WO2018232500A1 - Procédé de production de mélanges à mouler en feuille thermoplastique renforcés par des filaments cellulosiques et produits associés - Google Patents

Procédé de production de mélanges à mouler en feuille thermoplastique renforcés par des filaments cellulosiques et produits associés Download PDF

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Publication number
WO2018232500A1
WO2018232500A1 PCT/CA2018/050707 CA2018050707W WO2018232500A1 WO 2018232500 A1 WO2018232500 A1 WO 2018232500A1 CA 2018050707 W CA2018050707 W CA 2018050707W WO 2018232500 A1 WO2018232500 A1 WO 2018232500A1
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WIPO (PCT)
Prior art keywords
filler
pulp
suspension
reinforced
fiber
Prior art date
Application number
PCT/CA2018/050707
Other languages
English (en)
Inventor
Halim Chtourou
Original Assignee
Fpinnovations
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.)
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Publication date
Application filed by Fpinnovations filed Critical Fpinnovations
Publication of WO2018232500A1 publication Critical patent/WO2018232500A1/fr

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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene

Definitions

  • the present application relates to the field of reinforced thermoplastic sheet molding material, more particularly to thermoplastic sheet molding material reinforced with cellulosic filaments, methods for producing the same and related molded products.
  • thermoplastic resins commercially available mostly in the form of granules and pellets, have been extensively explored as matrices for thermoplastic composites.
  • Short- fiber reinforcements such as glass and carbon fibers, as well as, natural ligno-cellulosic fibers, have also been thoroughly investigated in thermoplastic composites using hot melt compounding with the thermoplastic resins.
  • thermoplastic composite materials To maximize the properties of the thermoplastic composite materials research have been carried out to improve the compatibility between the polymer matrix and the reinforcement material, the compounding equipment and/or the fiber pretreatment, with the objective of decreasing fiber degradation and increasing fiber dispersion into the polymer matrix.
  • Sears et al. (US 6,270,883) disclosed that dispersing cellulosic pulp fibers that have alpha-cellulose purity greater than 80% by weight in high melting temperature polymers, such as polyamides, polyethylene terephthalate, polybutylene terephthalate, and others, allows reducing the blending energy and the molding temperature.
  • high melting temperature polymers such as polyamides, polyethylene terephthalate, polybutylene terephthalate, and others.
  • the composite materials of Sears et al. can be molded by injection using temperatures below those used with conventional composites, even below the melting point of the polymeric matrix material itself. In order to minimize the thermal degradation of the cellulosic fibers, suitable melting temperature was preferred in the range of 180-200°C. Sears et al.
  • Mohanty (US 7,582,241) described the addition of several metal halides to reduce the processing temperatures of high melting temperature thermoplastic polymers (e.g. polyamides, polyethylene terephthalate, polybutylene terephthalate, etc.) used in the manufacture of thermoplastic natural fiber reinforced composites.
  • high melting temperature thermoplastic polymers e.g. polyamides, polyethylene terephthalate, polybutylene terephthalate, etc.
  • the use of lithium chloride (LiCI) salt in a water solution, allows reducing the melting temperature of Polyamine (PA6) to less than 392°F (200°C).
  • PA6 Polyamine
  • Mohanty reported that higher tensile and flexural modulus and higher tensile and flexural strengths were obtained using Hemp fiber in PA6 blended with 3% by weight of LiCI, with respect to non-reinforced matrix.
  • Korte In order to improve the homogeneous dispersion of single fibers in thermoplastic composites and maximize the mechanical properties, Korte (US 2013/0052448) disclosed a discontinuous process using internal kneaders that dispersed fiber agglomerates into single fibers that were distributed homogeneously in the thermoplastic matrix. The process of Korte allowed an increase in tensile strength of about 19% with long hemp fibers reinforcement, 4 % with short hemp fibers, 9% with hemp pulp and up to 68% with industrial cellulosic fibers for an injection-molded composite.
  • Barlow et al. (US 6,743,507) described cellulosic fiber reinforced thermoplastic composites having an improved homogeneity of the single fiber dispersion.
  • the composites were prepared by hot melt compounding and included cellulosic pulp fibers with an alpha-cellulose purity of at least 80% by weight, a water-soluble binder, a lubricant, a compatibilizer, and a thermoplastic matrix.
  • the water- soluble binder generally provides integrity to the cellulosic pulp fibers and improves the dispersion of the cellulosic pulp fibers within the thermoplastic matrix.
  • Bledzki and Faruk compared various parameters of the molding process: hardwood fibers vs softwood fibers, compression molding vs injection molding, 30% and 50% fiber loading, and optional addition of maleic anhydride-g-polypropylene coupling agent (2004, Polymer- Plastics Technology and Engineering, 43(3): 871-888). Bledzki and Faruk reported that composites obtained using compression molding had lower tensile and flexural properties than composites obtained using injection molding process.
  • CF Cellulosic filaments produced using the process of Hua et al. (US/2011/0277947) have been reported to have superior performances due to their morphology and high aspect ratios (ratios of filament length to its thickness and width).
  • NBSK Norther Bleached Softwood Kraft
  • thermoplastic polymers are supplied as synthetic pulp fibers or synthetic powders dispersed in an aqueous solution and blended with ligno-cellulosic pulp fibers.
  • Ture et al. (US 8,795,471) disclosed a wet web formation to produce a composite intermediate from a substantially homogeneous liquid mixture which contains natural fibers, plastic particles having a diameter of less than approximately 1 mm, styrene maleic anhydride (less than 3% by dry weight) as a compatibilizer between the natural fibers and the plastic particles.
  • the natural fibers can comprise microfibrillated cellulose fibers, cellulose nanofibers or mixtures thereof.
  • the suspension can further comprise an additive such as starch, fillers, surface-active agents, retention agents, dispersing agents, or anti- foam agents.
  • Backfolk (WO2015170262) disclosed the formation of thermoplastic composite material in a paper making machine and reinforced with fibers (organic fiber or inorganic fibers).
  • the method comprises the introduction of additives, like carbon dioxide and lime milk. Carbon dioxide and lime milk reacted to form calcium carbonate that precipitates onto or into the cellulosic fibers of an intermediate suspension.
  • the final aqueous composite suspension was formed after introducing and homogenizing a plastic material with or without a coupling agent with the other cellulosic fibers containing the precipitated reacted additive.
  • Laleg and Hua (US8608906) described a method to manufacture paper sheets reinforced with fibrillated long fibers and high mineral filler content (up to 90 wt%). In Laleg and Hua, anionic acrylic binders were used and were mixed at a temperature above the glass transition temperature of the used binders.
  • Page et al. (WO 2018/049537) described the production of binderless CF based wet-lap sheets having a consistency of 45-55%.
  • the binderless CF based wet lap sheets are suitable for hot compression molding at 150°C. No anionic binder was added in the suspension.
  • Page et al. used calcium carbonate well dispersed in a cellulosic filament pulp suspension having a dry consistency of 10% by weight before press dewatering. Dorris et al.
  • thermoplastic sheet molding ready-to-mold materials and the related molded products using the cellulosic filaments as a reinforcement material in order to improve the tensile and flexural properties of the related molded products.
