US20190055373A1 - Bacterial cellulose gels, process for producing and methods of use - Google Patents
Bacterial cellulose gels, process for producing and methods of use Download PDFInfo
- Publication number
- US20190055373A1 US20190055373A1 US16/017,319 US201816017319A US2019055373A1 US 20190055373 A1 US20190055373 A1 US 20190055373A1 US 201816017319 A US201816017319 A US 201816017319A US 2019055373 A1 US2019055373 A1 US 2019055373A1
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- United States
- Prior art keywords
- cellulose
- aerogel
- disclosed
- gels
- aerogels
- Prior art date
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- Abandoned
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Definitions
- cellulose-based flexible gels containing cellulose nanorods, ribbons, fibers, and the like, and cellulose-enabled inorganic or polymeric composites, wherein the gels have tunable optical, heat transfer, and stiffness properties.
- the disclosed gels are in the form of hydrogels, organogels, liquid-crystal (LC) gels, and aerogels.
- LC liquid-crystal
- highly transparent and flexible cellulose nanofiber-polysiloxane composite aerogels featuring enhanced mechanical robustness, tunable optical anisotropy, and low thermal conductivity.
- gels comprising cellulosic material derived from bacteria and processes for preparing bacterial cellulose gels and methods of use.
- FIG. 1 shows the schematic of fabrication procedures of cellulose-enabled ordered gels (a) cellulose nanomaterials aqueous dispersion, (b) hydrogel, (c) organogel (d) aerogel, and (e) liquid crystal gel.
- FIG. 2 shows transmission electron microscopy (TEM) images of cellulose nanorods, nanofibers, nanoribbons from different sources: (a) cellulose nanorods from cotton, (b) cellulose nanowires from cotton, (c) cellulose nanowires from wood pulp, and (d) cellulose nanoribbons from bacterial cellulose.
- TEM transmission electron microscopy
- FIG. 3 shows photographs of nematic cellulose (a) hydrogel, (b) organogel, (c) aerogel, (d) nematogel, and (e) scanning electron microscopy (SEM) image of the ordered aerogel.
- the scale bar is 1 cm.
- FIG. 4 shows photographs of cholesteric (a) cellulose-silica composition, (b) silica aerogel, (c) silica nematogel, and (d) SEM image of the ordered silica aerogel.
- the scale bar is 5 mm.
- FIG. 5 is a schematic representation of a spectrometer assembly that can be used for haze measurements at diffuse illumination and unidirectional viewing.
- FIG. 6 describes a general schematic of one embodiment for the fabrication of the disclosed aerogels.
- FIG. 7 shows the optical pathway of a typical pump-and-probe measurement system.
- FIG. 8 discloses the components of a hot box apparatus: a metering box (simulating interior temperature) on one side of the window specimen; a controlled guard box surrounding the metering box; a climate chamber box (simulating exterior temperature) on the other side; and the specimen frame providing specimen support & insulation.
- FIGS. 9A-C various TEMPO-oxidized cellulose nanoparticle modifying agents.
- FIG. 9A depicts surface modification by allylamine.
- FIG. 9B depicts surface modification by a 2-(carbamoyloxy)-N,N,N-trimethylethanaminium adduct.
- FIG. 9C depicts surface modification by example a methoxy polyethylene glycol amine (mPEG-amine).
- FIG. 10 depicts the disclosed process for forming polymethylsilsesquioxane (PMSQ) network cellulosic hydrogels, organogels and aerogels process in general.
- PMSQ polymethylsilsesquioxane
- FIG. 11 is a photograph showing the optical transparency of a hydrogel formed from the disclosed process.
- FIG. 12 is a photograph showing the optical transparency of an organogel formed from the disclosed process.
- FIG. 13 is photograph showing the optical transparency of an aerogel formed from the disclosed process wherein the surface modifying agent is allylamine.
- FIG. 14 is a photograph of an aerogel formed by the disclosed process wherein the surface modifying agent is an m-PEG-amine having an average molecular weight of 5000 daltons.
- FIG. 15 is a photograph of an aerogel formed by the disclosed process wherein the surface modifying agent is carbamoylcholine chloride.
- FIG. 16 depicts that the carbamoylcholine chloride-capped TOCN-PMSQ aerogels exhibit hydrophobic surface characteristics.
- FIGS. 17A-C are transmission electron microscopy (TEM) micrographs of the disclosed aerogels at various magnifications.
- FIGS. 17B and 17 C are scanning electron microscopy (SEM) that depict the well-defined and uniform-diameter 10-15 nm nanofibers that are formed by polysiloxane.
- SEM scanning electron microscopy
- FIG. 18 shows the visible transmission of a disclosed aerogel.
- FIG. 19 shows the haze coefficient of a disclosed aerogel.
- FIG. 20 depicts that the PMSQ matrix causes TOCN-PMSQ aerogels to exhibit strong absorption at a wavelength of 6-20 ⁇ m that is mainly due to the Si—O bond.
- FIG. 21 shows the measured thermal conductivity of a TOCN-PMSQ aerogel versus sample porosity.
- FIG. 22 depicts the comparison of thermal conductivity between an aerogel formed from carbamoylcholine chloride modified nanocellulose (quaternary-amine) and an allylamine modified aerogel.
- FIG. 23 depicts the compression stress-strain relation for a TOCN-PMSQ aerogel with 0.06 wt. % of TOCN.
- FIG. 24A and FIG. 24B depict the reorientation of an A. hansenii bacterium using the infrared laser beam of a laser trap.
- FIG. 25 is a photograph of dark field microscopy showing an A. hansenii bacterium producing a cellulose fiber.
- FIG. 26 shows A. xylinum bacteria producing cellulose fibers.
- FIG. 27A and FIG. 27B shows the effect on cellulose fibril thickness when 1.5% sodium carboxymethyl cellulose is added to A. xylinum .
- FIG. 27A the cellulose fibril is visible.
- FIG. 27B the thickness of the fibril is greatly reduced such that the fibril is invisible in the photograph.
- FIG. 28 is a depiction of an Acetobacter cell showing multiple cellulose synthase enzymes extruding cellulose fibrils from the cellular membrane. As the fibrils lengthen hydrogen bonding between adjacent strands cause the fibrils to coalesce and form ribbons.
- FIG. 29 is a depiction of an Acetobacter cell showing multiple cellulose synthase enzymes extruding cellulose fibrils from the cellular membrane. In this iteration, carboxymethyl cellulose is added to the growth media resulting in hydrogen bonds not forming the fibrils into ribbons of fiber.
- FIG. 30A and FIG. 30B show an example of the disclosed aerogel biofilms.
- FIG. 31A and FIG. 31B are thermal imaging photographs comparing a standard polysiloxane polymer with a gel formed by the disclosed process.
- a “gel” is understood to be a substantially dilute cross-linked system that exhibits no flow when in the steady state.
- the primary constituent of the gel is the ambient fluid surrounding it, whose form can be a liquid or gas.
- Prefixes such as “aero,” “organo,” “hydro,” and variations are understood to indicate the ambient fluid in the cross-linked gel matrix and primary component of the gel material.
- the disclosed gels contain cellulosic nanocomposites that are aligned in ordered liquid crystal phases.
- the disclosed gels allow the formulator to adjust the optical transmissivity of the gel, thereby configuring the optical properties of the gel to range from opaque to transparent.
- the properties can be adjusted to interact with a wide range of the electromagnetic spectra, for example, from the visible spectrum to infrared spectrum.
- the thermal conductivity of the gel can be adjusted.
- the bulk properties of the disclosed gels for example the level of stiffness or flexibility can be adjusted by the choice of the constituent cellulosic material, for example, nanorods, ribbons, fibers, and the like, as well as, the concentration of these materials in the resulting gels.
- a “film” and variations indicate non-porous lamellae ranging in thickness from about 10 nm to 1 mm and arbitrary lateral extent.
- cross-section means width and the terms are used interchangeably.
- the disclosed cellulosic nanomaterials have a width from about 10 nm to about 500 nm.
- the length of the nanomaterials is at least ten times the width.
- composition refers to the disclosed cellulose nanomaterial aqueous dispersions, hydrogels, organogels, aerogels, and liquid crystal gels.
- the compositions can be a single layer of material comprising nanomaterials or the composition can be formed from two or more distinct layers wherein each layer consists of only one material.
- one layer can consist of an ordered nematic cellulosic gel onto which a second layer of aligned cholesteric cellulose film is applied thereto. This layering thereby forms a unified composite material with distinct layers.
- hydrogel represents a network of cellulosic material as a colloidal gel dispersed in a carrier.
- the carrier is water.
- the carrier is a mixture of a water compatible (miscible) organic solvent.
- the cellulosic material can be crosslinked or non-crosslinked.
- organogel as used herein is a gel wherein the aqueous phase of a precursor hydrogel has had substantially all of the water removed and replaced by a water compatible solvent.
- compatible solvents include methanol, ethanol, propanol and isopropanol.
- the disclosed organogels have a two dimensional cross-linked network. In another embodiment the disclosed organogels have a three dimensional crosslinked network.
- anogel refers to a gel derived from the further processing of a disclosed organogel as described herein.
- liquid crystal gel refers to the compositions derived from the further processing of the disclosed organogels as described herein.
- nanomaterial refers to the disclosed cellulosic material. The width of these materials is in the nanometer range, whereas the length of the cellulosic material can vary from nanometer length to micrometer.
- nanomaterial refers to the disclosed cellulosic material. The width of these materials is in the nanometer range, whereas the length of the cellulosic material can vary from nanometer length to micrometer.
- nanomaterial refers to the disclosed cellulosic material. The width of these materials is in the nanometer range, whereas the length of the cellulosic material can vary from nanometer length to micrometer.
- nanomaterial “cellulosic material” and “cellulosic nanomaterial” are used interchangeably throughout the present disclosure.
- nematic refers to a composition wherein the disclosed cellulosic materials possess long-range orientational order. In addition, the cellulosic materials are free to flow and their center of mass positions are randomly distributed, but still maintain their long-range directional order.
- the disclosed nematic compositions are uniaxial: they have one axis that is longer and preferred, with the other two being equivalent.
- cholesteric refers to a composition with a helical structure and which is therefore chiral.
- the disclosed cholesteric compositions are organized in layers with no positional ordering within layers, but a director axis which varies with layers.
- the variation of the director axis can be periodic in nature. If present, the period of this variation (the distance over which a full rotation of 360° is completed) is known as the pitch, which can be adjusted by the formulator, and the degree of pitch determines the wavelength of electromagnetic radiation which is reflected.
- TOCK TEMPO-oxidized cellulose nanofibers
- low molecular weight compounds comprising a cationic moiety means a compound that has a moiety that can react with an oxidized cellulose carboxyl group in addition to a separate cationic moiety.
- Non-limiting examples of units that can react with an oxidized cellulose carboxyl group de hydroxyl group, an amino group, a thiol group, and the like.
- a non-limiting example of a cationic moiety includes a quaternary ammonium group.
- compositions comprising cellulosic nanoribbons that are aligned together and which orientation can be adjusted by the formulator.
- the disclosed nanoribbons have aspect ratios from about 1:100 to about 1:1000.
- the disclosed nanoribbons can be used to form a nematic flexible gel.
- These cellulose-based flexible gels can comprise cellulose ribbons, fibers, and other constituent-particle structures having in one embodiment aspect ratios of about 1:1000.
- These flexible gels are formed from linking the cellulose particle networks within the material.
- the original cellulose solvent which is used for the formation of the gel network can be retained or replaced to yield a variety of gel types, for example, hydrogels, alcogels, aerogels, and liquid-crystal gels.
- the use of the disclosed cellulosic material to form the gel network allows the formulator to adjust the flexibility of the gels.
- the aspect ratios allow for a greater degree of flexibility or rigidity depending upon the selection of cellulosic nanomaterial.
- the cellulose particles can be ordered through chemical and mechanical means to yield a lyotropic liquid crystalline dispersion with ordered phases. The ordering can be preserved during the cross-linking process to form various ordered gels, non-limiting examples of which are given above.
- FIG. 1 illustrates the fabrication procedure of cellulosic ordered gels.
- the optical transmissivity of the disclosed gels can be adjusted to range from opaque to transparent.
- the degree of opaqueness or transparency can also be matched of any wavelength or range of wavelength in the electromagnetic spectrum.
- a further property which can be tailored to the needs of the formulator is the degree of thermal resistance displayed by the gels.
- the thermal resistive properties (1) the intrinsically low thermal conductivity of cellulose, (2) the rarefication of fluid within the cellulose network thereby regulating the thermal convection, and (3) the thermal conductivity and convection properties of the fluids which comprise the cellulose-gel network.
- compositions comprising cellulosic nanorods that are aligned and which orientation can be adjusted by the formulator.
- the disclosed nanoribbons have aspect ratios from about 1:10 to about 1:100.
- the disclosed nanorods can be used to form compositions with a cholesteric phase.
- the disclosed nanocrystals form ordered films that can be ordered into a cholesteric phase in the film to form a periodic structure whose pitch and pitch gradient are adjustable for broad-band Bragg reflection of incident electromagnetic radiation.
- the resulting ordered gels are obtained because of the small relative aspect ratios of the cellulose nanorods or similar nanomaterials that comprise the nanocrystals. Nanorods result in the formation of different phases than other nanomaterials, i.e., nanofibers. Because of this fact broad-band reflection is enabled in ordered cellulose gels that are formed from cellulose structures with aspect ratios of about 1:10 to about 1:100.
- the mechanical flexibility, optical transmissivity, and thermal resistance can be configured by tuning the same parameters described nanofibers, except that those parameters now refer specifically to cellulose nanorods or other geometrically anisotropic cellulose structures.
- a further aspect of the present disclosure relates to composite structures comprising lamellae that are formed from the disclosed aerogels or liquid crystal gels.
- Composite structures with lamellae can be formed from the disclosed compositions that comprise nanofiber-like cellulosic materials (nematic phase) or from nanorod-like cellulosic materials (cholesteric phase). These composite structures comprise a plurality of layers.
- a portion of the cellulosic nanomaterial is replaced with liquid crystals.
- the nematic phase or cholesteric phase gels can have the liquid phase substituted by other anisotropic organic or inorganic materials.
- silica is introduced into the hydrogel.
- liquid crystal material for example, 1-(trans-4-hexylcyclohexyl)-4-isothiocyanatobenzene can replace the carrier of the hydrogel.
- the cellulose after the incorporation and alignment of non-cellulosic materials, the cellulose can be partially or totally removed, by chemical means, to yield gels and films with partial or total cellulose substitution.
- lamellae which comprise the disclosed composite structures.
- the lamellae are formed from two or more distinct layers wherein each layer comprises different materials.
- the cellulosic nanomaterials that comprise each layer can further serve as a template and can be substituted partially or totally by other materials such as silica or other polymers.
- the disclosed cellulose nanomaterials can have a variety of shapes and cross-sectional geometries that depend upon the nanomaterial's natural source and the process used to produce the particles.
- a disclosed cellulose nanomaterial can have a shape that is a rod, fiber, ribbon, whisker, and the like.
- the disclosed cellulose nanomaterials can be obtained by chemical or mechanical treatment of a variety of natural sources, for example, cotton, soft wood pulp, hard wood pulp, tunicate and bacterial cellulose and the like.
- nanorods and nanofibers can be obtained from multiple sources, for example, cotton and bacterial cellulose.
- the disclosed nanocellulose can have a length from about 10 ⁇ m to 100 ⁇ m with cross sections from about 10 nm to 50 nm. In another embodiment, the disclosed nanocellulose can have a length from about 1 ⁇ m to 10 ⁇ m with cross sections from about 3 nm to 10 nm. In a yet another embodiment, the disclosed nanocellulose can have a length from about 100 nm to 1 ⁇ m with cross sections from about 3 nm to 10 nm.
- FIG. 2 shows TEM micrographs of cellulose particles with characteristic length scales of the aforementioned embodiments: (a) cellulose nanorods of 10 nm ⁇ 200 nm depends upon the chemical treatment from cotton, (b) cellulose nanowires of 7 nm ⁇ 800 nm from cotton, (c) cellulose nanowires of 4.8 nm ⁇ 1 ⁇ m from wood pulp, and (d) cellulose nanoribbons of 10 nm ⁇ 50 nm ⁇ 10 ⁇ m from bacterial cellulose.
- the cellulose nanomaterials can be obtained by chemical hydrolysis of natural cellulose by sulfuric acid, hydrochloric acid, etc. or by 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-mediated oxidation.
- TEMPO 2,2,6,6-tetramethylpiperidine-1-oxyl radical
- the cellulose nanomaterials can be aligned by linear or circular shearing for nematic or cholesteric ordering, respectively. Nematic ordering of the disclosed cellulose nanofibers is shown in FIG. 1( b ) .
