SE546066C2 - Preparation of a cellulose foam comprising discrete units of foam embedded in a foam matrix - Google Patents

Preparation of a cellulose foam comprising discrete units of foam embedded in a foam matrix

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Publication number
SE546066C2
SE546066C2 SE2230301A SE2230301A SE546066C2 SE 546066 C2 SE546066 C2 SE 546066C2 SE 2230301 A SE2230301 A SE 2230301A SE 2230301 A SE2230301 A SE 2230301A SE 546066 C2 SE546066 C2 SE 546066C2
Authority
SE
Sweden
Prior art keywords
foam
discrete units
wet
cellulose
solid
Prior art date
Application number
SE2230301A
Other languages
Swedish (sv)
Other versions
SE2230301A1 (en
Inventor
Torron Daniel Hult
Martin Sterner
Oruç Köklükaya
Original Assignee
Stora Enso Oyj
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Stora Enso Oyj filed Critical Stora Enso Oyj
Priority to SE2230301A priority Critical patent/SE546066C2/en
Priority to PCT/IB2022/062666 priority patent/WO2023119215A1/en
Publication of SE2230301A1 publication Critical patent/SE2230301A1/en
Publication of SE546066C2 publication Critical patent/SE546066C2/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/30Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01GHORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G24/00Growth substrates; Culture media; Apparatus or methods therefor
    • A01G24/20Growth substrates; Culture media; Apparatus or methods therefor based on or containing natural organic material
    • A01G24/22Growth substrates; Culture media; Apparatus or methods therefor based on or containing natural organic material containing plant material
    • A01G24/27Pulp, e.g. bagasse
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01GHORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
    • A01G24/00Growth substrates; Culture media; Apparatus or methods therefor
    • A01G24/40Growth substrates; Culture media; Apparatus or methods therefor characterised by their structure
    • A01G24/48Growth substrates; Culture media; Apparatus or methods therefor characterised by their structure containing foam or presenting a foam structure
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B29C44/12Incorporating or moulding on preformed parts, e.g. inserts or reinforcements
    • B29C44/1285Incorporating or moulding on preformed parts, e.g. inserts or reinforcements the preformed part being foamed
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/065Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21FPAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F11/00Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines
    • D21F11/002Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines by using a foamed suspension
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00Foam properties
    • C08G2110/0041Foam properties having specified density
    • C08G2110/005< 50kg/m3
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00Foams characterised by the foaming process
    • C08J2201/04Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/05Elimination by evaporation or heat degradation of a liquid phase
    • C08J2201/0504Elimination by evaporation or heat degradation of a liquid phase the liquid phase being aqueous
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00Foams characterised by their properties
    • C08J2205/10Rigid foams
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02Cellulose; Modified cellulose

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

ABSTRACT The present invention relates to a method for the preparation of a solid foam, wherein the method comprises depositing discrete units of a foam on a surface to obtain a first foam deposition, followed by depositing a wet foam between the discrete units to obtain a subsequent foam deposition, and drying the wet foam. The width of a discrete units is less than 1.3 times its height. The invention further relates to a solid foam comprising discrete units of foam embedded in a foam matrix.

Description

The present invention relates to a method for the preparation of a solid foam, wherein the method comprises depositing discrete units of a foam on a surface to obtain a first deposition, followed by depositing a wet foam between the discrete units to obtain a subsequent deposition, and drying the wet foam to obtain a solid foam wherein discrete units of a foam are embedded in a foam matrix. The invention further relates to the solid foam comprising discrete units of foam embedded in a foam matrix. The width of each discrete unit is less than 1.3 times its height.
TECHNICAL BACKGROUND Today different techniques are used to deposit wet foam material and produce low- density thick foam materials. ln WO2020011587 A1 a porous material of cellulose fibres and gluten is prepared by depositing at once an aerated wet foam of cellulose fibres and gluten in a mould, followed by drying, to obtain a dried porous material with the shape of the mould and a homogeneous fibre network through the whole bulk. ln WO2015036659 A1 a wet fibrous foam is fed into a mould, where part of the water contained in the foam is mechanically withdrawn to produce a solidified, moist fibrous composition, and evaporating water to produce a dry fibrous product. These techniques are similar in that the final foam sheet might present a densified layer on the faces of the sheet, while the core of the foam sheet is a homogeneous fibre network of lower density.