  • a ready-to-mold reinforced thermoplastic sheet molding compound material comprising: 5 wt% to 50 wt% by dry weight of water dispersible cellulose filaments (CF), the CF having a length of at least 100 ⁇ , and a cross-sectional dimension of about 30 to about 300 nm, and being substantially free of fibrillated cellulose; 15 wt% to 25 wt% by dry weight of at least one filler, wherein the at least one filler has a particle size of up to 100 ⁇ ; and 25 wt% to 70 wt% by dry weight of a thermoplastic fiber pulp or powder, the thermoplastic fiber pulp or powder comprising a melting temperature below 200°C.
  • the ready-to-mold reinforced material has a bulk density of 350 to 650 kg/m 3 and a dry basis weight of 0.7 to 3.8 kg/m 2 .
  • a ready-to-mold reinforced thermoplastic sheet molding compound material comprising: 5 wt% to 50 wt% by dry weight of water dispersible cellulose filaments (CF), the CF having a length of at least 100 ⁇ , a cross-sectional dimension of about 30 to about 300 nm, and being substantially free of fibrillated cellulose; 5 wt% to 15 wt% by dry weight of a thermoplastic coupling agent in the form of fine powder or micro-fiber; 15 wt% to 25 wt% by dry weight of at least one filler, wherein the at least one filler has a particle size of up to 100 ⁇ ; and 25 wt% to 55 wt% by dry weight of a thermoplastic fiber pulp or powder, the thermoplastic fiber pulp or powder comprising a melting temperature below 200°C.
  • the ready-to-mold reinforced material has a bulk density of 350 to 650 kg/m 3 and a dry basis weight of 0.7 to 3.8 kg/m 2
  • the reinforced material has a bulk density of 450-550 kg/m 3 and a dry basis weight of 0.7-1.2 kg/m 2 .
  • a wet laid process for producing a ready-to-mold reinforced thermoplastic sheet molding compound material.
  • the wet laid process comprises the steps of providing water dispersible cellulose filaments (CF) in form of a CF pulp, the CF having a length of at least 100 ⁇ , and a cross-sectional of about 30 to about 300 nm, and being substantially free of fibrillated cellulose; providing at least one filler comprising a particle size of up to 100 ⁇ ; providing a thermoplastic (TP) polymer in form of fiber pulp or powder comprising a melting temperature below 200°C; blending the CF pulp, the at least one filler and the TP polymer to produce a suspension of 5 to 8 wt% dry solids; layering the suspension into a wet lap on a pressing device; compacting the wet lap to up to 50 wt% solids; and drying the wet lap above 95 wt% solids at a temperature below 200°C.
  • CF water dispersible cellulose filaments
  • TP thermo
  • the water dispersible CF is provided in an amount of 5 wt% to 50 wt% by dry weight; the filler is provided in an amount of 15 wt% to 25 wt% by dry weight; and the TP polymer is provided in an amount of 25 wt% to 70 wt% by dry weight.
  • the blending step comprises: adding and dispersing the CF pulp in an aqueous solution to form the suspension and reach 3 to 3.5 w% dry solids based on total weight of the suspension; adding and dispersing the at least one filler in the suspension to reach 4.5 to 5.3 wt% dry solids based on total weight of the suspension; and adding and dispersing the TP polymer in the suspension to reach 5 to 8 wt% dry solids based on total weight of the suspension.
  • the wet laid process further comprises providing a thermoplastic coupling agent in a form of a fine powder or chopped microfibers and wherein the coupling agent is blended with the CF pulp, the at least one filler and the TP polymer.
  • the coupling agent is a maleic-anhydride grafted polymer.
  • the maleic-anhydride grafted polymer can be maleic-anhydride grafted polyethylene (MAPE) and/or maleic-anhydride grafted polypropylene (MAPP).
  • the dispersible CF is provided in an amount of 5 wt% to 50 wt% by dry weight; the coupling agent is provided in an amount of 5 wt% to 15 wt% by dry weight; the filler is provided in an amount of 15 wt% to 25 wt% by dry weight; and the TP polymer is provided in an amount of 25 wt% to 70 wt% by dry weight.
  • the blending step comprises: adding and dispersing the CF pulp in an aqueous solution to form the suspension and reach 3 to 3.5 w% dry solids based on total weight of the suspension; adding and dispersing the at least one filler in the suspension to reach 4.5 to 5.3 wt% dry solids based on total weight of the suspension; adding and dispersing the coupling agent in the suspension to reach 6 to 7 wt% dry solids based on total weight of the suspension; and adding and dispersing the TP polymer in the suspension to reach 5 to 8 wt% dry solids based on total weight of the suspension.
  • the at least one filler is an inorganic filler, a functional filler and/or a lightweight filler.
  • the at least one filler can be selected from the group consisting of calcium carbonate microparticles, aluminium trihydrate microparticles, magnesium hydroxide microparticles, zinc borate microparticles, zinc phosphate microparticles, aluminium oxide microparticles, milled glass fiber microparticles, milled basalt fiber microparticles, milled aramid fiber microparticles, milled carbon fiber microparticles, wood flour, biochar, and mixtures thereof.
  • the filler can comprise calcium carbonate particles having an average diameter of 2.8 ⁇ .
  • the at least one filler can also be in a form of hollow microspheres, light-weight conventional microspheres or expandable polymeric microspheres.
  • the at least one filler can further comprise additional chopped reinforcing fibers of at least one of glass, basalt, aramid, and carbon fibers.
  • the TP fiber pulp is a chopped TP microfiber pulp comprising fibers having a diameter in the range of 5-20 ⁇ and a length of from 3 mm to 6 mm.
  • the TP fiber pulp or powder comprises at least one of polyethylene (PE), polypropylene (PP), polybutylene (PB), polybutylene succinate (PBS), poly(methyl methacrylate) (PMMA), polycarbonate (PC), and low melt point polyamide multipolymer resin.
  • the polyethylene (PE) can comprise at least one of high-density polyethylene (HDPE) pulp, medium-density polyethylene (MDPE), low-density polyethylene (LDPE), and cross-linkable polyethylene (XLPE).
  • the wet lap is compacted using double-wire at room temperature and wherein nip pressure is in the range of 200-300 psi.
  • the wet lap can be dried at a temperature equal to a melting-point range of the thermoplastic fiber pulp or powder.
  • water recovered in the compacting step and/or in the drying step can be re-injected in the blending step to form the suspension.
  • the CF pulp comprises between 10 wt% and 40 wt% of dry CF based on total weight of dry solid.
  • a molded reinforced thermoplastic product manufactured by molding of the ready-to-mold reinforced material as described herein.
  • the ready-to-mold reinforced material has been molded by compression, extrusion or injection molding.
  • the molded product has a tensile modulus of between 2.5 and 5 GPa and a flexural modulus of between 3 and 6 GPa.
  • the molded product can also have a tensile strength of between 20 and 60 MPa and a flexural strength of between 40 to 100 MPa.
  • the molded product can also have a tensile strength of between 20 and 45 MPa and a flexural strength of between 40 to 80 MPa.