- the cellulose nanomaterial dispersion can be confined between glass plates in a mold such that, when a shear stress is applied from the plates in the specified direction, individual nanocellulose particles align to form a singular director alignment across the confined dispersion.
- the nanocellulose suffers unidirectional alignment under extrusion from a sufficiently small diameter nozzle, syringe, or similar device.
- the aligned dispersion takes the form of a narrow bead, with linear extent much greater than its cross-sectional extent, which rests on a supportive substrate or other structure.
- the helical axis of cellulose nanorods in cholesteric phase can be aligned by anticlockwise circular shearing during the evaporation of the dispersion.
- the disclosed cellulose nanomaterials can also be aligned by magnetic or electric fields.
- the magnetic anisotropy of cellulose nanomaterial's relative permeability can be exploited to cause uniform alignment of nanocrystals.
- sufficiently strong magnetic fields about 1 T
- uniform alignment of nanocrystals perpendicular to the magnetic field is achieved through the magnetic interaction of the induced magnetic dipole moments of the cellulose nanomaterial with the applied magnetic field.
- an oscillating electric field can also be used to aligned the cellulose nanomaterials with their long axis along the electric field.
- the alignment of the disclosed cellulose nanomaterial dispersions can be preserved by its conversion to a hydrogel, example embodiments which are shown in FIG. 1( b ) and FIG. 3( a ) .
- the extent of cross-linking of the cellulose nanomaterial establishes the degree to which uniform ordering is preserved in the dispersion. For example, a low level of crosslinking provides a weaker gelation. Conversely a greater degree of cross-linking yields firmer gelation. Gelation is accomplished by the addition of an acid, photoacid generator and exposure to light, alcohol, or other cationic exchange reagent to a uniformly ordered cellulose nanomaterial dispersion.
- hydrochloric, acetic, nitric, sulfuric, and phosphoric acids can be added to instigate gelation.
- Ca 2+ can be added to provide cross-linking.
- the disclosed ordered hydrogels can be transformed into organogels, as shown in FIG. 1( c ) and FIG. 3( b ) using a solvent exchange procedure.
- a hydrogel can be gently shaken while immersed in an ethanol-filled bath followed by replacing the solvent at regular intervals. In this way, the water is sequentially removed from the matrix and replaced with ethanol.
- Other organic solvents can substitute for ethanol.
- Non-limiting examples of other solvents include methanol, ethanol, isopropanol, butanol, hexane, acetone, dichloromethane, dimethylformamide (DMF), dimethylsulfoxide (DMSO), and toluene.
- the disclosed cellulose aerogels or films herein can be produced from the disclosed nano-structured organogel herein above.
- Example aerogels are shown in FIG. 1( d ) and FIG. 3( c ) .
- the resulting cellulose nanomaterial aerogel is porous having a skeleton of about 0.1-99.9% of cellulose nanocrystals and a porosity of from about 0.01 to about 99.99%. In one embodiment the porosity is from about 97% to about 99%.
- Aerogels comprising a low percentage of of nanocellulosic material results aerogels having a high degree of transparency, for example, from about 1% to about 50% by weight of the aerogel. Aerogels comprising from about 50% to about 90% by weight of nanocellulosic material results aerogels having a high degree translucent scattering.
- supercritical drying, freeze drying, or ambient drying with a low surface-tension solvent are used to remove liquid solvent from cellulose nanocrystal composites while maintaining the disclosed liquid crystalline structure, such as nematic or cholesteric liquid crystalline ordering.
- the resulting monolithic cellulose nanomaterial film is a solid material with 100% cellulose composition.
- Ambient drying is used to remove liquid solvent.
- the disclosed cellulose LC gels herein can be produced from the disclosed nano-structured organogel.
- the organic solvent is replaced with LC by solvent exchange.
- the LC functions as the gel's solvent.
- FIG. 1( e ) portrays a schematic representation of LC gels while FIG. 3( d ) portrays an LC gel whose LC solvent is in the nematic phase.
- the disclosed compositions can comprise any LC that will serve as solvents for the gels.
- Non-limiting examples of nematic LCs include: 1-(trans-4-hexylcyclohexyl)-4-isothiocyanatobenzene; 4′-(hexyloxy)-4-biphenylcarbonitrile; 4′-(octyloxy)-4-biphenyl-carbonitrile; 4′-(pentyloxy)-4-biphenylcarbonitrile; 4′-heptyl-4-biphenylcarbonitrile; 4′-hexyl-4-biphenylcarbonitrile; 4′-octyl-4-biphenylcarbonitrile; 4′-pentyl-4-biphenylcarbonitrile; 4,4′-azoxyanisole; 4-isothiocyanatophenyl 4-pentylbicyclo[2.2.2]octane-1-carboxylate; 4-(trans-4-pentylcyclohexyl)benzonitrile; 4-methoxycinn
- FIG. 4 demonstrates cellulose-enabled cholesteric (a) cellulose-silica film composition, (b) silica aerogel, and (c) silica LC gel whose solvent is LC in its nematic phase.
- An SEM image of the ordered silica aerogel is displayed in FIG. 4( d ) .
- the cellulose nanomaterials can be removed to obtain inorganic gels or films.
- inorganic/cellulose composite gels or films are formed without etching the cellulose nanomaterials.
- the inorganic gels or films are made of silica, organo-silica, titanium dioxide, aluminum oxide, rare earth oxides, etc.
- the weight concentration of inorganic nanomaterial in the inorganic/cellulose composites can range from about 1% to about 99%.
- Polymers can be incorporated into the heretofore disclosed ordered gels or films using cellulose nanomaterials as a template.
- the cellulose nanomaterials can be removed to obtain polymeric gels or films.
- polymeric/cellulose composites gels or films are formed without etching the cellulose nanomaterials.
- the polymeric gels or films are made of phenol-formaldehyde, melamin-formaldehyde, urea-formaldehyde, poly(acrylic acid), polyester, etc.
- the weight concentration of polymeric nanomaterial in the polymeric/cellulose composites can range from about 1% to 99%.
- the surface properties of the disclosed gels can be modified by functionalizing the surface of the cellulosic network.
- the disclosed aerogels having no surface functionalization are hydrophilic and can dissolve or shrink its total volume upon contacting with water.
- Surface modifiers example, dimethyloctadecyl [3-(trimethoxysilyl) propyl] ammonium chloride (DMOAP) and trichloro(1H,1H,2H,2H-perfluoro-octyl)silane can be added to the hydrogel before conversion to an aerogel. This type of surface modification provides a hydrophobic aerogel that is stable upon exposure to water.
- colloidal particles having lengths ranging from about 1 nm to 10 ⁇ m can be homogeneously dispersed within the gels.
- the colloids can include gold and silver plasmonic nanoparticles such as rods, triangular platelets, and triangular frames; ferromagnetic nanoparticles such as ferromagnetic nanoplatelets; quantum dots such as nano-spheres, -cubes, -rods, and the like.
- the colloidal particles are introduced into the cellulose before cross-linking occurs. Cross-linking, through interaction with the colloidal surface ligands, binds the colloidal inclusions to the ordered cellulosic network as described previously herein.
- Any of the disclosed gels can contain one or more types of colloidal particles.
- the disclosed gels have a thickness from about 1 ⁇ m to about 10 cm. In one embodiment the thickness varies from about 10 ⁇ m to about 1 cm. In another embodiment the thickness varies from about 100 ⁇ m to about 10 cm. In a further embodiment the thickness varies from about 50 ⁇ m to about 1 cm. In still further embodiment the thickness varies from about 1 cm to about 10 cm. In a yet another embodiment the thickness varies from about 10 ⁇ m to about 100 cm. In a yet still further embodiment the thickness varies from about 500 ⁇ m to about 10 cm.
- the transmissivity of the disclosed gels relates to the amount of electromagnetic radiation that is blocked from passing through the gel. 0% transmission results in an opaque material which allows no transmission. 100% transmission results in a material that is transparent to electromagnetic radiation.
- the disclosed gels can have a transmission of from 0% to 100%. In one embodiment the gels have a transmission of from about 5% to about 15%. In another embodiment the gels have a transmission of from about 25% to about 50%. In a further embodiment the gels have a transmission of from about 95% to 100%. In a still further embodiment the gels have a transmission of from about 15% to about 35%. In a yet further embodiment the gels have a transmission of from about 50% to about 75%. In a yet another embodiment the gels have a transmission of from about 25% to about 75%.
- the disclosed gels and composite materials can have a thermal conductivity of from about 10 ⁇ 3 W/(m ⁇ K) to about 10 W/(m ⁇ K). In another embodiment the thermal conductivity is from about 10 ⁇ 2 W/(m ⁇ K) to about 10 W/(m ⁇ K). In a further embodiment the thermal conductivity is from about 10 ⁇ 1 W/(m ⁇ K) to about 10 W/(m ⁇ K). In a still further embodiment the thermal conductivity is from about 10 ⁇ 3 W/(m ⁇ K) to about 1 W/(m ⁇ K). In yet further embodiment the thermal conductivity is from about 10 ⁇ 2 W/(m ⁇ K) to about 1 W/(m ⁇ K). In yet another embodiment the thermal conductivity is from about 1 W/(m ⁇ K) to about 10 W/(m ⁇ K).
- the relative emissivity value of the disclosed gels ranges from about 10 ⁇ 2 to 0.99.
- the disclosed gels and composites can have a bulk modulus of from about 1 Pa to about 10 6 Pa. In one embodiment the modulus is from about 10 Pa to about 10 5 Pa. In another embodiment the modulus is from about 10 2 Pa to about 10 6 Pa. In a further embodiment the modulus is from about 10 3 Pa to about 10 5 Pa. In a still further embodiment the modulus is from about 10 Pa to about 10 3 Pa. In a yet further embodiment the modulus is from about 1 Pa to about 10 Pa. In a yet another embodiment the modulus is from about 10 4 Pa to about 10 6 Pa.
- Cellulosic starting material for the disclosed gels can be derived from a variety of sources.
- the surface-sulfuricated cellulose particles ( FIG. 1( a ) and FIG. 2 ) that are suspended in water can be prepared by sulfuric acid-mediated oxidation of the natural cellulose.
- the surface-carboxylated cellulose nanofibers and nanoribbons that are suspended in water can be prepared by 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)-mediated oxidation of the natural cellulose.
- TEMPO 2,2,6,6-tetramethyl-1-piperidinyloxy
- thermodynamically stable cholesteric for cellulose nanorods
- nematic for cellulose nanofibers or nanoribbons
- Cellulosic starting material for the disclosed aerogels can be biosynthesized by Acetobacter xylinum, Acetobacter hasenii or other examples of bacterial strains utilizing, for example, glucose as a carbon source.
- Acetobacter xylinum can be cultivated in a glucose medium for 1-3 weeks under static conditions to produce cellulose pellicles.
- bacterial cellulose can be boiled in a 1 wt. % NaOH aqueous solution for 2 hours, followed by washing with water and neutralization with 0.2% acetic acid.
- Natural cellulose material obtained in this way can easily be disintegrated into individual nanocrystals by a controlled TEMPO mediated oxidation.
- 2 g of bacterial cellulose was suspended in water (150 mL) containing TEMPO (0.025 g) and NaBr (0.25 g).
- a 1.8 M NaClO solution (4 mL) was added, and the pH of the suspension was maintained at 10 by adding 0.5 M NaOH. When no more decrease in pH was observed, the reaction was finished. The pH is then adjusted to 7 by adding 0.5M HCl.
- the TEMPO-oxidized products were cellulose nano-rods of controlled 4-10 nm diameter and 1000-3000 nm length, which were then thoroughly washed with water by filtration and stored at 4° C.
- Cellulose nanocrystals can also be synthesized by sulfuric acid hydrolysis method from natural cellulose.
- the aqueous suspension of such cellulose nanocrystals above the critical concentration ( ⁇ 3-6 wt. %) self-assemble into liquid crystalline structures-chiral nematic phase, which shows periodic helicoidal structures with a pitch that can be controlled in the range 5-70 ⁇ m.
- This structure can strongly reflect electromagnetic radiation of the wavelength comparable with the pitch, which simultaneously serves as a high efficiency low-emissivity structure by tuning the pitch to be appropriate range.
- the disclosed films can have a pre-designed gradient of cholesteric pitch in helicoidally ordered nanocrystal self-assembly and achieve broadband infrared selective reflection and low-emissivity (compare to the red infrared emission curve taken from solicitation) while being transparent in the visible spectral range and also transmitting solar radiation (blue curve) in near-IR range.
- the concentration of the liquid crystalline cellulose nanocrystal dispersions was then adjusted to 3 wt. % and used in preliminary studies.
- the chiral nematic liquid crystalline order of the nanocrystals was then poured into a mold and the orientation of the helix could be aligned uniformly perpendicular to the film plane using a circular shearing or magnetic field.
- the polarizing optical micrograph shown in FIG. 4 c was obtained for a sample with the helical axis aligned in the horizontal direction, providing a side view of the periodic helicoidal structure of the chiral nematic liquid crystal.
- this helical axis will be set orthogonal to the plane of the film and along the normal to the window ( FIG. 2 ), which will be achieved using the process of circular shearing (see, Park J. H. et al. “Macroscopic control of helix orientation in films dried from cholesteric liquid-crystalline cellulose nanocrystal suspensions”, ChemPhysChem. 15, 1477-1484, 2014).
- the cellulose nanomaterial can be dispersed in water and aligned by the following methods.
- the dispersion can be confined between glass plates in a mold such that, when a shear stress is applied from the plates in the specified direction (along a line or through a rotation), individual nanomaterial directors align to form a singular director alignment across the confined dispersion.
- the nanocrystals suffer uniform alignment under extrusion from a sufficiently small diameter nozzle, syringe, or similar device.
- extrusion alignment no confining plates are needed such that the aligned dispersion takes the form of a narrow bead, with linear extent much greater than cross-sectional extent, which rests on a supportive substrate or other structure.
- the magnetic anisotropy of cellulose nanomaterial's relative permeability can be exploited to cause uniform alignment of nanocellulose.
- sufficiently strong magnetic fields about 100 mT
- uniform alignment of nanocrystals is achieved through the magnetic interaction of the induced magnetic dipole moments of the cellulose nanomaterial with the applied magnetic field. (An oscillating electric field can be used to align nanocellulose with its long axis along the electric field.)
- the aligned cellulose nanomaterial dispersion can be cross-linked to convert into a hydrogel while preserving its ordering.
- the extent of cross-linking of chains of cellulose nanomaterials establishes the degree to which uniform ordering is preserved in the dispersion. That is, for loosely cross-linked cellulose nanomaterials, weak gelation results. Conversely, strong cross-linking yields firm gelation. Gelation results from the addition of an acid, a photoacid generator and exposure to light, an alcohol, or another cationic exchange mechanism to the uniformly ordered cellulose nanomaterial dispersion.
- the cellulose nanorods, inorganic/cellulose nanorods, or polymeric/cellulose nanorods can self-assemble into cholesteric phase by evaporation.
- the nanocellulose-based ordered hydrogel was transformed into organogels ( FIG. 1( c ) and FIG. 3( b ) ) by shaking the cellulose-nanomaterial hydrogel gently in an organic-solvent-filled bath while replacing the solvent regularly in order to prompt the replacement of water in the hydrogel by the organic solvent.
- twice per day for an extent of three days ethanol was replaced to facilitate total solvent exchange.
- the disclosed cellulose aerogels ( FIGS. 1( d ) and 3( c ) ) can be produced from the disclosed nano-structured organogel herein above.
- the resulting cellulose nanocrystal aerogel is a porous material with a skeleton of about 0.1-99.9% cellulose nanocrystals and a porosity of about 0.1-99.9%.
- supercritical drying, freeze drying, or ambient drying low-surface tension solvent are used to remove liquid solvent from cellulose nanocrystal composites while maintaining the disclosed liquid crystalline structure, such as nematic or cholesteric liquid crystalline ordering.
- the disclosed cellulose LC gels ( FIG. 1( e ) and FIG. 3( d ) ) can be produced from an ordered nano-structured organogel, in which an organic solvent completely miscible with LC is chosen.
- the organogel is placed in a bath of LC above the boiling point of the organic solvent so that the organic solvent is replaced with LC, which functions as the gel's replacement solvent.
- the disclosed cellulose-templated ordered inorganic and polymeric gels or films can be produced by mixing cellulose nanomaterials with silica precursors or prepolymer and drying the composites in the ambient environment. Then the cellulose nanomaterials will be removed either by acidic (for silica aerogel) or basic (for polymeric aerogel) treatment to form a hydrogel. The hydrogel can be further transferred into organogel, aerogel, and LC gel based on the methods described above.
