US20120090759A1 - Method of producing composite materials - Google Patents

Method of producing composite materials Download PDF

Info

Publication number
US20120090759A1
US20120090759A1 US13/255,942 US201013255942A US2012090759A1 US 20120090759 A1 US20120090759 A1 US 20120090759A1 US 201013255942 A US201013255942 A US 201013255942A US 2012090759 A1 US2012090759 A1 US 2012090759A1
Authority
US
United States
Prior art keywords
woody
mixing
particles
composite
melt
Prior art date
Legal status (The legal status 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 status listed.)
Abandoned
Application number
US13/255,942
Inventor
Antti Pärssinen
Petro Lahtinen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ONBONE Oy
Original Assignee
ONBONE Oy
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 ONBONE Oy filed Critical ONBONE Oy
Assigned to ONBONE OY reassignment ONBONE OY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: PARSSINEN, ANTTI, LAHTINEN, PETRO
Publication of US20120090759A1 publication Critical patent/US20120090759A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • AHUMAN NECESSITIES
    • A43FOOTWEAR
    • A43BCHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B17/00Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined
    • A43B17/003Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined characterised by the material
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F5/00Orthopaedic methods or devices for non-surgical treatment of bones or joints; Nursing devices; Anti-rape devices
    • A61F5/01Orthopaedic devices, e.g. splints, casts or braces
    • A61F5/04Devices for stretching or reducing fractured limbs; Devices for distractions; Splints
    • A61F5/05Devices for stretching or reducing fractured limbs; Devices for distractions; Splints for immobilising
    • A61F5/058Splints
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/12Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L31/125Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F5/00Orthopaedic methods or devices for non-surgical treatment of bones or joints; Nursing devices; Anti-rape devices
    • A61F5/01Orthopaedic devices, e.g. splints, casts or braces
    • A61F5/14Special medical insertions for shoes for flat-feet, club-feet or the like
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/07Stiffening bandages
    • A61L15/12Stiffening bandages containing macromolecular materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/07Stiffening bandages
    • A61L15/12Stiffening bandages containing macromolecular materials
    • A61L15/125Mixtures of macromolecular compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/07Stiffening bandages
    • A61L15/14Use of materials characterised by their function or physical properties
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • A61L27/44Composite materials, i.e. containing one material dispersed in a matrix of the same or different material having a macromolecular matrix
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/58Materials at least partially resorbable by the body
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00Compositions of lignin-containing materials
    • C08L97/02Lignocellulosic material, e.g. wood, straw or bagasse
    • AHUMAN NECESSITIES
    • A63SPORTS; GAMES; AMUSEMENTS
    • A63BAPPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B71/00Games or sports accessories not covered in groups A63B1/00 - A63B69/00
    • A63B71/08Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions
    • A63B71/12Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions for the body or the legs, e.g. for the shoulders
    • A63B71/1225Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions for the body or the legs, e.g. for the shoulders for the legs, e.g. thighs, knees, ankles, feet
    • A63B2071/1258Body-protectors for players or sportsmen, i.e. body-protecting accessories affording protection of body parts against blows or collisions for the body or the legs, e.g. for the shoulders for the legs, e.g. thighs, knees, ankles, feet for the shin, e.g. shin guards
    • AHUMAN NECESSITIES
    • A63SPORTS; GAMES; AMUSEMENTS
    • A63BAPPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B2209/00Characteristics of used materials
    • A63B2209/18Characteristics of used materials biodegradable
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/06Biodegradable
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/02Applications for biomedical use
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/249921Web or sheet containing structurally defined element or component