  • the molded product comprises two or more layers of the ready-to-mold reinforced material.
  • the two or more layers of the ready-to-mold reinforced material can have at least one of a different composition, a different density, a different tensile strength, and a different flexural strength.
  • Fig. 1 is a process flowchart of a wet laid process according to one embodiment described herein;
  • Fig. 2 is a graph of the tensile strength for a cellulosic filament (CF) reinforced thermoplastic sheet molding compound (TP-SMC) material according to one embodiment described herein, a TP-SMC material reinforced with Northern Bleached Softwood Kraft (NBSK) pulp and a TP-SMC material reinforced with Bleached Chemical Thermo- Mechanical Pulp (BCTMP);
  • CF cellulosic filament
  • NBSK Northern Bleached Softwood Kraft
  • BCTMP Chemical Thermo- Mechanical Pulp
  • Fig. 3A is a photograph of a laser cut of a NBSK reinforced TP-SMC material after compression molding
  • Fig. 3B is a photograph of a laser cut of a CF reinforced TP-SMC material according to one embodiment described herein, after compression molding;
  • Fig. 4A is a graph of the pressure and temperature as a function of time during compression molding cycles of a CF reinforced TP-SMC material according to one embodiment described herein, without thermoplastic coupling agent, without filler and with High Density Polyethylene (HDPE) thermoplastic pulp fiber;
  • HDPE High Density Polyethylene
  • Fig. 4B is a graph of the pressure and temperature as a function of time during compression molding cycles of a CF reinforced TP-SMC material according to another embodiment described herein, without thermoplastic coupling agent, without filler and with polypropylene (PP) thermoplastic pulp fiber;
  • PP polypropylene
  • Fig. 5A is a graph of the pressure and temperature as a function of time during compression molding cycles of a CF reinforced TP-SMC material according to another embodiment described herein, without thermoplastic coupling agent, with filler and with HDPE thermoplastic pulp fiber;
  • Fig. 5B is a graph of the pressure and temperature as a function of time during compression molding cycles of a CF reinforced TP-SMC material according to another embodiment described herein, without thermoplastic coupling agent, with filler and with HDPE and PP thermoplastic pulp fiber;
  • Fig. 5C is a graph of the pressure and temperature as a function of time during compression molding cycles of a CF reinforced TP-SMC material according to another embodiment described herein, without thermoplastic coupling agent, with filler and with PP thermoplastic pulp fiber;
  • Fig. 6A is a graph of the pressure and temperature as a function of time during compression molding cycles of a CF reinforced TP-SMC material according to an embodiment described herein, with thermoplastic coupling agent, without filler and with HDPE thermoplastic pulp fiber;
  • Fig. 6B is a graph of the pressure and temperature as a function of time during compression molding cycles of a CF reinforced TP-SMC material according to another embodiment described herein, with thermoplastic coupling agent, with filler and with HDPE thermoplastic pulp fiber;
  • Fig. 6C is a graph of the pressure and temperature as a function of time during compression molding cycles of a CF reinforced TP-SMC material according to another embodiment described herein, with thermoplastic coupling agent, with filler and with PP thermoplastic pulp fiber;
  • Fig. 7 A is a graph of the ultimate tensile and flexural strengths for CF reinforced TP-SMC materials according to various embodiments described herein after compression molding in monolayer panels;
  • Fig. 7B is a graph of the tensile and flexural Young's modulus for CF reinforced TP-SMC materials according to various embodiments described herein after compression molding in monolayer panels;
  • Fig. 8A is a graph of the ultimate tensile and flexural strengths for CF reinforced TP-SMC materials according to various embodiments described herein, neat HDPE material and neat PP material, after compression molding in monolayer panels;
  • Fig. 8B is a graph of the tensile and flexural modulus for CF reinforced TP-SMC materials according to various embodiments described herein, neat HDPE material and neat PP material, after compression molding in monolayer panels;
  • Fig. 9A is a graph of the ultimate tensile and flexural strengths for a CF reinforced PP-SMC material according to one embodiment described herein and a wood fiber reinforced material, after compression molding, and for a wood fiber reinforced material after injection molding;
  • Fig. 9B is a graph of the tensile and flexural modulus for a CF reinforced PP-SMC material according to one embodiment described herein and wood fiber reinforced material, after compression molding, and for wood fiber reinforced material after injection molding;
  • Fig. 10 is a process flowchart of a wet laid process according to another embodiment described herein;
  • Fig. 11 is a graph of the ultimate tensile and flexural strengths for a CF and a CF- NBSK reinforced PP-SMC materials according to two embodiments described herein, and a wood fiber reinforced PP material, after compression molding;
  • Fig. 12A is a photograph of an oven vacuum molding process of a CF reinforced HDPE-SMC material according to an embodiment described herein;
  • Fig. 12B is a photograph a CF reinforced HDPE-SMC material according to another embodiment described herein after oven vacuum molding process
  • Fig. 12C is a photograph of a compression molded panel formed of two layers of a CF reinforced HDPE-SMC material according to an embodiment described herein;
  • Fig. 13A is a photograph of an oven vacuum thermoforming process of a CF- reinforced PP-SMC material according to an embodiment described herein;
  • Fig. 13B is a photograph of a molded CF-reinforced PP-SMC material according to an embodiment described herein, after oven vacuum thermoforming.
  • Fig. 14A is a normal incidence sound absorption coefficient on hard wall backing for a multi-layered oven (200°C) vacuum molded 5 mm thick specimen tested in large 100 mm diameter acoustic tube.
  • Fig. 14B is a normal incidence sound absorption coefficient on 80 mm thick air layer for a multi-layered oven (200°C) vacuum molded 5 mm thick specimen tested in large 100 mm diameter acoustic tube.
  • Fig. 15A is a normal incidence sound absorption coefficient on hard wall backing (top) for a multi-layered oven (200°C) vacuum molded 5 mm thick specimen tested in large 100 mm diameter acoustic tube.
  • Fig. 15B is a normal incidence sound absorption coefficient on 80 mm thick air layer for a multi-layered oven (200°C) vacuum molded 5 mm thick specimen tested in large 100 mm diameter acoustic tube.
  • Fig. 16A is a normal incidence sound absorption coefficient on hard wall backing for a balsa specimen tested in large 100 mm diameter acoustic tube.
  • Fig. 16B is a normal incidence sound absorption coefficient on 80 mm thick air layer for a balsa specimen tested on both surfaces in large 100 mm diameter acoustic tube.
  • thermoplastic sheet molding compound material comprising: 5 wt% to 50 wt% by dry weight of water dispersible cellulose filaments (CF), the CF having a length of at least 100 ⁇ , and a cross-sectional dimension of about 30 to about 300 nm, and being substantially free of fibrillated cellulose; 15 wt% to 25 wt% by dry weight of at least one filler, wherein the at least one filler has a particle size of up to 100 ⁇ ; and 25 wt% to 70 wt% by dry weight of a thermoplastic fiber pulp or powder, the thermoplastic fiber pulp or powder comprising a melting temperature below 200°C.
