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WO2025053948A1 - Émulsions de pickering fonctionnelles et leurs procédés de fabrication et d'utilisation - Google Patents

Émulsions de pickering fonctionnelles et leurs procédés de fabrication et d'utilisation Download PDF

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WO2025053948A1
WO2025053948A1 PCT/US2024/041423 US2024041423W WO2025053948A1 WO 2025053948 A1 WO2025053948 A1 WO 2025053948A1 US 2024041423 W US2024041423 W US 2024041423W WO 2025053948 A1 WO2025053948 A1 WO 2025053948A1
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cellulose
bodies
amhcnc
anionic groups
emulsion stabilizer
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Amir SHEIKHI
Roya KOSHANI
Shang-Lin YEH
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Penn State Research Foundation
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Penn State Research Foundation
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C08B15/04—Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • C08L1/04—Oxycellulose; Hydrocellulose, e.g. microcrystalline cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof

Definitions

  • Embodiments relate to compositions and methods for emulsion stabilization and scale inhibition.
  • embodiments relate to polysaccharides such as amphiphilic hairy cellulose nanocrystals bearing hydrophilic and hydrophobic chemical groups configured to dually function as an emulsion stabilizer and antiscalant and methods for making and using thereof.
  • Emulsions play a pivotal role in a diverse range of consumer and industrial applications, from cosmetics and foods to oil and gas processes.
  • conventional emulsion stabilizers like surfactants and emulsifiers, pose environmental and health challenges, and their functionalities can be restrictive.
  • nucleation and growth of sparingly soluble salts referred to as scaling, has posed substantial challenges in industrial processes that deal with multiphase flows, including enhanced oil recovery (EOR).
  • EOR enhanced oil recovery
  • seawater is injected into oil reservoirs and yields water-in-oil (W/O) emulsions that may undergo calcium carbonate (CaCO3) scaling.
  • W/O water-in-oil
  • CaCO3 calcium carbonate
  • existing antiscaling macromolecules and nanoparticles often have adverse environmental impacts and/or are limited to functioning only in single-phase aqueous media.
  • Designing a bio-based, environmentally safe stabilizer without the use of traditional surfactants is critical for the future of emulsion stabilization.
  • developing scale- resistant W/O emulsions is integral for environmental and economic advancement in the oil industry.
  • Design criteria for such a material may include (i) preferential residence at the oil and water interface to function as a stabilizer, and (ii) simultaneous interaction with Ca 2+ to act as an antiscalant.
  • HCNCs hairy cellulose nanocrystals
  • AmHCNCs amphiphilic hairy cellulose nanocrystals
  • the AmHCNCs may feature densely packed hydrophilic and hydrophobic chemical groups anchored onto protruding disordered cellulose chains of hairy cellulose nanocrystals.
  • the AmHCNCs may facilitate the creation of exceptionally stable water-in-oil (W/O), water-in-organic solvent, oil-in-water (O/W), and/or organic solvent-in-water Pickering emulsions.
  • the AmHCNCs can also be used to stabilize droplets of polymers dissolved by organic solvents in water to reduce the amount of solvent required for processing water-insoluble polymers and materials, which enables the formation of particles, coatings, and/or bulk materials using non-water-soluble polymers in aqueous environments.
  • CaCO 3 calcium carbonate
  • a prevalent type of scale is calcium carbonate (CaCO 3 ), which emerges due to the interaction of calcium ions with dissolved carbon dioxide, yielding carbonate ions. If the concentration of these ions exceeds a certain limit, various forms of calcium carbonate can precipitate.
  • hydrophobic chemical groups anchored onto protruding disordered cellulose chains of hairy cellulose nanocrystals may stabilize organic-aqueous interfaces, and may further work alongside hydrophilic groups to prevent CaCO 3 scaling.
  • a method of producing an emulsion stabilizer comprises providing polysaccharide bodies, such as cellulose bodies; oxidizing the polysaccharide bodies to provide dialdehyde modified polysaccharide bodies; oxidizing the dialdehyde modified polysaccharide bodies to provide polysaccharide bodies bearing aldehyde and hydrophilic anionic groups; and subjecting the polysaccharide bodies bearing aldehyde and hydrophilic anionic groups to provide polysaccharide bodies bearing hydrophobic alkyl chains and hydrophilic anionic groups.
  • the hydrophobic alkyl chains comprise compounds with 8-22 carbons.
  • the hydrophilic anionic groups comprise dicarboxylate.
  • the polysaccharide bodies are cellulose bodies.
  • the cellulose bodies are oxidized with periodic acid or salts thereof.
  • dialdehyde modified polysaccharide bodies are oxidized with chlorite ions.
  • the method further comprises heating the polysaccharide bodies bearing hydrophobic alkyl chains and hydrophilic anionic groups; sonicating the polysaccharide bodies bearing hydrophobic alkyl chains and hydrophilic anionic groups; and centrifuging the polysaccharide bodies bearing hydrophobic alkyl chains and hydrophilic anionic groups.
  • the content of hydrophobic alkyl chains is between 0.5 and 7 mmol g -1
  • the content of hydrophilic anionic groups is between 0.5 and 7 mmol g -1 .
  • the content of hydrophobic alkyl chains is between 3.2-3.4 mmol g -1
  • the content of hydrophilic anionic groups is between 3.0-3.2 mmol g -1 .
  • the content of hydrophobic alkyl chains and the content of hydrophilic anionic groups are the same.
  • an emulsion stabilizer is made by a method comprising the steps of providing cellulose bodies; oxidizing the cellulose bodies to provide dialdehyde modified cellulose bodies; oxidizing the dialdehyde modified cellulose bodies to provide cellulose bodies bearing aldehyde and hydrophilic anionic groups; and subjecting the cellulose bodies bearing aldehyde and hydrophilic anionic groups to provide cellulose bodies bearing hydrophobic alkyl chains and hydrophilic anionic groups.
  • the hydrophilic anionic groups and the hydrophobic alkyl chains are attached to cellulose chains protruding from the cellulose bodies.