Definitions

  • the present invention relates, in general to the field of manufacturing wood-plastic composite (WPC).
  • WPC wood-plastic composite
  • present invention relates to the production of composite materials comprising wood particles and biodegradable thermoplastic polymer. More particularly, the present invention relates to a method of manufacturing novel wood-plastic composites useful as splints or casts in immobilization of a fractured body extremities.
  • thermoplastic polymers in particular polycaprolactone and finely divided wood powder or fibres and thermoplastic polymers.
  • these structures are of the “mesh type” consisting of cellulosic fibers with an average particle size less than 0.6 mm.
  • a mesh type casting material is presented in Published International Patent Application WO 94/03211.
  • the material is manufactured by using a powder deposition process. The process includes mixing, with a dispensing hopper, depositing the material to the non-woven fabric followed by a pressing procedure and a heat treatment procedure at a double-band press.
  • Powder deposition is however suitable only for manufacturing homogenized composites with fine particles. Moreover, the double-bend press cannot gently homogenize the wood particles with rather large dimensions to an evenly distributed mixture with polymer matrix.
  • the novel technology is based on the concept of mixing a thermoplastic polymer selected from the group of biodegradable polymers with at least one reinforcing material selected from woody materials in the form of platy and granular wood particles in particular under conditions of melt mixing.
  • the mixing is carried out in an apparatus for melt processing of polymers, e.g. an extruder or an equivalent device capable of producing a compounded mixture of thermoplastic and additives, at an elevated temperature and optionally at an increased pressure.
  • the elevated temperature corresponds to or is higher than the melt temperature of the polymer.
  • the present invention is characterized by what is stated in the characterizing part of claim 1 .
  • the method will produce light-weight dimensionally stable wood-thermoplastic composite materials composed of wood chips and a thermoplastic polycaprolactone. During the gentle manufacturing process fragile wood chips maintain their 3-D structural properties in polymer matrix resulting light, mechanically strong wood-plastic composite.
  • the material of the present invention can generally be manufactured by mixing a first component, i.e. a suitable polymer material, for example in the form of pellets, with the second component, i.e. wood particles or granules, by melt mixing.
  • the mixing can be carried out in any conventional apparatus designated for melt mixing or melt processing.
  • One example is a heatable vessel having a mechanical stirrer.
  • the composite can be formed by using an extruder, kneader or any device suitable for mixing thermoplastic polymers, in particular for mixing of polymers in melt phase.
  • the mixture of the first and second components prior to melting is a homogeneous mixture of the two components.
  • two hoppers each containing one of the components of the material, can deposited the desired amount of each component in to a mixing chamber of the apparatus. Then, by way of the mixing means in the mixing apparatus, there is formed a homogeneous mixture of the first and second components prior to the formation of the composite material.
  • One advantage to the material being formed by such a homogeneous mixture of the components is that the forces necessary to form a substantially homogeneous material are reduced. Therefore, little or no compression force is necessary to facilitate mixing of the components in a material formation step. The importance of this factor is that, by way of the homogeneous mixture, larger particles of each component can be used which would otherwise have been destroyed when subjected to high compression forces.
  • the material can be applied for use after it has been recovered from the mixing device and formed into the desired shape, for example into a sheet or plate or roll or any similar planar, folded, bent or tubular structure.
  • the material can even be formed directly on the patient.
  • the material mixed with an extruder can be shaped with an appropriate nozzle to the shape of, e.g. a rectangular sheet or plate which can be used directly after cutting, e.g. as a wrist splint.
  • a sheet or plate whose purpose is to be later formed in to a desired shape or size is referred to herein as a blank.
  • a desired specific profile or shape for the splints can be manufactured with the extruder manufactured sheet or plate by optical, chemical or mechanical cutting, e.g. laser cutting, water jet cutting, eccentric pressing, or with any tool capable for producing regular shape profiles, i.e. stamping.
  • the present material can also be processed with compression moulding, injection moulding, die-casting, and pressure die-casting. Ideally these specific profiles and shapes are in linear, two-dimensional form so as to be easily and compactly storable. To maintain the simplicity and cost effectiveness in the manufacturing process of the novel composite material of the present invention preferably the whole manufacturing process of the end-product is continuous.
  • the present method of producing a composite useful as an orthopedic material comprises the steps of;
  • the melt-mixing is carried out at a temperature sufficient for melting the thermoplastic polymer.
  • the mixing is generally carried out at a temperature of about 50 to 190° C., preferably about 90 to 150° C., in particular about 100 to 130° C., in order to achieve conditions of melt-mixing in the apparatus.
  • the temperature can also be in the range of about 50 to 150° C., in particularly about 100 to 140° C.
  • the molten polymer mass containing a mixture of biopolymer and reinforcing platy particles can be shaped manually or, according to a preferred embodiment by moulding in a mould.
  • the molten polymer mass can be subjected to tensile forces to achieve a desired orientation of the polymer and, in particular, the reinforcing particles.
  • the manufacturing process comprises several preferred embodiments.
  • a preferred embodiment of the manufacturing process of a composite material comprises the steps of compounding: virgin materials with an extruder and production of uniform homogeneous plate-like composite.
  • One particular embodiment consist of compounding wood chips and thermoplastic polymer with single screw extruder and profile manufacturing of therein produced composite by using calendaring techniques.
  • This manufacturing method is applicable for production of composites consisting of any thermoplastic polymer having a melting point below 100° C. and wood particles having volume between 1-50 mm 3 .
  • the manufacturing process is initiated by mixing wood chips and plastic granules to uniform blend before pouring to feed hopper of the extruder.
  • the mixing process can be carried out also by feeding of the virgin materials to the extruder directly by using separate feeding hoppers.
  • the profile of screw has to have dimensions that allow relatively lame wood chips (up to about 30 to 50 mm in one dimension) to move along the screw without crushing them. Simultaneously, appropriate dispersion between wood and polymer has to be achieved.
  • the screw-like channel width and flight depth are selected such that formation of local pressure increases can be avoided.
  • the temperature of cylinder and the screw rotation speed are selected to avoid decomposition of wood chip structure by high pressure during extrusion.
  • the appropriate barrel temperature is generally in the range of 80 to 190° C., preferably 100 to 150° C., e.g. 116-135° C., from hopper to die.
  • the screw rotation speed is typically about 10 to 100 rpm, for example 25 to 50 rpm.
  • the extruder compounded composite material can be further worked upon to obtain homogeneous plates or sheets with a thickness of about 1 to 5 mm, e.g. 3.5 mm, with preselected width and length by using calendering techniques.
  • composite material can be gently folded between calendering cylinders in a plurality of phases, each consisting of a number of cycles. For example 2 phases with at least 10 cycles each are preferred.
  • the melt mixing is carried out in an extruder and the calendering process comprises several cycles of folding, cooling and reheating steps.
  • the temperature of calender cylinders can be kept constant, for example at a temperature above the melting point of the thermoplastic material, to keep the composite moldable during calendering process.
  • Plates can be finished by sanding the edges with band sander.
  • the calender cylinders were kept at 100° C. Smooth surface to the final product were achieved by calendering the plate one time through at 100° C.
  • Alternative manufacturing process for the composite plates is press method after the mixing process carried out with extruder.
  • Pneumatic, mechanical and/or hydraulic presses are suitable for the press method of the composite. During pressing the heated plates of the press are kept at temperature
  • the density of composite manufactured with combination of extruder and calendaring or extruder and press vary between 600-1050, e.g. 600-850 kg/m 3 depending on the weight percent of wood in material.
  • the complete manufacturing process of the end-product is preferably continuous.
  • Low viscosities of the polymers at elevated temperatures complicate the manufacturing process of the multi-component composites. For example pressing of hook-and-loop fasteners to the surface of composite at elevated temperatures tearing and creeping of the composite material can be observed.
  • the present manufacturing method is therefore particularly well suited for the processing of highly viscous thermoplastics, such as PCL having an MFI value of 3, as a polymer component. After mixing procedure with extruder the formed mixture of wood and a PCL of the indicated MFI value can be directly used in calandering process. The creep phenomenon of the molten composite during pressing fasteners onto it can be avoided when the wood weight percentage in the composite is at least 20.
  • the adhesion of the composite can be improved by coating the surface of the composite with additional layer of virgin PCL or with any similarly behaving material.
  • the coating process can be performed practically either by extrusion coating or extrusion laminating in a continuous process.
  • extrusion coating a molten layer of extrudate is laid onto a composite.
  • the temperature of the extruded molten polymer is kept below 200° C. to avoid tarnishing of the wood component and at the same time above 100° C. to guarantee reasonable flow of the polymer on the substrate.
  • the polymer wets the entire surface evenly and smooth over uneven surface which is important contributor to adhesion.
  • Composite consisting of three layers of compounds can be performed by extrusion laminating. In the process two substrates (PCL) enters the nip formed by two rolls. The middle extrudate (composite) also enters the nip by traveling over each roll. The composite is therefore the center part of the resulting sandwich material.
  • the manufacturing of the multilayer composite consisting of composites layers having different weight percentage of wood can be performed by using calandering techniques. Two or more molten extrudates are combined to sandwich type of structures and pressed together in calender. By using similar calandering technique also padding and fasteners can be pressed to the molten composite extrudate consisting of one or multi layers.
  • the composite retains its shape as it cools down. It is substantially rigid but flexible so as to be supportive and comfortable. Rigidity is generally achieved, when a sample heated to the above indicated softening temperature is cooled to below 50° C., in particular to less than 45° C., preferably less than 40° C. Typically, the composite is rigid at ambient temperature; a suitable temperature of use is about ⁇ 40 to +50° C., in particular ⁇ 30 to +40° C.
  • the composite material sheet or plate can have a thickness of, generally about 0.2 to 50 mm, in particular about 1.5 to 30 mm, for example 1.5 to 20 mm. A typical thickness is about 2 to 6 mm.
  • the length and the width of the sheet or plate can vary in the range of about 1 to 150 cm (length) and to 50 cm (width), a typical length being about 10 to 60 cm and a typical width being about 5 to 20 cm.
  • a particular embodiment comprises producing a continuous product, collecting the product and rolling it or folding it. Such a product is then provided in the form of ribbons or tape which can be collected on a receiving roller.
  • a linear product e,g. a sheet or a plate
  • That laminar product can be further processed.
  • it can be perforated.
  • Another alternative is to use the linear product for making a laminate comprising at least two layers, each preferably being comprised of such linear products.
  • the laminate can be perforated, also,
  • One specific embodiment comprises the steps of providing on a laminate at least one surface layer having a reduced content of woody material.
  • the layer can be formed by neat polymer or by a polymer merely having a reduced content of the woody material. Such a surface layer will provide improve adhesive properties for the product.
