Ceramic cellulosic composites

Abstract

Polymer-ceramic composite materials and methods of manufacture of such materials are provided. The polymer-ceramic materials include a cellulose-containing polymer substrate and a deposited ceramic within the internal volume of the polymer matrix and on the surface of the substrate.

Description

[0001] CERAMIC CELLULOSIC COMPOSITES

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003]

[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 662,350, filed on June 20, 2024, which is incorporated herein by reference in its entirety.

[0004] FIELD OF THE INVENTION

[0005]

[0002] This application relates to integration of ceramic materials with cellulose-containing substrates, which provides improved mechanical properties and resistance to biological fouling when the substrates are exposed to water.

[0006] BACKGROUND

[0007]

[0003] Cellulosic based substrates, such as paper, when exposed to water tend to absorb, wick and hold water, which can result in mechanical failure, odor, and / or mold formation. Cellulosic substrates are a low cost bioresource, can be recycled, and as such are desirable engineering materials when compared to petroleum derived synthetic materials, highly engineered materials, such as carbon fiber and resin, or higher energy ceramic materials, such as glass fibers.

[0008]

[0004] Cellulosic substrates which have improved properties in terms of water repellency, vapor transport, anti-fouling properties, or other features would be desirable.

[0009] BRIEF SUMMARY OF THE INVENTION

[0010]

[0005] Cellulose-containing polymer-ceramic composites, and methods of making the composites, are provided herein.

[0011]

[0006] In one aspect, a cellulose-containing polymer-ceramic composite (CCPCC) is provided. The composite includes: a cellulose-containing polymer substrate (CCPS), which includes cellulose (e.g., cellulosic fibers) in a polymer matrix that has an external surface and an internal volume; and a deposited ceramic. The CCPCC includes deposited ceramic on at least a portion of the external surface of the polymer matrix and deposited ceramic or complementary inorganic elements at least partially occupy the internal volume of the polymer matrix

[0012]

[0007] In some aspects, the CCPCC is further processed to include one or more functional layer(s) or molecule(s) which may include organic or silicon-containing polymers or monolayers to impart functional properties to the composite

[0013]

[0008] In some embodiments, the CCPCC is a fiber, a laminate, a film, a textile material, a paper, or a combination thereof In some embodiments, the polymeric matrix of the CCPS includes a polyester, a polyamide, a polyolefin, a substituted polyolefin, a polyurethane, a polyol, a vinyl polymer, an acrylate polymer, a polycarbonate, a polyether, cotton, wool, paper, or a combination thereof. For example, the polymeric matrix of the CCPS may include polyethylene terephthalate (PET), a nylon, polyethylene, polypropylene, polyvinyl chloride (PVC), polyvinyl alcohol (PVOH), polyvinyl acetate (PVAc), polyvinylpyrrolidone, polyethylene glycol (PEG), polymethylmethacrylate (PMMA), or mixtures thereof.

[0014]

[0009] In some embodiments, the COPS may further include binders, thickeners, fillers, coatings, or combinations thereof. In some embodiments, filler materials may be ceramic materials, i.e., ceramic materials that are incorporated into the substrate prior to deposition of the deposited ceramic (e.g , the same or different ceramic as the ceramic that is pre-incorporated into the substrate) to form a composite as described herein.

[0015]

[0010] In some embodiments, deposited ceramic in the CCPCC includes a transition metal, an alkali metal, and / or an alkaline earth metal. In some embodiments, the deposited ceramic includes one or more of an oxide, a hydroxide, a phosphate, a layered double hydroxide, a sulfate, a carbonate, an oxalate of a transition metal, an alkali metal, and an alkaline earth metal In some embodiments, the deposited ceramic includes one or more of manganese oxide, iron oxide, calcium carbonate, hydroxyapatite, calcium phosphate, calcium oxalate, magnesium carbonate, calcium sulfate, titanium oxysulfate, and magnesium sulfate. In some embodiments, the deposited ceramic in the CCPCC includes calcium, sodium, potassium, sulfur, chlorine, manganese, iron, nickel, magnesium, titanium, lithium, and / or zinc.

[0016]

[0011] In another aspect, a method of manufacturing a CCPCC as described herein is provided. The method includes: (a) contacting a CCPS with at least one solution that includes a metal salt or a metal-organic complex, and optionally, an oxidizing agent, an amine, ammonia, a penetrant, a surfactant, a release agent, or other reactive precursor(s) (such as, but not limited to, a catalyst in a solvent), or a combination thereof, wherein the solution is at least partially absorbed into the polymer matrix; (b) heating or otherwise ensuring a temperature of the polymer substrate produced in step (a) to a temperature sufficient to remove the solvent from the polymer substrate, sufficient to drive a ceramic-forming reaction with one or more of the metal salt(s), or sufficient to decompose or react the metal-organic complex, thereby depositing a ceramic to form a polymer-ceramic composite; and (c) optionally, coating the polymer-ceramic composite produced in step (b) with one or more functional layer(s) or molecule(s). A functional layer herein may include one or more functional molecule(s). CCPCCs that are produced in accordance with any of the methods described herein are also provided

[0017]

[0012] In some embodiments, the metal salt in step (a) may include one or more of a transition metal nitrate, a transition metal chloride, a transition metal sulfate, an alkali metal nitrate, an alkaline earth metal nitrate, an alkali metal chloride, an alkaline earth metal chloride, an alkali metal sulfate, and an alkaline earth metal sulfate. In some embodiments, the metal-organic complex in step (a) may include a metal-amine complex. In some embodiments, the amine in step (a) may include a free amine.

[0018]

[0013] In some embodiments, the heating in step (b) may be at a temperature of about 30°C to about 200°C.

[0014] In some embodiments, the optional functional layer in step (c) may include a monolayer chemistry, wherein the functional layer is substantially a monolayer, e.g , with a thickness less than about 5 nm or a functional layer thickness that is about 1 to about 3 times the length of the functional molecule in its bound form. The mean thickness of the functional layer is the distance from the external surface of the deposited ceramic layer to the external thickness of the functional layer. For example, the monolayer chemistry may include a silane, a siloxane, a phosphonic acid, a phosphonate, a sulfonate, a sulfonic acid, a carboxylic acid, carboxylate (unprotonated carboxylic acid), a urethane, a vinyl group, or an acrylate, or a molecule with a head group and a tail group In some embodiments, the monolayer chemistry includes a molecule with a head group and a tail group, wherein the head group includes a silane group, a phosphonate group, a phosphonic acid group, a carboxylic acid group, a vinyl group, an alcohol group, a hydroxide group, a thiolate group, a thiol group, and / or an ammonium group, and wherein the tail group includes a hydrocarbon group, a fluorocarbon group, a vinyl group, a phenyl group, an epoxide group, an acrylic group, an acrylate group, a hydroxyl group, a carboxylic acid group, a thiol group, and / or a quaternary ammonium group. For example, the head group may include an ammonium group, such as a quaternary ammonium group. In a molecule with a head group and a tail group herein, the head group is often charged or polar and the tail group is often a non-polar, long hydrocarbon chain. In certain embodiments of self-assembled monolayers, the head group attaches to a substrate surface, while the tail groups extend away from the surface.

[0019]

[0015] In some embodiments, the optional functional layer in step (c) may include a polymer chemistry, for example, with a mean thickness of less than about 500 nm. The mean thickness of the functional layer is the distance from the external surface of the deposited ceramic layer to the external thickness of the functional layer. For example, the functional layer chemistry may include one or more functional molecule(s), such as a silane, a siloxane, a phosphonic acid, a phosphonate, a sulfonate, a sulfonic acid, a carboxylic acid, a carboxylate, a urethane, a vinyl group, or an acrylate, or a molecule with a head group and a tail group

[0020]

[0016] In some embodiments, the polymer chemistry includes a crosslinker molecule to improve mechanical and chemical properties.

[0021]

[0017] In some embodiments, the method includes formation of a CCPCC on a first substrate in steps (a) and (b), wherein the deposited ceramic of the polymer-ceramic composite on the first substrate is in the form of an interconnected nanostructured layer on the first substrate, and the method further includes contacting a second substrate with the polymer-ceramic composite in such a manner that at least a portion of the interconnected nanostructured layer is transferred to the second substrate, thereby forming a second substrate-ceramic composite. Optionally, the second substrate-ceramic composite may be coated with one or more functional layer(s) or molecule(s). In some embodiments, the first substrate is contacted with the second substrate at a suitable pressure in accordance with a standard method, such as, for example, ASTM D3359. For example, the polymer-ceramic composite on the first substrate may be contacted with the second substrate by a rolling lamination process or with a heat press at a temperature of about 40°C to about 200°C and a pressure of about 0.1 MPa to about 10 MPa In some embodiments, greater than about 50%, greater than about 60%, greater than about 70%, greater than about 80%, or greater than about 90% of the interconnected nanostructured layer is transferred to the second substrate. In some embodiments, greater than about 50%, greater than about 60%, greater than about 70%, greater than about 80%, or greater than about 90% of the transferred nanostructured layer is contiguous In some embodiments, greater than about 50%, greater than about 60%, greater than about 70%, greater than about 80%, or greater than about 90% of the transferred nanostructured layer remains interconnected. In some embodiments, the second substrate contains cellulose (e.g., a second CCPS). In other embodiments, the second substrate does not contain cellulose

[0022]

[0018] In some embodiments, the CCPCC further includes one or more functional molecule. For example, the functional molecule may include a silane, a siloxane, a phosphonic acid, a phosphonate, a sulfonate, a sulfonic acid, a carboxylic acid, a carboxylate, a urethane, a vinyl group, an acrylate, or a molecule with a head group and a tail group In certain embodiments, the functional molecule includes a molecule with a head group and a tail group, wherein the head group includes a silane group, a phosphonate group, a phosphonic acid group, a carboxylic acid group, a vinyl group, an alcohol group, a hydroxide group, a thiolate group, a thiol group, and / or an ammonium group (for example, a quaternary ammonium group), and wherein the tail group includes a hydrocarbon group, a fluorocarbon group, a vinyl group, a phenyl group, an epoxide group, an acrylic group, an acrylate group, a hydroxyl group, a carboxylic acid group, a thiol group, and / or a quaternary ammonium group.

[0023]

[0019] In some embodiments, at least a portion of the functional molecule occupies at least a portion of the polymer matrix internal volume that is not occupied by deposited ceramic or a complementary inorganic element thereof. In certain embodiments, the functional molecule penetrates more than 10 nanometers into the polymer matrix internal volume.

[0024]

[0020] In some embodiments, the functional molecule concentration decreases when measured from the external surface of the polymer substrate into the polymer matrix internal volume. In one embodiment, the functional molecule concentration decreases at a decreasing rate from the external surface of the polymer substrate into the polymer matrix internal volume In one embodiment, the functional molecule penetrates a shorter distance into the polymer matrix internal volume in comparison to an identical polymer substrate that does not contain the deposited ceramic. In one embodiment, the functional molecule diffusion coefficient in the polymer matrix internal volume is greater than about 5% less than the diffusion coefficient of the functional molecule in an identical polymer substrate that does not contain the deposited ceramic.

[0025]

[0021] In some embodiments, the deposited ceramic of the CCPCC includes a transition metal, an alkali metal, and / or an alkaline earth metal, such as, but not limited to, calcium, manganese, phosphorous, iron, nickel, magnesium, titanium, lithium, and / or zinc. In some embodiments, the deposited ceramic contains an oxide, a hydroxide, a layered double hydroxide, a phosphate, an oxalate, a sulfate, or a carbonate of the transition metal, the alkali metal, or the alkaline earth metal, or a combination thereof.

[0026]

[0022] In some embodiments, at least a portion of the external surface of the CCPS does not include the deposited ceramic, e.g., at least a portion of the external surface of the polymer substrate is devoid of deposited ceramic.

[0027]

[0023] In some embodiments, at least a portion of the CCPCC has a sessile drop water contact angle greater than about 90 degrees. In some embodiments, at least a portion of the CCPCC has a rugosity ratio greater than about 1.3.

[0028]

[0024] In some embodiments, the CCPCC is a textile material, a thin film, a paper, a laminate, or a combination thereof. In some embodiments, the CCPS is a textile material. In some embodiments, the CCPCC is a textile material that includes a polyamide, a polyester, a polyolefin, a substituted polyolefin, a polyurethane, a polyol, a vinyl group, cotton, wool, or a cellulosic material, or a combination thereof

[0029]

[0025] In some embodiments, the CCPCC includes one or more functional molecule, and the tear strength, tensile strength, gas, vapor, or liquid permeability, adhesion, mold resistance and / or abrasion resistance of the composite is improved relative to the polymer substrate In some embodiments, tear strength, tensile strength, gas permeability, vapor permeability, and / or abrasion resistance of the composite is improved in comparison to an identical CCPCC that does not include the functional molecule. In some embodiments, the tear strength as measured by the test method described in ASTM D1424 is greater than about 1000 gF.

[0030]

[0026] In some embodiments, at least a portion of the deposited ceramic is interconnected. In one embodiment, more than 50% of the deposited ceramic on a particle basis is interconnected. In some embodiments, at least a portion of the deposited ceramic within the void volume of the CCPS and is interconnected. In one embodiment, more than 50% of the deposited ceramic within the void volume of the CCPS and is interconnected. In one embodiment, the porosity of the CCPS is reduced by the interconnected, deposited ceramic within the void volume of the CCPS In one embodiment, the pore size distribution of the CCPS is reduced in pore size by the interconnected, deposited ceramic within the void volume of the CCPS In one embodiment, the permeance of the CCPS is increased by the interconnected, deposited ceramic within the void volume of the CCPS.

[0031]

[0027] In some embodiments, the deposited ceramic includes crystalline domains, and in some embodiments, one or more of the crystalline domains include crystalline particles. In some embodiments, the crystalline domains are embedded in an amorphous matrix. For example, the amorphous matrix may contain at least two elements not including carbon, hydrogen, oxygen or nitrogen, that are present in the crystalline domains. In some embodiments, the amorphous matrix contains three common elements not including carbon, hydrogen, oxygen, or nitrogen, with the crystalline particles or crystalline domains In some embodiments, the crystalline domains range in size from about 2 nm in nominal dimension to about 200 nm in nominal dimension In some embodiments, the crystalline domains include a rare earth metal, a transition metal, an alkali metal, an alkaline earth metal, or a combination thereof, such as, but not limited to, Ca, Zn, Ni, Li, Mg, Ti, Mn, or a combination thereof. In some embodiments, the crystalline domains include a phosphate group (e.g , a polyphosphate, a pyrophosphate, a hydrogen phosphate, a dihydrogen phosphate, an orthophosphate, or a combination thereof), a carbonate group, a sulfate group, or a combination thereof In some embodiments, the amorphous matrix includes calcium and / or phosphorus In some embodiments, the crystalline domains include octacalcium phosphate, hydroxyapatite, monetite, brushite, calcium triphosphate, and / or calcium pyrophosphate, and / or hydrates thereof.

[0032]

[0028] In another aspect, an assembly of composites is provided that contains a plurality of CCPCCs as described herein. In some embodiments, at least a portion of the CCPCCs are in the form of fibers, which in certain embodiments may be assembled into yarns, woven textiles, knit textiles, paper, or non-woven textiles.

[0033]

[0029] In another aspect, an assembly of materials, including at least one layer of a cellulose- containing polymer-ceramic composite is provided herein.

[0034]

[0030] In another aspect, the CCPCC is a facer paper, e.g., a facer paper for a gypsum board. The facer paper exhibits reduced water intrusion as measured by the Cobb?2oo test method as described in ISO 535, of at least about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 85%, about 90%, or about 95% in comparison to an identical paper CCPS (e.g., a standard paper) that does not include the deposited ceramic.