Collapse of a particulate or fibrous foam causes the thickness of a foam sheet to shrink, as tension forces pull the particles, or fibres, together. Drying shrinkage is an inherent property of cellulose, as fibres will collapse onto each other when water is removed from the system. Even in more complicated drying systems such as combined air impingement and IR-dryers, shrinkage above 10% is expected.
Similar to conventional papermaking techniques, foam-forming needs to be drained onto a screen. ln this case, there are limits to the shape and size ofthe material as it will level during draining. The density and thickness ofthe sample is determined by the wet fibrous foam concentration, which is usually from 1-4 wt%, and the amount of draining before drying. Generally dry content is about 1% to 8% after draining. For efficient draining to occur, the viscosity of the suspension needs to be kept rather low for efficient extraction of water. Any soluble binder would be limited to low concentrations and being able to retain on the fibre to avoid excessive losses. Therefore, draining limits the number of additives that could be used in this type of process. The strength ofthick low-density foam-formed paper is primarily controlled by the bulk of the material. The primary means of improving strength here is to increase density, with some limited control on fibre orientation, based on draining characteristics.
Higher dry-content techniques such as foams made from large quantities of protein- based foaming-agents, such as in WO2020011587 A1, hinders recyclability due to large fractions of the material not being water soluble or easily washed out from the product. The method also suffers from poor wet-foam stability, as protein particles start to agglomerate and bubbles coalesce, leading to gradual collapse of foam in the wet-state. This fact makes it a non-suitable candidate for free-standing wet foam deposition.
To avoid shrinkage, the foam needs to dry under tension, but when drying a very large surface area the tension obtained by the frame or mould is limited to the regions closest to the mould. Thus, shrinkage is a problem, especially when drying large surface areas. The drying time ofthe foam is typically long since both the wet foam and dry porous material are heat insulating. A short drying time is desired to enable a cost-efficient process. ln addition, the prepared foam should have a high impact resistance when used as a packaging material to enable protection also of heavier objects. Thus, there is still need for alternative methods for foam preparation.
SUMMARY OF THE INVENTION lt is an object of the present invention to provide a method suitable for the preparation of a foam where the shrinkage of the foam is reduced, and where the method enables a shorter drying time. The method enables a structural control of thick low-density foam materials, through a controlled wet-deposition technique and is particularly suitable for the preparation of cellulose foam sheets.
A further object is to provide a lightweight solid foam with good dimensional stability.
To be more specific, this invention relates to cellulose foam materials comprising discrete units of a cellulose foam embedded in a cellulose foam matrix, wherein the cellulose foam material has a low density i” t. t i ma. The cellulose foam matrix surrounding the discrete units may be composed of the same foam composition as was used for the discrete units. The width of each discrete unit of foam is less than 1.3 times its height. The discrete units may be distinguished from the matrix by a densified layer. Furthermore, this foam material can be made by two or more individual deposition- steps with a drying step after each deposition. The method allows for the creation and control of densified cellulose fibre walls. When dry, the fibres can be re-dispersed in water and as a result the foam can be recyclable in regular paper recycling streams. When the width of each discrete unit of foam is less than 1.3 times its height, it has been found that the drying time of the foam decreases.
Thus, this invention pertains both to a cellulose foam having a characteristic macrostructure with discrete units of cellulose foam embedded in a cellulose foam matrix, where the width of each discrete unit is less than 1.3 times its length, and the method to obtain the foam, which comprises a multistep deposition and drying method.
The cellulose foams are expected to contribute to technologies in protective packaging as a cushioning material, thermal insulation for cold chain logistics, and as a construction material, acoustic insulation panels, as a hydroponic plant growing media, and other applications that need lightweight, high-performance bio-based materials. Due to the excellent impact resistance, the cellulose foams ofthe present invention are particularly suitable for protection of heavy objects.
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 illustrates a two-step deposition with i) a first deposition of cellulose foam as discrete units, ii) an intermittent drying step drying the discrete units to create iii) self- standing discrete units of cellulose foam, iv) a second deposition of cellulose foam between the discrete units of cellulose foam, and v) a second drying step to obtain vi) a cellulose foam material comprising discrete units of cellulose foam.