  • a particularly interesting embodiment comprises producing an essentially linear product, and mechanically modifying, e.g. by corrugation, the linear product so as to increase its stiffness.
  • the product produced by the present invention can also comprise further fillers or enforcing components.
  • one embodiment comprises mixing the thermoplastic polymer with a first woody material and at least one second woody material, said second woody material being different from the first woody material.
  • a still further embodiment of producing a biodegradable linear composite material capable of being used to form an exo-skeletal device through thermal molding comprises the steps of;
  • obtaining a desired woody particle mixture comprises the step of taking a woody particle feed having a plurality of sized woody particles and sorting the feed to obtain the desired woody particle mixture.
  • the step of sorting the woody particle feed may comprise sifting the feed through one or more meshes.
  • more than 70% of the second component is formed by the woody particle mixture.
  • the first and second components may have pellets and particles of similar size.
  • the desired shape is a substantially rectangular blank formed from an extruder.
  • the desired shape may, however, be other than a rectangular blank and can be formed by optically, chemically or mechanically cutting or stamping the desired form from the composite material.
  • the proportions between the components of the material can vary in a broad range.
  • 5 to 99 wt-%, for example 40 to 99 wt-%, of the material is formed by the thermoplastic polymer component and 1 to 95 wt-%, for example 1 to 60 wt-%, by the woody material.
  • the weight ratio of polymer-to-wood can easily be modified. and the weight percent of wood, based on the total weight/volume of the composition, may vary between 1 and 70%, preferably however in the range of 10 to 60 weight percent, or 20 to 60 weight percent, and 15 to 50%, or 25 to 50%, by volume.
  • the second component comprises a woody material having a smallest diameter of greater than 0.1 mm. As will be discussed below, there can also be other wood particles present in the second component and the woody material can be granular or platy.
  • the size and the shape of the wood particles may be regular or irregular.
  • the particles have an average size (of the smallest dimension) in excess of 0.1 mm, advantageously in excess of 0.5 mm, for example in excess of 0.6 mm, suitably about 1 to 40 mm, in particular about 1.2 to 20 mm, preferably about L5 to 10 mm, for example about 1.5 to 7 mm
  • the length of the particles (longest dimension of the particles) can vary from a value of greater than 1 mm to value of about 1.8 to 200 mm, for example 3 to 21 mm.
  • the woody particles can be granular, platy or a mixture of both.
  • Woody particles considered to be platy means that they have generally a plate-shaped character, although particles of other forms are often included in the material.
  • the ratio of the thickness of the plate to the smaller of the width or length of the plate's edges is generally 1:1 to 1:500, in particular about 1:2 to 1:50.
  • the platy particles of the present invention generally comprise wood particles having at least two dimensions greater than 1 mm and one greater than 0.1 mm, the average volume of the wood particles being generally at least 1 min 3 ′ more specifically at least 1 mm 3 .
  • Derived from platy wood particles designates that the wood particles may have undergone some modification during the processing of the composition. For example, if blending of the first and second components is carried out with a mechanical melt processor, some of the original platy wood particles may be deformed to an extent.
  • the wood species can be freely selected from deciduous and coniferous wood species alike: beech, birch, alder, aspen, poplar, oak, cedar, Eucalyptus, mixed tropical hardwood, pine, spruce and larch tree for example.
  • woody material of the composite can also be any manufactured wood product.
  • the particles can be derived from wood raw-material typically by cutting or chipping of the raw-material. Wood chips of deciduous or coniferous wood species are preferred.
  • a particularly interesting raw-material comprises wood chips of any of the above mentioned wood species having a screened size of greater than 0.6 mm and up to about 3 mm, in particular about 1 to 2.5 mm on an average.
  • a composite useful as an orthopedic material comprises a first component formed by a polymer and a second component formed by a reinforcing material, wherein the first component comprises a thermoplastic polymer selected from the group of biodegradable polymers and mixtures thereof, and the second component comprises reinforcing fibres.
  • Such fibers can be selected from the group for example of cellulose fibers, such as flax or seed fibers of cotton, wood skin, leaf or bark fibers of jute, hemp, soybean, banana or coconut, stalk fibers (straws) of hey, rice, barley and other crops including bamboo and grass.
  • the wood filler may consist of or consist essentially of fibres of the indicated kind.
  • the polymer component can be any of the below listed polymers, caprolactone homo- or copolymers having a molecular weight of about 60,000 g/mol up to 250,000 g/mol being particularly preferred.
  • the polymer component is a caprolactone homopolymer or a blends of homo- or copolymers of epsilon-caprolactone having a molecular weight of above 80,000 g/mol.
  • polycaprolactone having a molecular weight of between 100,000 g/mol and 200,000 g/mol as been found to be advantageous both in terms of resultant properties and cost.
  • the woody particles Before the woody particles are mixed with the thermoplastic polymer they can be surface treated, e.g. sized, with agents which modify their properties of hydrophobicity/-hydrophobicity and surface tension. Such agents may introduce functional groups on the surface of the granules to provide for covalent bonding to the matrix. Even increased hydrogen bonding or bonding due to van der Waals forces is of interest.
  • the woody particles can also be surface treated with polymer e.g. PCL having low viscosity and molar mass values to increase holding powers between wood and PCL having high viscosity value.
  • the wood material can be also coated or treated with anti-rot compound e.g. vegetable oil to improve its properties against aging and impurities.
  • anti-rot compound e.g. vegetable oil
  • the wood material can be dehydrated to make it lighter before mixing it with polymer.
  • the mechanical and chemical properties of wood material can be improved with heat treatment, which is known to decrease e.g. swelling and shrinkage.
  • the first component (the polymer) forms the matrix of the composite, whereas the microstructure of the second component in the composition in discontinuous.
  • the particles of the second component can have random orientation or they can be arranged in a desired orientation.
  • the desired orientation may be a predetermined orientation.
  • composition may contain particulate or powdered material, such as sawdust, typically having particles with a size of less than 0.5 mm*0.5 mm*0.5 mm.
  • Particulate or powdered material is characterized typically as material of a size in which the naked eye can no longer distinguish unique sides of the particle. More specifically, powder particles are of such a size that their dimensions cannot be measured with traditional, Vernier, calipers.
  • non-powder particles are of such a size that they can be measured with traditional calipers.
  • platy particles are easily recognizable as one dimension is recognizable by the naked eye as being larger than another.
  • Granular particles while having substantially equal dimensions, are of such dimension that their unique sides can be determined by the naked eye and oriented.
  • particulate or powdered materials are of such a small or fine size that they cannot be easily oriented with respect to their neighbours.
  • Granular and platy particles are of such as size that their sides are recognizable and orientable.
  • the present material contains a significant portion of wood granules having a particle size greater than the micrometer range, for example a size of about 0.75 mm to 50 mm.
  • a size of about 0.75 mm to 50 mm When the material is shaped into a sheet, (at least most of) the wood granules become oriented in two dimensions within forming of the thermoplastic material into sheets.
  • the reinforced material typically exhibits properties selected from one or several of the following:
  • the desired composition of the second component can be achieved by sifting woody particles through one or more meshes having one or more varying qualities.
  • the desired composition can also be accomplished by other well known techniques in the art for sorting and separating particles in to desired categories.
  • the desired composition may be the resultant composition of one sifting or separating process.
  • the desired composition may also be a mixture of resultant compositions from several sifting or separation processes.
  • the weight ratio of fibrous material (optionally including said powdered material) to the platy material (dry weight) is about 1:100 to 100:1, preferably about 5:100 to 50:50.
  • the woody material derived from the platy wood particles forms at least 10%, preferably about 20 to 100%, in particular about 30 to 100%, of the total weight of the second component.
  • the powdered material may form up to 30%, typically about 1 to 20%, of the total weight of the second component.
  • inorganic particulates or powdered materials such as mica, silica, silica gel, calcium carbonate and other calcium salts such as tricalcium orthophosphate, carbon, clays and kaolin may be present or added.
  • the present method will produce a composition that can be used as a composite material.
  • Such materials are exemplified by finger splints, wrist casts and ankle casts.
  • the platy particles form about 30 to 70%, preferably in excess of 40 up to about 60%, of the total weight of the composition, for finger splints and for ankle casts about 20 to 60%, preferably about 30 to 50% of the total weight of the composition.
  • the composite material of the present invention is manufactured in to either a blank or in to a desired, specific shape or form.
  • the blanks and forms are linear, two dimensional and easily stackable.
  • the blanks can be either substantially larger than the intended size to be applied to the animal or human being, herein referred to as the patient, or of substantially similar size.
  • the blank can be cut with normal scissors or other conventional cutting means before application.
  • a large blank is preferable in the sense that one blank may be cut in to several splints at various times according to the size required by each. Therefore, it is not necessary to store many different shapes and sizes of the material, which take up room and may be rarely used.
  • multiple splints may be cut from one blank in such a way as to maximize the material used and not produce a large amount of waste product.
  • the material is then heated to the desired operating temperature by a heating means.
  • a heating means Numerous heating means are known in the art, but it is preferable to uniformly heat the material to a specific desired temperature. If the temperature is too high then there is risk of discomfort or harm to the patient's skin. If the temperature is not high enough then the material will not be able to properly conform to the patient's body.
  • Table 1 is a table chart showing the densities of the test specimens manufactured by calandering at different temperatures
  • Table 2 is a table chart showing the flexural strengths of the test specimens manufactured by calandering at different temperatures
  • Table 3 is a table chart showing the tensile strengths of the test specimens manufactured by calandering at different temperatures.
  • Table 4 is a table chart showing the densities of the test specimens with different wood weight percentage manufactured by extrusion and calandering at different temperatures.
  • the polycaprolactone polymer used was a commercially available PCL homopolymer supplied under the tradename CAPA 6800 by Perstorp Ltd., Sweden).
  • the polycaprolactone has a melt flow rate of about 3 g/10 min (measured at 150° C. and with a weight of 2.16 kg).
  • the wood material if not otherwise indicated, was conventional spruce chips produced at a Finnish saw mill. In some of the examples wood particles of other wood species were used.
  • the spruce chips were dried for 4 hours in 120° C. and polymer granules were used as received. Preliminary mixing of virgin materials was carried out in a sealed plastic vessel. The mixture (200 g wood chips/300 PCL granules) was poured to the feed hopper connected to the Brabender single-screw extruder. The rotational speed of the extruder was set to 50 rpm and the temperatures of all four zones were fixed at 130° C. After compounding process with the extruder, the formed composite material was heated in the oven to 125° C. to ensure its easy mouldability during calendering process.
  • the calendering of composite mixture to a homogeneous plate was carried out in three phases which all included several cycles, folding, cooling and reheating steps.
  • the temperature of calender cylinder was fixed at 100° C.
  • After calendering process the plate-like composite was cut with band-saw to size of 10 cm by 40 cm followed by one cycle calendering at 100° C. to achieve smooth surface to casting material.