  • the cellulose bodies are plant-based.
  • the cellulose bodies have a rod-like shape.
  • the cellulose bodies have a length between 10 and 1000 nanometers.
  • the cellulose bodies have a length between 77 and 125 nanometers.
  • an emulsion stabilizer is configured to maintain stability at concentrations up to 2.0 wt.%.
  • an emulsion stabilizer comprises cellulose bodies comprising cellulose chains protruding from the cellulose bodies; hydrophobic alkyl chains attached to a first portion of the cellulose chains; and hydrophilic alkyl groups attached to a second portion of the cellulose chains.
  • FIG. 1 shows an exemplary method of producing the AmHCNCs configured as a dual functioning Pickering emulsion stabilizer and scale inhibitor.
  • FIG. 2 shows a schematic illustration of exemplary AmHCNCs configured as a dual functioning Pickering emulsion stabilizer and scale inhibitor.
  • FIG. 3 shows a schematic illustration of an exemplary method of synthesizing AmHCNC from a source of cellulose fibrils and/or crystals via consecutive and controlled periodate oxidation (yielding DAMC), partial chlorite oxidation (yielding bifunctional fibrils bearing aldehyde and carboxylate groups), and Schiff base reaction (yielding AmHCNC after heating).
  • FIG. 4 shows a schematic illustration of an exemplary method of synthesizing S-CNC and AHCNC from a source of cellulose fibrils and/or crystals using H 2 SO 4 (65 wt.%) or consecutive periodate oxidation reactions, respectively.
  • FIG. 5 is a graph showing representative pH titration of DAMC fibrils to obtain the aldehyde content.
  • FIG. 6 is a graph showing representative pH titration of bifunctional cellulose fibrils and/or crystals for the aldehyde content measurement.
  • FIG. 7 shows a schematic illustration of alkylation chemistry involving a Schiff base reaction between primary amine groups of octylamine and aldehyde groups of bifunctional cellulose fibrils and/or crystals.
  • the imine bond enables hydrophobic alkyl chain grafting to carboxylate -bearing cellulose fibrils and/or crystals.
  • FIG. 8 is a graph showing charge (carboxylate) content of AHCNC and AmHCNC measured via conductometric titration.
  • FIG. 9 is a graph showing a representative conductometric titration curve of AHCNC to measure carboxylate content.
  • FIG. 10 is a graph showing a representative conductometric titration of AmHCNC to measure the carboxylate content.
  • FIG. 11 is an image showing water contact angles for S-CNC, AHCNC, and AmHCNC films, measured at room temperature after 1 s equilibrium.
  • the dashed lines and arrows show the film surface and tangent line of the water droplet, respectively, within the designated region for water contact angle (0) determination.
  • FIG. 12 shows a schematic illustration of exemplary antiscaling Pickering emulsion enabled by the dual function of AmHCNC: the anionic groups may impair CaCO 3 scaling, and the alkyl groups may contribute to the emulsion stabilization.
  • FIG. 13 is a graph showing ⁇ -potential values of S-CNC, AHCNC, and AmHCNC at pH ⁇ 8.
  • FIG. 14 is a graph showing hydrodynamic equivalent size of S-CNC, AHCNC, and AmHCNC at pH ⁇ 8.
  • FIG. 15 shows an Attenuated Total Reflection-Fourier Transform Infrared (ATR-FT1R) spectra of S-CNC, AHCNC, and AmHCNC.
  • FIG. 16 shows representative atomic force microscopy (AFM) images of S-CNC, AHCNC, and AmHCNC. All three nanocelluloses may have a needle-like morphology. The inset presents a magnified view of end-to-end assembled AmHCNC.
  • FIG. 17 is a graph showing violin plots for crystal length distribution of S-CNC, AHCNC, and AmHCNC, acquired by analyzing AFM images using ImageJ software. Solid and dashed lines represent median and quartiles, respectively.
  • FIG. 18 is a graph showing violin plots for shows crystal width distribution of S-CNC, AHCNC, and AmHCNC obtained by analyzing AFM images of greater than 50 particles using Gwyddion software. Solid and dashed lines represent median and quartiles, respectively.
  • FIG. 19 shows x-ray diffraction (XRD) diffractograms of S-CNC, AHCNC, and
  • FIG. 20 is a graph showing CI values of S-CNC, AHCNC, and AmHCNC, assessed by the XRD spectroscopy.
  • FIG. 21 shows a schematic illustration of AmHCNC-stabilized W/O Pickering emulsions generated using a flow focusing microfluidic device.
  • FIG. 22 shows optical microscopy images of W/O Pickering emulsions, containing varying AmHCNC concentrations at varying incubation times. The most stable emulsion was formed at an AmHCNC concentration of 1.00 wt. %. Scale bars are 100 ⁇ m.
  • FIG. 23 is a graph showing ⁇ -potentials (pH ⁇ 8) at varying initial AmHCNC concentrations.
  • FIG. 24 is a graph showing hydrodynamic sizes of AmHCNC at varying initial AmHCNC concentrations.
  • FIG. 25 is a graph showing interfacial tension of aqueous and oil phases in W/O emulsions stabilized by varying AmHCNC concentrations. The most stable W/O emulsions were stabilized by 1.0 wt.% of AmHCNC, which is associated with the surface coverage of ⁇ 51% and the lowest interfacial tension.
  • FIG. 26 shows pendant droplet images of varying AmHCNC concetrations (0.25, 0.5, 1.0, and 2.0 wt.%).
  • FIG. 27 shows optical microscopy images of W/O emulsions, stabilized by AmHCNC (1.0 wt.%) at varying Ca 2+ concentrations and incubation times, showing a Ca 2+ concentration higher than 1 mM destabilizes the emulsions. Scale bars are 100 pm.
  • FIG. 28 is a graph showing electrophoretic mobility of AmHCNC at varying Ca 2+ concentrations.
  • FIG. 29 is a graph showing hydrodynamic equivalent size of AmHCNC at varying Ca 2+ concentrations.