[0035]

[0031] In another aspect, the CCPCC includes a wherein polymer that contains pores, wherein the deposited ceramic reduces the mean pore size as measured by capillary flow porometry according to standard test method ASTM D6767 or ASTM F316, by more than 5um, by more than 3um, by more than 2.5um, by more than 2um, by more than 1.5um, by more than 1um, by more than 0.75um, by more than 0.5um, or by more than 0.25um, in comparison to an identical CCPS that does not include the deposited ceramic.

[0036]

[0032] In another aspect, the CCPCC has an increased adhesion strength to a formed and cured gypsum slurry by more than 20%, more than 30%, more than 40%, more than 50%, more than 60%, more than 70%, more than 80%, more than 90%, more than 100%, more than 200%, more than 300%, more than 500%, or more than 1000%, in comparison to an identical CCPS that does not include the deposited ceramic.

[0037]

[0033] In another aspect, the CCPCC has a reduced Cobb rating as measured in g / m2equivalent to 90% to 100%, 80% to 90%, 70% to 80%, 60% to 70%, or 50% to 60%, or less than 90%, 80%, 70%, 60%, or 50%, in comparison to an identical CCPS that does not include the deposited ceramic.

[0038]

[0034] In another aspect, the CCPCC has a mold resistance score according to ASTM 3273 of 5, 6, 7, 8, 9, or 10.

[0039] “mono

[0040] BRIEF DESCRIPTION OF THE DRAWINGS

[0041]

[0035] Figure 1 shows examples of ceramic deposition and subsequent functionalization of cellulosic substrates as described in Example 3. Fig. 1(a): Fiberglass mat with a Zn ceramic integration and functionalization. Fig. 1(b): Cellulose paper with a Zn ceramic and functionalization. Fig. 1(c): Oriented strand board (OSB) with a Zn ceramic and functionalization.

[0042]

[0036] Figure 2 shows examples of functionalization of cellulose-containing polymer substrates as described herein. Fig. 2(a): The front side of a gypsum board facer paper functionalized by a spray method using 0.175 ml of a silane-containing functionalization solution. Fig. 2(b): The back side of a gypsum board facer paper functionalized by a spray method using 0.175 ml of the silane-containing solution on the front surface only. Fig. 2(c): The front side of a gypsum board facer paper functionalized by a spray method using 0 350 ml of the silane-containing solution Fig. 2(d): The back side of a gypsum board facer paper functionalized by a spray method using 0.350 ml of the silane-containing solution on the front surface only Fig. 2(e): The front side of a gypsum board facer paper functionalized by a spray method using 0.525 ml of the silane-containing solution. Fig. 2(f): The back side of a gypsum board facer paper functionalized by a spray method using 0.525 ml of the silane-containing solution on the front surface only

[0043]

[0037] Figure 3 shows a process schematic for the treatment of cellulose-containing polymer substrates to form cellulose-containing polymer-ceramic composites.

[0044]

[0038] Figure 4 shows a scanning electron micrograph (SEM) of a cellulose-containing polymerceramic composite. The individual cellulosic fiber of the substrate has a diameter of approximately 10 pm, and the added interconnected, platelike ceramic walled nanostructure has features on the order of 0.5 pm in terms of unit cell dimensions and wall thicknesses of less than 100 nm. The deposited ceramic is shown to occupy at least a portion of the internal volume of the polymer substrate. Measurement of the surface roughness indicates a Sa(areal average roughness) of up to about 20 pm and a Sz (peak-to-valley height) of about 100pm for areas of about 2.5 mm x 2.5 mm

[0045] DETAILED DESCRIPTION

[0046]

[0039] Methods are described for the deposition of ceramic onto cellulose-containing polymer substrates (CCPS), without the use of a resin or a paint, to prepare cellulose-containing polymerceramic composites (CCPCC). CCPCCs are described that include one or more ceramic deposited onto the external surface of a CCPS. The ceramic deposited onto the polymer substrate typically also penetrates the interior volume of the polymer substrate, i.e., is integrated within the polymer matrix internal volume, thereby increasing durability and adhesion in comparison to a ceramic coating that adheres solely, or largely, to the external surface of the polymer substrate In some embodiments, one or more complementary inorganic elements penetrate the deposited ceramic on the polymer substrate and the polymer matrix internal volume. In some embodiments, one or more complementary inorganic elements penetrate the ceramic. In some embodiments, one or more complementary inorganic elements penetrate the ceramic on the polymer substrate. In some embodiments, one or more complementary inorganic elements penetrate the ceramic on the external surface of the polymer substrate. In some embodiments, one or more complementary inorganic elements penetrate the ceramic which occupies at least a portion of the polymer matrix internal volume. In some embodiments, one or more complementary inorganic elements penetrate the ceramic on the external surface of the polymer substrate and the deposited ceramic which occupies at least a portion of the polymer matrix internal volume. In some embodiments, one or more complementary inorganic elements penetrate the polymer matrix internal volume. In some embodiments, one or more complementary inorganic elements penetrate the ceramic and the polymer matrix internal volume In some embodiments, the complementary inorganic elements include potassium, magnesium, chlorine, bromine, iodine, phosphorus, sulfur, nitrogen, oxygen, carbon, hydrogen, manganese, aluminum, titanium, sodium, calcium, or a combination thereof.

[0047]

[0040] In some embodiments, ceramic is added to the CCPS prior to casting, forming, drying, extrusion, drawing or spinning the polymer, or other processing methods as described herein. The ceramic is typically in a powder or particulate form and may be added to alter one or more functional properties of the cellulose-containing polymer, such as, but not limited to, color, optical properties, electrical conductivity, catalytic or photocatalytic properties, and / or to provide or enhance antimicrobial properties of the base polymer Typically, the methods described herein involve a reaction of chemicals in the presence of the polymer substrate in order to generate a ceramic material in situ and conformally around and within the polymer substrate, that is, on the external surface and occupying a portion of the polymer matrix internal volume, improving the adhesion without melting or pressing the ceramic into the polymer substrate.

[0048]

[0041] The methods described herein may be performed on CCPS which have had ceramics previously integrated into the polymer matrix prior to the ceramic deposition, such as by blending, drawing, casting, or other mechanical addition methods, or may be performed on CPS which do not include previously integrated ceramic material.

[0049] Definitions

[0050]

[0042] Numeric ranges provided herein are inclusive of the numbers defining the range.

[0051]

[0043] Unless otherwise stated, average values herein refer to number averages.

[0052]

[0044] “A,” “an,” and “the” include plural references unless the context clearly dictates otherwise.

[0053]

[0045] The term “about” as used herein when referring to a measurable value such as an amount, a temporal duration, and the like, is meant to encompass variations of ±10%, ±5%, ±1%, or ±0.1% from the specified value, as such variations are appropriate to perform the disclosed methods or in connection with a disclosed composition. In some embodiments, may be used to mean plus or minus ten percent (10%) of a value; for example, “about 100” refers to any number between 90 and 110.

[0054]

[0046] The phrase “and / or,” as used herein in the specification and in the claims, should be understood to mean “either or both” of the elements so conjoined, i.e., elements that are conjunctively present in some cases and disjunctively present in other cases. Additional elements may optionally be present other than the elements specifically identified by the “and / or” clause, whether related or unrelated to those elements specifically identified, unless clearly indicated to the contrary Thus, as a non-limiting example, a reference to “A and / or B,” when used in conjunction with open ended language such as “comprising” can refer, in one embodiment, to A without B (optionally including elements other than B); in another embodiment, to B without A (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc

[0055]

[0047] “O-dimensional materials” are materials where all the dimensions of the material are less than about 100 nm and typically boundary or edge properties are important. Example materials are quantum dots

[0056]

[0048] “Agglomerate” or "agglomerated” refers to a collection of previously discrete particles or materials which when contacted remain connected and undergo some degree of coalescence, relative incorporation, or growth

[0057]

[0049] “Aggregate” or "aggregated” refers to a collection of previously discrete particles or materials that when contacted remain connected but do not appear to undergo an additional coalescence, relative incorporation, or growth.

[0058]

[0050] “Air permeability” is the rate of air transmission through a substrate according to ASTM D737 or similar methods The rate is reported in volumetric flow per unit time, typically in cubic feet per minute, or cfm.

[0059]

[0051] “Atomic percentage” refers to the number of atoms of one or more specifically named elements as a percentage of the total number of atoms present within a specified area or volume

[0060]

[0052] “Cellulosic” or “cellulose” in reference to a cellulose-containing polymer substrate herein refers to a polymer of p-linked D-glucose units or materials derived from these polymers such as carboxymethyl cellulose (CMC) or cellulose gum that is derived from cellulose by alkali-catalyzed reaction of cellulose with chloroacetic acid. A “cellulose-containing polymer substrate” (CCPS) refers to material that includes greater than 40% cellulose and / or hemicellulose, and which may optionally include additional fillers, colorants, and coating materials.

[0061]

[0053] A “ceramic” or “ceramic material” refers to a solid material including an inorganic compound of a metal or a metalloid, and a non-metal, with ionic or covalent bonds. In this context, “ceramics” or “ceramic materials" may include amorphous inorganic glasses, glass-ceramics, polycrystalline materials, and combinations thereof. Ceramics may contain at least one type of functional crystalline phase and a residual glass phase with the volume fraction crystallized may vary from ppm to almost 100%. A “non-metal” may include oxygen (oxide ceramic), or carbon (carbide) or nitrogen (nitride) (non-oxide ceramics). A “metal” may include a non-hydrogen element of Group 1 of the periodic table, an element of Groups 2-12 of the periodic table, or an element from the p-block (Groups 12- 17 of the periodic table), e.g., Al, Ga, In, Tl, Sn, Pb, Bi, or combinations thereof. A “metalloid” may include B, Si, Ge, As, Sb, Se, T e, or Po, or combinations thereof.

[0062]

[0054] “Complementary inorganic element” refers to an element present in a counterion, where a ceramic precursor includes one or more ions incorporated into the ceramic and one or more counterions that are not incorporated into the ceramic. For example, in some embodiments, the ceramic precursors include calcium chloride and / or calcium nitrate, calcium ions are incorporated into the ceramic, the counterions chloride and nitrate are not incorporated into the ceramic, and the complementary inorganic elements include chlorine, nitrogen, and / or oxygen. In a further example, in some embodiments, the ceramic precursors include ammonium dihydrogen phosphate, dihydrogen phosphate ions are incorporated into the ceramic, the counterion ammonium is not incorporated into the ceramic, and the complementary inorganic elements include nitrogen and / or hydrogen.

[0063]

[0055] “Contact angle” refers to the angle measured through a liquid from the surface and to the liquid-vapor interface at the contacting surface. The sessile drop method is the standard method of contact angle measurement in which the droplet used to characterize the surface is stationary. A standard method for the measurement of contact angle is ISO 19403.

[0064]

[0056] A “conversion coating” refers to a surface layer in which reactants are chemically reacted with the surface to be treated, which converts the substrate, or a coating thereon, such as a ceramic (e.g., metal oxide and / or hydroxide) coating into a different compound. This process is typically not additive or a deposition, but may result in a small mass change.

[0065]

[0057] The “diffusion coefficient” is a physical constant dependent on molecule size, properties of the diffusing substance, temperature, and pressure and is typically determined experimentally.

[0066]

[0058] A “functional material layer” refers to a layer of material which may serve as the uppermost surface layer interacting with the surrounding environment or may serve as an interfacial layer for subsequent materials (intermediate layer between two other layers of material). A functional material layer imparts or enhances one or more desirable functional properties to the underlying substrate and / or to the material on which it is deposited.

[0067]

[0059] A “gradient” refers herein to a quantitative increase or decrease in one or more physical or chemical property of a material observed by passing spatially from one point to another point along a substrate surface on which the material is situated or immobilized, and varying in an x, y, or z direction in Cartesian coordinates on or through the material. Nonlimiting examples of gradient properties include thickness, density, hardness, ductility, pore size, pore size distribution, pore filling fraction, or chemical or physical composition, including but not limited to, oxidation state, metal concentration, or crosslinking density, for example, resulting in variation in isoelectric point, electrical conductivity, thermal conductivity, capacitance, etc.

[0068]

[0060] “Hydraulic diameter” refers to a value that is 4 times the cross-sectional area divided by the perimeter of the cross-sectional area. In the case of a nominally cylindrical fiber of circular cross section, the hydraulic diameter is 2 times the radius of the circular cross-section.

[0069]

[0061] “Hydrophilic” refers to a surface that has a high affinity for water. Contact angles can be very low ( / .e., less than 30 degrees as measured from the surface through the liquid water in the presence of air) and / or immeasurable

[0070]

[0062] “Interconnected” refers to a network or matrix of ceramic material, wherein ceramic material in the network is in physical contact with (connected to) other ceramic material in the network, i.e., a majority of ceramic material is adjoined to other ceramic material resulting in a scaffolded structure either free-standing or supported on a substrate. The interconnected ceramic network described herein is a continuous ceramic phase over an area or volume defined by lengths greater than 100 mean particle diameters, and may contain pores (open spaces) with an accessible pore volume, which may be filled, or partially filled, with another material, such as, but not limited to, a polymer

[0071]

[0063] “Layered double hydroxide” refers a class of ionic solids characterized by a layered structure with the generic sequence [ACB Z AcB]n, where c represents layers of metal cations, A and B are layers of hydroxide anions, and Z are layers of other anions and / or neutral molecules (such as water). Layered double hydroxides are also described in PCT Application No. PCT / US2017 / 052120, which is incorporated by reference herein in its entirety.

[0072]

[0064] “Laminate” refers to a structure or composite that includes one or more thin layers affixed to other thin layers, or to structural layers, or to a substrate.

[0073]

[0065] “Mean” refers to the arithmetic mean or average

[0074]

[0066] A “monolayer” refers to a layer of a functional molecule with a thickness that is about 1 to about 3 times the length of the bound functional molecule in its bound orientation. For example, if a molecule such as oleic acid with a molecule length of about 2 nm binds normal to the surface, the thickness of the monolayer will be about 2 nm to about 6 nm. If the binding angle is 45 degrees, the thickness will be about 1.4 nm to about 4.2 nm.

[0075]

[0067] A "nanostructured” coating refers to a coating composition that has a feature in at least one dimension that is less than 100 nanometers.

[0076]

[0068] “Nominal” is used to refer to approximate sizes or dimensions of a material; the actual dimensions may be larger or smaller than the nominal dimension. When nominal dimensions are used to describe nanomaterials, the nominal dimension is the largest single dimension of the nanomaterial, such as the diameter of a sphere, or the length of a plate. When nominal is used to describe materials such as paper or fabrics, the term nominal is used to refer to the approximate value or measurement of the most prevalent feature, but not necessarily the exact measurement. An example is the nominal surface area of a paper or fabric. The nominal surface area is defined by the length multiplied by the width of the paper or fabric, and does not account for any increase in surface area as would be provided by the fibers that make up the fabric.

[0077]

[0069] “Paper” refers to material that contains cellulose or is manufactured from cellulose- containing feedstocks, e.g., derived from wood, grasses, or other vegetable sources, which may be used for printing, drawing, transportation packaging, or mechanical support for slurry formed materials. Paper contains cellulose polymers in the form of fibers or fibrils and may also contain various fillers that are added for optical or mechanical properties, and / or coatings for optical properties, barrier properties, color, or lubricity.

[0078]

[0070] “Rugosity ratio”, is the ratio of the rugosity of a polymer-ceramic composite to the rugosity of the polymer substrate. Rugosity is a measure of small-scale variations of amplitude in the height of a surface, and is a ratio of Ar, the real (true, actual) surface area, and Ag, the geometric surface area.