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Materials Engineering (AREA)
  • Epidemiology (AREA)
  • Medicinal Chemistry (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Vascular Medicine (AREA)
  • Nursing (AREA)
  • Biomedical Technology (AREA)
  • Orthopedic Medicine & Surgery (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Transplantation (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Composite Materials (AREA)
  • Dermatology (AREA)
  • Surgery (AREA)
  • Materials For Medical Uses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Orthopedics, Nursing, And Contraception (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)

Abstract

The invention relates to a method for making light-weight dimensionally stable wood-thermoplastic composite material composed of wood chips and a thermoplastic polycaprolactone. The manufacturing process of composite material comprising the steps of compounding virgin materials with single-screw extruder and production of uniform homogeneous plate-like composite with calendering apparatus. The calendering process comprises of several cycles, folding, cooling and reheating steps. During the gentle manufacturing process fragile wood chips maintain their 3-D structural properties in polymer matrix resulting light, mechanically strong wood-plastic composite.

Description

    BACKGROUND OF THE INVENTION
  • 1. Field of Invention
  • The present invention relates, in general to the field of manufacturing wood-plastic composite (WPC). In particular, present invention relates to the production of composite materials comprising wood particles and biodegradable thermoplastic polymer. More particularly, the present invention relates to a method of manufacturing novel wood-plastic composites useful as splints or casts in immobilization of a fractured body extremities.
  • 2. Description of Related Art
  • There are several orthopedic applications which comprise thermoplastic polymers, in particular polycaprolactone and finely divided wood powder or fibres and thermoplastic polymers. Primarily these structures are of the “mesh type” consisting of cellulosic fibers with an average particle size less than 0.6 mm. Thus, a mesh type casting material is presented in Published International Patent Application WO 94/03211. The material is manufactured by using a powder deposition process. The process includes mixing, with a dispensing hopper, depositing the material to the non-woven fabric followed by a pressing procedure and a heat treatment procedure at a double-band press.
  • Powder deposition is however suitable only for manufacturing homogenized composites with fine particles. Moreover, the double-bend press cannot gently homogenize the wood particles with rather large dimensions to an evenly distributed mixture with polymer matrix.
  • Another method of manufacturing medical composites is presented in the Published International Patent Application WO 2008/041215 in which one component of the structure is polycaprolactone but, like in the previous case, the material consists of many layers including spacer fabric. In addition, the splinting assembly is pre-shaped to match a fractured limb. The described manufacturing process includes both injection and compression molding. Due to large size of the wood particles, and the PCL having a very low melt flow index value, shaping of the material of the present invention by injection based systems is not practical. The pressure during processing may increase to so high levels that decomposition of wood's three dimensional structure is apparent.
  • Yet another alternative is presented in a U.S. Published Patent Application US2008/0262100, which concerns moldable composite splints consist of several layers, one being thermoplastic polycaprolactone. The composite material of the reference is manufactured by heat welding in a vacuum press followed by a perforating process with a turret punch press. This moldable perforated splint composite consists of a plurality of layers which can be nicely manufactured with techniques presented in reference. This technique will not make it possible to produce a composite having a uniform structure in which wood particles of granular or platy structure are thoroughly and evenly dispersed.
  • SUMMARY OF INVENTION
  • It is an aim of the present invention to eliminate at least some of the problems of the art and to provide a new method of producing dimensionally stable light-weight wood-thermoplastic composite material of constant quality.
  • The novel technology is based on the concept of mixing a thermoplastic polymer selected from the group of biodegradable polymers with at least one reinforcing material selected from woody materials in the form of platy and granular wood particles in particular under conditions of melt mixing. Preferably the mixing is carried out in an apparatus for melt processing of polymers, e.g. an extruder or an equivalent device capable of producing a compounded mixture of thermoplastic and additives, at an elevated temperature and optionally at an increased pressure. The elevated temperature corresponds to or is higher than the melt temperature of the polymer.
  • More specifically, the present invention is characterized by what is stated in the characterizing part of claim 1.
  • The invention provides considerable advantages. Thus, the method will produce light-weight dimensionally stable wood-thermoplastic composite materials composed of wood chips and a thermoplastic polycaprolactone. During the gentle manufacturing process fragile wood chips maintain their 3-D structural properties in polymer matrix resulting light, mechanically strong wood-plastic composite.
  • Further advantages and novel features and scope of applicability of the present invention will be set forth in the following detailed description and a number of non-limiting working examples.
  • DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
  • The material of the present invention can generally be manufactured by mixing a first component, i.e. a suitable polymer material, for example in the form of pellets, with the second component, i.e. wood particles or granules, by melt mixing. The mixing can be carried out in any conventional apparatus designated for melt mixing or melt processing. One example is a heatable vessel having a mechanical stirrer. The composite can be formed by using an extruder, kneader or any device suitable for mixing thermoplastic polymers, in particular for mixing of polymers in melt phase. Ideally, although not necessarily, the mixture of the first and second components prior to melting is a homogeneous mixture of the two components.
  • By using an extruder mixing apparatus, two hoppers, each containing one of the components of the material, can deposited the desired amount of each component in to a mixing chamber of the apparatus. Then, by way of the mixing means in the mixing apparatus, there is formed a homogeneous mixture of the first and second components prior to the formation of the composite material.
  • One advantage to the material being formed by such a homogeneous mixture of the components is that the forces necessary to form a substantially homogeneous material are reduced. Therefore, little or no compression force is necessary to facilitate mixing of the components in a material formation step. The importance of this factor is that, by way of the homogeneous mixture, larger particles of each component can be used which would otherwise have been destroyed when subjected to high compression forces.
  • The material can be applied for use after it has been recovered from the mixing device and formed into the desired shape, for example into a sheet or plate or roll or any similar planar, folded, bent or tubular structure. The material can even be formed directly on the patient.
  • The material mixed with an extruder can be shaped with an appropriate nozzle to the shape of, e.g. a rectangular sheet or plate which can be used directly after cutting, e.g. as a wrist splint. Such a sheet or plate whose purpose is to be later formed in to a desired shape or size is referred to herein as a blank.
  • A desired specific profile or shape for the splints can be manufactured with the extruder manufactured sheet or plate by optical, chemical or mechanical cutting, e.g. laser cutting, water jet cutting, eccentric pressing, or with any tool capable for producing regular shape profiles, i.e. stamping. The present material can also be processed with compression moulding, injection moulding, die-casting, and pressure die-casting. Ideally these specific profiles and shapes are in linear, two-dimensional form so as to be easily and compactly storable. To maintain the simplicity and cost effectiveness in the manufacturing process of the novel composite material of the present invention preferably the whole manufacturing process of the end-product is continuous.
  • According to an embodiment, the present method of producing a composite useful as an orthopedic material comprises the steps of;
      • mixing together 10 to 100 parts, preferably 50 to 100 parts, by weight of a first component formed by a polymer selected from the group of biodegradable polymers and mixtures thereof and
      • 1 to 100 parts, preferably 10 to 50 parts, by weight of a second component formed by a reinforcing material, present in the form of platy wood particles.
  • The melt-mixing is carried out at a temperature sufficient for melting the thermoplastic polymer. Thus, the mixing is generally carried out at a temperature of about 50 to 190° C., preferably about 90 to 150° C., in particular about 100 to 130° C., in order to achieve conditions of melt-mixing in the apparatus. The temperature can also be in the range of about 50 to 150° C., in particularly about 100 to 140° C.
  • The molten polymer mass containing a mixture of biopolymer and reinforcing platy particles can be shaped manually or, according to a preferred embodiment by moulding in a mould.
  • The molten polymer mass can be subjected to tensile forces to achieve a desired orientation of the polymer and, in particular, the reinforcing particles.
  • Within the above general concept, the manufacturing process comprises several preferred embodiments.
  • Generally, a preferred embodiment of the manufacturing process of a composite material comprises the steps of compounding: virgin materials with an extruder and production of uniform homogeneous plate-like composite.
  • One particular embodiment consist of compounding wood chips and thermoplastic polymer with single screw extruder and profile manufacturing of therein produced composite by using calendaring techniques. This manufacturing method is applicable for production of composites consisting of any thermoplastic polymer having a melting point below 100° C. and wood particles having volume between 1-50 mm3.
  • The manufacturing process is initiated by mixing wood chips and plastic granules to uniform blend before pouring to feed hopper of the extruder. The mixing process can be carried out also by feeding of the virgin materials to the extruder directly by using separate feeding hoppers.
  • In a compounding process using a single screw extruder, the profile of screw has to have dimensions that allow relatively lame wood chips (up to about 30 to 50 mm in one dimension) to move along the screw without crushing them. Simultaneously, appropriate dispersion between wood and polymer has to be achieved. The screw-like channel width and flight depth are selected such that formation of local pressure increases can be avoided. Similarly, the temperature of cylinder and the screw rotation speed are selected to avoid decomposition of wood chip structure by high pressure during extrusion.
  • The appropriate barrel temperature is generally in the range of 80 to 190° C., preferably 100 to 150° C., e.g. 116-135° C., from hopper to die. The screw rotation speed is typically about 10 to 100 rpm, for example 25 to 50 rpm.
  • The extruder compounded composite material can be further worked upon to obtain homogeneous plates or sheets with a thickness of about 1 to 5 mm, e.g. 3.5 mm, with preselected width and length by using calendering techniques. To avoid changes in wood chip structure during calendering process, composite material can be gently folded between calendering cylinders in a plurality of phases, each consisting of a number of cycles. For example 2 phases with at least 10 cycles each are preferred.
  • Thus, in one embodiment, the melt mixing is carried out in an extruder and the calendering process comprises several cycles of folding, cooling and reheating steps.
  • The temperature of calender cylinders can be kept constant, for example at a temperature above the melting point of the thermoplastic material, to keep the composite moldable during calendering process.
  • Plates can be finished by sanding the edges with band sander.
  • In one embodiment working on polycaprolactone and wood chips, the calender cylinders were kept at 100° C. Smooth surface to the final product were achieved by calendering the plate one time through at 100° C.
  • Alternative manufacturing process for the composite plates is press method after the mixing process carried out with extruder. Pneumatic, mechanical and/or hydraulic presses are suitable for the press method of the composite. During pressing the heated plates of the press are kept at temperature
  • The density of composite manufactured with combination of extruder and calendaring or extruder and press vary between 600-1050, e.g. 600-850 kg/m3 depending on the weight percent of wood in material.
  • To maintain the simplicity and cost effectiveness in the manufacturing process of the composite of the present invention the complete manufacturing process of the end-product is preferably continuous.
  • During the process development it was found out that excellent results were obtained with polycaprolactones having a low to moderate melt flow index of less than 7, preferably about 0.1 to 6 g/10 min, with 2.16 kg standard die at 160° C. By contrast, polycaprolactone polymers having a high melt flow index (MFI) (i.e. higher than the one preferred) will not give a material of desired composition. Thus, mixing of PCL having MFI values of 7 g/10 minutes with 2.16 kg standard die at 160° C. with wood particles using a single screw extruder the molten composite material resulted in one experiment in a material which was not self-supporting and calandering thereof was not possible. Even at temperatures close to the melting point further processing of the composite was complicated by using calandering techniques and to achieve plate-like shape for the composite heatable platen press was required.
  • Low viscosities of the polymers at elevated temperatures complicate the manufacturing process of the multi-component composites. For example pressing of hook-and-loop fasteners to the surface of composite at elevated temperatures tearing and creeping of the composite material can be observed. The present manufacturing method is therefore particularly well suited for the processing of highly viscous thermoplastics, such as PCL having an MFI value of 3, as a polymer component. After mixing procedure with extruder the formed mixture of wood and a PCL of the indicated MFI value can be directly used in calandering process. The creep phenomenon of the molten composite during pressing fasteners onto it can be avoided when the wood weight percentage in the composite is at least 20.
  • The adhesion of the composite can be improved by coating the surface of the composite with additional layer of virgin PCL or with any similarly behaving material. The coating process can be performed practically either by extrusion coating or extrusion laminating in a continuous process. In the extrusion coating a molten layer of extrudate is laid onto a composite. The temperature of the extruded molten polymer is kept below 200° C. to avoid tarnishing of the wood component and at the same time above 100° C. to guarantee reasonable flow of the polymer on the substrate. During this process of flowing, the polymer wets the entire surface evenly and smooth over uneven surface which is important contributor to adhesion.
  • Composite consisting of three layers of compounds (PCL-composite-PCL) can be performed by extrusion laminating. In the process two substrates (PCL) enters the nip formed by two rolls. The middle extrudate (composite) also enters the nip by traveling over each roll. The composite is therefore the center part of the resulting sandwich material. The manufacturing of the multilayer composite consisting of composites layers having different weight percentage of wood can be performed by using calandering techniques. Two or more molten extrudates are combined to sandwich type of structures and pressed together in calender. By using similar calandering technique also padding and fasteners can be pressed to the molten composite extrudate consisting of one or multi layers.
  • The composite retains its shape as it cools down. It is substantially rigid but flexible so as to be supportive and comfortable. Rigidity is generally achieved, when a sample heated to the above indicated softening temperature is cooled to below 50° C., in particular to less than 45° C., preferably less than 40° C. Typically, the composite is rigid at ambient temperature; a suitable temperature of use is about −40 to +50° C., in particular −30 to +40° C.
  • The composite material sheet or plate can have a thickness of, generally about 0.2 to 50 mm, in particular about 1.5 to 30 mm, for example 1.5 to 20 mm. A typical thickness is about 2 to 6 mm. The length and the width of the sheet or plate can vary in the range of about 1 to 150 cm (length) and to 50 cm (width), a typical length being about 10 to 60 cm and a typical width being about 5 to 20 cm.
  • A particular embodiment comprises producing a continuous product, collecting the product and rolling it or folding it. Such a product is then provided in the form of ribbons or tape which can be collected on a receiving roller.
  • As discussed above, in one embodiment, a linear product (e,g. a sheet or a plate) is produced. That laminar product can be further processed. For example it can be perforated. Another alternative is to use the linear product for making a laminate comprising at least two layers, each preferably being comprised of such linear products. Naturally, the laminate can be perforated, also,
  • One specific embodiment comprises the steps of providing on a laminate at least one surface layer having a reduced content of woody material. The layer can be formed by neat polymer or by a polymer merely having a reduced content of the woody material. Such a surface layer will provide improve adhesive properties for the product.
  • A particularly interesting embodiment comprises producing an essentially linear product, and mechanically modifying, e.g. by corrugation, the linear product so as to increase its stiffness.