  • FIG. 30 shows a schematic illustration of a destabilization process of W/O emulsions stabilized by AmHCNC containing 10 mM Ca 2+ .
  • FIG. 32 shows optical microscopy images of CaCO 3 scales in W/O emulsions, stabilized by Span 80 or AmHCNC at varying S Scale bars are 100 pm.
  • FIG. 34 is a graph showing mass of CaCO 3 scales formed in W/O emulsions, stabilized by Span 80 or AmHCNC at varying 5.
  • FIG. 35 shows pendant drop images of AmHCNC (1.0 wt.%) dispersion containing varying Ca 2+ concentrations (0-24.9 mM) with or without CO 3 2- (4.5 mM) injected in hexadecane, and a pendant drop image of Milli-Q water in Span 80 (1.0 wt.%)-containing hexadecane.
  • FIG. 36 is a graph showing the effect of Ca 2+ concentration on the water-oil interfacial tension, without or with CO 3 2- (4.5 mM) in the AmHCNC-containing aqueous phase.
  • FIG. 38 shows scanning electron microscope (SEM) images of CaCO 3 scale formation in Span 80-stabilized W/O emulsions.
  • FIG. 39 shows SEM images of CaCO 3 scale formation in AmHCNC -containing aqueous solutions.
  • FIG. 40 shows SEM images of CaCO 3 scale formation in AmHCNC-stabilized W/O emulsions.
  • FIG. 41 shows XRD spectra of CaCO 3 polymorphs in Span 80-stabilizcd emulsions.
  • FIG. 42 shows XRD spectra of CaCO 3 polymorphs in AmHCNC -containing aqueous solution.
  • FIG. 43 shows XRD spectra of CaCO 3 polymorphs in AmHCNC-stabilized emulsions.
  • the term “emulsion” is used to describe a macroscopically homogeneous but microscopically heterogeneous mixture of two or more immiscible phases.
  • the term “Pickering emulsion” is used to describe an emulsion that is stabilized by particles in colloidal suspension located at a water/oil interface. Such particles may be referred to herein as “Pickering stabilizers.”
  • compositions and methods for emulsion stabilization and scale inhibition generally relate to compositions and methods for emulsion stabilization and scale inhibition.
  • Exemplary compositions may comprise polysaccharides, such as amphiphilic hairy cellulose nanocrystals (AmHCNCs) bearing hydrophilic and hydrophobic chemical groups and configured to dually function as an emulsion stabilizer and antiscalant and methods for making and using thereof.
  • AmHCNCs amphiphilic hairy cellulose nanocrystals
  • the AmHCNCs may comprise cellulose (polysaccharide) bodies, such as cellulose fibrils and/or crystals.
  • the cellulose bodies may nanoscale (e.g., less than 100 nanometers in size) bodies.
  • the cellulose bodies may be nanofibrils and/or nanocrystals.
  • the cellulose bodies may be derived from any suitable source.
  • the cellulose bodies may be biosourced (e.g., derived from biomass).
  • the cellulose bodies may be plant-based, such as derived from wood pulp, cotton, algae, or any other suitable plant-base source. It is further contemplated that the cellulose bodies may be non-toxic and and/or biodegradable.
  • the cellulose bodies may have a plurality of cellulose chains (also referred to as “hairs”) protruding from their ends.
  • the cellulose chains may be configured to be functionalized with one or more chemical groups.
  • the cellulose chains may be disordered such that they are configured to accommodate a high content of chemical groups.
  • a portion of the cellulose chains may be functionalized with hydrophobic alkyl chains.
  • the hydrophobic alkyl chains may include any alkyl chain with 8-22 carbon atoms. It is contemplated that the hydrophobic alkyl chains may all have the same number of carbon atoms, or the hydrophobic alkyl chains may have any different numbers of carbon atoms.
  • the hydrophobic alkyl chains may be attached to any functional groups, such as amines (-NH 2 ), carboxylates (-COO”), etc., to facilitate functionalization of the cellulose chains.
  • the hydrophobicity of the alkyl chains may impart wettability properties to the AmHCNCs, thus enabling the AmHCNCs to form Pickering emulsions by residing at the water-oil interface.
  • AmHCNCs may serve as versatile Pickering stabilizers and facilitate the creation of stable water-in-oil (W/O), water-in-organic solvent, oil-in-water (O/W), and/or organic solvent-in-water Pickering emulsions.
  • the hydrophobic alkyl chains may be functionalized to the cellulose chains via a Schiff base reaction.
  • a portion of the cellulose chains may be functionalized with hydrophilic anionic groups.
  • the hydrophilic anionic groups may be selected from the group consisting of carboxylates, dicarboxylates, sulfates, or any other suitable anionic group. It is contemplated that the hydrophilic anionic groups may impart antiscaling properties to the AmHCNCs, thus enabling the AmHCNC to be used as scale inhibitors.
  • the hydrophilic anionic groups may be functionalized to the cellulose chains via a chlorite oxidation reaction.
  • one portion of the cellulose chains may be functionalized with hydrophobic alkyl chains and another portion of the cellulose chains may be functionalized with hydrophilic anionic groups, such the AmHCNCs may have functionality as both a Pickering stabilizer and an antiscalant.
  • the concentrations of the hydrophobic alkyl chains and hydrophilic anionic groups functionalized on the cellulose chains may be the same or approximately the same.
  • the concentration of the alkyl chains functionalized on the cellulose chains may be 0.5-7 mmol g -1 , preferably approximately 3.2-3.4 mmol g -1
  • the concentration of the anionic groups functionalized on the cellulose chains may be 0.5-7 mmol g’ 1 , preferably approximately 3.0-3.2 mmol g -1 .
  • a portion of the cellulose chains may be functionalized with additional chemical groups, such as cationic and/or electrically neutral groups, to impart additional functionality to the AmHCNCs.