Figure 2 shows a schematic representation of a solid foam sheet produced according to the method of the present invention, where A) illustrates the solid foam with a densified layer at the top and at the bottom in black colour, and looking externally similar to foam sheets produced with other techniques, B) illustrates the bulk ofthe material beneath the densified top and bottom, the bulk containing discrete units of cellulose foam (black cuboids), where each discrete unit is distinguished from the surrounding foam matrix by a densified layer of cellulose, and C) illustrates one discrete unit surrounded by a densified layer of cellulose (left), illustrated in black, and the homogenous cellulose foam inside the densified layers (right).
Figure 3a-b shows the drying times for cellulose foam planks with different sizes of the discrete units, and compared to the drying times for a single step foam deposition. 3a illustrates the drying time for discrete units with varying widths and a height of 2.1 cm. 3b illustrates the drying time for the subsequent wet foam deposition surrounding the discrete units in 3a, the height ofthe subsequent wet foam deposition is 2.1 cm.
DETAILED DESCRIPTION OF THE INVENTION ln a first aspect the present invention provides for a method for the preparation of a solid foam surface to obtain a first foam deposition, depositing a wet foam between the discrete units to obtain a subsequent foam deposition, and drying the wet foam in the subsequent foam deposition to obtain a solid foam wherein discrete units of a foam are embedded in a foam matrix, and wherein the width of each discrete unit is less than 1.3 times its height.
The term ”foam”, as used herein, refers to a substance made by trapping air or gas bubbles inside a solid or liquid. Typically, the volume of gas is much larger than that of the liquid or solid, with thin films separating gas pockets. Three requirements must be met in order for foam to form. I\/|echanical work is needed to increase the surface area. This can occur by agitation, dispersing a large volume of gas into a liquid, or injecting a gas into a liquid. The second requirement is that a foam forming agent, typically an amphiphilic substance, a surfactant or surface active component, must be present to decrease surface tension. Finally, the foam must form more quickly than it breaks down. The foam may be liquid or solid.
The term ”cellulose foam", as used herein, refers to a foam comprising cellulose, and other components such as thickeners, surfactants and additives. The main component of the cellulose foam is cellulose, such that cellulose constitutes at least 70 wt% of the dry content of the cellulose foam. Cellulose is in the form of fibres, and the foam can thus also be defined to be a fibrous foam or a cellulose fibre foam.
The term ”solid cellulose foam", or ”dry cellulose foam", as used herein, refers to a dry porous cellulose material that has been formed from a wet cellulose foam, i.e. a foam formed material. During the drying process, a closed wet cellulose foam is transformed into an open solid cellulose foam. The network of cellulose fibres is prevented from collapsing during drying. The solid cellulose foam will as a result have a shape that to a large extent corresponds to that of the wet cellulose foam. The dry content of the solid cellulose foam is at least 95 wt% as calculated based on the total weight of the solid cellulose foam. The shape and density ofthe solid cellulose foam is retained also in a non-confined state. The solid cellulose foam has an open cell structure, allowing air to occupy the pores within the foam. The solid cellulose foam can also be described as a porous material or a low-density material.
As used herein, the height ofthe discrete unit is measured perpendicular to the surface on which the unit has been deposited. As used herein, the width, or average of the length and width, ofthe discrete unit is measured at the bottom part ofthe discrete unit. For discrete units having a circular shape, such as having the shape of a cylinder, the width corresponds to the diameter of the discrete unit.
The width of a discrete unit is less than 1.3 times its height, such as less than 1.2, or from 0.5 to 1.3, or from 0.5 to 1.2, or from 0.7 to 1.3, orfrom 0.7 to 1.2, or from 0.9 to 1.3, or from 0.9 to 1.2 times its height. The total drying time of the foam is shortened when the width of the discrete units is less than 1.3 times its height.
The term ”total drying time” as used herein, refers to the time it takes for the foam to dry, i.e. the sum of the drying time for the discrete units and the drying time for the foam matrix.