[0079]

[0071] “Surface roughness” or “roughness factor” is the measurement of the relative smoothness of a surface’s profile, calculated via the deviations (macroscopic or microscopic) in a surface’s true or ideal form. The larger the deviation from the ideal form, the larger the surface roughness. A surface roughness factor commonly used is Rawhich is defined as the arithmetic average of profile height deviations from the mean line. This is the term used throughout this application when not otherwise specified The surface roughness may be characterized in a variety of ways including, but not limited to Ra, the arithmetic mean height or arithmetic mean roughness which is an average of the absolute value of height along a sampling line (R) or surface area (S) as measured by a Keyence VR-5000 Series Analyzer, or Rz, the maximum height of profile or maximum roughness which is the absolute vertical difference between the maximum profile peak height and the maximum profile valley depth along a sampling line (R) or surface area (S) as measured by a Keyence VR-5000 Series Analyzer.

[0080]

[0072] “Textile” is a term that includes various fiber-based materials including fibers, yarns, filaments, and / or threads that are combined or manufactured to create a flexible polymeric film, garment, or fabric. Textiles or textile materials can be described as woven or non-woven, whereas fabrics are a subset of textiles which include only woven fibers, yarns, filaments and / or threads

[0081]

[0073] “Thickness” of a material refers to the nominal distance between top and bottom edges or surfaces of a material, such as the surface defined by the edge of the interfacial layer in contact with the substrate or first material in the case of a second material, and the nominal top surface of the layer of surface modification material.

[0082]

[0074] “T unable” refers to the ability of a function, characteristic, or quality of a material to be changed or modified.

[0083] Cellulose-containing polymer substrate

[0084]

[0075] In some embodiments, a cellulose-containing polymer substrate (OCRS) contains cellulose and / or carboxymethyl cellulose, and may be in the form of but not limited to paper, or a thin sheet material produced by processing cellulose fibers, e.g., cellulose fibers derived from wood, rags, grasses, or other vegetable sources, such as but not limited to cotton, banana, or hemp. In some embodiments, cellulose fibers may be refined from natural materials by chemical processing, thermal processing, mechanical processing, or combinations therein. In some embodiments, cellulose fibers may be recycled from paper, newsprint or cardboard for reuse In some embodiments, cellulose fibers may be blended with other natural or synthetic materials such as gypsum, starch, or polymer fibers to modify the properties of the substrate (e.g., paper). In some embodiments, the CCPS may also be mixed and otherwise bonded to other materials including resin, lignin, and / or starch. In some embodiments, the CCPS may include other non-cellulose containing materials, including but not limited to woven glass, minerals, textiles, or polymer fibers, such as but not limited to polyvinyl alcohol or polyvinyl acetate. In some embodiments, the CCPS may include other natural materials including but not limited to silk, carrageenan, and / or starches. In some embodiments, the CCPS is coated, treated or finished with one or more processes and / or materials to promote color, adhesion, absorption, fire retardancy, reduced weight, increased strength, sound dampening, or other properties In some embodiments, CCPS may contain cellulose that has been reacted to form other products, such as carboxymethyl cellulose (CMC) or cellulose gum where carboxymethyl groups (-CH2-COOH) are bound to some of the hydroxyl groups of the glucopyranose monomers that make up the cellulose backbone. For example, CMC may be synthesized by the alkali-catalyzed reaction of cellulose with chloroacetic acid In some embodiments, cellulose in a polymer substrate containing cellulose, such as cotton or viscose rayon, is converted into CMC.

[0085]

[0076] In some embodiments, the CCPS may include one or more binder, thickener, filler, coating, or combinations thereof. In some embodiments, binders or co-binders include styrene maleic anhydride copolymer, styrene-acrylate copolymer, styrene butadiene latex, styrene acrylic, dextrin, oxidized starch, and / or carboxymethyl cellulose (CMC). In some embodiments, thickeners include CMC, cationic and anionic hydroxyethyl cellulose (EHEC), modified starch, and / or dextrin. In some embodiments, fillers may include mineral fillers such as China clay or kaolin, calcium carbonate, titanium dioxide, talc or other materials. In some embodiments, fillers may include natural or synthetic pigments, dyes, or optical brightening agents, or delusterants.

[0086]

[0077] In some embodiments, the CCPS includes one or more ceramic incorporated into the substrate, prior to deposition of a deposited ceramic material as described herein. For example, the ceramic that is in the substrate prior to deposition of the deposited ceramic may include, but is not limited to, kaolin, calcium carbonate (e.g., limestone or chalk), calcium sulfate, silica, titanium dioxide, aluminum trihydrate, and / or magnesium silicate (e.g., talc).

[0087]

[0078] In some embodiments, the CCPS contains greater than about 40%, greater than about 50%, greater than about 60%, greater than about 70%, greater than about 80%, or greater than about 90% cellulosic content by weight (e.g., greater than about 40%, greater than about 50%, greater than about 60%, greater than about 70%, greater than about 80%, or greater than about 90% cellulose and / or hemicellulose by weight)

[0088]

[0079] In some embodiments, a CCPS as described herein contains greater than about 40% cellulose and / or hemicellulose by weight. The CCPS may include a coating which may be up to about 30% by mass Mineral content of the substrate may be up to about 30% by mass

[0089]

[0080] In some embodiments, the density or weight per unit area or grammage of the CCPS may be about 10 g / m2to about 500 g / m2In some embodiments the density is about 15 g / m2to about 60 g / m2, e.g., for tissue, about 25 g / m2to about 60 g / m2, e.g., for newsprint, about 30 g / m2to about 170 g / m2, e.g., for paper, about 100 g / m2to about 500 g / m2, e.g., for paperboard, or about 50 g / m to about 100 g / m2, e.g., for copy paper. Ceramic

[0090]

[0081] In some embodiments, the ceramic deposited onto the cellulose-containing polymer substrate (CCPS) as described herein includes a transition metal oxide, a transition metal carbonate, a transition metal oxalate, a transition metal phosphate, a transition metal sulfate, or combinations thereof. In some embodiments, the ceramic includes an alkali metal oxide, an alkaline earth oxide, an alkali carbonate, an alkaline earth carbonate, an alkali oxalate, an alkaline earth oxalate, an alkali phosphate, an alkaline earth phosphate, an alkali sulfate, an alkaline earth sulfate, or combinations thereof In some embodiments, the ceramic includes a metal oxide, a metal hydroxide, a layered double hydroxide, a metal carbonate, a metal oxalate, a metal phosphate, a metal sulfate, or mixtures thereof, wherein the metal is a transition metal, an alkali metal, or an alkaline earth metal. In some embodiments, the ceramic includes a metal oxide, a metal hydroxide, a layered double hydroxide, a metal carbonate, a metal oxalate, a metal phosphate, a metal sulfate, or mixtures thereof, wherein the metal is aluminum, silicon, or tin. In some embodiments, the ceramic includes a transition metal, an alkali metal, an alkaline earth metal, aluminum, silicon, or tin. In some embodiments, the ceramic includes magnesium, calcium, titanium, manganese, iron, zinc, zirconium, tungsten, nickel, cobalt, or mixtures thereof. In some embodiments, the ceramic includes oxygen, phosphorus, sulfur, carbon, or mixtures thereof. In some embodiments, the ceramic includes manganese oxide, zinc oxide, silicon oxide, aluminum oxide, titanium dioxide, iron oxide, cobalt oxide, nickel oxide, zirconium oxide, or mixtures thereof. In some embodiments, the ceramic includes hydroxyapatite, calcium carbonate, magnesium carbonate, calcium sulfate, cerium oxide, octacalcium phosphate, calcium phosphate, or mixtures or hydrates thereof. In some embodiments, wherein the ceramic includes phosphate, the phosphate is present in partially protonated, partially hydrated, hydrated, partially dehydrated forms, and / or dehydrated forms In some embodiments, wherein the ceramic includes calcium phosphate, the calcium phosphate includes hydroxyapatite [Cas(PO4)3OH], brushite [Ca(PO3OH)*2H2O], monetite [Ca(POsOH)], or mixtures thereof. In some embodiments, wherein the ceramic includes sulfate, the sulfate is present in partially protonated, partially hydrated, and / or partially dehydrated forms.

[0091]

[0082] In some embodiments, additional inorganic elements, inorganic compounds, and / or ionic compounds may also penetrate the ceramic deposited onto the polymer substrate as well as the polymer matrix internal volume. In some embodiments, the inorganic elements, compounds and / or ionic compounds are contained within an amorphous, inorganic glass phase. In some embodiments, the inorganic elements, compounds and / or ionic compounds are contained within a crystalline, or multi-crystalline domain or phase. In some embodiments, the inorganic elements, compounds and / or ionic compounds are contained within a crystalline domain in an ordered manner. In some embodiments, the inorganic elements, compounds and / or ionic compounds are distributed or contained along crystalline domain boundaries, grain boundaries, defects, or pores. In some embodiments, the inorganic elements, compounds and / or ionic compounds are distributed along the polymer matrix exterior surface. In some embodiments, the inorganic elements, compounds and / or ionic compounds are distributed into the polymer substrate interior volume. In some embodiments, the inorganic elements, compounds and / or ionic compounds are distributed among the ceramic deposited onto the polymer substrate, along the polymer substrate exterior surface, within the polymer substrate interior volume, or combinations thereof.

[0092]

[0083] In some embodiments, one or more complementary inorganic elements also penetrate the ceramic deposited onto the polymer substrate as well as the polymer matrix internal volume. In some embodiments, the complementary inorganic elements are contained within an amorphous, inorganic glass phase In some embodiments, the complementary inorganic elements are contained within a crystalline, or multi-crystalline domain or phase. In some embodiments, the complementary inorganic elements are contained within a crystalline domain in an ordered manner. In some embodiments, the complementary inorganic elements are distributed or contained along crystalline domain boundaries, grain boundaries, defects, or pores. In some embodiments, the complementary inorganic elements are distributed along the polymer matrix exterior surface In some embodiments, the complementary inorganic elements are distributed into the polymer substrate interior volume. In some embodiments, the complementary inorganic elements are distributed among the ceramic deposited onto the polymer substrate, along the polymer substrate exterior surface, within the polymer substrate interior volume, or combinations thereof.

[0093]

[0084] In some embodiments, the complementary inorganic element includes potassium, magnesium, chlorine, bromine, iodine, phosphorus, sulfur, nitrogen, oxygen, carbon, hydrogen, manganese, aluminum, titanium, sodium, or calcium, or a combination thereof. In some embodiments, the complementary inorganic element is present as a counterion, present in a counterion, or present as a component of a counterion. In some embodiments, the counterion is a cation or an anion. In some embodiments, the counterion is a cation. In some embodiments, the complementary inorganic element is present in a potassium cation, a magnesium cation, a manganese cation, an aluminum cation, a titanium cation, a sodium cation, a calcium cation, an ammonium cation, or a combination thereof In some embodiments, the complementary inorganic element is present in a cation comprising potassium, magnesium, manganese, aluminum, titanium, sodium, calcium, nitrogen, or a combination thereof. In some embodiments, the complementary inorganic element is present as K+1, Mg+2Mn+2, Mn+3, Mn+5, Mn+7, Al+3, Ti+4, Na+1, Ca+2, NH4+1, or a combination thereof. In some embodiments, the cation is hydrated. In some embodiments, the hydrated cation is partially dehydrated. In some embodiments, the hydrated cation is partially deprotonated. In some embodiments, the hydrated cation is partially deprotonated, and the degree of deprotonation is dependent on the effective pH of the immediate environment of the hydrated cation In some embodiments, the counterion is an anion. In some embodiments, the complementary inorganic element is nitrogen and present in nitrate (NO31), nitrite (NO21), nitride (N3), amide (NH21), or a combination thereof. In some embodiments, the complementary inorganic element is oxygen and present in hydroxide (OH’1), oxide (O'2), peroxide (O2’2), hydroperoxide (HO2‘1), or a combination thereof. In some embodiments, the complementary inorganic element is chlorine and present in chloride (Cl'1), perchlorate (CIO41), chlorate (CIOs'1), chlorite (CIO2'1), hypochlorite (CIO-1), or a combination thereof. In some embodiments, the complementary inorganic element is bromine and present in bromide (Bn1), perbromate (BrO1), bromate (BrOs'1), bromite (BrO2'1), hypobromite (BrO'1), or a combination thereof In some embodiments, the complementary inorganic element is iodine and present in iodide (I1), periodate (IO4'1), iodate (IO31), iodite ( IO21), hypoiodite (IO-1), or a combination thereof In some embodiments, the complementary inorganic element is phosphorus and present in phosphate (PO43), hydrogen phosphate (HPCM-2), dihydrogen phosphate (H2PO4'1), or a combination thereof. In some embodiments, the complementary inorganic element is sulfur and present in sulfate (SO42), hydrogen sulfate (HSC '1), sulfite (SOs'2), hydrogen sulfite (HSOs'1), sulfide (S'2), thiosulfate (S20s‘2), thiocyanate (SON'1) or a combination thereof. In some embodiments, the complementary inorganic element is carbon or nitrogen and present in cyanate (OCN‘1), thiocyanate (SON1), or a combination thereof. In some embodiments the anion is permanganate (MnCM1) or hydride (H1). In some embodiments the anion is permanganate (MnC>41). In some embodiments, the complementary inorganic element is carbon and present in carbonate (COs'2), hydrogen carbonate (HCOs'1), or a combination thereof. In some embodiments, the complementary inorganic element is carbon and present in a carboxylate anion. In some embodiments, the carboxylate anion is formate, acetate, propionate, butyrate, iso-butyrate, or a combination thereof. In some embodiments, the complementary inorganic element is carbon and present in a dicarboxylate anion. In some embodiments, the dicarboxylate anion is succinate, malonate, oxalate, or a combination thereof. In some embodiments the dicarboxylate anion is partially protonated In some embodiments the dicarboxylate anion is partially protonated, and the degree of deprotonation is dependent on the effective pH of the immediate environment of the dicarboxylate anion. In some embodiments, the complementary inorganic element is present in an anion comprising chlorine, bromine, iodine, phosphorus, sulfur, nitrogen, oxygen, carbon, hydrogen, manganese, or a combination thereof.

[0094]

[0085] In some embodiments, the ceramic precursors include calcium nitrate and potassium phosphate, the counterions include nitrate and potassium, and the complementary inorganic elements include nitrogen, oxygen, and / or potassium. In some embodiments, the ceramic precursors calcium nitrate and potassium phosphate, the counterions include nitrate and potassium, the complementary inorganic elements include nitrogen, oxygen, and / or potassium, and nitrogen, oxygen, potassium, or a combination thereof penetrate the ceramic and / or the polymer matrix internal volume.

[0095]

[0086] In some embodiments, the ceramic precursors include calcium nitrate and sodium oxalate dihydrate, the counterions include nitrate and sodium, and the complementary inorganic elements include nitrogen, oxygen, and / or sodium. In some embodiments, the ceramic precursors include calcium nitrate and sodium oxalate dihydrate, the counterions include nitrate and sodium, the complementary inorganic elements include nitrogen, oxygen, and / or sodium, and nitrogen, oxygen, sodium, or a combination thereof penetrate the ceramic and / or the polymer matrix internal volume.

[0087] In some embodiments, the ceramic precursors include calcium nitrate and / or calcium chloride and ammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, sodium hydrogen phosphate, and / or sodium dihydrogen phosphate, the counterions include nitrate and / or chloride and ammonium, potassium, and / or sodium, and the complementary inorganic elements include nitrogen, chlorine, oxygen, potassium and / or sodium. In some embodiments, the ceramic precursors include calcium nitrate and / or calcium chloride and ammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, sodium hydrogen phosphate, and / or sodium dihydrogen phosphate, the counterions include nitrate and / or chloride and ammonium, potassium, and / or sodium, the complementary inorganic elements include nitrogen, chlorine, oxygen, potassium and / or sodium, and nitrogen, chlorine, oxygen, potassium, sodium, or a combination thereof penetrate the ceramic and / or the polymer matrix internal volume.

[0096]

[0088] In some embodiments, the ceramic precursors include manganese nitrate and sodium hydroxide, the counterions include nitrate and sodium, and the complementary inorganic elements include nitrogen, oxygen, and / or sodium. In some embodiments, the ceramic precursors include manganese nitrate and sodium hydroxide, the counterions include nitrate and sodium, the complementary inorganic elements include nitrogen, oxygen, and / or sodium, and nitrogen, oxygen, sodium, or a combination thereof penetrate the ceramic and / or the polymer matrix internal volume.

[0097]

[0089] In some embodiments, the ceramic precursors include manganese sulfate and potassium persulfate and / or ammonium hydroxide, the counterions include sulfate and ammonium and / or potassium, and the complementary inorganic elements include sulfur, oxygen, nitrogen, and / or potassium In some embodiments, the ceramic precursors include manganese sulfate and potassium persulfate and / or ammonium hydroxide, the counterions include sulfate and ammonium and / or potassium, the complementary inorganic elements include sulfur, oxygen, nitrogen, and / or potassium, and nitrogen, oxygen, sodium, or a combination thereof penetrate the ceramic and / or the polymer matrix internal volume.

[0098]

[0090] The ceramic that is deposited onto the COPS may be in the form of discrete particulates or smaller aggregates. In some embodiments, the size of the discrete particulates or smaller aggregates, i.e., the average particle size of the ceramic (e.g , mean diameter), is from about 0.05 pm to about 5 pm, from about 0.5 pm to about 10 pm, or from about 0.1 pm to about 0 5 pm. In some embodiments, the average particle size is less than about 10 pm, less than about 5pm, less than about 1 pm, less than about 0 5 pm, less than about 0 1 pm, or less than about 0 05 pm In some embodiments, the ceramic deposited onto the CCPS may be in the form of networked particulates, agglomerations or aggregates.

[0099]

[0091] In some embodiments, the ceramic may be nanostructured and have geometrically similar features or structures such as plates, rods, spheroids or agglomerates which have at least one dimension that is less than about 100 nm. Nonlimiting examples of nanostructured ceramic materials are described in PCT Publication Nos. WO2018 / 053452 and WO2018 / 053453, which are incorporated herein by reference in their entireties.

[0100]

[0092] In some embodiments, the ceramic deposited onto the CCPS may be in the form of an interconnected arrangement of plates or walls having one dimension that is less than about 100nm In some embodiments, the ceramic deposited onto the CCPS may be in the form of nanoclusters, nanoflowers, or other aggregates of crystalline morphologies. In some embodiments, the ceramic deposited onto the CCPS may be in the form of an arrangement of pyramid-like, or rhombohedral, domains having one edge length dimension that is about 50nm to about 1000nm

[0101]

[0093] In some embodiments, the ceramic that is deposited onto the CCPS has a thickness, e.g., a mean thickness, of from about 0 05 pm to about 5 pm, or from about 0 05 pm to about 10 pm, or from about 0 1 pm to about 0 5 pm, or less than about 10 pm, or less than about 5 pm, or less than about 1 pm, or less than about 0.5 pm, or less than about 0.25 pm, or less than about 0.2 pm, or less than about 0.15 pm, or less than about 0.1 pm, or less than about 0.075 pm, or less than about 0.05 pm outside of the polymer layer, i.e., as measured from the external surface of the polymer substrate. The mean thickness of the ceramic is the distance from the external surface of the polymer substrate to the external surface of the deposited ceramic.

[0102]

[0094] In some embodiments, the ceramic that is deposited onto the CCPS has a secondary structure in the form of plates or platelike morphology on the outer surface of the deposited ceramic.

[0103]

[0095] In some embodiments, the deposited ceramic is crystalline. In other embodiments the deposited ceramic is amorphous. In some embodiments, the deposited ceramic contains an aggregate of crystalline domains.

[0104]

[0096] In some embodiments, the ceramic that is deposited onto the CCPS is further processed in order to induce a conversion of the ceramic composition of the deposited ceramic. In some embodiments, this conversion is carried out in an environment where the gas phase is at elevated temperatures, in controlled atmospheric compositions, reduced or increased pressure, or more than one of these conditions. In some embodiments, this conversion is carried out in an environment where the liquid phase is at elevated temperatures, in variable compositions, at increased flow or shear rates near the surface, reduced or increased pressure, or more than one of these conditions.

[0105] Cellulose-containing polymer-ceramic composite

[0106]

[0097] Cellulose-containing polymer-ceramic composites (CCPCCs) are described herein. The CCPCC includes: a cellulose-containing polymer substrate (CCPS), which includes: cellulose in the form of a polymer matrix of p-linked D-glucose units, or materials derived from these polymers such as carboxymethyl cellulose (CMC) or cellulose gum, wherein the polymer matrix has an external surface and an internal volume having some porosity (e.g., a porous polymer matrix that includes pores); and a deposited ceramic.

[0107]

[0098] In some embodiments, the CCPCC includes a deposited ceramic on the external surface of the CCPS, and the ceramic and / or complementary inorganic elements at least partially occupies the internal volume of the polymer matrix, i.e., occupies at least a portion of the polymer matrix interior volume. In some embodiments, the COPS includes one or more ceramic incorporated into the substrate (first ceramic), in addition to the deposited ceramic (second ceramic) as described herein and prior to deposition of the second ceramic.

[0108]

[0099] In some embodiments, the CCPCC is in the form of a fiber or a film. In some embodiments, the CCPCC is in the form of a fiber with a mean diameter less than about 5 millimeters or less than about 1 millimeter. In some embodiments, the CCPCC is in the form of a film with a mean thickness less than about 5 millimeters or less than about 3 millimeters

[0109]

[0100] In some embodiments, greater than about 10%, or greater than about 20%, or greater than about 30%, or greater than about 40%, or greater than about 50%, or greater than about 60%, or greater than about 70%, or greater than about 80%, or greater than about 90% of total deposited ceramic in the CCPCC protrudes through the CCPS exterior (external) surface.

[0110]

[0101] In some embodiments, the deposited ceramic in the CCPCC is nanostructured and includes structures or features such as plates, rods, flowers, walls, pyramids, rhomboids, spheroids or agglomerates, which are geometrically similar and which have at least one dimension that is less than 100 nanometers. In some embodiments, the deposited ceramic in the CCPCC is formed in situ, within the CCPS internal volume, by the precipitation of one or more soluble precursor, or the reaction of two or more chemical reactants.

[0111]

[0102] In some embodiments, the CCPCC is coated with one or more functional molecules to impart or enhance one or more desired properties. In some embodiments, the CCPCC is functionalized with a thin film which has a thickness of less than about 1 micrometer (pm), or less than about 500 nanometers (nm), or less than about 200 nm, or less than about 150 nm, or less than about 100 nm, or less than about 50 nm, or less than about 20 nm, or less than about 10 nm. In some embodiments, the CCPCC is coated with a monolayer chemistry wherein a film conformally coats the CCPCC with a characteristic thickness of less than about 5 nm. In some embodiments, the CCPCC is coated with a functional layer. In certain embodiments, the functional layer includes a monolayer chemistry, i.e., the functional layer is substantially a monolayer of functional molecules. The monolayer may have a thickness less than about 5 nm. In some embodiments, the polymerceramic composite is coated with a silane, a siloxane, a urethane, an acrylate, or with a molecule with a head group and a tail group (for example, wherein the head group includes a silane group, a phosphonate group, a phosphonic acid group, a carboxylic acid group, a vinyl group, an alcohol group, a hydroxide group, a thiolate group, a thiol group, and / or an ammonium group (e g , a quaternary ammonium group), and wherein the tail group includes a hydrocarbon group, a fluorocarbon group, a vinyl group, a phenyl group, an epoxide group, an acrylic group, an acrylate group, a hydroxyl group, a carboxylic acid group, a thiol group, and / or a quaternary ammonium group.

[0112]

[0103] In some embodiments, the CCPCC contains a polymer core and a shell that includes a deposited ceramic. In some embodiments, the deposited ceramic in the CCPCC is formed in situ, within the CCPS internal volume, by the precipitation of one or more soluble precursor, or the reaction of two or more chemical reactants. In some embodiments, the ceramic shell of the CCPCC has a thickness less than about 20% of the hydraulic diameter of the polymer core. In some embodiments, the ceramic-containing shell of the CCPCC has a thickness less than about 1 pm. In some embodiments, the polymer core has a diameter or thickness greater than about 1 pm In some embodiments, the polymer core includes a thermoplastic, such as a polyester, a polyamide, a polyurethane, an acrylic (polyacrylate), a polyolefin, a polyol, acrylonitrile butadiene styrene (ABS), a polyvinyl alcohol, or a combination thereof. In some embodiments, the polymer core includes cotton, wool, and / or other cellulosic material. In some embodiments, the CCPCC material has a cylindrical polymer core and a ceramic shell. In some embodiments, the ceramic-containing shell includes a transition metal, an alkali metal, and / or an alkaline earth metal. In some embodiments, the transition metal or alkaline earth metal is iron, magnesium, zinc, manganese, calcium, or nickel. In some embodiments, the transition metal, alkali metal, or alkaline earth metal is in the form of an oxide, a hydroxide, a phosphate, a carbonate, a sulfate, or a combination thereof. In some embodiments, the phosphate, carbonate, sulfate, or combination thereof is present in varying degree of protonation or deprotonation. In some embodiments, a carbonate is present as carbonate or bicarbonate, or a combination thereof. In some embodiments the phosphate is present as hydrogen phosphate (HPO42'), dihydrogen phosphate (H2PO41-), phosphate (PC3-), or a combination thereof. In some embodiments, a sulfate is present as sulfate, bisulfate, or a combination thereof. In some embodiments, the ceramic weight fraction in the shell is less than about 0.9. In some embodiments, the ceramic in the shell has a morphology with at least one dimension less than about 100 nanometers. In some embodiments, the ceramic in the shell has a morphology of 0-dimensional, 1- dimensional or 2-dimensional materials. In some embodiments, the ceramic containing shell includes a siloxane, an acrylate, a phosphonate, a sulfonate, a urethane, or a combination thereof. In some embodiments, the shell includes a silicone polymer or an alkyl terminated silane or siloxane. In some embodiments, the shell includes an alkyl terminated functional group. In some embodiments, the alkyl terminated functional group includes a saturated chain length longer than three carbons. In some embodiments, the shell includes an isocyanate or an isocyanate terminated polymer. In some embodiments, the shell is adhered to the core. In some embodiments, the adhesion between the shell and the core is rated from 0 to 5 according to a standard method such as ASTM D3359 and the adhesion rating is increased in the core-shell configuration as compared to an initial textile. In some embodiments, textile test methods such as the single fiber pull out test or the fiber matrix adhesion tester (FIMATEST) are used to measure changes in fiber adhesion to the textile as an indicator of core-shell adhesion In some embodiments, textile tear strength methods such as ASTM D1424 or ASTM D5034 are used to measure changes in tear strength as an indicator of core-shell adhesion.

[0113]

[0104] In some embodiments, a CCPCC as described herein also contains a functional molecule as described herein, and at least a portion of the composite material has a sessile drop water contact angle greater than about 90 degrees, greater than about 100 degrees, greater than about 110 degrees, greater than about 115 degrees, than about 120 degrees, greater than about 125 degrees, greater than about 128 degrees, greater than about 130 degrees, greater than about 131 degrees, than about 132 degrees, greater than about 134 degrees, greater than about 136 degrees, greater than about 138 degrees, greater than about 140 degrees, greater than about 142 degrees, greater than about 144 degrees, greater than about 146 degrees, greater than about 148 degrees, greater than about 150 degrees, greater than about 155 degrees greater than about 160 degrees, greater than about 165 degrees, greater than about 170 degrees, greater than about 175 degrees, greater than about 178 degrees, or about 179 degrees, for example, as measured in accordance with ISO Standard 19403.

[0114]

[0105] In some embodiments, a CCPCC as described herein also contains a functional molecule or layer as described herein, and at least a portion of the functionalized composite has a water intrusion rate, measured as grams per square meter (g / m2) for water intrusion on the functionalized side, e.g., using the Cobb test method (ISO 535) for 7200 seconds (Oobb72oo), that is at least about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 85%, about 90%, or about 95% lower than the water intrusion rate in comparison to an identical CCPCC that does not contain the functional molecule or layer or to an identical CCPS that contains the same functional molecule or layer but does not contain the deposited ceramic

[0115]

[0106] In some embodiments, a CCPCC as described herein, and at least a portion of the composite (e.g., the polymer matrix of the CCPS) has a pore size distribution, e.g., as measured by capillary flow porometry (CFP) as outlined by standard test methods ASTM D6767 or ASTM F316, that is shifted by the deposited ceramic to smaller pore size as defined by the mean pore size of the distribution by about 5um, by about 3um, by about 2.5um, by about 2um, by about 1 5um, by about 1um, by about 0.75um, by about 0.5um, by about 0.25um, by about 0.5um to about 3um, or by about 1 urn to about 2um, in comparison to an identical CCPS that does not contain the deposited ceramic.

[0116]

[0107] In some embodiments, a CCPCC as described herein also contains a functional molecule or layer as described herein, and the functionalized CCPCC has a pore size distribution e.g., as measured by capillary flow porometry (CFP) as outlined by standard test methods ASTM D6767 or ASTM F316, that is shifted by the functional molecule or layer to smaller pore size as defined by the mean pore size of the distribution by about 5um, by about 3um, by about 2.5um, by about 2um, by about 1.5um, by about 1um, by about 0.75um, by about 0.5um, by about 0.25um, by about 0 5um to about 3um, or by about 1um to about 2um, in comparison an identical CCPCC that does not contain the functional molecule or layer or to an identical CCPS that contains the same functional molecule or layer but does not contain the deposited ceramic.

[0117]

[0108] In some embodiments, a CCPCC as described herein also contains a functional molecule or layer as described herein, and the functionalized CCPCC has a pore size distribution e.g., as measured by capillary flow porometry (CFP) as outlined by standard test methods ASTM D6767 or ASTM F316, that is shifted by the functional molecule or layer and the deposited ceramic to smaller pore size as defined by the mean pore size of the distribution by about 5um, by about 3um, by about 2.5um, by about 2um, by about 1.5um, by about 1um, by about 0 75um, by about 0.5um, by about 0.25um, by about 0.5um to about 3um, or by about 1 urn to about 2um, in comparison an identical CCPCC that does not contain the functional molecule or layer or to an identical CCPS that contains the same functional molecule or layer but does not contain the deposited ceramic

[0118]

[0109] In some embodiments, a CCPCC as described herein also contains a functional molecule or layer as described herein, and the functionalized CCPCC has a modified mechanical property of adhesion to a formed and cured gypsum slurry, e g , measured as described in ASTM C473 or C557, in comparison to an identical CCPS that does not include the deposited ceramic. In some embodiments, the adhesion strength is increased by about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, about 100%, about 200%, about 300%, about 500%, or up to about 1000%, in comparison to an identical CCPCC that does not contain the functional molecule or layer or to an identical CCPS that contains the same functional molecule or layer but does not contain the deposited ceramic.