- CNCs cellulose nanocrystals
- cellulose nanorods Colloidal suspensions of cellulose nanocrystals (CNCs) composed of cellulose nanorods were prepared by controlled sulfuric acid hydrolysis of cotton fibers, according to the method described by Revol and co-workers (J.-F. Revol, H. Bradford, J. Giasson, R. H. Marchessault, D. G. Gray, Int. J. Biol. Macromol. 14, 170 (1992)). During this process, disordered or paracrystalline regions of cellulose are preferentially hydrolyzed, whereas crystalline regions, which have a higher resistance to acid, remain intact. 7 g of cotton was added to 200 g of 65 wt % sulfuric acid and stirred at 45° C.
- CNF's Cellulose nanofibers with the dimension of 4.8 nm by several micrometers were synthesized following the literature (T. Saito, M. Hirota, N. Tamura, S. Kimura, H. Fukuzumi, L. Heux and A. Isogai, Biomacromolecules, 10, 1992 (2009)). Briefly, cellulose based bleached coffee filter (1 g) was suspended in 0.05 M sodium phosphate buffer (90 mL, pH 6.8) dissolving 16 mg of 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) and 1.13 g of 80% sodium chlorite in an airtight flask.
- TEMPO 2,2,6,6-tetramethylpiperidine-1-oxyl radical
- the 2 M sodium hypochlorite solution (0.5 mL, 1.0 mmol) was diluted to 0.1 M with the same 0.05 M buffer used as the oxidation medium and was added at one step to the flask. The flask was immediately stoppered, and the suspension was stirred at 500 rpm and 60° C. for 96 hours. After cooling the suspension to room temperature, the TEMPO-oxidized cellulose was thoroughly washed with water by filtration. Then 0.1-1.0 vol. % CNFs aqueous dispersion was poured into a mold, aligned by a shear force, and several drops of 1 M HCl solution was added to form a hydrogel after 2 hours.
- the hydrogel was immersed into ethanol for 2 days for solvent exchange to form an organogel.
- the organogel was immersed in a bath of liquid crystal 4-cyano-4′-pentylbiphenyl at 90° C. for 12 hours. Subsequent cooling to room temperature after solvent exchange caused the LC to enter its expected nematic phase.
- the aerogel was formed by critical point drying of the organogel.
- CNCs were synthesized according the method in Example 1. Then 5 mL of 3 wt % CNCs dispersion was mixed with 10-750 ⁇ L of silica precursor tetramethyl orthosilicate and stirred for 1 hour. Then the composites were cast into a Petri dish and dried over 1-2 days. The CNCs were then removed by pyrolysis method (e.g. 540° C. for 20 hours) or keeping in 16% sodium hydroxide solution for 16 hours. The silica hydrogel was formed and can be further transferred into organogel by solvent exchange and aerogel by critical point drying or ambient drying.
- pyrolysis method e.g. 540° C. for 20 hours
- CNCs were synthesized according the method in Example 1. Then 5 mL of 3 wt % CNCs dispersion was mixed with 10-75 mg of water-soluble preformed polymer and stirred for 10 min. Then the composites were casted into a Petri dish and dried over 1-2 days. The film was then cured at polymerization temperature for 24 hours. The CNCs were then removed by 16% sodium hydroxide solution for 16 hours. The polymer hydrogel was formed and can be further transferred into organogel by solvent exchange and aerogel by critical point drying or ambient drying.
- FIG. 5 describes an apparatus developed and adapted to measure the quality of the disclosed aerogels.
- the apparatus in FIG. 5 has the advantage of conducting haze measurements that also provides diagnostic data on the origins of the haze.
- the typical setup includes an integrating sphere where the measured film is placed against the sphere entrance port.
- the surface of the interior of the integrating sphere is highly reflecting throughout the visible wavelengths obtained from light sources.
- the light entering the integrating sphere is reflected from the surface towards the tested film.
- the light transmitted through the film is focused and directed to a photodetector.
- a photodetector in the spectrophotometer setup is computer driven and values for transmission and haze can be automatically calculated.
- FIG. 6 outlines a procedure for probing of the pore size, surface area, and structural properties of cholesteric cellulose-based aerogels under different preparation conditions.
- the ordering of nanocrystals on large scales will be probed using 3D imaging techniques such as Fluorescence Confocal Polarizing Microscopy (FCPM), Coherent Anti-Stokes Raman Scattering Polarizing Microscopy (CARS-PM), and Three-Photon Excitation Fluorescence Polarizing Microscopy (3PEF-PM).
- FCPM Fluorescence Confocal Polarizing Microscopy
- CARS-PM Coherent Anti-Stokes Raman Scattering Polarizing Microscopy
- 3PEF-PM Three-Photon Excitation Fluorescence Polarizing Microscopy
- the monitoring of the disclosed liquid crystal and aerogel uniformity in lateral directions can be accomplished by using conventional dark-field, bright-field, and polarizing optical microscopy.
- Visible- and infrared-range spectroscopy can also be utilized.
- the other properties of the disclosed aerogels include mechanical properties (both as-prepared aerogels and encapsulated, ready-to-install films), as well as soundproofing and condensation resistance of the films installed on single-pane windows.
- thermophysical properties Prior to the application of films onto a window the thermophysical properties (for example, thermal conductivity, heat capacity) are characterized by the optical pump-and-probe method in order to determine the type of film that is suitable for the specific application.
- This procedure uses a femtosecond laser to construct a high temporal resolution temperature measurement system.
- FIG. 7 shows the optical pathway of a typical pump-and-probe measurement system.
- sub-picosecond (ps) time resolution is made possible by splitting the ultrafast sub-ps laser pulse output into an intense heating pulse, i.e., a “pump” beam, and a weaker “probe” beam, and controlling the optical path length difference of the pump and probe beam through a mechanical delay stage.
- the decay of the temperature rise is measured by the reflected energy of the probe pulse series.
- the thermal conductivity can then be deduced by fitting the temperature decay curves.
- FIG. 8 discloses the components of a hot box apparatus: a metering box (simulating interior temperature) on one side of the window specimen; a controlled guard box surrounding the metering box; a climate chamber box (simulating exterior temperature) on the other side; and the specimen frame providing specimen support & insulation.
- the walls of the hot box are insulated panels of plywood adhered to either side of a solid layer of XPS insulation.
- the space conditioning system used in the meter box employs hydronic cooling and electric resistance heating.
- the meter box cooling is measured using high precision thermocouples in combination with a precision flow meter to accurately quantify the heat removed from the meter box.
- Heat is added into the meter box via PID-controlled electric heaters.
- Precision resistor circuits are employed to measure the heat added into the meter box. A constant and precise temperature can be maintained and the total heat addition/removal can be measured.
- the hot box employs an insulated guard box surrounds the meter box and a hydronic guard loop is installed over the outside surface of the meter box. The guard box minimizes the influence of temperature changes in the lab.
- the liquid guard loop further ensures the outside surface of the meter box remains at a constant temperature.
- An insulated baffle separates the air space from the mixing chamber of the meter box.
- the baffle panels are constructed using thermal insulation material. For a 1 m ⁇ 1 m test window sample, at least 25 calibrated precision thermocouples are used to measure temperatures on the baffle surface, 25 corresponding points in the air stream and at least 25 points on the interior surface of the test window specimen. Air drawn through the meter box baffle space at velocities representative of convection in real world conditions. DC powered axial draw-through circulation fans, at the top and bottom of the baffle, are used to ensure smooth flow along the surface of the wall sample in the direction that convection would occur.
- the climate box has the same dimensions and construction as the guard box.
- the climate side air baffles are constructed using the same materials and methods as the air baffles in the meter box. Heat is added to/removed from the climate box via four fan coils which are connected to a liquid chiller and a hydronic heater. Electric resistance heaters permits fine tuning of the temperatures and ensures that temperatures remain close to the set point for the duration of the test.
- the climate box has the capacity to run a range of realistic outdoor temperatures, from ⁇ 30° C. to 60° C. This enables the tested window assembly to remain undisturbed when tested from cold to hot climate conditions. Overall heat transfer coefficient is:
- Q is the time rate of net heat flow through the meter box opening, W;
- A is meter box opening area, m 2 ;
- T meter and T climate are temperatures of meter box and climate box, respectively.
- a cellulose-polysiloxane hybrid aerogel comprising:
- these characteristics are achieved by strictly controlling the dimensions of nanofibers and the homogeneous gel skeleton networks that they form, which can be tuned to form orientationally ordered liquid crystal (LC) states.
- LC liquid crystal
- an optimized acid/base catalyzed sol-gel reaction in a surfactant-based solution is used to form a polymethylsilsesquioxane (PMSQ) surface network.
- PMSQ polymethylsilsesquioxane
- Cellulose nanofibers having a uniform diameter are first surface functionalized. This functionalization can employ small charged molecules or polymer grafting resulting in increased cellulose nanofiber stability. Subsequently, these nanofibers are crosslinked with PMSQ fibers.
- the disclosed hybrid aerogels can be made optically isotropic or anisotropic, depending on the intended use by the formulator. In the case of anisotropic aerogels, they can be fabricated starting from the LC states of colloidal dispersions of nanofibers. The resulting compositions can have practical applications as they result can result in devices having optical polarization, thereby the ability to control visible light polarization while providing simultaneous thermal insulation.
- PMSQ polymethylsilsesquioxane
- the surface modifying agent is chosen from C 1 -C 6 linear or branched, saturated or unsaturated alkylamine, low molecular weight compounds comprising a cationic moiety, oligomers or polymers.
- the C 1 -C 6 linear or branched, saturated or unsaturated alkylamines react with the cellulose carboxyl units under the conditions of the present process to form a carboxylate-quaternary ammonium complex, for example, as depicted in FIG. 9A .
- One example of this embodiment comprises the use of allylamine as the modifying agent.
- Another embodiment comprises the use of an oligomer or polymer as the modifying agent.
- m-PEG-amines having an average molecular weight of from about 2000 to about 10,000 daltons are used to modify the surface of the oxidized cellulose nanofibers.
- the modifying agent is an m-PEG amine having an average molecular weight of 5000 daltons.
- Any oligomer or polymer that can covalently bond to the surface carboxylates of the oxidized nanofibers can be used to modify the cellulosic surface.
- a further embodiment comprises a modifying unit that is a low molecular weight compound comprising a cationic moiety.
- the molecular weight of compounds of this type are less than about 400 g/mol.
- FIG. 9B A non-limiting example of this embodiment is depicted in FIG. 9B wherein the use of a carbamoylcholine salt is the modifying agent.
- the salt can be chlorine, bromine and the like.
- the nanocellulose concentration In order for spontaneous nematic ordering of the nanofibers to occur, the nanocellulose concentration must be above the critical concentration. This behavior provides a unique opportunity for the formulator to impart LC ordering at low TOCN volume fractions which provides a means for obtaining the disclosed optical anisotropy and other properties.
- Raw cellulosic material obtained from natural sources is used to form the disclosed hydrogels, oranogels and aerogels.
- the cellulosic material is first oxidized at the C6 saccharide carbons thereby oxidizing the —CH 2 OH moieties to carboxylate moieties, —COOH.
- the oxidized cellulosic material is then treated with a modifying agent, which allows the cellulose nanofibers in the hydrogel to remain aligned and non-reactive to the subsequent treatment with the networking agent.
- a modifying agent which allows the cellulose nanofibers in the hydrogel to remain aligned and non-reactive to the subsequent treatment with the networking agent.
- the nanofibers are treated with methyltrimethoxysilane (networking agent) which is hydrolyzed under acidic conditions to form a polysiloxane network over the hydrogel. Gelation results in a highly-transparent monolithic hydrogel of functionalized TOCNs, cross-linked by an isotropic, bicontinuous polysiloxane nanofibrious network.
- the water is removed from the hydrogel by exchange with a volatile organic solvent to form the corresponding organogel.
- the resulting organogel exhibits both an isotropic and liquid-crystalline arrangement, which can be controlled by regulating the surface-modified TOCN concentration.
- These orientationally ordered self-assembled structures are locked in place by the formation of the polysiloxane network.
- the disclosed process preserves the small and uniform cross-sections of individual fibers and their network and, consequently, assures low light scattering.
- the corresponding aerogel is formed by drying of the organogel, which can be shaped to the needs of the formulator.
- many practical aerogel applications can require a high degree of hydrophobicity (for example, to assure that these aerogels are stable under ambient conditions and in humid environments).
- the disclosed cellulose nanofibers are produced through the oxidation of native cellulose by selectively modifying the C 6 primary hydroxyl groups on the surface of native cellulose to carboxylate groups catalyzed by TEMPO under mild pH aqueous conditions.
- the nanofibers with a diameter of 4.8 nm and micrometer-scale lengths are stabilized in a basic solution by the Coulombic repulsion of their anionic carboxylate moieties, which overpower their tendency to form hydrogen bonds.
- the aqueous TOCN dispersions are highly transparent.
- the TEMPO-mediated oxidation of cellulose produces a large density of carboxylic groups ( ⁇ 0.8 mmol/g) on the surface of nanofibrillated cellulose that is available for surface modification. This provides a means for altering the physical adsorption properties of the cellulose nanoparticles by covalently bonding either low molecular weight cationic molecules or polymeric chains to the surface thereby resulting in stabilized TOCNs by either electrostatic repulsion or steric hindrance.
- this modification is affected by physisorption of one or more polyelectrolytic monomers, in this example allylamine, to the anionic carboxylate groups of the oxidized cellulose.
- This process does not significantly affect the cross-sectional diameter of the TOCN's because of the size of the low molecular weight of the cationic small molecule.
- the surface functionalization can be accomplished by reaction of the carboxyl groups with a cationic-amine comprising adduct.
- FIG. 9B depicts the reaction of 2-(carbamoyloxy)-N,N,N-trimethylethanaminium (choline carbamate) with the TOCN's. This reaction introduces another form of cationic charge electrostatic repulsion
- the surface of the TOCN's are modified by reaction with a polymeric material, in this example a methoxy polyethylene glycol amine (mPEG-amine). Grafting of a polymer of this type provides a means for improving colloidal-TOCN stabilization.
- a polymeric material in this example a methoxy polyethylene glycol amine (mPEG-amine).
- the functionalization of the TOCN's produces cellulosic matrices that are stable to treatment with polysiloxane in the subsequent step of the disclosed process.
- FIG. 10 depicts the process in general.
- Oxidized and surface modified cellulose nanofibers as an aqueous suspension are represented by the long aligned fibers and the differently shaded dots represent water molecules and molecules of PMSQ (far left figure).
- the center figure represents Steps (c) and (d) of the process above wherein the nanofibers are first contacted with PMSQ then the PMSQ is hydrolyzed to form a PMSQ network cellulosic hydrogel.
- the resultant of Steps (e) and (f) is depicted in the figure on the far right, the resulting aerogel.
- the resulting transparent surface-modified TOCNs' aqueous colloidal dispersions can exhibit LC ordering, depending upon the volume fraction of the nanofibers in the colloidal dispersion.
- these solutions can exhibit birefringence when they are observed between cross polarizers as depicted in FIG. 10 .
- the surface of the TEMPO-oxidized cellulose nanofibers were then functionalized by physical adsorption of allylamine onto the nanofibers.
- 500 mg of 0.2 wt. % nanofiber aqueous solution was diluted by 2 mL of distilled and deionized water and combined with 10 mg of allylamine. The mixture was stirred overnight and dialyzed for 2 days in a deionized water bath across a cellulose acetate membrane with a cutoff molecular weight of 12,000-14,000 g/mol to obtain the desired allylamine-TOCNs.
- aqueous TOCN dispersion 500 mg of 0.38 wt. %) was diluted with 2 mL of deionized water followed by the addition of 24 mg of 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxid hexafluorophosphate (HATU), 20 ⁇ L of N,N-diisopropyl-ethylamine (DIPEA) and 50 mg carbamoylcholine chloride and 404, dimethylformamide (DMF). The mixture was stirred for 2 days and dialyzed for another 2 days affording the desired dispersed surface modified nanofibers.
- DIPEA N,N-diisopropyl-ethylamine
- DMF dimethylformamide
- the disclosed PMSQ network cellulosic hydrogels were fabricated by cross-linking functional TOCNs with polysiloxane.
- functional TOCNs For example and in general, cetyltrimethylammonium bromide (0.4 g)(CTAB) and 3.0 g of urea were dissolved in 8 mL of deionized (DI) water with sonication until the sol became homogeneous.
- DI deionized
- MTMS methyltrimethoxysilane
- the sol was degassed in a vacuum oven and then transferred into a polystyrene petri dish with a diameter of 5 cm, sealed for gelation and allowed to age for 3 days in a 60° C. furnace to form the desired hydrogels.
- FIG. 11 is a photograph showing the optical transparency of a hydrogel formed from the disclosed process.