  • the AmHCNCs may be any shape and/or size, though it is contemplated that the AmHCNCs may be rod-like or needle-like structures with lengths in the range of 10-1000 nm, preferably 77-125 nm, and widths (e.g., diameters) in the range of 1.5-10 nm.
  • the cellulose bodies are elongated in shape; that is, having a length/width ratio higher than 1.
  • the AmHCNCs may have improved wettability properties in comparison to other nanocelluloses.
  • the AmHCNCs may have a contact angle between 51.4 and 72.4 degrees.
  • the AmHCNCs may remain stable at weight percentages up to 2.0 wt.%, preferably up to 1.0 wt.%.
  • the AmHCNCs may remain stable for at least 120 min. at a weight percentage of 1.0 wt.%.
  • the AmHCNCs have a hydrodynamic equivalent size ranging from 269-281 nm.
  • Methods of preparing the AmHCNCs may generally comprise at least a periodate oxidation step, a chlorite oxidation step, and an alkyl amination (i.e., Schiff base reaction) step.
  • the method may comprise providing cellulose bodies, such as cellulose fibrils and/or crystals.
  • the cellulose bodies may be derived from any suitable source.
  • the method may further comprise oxidizing the cellulose bodies (e.g., with periodic acid or its salts) to synthesize dialdehyde modified cellulose (DAMC).
  • DAMC dialdehyde modified cellulose
  • the cellulose bodies may have vicinal diols (adj acent hydroxyl groups) in their structures, and this oxidation step may cleave the carbon-carbon bond between the diols, resulting in the formation of aldehydes. This step may be used to selectively oxidize the diols without affecting other functional groups present in the molecule.
  • the DAMC may comprise reactive aldehyde groups that may be subject to further processing.
  • the method may further comprise oxidizing the DAMC (e.g., with chlorite ions) to synthesize DAMC modified with anionic groups. It is contemplated that this step may be carried out in acidic conditions and may result in the formation of chlorate ions as the primary oxidation product. In preferred embodiments, this step may be carried out such that half or approximately half of the reactive aldehyde groups of the DAMC are converted to anionic groups. As described above, it is contemplated that anionic groups may impart antiscaling properties to the molecules, thus enabling the resulting AmHCNCs to be used as scale inhibitors. This chlorite oxidation step may therefore be critical in achieving the antiscaling properties of the AmHCNCs.
  • oxidizing the DAMC e.g., with chlorite ions
  • the chlorite oxidation step may comprise adding DAMC to a solution comprising NaCIO 2 , and H 2 O 2 may then be added (dropwise) to form DAMC modified with a desired amount of anionic groups.
  • the method may further comprise subjecting the remaining reactive aldehyde groups to alkyl amination, thus yielding cellulose bodies bearing both anionic groups and alkyl chains.
  • alkyl amination may involve introducing an alkyl group to the molecule by replacing a hydrogen atom with the alkyl group, thus resulting in the formation of an alkylamine.
  • alkyl chains may impart stabilizing properties to the molecules, thus enabling the resulting AmHCNCs to be used as Pickering stabilizers. This alkyl amination step may therefore be critical in achieving the antiscaling properties of the AmHCNCs.
  • the alkyl amination step may comprise subjecting the remaining reactive aldehyde groups of the cellulose bodies to a Schiff base rection (see FIG. 7).
  • a Schiff base rection see FIG. 7
  • half or approximately half of the reactive aldehyde groups of the DAMC are converted to anionic groups, and half or approximately half of the reactive aldehyde groups of the DAMC are converted to alkyl chains.
  • this step may comprise suspending the modified DAMC in DI water, adding alkyl chains, and stirring the resulting mixture.
  • the product may be collected and dialyzed.
  • the product may then be heated, sonicated (e.g., using a probe sonicator) in an ice bath, and centrifuged to remove un-fibrillated fibrils.
  • An AmHCNC- containing supernatant may then be finally separated from the mixture.
  • the method may further comprise functionalizing a portion of the reactive aldehyde groups with additional chemical groups, such as cationic and/or electrically neutral groups, to impart additional functionality to the AmHCNCs.
  • additional chemical groups such as cationic and/or electrically neutral groups
  • Exemplary methods of using the above-described AmHCNCs may include using the AmHCNCs in oil and gas operations.
  • the AmHCNCs comprises dual-functionality and may (i) form Pickering emulsions via residing at the water-oil interface (enabled by the alkyl chains) while also (ii) impairing scaling in the aqueous phase (enabled by decarboxylated hairs).
  • Exemplary methods of using the above-described AmHCNCs may further include using the AmHCNCs in cosmetic applications. It is contemplated that the AmHCNCs may effectively stabilize emulsions, resulting in cosmetic products with a smoother (e.g., less gritty) appearance and feel.
  • Exemplary methods of using the above-described AmHCNCs may further include using the AmHCNCs in food applications.
  • the above are only exemplary uses for the described AmHCNCs, and uses of the AmHCNCs are not limited to these listed examples.
  • T o assess the simultaneous Pickering stabilization and scale inhibition capability of nanocelluloses, AHCNC and AmHCNC were synthesized, and S-CNC was purchased.
  • FIG. 4 presents common synthesis pathways for S-CNC or AHCNC involving the strong acid hydrolysis or sequential oxidation of cellulose fibrils, respectively.
  • Sulfuric acid ( H 2 SO 4 , 65 wt %)-mediated hydrolysis of cellulose fibrils at 45°C for 45 minutes removes the disordered regions and yields negatively charged S-CNC, bearing sulfate half-ester groups, as shown in FIG. 4.
  • HCNC synthesis involves the conversion of cellulose fibrils to dialdehyde modified cellulose (DAMC) fibrils via NalO 4 -mediated oxidation.
  • DAMC dialdehyde modified cellulose
  • DAMC fibrils undergo further oxidation using NaCIO 2 to functionalize disordered cellulose regions with dicarboxylate groups and partially solubilize them, yielding AHCNC and DCC chains, which are then separated from each other via EtOH-mediated precipitation, as presented in FIG. 4.
  • a representative pH titration curve of DAMC fibrils is shown in FIG. 5, indicating the amount of NaOH required to neutralize the HC1 released from the hydroxylamine-aldehyde reaction. Accordingly, the DAMC aldehyde content was 6.3 ⁇ 0.1 mmol g -1 .
  • FIG. 3 presents the 3-step synthesis pathway of AmHCNC, including consecutive periodate oxidation, chlorite oxidation, and Schiff base reaction.
  • AmHCNC half of the DAMC aldehyde groups (i.e., ⁇ 3 mmol g -1 ) were subjected to chlorite oxidation, yielding bifunctional cellulose fibrils and/or crystals, bearing both aldehyde and dicarboxylate groups.
  • the aldehyde content of bifunctional cellulose fibrils was ⁇ 3.3 ⁇ 0.3 mmol g -1 , measured via pH titration, as shown in FIG. 6 for a representative sample.
  • FIGS. 9 and 10 show representative curves for the conductometric titration of AHCNC and AmHCNC, respectively.
  • the carboxylate group content was calculated from the NaOH volume required to neutralize the carboxylic acid (i.e., weak acid), resulting in 5.3 ⁇ 0.1 mmol g -1 for AHCNC and 3.1 ⁇ 0.1 mmol g -1 for AmHCNC. Almost 90% of DAMC aldehyde groups were converted to carboxylate groups to form AHCNC.
  • FIG. 11 presents the water contact angle on S-CNC, AHCNC, or AmHCNC films in air.
  • FIG. 12 schematically shows the dual-functionality of AmHCNC, forming Pickering emulsions via adsorbing to the water-oil interface, mediated by the alkyl chains, while impairing CaCO 3 scaling in the aqueous phase, enabled by the dicarboxylate- modified cellulose chains (hairs).
  • T o compare the colloidal behavior of hairy and non-hairy nanocelluloses, the ⁇ ,- potential and hydrodynamic equivalent size were measured in Milli-Q water (pH ⁇ 8, adjusted using NaOH), as presented in FIGS. 13 and 14.
  • AHCNC had the highest ⁇ -potential (-51 ⁇ 2 mV) compared with S-CNC (-35 ⁇ 2 mV) and AmHCNC (-36 ⁇ 2 mV) as it bears the highest content of charged groups (5.9 ⁇ 0.1 mmol of carboxylate g -1 ).
  • AHCNC had the largest hydrodynamic equivalent size (275 ⁇ 6 nm) compared with S-CNC (126 ⁇ 5 nm) and AHCNC (131 ⁇ 6 nm) likely because of the grafted, long alkyl chains on the protruding hairs, which facilitate supramolecular hydrophobic interactions.
  • FIG. 15 presents the ATR-FTIR spectra of S-CNC, AHCNC, and AmHCNC.
  • characteristic peaks of cellulose at ⁇ 3300 and ⁇ 2900 cm -1 were observed, corresponding to O-H and C-H stretching vibrations, respectively.
  • the peaks at ⁇ 1410, ⁇ 1300, and —1000 cm -1 in the spectra of all nanocelluloses were assigned to CH 2 scissor bending, O-H bending, and CH2-O-CH2 stretching vibrations in the cellulose structure, respectively.
  • the S-CNC spectrum had a peak at 868 cm -1 , which corresponds to the symmetrical C-O-S vibrations of sulfate half-ester groups introduced during H2SO4 hydrolysis.
  • AmHCNC the grafting of eight-carbon alkyl chains was reflected in the strong peaks at 2924 and 2855 cm -1 , corresponded to asymmetric and symmetric-CH2- stretching vibrations, respectively. Together, the FTIR spectra show that the aliphatic chains were successfully grafted to AmHCNC, which also bear dicarboxylate groups.
  • FIG. 16 shows the representative AFM images of S-CNC, AHCNC, and AmHCNC. All three nanocellulose had a rod- or needle-like morphology, which was consistent with the reported nano-celluloses isolated via oxidation or acid hydrolysis reactions.
  • AFM images of AmHCNC show some end-to-end assembled particles, which may be a result of interparticle hydrophobic interactions, induced by grafted alkyl chains on the hairs.
  • FIG. 17 presents the length of nanocellulose crystalline body, obtained via analyzing the AFM images of >50 particles using the ImageJ software (Version 1.53t 24). The average crystal lengths of S-
  • CNC, AHCNC, or AmHCNC were 108 ⁇ 32, 84 ⁇ 25, or 104 ⁇ 27 nm, respectively. Note that
  • AFM imaging captures the crystalline body of nano-celluloses, and visualizing protruding, disordered chains is not trivial. Indirect evidence of amorphous chains (hairs) is discussed in our previous publications.
  • the width of nanocellulose crystalline body, determined by AFM imaging (FIG. 18), is 8 ⁇ 4 nm for S-CNC, 3 ⁇ 1 nm for AHCNC, and 2.5 ⁇ 1.0 nm for AmHCNC.
  • the higher width of S-CNC may be a result of colloidal aggregation originating from low charge density.
  • FIG. 19 shows the X-ray diffractograms of S-CNC, AHCNC, and AmHCNC.
  • the diffractograms of all nanocelluloses included the cellulose I ⁇ characteristic peaks, i.e., the (110), (110), and (200) crystalline planes. This confirms that the crystalline regions of cellulose fibrils were preserved following oxidation or acid hydrolysis reactions.
  • FIG. 20 presents the CI of S-CNC, AHCNC, and AmHCNC, which was —90% for all three nanocelluloses without any significant differences.
  • the CI of softwood kraft pulp used for the synthesis of cellulose micro- and nanoparticles was ⁇ 79%.
  • the higher CI values for the nanocelluloses may be associated with the partial removal of disordered regions.
  • the CI values agreed with those previously reported for S- CNC (-90%) and AHCNC (-91%).
