US20160010283A1 - Enhanced bulk and high strength paper - Google Patents

Enhanced bulk and high strength paper Download PDF

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US20160010283A1
US20160010283A1 US14/745,594 US201514745594A US2016010283A1 US 20160010283 A1 US20160010283 A1 US 20160010283A1 US 201514745594 A US201514745594 A US 201514745594A US 2016010283 A1 US2016010283 A1 US 2016010283A1
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Prior art keywords
fibers
tether
starch
bearing
additive
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Gangadhar Jogikalmath
Andrea Schneider
David S. Soane
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NanoPaper LLC
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NanoPaper LLC
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Assigned to NANOPAPER, LLC reassignment NANOPAPER, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SOANE, DAVID S., JOGIKALMATH, GANGADHAR, SCHNEIDER, ANDREA
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/22—Agents rendering paper porous, absorbent or bulky
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/001—Modification of pulp properties
    • D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/14—Secondary fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/20—Chemically or biochemically modified fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D21H17/29—Starch cationic
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/72—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic material

Definitions

  • This application relates generally to making paper products.
  • High bulk is desirable in many paper and paperboard applications. High bulk is beneficial when same or higher thickness can be achieved by using the same amount of pulp (same basis weight). This is useful particularly in packaging applications where the stiffness of the packaging board is directly proportional to the cube of the thickness of the board. Thus doubling of the bulk or thickness of the board at same weight would increase the stiffness by a factor of eight. Many approaches have been used in the past towards achieveing high bulk. Use of debonding molecules that decrease the hydrogen bonding between fibers increase bulk, as does the use of expandable particles. Debonders make the paper weak, however, while expandable particles are expensive and fragile.
  • the fibers that are used in paper making are refined to increase fiber-fiber contact, thereby increasing the strength of the paper. This is done particularly when softwood (long fibers) and hardwood (stiff short fibers) are mixed to produce paper or paperboard. Hardwood is cheaper than softwood and usually is the predominant fiber in paper because of price and density.
  • the somewhat cylindrical softwood fibers are often refined (i.e., subjected to high shear) to produce flat ribbon-like fibers that have fibrillated surfaces to improve interfiber contacts and bonding among themselves and with the shorter hardwood fibers. Refined fibers also have improved surface properties that allow for a smoother surfaced with decreased pore size.
  • Refining also reduces the bulk of a paper matrix by turning a round reed-like fiber into a flat, ribbon-like structure. These flat fibers attach well to other fibers, yielding dense and strong sheets at the expense of bulk. If unrefined fibers are used in an effort to produce a bulkier paper product, the resulting sheet can be weak and even unusable.
  • High strength is desirable in many paper and paperboard applications, however, and there are many ways to achieve it.
  • One way to achieve this is by manufacturing dense, high-caliper sheets or boards. This requires the use of large amounts of expensive pulp, and produces a heavy product.
  • Another method of creating high strength in paper products is to add starch as sizing.
  • the sizing process uses cooked starch solutions to impart stiffness or strength to the paper.
  • the wet web is first dried to a pre-set moisture content and/or is re-wet to achieve uniform moisture content throughout; then the material is fed into a size press where a high loading of gelatinized starch is applied to the paper surface; then the material is dried again.
  • This process yields a strong paper, but involves a number of downstream processes that can be inefficient. Inefficiencies result from the number of steps involved in preparing the substrate, cooking the starch and applying it to form the finished product. A considerable amount of energy is required for these steps, which adds to the costs of the process.
  • gelatinized starch can be added to the wet end of the papermaking process, but its retention on the pulp fibers is often poor.
  • Such starch granules can gelatinize during the drying process, imparting stiffness and strength to the paper web once it is dry. Adding starch granules in this manner requires lower amounts of energy to dry the paper web, while also eliminating or reducing the use of a size press.
  • the contamination of the whitewater with gelatinized starch leads to increased biological oxygen demand of the effluent, so that the process is environmentally unfavorable.
  • Starch as a bonding agent between the fibers can also be incorporated in the form of ungelatinized starch granules.
  • Ungelatinized starch granules can be added to the wet end of papermaking, but they are poorly retained. Such starch granules can gelatinize during the drying process, imparting strength to the paper web once it is dry. Adding starch granules in this manner requires lower amounts of energy to dry the paper web, while also eliminating or reducing the use of a size press.
  • ungelatinized starch granules can be incorporated as fillers.
  • ungelatinized starch granules do not absorb water like the gelatinized starches, so they can be applied to paper webs that have not been pre-dried. Moreover, the granules once incorporated in the fiber matrix, gelatinize locally thereby acting as internal bonding between fiber joints without adequately impacting the bulking of the paper. To apply ungelatinized starch, these granules can be sprayed on the moving moist web, and gelatinization can be effected in the dryer. This yields an improvement in dry strength and stiffness of the paper. However, the spraying process does not disperse starch uniformly throughout the thickness of the paper, leading to anisotropic stiffness and strength properties.
  • FIG. 1 shows a graph comparing strength with starch loading.
  • FIG. 2 shows a graph comparing strength with starch retention.
  • FIG. 3 shows tensile strength of paper samples.
  • FIG. 4 shows results from hydrophobicity tests on paper samples.
  • FIG. 5 shows a flow chart for a papermaking system.
  • FIG. 6 shows caliper of paper sheets.
  • FIG. 7 shows tensile strength and caliper for paper sheets.
  • systems for papermaking comprising a population of cellulose fibers dispersed in an aqueous solution and complexed with an activator, and a tether-bearing particulate additive, wherein the addition of the tether-bearing particulate additive attaches the additive to the population of cellulose fibers by the interaction of the activator and the tether.
  • a papermaking precursor comprising a population of cellulose fibers in an aqueous solution wherein the population of cellulose fibers is dispersed in the aqueous solution and wherein the cellulose fibers are complexed with an activator, and wherein the aqueous solution further comprises a tether-bearing particulate additive, wherein the tether-bearing particulate additive attaches to the population of cellulose fibers by an interaction between the activator and the tether.
  • the particulate additive can be an organic additive.
  • the organic additive can comprise starch, and the starch can be a cationic starch or a hydrophobic starch.
  • the particulate additive can be an inorganic additive.
  • Also disclosed herein are systems for papermaking comprising a first set of processing stations, wherein a papermaking precursor is formed by combining a population of cellulose fibers dispersed in an aqueous solution and complexed with an activator, and a tether-bearing particulate additive, and wherein the addition of the tether-bearing particulate additive attaches the additive to the population of cellulose fibers by the interaction of the activator and the tether; and a second set of processing stations.
  • the particulate additive can be an organic additive.
  • the organic additive can comprise starch, and the starch can be a cationic starch or a hydrophobic starch.
  • the particulate additive can be an inorganic additive.
  • a paper product comprising activating a population of cellulose fibers with an activator, preparing a tether-bearing particulate additive, wherein the tether-bearing particulate additive comprises a tether capable of interacting with the activator; and adding the tether-bearing particulate additive to the activated population of cellulose fibers, thereby attaching the additive to the fibers by the interaction of the activator and the tether.
  • methods for increasing the strength of a paper product formed from a pulp slurry comprising cellulose fibers, comprising adding an activator polymer to the pulp slurry, forming complexes between the activator polymer and cellulose fibers in the pulp slurry, preparing tether-bearing starch granules, wherein the tether-bearing starch granules comprise a tether polymer capable of interacting with the activator polymer, and adding the tether-bearing starch granules to the pulp slurry, whereby the starch granules are attached to the cellulose fibers by the interaction of the activator polymer and the tether polymer, thereby increasing the strength of the paper product formed from the pulp slurry.
  • Further disclosed herein are paper products manufactured in accordance with these methods.
  • methods for increasing the bulk of a paper product formed from a pulp slurry comprising cellulose fibers, comprising providing a cellulose fiber mixture, forming a slurry comprising the cellulose fiber mixture, adding an activator polymer to the slurry to form an activated mixture comprising activated cellulose fibers, preparing tether-bearing starch granules, wherein the tether-bearing starch granules comprise a tether polymer capable of interacting with the activator polymer, combining the tether-bearing starch granules with the activated fiber mixture, whereby the tether-bearing starch granules affix the activated cellulose fibers to each other, thereby increasing the bulk of the paper product formed therefrom.
  • the cellulose fiber mixture comprises hardwood and softwood fibers.
  • the cellulose fiber mixture comprises refined and unrefined fibers. Further disclosed herein are paper products manufactured in accordance with these methods.
  • Disclosed herein are systems, precursors, and methods for enhancing the attachment of a particulate additive to a fibrous matrix, so that the particles are efficiently and durably attached to the coarser fibrous matrix. Also disclosed herein are processes for manufacturing a paper product by forming a complex between a particulate additive (such as starch) and the fibers. The invention also encompasses paper made by the processes or method described herein or from a precursor described herein.
  • the systems and methods disclosed herein involve three components: activating the fibers as they are dispersed in a solution, attaching a tethering agent to the particulate additive, and adding the tether-bearing particulate additive to the dispersion containing the activated fibers, so that the additive is attached to the fibers by the interaction of the activating agent and the tethering agent.
  • these systems and methods can be used to treat fibers used in papermaking with a cationic polymer of a specific molecular weight and composition as an activator, to treat starch granules with an anionic polymer as a tethering agent, and to combine these separately-treated populations so that the starch granules are attached to the pulp fibers.
  • activation refers to the interaction of an activating material, such as a polymer, with suspended particles or fibers in a liquid medium, such as an aqueous solution.
  • An “Activator polymer” can carry out this activation.
  • high molecular weight polymers can be introduced into the particulate or fibrous dispersion as Activator polymers, so that these polymers interact, or complex, with the dispersed particles or fibers.
  • the polymer-fiber complexes interact with other similar complexes, or with other fibers, and form agglomerates.
  • This “activation” step can function as a pretreatment to prepare the surface of the suspended material (e.g., fibers) for further interactions in the subsequent phases of the disclosed system and methods.
  • the activation step can prepare the surface of the suspended materials to interact with other polymers that have been rationally designed to interact therewith in a subsequent “tethering” step, as described below.
  • an activating material such as a polymer
  • these coated materials can adopt some of the surface properties of the polymer or other coating. This altered surface character in itself can be advantageous for retention, attachment and/or dewatering.
  • activation can be accomplished by chemical modification of the suspended material.
  • oxidants or bases/alkalis can increase the negative surface energy of fibers or particles, and acids can decrease the negative surface energy or even induce a positive surface energy on suspended material.
  • electrochemical oxidation or reduction processes can be used to affect the surface charge on the suspended materials. These chemical modifications can produce activated particulates that have a higher affinity for tethered anchor particles as described below.
  • Suspended materials suitable for modification, or activation can include organic or inorganic particles, or mixtures thereof.
  • Inorganic particles can include one or more materials such as calcium carbonate, dolomite, calcium sulfate, kaolin, talc, titanium dioxide, sand, diatomaceous earth, aluminum hydroxide, silica, other metal oxides and the like.
  • Organic particles can include one or more materials such as starch, modified starch, polymeric spheres (both solid and hollow), carbon based nanoparticles such as carbon nanotubes and the like. Particle sizes can range from a few nanometers to a few hundred microns. In certain embodiments, macroscopic particles in the millimeter range may be suitable.
  • suspended materials may comprise materials such as lignocellulosic material, cellulosic material, minerals, vitreous material, cementitious material, carbonaceous material, plastics, elastomeric materials, and the like.
