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Reinforcement Effects from Nanodiamond in Cellulose Nanofibril Films

Seira Morimune-Moriya, Michaela Salajkova, Qi Zhou, Takashi Nishino, and Lars A. Berglund
Biomacromolecules, Just Accepted Manuscript • DOI: 10.1021/acs.biomac.8b00010 • Publication Date (Web): 05 Apr 2018
Downloaded from http://pubs.acs.org on April 7, 2018

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Page 1 of 34 Biomacromolecules

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Reinforcement Effects from Nanodiamond in
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Cellulose Nanofibril Films
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16 Seira Morimune-Moriya1, Michaela Salajkova2,3, Qi Zhou3,4, Takashi Nishino5, Lars A.
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Berglund2,3*
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22 1. Department of Applied Chemistry, College of Engineering, Chubu University, Matsumoto,
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24 Kasugai 487-8501 (Japan) 2. Department of Fibre and Polymer Technology, Royal Institute of
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Technology, SE-100 44 Stockholm (Sweden) 3. Wallenberg Wood Science Center, Royal
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29 Institute of Technology, SE-100 44 Stockholm (Sweden) 4. School of Biotechnology, Royal
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31 Institute of Technology, AlbaNova University Centre, SE-106 91 Stockholm (Sweden) 5.
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33 Department of chemical science and engineering, Graduate School of Engineering, Kobe
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36 University, Rokko, Nada, Kobe 657-8501 (Japan)
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42 KEYWORDS. Biocomposite, Hardness, Nanocomposite, Decoration, Strength, Modulus,
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Nanopaper
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3 ABSTRACT.
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7 Although research on nanopaper structures from cellulose nanofibrils (CNF) is well established,
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9 the mechanical behavior is not well understood, especially not when CNF is combined with hard
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11 nanoparticles. Cationic CNF (Q-CNF) was prepared and successfully decorated by anionic
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nanodiamond (ND) nanoparticles in hydrocolloidal form. The Q-CNF/ND nanocomposites were
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16 filtered from a hydrocolloid and dried. Unlike many other carbon nanocomposites, the Q-
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18 CNF/ND nanocomposites were optically transparent. Reinforcement effects from the
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nanodiamond were remarkable, such as Young’s modulus (9.8 GPa
16.6 GPa) and tensile
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23 strength (209.5 MPa
277.5 MPa) at a content of only 1.9% v/v of ND, and the reinforcement
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25 mechanisms are discussed. Strong effects on CNF network deformation mechanisms were
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27 revealed by loading-unloading experiments. Scratch hardness also increased strongly with
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30 increased addition of ND.
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3 1. Introduction
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32 Figure 1 Transmission electron microscopy image of nanodiamond particles.
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35 Diamond has a Young’s modulus as high as 1 TPa and a hardnessas high as 10 on the Mohs
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38 scale1. Nanodiamond (ND), can be readily prepared by a detonation method and can now be used
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40 in nanocomposites. ND nanoparticles have a diameter below 10 nm (see Figure 1 and Supporting
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42 Info Figure 1). These ND nanoparticles can be described as core-shell particles. The diamond
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particle forms the core, whereas the shell has oxygen containing groups2 attached to graphite.
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47 The properties of these ND are characteristic of diamond, with the added feature of nanoscale
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49 particle form. The characteristics of the shell makes water dispersion of ND facile, and ND can
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51 also be modified and functionalized for specific purposes3,4. Nanodiamond is a candidate
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54 nanoparticle for nanocomposites,5–8 where hardness is a desirable property.
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3 In a previous study at Kobe University9, nanodiamond nanocomposites were prepared in
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6 water-assisted processing. Polyvinyl alcohol (PVA) was dissolved in water and used as a matrix.
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8 The properties of ND provided strong reinforcement of PVA in the nanocomposites, and an
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10 important reason for this was the good dispersion of nanodiamond in PVA. For example, from
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tensile tests, the Young’s modulus of PVA was doubled at a nanodiamond content of only 1
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15 weight percent. One challenge in the analysis of reinforcement effects on PVA, is that the
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17 nanoparticle will influence crystalline morphology, time-dependence of deformation behavior
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and physical ageing. As a consequence, part of the measured reinforcement effect may be due to
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22 ND-induced changes in PVA structure and properties10.
