston, E.D.; et al., Determination of Young’s modulus for nanofibrillated cellulose multilayer thin films using buckling mechanics. Biomacromolecules 2011, 12, 961-969. (3) Bardet, R.; Belgacem, N.; Bras, J. Flexibility and color monitoring of cellulose nanocrystal iridescent solid films using anionic or neutral polymers. ACS Appl. Mater. Interfaces 2015, 7, 4010-8. (4) Espinha, A.; Serrano, M.; Blanco, A.; López, C. Thermoresponsive Shape-Memory Photonic Nanostructures. Adv. Opt. Mater. 2014, 2, 516-521. (5) Arya, C., Design of structural elements: Concrete, steelwork, masonry and timber designs to British standards and Eurocodes. 2009: CRC Press. 

Shape Memory Cellulose-Based Photonic Reflectors.

André Espinha

Giulia Guidetti

María C. Serrano

Bruno Frka-Petesic

Ahu Gümrah Dumanli

Wadood Y. Hamad

Álvaro Blanco

Cefe López

Silvia Vignolini

Crossref

ACS Applied Materials & Interfaces

Shape Memory Cellulose-Based Photonic Reflectors

Biopolymer-based composites enable to combine different functionalities using renewable materials and cost-effective routes. Here we fabricate novel thermoresponsive photonic films combining cellulose nanocrystals (CNCs) with a polydiolcitrate elastomer exhibiting shape memory properties, known as hydroxyl-dominant poly(dodecanediol-co-citrate) (PDDC-HD). Iridescent films of CNCs are first made by evaporation-induced self-assembly, then embedded in the PDDC-HD prepolymer, and finally cured to obtain a cross-linked composite with shape memory properties. The fabricated samples are characterized by polarized optical microscopy, scanning electron microscopy, and thermomechanical cycling. The obtained hybrid material combines both intense structural coloration and shape memory effect. The association of stiff cellulose nanocrystals and soft polydiolcitrate elastomer enhances the overall mechanical properties (increased modulus and reduced brittleness). This hybrid nanocomposite takes advantage of two promising materials and expands their possibilities to cover a wide range of potential applications as multiresponsive devices and sensors. As they perform from room to body temperatures, they could be also good candidates for biomedical applications

Espinha, A.

Guidetti, G.

Serrano, M.C.

Frka-Petesic, B.

Dumanli, A.G.

Hamad, W.Y.

Blanco, A.

López, C.

Vignolini, S.

The University of Manchester - Institutional Repository

English

Shape memory cellulose-based photonic reflectors

Summary of available data Original or unprocessed data is provided in support of the article “Shape Memory Cellulose-based Photonic Reflectors”. The data is structured into two folders, each correlating to a specific data type presented in the published article. Folder 1: Polarised optical microscopy (POM) The polarised optical microscopy images (.png) used in Figures 1 and in Figure 2 of the Manuscript are provided into their corresponding folders. The scale bar is included in each folder for reference together with an image of the fiber used to collect the spectra. Both folder contain also the reflectivity spectra (.mat) used to plot the graph in Figure 1 and in Figure 2. The films were imaged under with polarizing filters, as described in the Experimental section of the Manuscript. Folder 2: Scanning electron microscopy (SEM) Micrographs cellulose films cross-sections showing the chiral nematic arrangement of cellulose nanocrystals retained after the shape memory polymer infiltration (.tif). The folder ‘Figure 3’ contains high and low magnification images, used for Figure 3 of the Manuscript, the folder ‘Figure S2’ contains the low magnification images, used for Figure S2 of the Supplementary Information. The folder ‘Table 2’ contains the low and high micrographs used to extrapolate the data presented in Table 2 of the Manuscript.Royal Society [2014/R2-IE140719], BBSRC [David Phillips fellowship BB/K014617/1], ERC [2014-STG H2020 639088], EPSRC [1525292], EU FP7 NoE Nanophotonics4Energy [248855], MINECO project [MAT2015-68075 (SIFE2)], Comunidad de Madrid [S2013/MIT-2740 (PHAMA_2.0) program], FPI PhD program from the MICINN, Instituto de Salud Carlos III of Spain for a Miguel Servet I contract (MS13/00060

Espinha, André

Guidetti, Giulia

Serrano, María C.

Frka-Petesic, Bruno

Dumanli, Ahu Gümrah

Hamad, Wadood Y.

Blanco, Álvaro

López, Cefe

Vignolini, Silvia

Research data supporting "Shape Memory Cellulose-based Photonic Reflectors"

Biopolymer-based composites enable
to combine different functionalities using renewable materials and
cost-effective routes. Here we fabricate novel thermoresponsive photonic
films combining cellulose nanocrystals (CNCs) with a polydiolcitrate
elastomer exhibiting shape memory properties, known as hydroxyl-dominant
poly­(dodecanediol-<i>co</i>-citrate) (PDDC-HD). Iridescent
films of CNCs are first made by evaporation-induced self-assembly,
then embedded in the PDDC-HD prepolymer, and finally cured to obtain
a cross-linked composite with shape memory properties. The fabricated
samples are characterized by polarized optical microscopy, scanning
electron microscopy, and thermomechanical cycling. The obtained hybrid
material combines both intense structural coloration and shape memory
effect. The association of stiff cellulose nanocrystals and soft polydiolcitrate
elastomer enhances the overall mechanical properties (increased modulus
and reduced brittleness). This hybrid nanocomposite takes advantage
of two promising materials and expands their possibilities to cover
a wide range of potential applications as multiresponsive devices
and sensors. As they perform from room to body temperatures, they
could be also good candidates for biomedical applications

André Espinha (2043565)

Giulia Guidetti (3092334)

María C. Serrano (3335211)

Bruno Frka-Petesic (1454254)

Ahu Gümrah Dumanli (1330257)

Wadood Y. Hamad (1882510)

Álvaro Blanco (2043562)

Cefe López (1400575)

Silvia Vignolini (1330251)

FigShare

Shape
Memory Cellulose-Based Photonic Reflectors

Biopolymer-based composites enable to combine different functionalities using renewable materials and cost-effective routes. Here we fabricate novel thermoresponsive photonic films combining cellulose nanocrystals (CNCs) with a polydiolcitrate elastomer exhibiting shape memory properties, known as hydroxyl-dominant poly(dodecanediol-co-citrate) (PDDC-HD). Iridescent films of CNCs are first made by evaporation-induced self-assembly, then embedded in the PDDC-HD prepolymer, and finally cured to obtain a cross-linked composite with shape memory properties. The fabricated samples are characterized by polarized optical microscopy, scanning electron microscopy, and thermomechanical cycling. The obtained hybrid material combines both intense structural coloration and shape memory effect. The association of stiff cellulose nanocrystals and soft polydiolcitrate elastomer enhances the overall mechanical properties (increased modulus and reduced brittleness). This hybrid nanocomposite takes advantage of two promising materials and expands their possibilities to cover a wide range of potential applications as multiresponsive devices and sensors. As they perform from room to body temperatures, they could be also good candidates for biomedical applications. © 2016 American Chemical Society

Serrano, M.

Dumanli, A.

Hamad, W.

MPG.PuRe

https://figshare.com/articles/Shape_Memory_Cellulose-Based_Photonic_Reflectors/4214703

Shape Memory Cellulose-Based Photonic Reflectors.

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Apollo (Cambridge)

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The University of Manchester - Institutional Repository

Apollo (Cambridge)

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