[0119] In some embodiments, a CCPCC as described herein also contains a functional molecule or layer as described herein, and the functionalized CCPCC has a modified functional property of mold resistance, e.g., measured as described in ASTM 3273, in comparison to an identical CCPCC that does not contain the functional molecule or layer or to an identical CCPS that contains the same functional molecule or layer but does not contain the deposited ceramic In some embodiments, the mold resistance visual score is increased by 1 , 2, 3, 4, 5, 6, 7, 8, 9, or 10, in comparison to an identical CCPCC that does not contain the functional molecule or layer or to an identical CCPS that contains the same functional molecule or layer but does not contain the deposited ceramic, or to an absolute score of 5, 6, 7, 8, 9, or 10

[0120] Methods

[0121] [HO] Methods are provided for production of cellulose-containing polymer-ceramic composite (CCPCC) compositions as described herein. The cellulose-containing polymer substrate (CCPS) of the CCPCC includes cellulose, e.g., a polymer matrix of |3-linked D-glucose units, or materials derived from these polymers such as carboxymethyl cellulose (CMC) or cellulose gum

[0122] [Hl] In some embodiments the cellulose-containing polymer substrate (CCPS) material absorbs metal salts or ceramic precursors, and deposited ceramic is produced in situ on the polymer substrate or on the surface of individual fibers or films. In some embodiments, the deposited ceramic is produced within the internal volume of the CCPS. In some embodiments these ceramic precursors or metal salts are dissolved into a solvent or solvent mixture that is absorbed into the CCPS. In some embodiments, the metal salts or ceramic precursors include a metal nitrate, a metal acetate, a metal sulfate, a metal chloride, or mixtures thereof In other embodiments, the metal salts or precursors include a phosphate, a carbonate, an oxalate, a hydroxide, a sulfate, or mixtures thereof. In some embodiments, the metal comprising salts or precursors include the components of the ceramic. In some embodiments, the metal salts or precursors include metal organic complexes, such as, but not limited to, transition metal amine complexes, transition metal amide complexes, alkaline earth metal amine complexes, alkaline earth metal amide complexes, and coordination complexes of transition metals and amines. In some embodiments, the precursors include an oxidizing agent such as a permanganate, a persulfate, hydrogen peroxide, a chlorate, a perchlorate, or a hypochlorite, which accelerates the formation of the ceramic on the polymer substrate In other embodiments, the ceramic precursors include an amine, an amide, or ammonia, which accelerates the formation of the ceramic on the CCPS In some embodiments, the precursors include a catalyst, which accelerates the precipitation of a ceramic on the substrate. In some embodiments, the ceramic precursors provide multiple benefits. In some embodiments, the ceramic precursors include one or more of a metal salt, components of the ceramic, metal organic complexes, an oxidizing agent, an amine, an amide, and ammonia

[0123]

[0112] Other nonlimiting examples of materials, one or more of which may be added to the reactive solutions or rinses, in order to provide process or operational benefits, are penetrants and solvents, wetting agents, surfactants and dispersants, pH modifiers, anti-scaling chemicals, colorants, and defoaming agents.

[0124]

[0113] In some embodiments, the metal salts and / or ceramic precursors are dissolved or dispersed into a solvent. In some embodiments, the CCPS is contacted with the solution that includes the metal salts and / or ceramic precursors and a solvent. In some embodiments, the solution is absorbed into the CCPS.

[0125]

[0114] In some embodiments, the CCPS is contacted or absorbed with multiple solutions ( / .e., two or more solutions) that contain different metal salt or precursor compositions. For example, the multiple solutions may contain the same or different solvents. In some embodiments, the multiple solutions, if mixed, react to form a precipitant, such as the ceramic. In some embodiments, the reaction between these multiple solutions results in a double replacement reaction to form products that include at least one precipitant.

[0126]

[0115] In some embodiments, the CCPS is contacted or absorbed with one solution that contains one or more metal salt and / or one or more ceramic precursor.

[0127]

[0116] In some embodiments, multiple solutions are used, which if exposed to a change in pH, would react under the new pH condition to form a precipitant, such as a ceramic. In some embodiments, the reaction between these solutions results in a double replacement reaction In some embodiments, the products include at least one precipitant.

[0128]

[0117] In some embodiments, the CCPS with absorbed solution that contains metal salt(s) and / or ceramic precursor(s) and solvent is heated. The heating may result in solvent evaporation and / or precipitation of ceramic. In some embodiments, there is a chemical reaction upon heating, such as, for example, precipitation of ceramic due to supersaturation, and / or migration of ceramic precipitant to the external surface of the CCPS In some embodiments, at least a portion of the ceramic precipitant remains within the interior volume of the polymer matrix

[0118] In some embodiments, the CCPS is dipped or submerged into a solution that includes a first metal salt and then dipped or submerged into a solution that includes a second metal salt, wherein the solutions absorb into the polymer or swell the polymer. In some embodiments, the polymer includes metal salts within the interior volume and / or on the external surface of the polymer substrate. In some embodiments, the polymer substrate is then heated to evaporate the solvent, react the metal salts, or a combination thereof. In some embodiments, the solutions migrate to the external surface of the CCPS during heating. In some embodiments, ceramic precipitates within the interior volume of the polymer matrix, on the external surface of the CCPS, or a combination thereof In some embodiments, the ceramic protrudes outward from the external surface of the CCPS.

[0129]

[0119] In some embodiments, the CCPS is contacted with a solution that includes a first metal salt, and then is contacted with a solution that includes a second metal salt, wherein the CCPS absorbs at least a portion of one or both of the solutions or swells upon being contacted with one or both of the solutions, and the solutions that independently include water or water and one or more cosolvents such as ethylene glycol monobutyl ether (EGBE) or diethylene glycol monobutyl ether (DEGBE). In some embodiments, the CCPS is contacted with a combination of a first metal salt and a second metal salt, wherein the CCPS is first contacted with the first metal salt and then contacted with the second metal salt, the first metal salt includes one or more first ionic compounds, nonlimiting examples of which include calcium nitrate tetrahydrate and magnesium nitrate hexahydrate, and the second metal salt includes one or more second ionic compounds, nonlimiting examples of which include potassium phosphate dibasic and sodium oxalate dihydrate. In some embodiments, contacting the CCPS includes dipping the polymer substrate into one or more of the solutions, submerging the polymer substrate in one or more of the solutions, spraying the polymer substrate with one or more of the solutions, or a combination thereof.

[0130]

[0120] In some embodiments, the CCPS is pre-treated before contacting with the solution that includes the one or more first ionic compounds. In some embodiments, the pre-treatment includes one or more of contacting the polymer substrate with a solution of sodium hydroxide from about 0.25% (w / w) to about 5% (w / w) for about 15 seconds to about 30 minutes, rinsing the polymer substrate with water or a solvent that includes water and a cosolvent, mechanically dewatering the polymer substrate, drying the polymer substrate under the ambient atmosphere at a temperature from about ambient temperature (e.g., about 20°C) to about 140°C, and / or equilibrating the polymer substrate against ambient conditions.

[0131]

[0121] In some embodiments, the polymer substrate is further treated after contacting with the solution that includes one or more first ionic compounds and before contacting with the solution that includes one or more second ionic compounds. In some embodiments, the first or second solution are at temperatures of about 20°C, about 20°C to about 90°C, about 20°C to about 50°C, about 30°C to about 60°C, about 40°C to about 80°C, about 50°C to about 90°C, about 30°C, about 40°C, about 50°C, about 60°C, about 70°C, about 80°C or about 90°C. In some embodiments, the first or second solutions are in contact with the substrates for about 1 second, about 2 seconds, about 5 seconds, about 1 second to about 120 seconds, about 5 seconds to about 20 seconds, about 10 seconds to about 30 seconds, about 20 seconds to about 60 seconds, about 30 seconds to about 80 seconds, about 40 seconds to about 90 seconds, about 50 seconds to about 100 seconds, about 60 seconds to about 120 seconds, about 70 seconds to about 110 seconds, about 80 seconds to about 120 seconds, about 10 seconds, about 15 seconds, about 20 seconds, about 30 seconds, about 60 seconds, about 90 seconds, or about 120 seconds before a drying step occurs In some embodiments, the further treatment includes one or more of mechanically dewatering the polymer substrate and / or drying the polymer substrate under ambient atmosphere at a temperature from about ambient temperature (e.g., about 20°C) to about 140°C.

[0132]

[0122] In some embodiments, the solution that includes the one or more first ionic compounds and the solution that includes the one or more second ionic compounds independently include water or a solvent that includes water and one or more cosolvents. In some embodiments where the solvent includes water and one or more cosolvents, the ratio of water to the total of one or more cosolvents is from about 1:99 (v / v) to about 999:1 (v / v). In some embodiments where the solvent includes water and one or more cosolvents, the ratio of water to the total of one or more cosolvents is from about 1 :99 (w / w) to about 999:1 (w / w). In some embodiments, the solvent is water. In some embodiments, the solvent is from about 0.25% (w / w) to about 50% EGBE in water (w / w). In some embodiments, the solvent is from about 0.5% (w / w) to about 5% EGBE in water (w / w) In some embodiments, the solvent is from about 1% (w / w) to about 2% EGBE in water (w / w) . In some embodiments, the solvent is from about 0.25% (w / w) to about 50% DEGBE in water (w / w) . In some embodiments, the solvent is from about 0.5% (w / w) to about 5% DEGBE in water (w / w). In some embodiments, the solvent is from about 1% (w / w) to about 2% DEGBE in water (w / w).

[0133]

[0123] In some embodiments, the solution that includes the one or more first ionic compounds and the solution that includes the one or more second ionic compounds, which independently include water or a solvent that includes water and one or more cosolvents, are independently or coincidentally sprayed or contacted onto the CCPS

[0134]

[0124] In some embodiments, the solution that includes the one or more first ionic compounds and the solution that includes the one or more second ionic compounds, which independently include water or a solvent that includes water and one or more cosolvents, are distributed uniformly or in a diffusion based pattern through the solution in a contact pattern with the substrate and the wicking of the substrate or the cellulose-containing polymer-ceramic composite.

[0135]

[0125] In some embodiments, the CCPS is dipped or submerged into a solution that includes a metal organic complex. In some embodiments, the CCPS includes the metal organic complex within the interior volume of the polymer matrix and / or on the external surface of the polymer substrate. In some embodiments, the CCPS is then heated to evaporate the solvent, decompose, or react with the metal organic complex, or a combination thereof. In some embodiments, the heating decomposes the metal-organic complex into ceramic. In some embodiments, the solutions migrate to the external surface of the polymer substrate during heating. In some embodiments, ceramic precipitates within the interior volume of the polymer matrix, on the external surface of the CCPS, or a combination thereof. In some embodiments, the ceramic protrudes outward from the external surface of the CCPS.

[0136]

[0126] In some embodiments the CCPS is dipped or submerged into a solution that includes a metal organic complex. In some embodiments, the CCPS includes the metal organic complex within the interior volume of the polymer matrix and / or on the external surface of the polymer substrate. In some embodiments, the CCPS is then contacted with a pH adjustment solution and / or with a catalyst-containing solution to form a precipitate of ceramic In some embodiments, the solutions migrate into the CCPS. In some embodiments, ceramic precipitates within the interior volume of the polymer matrix, on the external surface of the CCPS, or a combination thereof. In some embodiments, the ceramic protrudes outward from the external surface of the CCPS.

[0137]

[0127] In some embodiments, the CCPS is dipped or submerged into a solution that contains a metal salt and an oxidizing agent. In some embodiments, the CCPS includes the metal salt and / or the oxidizing agent within the interior volume of the polymer matrix and / or on the external surface of the CCPS. In some embodiments, the CCPS is dipped sequentially into a solution containing a metal salt, followed by a solution containing an oxidizing agent. In some embodiments, the CCPS is first dipped into a solution containing an oxidizing agent followed by a solution containing a metal salt. In some embodiments, the oxidizing agent oxidizes metal ions from the metal salt in solution and forms a ceramic precipitate within the interior volume of the polymer matrix and / or on the external surface of the CCPS In some embodiments the ceramic protrudes outward from the external surface of the CCPS

[0138]

[0128] In some embodiments, the CCPS is contacted by a solution that contains a metal salt and an oxidizing agent by spraying, flooding, padding, or gravure coating. In some embodiments, the CCPS includes the metal salt and / or the oxidizing agent within the interior volume of the polymer matrix and / or on the external surface of the CCPS. In some embodiments, the CCPS is sequentially contacted by spraying, flooding, padding, or gravure coating with a solution containing a metal salt, followed by a solution containing an oxidizing agent. In some embodiments, the polymer substrate is first sprayed, flooded, padded, or gravure coated into a solution containing an oxidizing agent, followed by a solution containing a metal salt In some embodiments, the oxidizing agent oxidizes metal ions from the metal salt in solution and forms a ceramic precipitate within the interior volume of the polymer matrix and / or on the external surface of the CCPS In some embodiments the ceramic protrudes outward from the external surface of the CCPS. In some embodiments, the ceramic precursor chemicals are added to the substrate via spraying, immersing, dipping, vapor depositing, spin coating, gravure coating, knife coating, or roll coating in such a manner that the ceramic precursor chemicals are only present on the external surface of one portion of the substrate (e.g., a one sided coating), or in such a manner to establish a gradient concentration through or across the substrate. In some embodiments, the gradient concentration is established by the addition of a limited amount of ceramic precursor chemical such that the wicking properties of the substrate do not result in a uniform concentration throughout the substrate.

[0139]

[0129] In some embodiments the CCPCC is functionalized via spraying, immersing, dipping, vapor depositing, spin coating, gravure coating, knife coating, or roll coating. In some embodiments, a functional molecule applied in the functionalization step is one or more of a silane, a siloxane, a urethane, an acrylate, and a molecule with a head group and a tail group (for example, wherein the head group includes a silane group, a phosphonate group, a phosphonic acid group, a carboxylic acid group, a vinyl group, an alcohol group, a hydroxide group, a thiolate group, a thiol group, and / or an ammonium group (e.g., a quaternary ammonium group), and wherein the tail group includes a hydrocarbon group, a fluorocarbon group, a vinyl group, a phenyl group, an epoxide group, an acrylic group, an acrylate group, a hydroxyl group, a carboxylic acid group, a thiol group, and / or a quaternary ammonium group. In some embodiments the functional molecule is dissolved in a solvent such as water, an alcohol, such as but not limited to isopropanol, methanol, or ethanol, an alkane such as a hexane or a heptane, or an aromatic hydrocarbon, such as, but not limited to a xylene or toluene. In some embodiments the functionalized CCPCC is cured at an elevated temperature to stabilize the functional molecule. In some embodiments, the CCPCC is functionalized via spraying, immersing, dipping, vapor depositing, spin coating, gravure coating, knife coating, or roll coating in such a manner that the functionalization agent or chemical is only present on the external surface of one portion of the substrate (e.g., a one sided coating), or in such a manner to establish a gradient concentration through or across the substrate. In some embodiments, the gradient concentration is established by the addition of a limited amount of the functionalization agent or chemical such that the wicking properties of the substrate do not result in a uniform concentration throughout the substrate

[0140]

[0130] In some embodiments the CCPCC is functionalized via lamination with a thin film. In some embodiments, the thin film applied in the functionalization step includes a polymer, such as but not limited to polyurethane or polyolefin In some embodiments, the CCPCC is a film or paperlike composite that is functionalized via lamination on a single side In some embodiments, the CCPCC is a film or paperlike composite that is functionalized via lamination on both sides. In some embodiments, the ratio of the lamination film thickness to the CCPCC surface roughness is about 0.1 , about 0.2, about 0.5, about 1 , about 1.5, about 2, about 5, about 0.1 to about 5, about 0.1 to about 1 , or about 0.1 to about 0.5 In some embodiments, the polymer-ceramic composite is a film or paperlike composite that is functionalized via a lamination process that includes a thermal processing step that softens or melts the lamination film material into the polymer-ceramic composite In some embodiments the CCPCC is functionalized via spraying or depositing a functionalization material that includes a polymer, such as but not limited to polyurethane or polyolefin, and further includes a thermal processing step that softens or melts the functionalization material into the CCPCC.