- This hydrogel is a highly-transparent monolithic hydrogel cross-linked by an isotropic, bicontinuous polysiloxane nanofibrious network as described herein.
- the hydrogel is contained within the outlined dotted area.
- FIG. 12 is a photograph showing the optical transparency of an organogel formed from the disclosed process.
- the organogel is contained within the outlined dotted area.
- FIG. 13 is photograph showing the optical transparency of an aerogel formed from the disclosed process wherein the surface modifying agent is allylamine.
- the aerogel is contained within the circle.
- FIG. 14 is a photograph of an aerogel formed by the disclosed process wherein the surface modifying agent is an m-PEG-amine having an average molecular weight of 5000 daltons.
- the circular aerogel is positioned on top of a copy of text. AS can be seen in the photograph the aerogel is transparent in that neither the color nor the text is distorted.
- FIG. 15 is a photograph of an aerogel formed by the disclosed process wherein the surface modifying agent is carbamoylcholine chloride.
- the circular aerogel is positioned on top of a copy of text.
- the aerogel is transparent in that neither the color nor the text is distorted.
- the carbamoylcholine chloride-capped TOCN-PMSQ aerogels exhibit hydrophobic surface characteristics with a typical contact angle of 148°, largely due to the presence of hydrophobic methyl groups on the polysiloxane fibers within the nanostructured aerogels.
- An advantage of the disclosed process is that there is no need for post-synthetic hydrophobization treatment when the disclosed gels are used for hydrophobic applications.
- the disclosed aerogels were analyzed for both their optical and electron imaging and spectra characteristics.
- a UV-VIS-NIR spectrometer ranging from 190 nm to 3200 nm, (UV-3101pc, from Shimadzu) equipped with a LabSphere brand integrating sphere attachment was employed.
- Haze is defined as the ratio of diffuse transmission to total transmission, where diffuse transmission is defined as transmitted light varying by greater than or equal to a 5° separation from the direction of incident light.
- Infrared transmission spectra from wavenumbers 400 cm ⁇ 1 to 4000 cm ⁇ 1 were recorded on a Fourier-transform infrared spectroscopy (FTIR) spectrometer (Nicolet AVATAR 370 DTGS from Thermo) equipped with an a integrating sphere (NIR IntegratIR, from Pike). Photographs of samples were taken using a digital camera. IR thermographs were obtained by an IR camera (T630sc, from FLIR). TEM images were obtained using a CM100 microscope (from FEI Philips) at 80 kV.
- FTIR Fourier-transform infrared spectroscopy
- the TOCN samples were negatively stained with phosphotungstic acid to increase imaging contrast: 2 ⁇ L of the sample is dropcasted on the formvar coated copper grid, allowed to settle for drying and then dipped into the stain solution (aqueous 2 wt. % phosphotungstic acid).
- the porous morphology of TOCN-PMSQ was characterized using an SEM using a Hitachi Su3500 and Carl Zeiss EVO MA 10 system. For this, freshly cut surfaces of the TOCN-PMSQ aerogels were sputtered with a thin layer of gold and observed under SEM at a low voltage of 5 kV (as optimized to avoid the distortion of the aerogel samples).
- FIGS. 17A-C are transmission electron microscopy (TEM) micrographs of the disclosed aerogels at various magnifications.
- FIGS. 17B and 17C are scanning electron microscopy (SEM) that depict the well-defined and uniform-diameter 10-15 nm nanofibers that are formed by polysiloxane treatment and individually dispersed TOCNs fibers within the aerogels as well as a narrow pore-size distribution of their resulting porous network.
- SEM scanning electron microscopy
- the depicted aerogel samples exhibit 3D bicontinuous network-like structures, in which both the smooth gel skeletons and the pores are interconnected without aggregation or clustering.
- the example depicted in FIGS. 17A-C have a bulk density ⁇ b that is calculated to be 69 mg/cm 3 by weight/volume ratio of the sample.
- the average pore size for this particular example is calculated to be approximately 100 nm, consistent with the value observed directly from the SEM images.
- the mesoscale morphology of the 2.0-mm thick QA-capped TOCN-PMSQ composite aerogel with ultrathin fibers and uniform pore size distribution yields hydrogels and organogels with very high light transmission greater than 90% and aerogels with visible transmission close to 90% at 600 nm as depicted in FIG. 18 .
- the exampled aerogel's haze coefficient defined as the ratio of diffuse transmittance and total light transmittance, was determined to equal to 8.4% FIG. 19 and is characterized following the ASTM D1003 standard using an integrating sphere setup when integrated across the visible range (390-700 nm), shown in Figure S1 .
- the PMSQ matrix causes TOCN-PMSQ aerogels to exhibit strong absorption at a wavelength of 6-20 ⁇ m, which is mainly due to the Si—O bonds FIG. 20 . This provides the formulator the opportunity to separately control transmission of visible and infrared light, in embodiments wherein control of solar gain and emissivity are important, i.e., in smart-window applications.
- the disclosed aerogels were analyzed for their thermal, mechanical, and durability characteristics.
- the thermal conductivity is measured by measuring both the heat capacity and thermal diffusivity of the aerogel samples.
- the heat capacity of aerogel is measured by differential scanning calorimetry (DSC 204 F1 Phoenix, Netzsch).
- the thermal diffusivity of aerogel is characterized by a laser flash apparatus (LFA 457, Netzsch). Briefly, an optical source instantaneously heats one side of the material and the temperature increment on the other side of the material is recorded by infrared thermography for facile, noninvasive temperature sensing. To prevent the direct heating of the detector by laser light, the top and the bottom of the aerogel were covered with highly conductive carbon tape to prevent the laser from penetrating through the sample.
- the thermal conductivity of the aerogel can be calculated by subtracting the contribution of carbon tape from the effective thermal conductivity of the sandwich structure, which was determined by performing measurements for samples of different thickness.
- the Instron 5965 material-test system was used to probe the mechanical properties and determine stress-strain relationships.
- the mechanical properties shown in FIG. 4 f were measured with TOCN-PMSQ aerogel samples with 0.25 vol. % QA-capped TOCN cut into rectangular strips of 20 mm ⁇ 6 mm ⁇ 1 mm. Aerogel durability testing was performed under a 500 Watt mercury lamp (Sun System 5, from Sunlight Supply Inc.) and in a Tenney environmental test chambers held at 80° C. and 80% relative humidity for 24 hours.
- FIG. 21 shows the measured thermal conductivity of a TOCN-PMSQ aerogel versus sample porosity.
- FIG. 22 depicts the comparison of thermal conductivity between an aerogel formed from carbamoylcholine chloride modified nanocellulose (quaternary-amine) and an allylamine modified aerogel.
- FIG. 23 depicts the compression stress-strain relation for a TOCN-PMSQ aerogel with 0.06 wt. % of TOCN.
- nanocellulose biofilms derived from bacterial cellulose are suitable for use in preparing insulating and structural gels.
- bacteria that can be used to provide the disclosed biofilms include Acetobacter hansenii and Acetobacter xylinum.
- the bacterial biofilms are formed in situ as depicted in the Figures.
- the resulting cellulose gels are formed from orientationally ordered material.
- the disclosed gels can be formed directly from the cellulose bacterial biofilm pellicle.
- the bacteria forming the biofilms can be directed and positioned to a desired orientation using an infrared laser beam. Using an infrared laser beam as a laser trap the bacteria can be moved, re-orientated and positioned adjacent to one another such that the resulting fibrils of cellulosic material can coalesce with one another.
- the disclosed cellulosic gels are orientationally ordered because of their alignment as they are being formed because of hydrogen bonding between fibrils. This results in the fibrils forming ribbons.
- the density of the fibrils hence, the ribbons can be determined by the formulator.
- modification of the bacterial culture can result in a change in the fibril diameter.
- modifications to the growth media and to the nutrient composition, as well as, a change in bacterium species, can be used to tune the resultant gel to be transparent or opaque, flexible or stiff, thermally insulating or conducting, and fragile or load-bearing.
- Resultant gels can be further chemically treated to tune material and thermal properties of the invention, such as crosslinking density, material composition, and hydrophobicity. Colloidal inclusions can be introduced into the resultant gel to tune optical, magnetic, and electric properties of the gel.
- FIG. 24A and FIG. 24B depict the reorientation of an A. hansenii bacterium using the infrared laser beam of a laser trap.
- the laser trap can be used to move a bacterium to a position in the growth media that provides easier harvesting of the pellicles or alternatively to determine the density of the pellicles.
- FIG. 25 is a photograph of dark field microscopy showing an A. hansenii bacterium producing a cellulose fiber. The cellulosic material is visible because the various single strands of cellulose have coaleased into a ribbon. This is depicted schematically in FIG. 28 .
- FIG. 26 shows A. xylinum bacteria producing cellulose fibers.
- FIG. 27A and FIG. 27B shows the effect on cellulose fibril thickness when 1.5% sodium carboxymethyl cellulose is added to A. xylinum .
- FIG. 27A the cellulose fibril is visible.
- FIG. 27B the thickness of the fibril is greatly reduced such that the fibril is invisible in the photograph. This is depicted schematically in FIG. 29 .
- Bacterial cellulose derived from A. hansenii is used in this example.
- the bacterial cellulose pellicles are purified by first washing in 70° C. 1 wt % NaOH aqueous solution for ⁇ 4 hours, to kill any remaining bacteria.
- the pellicles are then transferred to 70° C. or room temperature DI water to remove excess NaOH and reduce the ionic strength back to that near of pure DI water. Heating to 70° C. speeds up the process, but the process can be done at room temperature (RT) as well.
- the pellicle is washed 2 additional times in pure DI water (at RT or with mild heating, e.g. to 70° C.), for a total of 3 ⁇ DI water rinses.
- the pellicle is transferred into pure isopropanol (IPA) and allowed to solvent exchange.
- IPA isopropanol
- This solvent exchange from water to IPA can be done at RT or 60° C., depending on the urgency and speed desired.
- the pellicle is then placed into a fresh bath of IPA, to further dilute any remaining water in the solvent exchange bath.
- the number of times the pellicle is washed with fresh IPA depends on the pellicle thickness. For example, thin pellicles can require only need 2 total IPA baths to sufficiently remove water, whereas thicker pellicles can require 3-5 exchange cycles in IPA.
- the pellicle is dried via conventional critical point drying (CPD) techniques (using liquid CO 2 , same as drying the aerogel). Once at the CO 2 critical point, the pressure is bled off at ⁇ 50 PSI/min.
- CPD critical point drying
- FIG. 28 is a depiction of an Acetobacter cell showing multiple cellulose synthase enzymes extruding cellulose fibrils from the cellular membrane. As the fibrils lengthen hydrogen bonding between adjacent strands cause the fibrils to coalesce and form ribbons.
- FIG. 29 is a depiction of an Acetobacter cell showing multiple cellulose synthase enzymes extruding cellulose fibrils from the cellular membrane. In this iteration, carboxymethyl cellulose is added to the growth media resulting in hydrogen bonds not forming the fibrils into ribbons of fiber.
- FIG. 30A and FIG. 30B demonstrate to optical and mechanical properties of the disclosed aerogels prepared from bacterial cellulose.
- the aerogel is opaque whereas FIG. 30B depicts the flexibility of the corresponding aerogel.
- Bacterial cellulose derived from A. hansenii wherein 1.5% carboxymethyl cellulose was added to the culture media was used in this example.
- the bacterial cellulose pellicles are purified by first washing in 70° C. 1 wt % NaOH aqueous solution for ⁇ 4 hours, to kill any remaining bacteria.
- the pellicles are then transferred to 70° C. or room temperature DI water to remove excess NaOH and reduce the ionic strength back to that near of pure DI water. Heating to 70° C. speeds up the process, but the process can be done at room temperature (RT) as well.
- the pellicle is washed 2 additional times in pure DI water (at RT or with mild heating, e.g.
- pellicle is transferred into pure isopropanol (IPA) and allowed to solvent exchange.
- IPA isopropanol
- This solvent exchange from water to IPA can be done at RT or 60° C., depending on the urgency and speed desired.
- the pellicle is then placed into a fresh bath of IPA, to further dilute any remaining water in the solvent exchange bath.
- the number of times the pellicle is washed with fresh IPA depends on the pellicle thickness. For example, thin pellicles can require only need 2 total IPA baths to sufficiently remove water, whereas thicker pellicles can require 3-5 exchange cycles in IPA.
- the pellicle is dried via conventional critical point drying (CPD) techniques (using liquid CO 2 , same as drying the aerogel). Once at the CO 2 critical point, the pressure is bled off at ⁇ 50 PSI/min.
- CPD critical point drying
- FIG. 31A and FIG. 31B are thermal imaging photographs comparing a standard polysiloxane polymer, FIG. 31A , with a gel formed by the disclosed process, FIG. 31B .
- the patch of bacterial cellulosic aerogel is cold relative to the surrounding heated surface.
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Abstract
Description
- This application this Application is a Continuation-In-Part of U.S. application Ser. No. 15/868,714 filed Jan. 11, 2018, which claims the benefit of Provisional Application Ser. No. 62/444,896, filed on Jan. 11, 2017, the entire disclosure of which is incorporated herein by reference in its entirety.
- This discovery was made with Government support under grant DMR-1410735 awarded by the U.S. National Science Foundation and under grant DE-AR0000743 awarded by the U.S. Department of Energy. The Government has certain rights in the invention.
- Disclosed are cellulose-based flexible gels containing cellulose nanorods, ribbons, fibers, and the like, and cellulose-enabled inorganic or polymeric composites, wherein the gels have tunable optical, heat transfer, and stiffness properties. The disclosed gels are in the form of hydrogels, organogels, liquid-crystal (LC) gels, and aerogels. Further disclosed are highly transparent and flexible cellulose nanofiber-polysiloxane composite aerogels featuring enhanced mechanical robustness, tunable optical anisotropy, and low thermal conductivity. Further disclosed are gels comprising cellulosic material derived from bacteria and processes for preparing bacterial cellulose gels and methods of use.