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25 Here, a nanocomposite material is prepared from cellulose nanofibrils (CNF) reinforced by
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27 nanodiamond particles. Cellulose is a widely available nanofibrious polymer from renewable
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30 resources. Cellulose is a large research field, and it is widely used industrially. There is also
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32 substantial growth potential due to the increasing interest in eco-friendly materials11–13. CNF is
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34 cellulose in nanofibrillar form, and the fibrils are composed of high molar mass extended and
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ordered cellulose molecules. From X-ray diffraction studies of plant fibers under tension, the
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39 crystalline region of cellulose I is estimated to have an elastic modulus of around 135 GPa14,15
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41 and it is interesting to compare this with the modulus for aluminum (70 GPa) or glass fiber (76
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GPa), since the cellulose crystal density is much lower (≈1600 kg/m3). The strength of CNF
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46 disintegrated from wood pulp was estimated to be a few GPa16, although fibril strength in plants
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48 is expected to be higher (higher molar mass and fewer defects). Recently, the strength was
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50 suggested to be comparable to multiwalled carbon nanotubes17, although this will depend on the
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53 specific type of nanotube. In addition to high mechanical properties, CNF shows low thermal
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55 expansion in the axial direction and low density. Due to the properties and nanoscale dimensions,
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3 CNF has been widely used for nanocomposites18–29. In many cases, CNF was the reinforcement
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6 phase in polymer composites. For example, PVA20,21,24, epoxy resins21, polylactic acid22 and
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8 polyurethanes23 were investigated in their roles as matrix phase.
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11 Henriksson and colleagues.30 studied cellulose films (“nanopaper”) based on wood CNF. The
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nanopaper was not solvent cast, but rather filtered from a hydrocolloidal suspension. Despite
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16 high void content (28%), the modulus was high (≈13 GPa), the strength was high (≈210 MPa)
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18 and work to fracture (15 MJ/m3). High optical transparency31, oxygen barrier properties32 and
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favorable thermal expansion coefficient33,34 are other interesting characteristics of nanocellulose
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23 films. CNF is organized as a swirled, random-in-the-plane nanofiber network, where fibrils are
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25 strongly bonded due to small diameter (4-10nm), smooth fibril surfaces and the drying procedure.
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27 As water evaporates during drying of cellulose nanopaper, nanometer-sized fibrils are brought
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30 together facilitating molecular scale interaction, and the result is strong secondary fibril-fibril
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32 bonding. Benitez and Walther thoroughly reviewed the mechanical properties of cellulose
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34 nanopaper56. Effects from relative humidity are discussed as well as effects from fibril structure,
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counterions, porosity etc.
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40 An interesting possibility for increased property range and even new functionalities is to
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42 combine cellulose nanopaper with inorganic nanoparticles. Liu et al.35 combined CNF with
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montmorrillonite nanoclay for reinforcement purposes. The fire retardancy of the material was
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47 dramatically improved with delayed thermal degradation of cellulose. Furthermore,
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49 montmorrilonite strongly enhanced the gas barrier properties, also under humid conditions. Anti-
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51 bacterial properties were achieved by silver nanocluster addition36 and zinc oxide nanoparticles37.
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54 CNF/graphene nanocomposites38 showed greatly improved mechanical properties due to the high
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3 In the present study, another class of inorganic cellulose hybrids was investigated.
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6 Nanodiamond nanocomposites were prepared by combination of cellulose nanofibrils with
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8 nanodiamond particles, so that the hard ND particles were decorating the CNF fibrils in the
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10 nanopaper structure. A key was to use quaternized cellulose nanofibrils (Q-CNF), so that the
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electropositive charge on the CNF could attract the electronegative ND particles. (Supporting
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15 Info, Table 1). First, the cationic Q-CNF was just mixed with anionic ND in hydrocolloidal state,
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17 so that ND could attach along the CNF fibrils. The Q-CNF/ND filtered and the hybrid
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nanocomposites were obtained in a similar manner as has been previously reported Sehaqui et
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22 al.39 Nanostructural details of the materials were investigated, as well as the reinforcement
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24 effects from the nanodiamond particles. The property improvements were quite remarkable at
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26 low particle content, and possible mechanisms are discussed.