[0131] In some embodiments, cellulose-containing materials are added to processing or functionalization solutions, in order to modify the rheological properties of these solutions.

[0141]

[0132] In some embodiments, the CCPCC is subsequently contacted with a, ionic substitution reagent to form a substituted ceramic. For example, the ionic substitution reagent may include one or more of Mg, Co, Zn, Sr, Na, Ti, Ga, and Ag. As one nonlimiting example, equimolar TiOfSC ) is added to a CaH(PO4> containing ceramic composite, at elevated temperature conditions of about 50°C to about 80°C, thereby resulting in Ti substitution. The CCPCC sample is removed and rinsed to remove unbound reaction products. Titanium isopropoxide is another example for Ti substitution.

[0142]

[0133] In some embodiments, the CCPCC includes a CCPS that is a polymer film with an adhesive layer and a ceramic that is an interconnected nanostructured layer, which is transferred to the adhesive layer by direct or contact transfer. In some embodiments, direct or contact transfer is achieved by cold or hot pressing, rolling, peeling, or laminating. In some embodiments, an adhesive layer is used to facilitate the transfer In some embodiments, the interconnected nanostructured layer is directly transferred to the substrate. In some embodiments, the interconnected nanostructured layer is removed from the substrate and transferred using a liquid carrier. In some embodiments, two or more CCPCCs are contacted and interconnected by cold or hot pressing, rolling, peeling, or laminating.

[0143]

[0134] In some embodiments, a cellulosic paper is used as the polymer substrate for the formation of a CCPCC, as shown schematically in Fig. 3. In one embodiment, a roll 11 of cellulosic paper 12 can be passed into processing equipment 21 and a ceramic deposited making a cellulosic paper ceramic composite 29. In another embodiment, the paper ceramic composite 29 is passed to a drying section 43. In another embodiment, the dried paper ceramic composite is aligned with a second roll 41 of a polymer film 42 and adhered or laminated 49. The polymer film 42 can provide a functional benefit such as water repellency, oil repellency, vapor barrier properties, color, environmental protection, or adhesive transfer In some embodiments, additional processing or curing equipment 51 is used to generate the final laminated composite material 59. In some embodiments, the second roll 41 is a polymer film comprising polyurethane, acrylic, LCP, polyolefins, meltblown films or meltblown nonwoven material having desirable properties. In some embodiments, a liquid solution or slurry 32 is contacted with the cellulosic paper ceramic composite 29 with thickness controlled by a weir, blade or other means 33 and is dried 43. The processing steps of 31-39 may alternatively be an immersion process 35 with a nip roller 36 for dewatering, a gravure coater 37, or a spray coater 38 In other non-limiting embodiments, the formation of a paper ceramic composite 29 is achieved in the processing steps 21-29 by any of the methods described in the previous examples and the paper ceramic composite 29 is subsequently processed by several additional non-limiting methods 31-59 In some embodiments, paper ceramic composites 29 are formed with polymeric feature dimensions of about 5 to about 500 urn and characteristic ceramic feature dimensions of about 0.2 to about 20 urn. In some embodiments, the paper ceramic composites 29 having characteristic polymeric feature dimensions of about 5 urn to about 500 urn and characteristic ceramic feature dimensions of about 0.2 urn to about 20 urn are contacted with a film 42 having characteristic thickness of less than about 20% of the polymeric feature dimensions or less than about 500% of the ceramic dimensions. For the noted characteristic dimensions, this corresponds to film thicknesses of about 0.5 urn to about 100 urn. In some embodiments, the film 42 may be a large open structure nonwoven material having a density less than 20 g / m2that is melted in downstream curing equipment 58

[0144] EXAMPLES

[0145]

[0135] The following examples are intended to illustrate, but not limit, the invention.

[0146] Example 1

[0147]

[0136] Cellulosic facer paper with a density of about 250 g / m2was used as polymer substrate for the deposition of ceramic. Samples were immersed into a first solution, removed and dried at room temperature or at a temperature of about 140°C for about 10 min, immersed into a second solution, removed and rinsed twice in deionized (DI) water, and dried at a temperature of about 140°C for about 10 minutes.

[0148]

[0137] First solutions contained about 400 mM MnfSC ) and about 170mM ethylene glycol butyl ether (EGBE). Samples were immersed into the first solutions at a temperature of about 20°C for about 1 minute or less, at which point the substrate was observed to be wetted with the first solution. Samples were then removed and dried at room temperature to remove excess water or dried at about 140°C for about 10 minutes to remove excess water and water contained in the substrate.

[0149]

[0138] Each of the dried samples was then contacted with a second solution at a temperature of about 25°C for about 1.5 hrs. The second solutions contained about 75 mM of K2S2O8 and about 1453 mM, about 750 mM, about 150 mM, about 15 mM, or no NH3. Additional second solutions containing about 750 mM, about 150 mM, about 15 mM, or no NH3 were prepared and dosed with KOH to bring the solution to a pH of about 13.5. Samples were removed, rinsed twice with deionized DI (ASTM Type II having resistivity of S1 MQ-cm at 25°C) water, and dried at a temperature of about 140°C for about 10 minutes.

[0150]

[0139] The samples were imaged by scanning electron microscopy (SEM). The samples with exposure to 2S2O8 and second solution exposure greater than 150 mM NH3 exhibited a contiguous interconnected platelike, nanostructured layer and some larger discrete particulates, and some cracking of the contiguous structure was observed The nanostructured layers had a thickness of less than about 0.2 pm The sample of 15 mM NH3 showed some discrete particle like structures with dimensions less than 1 m in size No structures were observed in the no NH3 exposure The samples with second solution exposure greater than 150 mM of NH3 and KOH showed a contiguous interconnected platelike, nanostructured layer and some larger discrete particulates, and some cracking of the contiguous structure was observed The nanostructured layers had a thickness of less than about 0.2 pm The sample of both 15 mM NH3 and no NH3 with KOH added showed discrete particle like structures with dimensions less than 1 m in size. Energy dispersive spectroscopy (EDS) analysis indicated the structures contained Mn

[0151] Example 2

[0152]

[0140] Cellulosic polymer substrate (cellulose facer paper) and a control substrate (fiberglass mat that could be used for a glass faced gypsum board) were used as polymer substrates.

[0153]

[0141] Under constant stirring, 500 mM of ammonium acetate, 50mM of manganese acetate and 50mM of ammonium persulfate were added to DI water. Acetic acid was added to the solution to maintain pH. The solution was stirred continuously for about 30-60min until the solution became dark brown and turbid (similar appearance to black coffee) After the color change, the first solution was used for sample addition

[0154]

[0142] A second solution containing 1-2% hexadecyltriethoxysilane in ethanol was prepared.

[0155]

[0143] Samples were added to the first solution for about 30 minutes. Samples were removed and rinsed via immersion and swishing in DI water. After rinsing, samples were dried in a forced convection oven at 105°C for 60 minutes. Once dried, samples were immersed in the second solution for 18 hours Samples were removed and dried in a forced convection oven at 105°C for 60min

[0156]

[0144] For this round of experimentation, a 10 pl sessile water drop contact angle before and after a scotch tape adhesion test (ASTM D3359) was measured. The results are shown in Table 1.

[0157] Example 3

[0158]

[0145] Several cellulosic polymer substrates were used as polymer substrates for the deposition of ceramic. These include a sample of a cellulose (paper) faced gypsum board, oriented strand board (OSB), and a cellulose facer paper. A fiberglass mat that could be used for a glass faced gypsum board was included as a control. Of note, fiberglass mat and OSB both had a hydrophobic surface before any treatment was performed.

[0159]

[0146] A first solution containing zinc sulfate (400mM) and potassium persulfate (75mM) in DI water was prepared. Ammonium hydroxide was added and stirred until the first solution formed a homogeneous opaque white gel (approximately 1-2 minutes) Samples were then fully submerged in the solution. After 30 minutes in solution, the samples were removed from the deposit and rinsed in DI water by dipping until excess gel and particulate stopped coming off. The samples were then dried in a forced convection oven at 105°C for 60 min. After drying, samples were then functionalized (top coated) with hexadecyltriethoxysilane containing top coat from a suspension with a concentration of about 1 g / L suspension in isopropanol Samples were submerged in the top coat solution for about 90 minutes and then removed without rinsing, and were dried in a forced convection oven for about 75 minutes at about 140°C.

[0160]

[0147] All four substrates were coated with this formulation, as observed by high contact angles or large increases in contact angles when fully treated. The results are shown in Figs. 1a - 1c.

[0161] Example 4

[0162]

[0148] A cellulosic paper with density of about 150 g / m2was used as polymer substrate for the deposition of ceramic. Samples were immersed into a first solution for about 30 seconds, removed and allowed to drain for about 10 seconds, immersed into a second solution for about 30 seconds, and removed and allowed to drain for about 10 seconds. This process sequence was optionally repeated a total of three times to increase the amount of ceramic material deposited After the final immersion, the samples were dried at a temperature of about 140°C for about 10 minutes.

[0163]

[0149] First solutions contained about 50 mM Ca(NOs) and about 50mM TiO(SO4). Samples were immersed into the first solutions at a temperature of about 20°C to about 80°C. Second solutions contained about 60 mM foHfPC ). Samples were immersed into the second solutions at a temperature of about 20°C to about 80°C. Increasing the temperature increased the amount of ceramic material deposited.

[0164]

[0150] Samples were imaged by SEM and EDS to identify distributions of Ca and Ti across the sample.

[0165] Example 5

[0166]

[0151] Cellulosic paper with density of about 220 g / m2was used as polymer substrate for the deposition of ceramic. Samples of about 15 cm by about 15 cm dimension were prepared. The water uptake, determined by immersion into water and measuring the resulting weight of the sample, was about 84% (w / w), such that a sample area of 100 cm2had a saturated uptake of about 1.9 g of water. A sprayer containing a first solution was used to apply about 0.5 g of a first solution to an area of about 100 cm2. A second sprayer containing a second solution was used to apply about 0.5 g of a second solution to the same area of about 100 cm2. After the spray application, the samples were dried at a temperature of about 140°C for about 10 minutes

[0167]

[0152] First solutions contained about 100 mM Ca(NOs) and the solutions and sample were at a temperature of about 20°C. Second solutions contained about 60 mM K2H(PC>4) at about 20°C. An optional drying step after the first solution immersion increased the vertical rise of the second solution.

[0153] After drying, the samples treated with both the first and second solutions showed ceramic along the sprayed 100 cm2area, but little ceramic was found on either the back side of the sample or outside of the 100cm2area.

[0168]

[0154] A similar exposure using foam based first and second solutions, which limits the mass transfer into the absorbent substrate, generates similar observations.

[0169] Example 6

[0170]

[0155] A cellulosic paper with density of about 250 g / m2was used as polymer substrate for the deposition of ceramic. Samples of about 2.5 cm by about 10 cm dimension were partially submerged about 1 cm into a first solution for about 5 minutes. The first solution wicked into the sample by capillary rise. The sample was then removed and any excess liquid was removed. The sample was then similarly immersed into a second solution for about 5 minutes, removed and allowed to drain for about 10 seconds After the final immersion, the samples were dried at a temperature of about 140°C for about 10 minutes.

[0171]

[0156] First solutions contained about 100 mM Ca(NOs) and the solutions and sample were at a temperature of about 20°C Second solutions contained about 60 mM K2H(PC>4) at about 20°C An optional drying step after the first solution immersion increases the vertical rise of the second solution. After drying, the samples show a gradient of ceramic along the sample length.

[0172] Example 7

[0173]

[0157] A cellulosic facer paper with a density of about 250 g / m2, which has undergone a Ca addition step such as exposure to a lime wash, was used as polymer substrate for the deposition of ceramic. Samples were immersed into a solution for about 10 seconds to about 90 minutes, removed, and dried at 140°C for about 10 min.

[0174]

[0158] The solutions contained about 10 mM to about 500 mM of at least one of K2HPO4, KH2PO4, N32HPO4, and NaH2PO4. The solutions were maintained at temperatures of about 20°C to about 90°C.

[0175]

[0159] Investigation of the substrates did not indicate the formation of any additional ceramic structures after immersion in the solution.

[0176] Example 8

[0177]

[0160] A cellulosic paper with density of about 250 g / m2was used as polymer substrate for the deposition of ceramic. Samples of about 2.5 cm by about 10 cm dimension were prepared. One of the surfaces was lightly contacted into a first solution for about 15 seconds. The first solution wicked into the sample by capillary rise. The sample was then removed and any excess liquid was removed. The sample was then inverted and the opposite sample surface was similarly immersed into a second solution for about 15 seconds, removed, and allowed to drain for about 10 seconds. After the second immersion, the samples were dried at a temperature of about 140°C for about 10 minutes.

[0178]

[0161] First solutions contained about 100 mM Ca(NOs) and the solutions and sample were at a temperature of about 20°C. Second solutions contained about 60 mM K2H(PC>4) at about 20°C. An optional drying step after the first solution immersion increased the vertical rise of the second solution.

[0179]

[0162] After drying, the samples treated with both the first and second solutions exhibited a gradient of ceramic along the sample middle or center.

[0180] Example 9

[0181]

[0163] Cellulosic facer paper with a density of about 250 g / m2was used as polymer substrate for the deposition of ceramic. Samples were immersed into a first solution for about 30 seconds, removed and allowed to drain for about 10 seconds, immersed into a second solution for about 30 seconds, and removed and allowed to drain for about 10 seconds. This process sequence was repeated a total of three times. After the final immersion, the samples were dried at a temperature of about 140°C for about 10 minutes.

[0182]

[0164] First solutions contained about 100 mM Ca(NOs). Samples were immersed into the first solutions at a temperature of about 80°C. Second solutions contained about 60 mM K2H(PC>4). Samples were immersed into the second solutions at a temperature of about 80°C. The samples were noted to be very hydrophilic with 10 pil sessile water droplet contact angles less than 20 degrees and the added water droplets wicked into the substrate.

[0183]

[0165] A 100 cm2area of the polymer-ceramic composite samples were then treated by spraying a single side of the sample with a functionalization solution of an alkyl based silane in solvent, hexadecyltriethoxysilane in ethanol.

[0184]

[0166] Three separate cellulosic polymer ceramic samples were treated by addition of 0.175ml, 0.350ml, or 0.525ml of the functionalization solution to a 100 cm2area and the resulting observations are provided in Table 2.

[0185] Table 2

[0186]

[0167] The treated substrates are shown in Figs. 2a - 2f.

[0187] Example 10

[0188]

[0168] Cellulosic facer paper with a density of about 250 g / m2was used as polymer substrate for the deposition of ceramic Samples were immersed into a first solution for about 30 seconds, removed and allowed to drain for about 10 seconds, immersed into a second solution for about 30 seconds, and removed and allowed to drain for about 10 seconds. This process sequence was repeated a total of three times. After the final immersion, the samples were dried at a temperature of about 140°C for about 10 minutes.

[0189]

[0169] First solutions contained about 100 mM CafNOs). Samples were immersed into the first solutions at a temperature of about 80°C. Second solutions contained about 60 mM K2H(PC>4). Samples were immersed into the second solutions at a temperature of about 80°C.

[0190]

[0170] Two cellulosic ceramic composite samples were then pressed together using a manual roller to form an assembly of two cellulosic ceramic composite samples. Utilization of an adhesive increases the adhesion between the two samples.