  • The product produced by the present invention can also comprise further fillers or enforcing components. Thus, one embodiment comprises mixing the thermoplastic polymer with a first woody material and at least one second woody material, said second woody material being different from the first woody material.
  • A still further embodiment of producing a biodegradable linear composite material capable of being used to form an exo-skeletal device through thermal molding, comprises the steps of;
      • obtaining a desired woody particle mixture, the majority of the woody particles making up the mixture being greater in size than powder,
      • forming a first component comprising biodegradable polymer pellets,
      • forming a second component comprising the woody particle mixture,
      • mixing the first and second component into a single homogeneous mixture, and
      • forming, a linear composite material having a desired shape by heating the single homogeneous mixture and forming it as desired such that woody particles contained in the homogeneous mixture are not substantially degraded.
  • In this embodiment, obtaining a desired woody particle mixture comprises the step of taking a woody particle feed having a plurality of sized woody particles and sorting the feed to obtain the desired woody particle mixture.
  • As in all the above discussed embodiments, the step of sorting the woody particle feed may comprise sifting the feed through one or more meshes.
  • Generally, more than 70% of the second component is formed by the woody particle mixture.
  • The first and second components may have pellets and particles of similar size.
  • As in all the above discussed embodiments, in one preferred case, the desired shape is a substantially rectangular blank formed from an extruder. The desired shape may, however, be other than a rectangular blank and can be formed by optically, chemically or mechanically cutting or stamping the desired form from the composite material.
  • In all of the above discussed embodiments, the proportions between the components of the material can vary in a broad range. Thus, generally, 5 to 99 wt-%, for example 40 to 99 wt-%, of the material is formed by the thermoplastic polymer component and 1 to 95 wt-%, for example 1 to 60 wt-%, by the woody material.
  • The weight ratio of polymer-to-wood can easily be modified. and the weight percent of wood, based on the total weight/volume of the composition, may vary between 1 and 70%, preferably however in the range of 10 to 60 weight percent, or 20 to 60 weight percent, and 15 to 50%, or 25 to 50%, by volume.
  • The second component comprises a woody material having a smallest diameter of greater than 0.1 mm. As will be discussed below, there can also be other wood particles present in the second component and the woody material can be granular or platy.
  • The size and the shape of the wood particles may be regular or irregular. Typically, the particles have an average size (of the smallest dimension) in excess of 0.1 mm, advantageously in excess of 0.5 mm, for example in excess of 0.6 mm, suitably about 1 to 40 mm, in particular about 1.2 to 20 mm, preferably about L5 to 10 mm, for example about 1.5 to 7 mm The length of the particles (longest dimension of the particles) can vary from a value of greater than 1 mm to value of about 1.8 to 200 mm, for example 3 to 21 mm.
  • The woody particles can be granular, platy or a mixture of both. Woody particles considered to be granular have a cubic shape whose ratio of general dimensions are on the order of thickness:width:length=1:1:1. In practice it is difficult to measure each individual particle to determine if it is a perfect cube. Therefore, in practice, particles considered to be granular are those where one dimension is not substantially different than the other two.
  • Woody particles considered to be platy means that they have generally a plate-shaped character, although particles of other forms are often included in the material. The ratio of the thickness of the plate to the smaller of the width or length of the plate's edges is generally 1:1 to 1:500, in particular about 1:2 to 1:50. Preferably, the woody particles include at least 10% by weight of chip-like particles, in which the ratio of general dimension are on the order of thickness:width:length=1:1-20:1-100, with at least one of the dimension being substantially different than another.
  • Based on the above, the platy particles of the present invention generally comprise wood particles having at least two dimensions greater than 1 mm and one greater than 0.1 mm, the average volume of the wood particles being generally at least 1 min3′ more specifically at least 1 mm3.
  • Derived from platy wood particles designates that the wood particles may have undergone some modification during the processing of the composition. For example, if blending of the first and second components is carried out with a mechanical melt processor, some of the original platy wood particles may be deformed to an extent.
  • The wood species can be freely selected from deciduous and coniferous wood species alike: beech, birch, alder, aspen, poplar, oak, cedar, Eucalyptus, mixed tropical hardwood, pine, spruce and larch tree for example.
  • Other suitable raw-materials can be used, and the woody material of the composite can also be any manufactured wood product.
  • The particles can be derived from wood raw-material typically by cutting or chipping of the raw-material. Wood chips of deciduous or coniferous wood species are preferred.
  • A particularly interesting raw-material comprises wood chips of any of the above mentioned wood species having a screened size of greater than 0.6 mm and up to about 3 mm, in particular about 1 to 2.5 mm on an average.
  • According to an alternative embodiment, a composite useful as an orthopedic material, comprises a first component formed by a polymer and a second component formed by a reinforcing material, wherein the first component comprises a thermoplastic polymer selected from the group of biodegradable polymers and mixtures thereof, and the second component comprises reinforcing fibres. Such fibers can be selected from the group for example of cellulose fibers, such as flax or seed fibers of cotton, wood skin, leaf or bark fibers of jute, hemp, soybean, banana or coconut, stalk fibers (straws) of hey, rice, barley and other crops including bamboo and grass. According to an interesting embodiment, the wood filler may consist of or consist essentially of fibres of the indicated kind. The polymer component can be any of the below listed polymers, caprolactone homo- or copolymers having a molecular weight of about 60,000 g/mol up to 250,000 g/mol being particularly preferred.
  • Substantial advantage has been found for the polymer component to be a caprolactone homopolymer or a blends of homo- or copolymers of epsilon-caprolactone having a molecular weight of above 80,000 g/mol. Specifically, polycaprolactone having a molecular weight of between 100,000 g/mol and 200,000 g/mol as been found to be advantageous both in terms of resultant properties and cost.
  • Before the woody particles are mixed with the thermoplastic polymer they can be surface treated, e.g. sized, with agents which modify their properties of hydrophobicity/-hydrophobicity and surface tension. Such agents may introduce functional groups on the surface of the granules to provide for covalent bonding to the matrix. Even increased hydrogen bonding or bonding due to van der Waals forces is of interest. The woody particles can also be surface treated with polymer e.g. PCL having low viscosity and molar mass values to increase holding powers between wood and PCL having high viscosity value.
  • The wood material can be also coated or treated with anti-rot compound e.g. vegetable oil to improve its properties against aging and impurities.
  • The wood material can be dehydrated to make it lighter before mixing it with polymer. The mechanical and chemical properties of wood material can be improved with heat treatment, which is known to decrease e.g. swelling and shrinkage.
  • In the composition according to an aspect of the present invention, the first component (the polymer) forms the matrix of the composite, whereas the microstructure of the second component in the composition in discontinuous. The particles of the second component can have random orientation or they can be arranged in a desired orientation. The desired orientation may be a predetermined orientation.
  • Furthermore, the composition may contain particulate or powdered material, such as sawdust, typically having particles with a size of less than 0.5 mm*0.5 mm*0.5 mm.
  • Particulate or powdered material is characterized typically as material of a size in which the naked eye can no longer distinguish unique sides of the particle. More specifically, powder particles are of such a size that their dimensions cannot be measured with traditional, Vernier, calipers.
  • In contrast, non-powder particles are of such a size that they can be measured with traditional calipers. Moreover, platy particles are easily recognizable as one dimension is recognizable by the naked eye as being larger than another. Granular particles, while having substantially equal dimensions, are of such dimension that their unique sides can be determined by the naked eye and oriented.
  • More particularly, particulate or powdered materials are of such a small or fine size that they cannot be easily oriented with respect to their neighbours. Granular and platy particles are of such as size that their sides are recognizable and orientable.
  • The present material contains a significant portion of wood granules having a particle size greater than the micrometer range, for example a size of about 0.75 mm to 50 mm. When the material is shaped into a sheet, (at least most of) the wood granules become oriented in two dimensions within forming of the thermoplastic material into sheets.
  • The reinforced material typically exhibits properties selected from one or several of the following:
      • a density of the composition at least 5% less than that of the polymer component (e.g. epsilon-caprolactone homopolymer) as such;
      • a Young's modulus value in 3-bending test of the composition is at least 10% higher than that of the polymer component (e.g. epsilon-caprolactone homopolymer) as such; and
      • thermal conductivity on the order of about 0.5 W/m·K, at the most.
  • The desired composition of the second component can be achieved by sifting woody particles through one or more meshes having one or more varying qualities. The desired composition can also be accomplished by other well known techniques in the art for sorting and separating particles in to desired categories. The desired composition may be the resultant composition of one sifting or separating process. The desired composition may also be a mixture of resultant compositions from several sifting or separation processes.
  • According to one embodiment, the weight ratio of fibrous material (optionally including said powdered material) to the platy material (dry weight) is about 1:100 to 100:1, preferably about 5:100 to 50:50. In particular, the woody material derived from the platy wood particles forms at least 10%, preferably about 20 to 100%, in particular about 30 to 100%, of the total weight of the second component.
  • The powdered material may form up to 30%, typically about 1 to 20%, of the total weight of the second component.
  • In addition to wood-based powdered materials, inorganic particulates or powdered materials such as mica, silica, silica gel, calcium carbonate and other calcium salts such as tricalcium orthophosphate, carbon, clays and kaolin may be present or added.
  • The present method will produce a composition that can be used as a composite material. Such materials are exemplified by finger splints, wrist casts and ankle casts. Generally, the platy particles form about 30 to 70%, preferably in excess of 40 up to about 60%, of the total weight of the composition, for finger splints and for ankle casts about 20 to 60%, preferably about 30 to 50% of the total weight of the composition. There is typically a greater portion of the larger particles present in the larger casts which will reduce the total weight of the cast without impairing the strength properties thereof.
  • In particular, the composite material of the present invention is manufactured in to either a blank or in to a desired, specific shape or form. Ideally, the blanks and forms are linear, two dimensional and easily stackable. The blanks can be either substantially larger than the intended size to be applied to the animal or human being, herein referred to as the patient, or of substantially similar size.
  • In the instance when the blank is of a large size than desired, the blank can be cut with normal scissors or other conventional cutting means before application. Such a large blank is preferable in the sense that one blank may be cut in to several splints at various times according to the size required by each. Therefore, it is not necessary to store many different shapes and sizes of the material, which take up room and may be rarely used.
  • Additionally, multiple splints may be cut from one blank in such a way as to maximize the material used and not produce a large amount of waste product.
  • Once the proper size and shaped piece of material is obtained, cut or selected, the material is then heated to the desired operating temperature by a heating means. Numerous heating means are known in the art, but it is preferable to uniformly heat the material to a specific desired temperature. If the temperature is too high then there is risk of discomfort or harm to the patient's skin. If the temperature is not high enough then the material will not be able to properly conform to the patient's body.
  • The use of the present material as a splint or cast process is described in more detail in our co-pending patent application titled “Orthopaedic Splinting System”, the content of which is herewith incorporated by reference.
  • The following non-limiting examples illustrate the invention. In connection with the examples, reference is made to the tables below.
  • Table 1 is a table chart showing the densities of the test specimens manufactured by calandering at different temperatures;
  • Table 2 is a table chart showing the flexural strengths of the test specimens manufactured by calandering at different temperatures;
  • Table 3 is a table chart showing the tensile strengths of the test specimens manufactured by calandering at different temperatures; and
  • Table 4 is a table chart showing the densities of the test specimens with different wood weight percentage manufactured by extrusion and calandering at different temperatures.
  • In all the below presented examples, the polycaprolactone polymer used was a commercially available PCL homopolymer supplied under the tradename CAPA 6800 by Perstorp Ltd., Sweden). The polycaprolactone has a melt flow rate of about 3 g/10 min (measured at 150° C. and with a weight of 2.16 kg).
  • The wood material, if not otherwise indicated, was conventional spruce chips produced at a Finnish saw mill. In some of the examples wood particles of other wood species were used. The chips, in particular the spruce chips, were occasionally used in the form of a fraction sieved to an average size of 1-2.5 mm.
  • EXAMPLE 1
  • The spruce chips were dried for 4 hours in 120° C. and polymer granules were used as received. Preliminary mixing of virgin materials was carried out in a sealed plastic vessel. The mixture (200 g wood chips/300 PCL granules) was poured to the feed hopper connected to the Brabender single-screw extruder. The rotational speed of the extruder was set to 50 rpm and the temperatures of all four zones were fixed at 130° C. After compounding process with the extruder, the formed composite material was heated in the oven to 125° C. to ensure its easy mouldability during calendering process. The calendering of composite mixture to a homogeneous plate was carried out in three phases which all included several cycles, folding, cooling and reheating steps. The temperature of calender cylinder was fixed at 100° C. After calendering process the plate-like composite was cut with band-saw to size of 10 cm by 40 cm followed by one cycle calendering at 100° C. to achieve smooth surface to casting material.
  • EXAMPLE 2
  • Influence of the cylinder temperature of the calendering system to the density of composite specimens of the are shown in Table 1, flexural strengths of the specimens calendered at different temperatures are shown in Table 2 and tensile strengths of the cylinder temperature specimens are shown in Table 3. The standard deviations of measurements are included in the Tables 1 to 3. Wood weight percent in composite was fixed at 40%.
  • As will appear, calendering carried out at different temperatures had only a minor influence on the densities of the manufactured composite plates. Densities of the composite plates were increasing slightly at lower calandering temperatures but deviations of the measurements were varying greatly and no conclusions could be made. The flexural strengths of the corresponding materials, however, followed clear trend. At temperature of 100° C. flexural strength was ˜10 MPa and at lower temperature of 60° C. carried out calandering revealed flexural strength value of ˜14 MPa. The increase in bending force may seen as a result of orientation of PCL and wood particles in the composite structure.
  • EXAMPLE 3
  • Densities of the composite specimens manufactured with extruder and calendering processes. The dimensions of the wood particles are approximated values and are presented in millimeters in Table 4.
  • TABLE 1
    Temperature Density
    of the cylinders (kg/m3) STD
     60° C. 774.94 37.05
     80° C. 764.05 51.46
    100° C. 741.37 27.09
  • TABLE 2
    Temperature Flexural
    of the cylinders strength (MPa) STD
     60° C. 14.17 1.79
     80° C. 13.01 2.22
    100° C. 10.71 1.50
  • TABLE 3
    Temperature Tensile
    of the cylinders strength (MPa) STD
     60° C. 8.62 0.30
     80° C. 6.09 0.85
    100° C. 6.42 0.74
  • TABLE 4
    wood %/size Density (kg/m3) STD
    Spruce 35, 1-3 mm 669.56 30.81
    Spruce 40, 1-3 mm 662.90 58.19
    Spruce 45, 1-3 mm 617.35 26.69
    Spruce 50, 1-3 mm 603.62 18.19
    polycaprolactone 1043.53 24.82
    Aspen 40, 3-5 mm 710.79 18.13
    Aspen 40, 1-3 mm 733.71 22.72
  • EXAMPLE 5
  • 700 g of ε-polycaprolactone CAPA 6800 and 300 g of spruce particles (dust) with average dimensions of 2×2×0.2 mm and were fed separately into a hopper of a Gimac mini twin-screw extruder. Temperatures of screw, adapter and nozzle were close 130 deg C. The composite blend was pushed out through the compounder nozzle (diameter 4 mm) and collected to the rolling belt. The composite was cooled down by pressurized air while moving on the belt. As a result a cylinder shaped homogeneous mixture of wood particles and polymer was obtained.

