Nanocellulose-stabilized Pickering emulsions and their applications

Figures & data

Figure 1. Solid particle at a planar oil/water interface.

Table 1. Summary of cellulose-stabilized Pickering emulsions.

Type	Cellulose source	Cellulose [surface modification]	Disperse phase	Continuous phase	Reference
o/w	Bacterial cellulose	CNC	Hexadecane, Styrene	Water	Kalashnikova et al. [79]
	Bacterial cellulose, Cotton	CNC	Hexadecane, Styrene	Water	Kalashnikova et al. [41]
	Cotton	CNC	Styrene	Water	Nypelö et al. [75]
	Cotton	CNC	Hexadecane	Water	Capron and Cathala [76]
	Corncob	CNC	D-limonene	Water	Wen et al. [81]
	Cotton, Bacterial cellulose, Cladophora	CNC	Hexadecane, Styrene	Water	Kalashnikova et al. [77]
	Softwood sulfite pulp, Cotton	CNC, NFC	Hexadecane	Water	Cunha et al. [78]
	Wood pulp	CNC, NFC, TOCN	Dodecane	Water	Gestranius et al. [70]
	Wood pulp	CNF/NFC	Hexadecane/IPDI/DBDL	Water	Svagan et al. [71]
	Wood cellulose	MCC	Sunflower oil	Water	Kargar et al. [72]
	Bacterial cellulose, Wood cellulose	BCN, MCC, MFC	Vegetable oil, Kerosene	Water	Ougiya et al. [73]
	Mangosteen rind	MFC	Soybean oil	Water	Winuprasith and Suphantharika [80]
	Softwood sulfite pulp	TOCN	Paraffin	Water	Li et al. [82]
	Wood pulp	TOCN	Styrene	Water	Fujisawa et al. [74]
	Cotton	CNC [VAc, VCin]	Ethyl acetate, Toluene, Cyclohexane	Water	Sèbe et al. [84]
	Cotton	CNC [CTAB, DMAB]	Dodecane	Water	Hu et al. [91]
	Ramie fiber	CNC [Poly(NIPAM)]	Heptane	Water	Zoppe et al. [85]
	Wood pulp	CNC [PDMAEMA]	Heptane, Toluene	Water	Tang et al. [86]
w/o	Cotton	CNC [CTAB, DMAB]	Water	Dodecane	Hu et al. [91]
	Cotton, Softwood sulfite pulp	NFC, CNC [Lauroyl chloride]	Water	Hexadecane	Cunha et al. [78]
	Softwood sulfite pulp	MFC [CDMIPS]	Water	Toluene	Andresen and Stenius [87]
	Softwood pulp	MFC [CDMIPS]	Water	Toluene	Xhanari et al. [88]
	Softwood pulp	MFC [Octadecylamine, Poly(St-co-MA)]	Water	FT-diesel	Lif et al. [89]
	Bacterial cellulose	BCN [AA, HA, DA]	Water	Toluene	Lee et al. [90]

Notes:

CNC: cellulose nanocrystal. NFC: nanofibrillated cellulose. TOCN: TEMPO-oxidized cellulose nanofibril. MCC: microcrystalline cellulose. MFC: microfibrillated cellulose. BCN: bacterial cellulose nanofibrils. IPDI: Isophorone diisocyanate. DBDI: dibutyltin dilaurate. VAc: vinyl acetate. VCin: vinyl cinnamate. CTAB: cetyltrimethylammonium bromide. DMAB: didecyldimethylammonium bromide. Poly(NIPAM): Poly(N-isopropylacrylamide). PDMAEMA: poly[2-(dimethylamino)ethyl methacrylate]. CDMIPS: chlorodimethyl isopropylsilane. Poly(St-co-MA): Poly(styrene-co-maleic anhydride). FT-diesel: Fischer–Tropsch diesel. AA: acetic acid. HA: hexanoic acid. DA: dodecanoic acid.

Figure 2. Snapshots of the behavior of separated cellulose chains in the oil-in-water medium during molecular dynamics simulation. The molecules are drawn using the stick representation for cellulose (white), and the line representation for water (blue) and octane (yellow). (Color figure online). Modified from Ref. [83], with permission from Springer (© Springer 2017).

Figure 3. Droplet size dependence on bacterial cellulose nanofibril (BCN) content (upper figure) for droplet diameters D(3,2) versus BCN concentration in the water phase in an emulsion containing hexadecane with a 30/70 oil/water ratio. (lower images) Transmission optical micrographs of the same emulsions; the corresponding concentrations are given in the images. Modified from Ref. [79], with permission from American Chemical Society (© ACS 2011).

Figure 4. Phase behavior of nanocellulose-stabilized emulsions as a function of time. The samples in the images contain 1% nanocellulosic material and 20% oil, and the creaming layer is indicated with orange arrows. Samples for micrographs of the different phases were transferred to separate vials at 24 h after preparation, and images were taken at 72 h after preparation. The scale bar is 200 μm. Modified from Ref. [70], with permission from Elsevier (© Elsevier 2017).

Figure 5. Dispersions of untreated MFC (top image) and MFC-ODA (bottom image) in water, toluene, EU-diesel, dodecane, and FT-diesel (from left to right). Modified from Ref. [89], with permission from Elsevier (© Elsevier 2010).

Figure 6. Dark-field microscopy images of o/w emulsions stabilized by (a) NFC and (b) CNC; w/o emulsions stabilized by (c) NFC and (d) CNC modified with lauroyl chloride (C12) (NFCC12 and CNCC12, respectively); and o/w/o double emulsions stabilized by (e) NFC/NFCC12, (f) CNC/NFCC12, (g) NFC/CNCC12, and (h) CNC/CNCC12. Water was stained with fluorescein. Scale bar is 50 μm. Modified from Ref. [78], with permission from American Chemical Society (© ACS 2014).

Figure 7. (a) Photograph of polystyrene/nanocellulose composite film with 12% w/w nanocellulose after melt pressing, (b) UV–vis transmittance spectra, (c) stress–strain curves, and (d) thermal expansion behavior of the composite and polystyrene films. Modified from Ref. [74], with permission from American Chemical Society (© ACS 2017).

Figure 8. Confocal laser scanning microscopy images of emulsions stabilized by cotton CNCs containing increasing amounts of hexadecane stained with 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene from (a) the original 10/90 oil/water Pickering emulsion; (b) 65% of internal phase; (c) 85.6% of internal phase; (d) the same as panel c using a stacking of 2D 1 μm-thick optical cross-section images to form a 3D reconstruction. Modified from Ref. [76], with permission from American Chemical Society (© ACS 2013).

Figure 9. (a) Esterified bacterial cellulose/photopolymerized acrylated epoxidized soybean oil nanocomposite foam (23 mm in diameter). (b) Esterified cellulose nanofibrils are shown to line a pore. Modified from Ref. [105], with permission from Royal Society of Chemistry (© RSC 2009).

Figure 10. (a) Thermogravimetric analysis and (b) differential scanning calorimetry curves of nanocellulose paper, phase change material (PCM) paper, and pure PCM. c) Optical image of PCM paper during the heat/cool cycles between 20 °C (left) and 50 °C (right) after 10 cycles. d) Stress–strain curve of the PCM paper. Modified from Ref. [83], with permission from Elsevier (© Elsevier 2017).

Figure 11. Schematic of emulsion preparation and electrospinning of CNC−poly(lactic acid) (PLA) emulsions. Modified from Ref. [107], with permission from American Chemical Society (© ACS 2013).

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