  • the ready-to-mold reinforced material has a bulk density of 350 to 650 kg/m 3 and a dry basis weight of 0.7 to 3.8 kg/m 2 .
  • thermoplastic sheet molding compound TP-SMC
  • CF reinforced material cellulosic filaments
  • wet laid process consists in the formation of an aqueous suspension comprising thermoplastic matrix, a reinforcement material and other additive. During the wet laid process a wet lap is formed, and can further be compressed and dried in order to form the ready-to-mold CF reinforced material.
  • the term "wet lap” as used herein can be understood as a sheet of pulp formed by even distribution of a pulp on a surface. A wet lap is generally formed using a wet lapping machine.
  • the wet laid process described herein comprises the step of providing water dispersible cellulose filaments (CF) 10.
  • CF water dispersible cellulose filaments
  • the term "water dispersible CF” is intended to mean that the CF, which can be provided as an agglomeration of CF, can be separated into single CF in an aqueous solution, by mechanical agitation. Each of the CF therefore forms an interface with the aqueous solution so that the CF are suspended (with a statistical distribution) in the aqueous solution.
  • the CF 10 are provided in the form of a CF pulp.
  • Water 12 is added to the CF 10, producing a CF suspension 14.
  • the CF pulp can comprise between 10 wt% and 40 wt% of dry CF, based on total weight of the CF pulp. More particularly, the CF pulp can comprise 30 wt% of dry CF, based on total weight of the CF pulp.
  • the CF 10 have been produced by performing a specific process disclosed in Hua et al. (US/201 1/0277947), incorporated herein by reference, on a Northern Bleached Softwood Kraft (NBSK) pulp.
  • the resulting CF comprised a length of at least 100 ⁇ . More particularly, the length can be between 300 ⁇ and 500 ⁇ .
  • the CF have cross-sectional dimensions (thickness and width) of about 30 to about 300 nm.
  • the CF are substantially free of fibrillated cellulose, and more specifically of microfibri Hated cellulose.
  • microfibri Hated cellulose is defined as a cellulose having numerous strands of fine cellulose branching outward from one or a few points of a bundle in close proximity and the bundle has approximately the same width of the original fibers and typical fiber length in the range of 100 micrometers.
  • substantially free is defined herein as an absence or very near absence of the microfibrillated cellulose.
  • the CF 10 are physically detached from each other in the CF pulp.
  • the expression "physically detached from each other” means that the CF are individual threads that are not associated or attached to a bundle, i.e. they are not fibrillated. The CF may however be in contact with each other as a result of their respective proximity.
  • the CF pulp can be described as a random dispersion of individual CF forming a 3D network.
  • the present CF have a heterogeneous morphology that leads to the formation of a network having a superior ability to retain submicron filler, without the need of retention agent.
  • the water dispersible CF are provided in an amount of 5 wt% to 50 wt%, preferably of about 40 wt%, by dry weight (or based on total weight of solids in the CF reinforced material).
  • wt% by dry weight means the weight content as a percentage of the total weight of solids in the product after. Therefore, in the CF reinforced material produced by the present wet laid process, the amount of CF can be of 5 wt% to 50 wt%, more particularly of 40 wt% by dry weight.
  • the wet laid process also comprises providing at least one filler.
  • the filler can be an inorganic filler 16, a functional filler 18 (unmodified or modified) or a lightweight filler.
  • a functional filler 18 can be for instance a fire retardant filler, a conductive or magnetic filler, or a surface modifier.
  • the filler is selected from the list consisting of: calcium carbonate microparticles, aluminium trihydrate microparticles, magnesium hydroxide micro particles, zinc borate microparticles, zinc phosphate microparticles, aluminium oxide microparticles, milled glass fiber microparticles, milled basalt fiber microparticles, milled aramid fiber microparticles, milled carbon fiber microparticles, wood flour, biochar, and mixtures thereof.
  • biochar refers to a torrified biomass in the form of blackened solid hydrophobic material, such as the one produced by AIREX Energy using the Carbon FX ® process, for example.
  • the filler can also be in a form of hollow microspheres, light-weight conventional microspheres or expandable polymeric microspheres.
  • inorganic fillers accelerate the hot press molding process by improving the draining of the water entrapped in the CF based wet lap.
  • the particle size of the filler can be of up to 100 ⁇ .
  • the filler has a particle size of from 1 to 5 ⁇ .
  • the filler comprises particles having an average diameter of about 3 ⁇ , more particularly of 2.8 ⁇ .
  • additional fibers can be added in the wet laid process.
  • chopped reinforcing fibers 22 thermoplastic fiber pulp or powder for example
  • the additional fibers are added in a concentration lower than that of the filler.
  • the additional fibers can be at least one of glass fibers, basalt fibers, aramid fibers, and carbon fibers.
  • the filler is provided in an amount of 15 wt% to 25 wt%, preferably 20 wt%, by dry weight of the CF reinforced material. Therefore, in the CF reinforced material produced by the present wet laid process, the amount of filler will be of 15 wt% to 25 wt% by dry weight, more particularly of 20 wt%. As shown in the examples below, the presence of the filler in the present CF reinforced material, surprisingly allows improving the strength of products obtained by compression molding of the CF reinforced material. Fillers are usually added in the polymeric matrix to reduce the cost of the final product and no strength improvement associated with the presence of the filler has been reported up to now.
  • More than one filler can be added in the wet laid process. As shown in Fig. 1 , it is possible to add an inorganic filler 16 such as calcium carbonate, and for example two other functional fillers (18 and 18') providing specific properties to the molded product formed with the CF reinforced material.
  • an inorganic filler 16 such as calcium carbonate
  • two other functional fillers (18 and 18') providing specific properties to the molded product formed with the CF reinforced material.
  • the wet laid process further comprises providing a thermoplastic (TP) polymer 22 that forms a polymer matrix.
  • TP polymer provides the CF reinforced material with a higher flexibility when submitted to a compacting or preforming pressure, and more particularly with higher flowability when hot pressed for final thermoforming.
  • the TP polymer is provided in the form of a fiber pulp or a powder.
  • TP polymers in form of a fiber pulp are preferred.
  • the TP polymer can be a chopped thermoplastic microfiber pulp.
  • the fibers of the chopped thermoplastic microfiber pulp have a diameter in the range of 5-20 ⁇ and a length of from 3 mm to 6 mm.
  • the TP polymer has a melting temperature below 200°C. Using such melting temperature prevents the degradation of the CF during the wet laid process (drying) and during the following molding process (thermoforming).
  • the TP polymer can be at least one of polyethylene (PE), polypropylene (PP), polybutylene (PB), polybutylene succinate (PBS), poly(methyl methacrylate) (PMMA), polycarbonate (PC), and polyamide (PA) such as low melt point polyamide multipolymer resin.
  • polyethylene can be high-density polyethylene (HDPE) pulp, low-density polyethylene (LDPE), medium-density polyethylene (MDPE) and/or cross-linkable polyethylene (XLPE).
  • the TP fiber pulp or powder is provided in an amount of 25 wt% to 70 wt% by dry weight. Therefore, in the CF reinforced material produced by the present wet laid process, the amount of TP fiber pulp or powder will be of 25 wt% to 70 wt% by dry weight, preferably of 30 wt% to 60 wt%, and more preferably of about 40 wt%.