Claims (25)

1. A method of producing a composite useful as an orthopedic material, comprising the steps of;
mixing together a first component formed by a polymer,
a second component formed by a reinforcing material,
mixing a thermoplastic polymer selected from the group of biodegradable polymers and mixtures thereof with a reinforcing material selected from woody materials in the form of platy and granular wood particles, and
carrying out the mixing as melt mixing in an apparatus for melt processing of polymers.
2. The method according to claim 1, wherein 30 to 99 parts by weight of a thermoplastic polymer is mixed together with 1 to 70 parts by weight of reinforcing particles.
3. The method according to claim 1, wherein the mixing is carried out at a temperature of approximately 50 to 190° C. in order to achieve conditions of melt-mixing in the apparatus.
4. The method according to claim 1, wherein the thermoplastic polymer is selected from the group of epsilon-caprolactone homopolymers, blends of epsilon-caprolactone homopolymers and other biodegradable thermoplastic homopolymers, and copolymers of epsilon-caprolactone homopolymer and any thermoplastic biodegrable polymer.
5. The method according to claim 1, wherein the thermoplastic polymer has an average molecular weight of 60,000 to 500,000 g/mol.
6. The method according to claim 1, wherein the wood particles are orientated and aligned in a melt flow of the thermoplastic polymer before the reinforced material is shaped into an orthopedic material.
7. The method according to claim 1, wherein
the mixing comprises compounding the thermoplastic polymer with the woody material in a melt mixing apparatus to produce a compounded melt mixture,
providing an extrudate of the melt mixture by pultrusion of pulling-out through a mould or nozzle, and
optionally shaping the extrudate into the form of a plate or a sheet.
8. The method according to claim 1, wherein the mixture of the thermoplastic polymer and the woody material is compounded in a mixing apparatus under non-crushing conditions, said mixing apparatus being selected from extruders and kneaders capable of processing polymers in melt phase.
9. The method according to claim 1, wherein virgin materials are compounded in a melt mixing apparatus and shaped into a plate-like composite with calendering apparatus.
10. The method according to claim 1, wherein the melt mixing is carried out in an extruder and the calendering process comprises several cycles of folding, cooling and reheating steps.
11. The method according to claim 1, wherein the wood particles comprise chips of hardwood, softwood or a combination thereof.
12. The method according to claim 1, further comprising producing a continuous product, collecting the product and rolling it or folding it.
13. The method according to claim 1, further comprising the steps of producing a linear product and combining at least two linear products into a laminate.
14. The method according to claim 12, further comprising the steps of providing on said laminate at least one surface layer having a reduced content of woody material.
15. The method according to claim 1, further comprising mixing the thermoplastic polymer with a first woody material and at least one second woody material, said second woody material being different from the first woody material.
16. The method according to claim 1, further comprising the steps of producing an essentially linear product and perforating said linear product.
17. The method according to claim 1, further comprising the steps of producing an essentially linear product, and mechanically modifying the linear product so as to increase its stiffness.
18. A method of producing a biodegradable linear composite material capable of being used to form an exo-skeletal device through thermal molding, the method comprising the steps of;
obtaining a desired woody particle mixture, the majority of the woody particles making up the mixture being greater in size than powder,
forming a first component comprising biodegradable polymer pellets,
forming a second component comprising the woody particle mixture,
mixing the first and second component into a single homogeneous mixture, and
forming a linear composite material having a desired shape by heating the single homogeneous mixture and forming it as desired such that woody particles contained in the homogeneous mixture are not substantially degraded.
19. A method according to claim 18, wherein obtaining the desired woody particle mixture comprises the step of taking a woody particle feed having a plurality of sized woody particles and sorting the feed to obtain the desired woody particle mixture.
20. A method according to claim 19, wherein the step of sorting the woody particle feed comprises sifting the feed through one or more meshes.
21. A method according to claim 18, wherein more than 70% of the second component is formed by the woody particle mixture.
22. A method according to claim 18, wherein the first and second components have pellets and particles of similar size.
21. A method according to claim 18, wherein the desired shape is a substantially rectangular blank formed from an extruder.
22. A method according to claim 18, wherein the desired shape is other than a rectangular blank and is formed by optically, chemically or mechanically cutting or stamping the desired form from the composite material.
23. A composite material formed from a homogeneous mixture of a first and second compound according to the method comprising the steps of;
mixing together a first component formed by a polymer,
a second component formed by a reinforcing material,
mixing a thermoplastic polymer selected from the group of biodegradable polymers and mixtures thereof with a reinforcing material selected from woody materials in the form of platy and granular wood particles, and
carrying out the mixing as melt mixing in an apparatus for melt processing of polymers.
US13/255,942 2009-03-11 2010-03-11 Method of producing composite materials Abandoned US20120090759A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FI20095251 2009-03-11
FI20095251A FI125448B (en) 2009-03-11 2009-03-11 New materials
PCT/FI2010/050187 WO2010103188A2 (en) 2009-03-11 2010-03-11 Method of producing composite materials

Publications (1)

Publication Number Publication Date
US20120090759A1 true US20120090759A1 (en) 2012-04-19

Family

ID=40510249

Family Applications (5)

Application Number Title Priority Date Filing Date
US13/255,942 Abandoned US20120090759A1 (en) 2009-03-11 2010-03-11 Method of producing composite materials
US13/255,930 Active US10336900B2 (en) 2009-03-11 2010-03-11 Composite materials comprising a thermoplastic matrix polymer and wood particles
US13/255,936 Abandoned US20120073584A1 (en) 2009-03-11 2010-03-11 Orthopaedic splinting system
US14/106,973 Active 2030-10-10 US9803080B2 (en) 2009-03-11 2013-12-16 Orthopaedic splinting system
US15/347,280 Abandoned US20170058120A1 (en) 2009-03-11 2016-11-09 Novel composite materials comprising a thermoplastic matrix polymer and wood particles

Family Applications After (4)

Application Number Title Priority Date Filing Date
US13/255,930 Active US10336900B2 (en) 2009-03-11 2010-03-11 Composite materials comprising a thermoplastic matrix polymer and wood particles
US13/255,936 Abandoned US20120073584A1 (en) 2009-03-11 2010-03-11 Orthopaedic splinting system
US14/106,973 Active 2030-10-10 US9803080B2 (en) 2009-03-11 2013-12-16 Orthopaedic splinting system
US15/347,280 Abandoned US20170058120A1 (en) 2009-03-11 2016-11-09 Novel composite materials comprising a thermoplastic matrix polymer and wood particles

Country Status (16)

Country Link
US (5) US20120090759A1 (en)
EP (4) EP2405949B8 (en)
JP (2) JP5670361B2 (en)
KR (2) KR101706662B1 (en)
CN (2) CN102405062B (en)
AU (2) AU2010222771B2 (en)
BR (1) BRPI1008947A2 (en)
CA (2) CA2755128C (en)
EA (2) EA022386B1 (en)
ES (2) ES2836949T3 (en)
FI (1) FI125448B (en)
HR (2) HRP20201963T1 (en)
NZ (2) NZ595557A (en)
PL (1) PL2405949T3 (en)
WO (3) WO2010103188A2 (en)
ZA (2) ZA201107117B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120073584A1 (en) * 2009-03-11 2012-03-29 Onbone Oy Orthopaedic splinting system
US20130225731A1 (en) * 2011-02-28 2013-08-29 Jiangsu Jinhe Hi-Tech Co., Ltd Degradable plastic and manufacturing method thereof
FR3052781A1 (en) * 2016-06-16 2017-12-22 Greenpile
US11504878B2 (en) * 2017-03-02 2022-11-22 Sulapac Oy Materials for packaging

Families Citing this family (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI123137B (en) * 2010-09-11 2012-11-30 Onbone Oy Casting Materials
BE1019852A3 (en) * 2011-02-28 2013-01-08 Orfit Ind USE OF A SHAPED CARBON NANO-TUBE-POLYMER COMPOSITE MATERIAL.
WO2013107866A1 (en) * 2012-01-18 2013-07-25 Novortex Ab Splint
GB2513536A (en) * 2012-12-19 2014-11-05 Ronald Vincent Taylor Orthopaedic cast replacement
CN103330959B (en) * 2013-06-04 2014-12-17 东南大学 Prestress-reinforced light high-strength controllable-degradation medical composite material and preparation method thereof
KR20140148033A (en) * 2013-06-21 2014-12-31 (주)엘지하우시스 Panel and manufacturing method thereof
WO2015054128A1 (en) 2013-10-07 2015-04-16 Wichita State University Rapid setting composite article
FI126725B (en) * 2013-10-21 2017-04-28 Onbone Oy Aerated materials
FI20136038L (en) * 2013-10-21 2015-04-22 Onbone Oy New materials
BR102013029084B1 (en) * 2013-11-12 2021-11-30 Cleber Pereira Gama PROCESS FOR OBTAINING PLASTIC COMPOUND BASED ON FIBROUS VEGETABLE MATERIAL, PLASTIC COMPOUND BASED ON FIBROUS VEGETABLE MATERIAL OBTAINED AND EQUIPMENT FOR EXTRUSION OF PLASTIC COMPOUND BASED ON FIBROUS VEGETABLE MATERIAL
CN103736155B (en) * 2014-01-07 2015-04-01 东南大学 Cerium-loaded functional absorbable orthopedic instrument material and preparation method thereof
US9872795B2 (en) * 2014-03-12 2018-01-23 Rechargeable Battery Corporation Thermoformable medical member with heater and method of manufacturing same
US9642736B2 (en) 2014-03-12 2017-05-09 Rechargeable Battery Corporation Thermoformable splint structure with integrally associated oxygen activated heater and method of manufacturing same
JP2017055884A (en) * 2015-09-15 2017-03-23 東洋アルミエコープロダクツ株式会社 Medical fixing material and medical fixing tool
CN105546230B (en) * 2016-02-02 2018-05-15 浙江鑫宙竹基复合材料科技有限公司 A kind of stalk bamboo coiled composite tube and preparation method thereof
GB2551329A (en) * 2016-06-10 2017-12-20 Onbone Oy Personal protection device
GB2551190A (en) * 2016-06-10 2017-12-13 Onbone Sports Ltd Sports protection device
WO2018012548A1 (en) * 2016-07-12 2018-01-18 国立大学法人大阪大学 Body holder and method of using same
US20180037373A1 (en) * 2016-08-02 2018-02-08 Nomacorc Llc Closure for a product-retaining container
IL249400A0 (en) * 2016-12-05 2017-01-31 Cassit Orthopedics Ltd Orthopedic splints and methods therefor
CA3047384A1 (en) * 2016-12-15 2018-06-21 David Green Reusable custom insoles
CN107126308A (en) * 2017-03-17 2017-09-05 南京天朗制药有限公司 Shape memory point toe device and point toe socks and its application method
EP3420830A1 (en) * 2017-06-28 2019-01-02 Liiteguard ApS A knitted protective sock
GB201717223D0 (en) * 2017-10-20 2017-12-06 Onbone Oy Cast
TWI655941B (en) * 2017-11-07 2019-04-11 遠東科技大學 Splint and manufacturing method therefor
US20190308086A1 (en) * 2018-04-05 2019-10-10 Sport Maska Inc. Hockey goalkeeper leg pad
EP3781219B1 (en) * 2018-04-17 2022-06-01 MP Lumber d.o.o. A kit for in situ immobilization with antifungal and antimicrobial effects
RU182764U1 (en) * 2018-06-06 2018-08-30 Роман Юрьевич Бартош Composite functional material
FI130445B (en) * 2018-09-01 2023-09-01 Sulapac Oy Compostable wood composite material
EP3639998A1 (en) * 2018-10-15 2020-04-22 FCA Italy S.p.A. Forming process to manufacture a finishing/covering element for a component in a vehicle passenger compartment, and finishing/covering element manufactured by means of said process
FI20186033A1 (en) * 2018-12-02 2020-06-03 Sulapac Oy Compostable wood composite material for thin-walled articles
JP7045025B2 (en) * 2020-09-23 2022-03-31 東洋アルミエコープロダクツ株式会社 Medical fixtures and fixtures
RU2750712C1 (en) * 2020-11-24 2021-07-01 федеральное государственное бюджетное образовательное учреждение высшего образования "Казанский национальный исследовательский технологический университет" (ФГБОУ ВО "КНИТУ") Method of obtaining a biodegradable polymer composition