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2. Experimental
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7 2.1. Materials
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11 Q-CNF. Cationic CNF was prepared from chemical softwood pulp using glycidyl
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13 trimethylammonium chloride (GTAC, Sigma-Aldrich, USA), and the procedure provided in Pei
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15 et al.40 The sulphite pulp was never dried (Nordic Paper, Sweden) and subjected to beating in a
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18 PFI-mill (HAM-JERN, Norway), and mixed with a sodium hydroxide (Sigma-Aldrich, USA)
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20 solution in water. The quaternization reaction conditions were 65 °C for 8 h with stirring after
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22 adding GTAC to the suspension. The mixture was then neutralized with hydrochloric acid (37%,
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Sigma-Aldrich, USA) and washed with deionized water. The aqueous suspension of the
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27 chemically treated pulp (0.5% w/v) was stirred for 24 h at 600 rpm, and passed through a
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29 microfluidizer (M-110EH, Microfluidics Ind., USA) equipped with 200 and 100 µm chamber at
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31 a pressure of 1600 bar at room temperature (21 °C). The Q-CNF hydrocolloid showed a solid
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34 content of 0.3–0.4%.
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37 The ammonium chloride group content on the treated fibrils were determined by
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39 conductometric titration41. 100 mg (dry weight) of Q-CNF suspended in Milli-Q water (0.1%
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42 w/w) was titrated with 0.005 M silver nitrate (AgNO3, Sigma-Aldrich, USA) solution by adding
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44 200 µL. The conductivity was recorded with a conductivity meter (Mettler Toledo, USA) in 60
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46 second intervals. The amount of trimethylammonium groups in Q-CNF can be calculated based
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on the volume of AgNO3 used. The charge density of Q-CNF was 0.56 mmol/g.
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22 Scheme 1. Method for processing of Q-CNF/ND materials.
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25 Q-CNF/ND nanocomposites. The preparation of the Q-CNF/ND nanocomposites is described
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in Scheme 1. The Q-CNF suspension was added to the ND aqueous suspension (Bando Chem.
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30 Ind.) to reach a Q-CNF concentration of 0.2%w/w. The ND content in the suspension was 0–5%
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32 w/w and the rest was Q-CNF. The Q-CNF/ND suspension was stirred for 48 h and filtered on a
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34 glass filter funnel (7.2 cm in diameter) using filter membrane (0.65 µm DVPP, Millipore, USA).
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37 The Q-CNF/ND suspension was stable. After the filtration, the wet cake of the nanocomposite,
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39 which contained 78–81% of water, was placed between the metal mesh sheets on filter paper and
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41 then dried at 93 °C for 15 min under vacuum by using Rapid Köthen (PTI, Austria). This
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resulted in the Q-CNF/ND nanocomposites with thickness in the range of 50–60 µm.
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2.2. Characterization
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7 Atomic Force Microscopy (AFM). Nanoscope IIIa AFM (Picoforce SPM, Veeco, USA) was
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9 used to observe the Q-CNF decorated with ND. All measurements were performed in the tapping
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12 mode with a scan rate of 2 Hz/512 dots using standard noncontact silicon cantilevers (RTESP,
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14 Veeco, USA). The samples were prepared on a mica substrate by depositing the diluted Q-
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Transmission Electron Microscopy (TEM). A highly diluted Q-CNF/ND nanocomposite
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22 suspension was deposited on a copper grid (ultra-thin carbon film/holey carbon, Ted Pella,
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24 USA), and then stained by uranyl acetate negative stain. Excess suspension liquid was removed
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using filter paper and the remaining sample was carefully dried in order to minimize the risk for
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29 drying artifacts. The sample was observed at 80 kV using transmission electron microscopy
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31 (Hitachi HT-7700, Hitachi, Japan).
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34 Field-Emission Scanning Electron Microscopy (FE-SEM). The cross sections of the
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37 nanocomposites were observed by FE-SEM using Hitachi S-4800 (Hitachi, Japan) equipped with
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39 a cold field emission electron source. The samples were coated with graphite and platinum-
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41 palladium using Cressington 208 HR sputter coaters (Cressington Scientific Instruments Ltd.,
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UK). Secondary electron detector was used for capturing images at 3 kV/5 µA.
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47 Ultraviolet-visible spectroscopy (UV-VIS). UV-VIS spectra of the nanocomposites were
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Shimadzu, Japan) at a wavelength scan rate of 400 nm/min.
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3 Thermogravimetric analysis (TGA). The composition of the nanocomposites was obtained by
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6 TGA using Mellter-Toledo thermogravimetric analyzer (TGA/SDTA851, Switzerland). The
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8 heating rate of 10 °C/min was used under nitrogen flow. ND content of the nanocomposites was
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10 calculated by using the weight of residual at 550 °C, where the weight loss of CNF became
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constant, considering the weight loss of ND.
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16 Tensile test. The tensile properties were tested by Instron 5944 mechanical testing system
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18 (Instron, USA) equipped with 500 N load cell. The specimens were conditioned at 50%RH and
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23 °C. The gauge length was set at 20 mm and the cross-head speed was 2 mm/min. A minimum
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23 of 6 specimens were tested for each sample. The loading-unloading test was carried out with the
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25 same instrument. The loading-unloading cycle was repeated with the step of 1% strain.
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28 Scratch test. The scratch resistance of the nanocomposites was measured by Nano scratch tester
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31 (CSM Instrument, Switzerland). The test was performed with a sphero-conical diamond tip
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33 (diameter 2 µm) and the maximum load of 10 mN was applied. The scratch map over 3 points on
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35 each sample were made and the width of the scratch marks were measured. The scratch hardness
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was calculated using the following equation (1)42;
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ସி
41 ‫ݍ=ܪ‬ (1)
గ௪ మ
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45 where the F is normal load (N), w is residual width of the scratch mark and q is a function of the
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47 viscoelasticity of the material. q = 2 corresponds to the rigid plastic materials and 1 < q < 2 is for
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3. Results and Discussion
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7 3.1. Characterization of the Q-CNF decorated with ND
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3 The Q-CNF fibrils were decorated with ND as described in the experimental section. AFM
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6 height and phase images of the decorated Q-CNF can be observed in Figures 2A and B. The
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8 contrast in the phase image is high and this is due to the large difference in modulus between Q-
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10 CNF and ND. In the phase image in Figure 2B, ND is present as distinct dots, whereas Q-CNF
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has similar color as the background. The nanodiamond dots are apparent along the Q-CNF, and
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15 this strengthens the hypothesis that ND is indeed adsorbed to Q-CNF. The Q-CNF and
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17 nanodiamond distribution was also studied by transmission electron microscopy. Figure 2C
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presents decorated Q-CNF in diluted Q-CNF/ND nanocomposite suspension. Although there is
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22 some CNF agglomeration, the information in the image is helpful. In this figure, ND appears on
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24 the surface of Q-CNF, in support of successful ND-decoration of Q-CNF. In contrast, the neat Q-
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26 CNF showed a smooth surface with a width below 10 nm (Supporting figure 2) as previously
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29 reported40. According to this previous study, Q-CNF dimensions are below 5 nm in diameter and
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From TEM images, the distribution of ND was studied (Figure 2D and Supporting figure 3).
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39 Q-CNF was primarily combined with agglomerates of ND with a size up to 50 nm. ND adsorbed
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41 to Q-CNF because of the opposite charge on the fibrils and the ND nanoparticles. Images support
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good small-scale dispersion of nanodiamond in the Q-CNF network.
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3.2. Structure of CNF-nanodiamond materials
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3 Figure 3. (A) Photographic images for transparency impression and (B) UV-VIS spectra of Q-
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6 CNF film and Q-CNF/ND nanocomposites, (C) FE-SEM images comparing cross sections of Q-
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8 CNF reference film and (D) Q-CNF/ND nanocomposite (5% w/w).
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11 Table 1. Composition and estimated porosity of Q-CNF film and Q-CNF/ND nanocomposites.
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14 ND Porosity
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(%v/v) (%)
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0.5%w/w
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Q-CNF/ND
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5%w/w
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31 The optical transparency of nanocomposites based on carbon nanotubes or graphene tends to
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33 be poor even at low nanoparticle content. The transparency of polyvinyl alcohol (PVA) was
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35 reduced by about 35% when only 0.1 weight percent of carbon nanotubes (SWNT) were added.
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38 Nanocomposites based on graphene and cellulose nanofibrils with a thickness below 10 µm
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40 also lost transparency at 1.25% w/w graphene content38. In contrast, the present Q-CNF/ND
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42 nanocomposites maintain reasonably high optical transparency, even at a concentration of 5%
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w/w of ND, see Figures 3A and B. This indicates that the present composition and preparation
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47 strategy provide low porosity in the nanocomposites and fairly homogeneous dispersion of ND9.
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50 The content of nanodiamond was estimated from TGA and is presented in Table 1. The
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3 lower content compared with the initial value (Supporting Info, Table 2). This suggests that some
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6 excess free ND in the hydrocolloid was lost through the membrane, whereas ND particles
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8 adsorbed to the Q-CNF were preserved in the nanocomposites.
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11 Figure 3C shows FE-SEM images of the cross section of the Q-CNF. The structure is layered,
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which is typical for cellulose nanopaper30. For nanocomposites, a dense structure with low
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16 porosity was observed, see Figure 3D. Due to the filtration and drying procedure, the structural
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nanofibril network with swirled, intermingled fibrils <5nm in diameter by 1 µm in length.40 It
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23 was suggested that ND is located in interfibril regions, due to the Q-CNF/ND decoration
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25 approach. This is an unusual structure, since the Q-CNF “matrix” is fibrillar in nature, and the
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30 material is organized in sheets, a form of meso-scale material architecture.
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33 In nanocomposites with very high content of ND (> 10% w/w), large agglomerates were
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excess individual ND, in particular free ND which were not lost during filtration. The estimated
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3.3. Mechanical properties of nanocomposites in uniaxial tension
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Figure 4. (A) Stress versus strain curves of Q-CNF film and Q-CNF/ND nanocomposites in
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47 uniaxial tensile loading; (B) Stress versus strain curves of Q-CNF/ND nanocomposites (1% w/w)
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49 from loading-unloading experiment; (C) Young’s modulus as a function of number of loading
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steps for Q-CNF film and Q-CNF/ND nanocomposite (1% w/w) specimen tested by loading-
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54 unloading. The modulus determined during loading and initial unloading are represented as
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56 square and triangular dots, respectively.
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3 Table 2. Properties for Q-CNF nanopaper and Q-CNF/ND materials.
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6
Young’s Tensile Elongation at Work of
7 Yield strength
Sample modulus strength break fracture
8 (MPa) 3
9 (GPa) (MPa) (%) (MJ/m )
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11 Q-CNF 9.8 ± 0.9 210 ± 27 103 8.0 ± 0.7 8.2
12
13 Q-CNF/ND
10.0 ± 0.4 211 ± 17 110 8.0 ± 0.5 8.4
14 0.5%w/w
15 Q-CNF/ND
16 13.6 ± 0.8 250 ± 10 142 6.6 ± 1.3 8.1
1%w/w
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18 Q-CNF/ND
15.6 ± 0.8 265 ± 27 147 7.3 ± 0.8 9.7
19 2.5%w/w
20 Q-CNF/ND
21
16.6 ± 1.5 278 ± 29 147 6.8 ± 0.7 9.2
5%w/w
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23
24
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26 Figure 4A and Table 2 present results from uniaxial tensile tests for the Q-CNF film and the
27
28 Q-CNF/ND nanocomposites. The mechanical properties of the present Q-CNF nanopaper are
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30 lower than for films prepared from enzymatic CNF30,40. At low addition of nanodiamond, 0.5
31
32
33 weight percent the reinforcement effect was very small. Then at 1 weight percent of
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35 nanodiamond addition, the reinforcement effect was dramatic. For instance, modulus increased
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37 from 9.8 to 13.6 GPa and yield strength from 103 to 142 MPa. At 5% ND, the modulus was 16.6
38
39
40
GPa, and ultimate strength had increased from 210 MPa for neat CNF to 278 MPa for the
41
42 nanocomposite. The strain to failure of the Q-CNF film was preserved with ND addition,
43
44 resulting in increased work to fracture, corresponding to the area under the stress-strain curves.