  • the presence of TP polymer fiber pulp helps draining the material during compression of the wet lap.
  • the TP polymer in the form of fiber pulp or powder and depending on the respective volume fractions of CF and TP polymer, can cover (overlay or enrobe) the CF over their entire or partial outer surface, thereby preventing CF/CF hydrogen bonds or restricting the density of the CF in the CF reinforced material and the related molded product. Without contact between the CF, no hydrogen bond can be formed and the strength of the final molded product relies only on lower Van der Waals forces and weak mechanical bonds at the interface of the CF and the polymer matrix.
  • the use of coupling agents with polar groups that favor the creation of hydrogen bonds at the interface of the CF and the polymer matrix is therefore needed to improved tensile and flexural properties.
  • the wet laid process comprises blending 20 the CF pulp 10 in suspension 14, the at least one filler (16, 18 and/or 18') and the TP polymer 22 (fiber pulp or powder).
  • the CF pulp is dispersed in water to form a CF suspension 14.
  • the CF pulp is therefore diluted and the CF suspension has a consistency of 2 to 5 wt%, preferably 3 to 3.5 w% of solids, based on total weight of the CF suspension.
  • the CF are never-dried CF and are water dispersible, so that the distribution of the CF in the CF suspension is uniform, and the suspension can be considered homogeneous.
  • the term "never-dried” as used herein is understood to mean that the CF pulp used has not been dried before the process so that no CF/CF hydrogen bond has already been formed.
  • the CF as used in the present application provide the wet lap with an improved ability to retain the filler because of such uniform distribution of the CF network.
  • aqueous CF suspension with an homogenous dispersion.
  • aqueous dispersion of the CF pulp does not involve any high shear mixing apparatus, thereby avoiding breaking or thermal degradation of the CF.
  • Mechanical mixing can be performed using low shear impellers such as propeller, hydrofoils, turbines or any other suitable mixing apparatus preventing breakage of the CF.
  • Fig. 1 shows that the filler is added in the CF suspension 14 and blended 20.
  • the suspension with the CF and the filler can therefore reach a consistency of 4 to 6 wt%, preferably 4.5 to 5.3 wt% of solids, based on total weight of the suspension.
  • the filler will insert first between the CF and form a homogeneous CF based-composite suspension.
  • the TP polymer fiber pulp or powder
  • the suspension then comprising the CF, the filler and the TP polymer has a consistency of less than 10 wt%, preferably 5 to 8 wt% dry solids, based on total weight of the suspension. It is understood that any additional amount of water can be introduced during the blending step of the process in order to adjust the consistency of the suspension.
  • Blending 20 the CF pulp, the filler and the TP polymer results in the formation of a final aqueous composite suspension (hereafter the "final suspension") comprising at least the CF, the filler and the TP polymer, having a consistency of less than 10 wt%, preferably 5 to 8 wt% of solids based on total weight of the final suspension.
  • final suspension a final aqueous composite suspension
  • the heterogeneous morphology of the CF leads to a uniform dispersion of all the components within the final suspension.
  • thermoplastic coupling agent 24 can be added into the suspension.
  • Such coupling agent improves the interface between the TP polymer and the CF. Indeed, although it is important to prevent complete covering of the CF by the TP polymer, homogeneous blending must nevertheless be created to ensure uniform flowing of the material during the thermoforming compression.
  • the coupling agent 24 is preferably a maleic-anhydride grafted polymer.
  • it can be maleic-anhydride grafted polyethylene (MAPE) and/or maleic-anhydride grafted polypropylene (MAPP).
  • MAPP maleic-anhydride grafted polypropylene
  • Such chemically modified polymers are generally used as coupling agent for polyolefin matrixes reinforced with glass fiber, cellulose fiber and mineral filler. It is known that such compatibilizers improve processability and mechanical properties of the product.
  • the coupling agent 24 is provided in an amount of 5 wt% to 15 wt% by dry weight of the CF reinforced material.
  • the coupling agent can be added in a form of a fine powder or in form of chopped microfibers.
  • the coupling agent is dispersed in the CF based-composite suspension during blending, more particularly after addition of the filler, for the reasons described above.
  • the coupling agent is therefore added in the suspension comprising the CF pulp and the filler and dispersed so that the suspension can reach a consistency of 6 to 7 wt% dry solids based on total weight of the suspension.
  • the wet laid process comprises the step of layering 26 the suspension formed during blending 20.
  • Layering also called sheet forming or wet lapping, can be performed using a wet lapping machine allowing to evenly distribute the final suspension comprising the CF, the filler, the TP fiber or powder (and optionally the coupling agent) on a continuous forming wire.
  • the layering step results in the formation of a wet lap as defined above.
  • the wet lap has a bulk thickness of from 2-10 mm.
  • the wet lap formed by layering is then compacted 28 ("pressing" unit operation) and dried 30 ("drying" unit operation).
  • the compacting step can be a continuous compacting process.
  • double-wire press wet-lapping machines can be used, as generally known in pulp and paper art.
  • Compacting the wet lap provides an initial dewatering of the wet lap and can be achieved at room temperature. Such compacting result in an intermediate material (or compacted wet lap) having a consistency of up to 50 wt% of solids based on total weight of the compacted wet lap.
  • the nip pressure applied to the wet lap is in the range of 200-300 psi.
  • drying the compacted wet lap is performed at a temperature below 200°C, preferably between 140 and 170°C.
  • the drying temperature is set in function of the TP polymer used in the present wet laid process.
  • the compacted wet lap can therefore be dried at a temperature within the melting-point range of the TP polymer fiber pulp or powder.
  • the melting-point range corresponds to the range of temperatures over which the solid usually melts. Indeed, a solid usually melts over a range of temperatures rather than at one specific temperature.
  • the compressed wet lap is fully oven dried, preferably with slight pressure, to form the CF reinforced material.
  • the wet laid process can also comprising recycling of the water 32 recovered during compacting of the wet lap or drying of the compacted wet lap.
  • a first water stream can be recovered from the compacting 28 ("pressing" unit operation) step and be used to dilute the CF pulp 10 and form the CF suspension 14 that is blended 20 with the filler (16, 18 and/or 18'), the TP polymer 22 and optionally the coupling agent 24.
  • Water can also be recovered from the drying step 30 and recycled in the same CF suspension 14. It is understood that water recovered from the compacting and drying steps can be recycled for use in any step or process in which water is needed. For example, recovered water can be added to the TP fiber pulp during the blending step, in order to adjust the consistency of the final aqueous solution.
  • the particular morphology of the CF allow better retention of the filler, or any functional additives, within the network formed by the CF, thereby minimizing their drainage with the recovered water during the dewatering steps (compacting and drying).
  • the concentration of filler (for example of calcium carbonate) in the recovered water is at most of 1 g/L.
  • a CF reinforced 40 (hereafter CF reinforced material) produced by the wet laid process described herein and that is ready- to-mold.
  • the term "ready-to-mold" as used herein is intended to mean that the CF reinforced material produced by the present wet laid process can be molded in any shape by any thermoforming molding process.
  • Ready-to-mold materials are known as reinforced materials that are impregnated with resin and that can be, in the case of thermoset resins, partially cured.
  • the CF reinforced material then comprises 5 wt% to 50 wt% of the water dispersible cellulose filaments (CF) by dry weight of the CF reinforced material. More particularly, the CF reinforced material can comprise 40 wt% of CF. As described above, the CF of the CF reinforced material has a length of at least 100 ⁇ , and a cross-sectional dimension of about 30 to about 300 nm. Such CF are also substantially free of fibrillated cellulose.
  • the CF reinforced material also comprises 15 wt% to 25 wt% of the filler by dry weight, preferably about 20 wt%.
  • the filler has a particle size of 1 to 5 ⁇ , and can be one of the filler identified herein.
  • a specific example of filler is calcium carbonate particles having a diameter of 2.8 ⁇ .
  • the CF reinforced material also comprises from 25 wt% to 70 wt% of a thermoplastic polymer (in form of a fiber pulp or a powder) by dry weight. More particularly, the CF reinforced material can comprise 30 wt% to 60 wt% of TP polymer, preferably of about 40 wt% by dry weight. In a particular embodiment, the TP polymer has a melting temperature below 200°C.
  • the CF reinforced material comprises a coupling agent in an amount of 5 wt% to 15 wt% by dry weight of the CF reinforced material.
  • the coupling agent can be a maleic-anhydride grafted polymer (MAPE and/or MAPP).
  • the CF reinforced material is a ready-to-mold material having a bulk density of 350 to 650 kg/m 3 .
  • the bulk density can further be of 450-550 kg/m 3 .
  • the basis weight of such CF reinforced material is of 0.7 to 3.8 kg/m 2 , preferably from 0.7 to 1.2 kg/m 2 . It has also been found that, due to the heterogeneous morphology of the CF used herein, the CF reinforced material presents a high capacity to retain microparticles, such as filler micro particles, without the need of adding retention agent and despite the addition of TP polymer.
  • a CF reinforced thermoplastic molded product obtained by molding the CF reinforced material produced used the present wet laid process.
  • the molded product can be a thermoplastic sheet or 3D-product reinforced with CF.
  • the reinforced sheet is understood to be a layer of material while the reinforced 3D-product has more complex geometrical shape.
  • the thickness of the reinforced sheet is the same over the whole surface of the reinforced sheet.
  • the reinforced sheet can also have a different thickness over different portions of the surface.
  • the molded product can be molded in flat or non-flat shape.
  • the molded product can have a wave-like shape, a tooth- like shape, or any suitable shape selected in function of the final application of the molded product.
  • the CF reinforced material can be molded using a compression molding process or an injection molding process.
  • the compression molding system can be assisted by a vacuum system.
  • the CF reinforced material can be molded under low pressure such as by vacuum bagging composite molding process, known as oven vacuum molding.
  • the CF reinforced material can also be thermoformed by hot compression molding. A sealed mold can be used during compression of the CF reinforced material in order to increase the molding pressure while preventing an excessive flow of the thermoplastic polymer matrix.
  • the molded product can also comprise one or more reinforced sheets adjacent to each other. Indeed, two or more layers of CF reinforced material can be molded and bonded into flat panels or into 3D products. The molded product can therefore be a single layer or a multilayer molded product.
  • the molded product has a monolithic structure.
  • the molded product comprises one or more layers having similar composition and physical properties (porosity, density... ).
  • the molded product has a multifunctional structure. Therefore, the molded product has more than one layer and each layer can have a different composition, different physical properties and/or different functions.
  • the content of CF, the content and the nature of the filler, of the TP polymer and optionally of the coupling agent can vary between each of the layers.
  • each sheet can have a different porosity, so that the density of the molded product can be adjusted.
  • the density of the molded product is of 0.4 to 0.8 g/cm 3 .
  • a multilayer molded product has a top and a bottom outer layer having enhanced fire resistance properties, and at least one inner layer charged with low cost filler or with low density filler, as to control the cost and density of the molded product.
  • the molded product is a lightweight syntactic panel formed by low pressure thermoforming, such as oven vacuum molding.
  • the lightweight synthetic panel can comprise a plurality of layers.
  • the molded product has improved mechanical properties, notably tensile and flexural properties.
  • the molded product can have a tensile modulus of between 2.5 and 5 GPa and a flexural modulus of between 3 and 6 GPa.
  • the molded product also has a tensile strength of between 20 and 60 MPa and a flexural strength of between 40 to 100 MPa.
  • the flexural and tensile properties are improved in comparison with molded product reinforced with conventional fibers or with other microfibri Hated cellulosic materials. Surprisingly, the tensile and flexural properties are also improved in comparison with reinforced product without filler. In addition, when a coupling agent is used, the mechanical properties of the molded product are also superior than without any coupling agent.
  • the molded product has a multifunctional structure and can be used in thermal and acoustic insulations, in fire resistance, or potentially in ballistic windshield materials.
  • the molded product can also be used as a core between two structural composite materials that can be made from thermoset or thermoplastic resins and/or weaved prepreg fabrics comprising engineered fibers.
  • CF-reinforced molded product obtained by molding of a CF reinforced material (with HDPE as TP polymer) has been compared to those of molded products reinforced with conventional Bleached Chemical Thermo-Mechanical pulp (BCTMP) and Northern Bleached Softwood Kraft (NBSK) pulp, all produced by the present wet laid process.
  • BCTMP Chemical Thermo-Mechanical pulp
  • NBSK Northern Bleached Softwood Kraft
  • the CF pulp used for the CF-reinforced molded product was manufactured at Kruger Biomaterials Inc., from an NBSK pulp using the process as described by Hua et al. (US/2011/0277947), and the CF therefore have the aforementioned particular morphology.
  • the flat monolayer panels were then tested for tensile strength as per ASTM D638-10 standard.
  • the CF pulp as described in the present application provides higher reinforcing effect compared to traditional NBSK and BCTMP pulps.
  • the CF reinforced panel (CF/HDPE-SMC) has a tensile strength that is about 36% and 58% higher than NBSK and BCTMP reinforced panels, respectively (NBSK/HDPE-SMC and BCTMP/HDPE-SMC).
  • Figs. 3A and 3B it has been found that the specific CF used herein restrict the flow of the hot melted polymer matrix when the molded part is subjected to a Laser cutter. Compared with the traditional wood pulps (Fig. 3A), the present CF pulp allows sharp and clean Laser cuts (Fig. 3B).
  • Embodiments 1-5 were prepared without any coupling agent.
  • Embodiments 3, 4, 5, 7, and 8, were prepared with calcium carbonate filler particles having an average diameter of 2.8 ⁇ .
  • Embodiments 6 and 7 were prepared using a MAPE grade (NOVACOM-PTM HFS2100P) coupling agent having a maleic anhydride content of 1 % (tested by FTIR method), a D50 particle size of 38 ⁇ (determined by laser diffraction), a D100 particle size of 300 ⁇ (determined by sieve analysis), and a melting point of 130°C (determined by DSC, as per ASTM D3418).