Citations (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3921333A (en) * 1972-07-28 1975-11-25 Union Carbide Corp Transplanter containers made from biodegradable-environmentally degradable blends
US4021388A (en) * 1972-05-18 1977-05-03 Coloroll Limited Synthetic resin sheet material
US5827905A (en) * 1995-09-26 1998-10-27 Bayer Aktiengesellschaft Biodegradable plastics filled with reinforcing materials
US5863480A (en) * 1994-08-29 1999-01-26 Srp Industries Ltd. Process for making a filler reinforced thermoplastic composites having biaxially oriented components
US6071984A (en) * 1995-09-26 2000-06-06 Bayer Aktiengesellschaft Biodegradable plastics filled with reinforcing materials
US6124384A (en) * 1997-08-19 2000-09-26 Mitsui Chemicals, Inc. Composite resin composition
US6143811A (en) * 1998-08-14 2000-11-07 The Japan Steel Works, Ltd. Method of producing compound pellets containing wood flour
US6184272B1 (en) * 1997-02-12 2001-02-06 Diamlerchrysler Ag Fiber-reinforced molded plastic part and process for its manufacture
US20010030031A1 (en) * 2000-03-03 2001-10-18 Trespa International B.V. Process for the continuous production of a preform mat, and a preform and its use
US6479002B1 (en) * 1998-12-30 2002-11-12 Haller Formholz Extrusion of plant materials encapsulated in a thermoplastic
US20040028927A1 (en) * 2000-07-14 2004-02-12 Leckey Richard Anthony Biodegradable composition and products prepared therefrom
US6780359B1 (en) * 2002-01-29 2004-08-24 Crane Plastics Company Llc Synthetic wood composite material and method for molding
US20050137304A1 (en) * 2003-12-18 2005-06-23 Strand Marc A. Process for calendering of polyesters
US6911522B2 (en) * 2000-01-20 2005-06-28 Solvay (Societe Anonyme) Filled epsilon-caprolactone based polymer compositions, method for preparing same and articles based on said compositions
US20060241216A1 (en) * 2003-03-17 2006-10-26 Jean-Pierre Varachez Adjustably biodegradable material for a horticultural container and overpackaging for containers
US20070132133A1 (en) * 2005-12-07 2007-06-14 Katuyuki Hasegawa Method for manufacturing resin composite formed product
US20070243782A1 (en) * 2006-04-14 2007-10-18 Aichi Prefecture Synthetic board and method of producing the same
US20070259584A1 (en) * 2006-05-04 2007-11-08 Ronald Whitehouse Biodegradable polymer composites and related methods
US20070264460A1 (en) * 2004-05-25 2007-11-15 Novamont S.P.A. Perforated Biodegradable Films and Sanitary Products Obtained Therefrom
US20070287795A1 (en) * 2006-06-08 2007-12-13 Board Of Trustees Of Michigan State University Composite materials from corncob granules and process for preparation
US20080015285A1 (en) * 2006-07-14 2008-01-17 Steven Richard Oriani Process aid for extruded wood composites
US20080032125A1 (en) * 2006-07-31 2008-02-07 Mitsubishi Jidosha Kogyo Kabushiki Kaisha Synthetic board
US20080145656A1 (en) * 2006-12-13 2008-06-19 Cheil Industries Inc. Natural Fiber-Reinforced Polylactic Acid-based Resin Composition
US20090036575A1 (en) * 2005-09-16 2009-02-05 University Of Maine System Board Of Trustees Thermoplastic composites containing lignocellulosic materials and methods of making same
US20090105378A1 (en) * 2007-10-11 2009-04-23 Idemitsu Kosan Co., Ltd. Aromatic polycarbonate resin composition and molded article thereof
US20090236766A1 (en) * 2006-11-15 2009-09-24 Entex Rust & Mitschke Gmbh Blend of plastics with wood particles
US7601282B2 (en) * 2005-10-24 2009-10-13 Johns Manville Processes for forming a fiber-reinforced product
US20100093890A1 (en) * 2007-04-19 2010-04-15 Gaia Basis Co., Ltd. Biodegradable resin composition and method for producing the same
US20100136324A1 (en) * 2007-05-01 2010-06-03 Agri Future Joetsu Co., Ltd Polymer composite material, apparatus for manufacturing the same and method of manufacturing the same
US20100240806A1 (en) * 2006-05-23 2010-09-23 Tetsuo Kondo Materials containing polyactic acid and cellulose fibers
US7988905B2 (en) * 2004-03-17 2011-08-02 Toyota Boshoku Kabushiki Kaisha Process for producing woody molding
US20110263762A1 (en) * 2008-11-05 2011-10-27 Teijin Limited Polylactic acid composition and molded article thereof
US20120171446A1 (en) * 2009-09-24 2012-07-05 Jong Sung Park Wood plastic composite panel with contractility
US20130172795A1 (en) * 2010-09-11 2013-07-04 Onbone Oy Bandaging material
US20130225731A1 (en) * 2011-02-28 2013-08-29 Jiangsu Jinhe Hi-Tech Co., Ltd Degradable plastic and manufacturing method thereof

Family Cites Families (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT298391B (en) 1967-11-23 1972-04-15 Turcksin C METHOD FOR PRODUCING BOTH IN LONG-DIRECTION AND ALSO IN TRANSVERSAL DIRECTION, ELASTIC FABRIC, AND ELASTIC, FABRIC
US4019505A (en) 1974-09-30 1977-04-26 Norman S. Blodgett Method of forming an orthopedic cast
DE2651089C3 (en) 1976-11-09 1980-06-12 Bayer Ag, 5090 Leverkusen Self-retaining material for support bandages
US4153051A (en) 1977-07-08 1979-05-08 Shippert Ronald D Compound splint and kit
US4240415A (en) * 1978-12-18 1980-12-23 WFR/Aquaplast Corp. Orthopedic cast
US4273115A (en) 1979-03-12 1981-06-16 Hexcel Corporation Moldable plastic orthopedic cast
US4213452A (en) 1979-05-03 1980-07-22 The Denver Splint Company Compound splint and kit
JPS56148355A (en) * 1980-04-17 1981-11-17 Daicel Ltd Fixing bandage material
JPS5819253A (en) * 1981-07-28 1983-02-04 藤倉ゴム工業株式会社 Molded article for surgical treatment
JPS59194746A (en) * 1983-04-19 1984-11-05 テルモ株式会社 Medical tool
US4473671A (en) 1983-09-01 1984-09-25 Johnson & Johnson Products, Inc. Formable orthopedic casts and splints
GB8417872D0 (en) * 1984-07-13 1984-08-15 Johnson & Johnson Thermoplastic composition
US4784123A (en) * 1986-01-03 1988-11-15 Union Carbide Corporation Orthopedic/orthotic splint materials
EP0393003B1 (en) 1986-10-08 1993-05-26 Tom Paul Marthe Ghislain Ponnet Composite material for medical or paramedical, particularly orthopaedic use
JP2733610B2 (en) * 1989-01-25 1998-03-30 ダイセル化学工業株式会社 Medical fixation material
US5273802A (en) 1989-07-07 1993-12-28 Minnesota Mining And Manufacturing Company Orthopedic casting materials having superior lamination characteristics due to napped surface
GB9216775D0 (en) 1992-08-07 1992-09-23 British United Shoe Machinery Orthopaedic splinting/casting material
JPH06118460A (en) 1992-09-30 1994-04-28 Nippon Telegr & Teleph Corp <Ntt> Optical phase modulation circuit
WO1994023679A1 (en) 1993-04-16 1994-10-27 Minnesota Mining And Manufacturing Company Orthopedic casting materials
US5417904A (en) * 1993-05-05 1995-05-23 Razi; Parviz S. Thermoplastic polymer composites and their manufacture
JPH07328058A (en) * 1994-06-09 1995-12-19 Mitsubishi Rayon Co Ltd Orthopedic cast interior material
US5681649A (en) * 1994-07-29 1997-10-28 Bridgestone Corporation Footwear member
JP2810864B2 (en) 1995-06-15 1998-10-15 株式会社モルテン Singard
US5801224A (en) * 1996-04-26 1998-09-01 Board Of Trustees Operating Michigan State University Bulk reactive extrusion polymerization process producing aliphatic ester polymer compositions
US20060065993A1 (en) * 1998-04-03 2006-03-30 Certainteed Corporation Foamed polymer-fiber composite
AU1569699A (en) 1998-12-16 2000-07-03 Smith & Nephew Plc Casting material
FI108403B (en) 2000-02-25 2002-01-31 Yli Urpo Antti Material suitable for tissue reconstruction in an individual
US20020128420A1 (en) * 2000-12-27 2002-09-12 Simpson Scott S. Polyurethane elastomers and method of manufacture thereof
US6482167B2 (en) 2001-03-29 2002-11-19 Royce Medical Product Sealed edge orthopaedic casting technique
US6617376B2 (en) 2001-03-30 2003-09-09 Crane Plastics Company Llc Flexible wood composition
JP4081579B2 (en) 2001-09-14 2008-04-30 愛知県 Lignocellulosic material and use thereof
DK176535B1 (en) * 2002-05-08 2008-07-21 Inter Ikea Sys Bv Particleboard and method of manufacture thereof
JP2006016461A (en) * 2004-06-30 2006-01-19 Fa M Inc Method for producing naturally occurring filler-including resin composition and resin composition produced thereby
IE20050593A1 (en) 2004-09-09 2006-03-22 Fastform Res Ltd Geometrically apertured protective and/or splint device comprising a re-mouldable thermoplastic material
EP1791502A1 (en) 2004-09-09 2007-06-06 Fastform Research Limited Geometrically apertured protective and/or splint device comprising a re-mouldable thermoplastic material
WO2006076932A1 (en) * 2005-01-24 2006-07-27 T Tape Company Bv Orthosis and method for manufacture thereof
JP5181413B2 (en) 2005-09-13 2013-04-10 日立電線株式会社 Electrode for electrochemical device, solid electrolyte / electrode assembly and method for producing the same
WO2007035875A2 (en) * 2005-09-21 2007-03-29 Qfix Systems, Llc Reinforced low temperature thermoplastic material
BRPI0600787A (en) * 2006-02-24 2007-11-20 Phb Ind Sa environmentally degradable polymer composition and its method of obtaining
BRPI0600683A (en) * 2006-02-24 2007-11-20 Phb Ind Sa environmentally degradable polymer composition and its process of obtaining
EP2068786A1 (en) * 2006-10-03 2009-06-17 Fastform Research Limited Orthopaedic devices
CN101172164A (en) * 2006-11-03 2008-05-07 中国科学院化学研究所 Biopolymer nano tunica fibrosa material capable of being biological degraded and absorbed, preparing method and uses of the same
TWM321371U (en) 2006-12-22 2007-11-01 Chun-Chih Lai Flaky texture for polylactic acid and thin wood sheet
US20080269914A1 (en) * 2007-03-19 2008-10-30 Qfix Systems, Llc Direct contact moldable low temperature thermoplastic prosthetic devices
US7671140B2 (en) * 2007-04-09 2010-03-02 The University Of Connecticut Ring-opening polymerization of cyclic esters, polyesters formed thereby, and articles comprising the polyesters
US7942837B2 (en) 2007-04-21 2011-05-17 Prosthotics Functional Systems, Llc Composite moldable splint and method of forming same
US8303527B2 (en) 2007-06-20 2012-11-06 Exos Corporation Orthopedic system for immobilizing and supporting body parts
US8937135B2 (en) 2008-09-29 2015-01-20 Basf Se Biodegradable polymer mixture
FI125448B (en) * 2009-03-11 2015-10-15 Onbone Oy New materials
WO2012037529A2 (en) 2010-09-16 2012-03-22 Nistevo Sport Manufacturing Corporation User-moldable sports equipment using heated water bath
BE1020363A3 (en) 2011-12-23 2013-08-06 Orfit Ind METHOD FOR MANUFACTURING A POLYMER SHEET FOR USE AS AN IMMOBILIZATION ELEMENT.
US9198471B2 (en) 2013-03-14 2015-12-01 Nike, Inc. Articulated protective apparatus
FI126725B (en) 2013-10-21 2017-04-28 Onbone Oy Aerated materials