The wet foam used in the discrete units may be a fibrous foam, such that the wet foam is a wet cellulose foam. The foam may comprise at least 10 wt% cellulose fibres, or at least 11 wt% cellulose fibres. The wet foam may comprise 10 - 40 wt%, 11 - 40 wt%, 10 - 30 wt%, 11 - 30 wt%, 10 - 20 wt%, or 11 - 20 wt%, cellulose fibres, as calculated on the total weight of the wet foam. The cellulose fibres may be selected from wood pulp; regenerated cellulose fibres; or plant fibres, such as fibres from bamboo, cotton, hemp, flax, and jute. Preferably, the cellulose fibres are selected from wood pulp, such as softwood kraft bleached pulp, chemicaI-thermomechanical pulp, dissolving pulp (such as bleached wood pulp or cotton linters), and hardwood pulp; more preferably from softwood kraft bleached pulp and chemical-thermomechanicaI pulp; and most preferably softwood kraft bleached pulp.
The discrete units may be made by dispensing a wet foam in discrete units on to a surface followed by drying of the discrete units. The wet foam forming the discrete units may have a density from 70 - 600 kg/m3, or from 100 - 500 kg/m3, or from 100 - 400 kg/m3, or from 125 - 375 kg/m3, or from 140 - 375 kg/m3. A large number of small bubbles provides stability to the foam and provides for a low density. The wet foam used in the present method has a sufficiently high viscosity and low density to enable the formation of discrete units that do not collapse before they are dried. Each discrete unit may thus stand by itself without collapsing before being dried. Further, each discrete unit may be self-standing during drying without collapsing. Drying ofthe discrete units of the wet foam is at least made until a crust, i.e. a thin densified layer of cellulose fibres, is formed on an outer surface of the discrete unit, such as on each of the faces of the discrete unit. The densified layer is a very thin layer that is formed on the very outer surface ofthe foam during drying. The densified layer is made up of cellulose fibres that are mainly oriented in a two-dimensional plane (x-y-plane), while the fibres in the bulk ofthe foam comprises clusters of fibres oriented in a three- dimensional space with more empty space in between clusters. The two-dimensional structure of cellulose fibres in the densified layer transitions rapidly, but gradually, to the three-dimensional structure found in the bulk of the foam. The thin thickness of the densified layer implies that it practically does not affect the overall density of the foam, while it still contributes to the good mechanical properties of the discrete units.
Optionally, further foam depositions of discrete units may be made on the surface, preferably between the discrete units of the first deposition. The wet foam forming the discrete units in the further deposition may have a density of from 70 - 600 kg/m3, or from 100 - 500 kg/m3, or from 100 - 400 kg/m3, or from 125 - 375 kg/m3, or from 140 - 375 kg/m3. The density of the wet foam used in the further deposition may be the same for the wet foam in the first deposition, or it may be different.
When discrete units of a foam comprising cellulose fibres have been dried, their core consists of a homogeneous fibre network having a density, and their outer surfaces, such as their bottom, top and side faces, consists of a more densely packed fibre network. The formation of a densified layer on the faces of the deposited discrete units in the first foam deposition makes the discrete units stronger and prevents them from being demolished during subsequent foam depositions, when wet foam is deposited between the discrete units. The dried discrete units may have an overall density of from 10 - 80 kg/m3, or from 10 - 60 kg/m3 or from 20 - 50 kg/m ln an alternative embodiment, the discrete units may be made by extruding or casting a wet foam, drying the wet foam to obtain a dry foam, cutting said dry foam into discrete units, and depositing said discrete units on to a surface. Preferably the wet foam is extruded into a board, plank, bar or rod. The board, plank, bar or rod can be cut into discrete units, which may be deposited on to a surface.
Each discrete unit may have a three-dimensional shape, such as a cylinder, or a polyhedron. Examples of symmetric polyhedrons are cubes, cuboids, and hexagonal prisms. Small variations in the symmetry ofthe discrete units may exist without changing their main purpose to impart stability to the foam. For example, the cylinder, cube, cuboid, and hexagonal prism may be slightly distorted so that their opposite bases are not always exactly parallel and over each other. For example, the discrete unit may have the shape of a truncated cone. Preferably, each discrete unit has the shape of a cylinder. The term ”cylinder” is used herein for the geometrical figure that is commonly defined as a closed solid with two principally parallel, congruent, and circular or oval, bases that are connected by a curved surface. Discrete units obtained in further foam depositions may have the same or a different three-dimensional shape as the discrete units obtained in the first deposition. The width of each discrete unit obtained in any further foam deposition may be less than 1.3 times its height, such as less than 1.2, or from 0.5 to 1.3, or from 0.5 to 1.2, or from 0.7 to 1.3, or from 0.7 to 1.2, or from 0.9 to 1.3, or from 0.9 to 1.2 times its height.
A subsequent deposition of wet foam is made between the already dried discrete units. The height of the wet foam in this subsequent deposition may be slightly higher or equal to the height of the discrete units. After said deposition of foam between the discrete units, the height of the discrete units may be from 90 to 100 %, or from 95 to 100 %, or from 98 to 100 %, of the height ofthe foam matrix surrounding said discrete units. ln some embodiments a deposition of wet foam may also be made on top ofthe discrete units, either simultaneously with the previously mentioned deposition ofthe wet foam between the discrete units or in a successive deposition. The surface ofthe subsequent deposition of wet foam may be scraped before drying to provide an even surface.
The wet foam in the subsequent deposition may be a fibrous foam, such that the wet foam is a wet cellulose foam. The wet foam may comprise at least 10 wt% cellulose fibres, or at least 11 wt% cellulose fibres. The wet foam may comprise 10 - 40 wt%, 11 - 40 wt%, 10 - 30 wt%, 11 - 30 wt%, 12 - 30 wt%, 10 - 20 wt%, or 11 - 20 wt%, or 12- 20 wt% cellulose fibres, as calculated on the total weight of the wet foam. The cellulose fibres used in the subsequent deposition are suitably selected from different kinds of wood pulp; regenerated cellulose fibres; or plant fibres, such as fibres from bamboo, cotton, hemp, flax, and jute. Preferably, the cellulose fibres are selected from wood pulp, such as from softwood kraft bleached pulp, chemicaI-thermomechanical pulp (CTMP), dissolving pulp (such as bleached wood pulp or cotton linters), and hardwood pulp; more preferably from softwood kraft bleached pulp and chemical- thermomechanical pulp; and most preferably softwood kraft bleached fibres. The cellulose fibres used in the subsequent deposition may be ofthe same sort as the cellulose fibres used in the discrete units of earlier depositions, i.e. the first and optionally further depositions.
The wet foam used in the subsequent deposition may have a density from 70 - 600 kg/m3, or from 100 - 500 kg/m3, or from 100 - 400 kg/m3, or from 125 - 375 kg/m3, or from 140 - 375 kg/m3. The solid foam prepared with the method according to the present invention may have a density of 10 - 80 kg/m3, or from 10 - 60 kg/m3, or from - 50 kg/m ln a wet foam, resistance forces keep the cellulose fibres in place. During drying, the water level between the fibres recedes causing capillary forces to build up inside the foam material, and when the capillary forces exceed the resistance forces, the fibres slip. As water evaporates the resistance forces increase and causes the fibres to get stuck in a position closer to each other than before drying, which causes the material to shrink. On a macroscopic level, the geometry of the foam influences the direction and magnitude of tension vectors that build up in the material during drying. Points of contact, such as a frame or a perforated surface, causes tension in the opposite direction and will impact the net tension forces. Deformation, such as shrinkage, will occur when the net tension forces, i.e. the tension vector, dominate in any particular direction. Thus, the ratio of the width, or surface area, to the height of cellulose foam planks affects the distribution of the net tension forces in a foam material upon drying, and the greater the ratio, the greater the net tension forces that arise.
Preparation of a foamed material according to the method of the present invention reduces the net tension forces arising in the material upon drying and the shrinkage of the material may thus be mitigated. Figure 1 illustrates one embodiment of the method ofthe present invention, wherein a wet fibrous foam is deposited on a surface as small discrete units to obtain a first deposition (i). Each discrete unit has width that is less than 1.3 times its height, which eliminates or significantly reduces shrinkage of each discrete unit when the units are dried (ii). When the discrete units are dried, they will consist of a core comprising a homogeneous fibre network, and densified outer faces (i.e. the top, bottom and sides) (iii). A subsequent deposition of a wet foam is then made on the surface between the already dried discrete units (iv). When the wet foam of the subsequent deposition is being dried (v) the discrete units of the first deposition that are already distributed on the surface provides for a low width to height ratio of the wet foam in the subsequent deposition. The tension forces of each discrete unit will act against each other thus reducing the net tension forces in the foam of the subsequent deposition, which restrains build-up of the tension during drying and as a result mitigates the effect of shrinkage on the outer dimensions ofthe obtained solid foam (vi). The method of the present invention thus provides for formation of a solid foam object with a reduced shrinkage, especially in the z-direction.
Further, the present method allows for the formation of a foamed object without having to use a mould with walls, which implies that very large objects can be produced with this method, such as boards or planks for use in large constructions, such as buildings, and other large structures. The size ofthe solid foam object to be produced may depend on the number of individual discrete units that can be placed in the first and optionally further depositions and the distance between them. The present method allows for the manufacturing of foam formed planks that are at least 60 * 60 cm, or at least 100 * 100 cm, or at least 200 * 200 cm, or at least 300 * 300 cm. With the multi-step deposition method according to the present invention foam formed objects can be produced with reduced shrinkage compared to similar foam formed objects obtained with the single-step deposition. The present method also allows for a process with continuous formation of a foam formed object, such as foam forming on a continuous belt.
The total time required for drying the foam is reduced when the width of each discrete unit is less than 1.3 times its height. By selection of an appropriate width to height ratio of the discrete units, properties ofthe foam may thus be controlled.The present invention provides for a low-density cellulose foam, i.e. a solid cellulose foam, comprising discrete units of cellulose foam, with stiffer densified cellulose fibre walls, embedded in a cellulose foam matrix. The incorporation of the discrete units as structural elements in solid foams, enables the formation of stiffer foams while maintaining the same low density. The discrete units constitute from 30 to 90 % ofthe total volume, or from 30 to 80%, or from 40 to 80 %, or from 50 to 80 % of the total volume or from 60 to 80% of the total volume, or from 40 to 78 % of the total volume, or from 50 to 78 % ofthe total volume, or from 40 to 75 % ofthe total volume, or from 50 to 75% of the total volume ofthe foam formed material comprising the discrete units and the surrounding foam matrix.
The wet foams used for the depositions in the method according to the present invention may be prepared by mixing cellulose fibres and one or more thickeners in water to obtain a flowable fibre mixture, adding a surfactant mixture and agitating to obtain a wet foam. The mixture of cellulose fibres and one or more thickeners in water may form an adequately flowable non-flocculated fibre paste. The mixture can be aerated by the addition of a surfactant mixture and agitation, such as by mechanical agitation. The aeration may form fine micron-sized air bubbles separating the fibres. The micron-sized air bubbles will stabilize the foam, which contributes to the preservation of the shape during drying of the discrete units.
Since cellulose fibres are mixed in high concentrations a drainage step is not needed. This may reduce the overall time and costs for the method and prevent leakage of water-soluble substances added during manufacturing, thereby allowing higher concentrations of water-soluble additives in in the final foam.
The performance ofthe dry foam can be tailored by the amount ofthickener used and hence the dry material fibre-fibre bonding strength. The amount ofthickener may be from 4 to 24 % or from 5 to 20 %, as calculated per weight of solid content in the foam.
The method according to the present invention allows adjustment ofthe stability ofthe wet foam with the use ofthickeners and more stable surfactant combinations, enabling the provision of a free-standing cellulose foam. Further, the method allows for simple inclusion of different types of additives.
During drying ofthe discrete free-standing foam units, a densified layer is formed on the face ofthe foam of each discrete unit, which helps to preserve the shape of the discrete unit. After the free-standing discrete units of foam has been dried, new wet foam can be added to fill in the gaps between the dried discrete units (as illustrated by (iv) in Figure 1). This allows for the creation of low-density cellulose foam divided into discrete units having stiffer densified cellulose fibre walls. By the incorporation of the densified thin layers the final foams can be made more rigid while maintaining the same light weight. Furthermore, this process provides for many units of a wet foam having a width less than 1.3 times its height, minimizing the effect of tension buildup during drying and as a result mitigating the effect of shrinkage on the outer dimensions ofthe plank.