  • cellulosic and lignocellulosic materials may include wood materials such as wood flakes, wood fibers, wood waste material, wood powder, lignins, wood pulp, or fibers from woody plants.
  • the “activation” step may be performed using flocculants or other polymeric substances.
  • the polymers or flocculants can be charged, including anionic or cationic polymers.
  • anionic polymers can be used, including, for example, olefinic polymers, such as polymers made from polyacrylate, polymethacrylate, partially hydrolyzed polyacrylamide, and salts, esters and copolymers thereof (such as sodium acrylate/acrylamide copolymers), sulfonated polymers, such as sulfonated polystyrene, and salts, esters and copolymers thereof.
  • olefinic polymers such as polymers made from polyacrylate, polymethacrylate, partially hydrolyzed polyacrylamide, and salts, esters and copolymers thereof (such as sodium acrylate/acrylamide copolymers)
  • sulfonated polymers such as sulfonated polystyrene, and salts, esters and copolymers thereof.
  • Suitable polycations include: polyvinylamines, polyallylamines, polydiallyldimethylammoniums (e.g., the chloride salt), branched or linear polyethyleneimine, crosslinked amines (including epichlorohydrin/dimethylamine, and epichlorohydrin/alkylenediamines), quaternary ammonium substituted polymers, such as (acrylamide/dimethylaminoethylacrylate methyl chloride quat) copolymers and trimethylammoniummethylene-substituted polystyrene, and the like.
  • polyvinylamines polyallylamines
  • polydiallyldimethylammoniums e.g., the chloride salt
  • branched or linear polyethyleneimine branched or linear polyethyleneimine
  • crosslinked amines including epichlorohydrin/dimethylamine, and epichlorohydrin/alkylenediamines
  • Nonionic polymers suitable for hydrogen bonding interactions can include polyethylene oxide, polypropylene oxide, polyhydroxyethylacrylate, polyhydroxyethylmethacrylate, and the like.
  • an activator such as polyethylene oxide can be used as an activator with a cationic tethering material in accordance with the description of tethering materials below.
  • activator polymers with hydrophobic modifications can be used. Flocculants such as those sold under the trademark MAGNAFLOC® by Ciba Specialty Chemicals can be used.
  • activators such as polymers or copolymers containing carboxylate, sulfonate, phosphonate, or hydroxamate groups can be used. These groups can be incorporated in the polymer as manufactured, alternatively they can be produced by neutralization of the corresponding acid groups, or generated by hydrolysis of a precursor such as an ester, amide, anhydride, or nitrile group. The neutralization or hydrolysis step could be done on site prior to the point of use, or it could occur in situ in the process stream.
  • the activated suspended material can also be an amine functionalized or modified material.
  • modified material can include any material that has been modified by the attachment of one or more amine functional groups as described herein.
  • the functional group on the surface of the suspended material can be from modification using a multifunctional coupling agent or a polymer.
  • the multifunctional coupling agent can be an amino silane coupling agent as an example. These molecules can bond to a material's surface and then present their amine group for interaction with the particulate matter.
  • the polymer on the surface of a suspended fiber or particle can be covalently bound to the surface or interact with the surface of the particle and/or fiber using any number of other forces such as electrostatic, hydrophobic, or hydrogen bonding interactions.
  • a multifunctional coupling agent can be used such as a silane coupling agent. Suitable coupling agents include isocyano silanes and epoxy silanes as examples.
  • a polyamine can then react with an isocyano silane or epoxy silane for example.
  • Polyamines include polyallyl amine, polyvinyl amine, chitosan, and polyethylenimine.
  • polyamines can also self-assemble onto the surface of the suspended particles or fibers to functionalize them without the need of a coupling agent.
  • polyamines can self-assemble onto the surface of the particles or fibers through electrostatic interactions. They can also be precipitated onto the surface in the case of chitosan for example. Since chitosan is soluble in acidic aqueous conditions, it can be precipitated onto the surface of suspended material by adding a chitosan solution to the suspended material at a low pH and then raising the solution pH.
  • the amines or a majority of amines are charged. Some polyamines, such as quarternary amines are fully charged regardless of the pH. Other amines can be charged or uncharged depending on the environment.
  • the polyamines can be charged after addition onto the suspended particles or fibers by treating them with an acid solution to protonate the amines.
  • the acid solution can be non-aqueous to prevent the polyamine from going back into solution in the case where it is not covalently attached to the particle or fiber.
  • the polymers or particles can complex via forming one or more ionic bonds, covalent bonds, hydrogen bonding and combinations thereof, for example. Ionic complexing is preferred.
  • the activator could be introduced into a liquid medium through several different means.
  • a large mixing tank could be used to mix an activating material with fine particulate materials.
  • Activated particles or fibers are produced that can be treated with one or more subsequent steps of attachment to tether-bearing anchor particles.
  • tethering refers to an interaction between an activated suspended particle or fiber and an anchor particle (as described below).
  • the anchor particle can be treated or coated with a tethering material.
  • the tethering material such as a polymer, forms a complex or coating on the surface of the anchor particles such that the tethered anchor particles have an affinity for the activated suspended material.
  • the selection of tether and activator materials is intended to make the two solids streams complementary so that the activated particles or fibers in the suspension become tethered, linked or otherwise attached to the anchor particle.
  • the tethering material acts as a complexing agent to affix the activated particles or fibers to an anchor material.
  • a tethering material can be any type of material that interacts strongly with the activating material and that is connectable to an anchor particle.
  • an anchor particle may comprise materials such as lignocellulosic material, cellulosic material, minerals, vitreous material, cementitious material, carbonaceous material, plastics, elastomeric materials, and the like.
  • cellulosic and lignocellulosic materials may include wood materials such as wood flakes, wood fibers, wood waste material, wood powder, lignins, or fibers from woody plants.