Patent Citations (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4021388A (en) * 1972-05-18 1977-05-03 Coloroll Limited Synthetic resin sheet material
US3921333A (en) * 1972-07-28 1975-11-25 Union Carbide Corp Transplanter containers made from biodegradable-environmentally degradable blends
US5863480A (en) * 1994-08-29 1999-01-26 Srp Industries Ltd. Process for making a filler reinforced thermoplastic composites having biaxially oriented components
US5827905A (en) * 1995-09-26 1998-10-27 Bayer Aktiengesellschaft Biodegradable plastics filled with reinforcing materials
US6071984A (en) * 1995-09-26 2000-06-06 Bayer Aktiengesellschaft Biodegradable plastics filled with reinforcing materials
US6184272B1 (en) * 1997-02-12 2001-02-06 Diamlerchrysler Ag Fiber-reinforced molded plastic part and process for its manufacture
US6124384A (en) * 1997-08-19 2000-09-26 Mitsui Chemicals, Inc. Composite resin composition
US6143811A (en) * 1998-08-14 2000-11-07 The Japan Steel Works, Ltd. Method of producing compound pellets containing wood flour
US6479002B1 (en) * 1998-12-30 2002-11-12 Haller Formholz Extrusion of plant materials encapsulated in a thermoplastic
US6911522B2 (en) * 2000-01-20 2005-06-28 Solvay (Societe Anonyme) Filled epsilon-caprolactone based polymer compositions, method for preparing same and articles based on said compositions
US20010030031A1 (en) * 2000-03-03 2001-10-18 Trespa International B.V. Process for the continuous production of a preform mat, and a preform and its use
US20040028927A1 (en) * 2000-07-14 2004-02-12 Leckey Richard Anthony Biodegradable composition and products prepared therefrom
US6780359B1 (en) * 2002-01-29 2004-08-24 Crane Plastics Company Llc Synthetic wood composite material and method for molding
US20060241216A1 (en) * 2003-03-17 2006-10-26 Jean-Pierre Varachez Adjustably biodegradable material for a horticultural container and overpackaging for containers
US20050137304A1 (en) * 2003-12-18 2005-06-23 Strand Marc A. Process for calendering of polyesters
US7988905B2 (en) * 2004-03-17 2011-08-02 Toyota Boshoku Kabushiki Kaisha Process for producing woody molding
US20070264460A1 (en) * 2004-05-25 2007-11-15 Novamont S.P.A. Perforated Biodegradable Films and Sanitary Products Obtained Therefrom
US20090036575A1 (en) * 2005-09-16 2009-02-05 University Of Maine System Board Of Trustees Thermoplastic composites containing lignocellulosic materials and methods of making same
US7601282B2 (en) * 2005-10-24 2009-10-13 Johns Manville Processes for forming a fiber-reinforced product
US20070132133A1 (en) * 2005-12-07 2007-06-14 Katuyuki Hasegawa Method for manufacturing resin composite formed product
US20070243782A1 (en) * 2006-04-14 2007-10-18 Aichi Prefecture Synthetic board and method of producing the same
US20070259584A1 (en) * 2006-05-04 2007-11-08 Ronald Whitehouse Biodegradable polymer composites and related methods
US20100240806A1 (en) * 2006-05-23 2010-09-23 Tetsuo Kondo Materials containing polyactic acid and cellulose fibers
US20070287795A1 (en) * 2006-06-08 2007-12-13 Board Of Trustees Of Michigan State University Composite materials from corncob granules and process for preparation
US20080015285A1 (en) * 2006-07-14 2008-01-17 Steven Richard Oriani Process aid for extruded wood composites
US20080032125A1 (en) * 2006-07-31 2008-02-07 Mitsubishi Jidosha Kogyo Kabushiki Kaisha Synthetic board
US20090236766A1 (en) * 2006-11-15 2009-09-24 Entex Rust & Mitschke Gmbh Blend of plastics with wood particles
US20080145656A1 (en) * 2006-12-13 2008-06-19 Cheil Industries Inc. Natural Fiber-Reinforced Polylactic Acid-based Resin Composition
US20100093890A1 (en) * 2007-04-19 2010-04-15 Gaia Basis Co., Ltd. Biodegradable resin composition and method for producing the same
US20100136324A1 (en) * 2007-05-01 2010-06-03 Agri Future Joetsu Co., Ltd Polymer composite material, apparatus for manufacturing the same and method of manufacturing the same
US20090105378A1 (en) * 2007-10-11 2009-04-23 Idemitsu Kosan Co., Ltd. Aromatic polycarbonate resin composition and molded article thereof
US20110263762A1 (en) * 2008-11-05 2011-10-27 Teijin Limited Polylactic acid composition and molded article thereof
US20120171446A1 (en) * 2009-09-24 2012-07-05 Jong Sung Park Wood plastic composite panel with contractility
US20130172795A1 (en) * 2010-09-11 2013-07-04 Onbone Oy Bandaging material
US20130225731A1 (en) * 2011-02-28 2013-08-29 Jiangsu Jinhe Hi-Tech Co., Ltd Degradable plastic and manufacturing method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Balasuriya et al., Composites Part A, 32, 2001, 619-629 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120073584A1 (en) * 2009-03-11 2012-03-29 Onbone Oy Orthopaedic splinting system
US9803080B2 (en) 2009-03-11 2017-10-31 Onbone Oy Orthopaedic splinting system
US10336900B2 (en) 2009-03-11 2019-07-02 Onbone Oy Composite materials comprising a thermoplastic matrix polymer and wood particles
US20130225731A1 (en) * 2011-02-28 2013-08-29 Jiangsu Jinhe Hi-Tech Co., Ltd Degradable plastic and manufacturing method thereof
US9051466B2 (en) * 2011-02-28 2015-06-09 Jiangsu Jinhe Hi-Tech Co., Ltd. Degradable plastic and manufacturing method thereof
FR3052781A1 (en) * 2016-06-16 2017-12-22 Greenpile
US11504878B2 (en) * 2017-03-02 2022-11-22 Sulapac Oy Materials for packaging

Also Published As

Publication number Publication date
US20140188021A1 (en) 2014-07-03
FI20095251A (en) 2010-09-12
JP5761719B2 (en) 2015-08-12
CA2755128A1 (en) 2010-09-16
EA201190165A1 (en) 2012-03-30
JP2012520099A (en) 2012-09-06
HRP20201971T1 (en) 2021-02-05
EP2405951B1 (en) 2017-11-22
EP2405951A2 (en) 2012-01-18
KR101756305B1 (en) 2017-07-10
EP3106180A2 (en) 2016-12-21
EP2405950B8 (en) 2020-11-18
KR20120026033A (en) 2012-03-16
NZ595557A (en) 2015-01-30
BRPI1008947A2 (en) 2016-08-16
FI125448B (en) 2015-10-15
AU2010222772A1 (en) 2011-10-27
ES2835653T3 (en) 2021-06-22
US20170058120A1 (en) 2017-03-02
CN102387818A (en) 2012-03-21
CN102405062B (en) 2014-12-17
US10336900B2 (en) 2019-07-02
CA2755126C (en) 2019-03-05
JP2012520368A (en) 2012-09-06
ZA201107118B (en) 2012-06-27
EA022386B1 (en) 2015-12-30
EP2405949A2 (en) 2012-01-18
FI20095251A0 (en) 2009-03-11
CA2755126A1 (en) 2010-09-16
JP5670361B2 (en) 2015-02-18
EP2405949B1 (en) 2020-09-16
WO2010103186A3 (en) 2011-01-06
CN102405062A (en) 2012-04-04
EP3106180A3 (en) 2017-02-22
EP2405949B8 (en) 2020-11-18
NZ595696A (en) 2014-03-28
ZA201107117B (en) 2012-06-27
EA201190164A1 (en) 2013-01-30
AU2010222771B2 (en) 2015-02-26
WO2010103188A2 (en) 2010-09-16
US9803080B2 (en) 2017-10-31
EA023530B1 (en) 2016-06-30
EP2405950A2 (en) 2012-01-18
KR20120044921A (en) 2012-05-08
KR101706662B1 (en) 2017-02-14
AU2010222772B2 (en) 2014-10-23
US20120073584A1 (en) 2012-03-29
ES2836949T3 (en) 2021-06-28
WO2010103187A3 (en) 2011-01-06
CA2755128C (en) 2019-01-08
HRP20201963T1 (en) 2021-02-05
WO2010103187A2 (en) 2010-09-16
PL2405949T3 (en) 2021-04-19
US20120071590A1 (en) 2012-03-22
WO2010103186A2 (en) 2010-09-16
CN102387818B (en) 2014-10-22
EP2405950B1 (en) 2020-09-16
WO2010103188A3 (en) 2010-12-29
AU2010222771A1 (en) 2011-11-03

Similar Documents

Publication Publication Date Title
US20120090759A1 (en) Method of producing composite materials
EP0477203B1 (en) Process and device for producing mouldings, in particular for structural elements, insulations and/or packaging, and mouldings so obtained
JP5656167B2 (en) Bamboo fiber, method for producing the same, and method for producing a composite material using bamboo fiber
US8716371B2 (en) Reed composite, manufacturing method thereof and building material using the same
EP0976790A1 (en) Process for the manufacture of composite materials
US8951452B2 (en) Process for particleboard manufacture
CN1158628A (en) Biodegradable material comprising regenerative raw material and method of producing the same
JP2010241986A (en) Method of producing thermoplastic resin composition
EP2961580B1 (en) Wood and composite-material plate and method for its manufacturing
Yee et al. Mechanical and water absorption properties of poly (vinyl alcohol)/sago pith waste biocomposites
US11267206B2 (en) Process for manufacturing composite product
JP2006082353A (en) Woody thermoplastic resin composition and method for producing woody thermoplastic resin molding
EP3377562B1 (en) Process for producing fiber-polymer-composites
CN110914373A (en) Surface-coated plant fibers, process for their production and their use in the production of manufactured articles
Kashytskyi et al. PROPERTIES AND FORMATION TECHNOLOGY OF GLUTINOUS BIOCOMPOSITE MATERIALS
JP2010275400A (en) Method for manufacturing thermoplastic resin composition
JP2022178346A (en) Sheet-like molding material, molded body and manufacturing method of them
BR102019004110A2 (en) PROCESS OF OBTAINING GRANULATED WOOD PRODUCT WITH SURFACE FINISHING IN MATTE BLACK COLOR
Nunes et al. Production of New Thermoplastic Matrix Composites For High Demanding Applications
Noyon et al. FABRICATION OF LINEAR LOW-DENSITY POLYETHYLENE BASED BIODEGRADABLE COMPOSITE INCORPORATED LEATHER SHAVINGS

Legal Events

Date Code Title Description
AS Assignment

Owner name: ONBONE OY, FINLAND

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:PARSSINEN, ANTTI;LAHTINEN, PETRO;SIGNING DATES FROM 20110927 TO 20110928;REEL/FRAME:027297/0976

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION