Supporting Information

Strongly improved mechanical properties of

thermoplastic biocomposites by PCL-grafting inside

holocellulose wood fibers

Natalia Herrera a,*, Peter Olsén a,*, Lars A. Berglund a

a Wallenberg Wood Science Center, WWSC, Department of Fibre and Polymer Technology,

KTH Royal Institute of Technology, Teknikringen 56-58, 100 44 Stockholm, Sweden.

Corresponding Authors:

*Email: Natalia Herrera: nhv@kth.se

*Email: Peter Olsén: polsen@kth.se

Includes NMR data (Figures S1 to S6), photographs of the visual appearance of unmodified

holocellulose fibers, and modified fibers (Figures S7), full scale stress-strain curves of PCL

composites (Figures S8), X-ray microtomography 3D images of composites (Figures S9), SEM

imagines of cryofractured surfaces of the PCL composites (Figures S10 and Figures S11), thermal

properties and crystallinity of composites (table S1 and Figures S12) distributed over 12 pages

(PDF).

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Contents
Calculating the DP from the fibers surface .......................................................................3

Scheme S1. Showing the repeating unit structure and 1H NMR assignment for poly(e-
caprolactone) (PCL) ..................................................................................................3

Equation S1. DP calculation for PCL grafted from the fibers surface........................3

Fiber Analysis ...................................................................................................................4

NMR assessment of graft length ......................................................................................4

Figure S1. 1H NMR for graft length calculation for fiber gHC-B10 ..............................4

Figure S2. 1H NMR for graft length calculation for fiber gHC-B20 ..............................5

Figure S3. 1H NMR for graft length calculation for fiber gHC-B40 ..............................5

Figure S4. 1H NMR for graft length calculation for fiber gHC-A10 ..............................6

Figure S5. 1H NMR for graft length calculation for fiber gHC-A20 ..............................6

Figure S6. 1H NMR for graft length calculation for fiber gHC-A40 ..............................7

Visual appearance of the fibers.............................................................................................7

Figure S7. Visual appearance of the unmodified fibers, dried fibers after swelling in
acetic acid and dried grafted fibers with acetic acid as a solvent. .............................7

Composite Properties .......................................................................................................7

Mechanical properties.......................................................................................................8

Figure S8. Full scale stress-strain curves of PCL and its composites showing the
curves of the two specimens tested per material ......................................................9

Dispersion via X-ray microtomography .............................................................................9

Figure S9. X-ray microtomography 3D reconstruction images of injection molded

composites, ...............................................................................................................9

SEM on Cryo-fractured surfaces ......................................................................................9

Figure S10.. SEM images, .......................................................................................10

Figure S11. SEM imagines of cry-fractured surfaces, .............................................10

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Thermal properties..........................................................................................................11

Figure S12. Thermal properties of PCL and its composites with unmodified fibers and
grafted fibers. a) TGA thermograms at 10 C/min. and b) DSC curves 10 C/min. ...12

Calculating the graft coverage on the fibers surface ......................................................13

Equation S2 for calculation of the surface graft coverage. ......................................13

Reference .......................................................................................................................13

Calculating the DP from the fibers surface

The DP of PCL was performed in accordance to Equation S1. The chemical shift of the -proton
is dependent if it is located at in the repeating unit or at the chain end.

O
a e
O OH
R O a
E
O n-1
Scheme S1. Showing the repeating unit structure and 1H NMR assignment for poly(e-caprolactone)
(PCL)

2.37𝑝𝑝𝑚
𝑎 ∫2.27𝑝𝑝𝑚𝑎
𝐷𝑃 = = 2.37𝑝𝑝𝑚
𝐸 ∫ 𝑎 ― ∫
4.12 𝑝𝑝𝑚
𝑒
2.27𝑝𝑝𝑚 4.02 𝑝𝑝𝑚
Equation S1. DP calculation for PCL grafted from the fibers surface.

The assessment of DP was based on three samples with the average taken as the actual DP

3
Fiber Analysis
NMR assessment of graft length

Figure S1. 1H NMR for graft length calculation for fiber gHC-B10

4
Figure S2. 1H NMR for graft length calculation for fiber gHC-B20

Figure S3. 1H NMR for graft length calculation for fiber gHC-B40

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Figure S4. 1H NMR for graft length calculation for fiber gHC-A10

Figure S5. 1H NMR for graft length calculation for fiber gHC-A20

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Figure S6. 1H NMR for graft length calculation for fiber gHC-A40

Visual appearance of the fibers

Figure S7. Visual appearance of the unmodified fibers, dried fibers after swelling in acetic acid and dried
grafted fibers with acetic acid as a solvent.

Composite Properties

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Mechanical properties

8
Figure S8. Full scale stress-strain curves of PCL and its composites showing the curves of the two
specimens tested per material

Dispersion via X-ray microtomography

Figure S9. X-ray microtomography 3D reconstruction images of injection molded composites,

of a) PCL-gHC-A40 and b) PCL-gHC-B40. PCL with lower density than cellulose is represented

in orange and fibers larger than 500 nm in a lighter color.

SEM on Cryo-fractured surfaces

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Figure S10.. SEM images,
at low (upper row) and higher (bottom row) magnification of cryo-fractured composite surfaces

of a) PCL-HC, b) PCL-gHC-B40 and c) PCL-gHC-A40. The PCL-gHC-A40 composite shows small

white homogeneously distributed dots among the matrix which are attributed to the nanofibers

produced during compounding.

Figure S11. SEM imagines of cry-fractured surfaces,

of the PCL composites prepared with the grafted fibers a) gHC-A10, b) gHC-A20 and c) gHC-A40

with acetic acid as a solvent,

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 Regarding the thermal properties of the composites, it was found that the addition of 5 wt.%

grafted HC fibers did not affect significantly the thermal properties of PCL, whereas the addition

of 5 wt.% unmodified HC fibers had a negative effect, see Figure S12 and Table S1. The presence

of unmodified HC fibers decreased the thermal stability of PCL and decreased its maximum

degradation temperature from 404 °C to 383 °C. This behavior is explained due to a higher water

content into the unmodified fibers, which speeded up the degradation process. The melt

temperature and crystallinity of PCL were also not affected by the addition of 5 wt.% HC fibers.

Only a slight higher melt temperature was observed for the PCL-gHC-A40 composite and an

increase in the crystallinity for PCL-gHC-B10.

Thermal properties
Table S1. Thermal properties and crystallinity of PCL and its composites.
Tm ΔHm Xc* Onset Max. T
Materials
(°C) (J/g) (%) (°C) (°C)

PCL 57 69 51 381 404

PCL-HC 57 65 50 365 383

PCL-gHC-B10 57 70 55 383 404

PCL-gHC-B20 57 66 51 382 402
PCL-gHC-B40 57 66 52 379 398

PCL-gHC-A10 58 64 50 379 398

PCL-gHC-A20 58 64 50 379 399
PCL-gHC-A40 60 67 52 380 403

* The crystallinity (Xc) of the materials was calculated as follows:

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 ∆𝐻𝑚 100
𝑋𝑐 = ∆𝐻°𝑚𝑥 𝑤 (Eq. S1)

Where Hm is are the melting enthalpy, H°m is the enthalpy of melting for 100% crystalline
PCL material (135.56 J/g) [Khambatta et al.] and w is the weight fraction of PCL in the sample.

Figure S12. Thermal properties of PCL and its composites with unmodified fibers and grafted fibers. a)
TGA thermograms at 10 C/min. and b) DSC curves 10 C/min.

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Calculating the graft coverage on the fibers surface
Equation S2 for calculation of the surface graft coverage.

The estimated surface area is extracted from literature. The surface area of wood pulp in the dry
and wet state are in the vicinity of 150 to 290 m2/g. Thus we estimated a surface area of 200 m2/g.
The equation used to calculate the graft coverage was the following. The calculation was
performed under the assumption that the surface area of the holo-cellulose fiber was 200m2/g and
that the weight loss during purification was the same for all fibers.

(Weight Change in gram)/((DP*MCL*N*Surface area) (Eq. S2)

Reference
Khambatta, F.B.; Warner. F.; Russel, T.; Stein, R.S. Small‐angle x‐ray and light scattering

studies of the morphology of blends of poly(ϵ‐caprolactone) with poly(vinyl chloride). J. Polym.

Sci.: Polym. Phys. 1976, 14, 1391- 1424.

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