  • inorganic particles useful as anchor particles include clays such as attapulgite and bentonite.
  • the inorganic compounds can be vitreous materials, such as ceramic particles, glass, fly ash, PCC, GCC, chalk, TiO 2 , silica, bentonite, kaolin, talc, and the like.
  • the anchor particles may be solid or may be partially or completely hollow.
  • glass or ceramic microspheres may be used as particles.
  • Vitreous materials such as glass or ceramic may also be formed as fibers to be used as particles.
  • Cementitious materials may include gypsum, Portland cement, blast furnace cement, alumina cement, silica cement, and the like.
  • Carbonaceous materials may include carbon black, graphite, carbon fibers, carbon microparticles, and carbon nanoparticles, for example carbon nanotubes.
  • plastic materials may be used as anchor particles. Both thermoset and thermoplastic resins may be used to form plastic particles.
  • Plastic particles may be shaped as solid bodies, hollow bodies or fibers, or any other suitable shape.
  • Plastic particles can be formed from a variety of polymers.
  • a polymer useful as a plastic particle may be a homopolymer or a copolymer. Copolymers can include block copolymers, graft copolymers, and interpolymers.
  • suitable plastics may include, for example, addition polymers (e.g., polymers of ethylenically unsaturated monomers), polyesters, polyurethanes, aramid resins, acetal resins, formaldehyde resins, and the like.
  • Addition polymers can include, for example, polyolefins, polystyrene, and vinyl polymers.
  • Polyolefins can include, in embodiments, polymers prepared from C 2 -C 10 olefin monomers, e.g., ethylene, propylene, butylene, dicyclopentadiene, and the like.
  • poly(vinyl chloride) polymers, acrylonitrile polymers, and the like can be used.
  • useful polymers for the formation of particles may be formed by condensation reaction of a polyhydric compound (e.g., an alkylene glycol, a polyether alcohol, or the like) with one or more polycarboxylic acids.
  • Polyethylene terephthalate is an example of a suitable polyester resin.
  • Polyurethane resins can include, e.g., polyether polyurethanes and polyester polyurethanes. Plastics may also be obtained for these uses from waste plastic, such as post-consumer waste including plastic bags, containers, bottles made of high density polyethylene, polyethylene grocery store bags, and the like.
  • plastic particles for anchor particles can be formed as expandable polymeric pellets.
  • Such pellets may have any geometry useful for the specific application, whether spherical, cylindrical, ovoid, or irregular.
  • Expandable pellets may be pre-expanded before using them. Pre-expansion can take place by heating the pellets to a temperature above their softening point until they deform and foam to produce a loose composition having a specific density and bulk. After pre-expansion, the particles may be molded into a particular shape and size. For example, they may be heated with steam to cause them to fuse together into a lightweight cellular material with a size and shape conforming to the mold cavity. Expanded pellets may be 2-4 times larger than unexpanded pellets.
  • expandable polymeric pellets may be formed from polystyrenes and polyolefins. Expandable pellets are available in a variety of unexpanded particle sizes. Pellet sizes, measured along the pellet's longest axis, on a weight average basis, can range from about 0.1 to 6 mm.
  • the expandable pellets may be formed by polymerizing the pellet material in an aqueous suspension in the presence of one or more expanding agents, or by adding the expanding agent to an aqueous suspension of finely subdivided particles of the material.
  • An expanding agent also called a “blowing agent,” is a gas or liquid that does not dissolve the expandable polymer and which boils below the softening point of the polymer. Blowing agents can include lower alkanes and halogenated lower alkanes, e.g., propane, butane, pentane, cyclopentane, hexane, cyclohexane, dichlorodifluoromethane, and trifluorochloromethane, and the like.
  • elastomeric materials can be used as particles. Particles of natural or synthetic rubber can be used, for example.
  • various interactions such as electrostatic, hydrogen bonding or hydrophobic behavior can be used to affix an activated complex to a tethering material complexed with an anchor particle.
  • an anchor particle can be selected from any particulate matter that is desirably attached to cellulose fibers in the final paper product.
  • the tether-bearing anchor particle comprising the desirable additive can then interact with the activated cellulose fibers in the wet paper stream.
  • starch granules can be used as an anchor particle to be attached to the cellulose fibers, as is described in more detail below.
  • organic and inorganic particulate matter can be attached to celluose fibers to achieve desired properties.
  • inorganic materials like calcium carbonate, dolomite, calcium sulfate, kaolin, talc, titanium dioxide, sand, diatomaceous earth, aluminum hydroxide, silica, various other metal oxides, and the like, can be used as anchor particles in accordance with these systems and methods.
  • organic particles such as starch, modified starch, polymeric spheres (both solid and hollow), carbon based nanoparticles such as carbon nanotubes and the like, can be used as anchor particles in accordance with these systems and methods.
  • polymers such as linear or branched polyethyleneimine can be used as tethering materials. It would be understood that other anionic or cationic polymers could be used as tethering agents, for example polydiallyldimethylammonium chloride (poly(DADMAC)).
  • cationic tethering agents such as epichlorohydrin dimethylamine (epi/DMA), styrene maleic anhydride imide (SMAI), polyethylene imide (PEI), polyvinylamine, polyallylamine, amine-aldehyde condensates, poly(dimethylaminoethyl acrylate methyl chloride quaternary) polymers and the like can be used.
  • cationic polymers useful as tethering agents can include quaternary ammonium or phosphonium groups.
  • polymers with quaternary ammonium groups such as poly(DADMAC) or epi/DMA can be used as tethering agents.