-
FIG. 1 shows the schematic of fabrication procedures of cellulose-enabled ordered gels (a) cellulose nanomaterials aqueous dispersion, (b) hydrogel, (c) organogel (d) aerogel, and (e) liquid crystal gel. -
FIG. 2 shows transmission electron microscopy (TEM) images of cellulose nanorods, nanofibers, nanoribbons from different sources: (a) cellulose nanorods from cotton, (b) cellulose nanowires from cotton, (c) cellulose nanowires from wood pulp, and (d) cellulose nanoribbons from bacterial cellulose. -
FIG. 3 shows photographs of nematic cellulose (a) hydrogel, (b) organogel, (c) aerogel, (d) nematogel, and (e) scanning electron microscopy (SEM) image of the ordered aerogel. The scale bar is 1 cm. -
FIG. 4 shows photographs of cholesteric (a) cellulose-silica composition, (b) silica aerogel, (c) silica nematogel, and (d) SEM image of the ordered silica aerogel. The scale bar is 5 mm. -
FIG. 5 is a schematic representation of a spectrometer assembly that can be used for haze measurements at diffuse illumination and unidirectional viewing. -
FIG. 6 describes a general schematic of one embodiment for the fabrication of the disclosed aerogels. -
FIG. 7 shows the optical pathway of a typical pump-and-probe measurement system. -
FIG. 8 discloses the components of a hot box apparatus: a metering box (simulating interior temperature) on one side of the window specimen; a controlled guard box surrounding the metering box; a climate chamber box (simulating exterior temperature) on the other side; and the specimen frame providing specimen support & insulation. -
FIGS. 9A-C various TEMPO-oxidized cellulose nanoparticle modifying agents.FIG. 9A depicts surface modification by allylamine.FIG. 9B depicts surface modification by a 2-(carbamoyloxy)-N,N,N-trimethylethanaminium adduct.FIG. 9C depicts surface modification by example a methoxy polyethylene glycol amine (mPEG-amine). -
FIG. 10 depicts the disclosed process for forming polymethylsilsesquioxane (PMSQ) network cellulosic hydrogels, organogels and aerogels process in general. -
FIG. 11 is a photograph showing the optical transparency of a hydrogel formed from the disclosed process. -
FIG. 12 is a photograph showing the optical transparency of an organogel formed from the disclosed process. -
FIG. 13 is photograph showing the optical transparency of an aerogel formed from the disclosed process wherein the surface modifying agent is allylamine. -
FIG. 14 is a photograph of an aerogel formed by the disclosed process wherein the surface modifying agent is an m-PEG-amine having an average molecular weight of 5000 daltons. -
FIG. 15 is a photograph of an aerogel formed by the disclosed process wherein the surface modifying agent is carbamoylcholine chloride. -
FIG. 16 depicts that the carbamoylcholine chloride-capped TOCN-PMSQ aerogels exhibit hydrophobic surface characteristics. -
FIGS. 17A-C are transmission electron microscopy (TEM) micrographs of the disclosed aerogels at various magnifications.FIG. 17A shows that the colloidal dispersions consist of mostly individualized TOCNs, each of diameter Dc≈5 nm and length Lc=1-2 μm.FIGS. 17B and 17C are scanning electron microscopy (SEM) that depict the well-defined and uniform-diameter 10-15 nm nanofibers that are formed by polysiloxane. -
FIG. 18 shows the visible transmission of a disclosed aerogel. -
FIG. 19 shows the haze coefficient of a disclosed aerogel. -
FIG. 20 depicts that the PMSQ matrix causes TOCN-PMSQ aerogels to exhibit strong absorption at a wavelength of 6-20 μm that is mainly due to the Si—O bond. -
FIG. 21 shows the measured thermal conductivity of a TOCN-PMSQ aerogel versus sample porosity. -
FIG. 22 depicts the comparison of thermal conductivity between an aerogel formed from carbamoylcholine chloride modified nanocellulose (quaternary-amine) and an allylamine modified aerogel. -
FIG. 23 depicts the compression stress-strain relation for a TOCN-PMSQ aerogel with 0.06 wt. % of TOCN. -
FIG. 24A andFIG. 24B depict the reorientation of an A. hansenii bacterium using the infrared laser beam of a laser trap. -
FIG. 25 is a photograph of dark field microscopy showing an A. hansenii bacterium producing a cellulose fiber. -
FIG. 26 shows A. xylinum bacteria producing cellulose fibers. -
FIG. 27A andFIG. 27B shows the effect on cellulose fibril thickness when 1.5% sodium carboxymethyl cellulose is added to A. xylinum. InFIG. 27A the cellulose fibril is visible. InFIG. 27B the thickness of the fibril is greatly reduced such that the fibril is invisible in the photograph. -
FIG. 28 is a depiction of an Acetobacter cell showing multiple cellulose synthase enzymes extruding cellulose fibrils from the cellular membrane. As the fibrils lengthen hydrogen bonding between adjacent strands cause the fibrils to coalesce and form ribbons. -
FIG. 29 is a depiction of an Acetobacter cell showing multiple cellulose synthase enzymes extruding cellulose fibrils from the cellular membrane. In this iteration, carboxymethyl cellulose is added to the growth media resulting in hydrogen bonds not forming the fibrils into ribbons of fiber. -
FIG. 30A andFIG. 30B show an example of the disclosed aerogel biofilms. -
FIG. 31A andFIG. 31B are thermal imaging photographs comparing a standard polysiloxane polymer with a gel formed by the disclosed process. - As used herein, a “gel” is understood to be a substantially dilute cross-linked system that exhibits no flow when in the steady state. The primary constituent of the gel is the ambient fluid surrounding it, whose form can be a liquid or gas. Prefixes such as “aero,” “organo,” “hydro,” and variations are understood to indicate the ambient fluid in the cross-linked gel matrix and primary component of the gel material.
- The disclosed gels contain cellulosic nanocomposites that are aligned in ordered liquid crystal phases. As such, the disclosed gels allow the formulator to adjust the optical transmissivity of the gel, thereby configuring the optical properties of the gel to range from opaque to transparent. In addition, the properties can be adjusted to interact with a wide range of the electromagnetic spectra, for example, from the visible spectrum to infrared spectrum. In one embodiment, the thermal conductivity of the gel can be adjusted. The bulk properties of the disclosed gels, for example the level of stiffness or flexibility can be adjusted by the choice of the constituent cellulosic material, for example, nanorods, ribbons, fibers, and the like, as well as, the concentration of these materials in the resulting gels.
- As used herein, a “film” and variations indicate non-porous lamellae ranging in thickness from about 10 nm to 1 mm and arbitrary lateral extent.
- As used herein the term “cross-section” means width and the terms are used interchangeably. The disclosed cellulosic nanomaterials have a width from about 10 nm to about 500 nm. The length of the nanomaterials is at least ten times the width.
- The term “composition” as used herein refers to the disclosed cellulose nanomaterial aqueous dispersions, hydrogels, organogels, aerogels, and liquid crystal gels. The compositions can be a single layer of material comprising nanomaterials or the composition can be formed from two or more distinct layers wherein each layer consists of only one material. As a non-limiting example, one layer can consist of an ordered nematic cellulosic gel onto which a second layer of aligned cholesteric cellulose film is applied thereto. This layering thereby forms a unified composite material with distinct layers.
- The term “hydrogel” as used herein represents a network of cellulosic material as a colloidal gel dispersed in a carrier. In one embodiment the carrier is water. In another embodiment the carrier is a mixture of a water compatible (miscible) organic solvent. The cellulosic material can be crosslinked or non-crosslinked.
- The term “organogel” as used herein is a gel wherein the aqueous phase of a precursor hydrogel has had substantially all of the water removed and replaced by a water compatible solvent. Non-limiting examples of compatible solvents include methanol, ethanol, propanol and isopropanol. In one embodiment, the disclosed organogels have a two dimensional cross-linked network. In another embodiment the disclosed organogels have a three dimensional crosslinked network.
- The term “aerogel” as used herein refers to a gel derived from the further processing of a disclosed organogel as described herein.
- The term “liquid crystal gel” refers to the compositions derived from the further processing of the disclosed organogels as described herein.
- The term “nanomaterial” refers to the disclosed cellulosic material. The width of these materials is in the nanometer range, whereas the length of the cellulosic material can vary from nanometer length to micrometer. The terms “nanomaterial,” “cellulosic material” and “cellulosic nanomaterial” are used interchangeably throughout the present disclosure.
- The term “nematic” as used herein refers to a composition wherein the disclosed cellulosic materials possess long-range orientational order. In addition, the cellulosic materials are free to flow and their center of mass positions are randomly distributed, but still maintain their long-range directional order. The disclosed nematic compositions are uniaxial: they have one axis that is longer and preferred, with the other two being equivalent.
- The term “cholesteric” as used herein refers to a composition with a helical structure and which is therefore chiral. The disclosed cholesteric compositions are organized in layers with no positional ordering within layers, but a director axis which varies with layers. The variation of the director axis can be periodic in nature. If present, the period of this variation (the distance over which a full rotation of 360° is completed) is known as the pitch, which can be adjusted by the formulator, and the degree of pitch determines the wavelength of electromagnetic radiation which is reflected.
- The abbreviation “TOCK” as used throughout the specification means “TEMPO-oxidized cellulose nanofibers.”
- The term “low molecular weight compounds comprising a cationic moiety” means a compound that has a moiety that can react with an oxidized cellulose carboxyl group in addition to a separate cationic moiety. Non-limiting examples of units that can react with an oxidized cellulose carboxyl group de hydroxyl group, an amino group, a thiol group, and the like. A non-limiting example of a cationic moiety includes a quaternary ammonium group.
- In one aspect of the present disclosure are compositions comprising cellulosic nanoribbons that are aligned together and which orientation can be adjusted by the formulator. The disclosed nanoribbons have aspect ratios from about 1:100 to about 1:1000. In one aspect, the disclosed nanoribbons can be used to form a nematic flexible gel.
- These cellulose-based flexible gels, can comprise cellulose ribbons, fibers, and other constituent-particle structures having in one embodiment aspect ratios of about 1:1000. These flexible gels are formed from linking the cellulose particle networks within the material. The original cellulose solvent which is used for the formation of the gel network can be retained or replaced to yield a variety of gel types, for example, hydrogels, alcogels, aerogels, and liquid-crystal gels. The use of the disclosed cellulosic material to form the gel network allows the formulator to adjust the flexibility of the gels.
- The aspect ratios allow for a greater degree of flexibility or rigidity depending upon the selection of cellulosic nanomaterial. In addition, the cellulose particles can be ordered through chemical and mechanical means to yield a lyotropic liquid crystalline dispersion with ordered phases. The ordering can be preserved during the cross-linking process to form various ordered gels, non-limiting examples of which are given above.
FIG. 1 illustrates the fabrication procedure of cellulosic ordered gels. - In addition to flexibility, the optical transmissivity of the disclosed gels can be adjusted to range from opaque to transparent. The degree of opaqueness or transparency can also be matched of any wavelength or range of wavelength in the electromagnetic spectrum. These results can be obtained by adjusting the various properties of the disclosed composites, i.e., density of cellulosic nanomaterial or size distribution. Also, the addition of adjunct ingredients such as liquid crystal materials can be used to tune the optical properties of the disclosed composites.
- A further property which can be tailored to the needs of the formulator is the degree of thermal resistance displayed by the gels. Several factors enable the adjustment of the thermal resistive properties: (1) the intrinsically low thermal conductivity of cellulose, (2) the rarefication of fluid within the cellulose network thereby regulating the thermal convection, and (3) the thermal conductivity and convection properties of the fluids which comprise the cellulose-gel network.
- In another aspect of the present disclosure are compositions comprising cellulosic nanorods that are aligned and which orientation can be adjusted by the formulator. The disclosed nanoribbons have aspect ratios from about 1:10 to about 1:100. In one aspect, the disclosed nanorods can be used to form compositions with a cholesteric phase.
- In one embodiment the disclosed nanocrystals form ordered films that can be ordered into a cholesteric phase in the film to form a periodic structure whose pitch and pitch gradient are adjustable for broad-band Bragg reflection of incident electromagnetic radiation. In another embodiment the resulting ordered gels are obtained because of the small relative aspect ratios of the cellulose nanorods or similar nanomaterials that comprise the nanocrystals. Nanorods result in the formation of different phases than other nanomaterials, i.e., nanofibers. Because of this fact broad-band reflection is enabled in ordered cellulose gels that are formed from cellulose structures with aspect ratios of about 1:10 to about 1:100.
- As such, the mechanical flexibility, optical transmissivity, and thermal resistance can be configured by tuning the same parameters described nanofibers, except that those parameters now refer specifically to cellulose nanorods or other geometrically anisotropic cellulose structures.
- A further aspect of the present disclosure relates to composite structures comprising lamellae that are formed from the disclosed aerogels or liquid crystal gels. Composite structures with lamellae can be formed from the disclosed compositions that comprise nanofiber-like cellulosic materials (nematic phase) or from nanorod-like cellulosic materials (cholesteric phase). These composite structures comprise a plurality of layers.
- In a still further aspect of the present disclosure are composite structures wherein an amount of the cellulosic nanomaterial is replaced with one or more adjunct materials which can affect the alignment of the composite nanomaterials. In one embodiment a portion of the cellulosic nanomaterial is replaced with liquid crystals. As such, the nematic phase or cholesteric phase gels can have the liquid phase substituted by other anisotropic organic or inorganic materials. In one embodiment silica is introduced into the hydrogel. In another embodiment liquid crystal material, for example, 1-(trans-4-hexylcyclohexyl)-4-isothiocyanatobenzene can replace the carrier of the hydrogel. In another embodiment, after the incorporation and alignment of non-cellulosic materials, the cellulose can be partially or totally removed, by chemical means, to yield gels and films with partial or total cellulose substitution.
- In a yet further aspect of the present disclosure are lamellae which comprise the disclosed composite structures. According to this aspect the lamellae are formed from two or more distinct layers wherein each layer comprises different materials. The cellulosic nanomaterials that comprise each layer can further serve as a template and can be substituted partially or totally by other materials such as silica or other polymers.
- Further disclosed are methods for the preparation of the composite structures.
- The disclosed cellulose nanomaterials can have a variety of shapes and cross-sectional geometries that depend upon the nanomaterial's natural source and the process used to produce the particles. A disclosed cellulose nanomaterial can have a shape that is a rod, fiber, ribbon, whisker, and the like.
- The disclosed cellulose nanomaterials can be obtained by chemical or mechanical treatment of a variety of natural sources, for example, cotton, soft wood pulp, hard wood pulp, tunicate and bacterial cellulose and the like. Typically nanorods and nanofibers can be obtained from multiple sources, for example, cotton and bacterial cellulose.
- In one embodiment, the disclosed nanocellulose can have a length from about 10 μm to 100 μm with cross sections from about 10 nm to 50 nm. In another embodiment, the disclosed nanocellulose can have a length from about 1 μm to 10 μm with cross sections from about 3 nm to 10 nm. In a yet another embodiment, the disclosed nanocellulose can have a length from about 100 nm to 1 μm with cross sections from about 3 nm to 10 nm.
FIG. 2 shows TEM micrographs of cellulose particles with characteristic length scales of the aforementioned embodiments: (a) cellulose nanorods of 10 nm×200 nm depends upon the chemical treatment from cotton, (b) cellulose nanowires of 7 nm×800 nm from cotton, (c) cellulose nanowires of 4.8 nm×1 μm from wood pulp, and (d) cellulose nanoribbons of 10 nm×50 nm×10 μm from bacterial cellulose. - The cellulose nanomaterials can be obtained by chemical hydrolysis of natural cellulose by sulfuric acid, hydrochloric acid, etc. or by 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-mediated oxidation.
- The cellulose nanomaterials can be aligned by linear or circular shearing for nematic or cholesteric ordering, respectively. Nematic ordering of the disclosed cellulose nanofibers is shown in
FIG. 1(b) . In one embodiment, the cellulose nanomaterial dispersion can be confined between glass plates in a mold such that, when a shear stress is applied from the plates in the specified direction, individual nanocellulose particles align to form a singular director alignment across the confined dispersion. In another embodiment, the nanocellulose suffers unidirectional alignment under extrusion from a sufficiently small diameter nozzle, syringe, or similar device. With extrusion alignment, no confining plates are needed such that the aligned dispersion takes the form of a narrow bead, with linear extent much greater than its cross-sectional extent, which rests on a supportive substrate or other structure. In yet another embodiment, the helical axis of cellulose nanorods in cholesteric phase can be aligned by anticlockwise circular shearing during the evaporation of the dispersion. - The disclosed cellulose nanomaterials can also be aligned by magnetic or electric fields. In one embodiment, the magnetic anisotropy of cellulose nanomaterial's relative permeability can be exploited to cause uniform alignment of nanocrystals. Under sufficiently strong magnetic fields (about 1 T), uniform alignment of nanocrystals perpendicular to the magnetic field is achieved through the magnetic interaction of the induced magnetic dipole moments of the cellulose nanomaterial with the applied magnetic field. In another embodiment, an oscillating electric field can also be used to aligned the cellulose nanomaterials with their long axis along the electric field.
- The alignment of the disclosed cellulose nanomaterial dispersions can be preserved by its conversion to a hydrogel, example embodiments which are shown in
FIG. 1(b) andFIG. 3(a) . The extent of cross-linking of the cellulose nanomaterial establishes the degree to which uniform ordering is preserved in the dispersion. For example, a low level of crosslinking provides a weaker gelation. Conversely a greater degree of cross-linking yields firmer gelation. Gelation is accomplished by the addition of an acid, photoacid generator and exposure to light, alcohol, or other cationic exchange reagent to a uniformly ordered cellulose nanomaterial dispersion. In one embodiment, hydrochloric, acetic, nitric, sulfuric, and phosphoric acids can be added to instigate gelation. In another embodiment, Ca2+ can be added to provide cross-linking. - The disclosed ordered hydrogels can be transformed into organogels, as shown in
FIG. 1(c) andFIG. 3(b) using a solvent exchange procedure. For example, a hydrogel can be gently shaken while immersed in an ethanol-filled bath followed by replacing the solvent at regular intervals. In this way, the water is sequentially removed from the matrix and replaced with ethanol. Other organic solvents can substitute for ethanol. Non-limiting examples of other solvents include methanol, ethanol, isopropanol, butanol, hexane, acetone, dichloromethane, dimethylformamide (DMF), dimethylsulfoxide (DMSO), and toluene. - The disclosed cellulose aerogels or films herein can be produced from the disclosed nano-structured organogel herein above. Example aerogels are shown in
FIG. 1(d) andFIG. 3(c) . The resulting cellulose nanomaterial aerogel is porous having a skeleton of about 0.1-99.9% of cellulose nanocrystals and a porosity of from about 0.01 to about 99.99%. In one embodiment the porosity is from about 97% to about 99%. - Aerogels comprising a low percentage of of nanocellulosic material results aerogels having a high degree of transparency, for example, from about 1% to about 50% by weight of the aerogel. Aerogels comprising from about 50% to about 90% by weight of nanocellulosic material results aerogels having a high degree translucent scattering.
- To prevent deformation and crumbling of aerogels during the drying due to surface tension and capillary pressure in the ambient atmosphere, supercritical drying, freeze drying, or ambient drying with a low surface-tension solvent are used to remove liquid solvent from cellulose nanocrystal composites while maintaining the disclosed liquid crystalline structure, such as nematic or cholesteric liquid crystalline ordering.
- As disclosed previously herein, the resulting monolithic cellulose nanomaterial film is a solid material with 100% cellulose composition. Ambient drying is used to remove liquid solvent.
- The disclosed cellulose LC gels herein can be produced from the disclosed nano-structured organogel. The organic solvent is replaced with LC by solvent exchange. For the case of LC gels, the LC functions as the gel's solvent.
FIG. 1(e) portrays a schematic representation of LC gels whileFIG. 3(d) portrays an LC gel whose LC solvent is in the nematic phase. The disclosed compositions can comprise any LC that will serve as solvents for the gels. Non-limiting examples of nematic LCs include: 1-(trans-4-hexylcyclohexyl)-4-isothiocyanatobenzene; 4′-(hexyloxy)-4-biphenylcarbonitrile; 4′-(octyloxy)-4-biphenyl-carbonitrile; 4′-(pentyloxy)-4-biphenylcarbonitrile; 4′-heptyl-4-biphenylcarbonitrile; 4′-hexyl-4-biphenylcarbonitrile; 4′-octyl-4-biphenylcarbonitrile; 4′-pentyl-4-biphenylcarbonitrile; 4,4′-azoxyanisole; 4-isothiocyanatophenyl 4-pentylbicyclo[2.2.2]octane-1-carboxylate; 4-(trans-4-pentylcyclohexyl)benzonitrile; 4-methoxycinnamic acid; N-(4-ethoxybenzylidene)-4-butylaniline; and N-(4-methoxybenzylidene)-4-butylaniline. - Inorganic nanomaterials can be incorporated into the heretofore disclosed ordered gels or films using cellulose nanomaterials as a template. As a non-limiting example,
FIG. 4 demonstrates cellulose-enabled cholesteric (a) cellulose-silica film composition, (b) silica aerogel, and (c) silica LC gel whose solvent is LC in its nematic phase. An SEM image of the ordered silica aerogel is displayed inFIG. 4(d) . At the final processing stage, the cellulose nanomaterials can be removed to obtain inorganic gels or films. Alternatively, inorganic/cellulose composite gels or films are formed without etching the cellulose nanomaterials. As one non-limiting example, the inorganic gels or films are made of silica, organo-silica, titanium dioxide, aluminum oxide, rare earth oxides, etc. The weight concentration of inorganic nanomaterial in the inorganic/cellulose composites can range from about 1% to about 99%. - Polymers can be incorporated into the heretofore disclosed ordered gels or films using cellulose nanomaterials as a template. At the final processing stage, the cellulose nanomaterials can be removed to obtain polymeric gels or films. Alternatively, polymeric/cellulose composites gels or films are formed without etching the cellulose nanomaterials. As one non-limiting example, the polymeric gels or films are made of phenol-formaldehyde, melamin-formaldehyde, urea-formaldehyde, poly(acrylic acid), polyester, etc. The weight concentration of polymeric nanomaterial in the polymeric/cellulose composites can range from about 1% to 99%.
- The surface properties of the disclosed gels can be modified by functionalizing the surface of the cellulosic network. The disclosed aerogels having no surface functionalization are hydrophilic and can dissolve or shrink its total volume upon contacting with water. Surface modifiers, example, dimethyloctadecyl [3-(trimethoxysilyl) propyl] ammonium chloride (DMOAP) and trichloro(1H,1H,2H,2H-perfluoro-octyl)silane can be added to the hydrogel before conversion to an aerogel. This type of surface modification provides a hydrophobic aerogel that is stable upon exposure to water.
- Colloidal particles having lengths ranging from about 1 nm to 10 μm can be homogeneously dispersed within the gels. In one embodiment the colloids can include gold and silver plasmonic nanoparticles such as rods, triangular platelets, and triangular frames; ferromagnetic nanoparticles such as ferromagnetic nanoplatelets; quantum dots such as nano-spheres, -cubes, -rods, and the like. The colloidal particles are introduced into the cellulose before cross-linking occurs. Cross-linking, through interaction with the colloidal surface ligands, binds the colloidal inclusions to the ordered cellulosic network as described previously herein. Any of the disclosed gels can contain one or more types of colloidal particles.
- The disclosed gels have a thickness from about 1 μm to about 10 cm. In one embodiment the thickness varies from about 10 μm to about 1 cm. In another embodiment the thickness varies from about 100 μm to about 10 cm. In a further embodiment the thickness varies from about 50 μm to about 1 cm. In still further embodiment the thickness varies from about 1 cm to about 10 cm. In a yet another embodiment the thickness varies from about 10 μm to about 100 cm. In a yet still further embodiment the thickness varies from about 500 μm to about 10 cm.
- The transmissivity of the disclosed gels relates to the amount of electromagnetic radiation that is blocked from passing through the gel. 0% transmission results in an opaque material which allows no transmission. 100% transmission results in a material that is transparent to electromagnetic radiation. The disclosed gels can have a transmission of from 0% to 100%. In one embodiment the gels have a transmission of from about 5% to about 15%. In another embodiment the gels have a transmission of from about 25% to about 50%. In a further embodiment the gels have a transmission of from about 95% to 100%. In a still further embodiment the gels have a transmission of from about 15% to about 35%. In a yet further embodiment the gels have a transmission of from about 50% to about 75%. In a yet another embodiment the gels have a transmission of from about 25% to about 75%.
- The disclosed gels and composite materials can have a thermal conductivity of from about 10−3 W/(m·K) to about 10 W/(m·K). In another embodiment the thermal conductivity is from about 10−2 W/(m·K) to about 10 W/(m·K). In a further embodiment the thermal conductivity is from about 10−1 W/(m·K) to about 10 W/(m·K). In a still further embodiment the thermal conductivity is from about 10−3 W/(m·K) to about 1 W/(m·K). In yet further embodiment the thermal conductivity is from about 10−2 W/(m·K) to about 1 W/(m·K). In yet another embodiment the thermal conductivity is from about 1 W/(m·K) to about 10 W/(m·K).
- The relative emissivity value of the disclosed gels ranges from about 10−2 to 0.99.
- The disclosed gels and composites can have a bulk modulus of from about 1 Pa to about 106 Pa. In one embodiment the modulus is from about 10 Pa to about 105 Pa. In another embodiment the modulus is from about 102 Pa to about 106 Pa. In a further embodiment the modulus is from about 103 Pa to about 105 Pa. In a still further embodiment the modulus is from about 10 Pa to about 103 Pa. In a yet further embodiment the modulus is from about 1 Pa to about 10 Pa. In a yet another embodiment the modulus is from about 104 Pa to about 106 Pa.
- Cellulosic starting material for the disclosed gels can be derived from a variety of sources. The surface-sulfuricated cellulose particles (
FIG. 1(a) andFIG. 2 ) that are suspended in water can be prepared by sulfuric acid-mediated oxidation of the natural cellulose. The surface-carboxylated cellulose nanofibers and nanoribbons that are suspended in water can be prepared by 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO)-mediated oxidation of the natural cellulose. The dispersions of these nanomaterials spontaneously form a thermodynamically stable cholesteric (for cellulose nanorods) or nematic (for cellulose nanofibers or nanoribbons) liquid crystal phase that can be transformed into a hydrogel (FIG. 1(b) andFIG. 3(a) ) with a similarly ordered spatial organization of cellulose particles. - Cellulosic starting material for the disclosed aerogels can be biosynthesized by Acetobacter xylinum, Acetobacter hasenii or other examples of bacterial strains utilizing, for example, glucose as a carbon source. As one example, Acetobacter xylinum can be cultivated in a glucose medium for 1-3 weeks under static conditions to produce cellulose pellicles. To remove bacterial cell debris, bacterial cellulose can be boiled in a 1 wt. % NaOH aqueous solution for 2 hours, followed by washing with water and neutralization with 0.2% acetic acid.
- Natural cellulose material obtained in this way can easily be disintegrated into individual nanocrystals by a controlled TEMPO mediated oxidation. For example, 2 g of bacterial cellulose was suspended in water (150 mL) containing TEMPO (0.025 g) and NaBr (0.25 g). A 1.8 M NaClO solution (4 mL) was added, and the pH of the suspension was maintained at 10 by adding 0.5 M NaOH. When no more decrease in pH was observed, the reaction was finished. The pH is then adjusted to 7 by adding 0.5M HCl. The TEMPO-oxidized products were cellulose nano-rods of controlled 4-10 nm diameter and 1000-3000 nm length, which were then thoroughly washed with water by filtration and stored at 4° C.
- Cellulose nanocrystals can also be synthesized by sulfuric acid hydrolysis method from natural cellulose. The aqueous suspension of such cellulose nanocrystals above the critical concentration (˜3-6 wt. %) self-assemble into liquid crystalline structures-chiral nematic phase, which shows periodic helicoidal structures with a pitch that can be controlled in the range 5-70 μm. This structure can strongly reflect electromagnetic radiation of the wavelength comparable with the pitch, which simultaneously serves as a high efficiency low-emissivity structure by tuning the pitch to be appropriate range. The disclosed films can have a pre-designed gradient of cholesteric pitch in helicoidally ordered nanocrystal self-assembly and achieve broadband infrared selective reflection and low-emissivity (compare to the red infrared emission curve taken from solicitation) while being transparent in the visible spectral range and also transmitting solar radiation (blue curve) in near-IR range.
- The concentration of the liquid crystalline cellulose nanocrystal dispersions was then adjusted to 3 wt. % and used in preliminary studies. The chiral nematic liquid crystalline order of the nanocrystals was then poured into a mold and the orientation of the helix could be aligned uniformly perpendicular to the film plane using a circular shearing or magnetic field. The polarizing optical micrograph shown in
FIG. 4c was obtained for a sample with the helical axis aligned in the horizontal direction, providing a side view of the periodic helicoidal structure of the chiral nematic liquid crystal. In the design and fabrication of AIR FILMs, this helical axis will be set orthogonal to the plane of the film and along the normal to the window (FIG. 2 ), which will be achieved using the process of circular shearing (see, Park J. H. et al. “Macroscopic control of helix orientation in films dried from cholesteric liquid-crystalline cellulose nanocrystal suspensions”, ChemPhysChem. 15, 1477-1484, 2014). - After cellulose nanomaterial preparation from one or multiple sources the cellulose nanomaterial can be dispersed in water and aligned by the following methods. First, the aqueous suspension of cellulose nanorods above the critical concentration (about 0.1-4%) self-assemble into a liquid crystalline phase with nematic or cholesteric ordering. Second, in order to induce uniform alignment across the entire dispersion, linear or circular shearing can be used for nematic or cholesteric phases, respectively. Specifically, the dispersion can be confined between glass plates in a mold such that, when a shear stress is applied from the plates in the specified direction (along a line or through a rotation), individual nanomaterial directors align to form a singular director alignment across the confined dispersion. As an alternate but complementary approach to dispersion alignment, the nanocrystals suffer uniform alignment under extrusion from a sufficiently small diameter nozzle, syringe, or similar device. With extrusion alignment, no confining plates are needed such that the aligned dispersion takes the form of a narrow bead, with linear extent much greater than cross-sectional extent, which rests on a supportive substrate or other structure. Additionally, the magnetic anisotropy of cellulose nanomaterial's relative permeability can be exploited to cause uniform alignment of nanocellulose. Under sufficiently strong magnetic fields (about 100 mT), uniform alignment of nanocrystals is achieved through the magnetic interaction of the induced magnetic dipole moments of the cellulose nanomaterial with the applied magnetic field. (An oscillating electric field can be used to align nanocellulose with its long axis along the electric field.)
- The aligned cellulose nanomaterial dispersion can be cross-linked to convert into a hydrogel while preserving its ordering. The extent of cross-linking of chains of cellulose nanomaterials establishes the degree to which uniform ordering is preserved in the dispersion. That is, for loosely cross-linked cellulose nanomaterials, weak gelation results. Conversely, strong cross-linking yields firm gelation. Gelation results from the addition of an acid, a photoacid generator and exposure to light, an alcohol, or another cationic exchange mechanism to the uniformly ordered cellulose nanomaterial dispersion. Alternatively, the cellulose nanorods, inorganic/cellulose nanorods, or polymeric/cellulose nanorods can self-assemble into cholesteric phase by evaporation.
- The nanocellulose-based ordered hydrogel was transformed into organogels (
FIG. 1(c) andFIG. 3(b) ) by shaking the cellulose-nanomaterial hydrogel gently in an organic-solvent-filled bath while replacing the solvent regularly in order to prompt the replacement of water in the hydrogel by the organic solvent. As one example, twice per day for an extent of three days ethanol was replaced to facilitate total solvent exchange. - The disclosed cellulose aerogels (
FIGS. 1(d) and 3(c) ) can be produced from the disclosed nano-structured organogel herein above. The resulting cellulose nanocrystal aerogel is a porous material with a skeleton of about 0.1-99.9% cellulose nanocrystals and a porosity of about 0.1-99.9%. To prevent deformation and crumbling of aerogels during the drying stage due to surface tension and capillary pressure in the ambient atmosphere, supercritical drying, freeze drying, or ambient drying low-surface tension solvent are used to remove liquid solvent from cellulose nanocrystal composites while maintaining the disclosed liquid crystalline structure, such as nematic or cholesteric liquid crystalline ordering. - The disclosed cellulose LC gels (
FIG. 1(e) andFIG. 3(d) ) can be produced from an ordered nano-structured organogel, in which an organic solvent completely miscible with LC is chosen. The organogel is placed in a bath of LC above the boiling point of the organic solvent so that the organic solvent is replaced with LC, which functions as the gel's replacement solvent. - The disclosed cellulose-templated ordered inorganic and polymeric gels or films can be produced by mixing cellulose nanomaterials with silica precursors or prepolymer and drying the composites in the ambient environment. Then the cellulose nanomaterials will be removed either by acidic (for silica aerogel) or basic (for polymeric aerogel) treatment to form a hydrogel. The hydrogel can be further transferred into organogel, aerogel, and LC gel based on the methods described above.
- Colloidal suspensions of cellulose nanocrystals (CNCs) composed of cellulose nanorods were prepared by controlled sulfuric acid hydrolysis of cotton fibers, according to the method described by Revol and co-workers (J.-F. Revol, H. Bradford, J. Giasson, R. H. Marchessault, D. G. Gray, Int. J. Biol. Macromol. 14, 170 (1992)). During this process, disordered or paracrystalline regions of cellulose are preferentially hydrolyzed, whereas crystalline regions, which have a higher resistance to acid, remain intact. 7 g of cotton was added to 200 g of 65 wt % sulfuric acid and stirred at 45° C. in a water bath for up to several hours until the cellulose had fully hydrolyzed. The mixture was sonicated occasionally, which was found to help degrade the amorphous cellulose regions. The suspensions of cellulose were then centrifuged at 9000 rpm for 10 min and re-dispersed in deionized water 6 times to remove the excess sulfuric acid. The resulting precipitate was placed into a dialysis tubing (MWCO 12000-14000, Thermo Fisher Scientific Inc.) in de-ionized water for three days until the water pH remained constant. The dimensions of CNCs are about 5-10 nm in cross-section and, on average, 100-300 nm in length. Then 3 wt % CNCs solution was cast in a mold and evaporated under ambient conditions to obtain an aerogel.
- Cellulose nanofibers (CNF's) with the dimension of 4.8 nm by several micrometers were synthesized following the literature (T. Saito, M. Hirota, N. Tamura, S. Kimura, H. Fukuzumi, L. Heux and A. Isogai, Biomacromolecules, 10, 1992 (2009)). Briefly, cellulose based bleached coffee filter (1 g) was suspended in 0.05 M sodium phosphate buffer (90 mL, pH 6.8) dissolving 16 mg of 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO) and 1.13 g of 80% sodium chlorite in an airtight flask. The 2 M sodium hypochlorite solution (0.5 mL, 1.0 mmol) was diluted to 0.1 M with the same 0.05 M buffer used as the oxidation medium and was added at one step to the flask. The flask was immediately stoppered, and the suspension was stirred at 500 rpm and 60° C. for 96 hours. After cooling the suspension to room temperature, the TEMPO-oxidized cellulose was thoroughly washed with water by filtration. Then 0.1-1.0 vol. % CNFs aqueous dispersion was poured into a mold, aligned by a shear force, and several drops of 1 M HCl solution was added to form a hydrogel after 2 hours. The hydrogel was immersed into ethanol for 2 days for solvent exchange to form an organogel. To form a liquid-crystal gel, the organogel was immersed in a bath of liquid crystal 4-cyano-4′-pentylbiphenyl at 90° C. for 12 hours. Subsequent cooling to room temperature after solvent exchange caused the LC to enter its expected nematic phase. The aerogel was formed by critical point drying of the organogel.