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46
47
Modulus data are examined as a function of ND content. At 0.5% w/w, the ND is not effective
48
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50 in increasing modulus very much. At 1% w/w (0.4% v/v), the reinforcement effect is very strong,
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52 but then the relative effect decreases with higher ND content, due to agglomeration effects. The
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54 mechanism for strong reinforcement effects is unclear. Theoretical predictions based on the
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3 Halpin-Tsai model for spherical particles in a polymer matrix44 do not predict strong
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6 reinforcement effects at low particle content. The presence of ND at the interfibril interface is
7
8 significant. In interfibril stress transfer, shear deformation is important for modulus. One may
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10 speculate that in the present system, viscoelastic deformation effects are suppressed due to
11
12
13
improved shear stress transfer as interfibril interactions are influenced by the presence of ND.
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15 Stress relaxation effects normally included in quasi-static tensile tests may be reduced and the
16
17 material becomes strongly reinforced by the ND. Another factor, possibly related, is that the
18
19
composites have lower porosity than Q-CNF as shown in Table 145.
20
21
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23 From Figure 4A, it is also apparent that yield strength is substantially increased. Yielding is
24
25 related to irreversible interfibril deformation,30 so the yield strength effect is in support of the
26
27 proposed reinforcement mechanism. Ultimate strength increases as a consequence of increased
28
29
30 yield strength and conserved, or even increased strain hardening coefficient in the plastic
31
32 deformation region. Strain-to-failure is similar for all materials, suggesting strain-controlled
33
34 failure.
35
36
37
38
Strongly increased mechanical properties were also reported for CNF/graphene
39
40 nanocomposites38. There were substantial improvements in the Young’s modulus, toughness and
41
42 tensile strengths. It was stated that the interface was a key reason, and that the amphiphilic nature
43
44
of CNF and the hydrophobic nature of graphene was stabilized by π-interaction. The present
45
46
47 explanation is more centered around effects of ND on CNF network deformation. The ND
48
49 decoration of the Q-CNF, may constrain network deformation, in particular for nanocomposites
50
51 where the nanodiamond content is higher than 1 weight percent. In the case of nanocomposites
52
53
54 with exceptionally high ND content (7.5, 10, 25, 50% w/w) the reinforcement efficiency was
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3 very low, most likely since ND formed large agglomerates (Supporting Info, Table 3). An
4
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6 interesting observation is that scratch hardness increased with increased ND content (SI, Table 3).
7
8
9 Another experiment was conducted by loading the material, followed by unloading, and this
10
11 was repeated with increasing levels of strain. In Figure 4B, stress versus strain diagrams of Q-
12
13
14
CNF/ND nanocomposites (1% w/w) are presented. The modulus determined during loading and
15
16 initial unloading for Q-CNF nanopaper and Q-CNF/ND materials (1% w/w) is presented in
17
18 Figure 4C. The modulus of the Q-CNF film increased with increased strain during loading steps,
19
20
as previously observed for CNF nanopaper from enzymatic CNF30. The reason is increased
21
22
23 orientation of the CNF fibrils in the network. For the nanocomposite, the yield strength is
24
25 increased with increasing plastic strain, possibly due to increased CNF orientation. Interestingly,
26
27 the nanocomposite modulus showed stronger increase than for the Q-CNF nanopaper.
28
29
30 Henriksson et al.30 proposed that increased Young’s modulus and yield strength are due to
31
32 network and CNF fibril orientation effects in the deformation direction46. One possibility is that
33
34 the presence of ND nanoparticles is increasing the degree of Q-CNF orientation at a given strain,
35
36
37
although the mechanism for such an effect is unclear.