  • polyvalent metal salts e.g., calcium, magnesium, aluminum, iron salts, and the like
  • cationic surfactants such as dimethyldialkyl(C8-C22)ammonium halides, alkyl(C8-C22)trimethylammonium halides, alkyl(C8-C22)dimethylbenzylammonium halides, cetyl pyridinium chloride, fatty amines, protonated or quaternized fatty amines, fatty amides and alkyl phosphonium compounds can be used as tethering agents.
  • polymers having hydrophobic modifications can be used as tethering agents.
  • a tethering material can depend on the activating material.
  • a high affinity between the tethering material and the activating material can lead to a strong and/or rapid interaction there between.
  • a suitable choice for tether material is one that can remain bound to the anchor surface, but can impart surface properties that are beneficial to a strong complex formation with the activator polymer.
  • a polyanionic activator can be matched with a polycationic tether material or a polycationic activator can be matched with a polyanionic tether material.
  • a poly(sodium acrylate-co-acrylamide) activator is matched with a chitosan tether material.
  • a hydrogen bond donor should be used in conjunction with a hydrogen bond acceptor.
  • the tether material can be complementary to the chosen activator, and both materials can possess a strong affinity to their respective deposition surfaces while retaining this surface property.
  • cationic-anionic interactions can be arranged between activated suspended materials and tether-bearing anchor particles.
  • the activator may be a cationic or an anionic material, as long as it has an affinity for the suspended material to which it attaches.
  • the complementary tethering material can be selected to have affinity for the specific anchor particles being used in the system.
  • hydrophobic interactions can be employed in the activation-tethering system.
  • tether-bearing anchor particles could be designed to complex with a specific type of activated particulate matter.
  • the systems and methods disclosed herein could be used for complexing with organic waste particles, for example.
  • Other activation-tethering-anchoring systems may be envisioned for removal of suspended particulate matter in fluid streams, including gaseous streams.
  • the complexes formed from the anchor particles and the activated fibrous matter can form a homogeneous part of a fibrous product like paper.
  • the interactions between the activated suspended fibers and the tether-bearing anchor particles can enhance the mechanical properties of the complex that they form.
  • an activated suspended material can be durably bound to one or more tether-bearing anchor particles, so that the tether-bearing anchor particles do not segregate or move from their position on the fibers.
  • Increased compatibility of the activated fine materials with a denser (anchor) matrix modified with the appropriate tether polymer can lead to further mechanical stability of the resulting composite material.
  • cationic and anionic polymers for activators and tethering agents can be selected from a wide variety of available polymers, as described above.
  • Starch granules or other desirable particles can be selected as anchor particles, where their attachment to pulp fibers would be advantageous.
  • desirable particles include, but are not limited to inorganic and organic anchor particles such as have been described above (e.g., for inorganic materials, calcium carbonate, dolomite, calcium sulfate, kaolin, talc, titanium dioxide, sand, diatomaceous earth, aluminum hydroxide, silica, various other metal oxides and the like, and for organic materials, starch, modified starch, polymeric spheres (both solid and hollow), carbon based nanoparticles such as carbon nanotubes and the like).
  • inorganic and organic anchor particles such as have been described above (e.g., for inorganic materials, calcium carbonate, dolomite, calcium sulfate, kaolin, talc, titanium dioxide, sand, diatomaceous earth, aluminum hydroxide, silica, various other metal oxides and the like, and for organic materials, starch, modified starch, polymeric spheres (both solid and hollow), carbon based nanoparticles such as carbon nanotubes and the like).
  • starch granules When starch granules are used as anchor particles for attachment to cellulose fibers, they can be used in their native state, or they can be modified with short amine side-groups, with amine polymers, or with hydrophobic side groups (each a “modified starch”). The presence of amines on the surface of the starch granules can help in attaching an anionic tethering polymer.
  • cationic polymers can be used for activating the cellulose fibers.
  • the polycation can be linked to the fiber surface using a coupling agent, for example a bifunctional crosslinking agent such as a carbonyldiimidazole or a silane, or the polyamine can self-assemble onto the surface of the cellulose fiber through electrostatic, hydrogen bonding, or hydrophobic interactions.
  • the polyamine can spontaneously self-assemble onto the fiber surface or it can be precipitated onto the surface.
  • chitosan can be precipitated on the surface of the cellulose fibers to activate them.
  • chitosan is soluble only in an acidic solution, it can be added to a cellulose fiber dispersion at an acidic pH, and then can be precipitated onto the surface of the cellulose fibers by slowly adding base to the dispersion until chitosan is no longer soluble.
  • a difunctional crosslinking agent can be used to attach the polycation to the fiber, by reacting with both the polycation and the fiber.
  • a polycation such as a polyamine can be added directly to the fiber dispersion or slurry.
  • the addition level of the polycation can be between about 0.01% to 5.0% (based on the weight of the fiber), e.g., between 0.1% to 2%.
  • a separately treated population of tether-bearing starch granules can be mixed in thereafter, resulting in the attachment of the starch granules to the cellulose fibers by the interaction of the activator polymer and the tether polymer.
  • Starch granules can be treated with a variety of anionic polymers, such as anionic polyacrylamide, which then act as tethers.
  • Starch that is to be treated in accordance with these systems and methods can be further derivatized or coated with moieties that impart desirable properties, e.g., hydrophobicity, oleophobicity or both. Starches thus modified may be also termed “modified starches.”
  • Preferred oil resistant coating formulations are aqueous solutions of cellulose derivatives such as methylcellulose, ethyl cellulose, propyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, ethylhydroxypropyl cellulose, and ethylhydroxyethyl cellulose, cellulose acetate butyrate, which may further comprise polyvinyl alcohol and/or its derivatives.
  • Another group of preferred oil resistant coating compositions are latex emulsions such as the emulsions of polystyrene, styrene-acrylonitrile copolymer, carboxylated styrene-butadiene copolymer, ethylene-vinyl chloride copolymer, styrene-acrylic copolymer, polyvinyl acetate, ethylene-vinyl acetate copolymer, and vinyl acetate-acrylic copolymer.