- CNCs were synthesized according the method in Example 1. Then 5 mL of 3 wt % CNCs dispersion was mixed with 10-750 μL of silica precursor tetramethyl orthosilicate and stirred for 1 hour. Then the composites were cast into a Petri dish and dried over 1-2 days. The CNCs were then removed by pyrolysis method (e.g. 540° C. for 20 hours) or keeping in 16% sodium hydroxide solution for 16 hours. The silica hydrogel was formed and can be further transferred into organogel by solvent exchange and aerogel by critical point drying or ambient drying.
- CNCs were synthesized according the method in Example 1. Then 5 mL of 3 wt % CNCs dispersion was mixed with 10-75 mg of water-soluble preformed polymer and stirred for 10 min. Then the composites were casted into a Petri dish and dried over 1-2 days. The film was then cured at polymerization temperature for 24 hours. The CNCs were then removed by 16% sodium hydroxide solution for 16 hours. The polymer hydrogel was formed and can be further transferred into organogel by solvent exchange and aerogel by critical point drying or ambient drying.
- The light scattered upon passing through aerogels can produce a hazy appearance, which can result in the reduction of contrast of objects viewed through the film. Haze measurements can be performed using a hazemeter or spectrometer.
FIG. 5 describes an apparatus developed and adapted to measure the quality of the disclosed aerogels. The apparatus inFIG. 5 has the advantage of conducting haze measurements that also provides diagnostic data on the origins of the haze. - The typical setup includes an integrating sphere where the measured film is placed against the sphere entrance port. The surface of the interior of the integrating sphere is highly reflecting throughout the visible wavelengths obtained from light sources. The light entering the integrating sphere is reflected from the surface towards the tested film. Then the light transmitted through the film is focused and directed to a photodetector. A photodetector in the spectrophotometer setup is computer driven and values for transmission and haze can be automatically calculated. The haze can be determined as haze=100×(Td/Tt), where Tt is a total transmittance depending on intensity of incident light & total light transmitted by the film & Td is diffuse transmittance depending on light scattered by a measuring setup & the film.
- Sound proofing characterization can be conducted by imaging of nanoparticles using TEM and SEM.
FIG. 6 outlines a procedure for probing of the pore size, surface area, and structural properties of cholesteric cellulose-based aerogels under different preparation conditions. The ordering of nanocrystals on large scales will be probed using 3D imaging techniques such as Fluorescence Confocal Polarizing Microscopy (FCPM), Coherent Anti-Stokes Raman Scattering Polarizing Microscopy (CARS-PM), and Three-Photon Excitation Fluorescence Polarizing Microscopy (3PEF-PM). In addition, the monitoring of the disclosed liquid crystal and aerogel uniformity in lateral directions can be accomplished by using conventional dark-field, bright-field, and polarizing optical microscopy. Visible- and infrared-range spectroscopy can also be utilized. The other properties of the disclosed aerogels include mechanical properties (both as-prepared aerogels and encapsulated, ready-to-install films), as well as soundproofing and condensation resistance of the films installed on single-pane windows. - Prior to the application of films onto a window the thermophysical properties (for example, thermal conductivity, heat capacity) are characterized by the optical pump-and-probe method in order to determine the type of film that is suitable for the specific application. This procedure uses a femtosecond laser to construct a high temporal resolution temperature measurement system.
FIG. 7 shows the optical pathway of a typical pump-and-probe measurement system. In the optical pump and probe method, sub-picosecond (ps) time resolution is made possible by splitting the ultrafast sub-ps laser pulse output into an intense heating pulse, i.e., a “pump” beam, and a weaker “probe” beam, and controlling the optical path length difference of the pump and probe beam through a mechanical delay stage. The decay of the temperature rise is measured by the reflected energy of the probe pulse series. The thermal conductivity can then be deduced by fitting the temperature decay curves. - After determining the thermal conductivity of a disclosed aeropgel, films can be applied atop of a window to determine the thermal insulation and condensation resistance performance, following the current standards of ASTM C1363-11 and ASTM C1199-14. This test method establishes principles for design of a hot box apparatus & requirements for the determination of the steady-state thermal performance of windows when exposed to controlled laboratory conditions. The window thermal insulation and condensation performance is represented by the overall heat transfer coefficient, U.
FIG. 8 discloses the components of a hot box apparatus: a metering box (simulating interior temperature) on one side of the window specimen; a controlled guard box surrounding the metering box; a climate chamber box (simulating exterior temperature) on the other side; and the specimen frame providing specimen support & insulation. - The walls of the hot box are insulated panels of plywood adhered to either side of a solid layer of XPS insulation. The space conditioning system used in the meter box employs hydronic cooling and electric resistance heating. The meter box cooling is measured using high precision thermocouples in combination with a precision flow meter to accurately quantify the heat removed from the meter box. Heat is added into the meter box via PID-controlled electric heaters. Precision resistor circuits are employed to measure the heat added into the meter box. A constant and precise temperature can be maintained and the total heat addition/removal can be measured. The hot box employs an insulated guard box surrounds the meter box and a hydronic guard loop is installed over the outside surface of the meter box. The guard box minimizes the influence of temperature changes in the lab. The liquid guard loop further ensures the outside surface of the meter box remains at a constant temperature. An insulated baffle separates the air space from the mixing chamber of the meter box. The baffle panels are constructed using thermal insulation material. For a 1 m×1 m test window sample, at least 25 calibrated precision thermocouples are used to measure temperatures on the baffle surface, 25 corresponding points in the air stream and at least 25 points on the interior surface of the test window specimen. Air drawn through the meter box baffle space at velocities representative of convection in real world conditions. DC powered axial draw-through circulation fans, at the top and bottom of the baffle, are used to ensure smooth flow along the surface of the wall sample in the direction that convection would occur.
- The climate box has the same dimensions and construction as the guard box. The climate side air baffles are constructed using the same materials and methods as the air baffles in the meter box. Heat is added to/removed from the climate box via four fan coils which are connected to a liquid chiller and a hydronic heater. Electric resistance heaters permits fine tuning of the temperatures and ensures that temperatures remain close to the set point for the duration of the test. The climate box has the capacity to run a range of realistic outdoor temperatures, from −30° C. to 60° C. This enables the tested window assembly to remain undisturbed when tested from cold to hot climate conditions. Overall heat transfer coefficient is:
-
- where Q is the time rate of net heat flow through the meter box opening, W; A is meter box opening area, m2; Tmeter and Tclimate are temperatures of meter box and climate box, respectively.
- Further disclosed are transparent cellulose-polysiloxane hybrid hydrogels, organogels and aerogels and a process for preparing the disclosed transparent cellulose-polysiloxane hybrid transparent cellulose-polysiloxane hybrid hydrogels, organogels and aerogels. Disclosed is a cellulose-polysiloxane hybrid aerogel, comprising:
- a) a cellulosic matrix; and
- b) a polysiloxane surface network
- Without wishing to be limited by theory, these characteristics are achieved by strictly controlling the dimensions of nanofibers and the homogeneous gel skeleton networks that they form, which can be tuned to form orientationally ordered liquid crystal (LC) states. In the gel fabrication process, an optimized acid/base catalyzed sol-gel reaction in a surfactant-based solution is used to form a polymethylsilsesquioxane (PMSQ) surface network.
- Cellulose nanofibers having a uniform diameter are first surface functionalized. This functionalization can employ small charged molecules or polymer grafting resulting in increased cellulose nanofiber stability. Subsequently, these nanofibers are crosslinked with PMSQ fibers. In addition to their high optical transparency, super thermal insulation, flexibility and mechanical robustness, the disclosed hybrid aerogels can be made optically isotropic or anisotropic, depending on the intended use by the formulator. In the case of anisotropic aerogels, they can be fabricated starting from the LC states of colloidal dispersions of nanofibers. The resulting compositions can have practical applications as they result can result in devices having optical polarization, thereby the ability to control visible light polarization while providing simultaneous thermal insulation.
- Disclosed herein is a process for preparing polymethylsilsesquioxane (PMSQ) network cellulosic aerogels, comprising:
-
- a) contacting an aqueous dispersion of cellulose with a oxidizing system that oxidizes the C6 hydroxyl units of cellulose to carboxylate units to form an aqueous solution of oxidized cellulose nanofibers;
- b) reacting the oxidized cellulose nanofibers with a surface modifying agent to form an aqueous solution of surface modified cellulose nanofibers;
- c) contacting the surface modified cellulose nanofibers with polymethylsilsesquioxane (PMSQ) to form an aqueous polysiloxane precursor;
- d) hydrolyzing the polysiloxane precursor in the presence of an acid catalyst to form a PMSQ network cellulosic hydrogel;
- e) exchanging the water contained in the hydrogel with a volatile solvent to form an organogel; and
- f) removing the volatile solvent to form an aerogel.
- In one embodiment the oxidizing system comprises:
-
- a) an admixture of (2,2,6,6-Tetramethylpiperidin-1-yl)oxyl (TEMPO) and NaClO.
- In one embodiment the surface modifying agent is chosen from C1-C6 linear or branched, saturated or unsaturated alkylamine, low molecular weight compounds comprising a cationic moiety, oligomers or polymers.
- The C1-C6 linear or branched, saturated or unsaturated alkylamines react with the cellulose carboxyl units under the conditions of the present process to form a carboxylate-quaternary ammonium complex, for example, as depicted in
FIG. 9A . One example of this embodiment comprises the use of allylamine as the modifying agent. - Another embodiment comprises the use of an oligomer or polymer as the modifying agent. In one iteration m-PEG-amines having an average molecular weight of from about 2000 to about 10,000 daltons are used to modify the surface of the oxidized cellulose nanofibers. In one non-limiting example of this iteration the modifying agent is an m-PEG amine having an average molecular weight of 5000 daltons. For example, the m-PEG amine depicted in
FIG. 9C wherein the index n is approximately 112. Any oligomer or polymer that can covalently bond to the surface carboxylates of the oxidized nanofibers can be used to modify the cellulosic surface. - A further embodiment comprises a modifying unit that is a low molecular weight compound comprising a cationic moiety. The molecular weight of compounds of this type are less than about 400 g/mol. A non-limiting example of this embodiment is depicted in
FIG. 9B wherein the use of a carbamoylcholine salt is the modifying agent. The salt can be chlorine, bromine and the like. - In order for spontaneous nematic ordering of the nanofibers to occur, the nanocellulose concentration must be above the critical concentration. This behavior provides a unique opportunity for the formulator to impart LC ordering at low TOCN volume fractions which provides a means for obtaining the disclosed optical anisotropy and other properties.
- Raw cellulosic material obtained from natural sources is used to form the disclosed hydrogels, oranogels and aerogels. For example, cotton, grains, paper products made from natural sources and the like. The cellulosic material is first oxidized at the C6 saccharide carbons thereby oxidizing the —CH2OH moieties to carboxylate moieties, —COOH.
- The oxidized cellulosic material is then treated with a modifying agent, which allows the cellulose nanofibers in the hydrogel to remain aligned and non-reactive to the subsequent treatment with the networking agent. Next, following treatment with the modifying agent, the nanofibers are treated with methyltrimethoxysilane (networking agent) which is hydrolyzed under acidic conditions to form a polysiloxane network over the hydrogel. Gelation results in a highly-transparent monolithic hydrogel of functionalized TOCNs, cross-linked by an isotropic, bicontinuous polysiloxane nanofibrious network.
- The water is removed from the hydrogel by exchange with a volatile organic solvent to form the corresponding organogel. The resulting organogel exhibits both an isotropic and liquid-crystalline arrangement, which can be controlled by regulating the surface-modified TOCN concentration. These orientationally ordered self-assembled structures are locked in place by the formation of the polysiloxane network. The disclosed process preserves the small and uniform cross-sections of individual fibers and their network and, consequently, assures low light scattering.
- The corresponding aerogel is formed by drying of the organogel, which can be shaped to the needs of the formulator. In addition to mechanical flexibility and robustness, many practical aerogel applications can require a high degree of hydrophobicity (for example, to assure that these aerogels are stable under ambient conditions and in humid environments).
- The disclosed cellulose nanofibers are produced through the oxidation of native cellulose by selectively modifying the C6 primary hydroxyl groups on the surface of native cellulose to carboxylate groups catalyzed by TEMPO under mild pH aqueous conditions. The nanofibers with a diameter of 4.8 nm and micrometer-scale lengths are stabilized in a basic solution by the Coulombic repulsion of their anionic carboxylate moieties, which overpower their tendency to form hydrogen bonds. As a result, the aqueous TOCN dispersions are highly transparent. To eliminate the strong light scattering originating from bundling and clustering of TOCNs which are uncontrollably crosslinked by direct hydrogel bonds, as often observed in polymeric fibrous aerogels, we instead cross-link TOCNs with polysiloxane. This technique precludes the direct contacts between TOCNs and thereby generates a uniform nanofibrious network that exhibits small scattering cross-sectional areas. Hydrolysis of the polysiloxane precursor is acid-catalyzed. However, even under mildly acidic conditions and dilute concentrations, TOCNs tend to form a gel-like phase due to the hydrogen bonding between carboxylic acid functional groups. To stably disperse TOCNs in polysiloxane precursor solutions, we implement various TOCN surface functionalization schemes, as illustrated in
FIGS. 9A-C . - The TEMPO-mediated oxidation of cellulose produces a large density of carboxylic groups (˜0.8 mmol/g) on the surface of nanofibrillated cellulose that is available for surface modification. This provides a means for altering the physical adsorption properties of the cellulose nanoparticles by covalently bonding either low molecular weight cationic molecules or polymeric chains to the surface thereby resulting in stabilized TOCNs by either electrostatic repulsion or steric hindrance.
- In one embodiment as depicted in
FIG. 9A this modification is affected by physisorption of one or more polyelectrolytic monomers, in this example allylamine, to the anionic carboxylate groups of the oxidized cellulose. This process does not significantly affect the cross-sectional diameter of the TOCN's because of the size of the low molecular weight of the cationic small molecule. - In another embodiment as depicted in
FIG. 9B the surface functionalization can be accomplished by reaction of the carboxyl groups with a cationic-amine comprising adduct.FIG. 9B depicts the reaction of 2-(carbamoyloxy)-N,N,N-trimethylethanaminium (choline carbamate) with the TOCN's. This reaction introduces another form of cationic charge electrostatic repulsion - In a further embodiment as depicted in
FIG. 9C the surface of the TOCN's are modified by reaction with a polymeric material, in this example a methoxy polyethylene glycol amine (mPEG-amine). Grafting of a polymer of this type provides a means for improving colloidal-TOCN stabilization. - The functionalization of the TOCN's produces cellulosic matrices that are stable to treatment with polysiloxane in the subsequent step of the disclosed process.
-
FIG. 10 depicts the process in general. Oxidized and surface modified cellulose nanofibers as an aqueous suspension are represented by the long aligned fibers and the differently shaded dots represent water molecules and molecules of PMSQ (far left figure). The center figure represents Steps (c) and (d) of the process above wherein the nanofibers are first contacted with PMSQ then the PMSQ is hydrolyzed to form a PMSQ network cellulosic hydrogel. The resultant of Steps (e) and (f) is depicted in the figure on the far right, the resulting aerogel. The resulting transparent surface-modified TOCNs' aqueous colloidal dispersions can exhibit LC ordering, depending upon the volume fraction of the nanofibers in the colloidal dispersion. In addition, these solutions can exhibit birefringence when they are observed between cross polarizers as depicted inFIG. 10 . - The surface of the TEMPO-oxidized cellulose nanofibers were then functionalized by physical adsorption of allylamine onto the nanofibers. 500 mg of 0.2 wt. % nanofiber aqueous solution was diluted by 2 mL of distilled and deionized water and combined with 10 mg of allylamine. The mixture was stirred overnight and dialyzed for 2 days in a deionized water bath across a cellulose acetate membrane with a cutoff molecular weight of 12,000-14,000 g/mol to obtain the desired allylamine-TOCNs.
- An aqueous TOCN dispersion (500 mg of 0.38 wt. %) was diluted with 2 mL of deionized water followed by the addition of 24 mg of 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxid hexafluorophosphate (HATU), 20 μL of N,N-diisopropyl-ethylamine (DIPEA) and 50 mg carbamoylcholine chloride and 404, dimethylformamide (DMF). The mixture was stirred for 2 days and dialyzed for another 2 days affording the desired dispersed surface modified nanofibers.
- An aqueous TOCN dispersion (500 mg of 0.2 wt. %) was diluted with 2 mL of DI water and followed by mixing with 28 mg of HATU, 20 μL of DIPEA, 18 mg mPEG-amine (MW=5000) and 40 μL DMF. The mixture was stirred for 2 days and then dialyzed for another 2 days to finally obtain mPEG-TOCNs. All of the functionalized TOCN dispersions were concentrated by a rotary evaporator to the desired concentration.