A foam composition suitable for the preparation of a solid foam with the method according to the present invention is a foam that is self-standing and do not collapse. Other foams might be used for extrusion and cutting into discrete units, or for deposition between the discrete units, such as foams and cellular solid materials described in WO2016068771 A1, WO2016068787 A1, and WO2020011587 A ln another aspect, the present invention relates to a solid foam comprising discrete units of a foam, and a foam matrix surrounding said discrete units. The width of each discrete unit is less than 1.3 times its height. Each discrete unit may be surrounded by a densified layer of the foam. The total solid foam, as well as the discrete units and the foam matrix ~=§xa<§==~comprise from 75 to 95 wt%, or from 80 to 95 wt%, or from 85 to 92 wt% or from or from 85 to 90 wt% cellulose fibres as calculated on the total weight of the dry foam. The height ofthe discrete units may be from 90 to 100 %, or from 95 to100 %, or from 98 to 100 %, or equal to the height of the total solid foam prepared.
The solid foam may have a density of 10 - 60 kg/m3, or from 20 - 50 kg/m The density and properties of the final solid foam can be adjusted by using discrete units with the same or different densities as the foam matrix. The discrete units may also have densities that may differ from each other to provide the solid foam with different densities at different locations. The density of the discrete units in the solid foam may be from 83 % to 500 %, or from 60 % to 150 %, or from 90 % to 110 % ofthe density of the foam matrix surrounding said discrete units. Preferably, the discrete units have a density that is from 90 % to 110 % of the density of the foam matrix surrounding said discrete units. ln one embodiment, the density ofthe discrete units is higher than the density of the surrounding foam matrix, such that the density of the foams in the discrete units is from 110 to 330% of the density ofthe surrounding foam matrix. The total drying time of the foam is reduced when the density of the discrete units is higher than that of the surrounding foam matrix.
Each discrete unit may have a three-dimensional shape, such as a cylinder or a polyhedron. Examples of symmetric polyhedrons are cubes, cuboids (such as rectangular cuboids), and hexagonal prisms. Small variations in symmetry ofthe discrete units may exist without changing their main purpose to impart stability to the foam. Preferably, each discrete unit has the form of a cylinder. The width of each discrete unit is less than 1.3 times its height, such as less than 1.2, or from 0.5 to 1.3, or from 0.5 to 1.2, orfrom 0.7 to 1.3, orfrom 0.7 to 1.2, orfrom 0.9 to 1.3, or from 0.9 to 1.2 times its height. The drying time of the foam in the discrete units is shortened when the width of each discrete units is less than 1.3 times its height, and thus the total drying time ofthe foam will also be shortened. The width ofthe discrete units in the foam may also differ from each other in order to provide a solid foam with different properties at different locations. However, the width of each discrete unit in the foam is still less than 1.3 times its width.ln a further aspect, the present invention relates to a solid foam prepared by the method according to the present invention. A foam according to the present invention may be used in large sheets.
The invention will now be described by the following examples which do not limit the invention in any respect. All cited documents and references mentioned herein are incorporated by reference in their entireties.
EXAMPLES EXAMPLEA uniform wet paste comprising 12 wt% cellulose pulp in water and a thickener was prepared. The paste was aerated with a surfactant mixture until a wet foam density of 208 kg/m3_was obtained. The foam was filled in a frame on a perforated tray and the surface was scraped to remove any possible extra foam and levelling out the surface to the height ofthe frame. The foams were prepared in the height of 2.1 cm using a frame that sets the height. From the foam wet foam squares were cut out and removed to leave a pattern of deposited material in a precise squared pattern with every second square not filled, as filling out only the white squares of a chess board. The square widths used were 2.5 cm, 5 cm and 10 cm. The frames were sufficiently large to allow a few repetitions ofthe pattern 43 * 24.5 cm. The wet foam was used for a drying study in which three scenarios were tested: (1) To dry the material that was deposited as divided in uniform squares. (2) to fill up with new foam in each void between the squares, scrape the surface again and dry the second deposition. (3) to fill the whole frame with one single deposition, scrape it, and dry it.
The foams were weighted while drying in regular intervals and plotted as drying curves. These drying curves are found in Figure 3a-b.
EXPERll\/IENTAL l\/IETHODS Characterization The solid cellulose foam produced according to Example 1 also presents a densification on the top, bottom and side faces of the sheet (as illustrated in Figure 2A) while the bulk of the material contains discrete units of cellulose foam that are distinguished from the cellulose foam matrix by border walls of densified cellulose fibre material (Figure 2B).