  • FIG. 21 presents a schematic of W/O emulsion preparation using a three-dimensional (3D) printed flow focusing microfluidic device. Droplets with a diameter of 115 ⁇ 5 pm were formed via pinching the aqueous phase with an oil phase (hexadecane). Neither the S-CNC nor AHCNC were able to form stable W/O emulsions likely because of their highly hydrophilic surface.
  • the crystalline part of S-CNC or AHCNC may be adsorbed at the water-oil interface; however, the sulfate half-ester groups of CNC or dicarboxylate groups of AHCNC favor the nanoparticles to stay in the aqueous phase, hindering their adsorption at the interface.
  • the wettability of intact nanocellulose i.e., crystalline body
  • CNC-stabilized Pickering emulsions reported in the literature have been prepared by intensive homogenization or sonication techniques in which the size of droplets was much smaller ( ⁇ 1 pm) than the emulsion droplets generated by the flow focusing device here ( ⁇ 115 pm).
  • FIG. 22 shows the optical microscopy images of W/O Pickering emulsions, stabilized using varying AmHCNC concentrations over time.
  • AmHCNC concentration 0.50 to 1.00 wt %
  • the emulsions remained stable from ⁇ 5 min up to ⁇ 120 min, whereas using 2.00 wt % of AmHCNC, the emulsions were destabilized in ⁇ 10 min.
  • the W/O emulsions were unstable when the initial AmHCNC concentration was below 1.00 wt % because of insufficient/low surface coverage of water droplets by the nanoparticles.
  • the surface coverage (C) was calculated from the ratio of theoretical maximum surface of AmHCNC in the emulsion to the total surface of dispersed water droplets, using Equation (1):
  • the surface coverage for emulsions stabilized by 0.25, 0.50, 1.00, and 2.00 wt % of AmHCNC were 13%, 26%, 51%, or —100%, respectively.
  • AmHCNC concentration higher than 1.00 wt.% e.g., 2.00 wt %), an excessive number of grafted alkyl chains may trigger colloidal aggregations in droplets via hydrophobic interactions, causing droplet coalescence.
  • FIGS. 23 and 24 present the
  • FIGS. 25 and 26 present the interfacial tension between the aqueous and oil phases at varying AmHCNC concentrations and representative images of pendant droplets, respectively.
  • the interfacial tension of water and hexadecane is 52 mM m -1 .
  • the interfacial tension decreased from 41 ⁇ 2 to 29 ⁇ 4 mN m -1 , followed by an increase to 37 ⁇ 2 mN m -1 at 2.00 wt % of AmHCNC.
  • the alkyl chains grafted to AmHCNC increased the oil wettability of nanoparticles, likely reducing the interfacial tension.
  • steric stabilization originated from the AmHCNC crystalline body and the cellulose hairs as well as electrostatic stabilization as a result of anionic functional groups of hairs may significantly contribute to the Pickering stabilization. Accordingly, AmHCNC may also enable Pickering emulsions via the electrosteric stabilization of water droplets, dispersed in the oil phase.
  • FIG. 27 presents the optical microscopy images of W/O Pickering emulsions, stabilized by AmHCNC (1.00 wt %) at Ca 2+ concentrations ranging from 0 to 62.2 mM over 1 week (168 h). As observed in the figure, the emulsions became significantly less stable by increasing the Ca 2+ concentration. To investigate the colloidal interactions between Ca 2+ and AmHCNC, FIGS.
  • FIG. 30 schematically presents the evolution of a W/O Pickering emulsion, containing AmHCNC and Ca 2+ , over time.
  • FIG. 31 presents the electrically neutral Span 80-stabilized W/O emulsions at varying Ca 2+ concentrations, demonstrating stable emulsions without undergoing coalescence for at least 1 week.
  • FIG. 32 presents the optical microscopy images of aqueous droplets stabilized by Span 80 or AmHCNC in the oil, undergoing CaCO 3 scaling at varying S over time.
  • FIG. 32 presents the optical microscopy images of aqueous droplets stabilized by Span 80 or AmHCNC in the oil, undergoing CaCO 3 scaling at varying S over time.
  • FIG. 34 presents the mass of CaCOi formed in the W/O emulsions stabilized by Span 80 (at S ⁇ 101) or by AmHCNC (at S ⁇ 101, 124, or 143) after 4 h and 1 day of incubation at room temperature.
  • the CaCO 3 mass after 4 h was almost the same as that after 1 day in all samples, indicating that 4 h of incubation was sufficient to reach the maximum CaCO 3 crystal formation at the selected initial ion concentrations.
  • the antiscaling mechanism is associated with AmHCNC role as a threshold inhibitor, which at the ppm level interferes with the nucleation and growth of early stage CaCO 3 crystals via the electrostatic interactions between the anionic carboxylate groups on its hairs and Ca 2+ in CaCO 3 .
  • FIGS. 35 and 36 present the interfacial tension of aqueous phase-oil phase, used in the AmHCNC-stabilized W/O Pickering emulsions, as well as the corresponding pendant droplets at varying concentrations of Ca 2+ without or with CO 3 2- (4.5 mM), respectively.
  • the interfacial tension increased from 29 ⁇ 4 to 43 ⁇ 4 mN m -1 .
  • FIG. 37 presents the time to break AmHCNC-enabled W/O Pickering emulsions at varying Ca 2+ concentrations without or with CO 3 2- (4.5 mM).
  • the incubation time to break the emulsions decreased from ⁇ 76 to ⁇ 42 h by increasing the Ca 2+ concentration from 10 to 20 mM as a result of Ca 2+ 'mediated AmHCNC aggregation.
  • the time to break the emulsions remained almost unchanged ( ⁇ 150 h) in the scaling system (i.e., with both Ca 2+ and CO 3 2- ), implying that the coexistence of Ca 2+ and CO 3 2- reduced the concentration of free Ca 2+ that would otherwise bridge AmHCNC and compromise the emulsion stability.
  • the dual functional AmHCNC not only impaired CaCO 3 scale fomiation but also imparted Pickering stability to the emulsion.
  • AmHCNC is compared with other previously-used nano-celluloses used to form Pickering emulsions.