[0191] Example 11

[0192]

[0171] Cellulosic facer paper with a density of about 250 g / m2is used as polymer substrate for the deposition of ceramic. Samples are immersed into a first solution for about 30 seconds, removed, and allowed to drain for about 10 seconds. A second sample is immersed into a second solution for about 30 seconds, removed, and allowed to drain for about 10 seconds. The two paper samples are placed into direct contact prior to drying. The samples are dried at a temperature of about 140°C for about 10 minutes. The samples form a two layer polymer ceramic composite laminate with ceramic primarily located in the region near the interface of the two samples.

[0193]

[0172] First solutions contain about 100 mM Ca(NOs). Samples are immersed into the first solutions at a temperature of about 80°C. Second solutions contain about 60 mM K2H(PC>4). Samples are immersed into the second solutions at a temperature of about 80°C.

[0194] Example 12

[0195]

[0173] Cellulosic facer paper with a density of about 250 g / m2is used as polymer substrate for the deposition of ceramic. Samples are immersed into a first solution for about 30 seconds, removed and allowed to drain for about 10 seconds, then immersed into a second solution for about 30 seconds, removed, and allowed to drain for about 10 seconds. A second sample is immersed into a first solution for about 30 seconds, removed and allowed to drain for about 10 seconds, then immersed into a second solution for about 30 seconds, removed, and allowed to drain for about 10 seconds. The two paper samples are placed into direct contact prior to drying. The samples are dried at a temperature of about 140°C for about 10 minutes. The samples form a two layer polymer ceramic composite laminate

[0196]

[0174] First solutions contain about 100 mM CafNOs). Samples are immersed into the first solutions at a temperature of about 80°C. Second solutions contain about 60 mM K2H(PC>4). Samples are immersed into the second solutions at a temperature of about 80°C

[0197] Example 13

[0198]

[0175] Cellulosic paper with density of about 100 g / m2to about 300 g / m2is used as polymer substrate for the deposition of ceramic. Samples are immersed into a first solution for about 30 seconds, removed and allowed to drain for about 10 seconds, immersed into a second solution for about 30 seconds, and removed and allowed to drain for about 10 seconds. This process sequence is optionally repeated a total of three times to increase the amount of ceramic material deposited. After the final immersion, the samples are dried at a temperature of about 140°C for about 10 minutes to form a polymer ceramic composite.

[0199] First solutions contain about 100 mM Ca(NOs). Samples are immersed into the first solutions at a temperature of about 20°C to about 80°C. Second solutions contain about 60 mM K2H(PC>4). Samples are immersed into the second solutions at a temperature of about 20°C to about 80°C. Increasing the temperature increases the amount of material present.

[0200]

[0176] The polymer ceramic composite samples are then placed into a solution that contains at least one of Mg, Co, Zn, Sr, Na, Ti, Ga, and Ag. The polymer ceramic composite is introduced to the solution and an ion substitution takes place. As one nonlimiting example, equimolar TiOfSC ) is added to the CaHfPCU) containing ceramic composite, at elevated temperature conditions of about 50°C to about 80°C. The ceramic composite sample is removed and rinsed to remove unbound reaction products. Titanium isopropoxide is another example for Ti substitution.

[0201] Example 14

[0202]

[0177] Cellulosic paper with density of about 150 g / m2was used as polymer substrate for the deposition of ceramic. Samples were immersed into a first solution for about 30 seconds, removed and allowed to drain for about 10 seconds, immersed into a second solution for about 30 seconds, and removed and allowed to drain for about 10 seconds. This process sequence was optionally repeated a total of three times to increase the amount of ceramic material deposited After the final immersion, the samples were dried at a temperature of about 140°C for about 10 minutes.

[0203]

[0178] First solutions contained about 100 mM CafNOs) and about 5mM Ag(NOs). Samples were immersed into the first solutions at a temperature of about 20°C to about 80°C. Second solutions contained about 60 mM K2H(PO4). Samples were immersed into the second solutions at a temperature of about 20°C to about 80°C. Increasing the temperature increases the amount of ceramic material deposited.

[0204] Example 15

[0205]

[0179] The procedures described in Example 2 are carried out with the addition of 2-20% of hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), hydroxypropyl methylcellulose (HPMC), and sodium carboxymethyl cellulose (CMC) into the silane containing ethanol solution, in order to increase the viscosity of the mixture, which reduces the amount of wicking of the top coat The additions result in a gelation that can be used for distribution and operations, or for thicker coating layers.

[0206] Example 16

[0207]

[0180] Cellulosic paper with a density of about 250 g / m2is used as polymer substrate for a binderless sol deposition of ceramic. Dried paper samples are contacted with a first solution containing a binderless sol comprising Ca and P. The first solution contacted paper is then removed and dried at about 105°C to about 140°C for about 1 to about 10 min. The first solution contacted paper may optionally be mechanically dewatered prior to the drying step. The dried first solution contacted paper is optionally functionalized via spraying, immersing, dipping, vapor depositing, spin coating, gravure coating, knife coating, roll coating, or lamination.

[0208] Example 17

[0209]

[0181] Cellulosic paper with a density of about 250 g / m2was used as polymer substrate for the formation of a mixed metal oxide. A first solution comprising Fe and Mn was prepared by adding Fe(NOs)2 and / or Mn(NOs)2 with a total cation concentration of about 150mM and about 150mM of hexamethylenetetramine (HMTA) or urea. Several cation ratios were prepared including [Fe]:[Mn] of 1 :0, 10:1, 5:1 , 5:2, 2:1 , 1 :1 , 1 :2, 2:5, 1 :5, 1:10, 0:1 , with the first solution pH in the range of 6.0 to 7.4 and held at a temperature of about 80°C. Samples were contacted with the first solution for about 60 minutes, and after this time were removed and dried at about 105°C to about 230°C for about 1 to about 60 min An optional functionalization step may be carried out after drying

[0210]

[0182] In each case, a platelike interconnected ceramic was formed. Increasing ratios of Mn increased the unit cell dimension and resulted in darker brown colors.

[0211] Example 18

[0212]

[0183] Cellulosic paper with a density of about 250 g / m2was used as polymer substrate for the formation of mixed metal oxide ceramic composites. A solution of 15ml of DI water was prepared by adding two metal nitrates of Fe, Zn, Mn, Al, or Co and 2 g of urea. The metal nitrates used were (a) Fe (0.5 g) and Zn (1 g), (b) Fe (0.5 g) and Mg (1 g), (c) Fe (0.5 g) and Mn (1 g), (d) Fe (0.5 g) and Co (1 g), (e) Al (0.5 g) and Zn (1 g), (f) Al (0.5 g) and Mg (1 g), (g) Al (0.5 g) and Mn (1 g). The solutions were held at a temperature of about 85°C. Samples were contacted with the solution for about 20 hours, and after this time are removed and dried at about 105°C to about 230°C for about 1 to about 60 min. An optional functionalization step may be carried out after drying. Ceramic structures were observed on the polymer-ceramic composite. Several distinct morphologies were observed, including (a) farfalle pasta shape, (b) dense rhomboids and pyramids, (c) spherical flowers, and (d) high stressed rhomboids

[0213] Example 19

[0214]

[0184] Cellulosic paper with a density of about 250g / m2was used as a polymer substrate for the formation of polymer-ceramic composites. Reference metal ceramic composite materials were used as control. In this case, a nanostructured Zn-LDH ceramic, having a characteristic pore size dimension of about 5um, was prepared on an aluminum substrate and used as the control.

[0215]

[0185] A 500|im thick polyurethane film was applied to the aluminum substrate by placing the film on the substrate and placing a hot iron on the paper backing of the film for about 30 seconds. The paper was then peeled off and the film was observed to partially penetrate the pores and left a visual residue on the top of the sample surface. The resulting sessile droplet contact angle of the sample was unchanged from the virgin film. Alternatively, the polyurethane film was applied by placing the substrate in the oven at 200°C with a film and a stainless steel weight to press the film down. Again, the film was observed to partially penetrate the porous structure but left a significant amount of the film above the structured layer and no change to the sessile droplet contact angle was observed, indicating a loss of the underlying structure due to the film thickness.

[0216]

[0186] A 15um thick polyester film was applied to the aluminum substrate by placing the film on the substrate and placing a hot iron on the paper backing of the film for about 30 seconds. The paper was then peeled off and the film was observed to partially penetrate the pores and left a visual residue on the top of the sample surface. The resulting sessile droplet contact angle of the sample was increased in comparison to the virgin film.

[0217]

[0187] A cellulosic paper having density of about 250g / m2was used as a polymer substrates for the formation of polymer-ceramic composites. The cellulosic polymer substrate included many individual fibers having a dimension of 5-10um and an overall surface roughness Raof about 5 urn. A 15um thick polyester film layer was applied by placing a hot iron on the paper backing. The resulting sessile droplet contact angle of the sample was increased in comparison to the virgin film.

[0218] Example 20

[0219]

[0188] A cellulosic paper is used as polymer substrates for the formation of polymer-ceramic composites, as shown schematically in Fig. 3. In one embodiment, a roll 11 of cellulosic paper 12 can be passed into processing equipment 21 and a ceramic deposited, thereby making a cellulosic paper ceramic composite 29. In another embodiment, the paper ceramic composite 29 is passed to a drying section 43. In another embodiment, the dried paper ceramic composite is aligned with a second roll 41 of a polymer film 42 and adhered or laminated 49. The polymer film 42 can provide one or more functional benefit, such as water repellency, oil repellency, vapor barrier properties, color, environmental protection, and / or adhesive transfer In some embodiments, additional processing or curing equipment 51 is used to generate the final laminated composite material 59. In some embodiments, the second roll 41 is a polymer film including polyurethane, acrylic, LCP, polyolefins, meltblown films or meltblown nonwoven material having desirable properties In some embodiments, a liquid solution or slurry 32 is contacted with the cellulosic paper ceramic composite 29 with thickness controlled by a weir, blade, or other means 33 and is dried 43. The processing steps of 31-39 may alternatively be an immersion process 35 with a nip roller 36 for dewatering, a gravure coater 37, or a spray coater 38. In other non-limiting embodiments, the formation of a paper ceramic composite 29 is achieved in the processing steps 21-29 by any of the methods described in the previous examples and the paper ceramic composite 29 is subsequently processed by several additional non-limiting methods 31-59 In some embodiments, paper ceramic composites 29 are formed with polymeric feature dimensions of about 5 to about 500 urn and characteristic ceramic feature dimensions of about 0.2 to about 20 urn. In some embodiments, the paper ceramic composites 29 having characteristic polymeric feature dimensions of about 5 urn to about 500 urn and characteristic ceramic feature dimensions of about 0.2 urn to about 20 urn are contacted with a film 42 having characteristic thickness of less than about 20% of the polymeric feature dimensions or less than about 500% of the ceramic dimensions. For the noted characteristic dimensions, this corresponds to film thicknesses of about 0.5 urn to about 100 urn. In some embodiments, the film 42 may be a large open structure nonwoven material having a density less than 20 g / m2that is melted in downstream curing equipment 58.

[0220]

[0189] In some embodiments, paper ceramic composites 29 are formed with polymeric feature dimensions of about 5 to about 500 urn and characteristic ceramic feature dimensions of about 0 2 to about 20 urn. In some embodiments, the paper ceramic composites 29 having characteristic polymeric feature dimensions of about 5 urn to about 500 urn and characteristic ceramic feature dimensions of about 0.2 urn to about 20 urn are contacted with a film 42 having characteristic thickness of less than about 20% of the polymeric feature dimensions or less than about 500% of the ceramic dimensions. For the noted characteristic dimensions, this corresponds to film thicknesses of about 0.5 urn to about 100 urn. In some embodiments, the film 42 may be a large open structure nonwoven material having a density less than 25 g / m2or about 10% of the bulk substrate that is melted in downstream curing equipment 58. Applied films having the characteristics noted above demonstrate an increase in sessile drop contact angle over the virgin film (as measured according to ISO 19403), demonstrating at least a partial pattern or roughness transfer. Example 21

[0221]

[0190] A cellulosic paper with density of about 220 g / m2was used as polymer substrates for the deposition of ceramic. Samples were immersed into a first solution for about 30 seconds, removed and passed through a padder, immersed into a second solution for about 30 seconds, removed and passed through a padder. After the final padding, the samples were dried at a temperature of about 140°C for about 10 minutes to form a polymer ceramic composite. %

[0222]

[0191] First solutions contained about 25 mM to about 400mM Ca(NC>3) . Samples were immersed into the first solutions at a temperature of about 80°C. Second solutions contained about 15 mM to about 240mM K2H(PO4). Samples were immersed into the second solutions at a temperature of about 80°C Increasing the concentration of both solutions increases the amount of material present

[0223] Example 22

[0224]

[0192] A cellulosic paper with density of about 100 g / m2to about 300 g / m2was used as polymer substrates for the deposition of ceramic. Samples were immersed into a first solution for about 30 seconds, removed and allowed to drain for about 10 seconds, immersed into a second solution for about 30 seconds, removed and allowed to drain for about 10 seconds. This process sequence was optionally repeated a total of three times to increase the amount of material present. After the final immersion, the samples were dried at a temperature of about 140°C for about 10 minutes to form a polymer ceramic composite. %

[0225]

[0193] First solutions contained about 25 mM Ca(NOs). Samples were immersed into the first solutions at a temperature of about 20°C to about 80°C. Second solutions contained about 15 mM K2H(PO4). Samples were immersed into the second solutions at a temperature of about 20°C to about 80°C. Increasing the temperature increases the amount of material present.

[0226]

[0194] The polymer ceramic composite samples were then treated by spraying a single side of the samples with a functionalization solution of an alkyl based silane in solvent, hexadecyltriethoxysilane in isopropanol. The samples were dried at a temperature of about 140°C for about 10 minutes to functionalize the polymer ceramic composite.

[0227]

[0195] The polymer ceramic composite samples were measured for water intrusion on the functionalized side using the Cobb test method (ISO 535) for 7200 seconds and compared to the untreated cellulosic paper, as shown in Table 3.

[0228] Table 3 Example 23

[0229]

[0196] A cellulosic paper with density of about 220 g / m2was used as polymer substrates for the deposition of ceramic. Samples were immersed into a first solution for about 30 seconds, removed and allowed to drain for about 10 seconds, immersed into a second solution for about 30 seconds, removed and allowed to drain for about 10 seconds. This process sequence was optionally repeated a total of three times to increase the amount of material present. After the final immersion, the samples were dried at a temperature of about 140°C for about 10 minutes to form a polymer ceramic composite which was observed by scanning electron microscopy (SEM) of sample cross section area as an interconnected ceramic structure coating the individual fibers and occupying the interior volume of the paper.

[0230]

[0197] First solutions contained about 25 mM CafNOs) Samples were immersed into the first solutions at a were immersed into the second solutions at a temperature of about 20°C to about 80°C. Increasing the temperature increases the amount of material present. The polymer ceramic composite samples were then treated by spraying the front side of the samples with a functionalization solution of an alkyl based silane in solvent, hexadecyltriethoxysilane in isopropanol. The samples were dried at a temperature of about 140°C for about 10 minutes to functionalize the polymer ceramic composite. XPS scans were used to characterize the amount of functional chemical after curing

[0231]

[0198] Five sample types were interrogated, (a) untreated substrate, (b) first and second solution treated samples with no functionalization, (c) first and second solution treated samples with front side functionalization, (d) first and second solution treated samples with front side functionalization in excess such that functionalization was visually observed on the opposite face, and (e) first and second solution treated samples with front and back side functionalization.

[0232]

[0199] The polymer ceramic composite samples were measured for water intrusion on the functionalized side using the Cobb test method (ISO 535) for 7200 seconds and compared to the untreated cellulosic paper.