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3.4. Scratch resistance in Q-CNF/ND materials
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26
27
Figure 5. Hardness obtained by model predictions (Equation (2) and (3)) as well as experimental
28
29 scratch hardness data (Experimental) for Q-CNF/ND nanocomposites as a function of ND
30
31 content.
32
33
34 Table 3. Scratch hardness of Q-CNF film and Q-CNF/ND nanocomposites.
35
36
37
Scratch hardness
38 Sample
(MPa)
39
40
Q-CNF 272 ± 88
41
42
43 Q-CNF/ND 0.5%w/w 302 ± 73
44
45 Q-CNF/ND 1%w/w 344 ± 92
46
47
48 Q-CNF/ND 2.5%w/w 352 ± 69
49
50 Q-CNF/ND 5%w/w 466 ± 64
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52
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54 Experiments were performed as described in experimental section. The scratch hardness is
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56 based on the width of the scratch mark. If the scratch mark is more narrow, then the scratch
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3 hardness and the scratch resistance is increased47. Increased scratch hardness is often expected
4
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6 when inorganic fillers are added to polymers48,49. Although the hardness of the filler is a key
7
8 parameter, the filler can also act as a nucleation agent so that the intrinsic polymer properties are
9
10 improved by increased crystallinity, resulting in improved scratch resistance50. Neizel et al.51
11
12
13
presented scratch resistance data for epoxy/nanodiamond materials of high ND content. The ND
14
15 particles formed a connected network structure There was a decrease in penetration depth by 1.5
16
17 µm at 25 weight percent nanodiamond content. Zhang et al.52 showed 1% w/w acyl chloride
18
19
functionalized ND enhanced the hardness of polyimide by ~30%. In this system, it was
20
21
22 suggested that due to the modification of ND, strong chemical bonding was produced between
23
24 polyimide and ND contributing to the significant increase in hardness.
25
26
27 The hardness can be roughly estimated from the Young’s modulus and the yield strength. The
28
29
30 following equations (2) and (3) were used53,54:
31
32
ଶ ா ୲ୟ୬ ఉ
‫ߪ × = ܪ‬௬ ቆ1 + ݈݊ ൬ ൰ቇ
33
(2)
34 ଷ ଷ(ଵିఔ మ )ఙ೤
35
36
37
ଶ ா ୡ୭ୱ ఏ
‫ߪ × = ܪ‬௬ ቆ1 + ݈݊ ൬ ൰ቇ
38
39 ଷ ଷఙ೤
(3)
40
41
42
43 where H is hardness, σy is yield strength, E is Young’s modulus and ν is Poisson’s ratio. β and θ
44
45 correspond to the indenter angles.
46
47
48 Note that this hardness is not strictly equal to scratch hardness, so the comparison is rough, for
49
50
51
the purpose of identifying underlying physical properties of the material. Figure 5 shows the
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53 predicted hardness and experimental data for scratch hardness for the Q-CNF/ND materials with
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55 increasing nanodiamond fraction. Predictions and experimental data show agreement up to 1
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3 weight percent nanodiamond content. The hardness of the material is increasing since the
4
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6 nanostructured composite has well-dispersed nanodiamond particles. The width of the scratch
7
8 mark is decreased in materials with nanodiamond. At 1 weight percent of nanodiamond, the
9
10 width was decreased by 1 µm and as a consequence, the scratch hardness increased by 26%, see
11
12
13
Table 3. The larger difference between experimental hardness and predicted data for the
14
15 material with 5 weight percent nanodiamond is due to the less favorable dispersion of ND at
16
17 higher reinforcement contents55. Interestingly, the scratch hardness of the Q-CNF/ND
18
19
nanocomposites was increased by further addition of ND (> 10% w/w) while the Young’s
20
21
22 modulus and the yield strength decreased (Supporting Table 3).