  • the starch granule thus coated with grease resistant formulations could be attached to the activated pulp fibers via tethering, such that the surface segregation of the starch granule will modify the surface of the paper product.
  • the presence of hydrophobic starch also improves the hydrophobicity of the resulting paper without needing an internal sizing such as alkyl succinic anhydride (ASA), alkyl ketene dimer (AKD) or Rosin.
  • ASA alkyl succinic anhydride
  • ALD alkyl ketene dimer
  • Rosin Rosin.
  • the gelatinized hydrophobic starch sizes the entire thickness of the paper. This property is useful in reducing the coating requirements in making coated sheets. The coating applied using a roller or a metering bar or any such methods, would remain on the surface of the paper and not impregnate the bulk of the paper thus needing less coating to achieve the same amount of gloss and surface finish.
  • the addition of a coating agent to the starch can improve its mechanical properties such as bending stiffness or tensile strength, or could improve its optical properties (e.g., TiO2 nanoparticles bound to starch).
  • paper products refers to a product made from natural cellulose fibers, such as hardwood, softwood or recycled fibers.
  • certain paper products for packaging applications can be made from recycled fibers, e.g., cardboard and corrugated board.
  • These packaging products need a combination of bulk and stiffness to effective during stacked storage and shipment.
  • the recycling process truncates the length of the fibers and reduces both the bulk and strength.
  • One way to improve strength is by refining the recycled fibers which further reduces bulk. Bulking with stiffness improvement also allows for reducing packaging weight by using less fibers to attain a required bulk and stiffness.
  • Recycled fibers can be derived from hardwood could be made from both hardwood and softwood depending on the source of the paper product.
  • papermaking refers to the formation of a paper product using hardwood fibers, softwood fibers, recycled fibers or any combination thereof.
  • cellulose mixture refers to any mixture of natural cellulose fibers, whether hardwood, softwood or recycled.
  • a “papermaking precursor” is a solution or mixture comprising cellulose fibers, wherein the solution or mixture has not been subjected to complete drying.
  • an exemplary papermaking system 100 can involve a number of processing stations, 102 , 104 , 108 , 110 , 112 , 114 , 118 , 120 , and 122 .
  • a pulp mill 102 wood chips are broken down mechanically or chemically, and may be bleached.
  • the pulp-based components are repulped in a pulp mill 102 .
  • Additives may be added to the pulp stream as it exits the pulp mill 102 , as shown at Point C.
  • the processed pulp can then proceed to a refiner 104 , where the pulp is mechanically treated to increase surface area of fibers, thereby increasing bonding between fibers, resulting in flatter, denser pulp fibers.
  • Additives may be added to the pulp stream as it exits the refiner 104 , as shown at Point A.
  • the pulp stream can then proceed to a machine chest 108 , where the pulp comes into contact with certain chemicals used in papermaking.
  • This processing station 108 is where multi-stream pulps can meet and become admixed (e.g., hardwood and softwood pulp).
  • Additives may be added to the pulp stream as it exits the machine chest, as shown at Point B.
  • the pulp stream can then proceed to the headbox 110 , where the pulp can be diluted further and released from the headbox onto the forming wire.
  • the first set of processing stations 102 - 110 comprise the wet end of a papermaking system or machine.
  • the pulp stream can then proceed to a second set of processing stations for forming the paper sheet.
  • These processing stations can include a vacuum section 112 , a press section 114 , a first drying section 118 , a size press 120 , and a second drying section 122 .
  • the fiber web can be drained by gravity and then by high vacuum to about 10-15% solids.
  • the fiber web can then proceed to a press section 114 , where the formed fiber web can be pressed through high-pressure rollers to a consistency of about 20-25% solids.
  • the wet paper web can then proceed to a first drying section 118 , where the wet paper web can make contact with steam-heated dryers that contact-dry the sheet up to 98% solids.
  • the paper sheet can then proceed to a size press 120 , where gelatinized starch and other chemicals can be applied to the surface of the paper.
  • the paper sheet can then proceed to a second drying section 122 , where a second set of dryers dry the sheet after it has been wetted in the size press 120 .
  • additives can be added at Points A, B, and/or C to improve the quality of paper product emerging from a papermaking system 100 .
  • a pulp product combined with the activator polymer and tether-bearing anchor particles as described below is a specific example of a “papermaking precursor.”
  • an activator polymer can be added at Point A, and tether-bearing anchor particles comprising a desirable additive (e.g., a starch) can be added at Point B.
  • a desirable additive e.g., a starch
  • an activator polymer can be added to a softwood stream only at Point A, which can then be admixed with a second stream (e.g., a hardwood stream) in the machine chest 108 or comparable component of the papermaking system 100 .
  • tether-bearing anchor particles comprising a desirable additive can be added at Point B.
  • an activator polymer can be added to a hardwood stream only at Point A, which can then be admixed with a second stream (e.g., a softwood stream) in the machine chest 108 or comparable component of the papermaking system 100 .
  • tether-bearing anchor particles comprising a desirable additive e.g., a starch
  • an activator polymer can be added to a hardwood stream at Point C, and the activated stream proceeds through the refiner 104 ; this activated hardwood stream can be admixed with a second stream (e.g., a softwood stream) in the machine chest 108 or comparable component of the papermaking system 100 .
  • tether-bearing anchor particles comprising a desirable additive (e.g., a starch) can be added at Point B.
  • an activator polymer can be added to a softwood stream at Point C, and the activated stream proceeds through the refiner 104 ; this activated softwood stream can be admixed with a second stream (e.g., a hardwood stream) in the machine chest 108 or comparable component of the papermaking system 100 .
  • tether-bearing anchor particles comprising a desirable additive (e.g., a starch) can be added at Point B, or at Point A.
  • an activator polymer can be added to a hardwood stream at Point C, and the activated stream proceeds through the refiner 104 ; this activated hardwood stream can be admixed with a second stream (e.g., a softwood stream) in the machine chest 108 or comparable component of the papermaking system 100 .
  • tether-bearing anchor particles comprising a desirable additive e.g., a starch
  • an activator polymer can be added at Point C, and the activated stream proceeds through the refiner 104 .
  • tether-bearing anchor particles comprising a desirable additive e.g., a starch
  • a combination of hardwood and softwood fibers in a pulp mixture may be desirable, and that a combination of refined and unrefined fibers (either hardwood or softwood) may be desirable.
  • unrefined fibers offer bulk and refined fibers offer strength in the final paper sheet.
  • a cellulose fiber mixture containing between about 10% and about 90% hardwood can be used.
  • a cellulose fiber mixture containing between about 40% and about 80% hardwood can be used.
  • a cellulose fiber mixture containing between about 60% and about 80% hardwood can be used, or between about 65% and about 75%.
  • a cellulose fiber mixture containing between about 5% and about 75% unrefined fibers can be used. In other embodiments, a cellulose fiber mixture containing between about 20% and about 60% unrefined fibers can be used. In other embodiments, a cellulose fiber mixture containing between about 30% and about 50% unrefined fibers can be used.
  • a 0.5% slurry was prepared by blending 3.5% by weight softwood and hardwood pulp mixture (in the ratio of 20:80) in water.
  • a 0.5% slurry was prepared by blending 3.1% recycled deinked pulp in water.
  • Handsheets were prepared using a Mark V Dynamic Paper Chemistry Jar and Hand-Sheet Mold from Paper Chemistry Laboratory, Inc. (Larchmont, N.Y.). Handsheets were prepared without addition of polymers as controls, using the control pulps as described in Example 1 and 2. Handsheets were prepared with the addition of polymers as experimental samples, as described below. For preparing each experimental handsheet, the appropriate volume of 0.5% pulp slurry prepared in accordance with Examples 1 or 2 (as applicable) was activated with up to 2% of the selected polymer(s) (based on dry weight), as described below in more detail. Polymer additions were performed at 5 minute intervals.
  • This polymer-containing slurry was diluted with up to 2 L of water and added to the handsheet maker, where it was mixed at a rate of 1100 RPM for 5 seconds, 700 RPM for 5 seconds, and 400 RPM for 5 seconds. The water was then drained off. The subsequent sheet was then transferred off of the wire, pressed and dried.
  • Sta Lok 356 or Filmkote starches were dispersed in water such that the solids content was about 20 to 25% to get a slurry of cationic and hydrophobic starches respectively.
  • 1% by weight of anionic polyacrylamide magnafloc LT30 was used as the tethering agent.
  • Starch retention was determined by first analyzing the effluent created after making the handsheets in Example 6. A piece of VWR Grade 413 filter paper with 5 ⁇ m particle retention was initially dried in an oven at 110 C to remove any moisture and then weighed. The effluent from the handsheet preparation carried out in Example 5 was then filtered through the paper using vacuum filtration. The filter paper was dried again at 110° C. to remove any moisture, and was weighed to determine the lost solids from the handsheet. These solids included the fines from the papermaking process and starch granules. To normalize for only the starch contribution to the effluent, a control experiment was run using the effluent from the preparation of a control pulp using the activator polymer but no starch addition. The filtered solid content in the control effluent was subtracted from the filtered solid content in the starch-bearing effluent, to yield the amount of starch therein. This amount was used to determine the starch retention of the pulp in Example 6.
  • Example 6 Samples were prepared as in Example 6, where the amount of tether-bearing starch (Sta Lok 356) starch ranged from 0.18 g to 2.0 g, i.e., initial loadings of 4% to 33% of the solids weight.
  • the tether-bearing starch was prepared in accordance with Example 5. Samples were made both with activator and tether and without either activator or tether.
  • the tether used on the starch was 1% MagnaFloc LT30 by solids and the activator on the pulp was 1% polyDADMAC by solids.
  • Starch retention was measured as set forth in Example 7, and the max load for each sample was measured using an Instron as in Example 4.
  • FIG. 1 shows the strength improvement with starch loading with and without the ATA process chemistry.
  • the starch granule retention was >98%.
  • ATA a greater amount of starch can be attached effectively to the cellulose, progressively increasing strength as shown in FIG. 1 .
  • the amount of ATA-bound starch increases, it yields a maximum benefit in strength, which then decreases at higher loadings. It is hypothesized that the higher loadings beyond the maximum exceed the capacity of the hydrogen bonding network of the cellulose fibers.
  • Example 6 Samples were prepared as in Example 6 with tether-bearing Sta Lok 356 starch. Starch retention was measured as set forth in Example 7, and the tensile strength for each sample was measured using an Instron as in Example 4. As set forth in Table 2, certain of the samples were treated with polyDADMAC as activator in concentrations of 1% by solids, and with MagnaFloc LT30 as the tethering agent attached to the starch in concentrations of 1% by solids all in accordance with Example 6. These samples are designated as ATA Process samples in the table below (Table 2).
  • Graph 2 ( FIG. 2 ) illustrates the effect of starch retention on the strength of the paper.
  • Graph 2 compares the difference between strength of the handsheets made with the ATA Process compared to handsheets that have not been treated with any polymer addition.
  • Recycled fibers are relatively weak due to fiber length reduction during fiber recovery and processing.
  • the ATA process is applied to improve the strength of handsheets made from recycled fibers by incorporating starch within the fibrous web.
  • a recycled pulp slurry prepared in accordance with Example 3 was treated in accordance with Example 6, using Filmkote hydrophobic starches as tether-bearing starches. Filmkote starches of varying degrees of hydrophobicity were used, as set forth in Graph 3 ( FIG. 3 ).
  • the starch Filmkote 550 is more hydrophobic than Filmkote 54 .
  • the tensile strength of the paper samples was measured as set forth in Example 4.
  • the ATA process as applied to recycled paper improved the strength of the paper samples by amounts from about 25-40%.
  • hydrophobicity was tested by depositing a 15 microliter water droplet on the surface of the paper and recording the time for the droplet to completely absorbed by the paper. The results of the hydrophobicity tests are shown in Graph 4 ( FIG. 4 ). These results demonstrate that the use of the ATA process to attach hydrophobic starches to recycled pulp fibers improves the water resistance of the paper by nearly 500% compared to control samples having no added no starch.
  • a 0.3% slurry was prepared by blending 14% by weight unrefined softwood and hardwood pulp mixture (in the ratio of 30:70) in water.
  • a 0.3% slurry was prepared by blending 3.5% by weight refined softwood and hardwood pulp mixture (in the ratio of 30:70) in water.
  • Handsheets were prepared using a Mark V Dynamic Paper Chemistry Jar and Hand-Sheet Mold from Paper Chemistry Laboratory, Inc. (Larchmont, N.Y.). Handsheets were prepared without addition of polymers as controls, using the control pulps as described in Examples 14 and 15 and mixtures of the two. Handsheets were prepared with the addition of polymers as experimental samples, as described below. For preparing each experimental handsheet, the appropriate volume of 0.3% pulp slurry prepared in accordance with Examples 13 or 14 or mixtures of the two (as applicable) was activated with up to 2% of the selected polymer(s) (based on dry weight), as described below in more detail. Polymer additions were performed at 5 minute intervals.
  • This polymer-containing slurry was diluted with up to 2 L of water and added to the handsheet maker, where it was mixed at a rate of 1100 RPM for 5 seconds, 700 RPM for 5 seconds, and 400 RPM for 5 seconds. The water was then drained off. The subsequent sheet was then transferred off of the wire, pressed and dried.
  • Penford Douglas Pearl starch were dispersed in water such that the solids content was about 20 to 25%. 1% by weight of anionic polyacrylamide Magnafloc 919 was used as the tethering agent.
  • Handsheets prepared in Example 17 were each cut into strips and stacked to measure the caliper of 10 ⁇ that of a single handsheet.
  • the calipers were normalized by basis weight and compared to one another in Table 3 below. These results are also shown in FIG. 6 .
  • the data illustrated in FIG. 7 show the results of tensile strength measurements and bulk measurements conducted on handsheet samples prepared with a mixture of 70% unrefined and 30% refined fiber mixture with and without starch granule addition of 8% by weight of the fibers and with and without the use of anchor-tether chemistry.
  • the results demonstrate that the ATA chemistry enhances the strength of the handsheets made with a mixture of refined and unrefined fibers compared to 100% unrefined fiber sheet and the one made without ATA chemistry.
  • the strength is comparable to the sheet made with 100% refined fibers while showing an effective bulk increase of ⁇ 10%.

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US20160039985A1 (en) * 2013-03-28 2016-02-11 Siemens Aktiengesellschaft Cellulose material having impregnation and use of the cellulose material
WO2018140251A1 (fr) * 2017-01-26 2018-08-02 Kimberly-Clark Worldwide, Inc. Fibres traitées et structures fibreuses les comprenant
US12516472B2 (en) 2020-09-09 2026-01-06 Westrock Mwv, Llc Pulping methods, methods for manufacturing paperboard, and paperboard structures

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US10669675B2 (en) 2015-10-16 2020-06-02 General Mills, Inc. Paperboard product

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US3298902A (en) * 1964-06-26 1967-01-17 Chemirad Corp Process of forming cellulosic paper containing tris-(1-aziridinyl) phosphine oxide and polyethylene imine and paper thereof
US5049235A (en) * 1989-12-28 1991-09-17 The Procter & Gamble Company Poly(methyl vinyl ether-co-maleate) and polyol modified cellulostic fiber
WO2006084883A1 (fr) * 2005-02-10 2006-08-17 Stora Enso Ab Carton de grande qualite et produits fabriques a partir de celui-ci
US7842162B1 (en) * 2005-03-14 2010-11-30 Louisiana Tech University Foundation, Inc. Layer-by-layer nanocoating for paper fabrication
EP1918456A1 (fr) * 2006-10-31 2008-05-07 M-real Oyj Procédé de fabrication d'une feuille fibreuse contenant des charges
EP2246472A1 (fr) * 2009-03-24 2010-11-03 Mondi Limited South Africa Procédé pour la préparation de particules de gel de polysaccharides et fourniture de pâte pour la fabrication de papier
US8980059B2 (en) * 2009-08-12 2015-03-17 Nanopaper, Llc High strength paper

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US20160039985A1 (en) * 2013-03-28 2016-02-11 Siemens Aktiengesellschaft Cellulose material having impregnation and use of the cellulose material
US9718934B2 (en) * 2013-03-28 2017-08-01 Siemens Aktiengesellschaft Cellulose material having impregnation and use of the cellulose material
WO2018140251A1 (fr) * 2017-01-26 2018-08-02 Kimberly-Clark Worldwide, Inc. Fibres traitées et structures fibreuses les comprenant
US10487452B1 (en) 2017-01-26 2019-11-26 Kimberly-Clark Worldwide, Inc. Treated fibers and fibrous structures comprising the same
US10563355B1 (en) 2017-01-26 2020-02-18 Kimberly-Clark Worldwide, Inc. Treated fibers and fibrous structures comprising the same
US12516472B2 (en) 2020-09-09 2026-01-06 Westrock Mwv, Llc Pulping methods, methods for manufacturing paperboard, and paperboard structures

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