[0233]

[0200] The functionalized polymer ceramic composite samples were then used as the facer material for gypsum board. The prepared gypsum boards were conditioned following the procedures listed in ASTM C473. The gypsum boards were tested for bond strength between the gypsum core and the polymer ceramic composite by peeling the ceramic polymer composite away from the gypsum core while measuring the force required to peel the sections apart during elongation. The Peel strengths and Cobb ratings are normalized to the bare sample. The results of the Cobb test and peel testing results are shown in Table 4.

[0234] Table 4

[0201] Although the foregoing invention has been described in some detail by way of illustration and examples for purposes of clarity of understanding, it will be apparent to those skilled in the art that certain changes and modifications may be practiced without departing from the spirit and scope of the invention, which is delineated in the appended claims. Therefore, the description should not be construed as limiting the scope of the invention

[0235]

[0202] All publications, patents, and patent applications cited herein are hereby incorporated by reference in their entireties for all purposes and to the same extent as if each individual publication, patent, or patent application were specifically and individually indicated to be so incorporated by reference

Claims

CLAIMSWe claim:

1. A cellulose-containing polymer-ceramic composite (CCPCC), comprising composition comprising: a cellulose-containing polymer substrate (CCPS); and a ceramic that is deposited on the CCPS, wherein the CCPS comprises cellulosic fibers in a polymer matrix that has an external surface and an internal volume with an overall density of about 50 g / m2to about 300 g / m2, wherein the CCPCC comprises the deposited ceramic on the external surface of the polymer matrix, and wherein the deposited ceramic or a complementary inorganic element at least partially occupies the internal volume of the polymer matrix, wherein the CCPS comprises paper, wherein the deposited ceramic or complementary inorganic element comprises at least one of a transition metal, an alkali metal, and an alkaline earth metal, wherein the deposited ceramic is nanostructured, wherein the deposited ceramic at least partially conformally coats the cellulosic fibers in the polymer matrix, and optionally, wherein the CCPCC is further processed to include one or more functional layers which comprise organic or silicon-containing polymers or monolayers and which impart one or more functional property to the composition.

2. A CCPCC, comprising: a CCPS, wherein the CCPS comprises cellulose in a polymer matrix that has an external surface and an internal volume; and a ceramic that is deposited on the CCPS.3 The CCPCC according to claim 2, wherein the deposited ceramic is on at least a portion of the external surface of the polymer matrix, and wherein the deposited ceramic or a complementary inorganic element at least partially occupies the internal volume of the polymer matrix.

4. The CCPCC according to claim any of claims 1 to 3, further comprising one or more functional layer that imparts or enhances one or more functional property to the CCPCC.

5. The CCPCC according to claim 4, wherein the one or more functional layer comprises an organic or silicon-containing polymer or monolayer.

6. The CCPCC according to claim 2 or 3, wherein the CCPCC is in the form of a fiber, a laminate, a film, a textile material, a paper, or a combination thereof.

7. The CCPCC according to any of claims 1 to 3, wherein the CCPS comprises a polyester, a polyamide, a polyolefin, a substituted polyolefin, a polyurethane, a polyol, a vinyl polymer, an acrylate polymer, a polycarbonate, a polyether, cotton, wool, paper, or a combination thereof.8 The CCPCC according to claim 7, wherein the polymeric matrix comprises polyethylene terephthalate (PET), a nylon, polyethylene, polypropylene, polyvinyl chloride (PVC), polyvinyl alcohol (PVOH), polyvinyl acetate (PVAc), polyvinylpyrrolidone, polyethylene glycol (PEG), polymethylmethacrylate (PMMA), or a mixture thereof.

9. The CCPCC according to any of claims 1 to 3, wherein the CCPS further comprises a binder, a thickener, a filler, a coating, or a combination thereof.

10. The CCPCC according to claim 9, wherein the filler comprises a ceramic material that is incorporated into the CCPS prior to deposition of the deposited ceramic.

11. The CCPCC according to any of claims 1 to 3, wherein the deposited ceramic comprises a transition metal, an alkali metal, and / or an alkaline earth metal.

12. The CCPCC according to any of claims 1 to 3, wherein the deposited ceramic comprises one or more of an oxide, a hydroxide, a layered double hydroxide, a phosphate, an oxalate, a sulfate, and a carbonate13. The CCPCC according to claim 12, wherein the deposited ceramic comprises one or more of manganese oxide, iron oxide, calcium carbonate, hydroxyapatite, calcium phosphate, calcium oxalate, magnesium carbonate, calcium sulfate, titanium oxysulfate, and magnesium sulfate.

14. The CCPCC according to claim 12, wherein the deposited ceramic comprises calcium, sodium, potassium, phosphorous, sulfur, chlorine, manganese, iron, nickel, magnesium, titanium, lithium, and / or zinc.

15. The CCPCC according to any of claims 1 to 3, further comprising a functional molecule that imparts or enhances one or more functional property in the CCPCC in comparison to an identical CCPCC that does not comprise the functional molecule.

16. The CCPCC according to claim 15, wherein the CCPCC the functional property comprises tear strength, tensile strength, gas, vapor, or liquid permeability, adhesion, mold resistance, and / or abrasion17. The CCPCC according to claim 15, wherein the functional molecule comprises a silane, a siloxane, a phosphonic acid, a phosphonate, a sulfonate, a sulfonic acid, a carboxylic acid, a carboxylate, a urethane, a vinyl group, an acrylate, or a molecule with a head group and a tail group.18 The CCPCC according to claim 17, wherein the functional molecule comprises a molecule with a head group and a tail group, wherein the head group comprises a silane group, a phosphonate group, a phosphonic acid group, a carboxylic acid group, a vinyl group, an alcohol group, a hydroxide group, a thiolate group, a thiol group, and / or an ammonium group, and wherein the tail group comprises a hydrocarbon group, a fluorocarbon group, a vinyl group, a phenyl group, an epoxide group, an acrylic group, an acrylate group, a hydroxyl group, a carboxylic acid group, a thiol group, and / or a quaternary ammonium group.

19. The CCPCC according to claim 15, wherein at least a portion of the functional molecule occupies at least a portion of the polymer matrix internal volume that is not occupied by the deposited ceramic or the complementary inorganic element.

20. The CCPCC according to claim 19, wherein the functional molecule penetrates more than 10 nanometers into the polymer matrix internal volume.

21. The CCPCC according to claim 19, wherein concentration of the functional molecule decreases when measured from the external surface of the polymer substrate into the polymer matrix internal volume.

22. The CCPCC according to claim 21 , wherein the concentration of the functional molecule decreases at a decreasing rate from the external surface of the polymer substrate into the polymer matrix internal volume.

23. The CCPCC according to claim 19, wherein the functional molecule penetrates a shorter distance into the polymer matrix internal volume in comparison to an identical polymer substrate that does not comprise the deposited ceramic.

24. The CCPCC according to claim 19, wherein the functional molecule comprises a diffusion coefficient in the polymer matrix internal volume that is greater than about 5% less than the diffusion coefficient of the functional molecule in an identical polymer substrate that does not comprise the deposited ceramic.25 The CCPCC according to any of claims 1 to 3, wherein at least a portion of the external surface of the CCPS does not comprise the deposited ceramic.

26. The CCPCC according to any of claims 1 to 3, wherein at least a portion of the CCPCC comprises a sessile drop water contact angle greater than about 90 degrees.

27. The CCPCC according to any of claims 1 to 3, wherein at least a portion of the CCPCC has a rugosity ratio greater than about 1 328. The CCPCC according to claims 2 or 3, the CCPCC is a textile material that comprises a polyamide, a polyester, a polyolefin, a substituted polyolefin, a polyurethane, a polyol, a vinyl group, cotton, wool, or a cellulosic material, or a combination thereof.

29. The CCPCC according to any of claims 1 to 3, wherein at least a portion of the deposited ceramic is interconnected.

30. The CCPCC according to claim 29, wherein greater than 50% of the deposited ceramic on a particle basis is interconnected.

31. The CCPCC according to any of claims 1 to 3, wherein the deposited ceramic comprises crystalline domains.

32. The CCPCC according to claim 31, wherein one or more of the crystalline domains comprises crystalline particles33. The CCPCC according to claim 31 , wherein the crystalline domains are embedded in an amorphous matrix.

34. The CCPCC according to claim 33, wherein the amorphous matrix comprises calcium and / or phosphorus.

35. The CCPCC according to claim 34, wherein the amorphous matrix comprises at least two elements, not including carbon, hydrogen, oxygen or nitrogen, that are present in the crystalline domains.

36. The CCPCC according to claim 34, wherein the amorphous matrix comprises three common elements, not including carbon, hydrogen, oxygen, or nitrogen, with the crystalline domains.

37. The CCPCC according to claim 31 , wherein the crystalline domains range in size from about 2 nm in nominal dimension to about 200 nm in nominal dimension38. The CCPCC according to claim 31 , wherein the crystalline domains comprises a rare earth metal, a transition metal, an alkali metal, an alkaline earth metal, or a combination thereof.

39. The CCPCC according to claim 38, wherein the crystalline domains comprises calcium, zinc, nickel, lithium, magnesium, titanium, and / or manganese40. The CCPCC according to claim 31 , wherein the crystalline domains comprise a phosphate group, a carbonate group, a sulfate group, or a combination thereof.

41. The CCPCC according to claim 40, wherein the crystalline domains comprises octacalcium phosphate, hydroxyapatite, monetite, brushite, calcium triphosphate, and / or calcium pyrophosphate, and / or hydrates thereof.

42. An assembly of materials, comprises a plurality of CCPCCs according to any of claims 1 to 3.

43. The assembly according to claim 42, wherein at least a portion of the plurality of CCPCCs is in the form of fibers.

44. The assembly according to claim 42, wherein the fibers are assembled into a yarn, a woven textile, a knit textile, a non-woven textile, or a paper45. An assembly of materials, comprising at least one layer of the CCPCC according to any of claims 1 to 3.

46. The CCPCC according to any of claims 1 to 3, wherein the CCPS is a facer paper, and wherein the CCPCC comprises reduced water intrusion of at least about 20%, as measured by the Cobb?2oo test method in accordance with ISO 535, in comparison to an identical CCPS that does not comprise the deposited ceramic.

47. A method of manufacturing a CCPCC, said method comprising:(a) contacting a CCPS with at least one solution that comprises one or more metal salt or metal-organic complex, wherein the solution is at least partially absorbed into the polymer matrix;(b) heating or otherwise ensuring a temperature of the CCPS contacted with the solution in step (a) to a temperature sufficient to remove the solvent from the CCPS, sufficient to drive a ceramic-forming reaction with the one or more metal salt, or sufficient to decompose or react the metal-organic complex, thereby depositing a ceramic to form a CCPCC48. The method of claim 47, further comprising:(c) coating the CCPCC produced in step (b) with one or more functional layer(s) or molecule(s) that imparts or enhances one or more functional property of the CCPCC.

49. The method according to claim 47 or 48, wherein the at least one solution in step (a) further comprises an oxidizing agent, an amine, ammonia, a penetrant, a surfactant, a release agent, or other reactive precursor(s), or a combination thereof50. The method according to claim 49, wherein the amine is a free amine.

51. The method according to claim 47 or 48, wherein the metal salt in step (a) comprises one or more of a transition metal nitrate, a transition metal chloride, a transition metal sulfate, an alkali metal nitrate, an alkaline earth metal nitrate, an alkali metal chloride, an alkaline earth metal chloride, an alkali metal sulfate, and an alkaline earth metal sulfate.

52. The method of claim 47 or 48, wherein, the metal-organic complex in step (a) comprises a metal-amine complex.

53. The method of claim 52, wherein the amine in step (a) comprises a free amine.

54. The method of claim 47 or 48, wherein the heating in step (b) is at a temperature of about 30°C to about 200°C55. The method according to claim 48, wherein the functional layer in step (c) comprises a monolayer with a thickness less than about 5 nm.

56. The method according to claim 55, wherein the monolayer comprises a silane, a siloxane, a phosphonic acid, a phosphonate, a sulfonate, a sulfonic acid, a carboxylic acid, carboxylate, a urethane, a vinyl group, or an acrylate, or a molecule with a head group and a tail group.

57. The method according to claim 56, wherein the In some embodiments, the monolayer comprises a molecule with a head group and a tail group, wherein the head group includes a silane group, a phosphonate group, a phosphonic acid group, a carboxylic acid group, a vinyl group, an alcohol group, a hydroxide group, a thiolate group, a thiol group, and / or an ammonium group, and wherein the tail group includes a hydrocarbon group, a fluorocarbon group, a vinyl group, a phenyl group, an epoxide group, an acrylic group, an acrylate group, a hydroxyl group, a carboxylic acid group, a thiol group, and / or a quaternary ammonium group58. The method according to claim 57, wherein the head group comprises a quaternary ammonium group.

59. The method according to claim 48, wherein the functional layer in step (c) comprises a polymer.60 The method according to claim 59, wherein the polymer comprises a mean thickness less than about 500 nm61. The method according to claim 60, wherein the polymer comprises a crosslinker molecule to improve mechanical and / or chemical properties of the CCPCC.

62. The method according to claim 47, wherein a CCPCC is formed on a first CCPS in steps (a) and (b), wherein the deposited ceramic of the on the first CCPS is in the form of an interconnected nanostructured layer on the first CCPS, and wherein the method further comprises contacting a second substrate with the CCPCC such that at least a portion of the interconnected nanostructured layer is transferred to the second substrate, thereby forming a second substrate-ceramic composite.

63. The method according to claim 62, further comprising coating the second substrate-ceramic composite is coated with one or more functional layer(s) or molecule(s).

64. The method according to claim 62 or 63, wherein the second substrate is contacted with the CCPCC at a pressure in accordance with ASTM D3359.

65. The method according to claim 62 or 63, wherein the second substrate is contacted with the CCPCC by a rolling lamination process or with a heat press at a temperature of about 40°C to about 200°C and a pressure of about 0.1 MPa to about 10 MPa.

66. The method according to claim 62 or 63, wherein greater than about 50% of the interconnected nanostructured layer is transferred to the second substrate.

67. The method according to claim 66, wherein greater than about 50% of the transferred nanostructured layer is contiguous.

68. The method according to claim 66, wherein greater than about 50% of the transferred nanostructured layer remains interconnected.

69. A CCPCC that is produced by a method according to claim 47 or 48.

70. The CCPCC according to any of claims 1 to 3, wherein the polymer matrix comprises pores, wherein the deposited ceramic reduces the mean pore size as measured by capillary flow porometry according to standard test method ASTM D6767 or ASTM F316, by more than 5um, by more than 3um, by more than 2 5um, by more than 2um, by more than 1 ,5um, by more than 1 urn, by more than 0 75um, by more than 0 5um, or by more than 0 25um, in comparison to an identical CCPS that does not comprise the deposited ceramic71. The CCPCC according to any of claims 1 to 3, wherein the CCPCC comprises an increased adhesion strength to a formed and cured gypsum slurry by more than 20%, more than 30%, more than 40%, more than 50%, more than 60%, more than 70%, more than 80%, more than 90%, more than 100%, more than 200%, more than 300%, more than 500%, or more than 1000%, in comparison to an identical CCPS that does not comprise the deposited ceramic.

72. The CCPCC according to claim 71 , wherein the CCPCC comprises a reduced Cobb rating as measured in g / m2equivalent to 90% to 100%, 80% to 90%, 70% to 80%, 60% to 70%, 50% to 60%, or less than 50%, in comparison to an identical CCPS that does not comprise the deposited ceramic.

73. The CCPCC according to any of claims 1 to 3, wherein the CCPCC comprises a mold resistance score according to ASTM 3273 of 5, 6, 7, 8, 9, or 10

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