  • MAPE grade NOVACOM-PTM HFS2100P
  • Embodiment 8 was prepared using a MAPP grade (PROPOLDERTM MPP2040) coupling agent having a maleic anhydride content of 3.5%, a mean average volume weighted particle size of 40 ⁇ , and a melting point of 160°C.
  • MAPP grade PROPOLDERTM MPP2040
  • Table 1 Composition, wet-lap consistency and bulk density of different CF reinforced TP- SMC sheet embodiments (final suspension consistency of -10% OD; sheet basis of -3800 g/m 2 OD).
  • Fig. 4A shows the molded cycle for the thermoplastic sheet molding compound (TP-SMC) sheets comprising HDPE polymer, without coupling agent nor filler (embodiment 1)
  • Fig. 4B shows the molded cycle for the TP-SMC sheets comprising PP polymer, without coupling agent nor filler (embodiment 2).
  • Fig. 5A shows the molded cycle for the TP-SMC sheets comprising HDPE polymer, without coupling agent and with filler (embodiment 3)
  • Fig. 5B shows the molded cycle for the TP-SMC sheets comprising HDPE and PP polymers, without coupling agent and with filler (embodiment 4)
  • FIG. 5C shows the molded cycle for the TP-SMC sheets comprising PP polymer, without coupling agent and with filler (embodiment 5).
  • Fig. 6A shows the molded cycle for the TP- SMC sheets comprising HDPE polymer, with coupling agent and without filler (embodiment 6)
  • Fig. 6B shows the molded cycle for the TP-SMC sheets comprising HDPE polymer, with coupling agent and filler (embodiment 7)
  • Fig. 6C shows the molded cycle for TP-SMC sheets comprising PP polymer, with coupling agent and filler (embodiment 8).
  • the compression molding cycles shown in this application are illustrative only. Indeed, the heating and cooling rates may be accelerated in order to reduce the total molding time to a few minutes.
  • Table 2 Compositions, mechanical and water absorption results of the compression molded CF reinforced HDPE and PP-SMC sheet embodiments.
  • Figs. 7A and 7B summarize the ultimate tensile and flexural strengths (Fig. 7A) and tensile and flexural modulus (Fig. 7B) of the PP-SMC panels of embodiments 1 to 5. As illustrated, the panels without and with calcium carbonate were stronger in tensile and flexural tests than their respective HDPE-SMC panels (embodiment 2 vs embodiment 1 and embodiment 5 vs embodiment 3). Such higher performances are due to the greater intrinsic properties of the PP compared with the HDPE.
  • the panel of embodiment 4 containing by dry weight 40% CF, 20% CaC0 3 , 10% HDPE pulp, and 30% PP pulp showed tensile and flexural properties that stand between those of the embodiments 3 and 5, which contain by dry weight 40% CF, 20% CaC0 3 , 40% HDPE pulp, and 40% CF, 20% CaC0 3 , 40% PP pulp, respectively.
  • the panels containing 20% calcium carbonate by dry weight performed better in tensile and flexural properties than their respective panels without calcium carbonate (embodiment 1 vs embodiment 3 and embodiment 2 vs embodiment 5, respectively).
  • the effect of calcium carbonate in the shape of microparticles is usually reported as having negative effect on the tensile strength of thermoplastic resins.
  • the tensile yield strength of HDPE composite comprising CaC0 3 drops by up to 16% with respect to the neat HDPE when the CaC0 3 volume fraction is around 8% (or 20% by weight fraction).
  • the panels containing by weight 40% CF and 60% TP fiber pulp may be considered as panels containing by weight 40% CF, 20% TP fiber pulp, and additional 40% TP fiber pulp.
  • This division between the 60% of TP fiber pulp into 20% plus 40% of the same TP fiber pulp allows the comparison with the respective panel containing by weight 40% CF, 20% CaC0 3 , and 40% thermoplastic pulp.
  • the embodiments without coupling agent and comprising 40% CF and 20% CaC0 3 show better tensile and flexural properties than the embodiments without CaC0 3 (embodiments 1 and 2). It is believed that the presence of CaC0 3 prevent the TP fiber pulp from covering the whole surface of the CF and allow formation of hydrogen-bonds between the CF, the substitution of 20% by weight of the TP fiber pulp by CaC0 3 will affect the potential hydrogen-bonds between the CF in the CF network. In absence of coupling agent, the CF network formed by the hydrogen-bonding between the CF constitutes the only reinforcing component within the panels. It can be considered that there is a higher hydrogen-bonds density within the CF in the embodiments comprising 40% CF and 20% CaC0 3 than in the embodiments comprising 40% CF and 20% TP fiber pulp, thereby improving the mechanical properties of the panels.
  • Fig. 7A shows that, without coupling agents, the mean ratio of flexural to ultimate tensile strength is of about 2 (embodiments 1 to 5), while according to Fig. 8A the mean ratio of flexural to ultimate tensile strengths in presence of coupling agent is of about 1.7 (embodiments 7 and 8).
  • the mean ratio of flexural to ultimate tensile strengths in presence of coupling agent is of about 1.7 (embodiments 7 and 8).
  • Fig. 8A in accordance with the results of Table 2, addition of a coupling agent leads to an improvement of the ultimate tensile and flexural strengths.
  • the results show about 45% and about 19% increase in tensile and ultimate flexural strengths of CF reinforced HDPE-SMC panel containing 10 wt% by dry weight MAPE coupling agent (embodiment 7) compared to embodiment 3 that has no coupling agent (MAPE).
  • Fig. 8A also shows an increase of about 37% in tensile strengths and about 25% increase in flexural strengths, between embodiment 5 comprising no coupling agent and embodiment 8 comprising MAPP coupling agent.
  • the presence of coupling agent also leads to an increase in tensile modulus of up to about 34% (embodiment 3 compared to embodiment 7).
  • the MAPE coupling agent used in embodiment 7 has a maleic anhydride content of only 1wt%. Therefore, it results in a relatively weak improvement with respect to the flexural young modulus.
  • the flexural modulus increases by about 5% between embodiments 3 and 7 (Fig. 8B).
  • the CF reinforced PP-SMC panel containing 10% by dry weight of MAPP (embodiment 8), showed an increase of about 22% and about 17% in tensile and flexural modulus, respectively, compared to embodiment 5 that has no coupling agent.
  • This higher performance of the MAPP coupling agent with respect to MAPE can be explained by a higher maleic anhydride content in the MAPP, i.e. 3,5 wt%.
  • a panel comprising PP and 40 wt% of CF and molded by compression shows up to 11 1 % and 63% increase in tensile and flexural strengths, respectively, compared to a panel comprising PP and reinforced with wood fibers: 40.8 MPa vs 19.3 MPa for the tensile strength and 72.9 MPa vs 44.8 MPa for the flexural strength.
  • the wood fiber reinforced panel comprises by dry weight an average of 40% wood fiber with respect to the panel weight and 5 wt% of MAPP coupling agent with respect to wood fiber.