- The disclosed PMSQ network cellulosic hydrogels were fabricated by cross-linking functional TOCNs with polysiloxane. For example and in general, cetyltrimethylammonium bromide (0.4 g)(CTAB) and 3.0 g of urea were dissolved in 8 mL of deionized (DI) water with sonication until the sol became homogeneous. To this solution is added 2 mL of a functionalized surface modified TOCN at differing concentrations, 1-5 mL of methyltrimethoxysilane (MTMS) and 0.01 mmol acetic acid under vigorous stirring. After stirring each sample for 30 minutes at room temperature, the sol was degassed in a vacuum oven and then transferred into a polystyrene petri dish with a diameter of 5 cm, sealed for gelation and allowed to age for 3 days in a 60° C. furnace to form the desired hydrogels.
- The hydrogels formed above were taken from the petri dish and immersed in DI water for 24 hours to remove the urea and residual CTAB. This was followed by solvent exchange with isopropanol, which was replaced every 12 hours, at 60° C. for 2 days. Finally, CO2 supercritical drying at 38° C. under 8.6 MPa was conducted to obtain dried aerogel samples in a critical point dryer. This provided aerogels having bulk densities ranging from 30-200 mg/cm3 depending upon the amount of MTMS added to the functionalized surface modified cellulose in the above step. In one embodiment an aerogel having a density of 69 mg/cm3 promotes optimal optical transmission and mechanical flexibility. In one iteration of the disclosed process no stress is introduced to TOCN-PMSQ aerogel during processing.
-
FIG. 11 is a photograph showing the optical transparency of a hydrogel formed from the disclosed process. This hydrogel is a highly-transparent monolithic hydrogel cross-linked by an isotropic, bicontinuous polysiloxane nanofibrious network as described herein. The hydrogel is contained within the outlined dotted area.FIG. 12 is a photograph showing the optical transparency of an organogel formed from the disclosed process. The organogel is contained within the outlined dotted area.FIG. 13 is photograph showing the optical transparency of an aerogel formed from the disclosed process wherein the surface modifying agent is allylamine. The aerogel is contained within the circle.FIG. 14 is a photograph of an aerogel formed by the disclosed process wherein the surface modifying agent is an m-PEG-amine having an average molecular weight of 5000 daltons. The circular aerogel is positioned on top of a copy of text. AS can be seen in the photograph the aerogel is transparent in that neither the color nor the text is distorted.FIG. 15 is a photograph of an aerogel formed by the disclosed process wherein the surface modifying agent is carbamoylcholine chloride. The circular aerogel is positioned on top of a copy of text. The aerogel is transparent in that neither the color nor the text is distorted. - As depicted in
FIG. 16 the carbamoylcholine chloride-capped TOCN-PMSQ aerogels exhibit hydrophobic surface characteristics with a typical contact angle of 148°, largely due to the presence of hydrophobic methyl groups on the polysiloxane fibers within the nanostructured aerogels. An advantage of the disclosed process is that there is no need for post-synthetic hydrophobization treatment when the disclosed gels are used for hydrophobic applications. - The disclosed aerogels were analyzed for both their optical and electron imaging and spectra characteristics. For both polarized and unpolarized brightfield optical microscopic imaging, an Olympus BX-51 polarizing optical microscope was equipped with 10×, 20×, and 50× air objectives with a numerical aperture NA=0.3-0.9 and a 0.5× tube lens mounted right before a CCD camera Spot 14.2 ColorMosaic (Diagnostic Instruments, Inc.). Transmission spectra were studied using a spectrometer USB2000-FLG (Ocean Optics) mounted on the microscope. For light transmittance and haze measurements of aerogels, a UV-VIS-NIR spectrometer, ranging from 190 nm to 3200 nm, (UV-3101pc, from Shimadzu) equipped with a LabSphere brand integrating sphere attachment was employed. Haze is defined as the ratio of diffuse transmission to total transmission, where diffuse transmission is defined as transmitted light varying by greater than or equal to a 5° separation from the direction of incident light. Infrared transmission spectra from
wavenumbers 400 cm−1 to 4000 cm−1 (wavelengths 2.5 μm-25 μm) were recorded on a Fourier-transform infrared spectroscopy (FTIR) spectrometer (Nicolet AVATAR 370 DTGS from Thermo) equipped with an a integrating sphere (NIR IntegratIR, from Pike). Photographs of samples were taken using a digital camera. IR thermographs were obtained by an IR camera (T630sc, from FLIR). TEM images were obtained using a CM100 microscope (from FEI Philips) at 80 kV. The TOCN samples were negatively stained with phosphotungstic acid to increase imaging contrast: 2 μL of the sample is dropcasted on the formvar coated copper grid, allowed to settle for drying and then dipped into the stain solution (aqueous 2 wt. % phosphotungstic acid). The porous morphology of TOCN-PMSQ was characterized using an SEM using a Hitachi Su3500 and CarlZeiss EVO MA 10 system. For this, freshly cut surfaces of the TOCN-PMSQ aerogels were sputtered with a thin layer of gold and observed under SEM at a low voltage of 5 kV (as optimized to avoid the distortion of the aerogel samples). -
FIGS. 17A-C are transmission electron microscopy (TEM) micrographs of the disclosed aerogels at various magnifications.FIG. 17A shows that the colloidal dispersions consist of mostly individualized TOCNs, each of diameter Dc≈5 nm and length Lc=1-2 μm.FIGS. 17B and 17C are scanning electron microscopy (SEM) that depict the well-defined and uniform-diameter 10-15 nm nanofibers that are formed by polysiloxane treatment and individually dispersed TOCNs fibers within the aerogels as well as a narrow pore-size distribution of their resulting porous network. The depicted aerogel samples exhibit 3D bicontinuous network-like structures, in which both the smooth gel skeletons and the pores are interconnected without aggregation or clustering. The example depicted inFIGS. 17A-C have a bulk density ρb that is calculated to be 69 mg/cm3 by weight/volume ratio of the sample. The porosity, defined as c=(1-ρb/ρs)×100%, is then determined to be ε≈94.9%, where ρs is the skeletal density taken to be 1.35 g/cm3. The average pore size for this particular example is calculated to be approximately 100 nm, consistent with the value observed directly from the SEM images. The mesoscale morphology of the 2.0-mm thick QA-capped TOCN-PMSQ composite aerogel with ultrathin fibers and uniform pore size distribution yields hydrogels and organogels with very high light transmission greater than 90% and aerogels with visible transmission close to 90% at 600 nm as depicted inFIG. 18 . - The exampled aerogel's haze coefficient, defined as the ratio of diffuse transmittance and total light transmittance, was determined to equal to 8.4%
FIG. 19 and is characterized following the ASTM D1003 standard using an integrating sphere setup when integrated across the visible range (390-700 nm), shown inFigure S1 . The PMSQ matrix causes TOCN-PMSQ aerogels to exhibit strong absorption at a wavelength of 6-20 μm, which is mainly due to the Si—O bondsFIG. 20 . This provides the formulator the opportunity to separately control transmission of visible and infrared light, in embodiments wherein control of solar gain and emissivity are important, i.e., in smart-window applications. - The disclosed aerogels were analyzed for their thermal, mechanical, and durability characteristics. The thermal conductivity is measured by measuring both the heat capacity and thermal diffusivity of the aerogel samples. The heat capacity of aerogel is measured by differential scanning calorimetry (DSC 204 F1 Phoenix, Netzsch). The thermal diffusivity of aerogel is characterized by a laser flash apparatus (LFA 457, Netzsch). Briefly, an optical source instantaneously heats one side of the material and the temperature increment on the other side of the material is recorded by infrared thermography for facile, noninvasive temperature sensing. To prevent the direct heating of the detector by laser light, the top and the bottom of the aerogel were covered with highly conductive carbon tape to prevent the laser from penetrating through the sample. The thermal conductivity of the aerogel can be calculated by subtracting the contribution of carbon tape from the effective thermal conductivity of the sandwich structure, which was determined by performing measurements for samples of different thickness. The Instron 5965 material-test system was used to probe the mechanical properties and determine stress-strain relationships. The mechanical properties shown in
FIG. 4f were measured with TOCN-PMSQ aerogel samples with 0.25 vol. % QA-capped TOCN cut into rectangular strips of 20 mm×6 mm×1 mm. Aerogel durability testing was performed under a 500 Watt mercury lamp (Sun System 5, from Sunlight Supply Inc.) and in a Tenney environmental test chambers held at 80° C. and 80% relative humidity for 24 hours. -
FIG. 21 shows the measured thermal conductivity of a TOCN-PMSQ aerogel versus sample porosity.FIG. 22 depicts the comparison of thermal conductivity between an aerogel formed from carbamoylcholine chloride modified nanocellulose (quaternary-amine) and an allylamine modified aerogel.FIG. 23 depicts the compression stress-strain relation for a TOCN-PMSQ aerogel with 0.06 wt. % of TOCN. - Disclosed herein are nanocellulose biofilms derived from bacterial cellulose. The disclosed biofilms are suitable for use in preparing insulating and structural gels. Non-limiting examples of bacteria that can be used to provide the disclosed biofilms include Acetobacter hansenii and Acetobacter xylinum.
- The bacterial biofilms are formed in situ as depicted in the Figures. The resulting cellulose gels are formed from orientationally ordered material. The disclosed gels can be formed directly from the cellulose bacterial biofilm pellicle. As disclosed herein the bacteria forming the biofilms can be directed and positioned to a desired orientation using an infrared laser beam. Using an infrared laser beam as a laser trap the bacteria can be moved, re-orientated and positioned adjacent to one another such that the resulting fibrils of cellulosic material can coalesce with one another.
- The disclosed cellulosic gels are orientationally ordered because of their alignment as they are being formed because of hydrogen bonding between fibrils. This results in the fibrils forming ribbons. In addition, by modification of the growth nutrients, the density of the fibrils, hence, the ribbons can be determined by the formulator. In addition, modification of the bacterial culture can result in a change in the fibril diameter.
- Therefore, modifications to the growth media and to the nutrient composition, as well as, a change in bacterium species, can be used to tune the resultant gel to be transparent or opaque, flexible or stiff, thermally insulating or conducting, and fragile or load-bearing. Resultant gels can be further chemically treated to tune material and thermal properties of the invention, such as crosslinking density, material composition, and hydrophobicity. Colloidal inclusions can be introduced into the resultant gel to tune optical, magnetic, and electric properties of the gel.
-
FIG. 24A andFIG. 24B depict the reorientation of an A. hansenii bacterium using the infrared laser beam of a laser trap. The laser trap can be used to move a bacterium to a position in the growth media that provides easier harvesting of the pellicles or alternatively to determine the density of the pellicles.FIG. 25 is a photograph of dark field microscopy showing an A. hansenii bacterium producing a cellulose fiber. The cellulosic material is visible because the various single strands of cellulose have coaleased into a ribbon. This is depicted schematically inFIG. 28 .FIG. 26 shows A. xylinum bacteria producing cellulose fibers. -
FIG. 27A andFIG. 27B shows the effect on cellulose fibril thickness when 1.5% sodium carboxymethyl cellulose is added to A. xylinum. InFIG. 27A the cellulose fibril is visible. InFIG. 27B the thickness of the fibril is greatly reduced such that the fibril is invisible in the photograph. This is depicted schematically inFIG. 29 . - Bacterial cellulose derived from A. hansenii is used in this example. The bacterial cellulose pellicles are purified by first washing in 70° C. 1 wt % NaOH aqueous solution for ˜4 hours, to kill any remaining bacteria. The pellicles are then transferred to 70° C. or room temperature DI water to remove excess NaOH and reduce the ionic strength back to that near of pure DI water. Heating to 70° C. speeds up the process, but the process can be done at room temperature (RT) as well. The pellicle is washed 2 additional times in pure DI water (at RT or with mild heating, e.g. to 70° C.), for a total of 3×DI water rinses. Then the pellicle is transferred into pure isopropanol (IPA) and allowed to solvent exchange. This solvent exchange from water to IPA can be done at RT or 60° C., depending on the urgency and speed desired. The pellicle is then placed into a fresh bath of IPA, to further dilute any remaining water in the solvent exchange bath. The number of times the pellicle is washed with fresh IPA depends on the pellicle thickness. For example, thin pellicles can require only need 2 total IPA baths to sufficiently remove water, whereas thicker pellicles can require 3-5 exchange cycles in IPA. After the water/IPA solvent exchange is complete, the pellicle is dried via conventional critical point drying (CPD) techniques (using liquid CO2, same as drying the aerogel). Once at the CO2 critical point, the pressure is bled off at ˜50 PSI/min.
-
FIG. 28 is a depiction of an Acetobacter cell showing multiple cellulose synthase enzymes extruding cellulose fibrils from the cellular membrane. As the fibrils lengthen hydrogen bonding between adjacent strands cause the fibrils to coalesce and form ribbons. -
FIG. 29 is a depiction of an Acetobacter cell showing multiple cellulose synthase enzymes extruding cellulose fibrils from the cellular membrane. In this iteration, carboxymethyl cellulose is added to the growth media resulting in hydrogen bonds not forming the fibrils into ribbons of fiber. -
FIG. 30A andFIG. 30B demonstrate to optical and mechanical properties of the disclosed aerogels prepared from bacterial cellulose. InFIG. 30A the aerogel is opaque whereasFIG. 30B depicts the flexibility of the corresponding aerogel. - Bacterial cellulose derived from A. hansenii wherein 1.5% carboxymethyl cellulose was added to the culture media was used in this example. The bacterial cellulose pellicles are purified by first washing in 70° C. 1 wt % NaOH aqueous solution for ˜4 hours, to kill any remaining bacteria. The pellicles are then transferred to 70° C. or room temperature DI water to remove excess NaOH and reduce the ionic strength back to that near of pure DI water. Heating to 70° C. speeds up the process, but the process can be done at room temperature (RT) as well. The pellicle is washed 2 additional times in pure DI water (at RT or with mild heating, e.g. to 70° C.), for a total of 3×DI water rinses. Then the pellicle is transferred into pure isopropanol (IPA) and allowed to solvent exchange. This solvent exchange from water to IPA can be done at RT or 60° C., depending on the urgency and speed desired. The pellicle is then placed into a fresh bath of IPA, to further dilute any remaining water in the solvent exchange bath. The number of times the pellicle is washed with fresh IPA depends on the pellicle thickness. For example, thin pellicles can require only need 2 total IPA baths to sufficiently remove water, whereas thicker pellicles can require 3-5 exchange cycles in IPA. After the water/IPA solvent exchange is complete, the pellicle is dried via conventional critical point drying (CPD) techniques (using liquid CO2, same as drying the aerogel). Once at the CO2 critical point, the pressure is bled off at −50 PSI/min.
- The thermal conductivity of the disclosed bacterial cellulosic gels can be measured by known processes (See, Hayase et al., App. Materials & Interfaces 6, 9466 (2014) and Zu et al., Chem. Mater. 30, 2759 (2018).
FIG. 31A andFIG. 31B are thermal imaging photographs comparing a standard polysiloxane polymer,FIG. 31A , with a gel formed by the disclosed process,FIG. 31B . The patch of bacterial cellulosic aerogel is cold relative to the surrounding heated surface. - While particular embodiments of the present disclosure have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the disclosure. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this disclosure.
Claims (16)
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US16/017,319 US20190055373A1 (en) | 2017-01-11 | 2018-06-25 | Bacterial cellulose gels, process for producing and methods of use |
CA3103620A CA3103620A1 (en) | 2018-06-13 | 2019-06-13 | Bacterial cellulose gels, process for producing and methods of use |
JP2020569102A JP2021533213A (en) | 2018-06-13 | 2019-06-13 | Bacterial Cellulose Gel, Manufacturing and Usage |
AU2019287564A AU2019287564B2 (en) | 2018-06-13 | 2019-06-13 | Bacterial cellulose gels, process for producing and methods of use |
EP19819280.9A EP3807349A4 (en) | 2018-06-13 | 2019-06-13 | Bacterial cellulose gels, process for producing and methods of use |
CN201980054456.7A CN112930366A (en) | 2018-06-13 | 2019-06-13 | Bacterial cellulose gel, production process and use method |
PCT/US2019/037122 WO2019241603A1 (en) | 2018-06-13 | 2019-06-13 | Bacterial cellulose gels, process for producing and methods of use |
US18/530,194 US20240158601A1 (en) | 2017-01-11 | 2023-12-05 | Bacterial cellulose gels, process for producing and methods for use |
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US15/868,714 US11180627B2 (en) | 2017-01-11 | 2018-01-11 | Cellulose enabled orientationally ordered flexible gels |
US16/017,319 US20190055373A1 (en) | 2017-01-11 | 2018-06-25 | Bacterial cellulose gels, process for producing and methods of use |
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