From figure 3a it is clear that the drying time decreases when the width of the discrete unit is decreased. This is due to the smaller volume of the discrete unit. lt is also evident that the drying time for a single-step deposition is significantly longer. From figure 3b it is clear that also the drying time for the subsequent foam deposition surrounding the discrete units is faster than the drying time for a single -step deposition. Thus, the total drying time, i.e. the combined drying time for the first and subsequent foam depositions, is shorter when discrete units having a width that is less than 1.3 times its height are used, as compared to a single-step deposition.

Claims (1)

1. A method for the preparation of a solid foam comprising 75-95 wt% cellulose fibres, as calculated on the total weight ofthe foam, wherein the method comprises depositing discrete units of a foam on a surface to obtain a first foam deposition, depositing a wet foam between the discrete units to obtain a subsequent foam deposition, and drying the wet foam to obtain a solid foam wherein discrete units of a foam are embedded in a foam matrix, and wherein the width of each discrete unit is less than 1.3 times its height. The method according to claim 1, wherein the height of the discrete units is from 90 to 100 % of the height of the wet foam in the subsequent foam deposition. The method according to claim 1 or 2, wherein the wet foam in the subsequent foam deposition comprises at least 10 wt% cellulose, as calculated on the total weight of the wet foam. The method according to any one of claims 1-3, wherein the discrete units are obtained by dispensing a wet foam as discrete units on to a surface, preferably in the form of cylinders, followed by drying of the wet foam. The method according to any one of claims 1-3, wherein the discrete units are obtained by extruding a wet foam, drying the foam, cutting the dried foam into discrete units, and depositing said discrete units on to a surface. The method according to any one of claims 4-5, wherein the wet foam used in the discrete units comprises at least 10 wt% cellulose, as calculated on the total weight of the wet foam. The method according to any one of claims 1-6, wherein the wet foam has a density from 70 - 600 kg/m The method according to any one of claims 1-7, wherein the solid foam has a density of 10 - 80 kg/m A solid foam characterized in that it comprises discrete units of a foam embedded in a foam matrix, and wherein the solid foam comprises at least 75-95 wt% cellulose fibres as calculated on the total weight of the foam, and wherein the width of each discrete unit is less than 1.3 times its height. A solid foam according to claim 9, wherein the height of the discrete units is from 90 to 100 % of the height of the foam matrix. A solid foam according to claim 9 or 10, wherein the solid foam has a density of-80 kg/m A solid foam according to any one of claims 9-11, wherein each discrete unit is surrounded by a densified layer of the foam. A solid foam according to any one of claims 9-12, wherein each discrete unit is in the form of a cylinder. Use of a solid foam according to any one of claims 9-13 in packaging or large constructions, or as a hydroponic plant growing media.
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Citations (5)

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US2320425A (en) * 1940-08-02 1943-06-01 Mishawaka Rubber & Woolen Mfg Combining foam rubber
US4073839A (en) * 1976-04-19 1978-02-14 The Goodyear Tire & Rubber Company Method of zone pouring foam products
DE3705409A1 (en) * 1987-02-20 1988-09-01 Bayer Ag METHOD FOR PRODUCING UPHOLSTERY, IN PARTICULAR SEAT UPHOLSTERY FOR MOTOR VEHICLES
US5549858A (en) * 1995-02-08 1996-08-27 Manni-Kit, Inc. Silicone foam symmetrical inversion molding process
US20020061386A1 (en) * 1999-06-18 2002-05-23 The Procter & Gamble Company Multi-purpose absorbent and cut-resistant sheet materials

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2320425A (en) * 1940-08-02 1943-06-01 Mishawaka Rubber & Woolen Mfg Combining foam rubber
US4073839A (en) * 1976-04-19 1978-02-14 The Goodyear Tire & Rubber Company Method of zone pouring foam products
DE3705409A1 (en) * 1987-02-20 1988-09-01 Bayer Ag METHOD FOR PRODUCING UPHOLSTERY, IN PARTICULAR SEAT UPHOLSTERY FOR MOTOR VEHICLES
US5549858A (en) * 1995-02-08 1996-08-27 Manni-Kit, Inc. Silicone foam symmetrical inversion molding process
US20020061386A1 (en) * 1999-06-18 2002-05-23 The Procter & Gamble Company Multi-purpose absorbent and cut-resistant sheet materials

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