  • FIG. 9A also shows that the same wood fiber reinforced panel processed by injection molding has a tensile strength and a flexural strength lower than the compressed CF reinforced panel by about 1 1 % and 15% respectively: 36.3 MPa vs 40.8 MPa for tensile strength, and 62.3 MPa vs 72.9 MPa for flexural strength.
  • the flexural modulus is also improved for the CF reinforced panel compared with the wood fiber reinforced panel.
  • the highest notched Charpy impact strength reported in Table 2 can also be compared with the notched and the unnotched Charpy impact strengths of regenerated cellulosic fiber reinforced PP-SMC composites of US 2013/0052448 (Table 3).
  • the average values of Table 3 of US 2013/005248 are of 3.98 KJ/m 2 and 45.95 KJ/m 2 , respectively.
  • the cellulosic fiber reinforced composite comprises 30% by weight of regenerated cellulosic fibers and 2% of MAPP coupling agent.
  • the water absorption % of an injection molded CF reinforced PP-SMC panel comprising 20 wt% of CF and 20 wt% of CaC0 3 , was found below 0.5% after 24 hours and at an average value of 1 % after 7 days.
  • the water absorption was of 0.8% after 24h and of 2% after 7 days. It shows that, in addition to the presence of the CF, the molding pressure may have a critical effect on the water absorption of the molded CF reinforced TP-SMC product.
  • the compression molded CF reinforced TP-SMC products were process at up to 1000 psi (about 69 bars), while the injection molded CF reinforced TP-SMC products were processed at 1000-1500 bars.
  • Table 3 shows more PP-SMC embodiments where new fresh batch of CF pulp was used alone and in conjunction with NBSK pulp. Mainly, it presents mechanical results after compression molding at up to 1990 psi at a mold temperature of ⁇ 200°C. Also, presents results after injection molding trials (embodiments 14 and 15).
  • conventional pulp like NBSK 50 may be used as reinforcement in conjunction with CF pulp 10, producing thermoplastic sheet molding compound material comprising CF/NSBK 60. While this approach allows reduction in the raw material cost, it may also reduce the processing cost mainly during the drying phase. Furthermore, a better synergy may be achieved between the different components allowing higher efficiency of the coupling agent (CA) and thus potentially higher performance to cost ratios.
  • CA coupling agent
  • a PP- SMC compression molded panel containing by weight CF and NBSK respectively at 15% and 25% (OD), has somehow similar or higher properties than that reinforced with only CF at 40 wt.%.
  • the coupling agent here the MAPP
  • the MAPP may have achieved due the reduction of total cellulosic specific surface induced by the partial substitution of the CF by the NBSK, equivalent to a portion of 62.5% with regards to the original CF fraction
  • a PP-SMC panel comprising by weight CF and NBSK respectively at 15% and 25% (OD), and molded by compression, shows up to 210% and 104% increase in tensile and flexural strengths, respectively, compared to a panel comprising PP and reinforced with wood fibers: 59.9 MPa vs 19.3 MPa for the tensile strength and 91.5 MPa vs 44.8 MPa for the flexural strength.
  • the wood fiber reinforced panel comprises by dry weight an average of 40% wood fiber with respect to the panel weight and 5 wt% of MAPP coupling agent with respect to wood fiber (Bledzki and Faruk, 2004, Polymer-Plastics Technology and Engineering, 43: 871-888).
  • FIG. 12A Vacuum bagging (Fig. 12A) with a pressure of 1 bar was used to produce a multilayer molded product (Fig. 12B). Such low pressure is enough to get the CF reinforced material layers bonded to each other as soon as the adjacent layers are heated to or above the melting point of the thermoplastic fiber pulp. The CF reinforced material can therefore be processed into a thermoforming pre-mold and then be subsequently transferred into a final compression mold capable to withstand high pressure.
  • Fig. 12C shows a corrugated panel molded at 1000 psi/140°C made from two layers of CF reinforced material comprising HDPE and which have been preformed under low pressure (about 14 psi) and bonded to each other at 140-150°C.
  • Table 4 presents the composition and density of six lightweight syntactic embodiments.
  • Low density panels may be formed by low pressure thermoforming (oven vacuum molding). Different layers of CF reinforced materials like comprising typical fillers and/or hollow microspheres or expandable polymeric microballoons may be co-molded to design the final products as per required specifications.
  • the lightweight syntactic flat panel of Fig. 13B was oven (155°C) vacuum molded as shown in Fig. 13A using three layers of embodiment #16 (Table 4).
  • balsa was not completely impervious to air. It absorbs sound as frequency increases in the first few millimeters in its thickness. For balsa specimens, sound transmission losses (STL) starts horizontally (typical for rigid frame open-cell porous materials) till about 1275 Hz.
  • Table 4 Composition, density and thermal conductivity of syntactic CF reinforced HDPE and PP-SMC sheets thermoformed by oven vacuum molding.

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Abstract

L'invention concerne un matériau de mélange à mouler en feuille thermoplastique (TP-SMC) renforcé, prêt au moulage, comprenant des filaments cellulosiques (FC) dispersibles dans l'eau. La teneur en FC est de 5 % en poids à 50 % en poids par poids sec. Les FC présentent une longueur d'au moins 100 μm et une dimension de section transversale d'environ 30 à environ 300 nm, et sont sensiblement exempts de cellulose fibrillée. Le matériau de TP-SMC comprend également de 15 % en poids à 25 % en poids par poids sec d'au moins une charge présentant une taille de particule allant jusqu'à 100 μm ; et de 25 % en poids à 70 % en poids par poids sec d'une pâte ou d'une poudre de fibres thermoplastiques présentant une température de fusion inférieure à 200 °C. Le matériau renforcé prêt au moulage peut également comprendre un agent de couplage et présente une masse volumique apparente de 350 à 650 kg/m3 et un poids de base sec de 0,7 à 3,8 kg/m2.L'invention concerne également un procédé par voie humide destiné à produire ledit matériau renforcé prêt au moulage et un produit moulé associé.
PCT/CA2018/050707 2017-06-19 2018-06-13 Procédé de production de mélanges à mouler en feuille thermoplastique renforcés par des filaments cellulosiques et produits associés WO2018232500A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113480007A (zh) * 2021-08-19 2021-10-08 浙江沃乐环境科技有限公司 一种水处理设备及水处理系统
US11832559B2 (en) 2020-01-27 2023-12-05 Kruger Inc. Cellulose filament medium for growing plant seedlings

Citations (1)

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Publication number Priority date Publication date Assignee Title
WO2012013810A1 (fr) * 2010-07-30 2012-02-02 Rockwool International A/S Procédé de fabrication d'éléments fibreux et élément produit par ce procédé

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
WO2012013810A1 (fr) * 2010-07-30 2012-02-02 Rockwool International A/S Procédé de fabrication d'éléments fibreux et élément produit par ce procédé

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11832559B2 (en) 2020-01-27 2023-12-05 Kruger Inc. Cellulose filament medium for growing plant seedlings
US11871705B2 (en) 2020-01-27 2024-01-16 Kruger Inc. Cellulose filament medium for growing plant seedlings
CN113480007A (zh) * 2021-08-19 2021-10-08 浙江沃乐环境科技有限公司 一种水处理设备及水处理系统

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