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4. Conclusions
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7 A nanocomposite based on Q-CNF nanofibrils decorated with ND was prepared by a simple
8
9 paper-making process using an aqueous suspension. The Q-CNF was successfully decorated by
10
11
12 ND. In the nanocomposite structure, ND nanoparticles appeared to reduce the slight porosity of
13
14 the Q-CNF network. Despite the incorporation of nanocarbon material, the Q-CNF/ND
15
16 nanomaterials were optically transparent since the nanodiamond particles were well dispersed in
17
18
19
a low-porosity material. ND nanoparticles are embedded at the interfibril interface in a fibril
20
21 “matrix” of very long (≈1µm) random-in-the-plane swirled Q-CNF nanofibrils, below 5 nm in
22
23 diameter, forming an unusual type of nanocomposite material.
24
25
26
The reinforcement effect from addition of nanodiamond particles by ionic interaction to
27
28
29 nanofibrils and cellulose nanopaper was very strong, and ductility was preserved. For instance, at
30
31 1% of ND, modulus increased from 9.8 to 13.6 GPa and yield strength from 103 to 142 MPa. At
32
33 5% ND, the ultimate strength increased from 210 MPa for neat CNF to 278 MPa for the
34
35
36 nanocomposite.. The modulus increase cannot be predicted by conventional micromechanics
37
38 models. It may be speculated that the ND nanoparticles located at fibril-fibril interfaces, are
39
40 constraining the viscoelastic nature of CNF network deformation, and thus causing a stronger
41
42
43
reinforcement effect than expected. Loading-unloading experiments in the strain-hardening
44
45 plastic deformation region, revealed stronger orientation effects in the Q-CNF/ND
46
47 nanocomposites, compared with the neat Q-CNF cellulose nanopaper. This supports that there
48
49
are specific effects of interfacially located ND on the deformation mechanisms in the Q-CNF
50
51
52 network “matrix”. The scratch hardness was also strongly increased at ND contents up to 1
53
54 percent by weight, and comparable with rough theoretical estimates of hardness. The hardness
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3 was also increased at very high ND content (5, 7.5, 10, 25, 50 wt%). The increase continued
4
5
6 although ND agglomeration effects were significant. Strength and modulus data did not increase
7
8 beyond 7.5wt% ND content.
9
10
11 In summary, by attaching ND ionically to Q-CNF, the unique properties of ND were
12
13
14
synergetically exploited for strongly improved properties of Q-CNF/ND hybrid nanomaterials.
15
16 The present nanocomposite is of renewable resource base, it is strong, exceptionally stiff and
17
18 optically transparent, at very low content of ND (0.1-1.9% v/v). Most “homeopathic”
19
20
reinforcement effects reported for nanocomposites in literature are due to significant changes in
21
22
23 the polymer matrix structure compared with the neat polymer reference, such as increased
24
25 crystallinity or orientation. The present “matrix” is unchanged in structure. It is therefore an
26
27 interesting system for further studies on reinforcement effects in this class of nanoparticle
28
29
30 composites.
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3 Supporting Information.
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5
6
7 Figures showing size distribution of ND in aqueous suspension, STEM image and AFM images
8
9 of Q-CNF from the diluted suspension, TEM image of distribution of ND in Q-CNF/ND
10
11 nanocomposite suspension, FE-SEM image of the cross section of Q-CNF/ND nanocomposite
12
13
14
(25% w/w). Table presenting zeta potential of ND, composition (TGA) and the porosity of Q-
15
16 CNF film and Q-CNF/ND nanocomposites and table summarizing mechanical properties and
17
18 scratch hardness of Q-CNF film and Q-CNF/ND nanocomposites. This material is available free
19
20
of charge via the Internet at http://pubs.acs.org.
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22
23
24
25
26 AUTHOR INFORMATION
27
28 Corresponding Author
29
30 *Tel: 46-8-7908118, Fax: 46-8-7908108, E-mail: blund@kth.se
31
32
33
34 Notes.
35
36 The authors declare no competing financial interest.
37
38
39 ACKNOWLEDGMENT
40
41 This work was supported by Grant-in-Aid for Japan Society for the Promotion of Science (JSPS)
42
43 Fellows. We are grateful to staff at WWSC and in the Biocomposites group at KTH for technical
44
45
46
help and the thoughtful discussions.
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