  • AmHCNC is the only nanocellulose that enables scale reduction in the emulsions, performing simultaneously as a “scale inhibitor” and an “emulsion stabilizer.”
  • FIGS. 38-40 present the SEM images of CaCO 3 scales formed in the Span 80 (1.00 wt %)-containing W/O emulsion, AmHCNC (1.00 wt %)-containing aqueous solution, and AmHCNC-stabilized W/O Pickering emulsion, respectively.
  • the CaCO 3 scales in the Span 80-containing medium had a typical calcite structure, whereas the CaCO 3 scales in an AmHCNC -containing medium had both calcite and vaterite structures.
  • FIGS. 41-43 present the XRD patterns of CaCO 3 scales formed in the Span 80 (1.00 wt %)-containing W/O emulsion, AmHCNC (1.00 wt %)-containing aqueous solution, and AmHCNC (1.00 wt %)-stabilized W/O Pickering emulsion, respectively.
  • the calcite crystal structure was identified in the Span 80-stabilized emulsions, whereas both calcite and vaterite structures were found in the AmHCNC-containing aqueous solution or AmHCNC-stabilized Pickering emulsions.
  • the stoichiometric molar ratio of COO- (3.1 mmol g -1 , 1.00 wt % AmHCNC) to the Ca 2+ (12.4 mM) is 2.5, far exceeding the required stoichiometric molar ratio ( ⁇ 0.049) for AHCNC-mediated scale inhibition, based on AHCNC used in a single-phase aqueous system.16
  • a significant portion of AmHCNC are at the water-oil interface ( ⁇ 51% surface coverage), stabilizing the emulsion.
  • Custom-built micro fluidic flow focusing devices fabricated using acrylonitrile butadiene styrene (ABS) via stereolithography three-dimensional (3D) printing were provided by Proto Labs Inc. (MN, USA).
  • the devices with dimensions of 24 mm (length) x 26 mm (width) x 9 mm (height), featured three l/4”-28 holes positioned equidistantly.
  • Tygon® tubing with a 1/4” outer diameter (OD) and 1/8” inner diameter (ID) was purchased from Saint-Gobain Life Sciences (OH, USA). Unless otherwise specified, all experiments were conducted using Milli-Q water (resistivity ⁇ 18 M ⁇ cm) at room temperature.
  • DAMC dialdehyde modified cellulose
  • the reaction mixture was stirred at room temperature for 12 h while maintaining the pH at 5.0 ⁇ 0.2 via gradually adding NaOH (0.5 M) during the first 5 h.
  • Nonfibrillated fibers in the suspension were then separated via centrifugation at 27,000g for 15 min, and AHCNC were isolated from the supernatant by ethanol addition (0.8 g per 5 g of suspension) and centrifugation at 3000g for 15 min.
  • the gel-like AHCNC precipitate was dispersed in DI water ( ⁇ 250 mL) and purified via dialysis (Spectra/Por dialysis bags, 6-8 kDa cutoff) against DI water for at least 3 days.
  • H 2 O 2 (1.7 mL) was added dropwise within ⁇ 1 min. Note that only half of the aldehyde groups were converted to carboxylate groups for AmHCNC synthesis, whereas for AHCNC preparation, the majority of aldehyde groups were converted.
  • the reaction mixture was stirred at room temperature for 12 h while maintaining the pH at 5 ⁇ 0.2 by NaOH (0.5 M) addition.
  • the bifunctional cellulose fibrils and/or crystals were then separated through vacuum filtration and washed using an ethanol solution (80% v/v) five times.
  • the suspension was heated to 60 °C for 1 h, sonicated using a probe sonicator (Qsonica Q500, CT, USA) in an ice bath for 20 min, and centrifuged at 5000 Xg for 15 min to remove the unfibrillated fibrils.
  • the AmHCNC-containing supernatant was collected and stored in the fridge (4-7 °C).
  • HC1 was titrated against a NaOH solution (10 mM) at a flow rate of 0.1 mL min -1 using an automatic titrator (Mctrohm 907 Titrando, USA). The titration endpoint was obtained where the pH was stabilized at 3.5 (i.e., the initial pH).
  • the nanocrystals Prior to the measurements, the nanocrystals were completely dried in an oven at 37 °C overnight. The spectra were the average of 100 scans recorded at a resolution of 6 cm’ 1 . The bare diamond spectrum was used as a reference to obtain a baseline and normalize the sample absorbance values.
  • Disks were then rinsed with Milli-Q water five times, and one drop of a S-CNC, AHCNC, or AmHCNC dispersion (0.1 mg mL-1) was deposited onto the mica and air-dried overnight.
  • the disks were then rinsed with Milli-Q water five more times and air-dried overnight before imaging.
  • the acquired images were analyzed by the NanoScope Analysis software (Version 1.80, accessed through Penn State Materials Characterization Laboratory, MCL). Dimensions of >50 particles per sample were quantified by the Gwyddion software (Version 2.49, accessed through Penn State MCL).
  • DLS dynamic light scattering
  • ⁇ is the electrophoretic mobility of particles in the parallel direction to the electric field
  • Pi is the electrophoretic mobility of particles in the perpendicular direction to the electric field
  • K is the Debye-Hüickel parameter
  • a is the radius of the cylindrical particles (obtained from AFM images)
  • f(K ⁇ ) is Henry’s function
  • ⁇ r is the dielectric constant of vacuum
  • ⁇ 0 is the dielectric constant of water
  • ⁇ is the viscosity.
  • the interfacial tension measurements were carried by a Goniometer/Tensiometer 260 (Ramehart, USA) using the pendant drop method.
  • the effect of AmHCNC on interfacial tension between an aqueous solution and hexadecane was investigated by varying AmHCNC concentrations from 0.25 to 2.0 wt.%.
  • the Ca 2+ concentrations varied from 0 to 20 mM with or without 4.54 mM of CO 3 2- while the AmHCNC concentration was maintained constant at 1.0 wt.% for all samples.
  • a droplet of an aqueous solution was suspended from a metallic 28 Gauge needle (Fisher Scientific, USA) into hexadecane (continuous phase) at room temperature.
  • Multiple images of an individual drop with a known volume of 5 pL were taken at 0.2 s intervals for a total of 6 s.
  • the drop radius of curvature at the apex (Ro) and the shape factor (P) were analyzed for at least 10 images to determine the interfacial tension (y) using Equation (4).
  • ⁇ p denotes the density difference between water (999 kg m -3 ) and hexadecane (773 kg m -3 ), and g shows the gravitational acceleration of earth (i.e., 9.8 m s -2 ).
  • Surfactant- stabilized W/O emulsions were prepared using ABS flow focus device at fixed flow rates (oil phase: 480 pL min -1 , aqueous phase: 120 pL min -1 ) and room temperature.
  • the oil phase was prepared via dissolving Span 80 (1.0 wt.%) in hexadecane while the aqueous phase was Milli-Q water with the pH adjusted to 8. Both oil and aqueous phases were then injected into the flow focusing device using two separate syringe pumps to generate the W/O emulsions.
  • the aqueous phase was prepared via dissolving 19 mg of NaHCO3 in 50 mL of an AmHCNC dispersion (1.00 wt %, pH adjusted to 8 using 0.5 M NaOH), resulting in a HCO 3- concentration of 4.5 mM. Then, 91.5, 137.3, or 183.0 mg of CaCl 2 2 H 2 O was added to the AmHCNC/HCO 3- dispersion to obtain a Ca 2+ concentration of ⁇ 12.4, 18.7, or 24.9 mM, respectively.
  • the oil phase for the AmCHCNC-stabilized emulsions was hexadecane.
  • the aqueous phase was prepared via dissolving 19 mg of NaHCO3 and 91.5 mg of CaCl 22 H 2 O in 50 mL of Milli-Q water (pH adjusted to 8 using 0.5 M NaOH), yielding a HCO 3- concentration of 4.5 mM and a Ca 2+ concentration of 12.4 mM.
  • the oil phase was hexadecane containing Span 80 (1.00 wt %). Assuming that HCO 3- is fully dissociated to CO3 2- , the supersaturation degree (5) was calculated using Equation (5).
  • a denotes the activity of Ca 2+ or CO 3 2-
  • K sp is the solubility product constant.
  • Emulsions containing a Ca 2+ concentration of 10, 15, or 20 mM result in S of 90, 135, or 180, respectively, with respect to calcite, which has a K SP of 5.5 x 10 -9 at room temperature.
  • the AmHCNC- or Span 80-stabilized aqueous droplets in the oil phase were then generated via injecting the aqueous and oil phases into the flow focusing device at fixed flow rates (oil phase: 480 pL min -1 and aqueous phase: 120 pL min -1 ) and room temperature.
  • the emulsions were incubated for 4 h or 24 h at room temperature, and subsequently centrifuged at 5000 Xg for 5 min.
  • the samples were coated with a 3 nm-thick layer of indium using a vacuum sputtering instrument (Leica sputter coating EM ACE 600, USA). SEM imaging was conducted using an accelerating voltage of 3 kV and a beam current of 6.3 pA with the through-the-lens detector (TLD) in the field-free mode.
  • TLD through-the-lens detector

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Abstract

Des modes de réalisation concernent des polysaccharides tels que des nanocristaux de cellulose capillaire amphiphiles et leurs procédés de fabrication et d'utilisation. Les nanocristaux de cellulose capillaire amphiphiles peuvent une fonction double en tant que stabilisant de Pickering polyvalent et en tant qu'agent antitartre. Les nanocristaux de cellulose capillaire amphiphiles peuvent comprendre des chaînes alkyle hydrophobes et des groupes carboxylate hydrophiles ancrés sur des chaînes de cellulose désordonnées en saillie de corps de cellulose. D'autres groupes, tels que des groupes cationiques et/ou électriquement neutres, peuvent être ancrés sur des chaînes désordonnées en saillie pour conférer une fonctionnalité supplémentaire.
PCT/US2024/041423 2023-09-07 2024-08-08 Émulsions de pickering fonctionnelles et leurs procédés de fabrication et d'utilisation Pending WO2025053948A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112851976B (zh) * 2021-03-05 2021-12-21 厦门大学 一种用于染料降解的纤维素基水凝胶制备方法
US11576851B2 (en) * 2016-07-12 2023-02-14 L'oreal Composition of pickering emulsion

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Publication number Priority date Publication date Assignee Title
US11576851B2 (en) * 2016-07-12 2023-02-14 L'oreal Composition of pickering emulsion
CN112851976B (zh) * 2021-03-05 2021-12-21 厦门大学 一种用于染料降解的纤维素基水凝胶制备方法

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TANG CHUNXIA, SPINNEY STEWART, SHI ZENGQIAN, TANG JUNTAO, PENG BAOLIANG, LUO JIANHUI, TAM KAM C.: "Amphiphilic Cellulose Nanocrystals for Enhanced Pickering Emulsion Stabilization", LANGMUIR, AMERICAN CHEMICAL SOCIETY, vol. 34, no. 43, 30 October 2018 (2018-10-30), pages 12897 - 12905, XP093286814, ISSN: 0743-7463, DOI: 10.1021/acs.langmuir.8b02437 *
VISANKO MIIKKA, LIIMATAINEN HENRIKKI, SIRVIÖ JUHO ANTTI, HEISKANEN JUHA PENTTI, NIINIMÄKI JOUKO, HORMI OSMO: "Amphiphilic Cellulose Nanocrystals from Acid-Free Oxidative Treatment: Physicochemical Characteristics and Use as an Oil–Water Stabilizer", BIOMACROMOLECULES, AMERICAN CHEMICAL SOCIETY, US, vol. 15, no. 7, 14 July 2014 (2014-07-14), US , pages 2769 - 2775, XP093286813, ISSN: 1525-7797, DOI: 10.1021/bm500628g *
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