WO2020049211A1 - Filament composite - Google Patents

Filament composite Download PDF

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Publication number
WO2020049211A1
WO2020049211A1 PCT/FI2018/050632 FI2018050632W WO2020049211A1 WO 2020049211 A1 WO2020049211 A1 WO 2020049211A1 FI 2018050632 W FI2018050632 W FI 2018050632W WO 2020049211 A1 WO2020049211 A1 WO 2020049211A1
Authority
WO
WIPO (PCT)
Prior art keywords
filament
polymer
composite
composition
filler
Prior art date
Application number
PCT/FI2018/050632
Other languages
English (en)
Inventor
Mikko Huttunen
Timo Lehtonen
Arto MESKANEN
Marjo KETONEN
Original Assignee
Arctic Biomaterials 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 Arctic Biomaterials Oy filed Critical Arctic Biomaterials Oy
Priority to PCT/FI2018/050632 priority Critical patent/WO2020049211A1/fr
Publication of WO2020049211A1 publication Critical patent/WO2020049211A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • D01F6/625—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters derived from hydroxy-carboxylic acids, e.g. lactones
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing

Definitions

  • the present invention relates to a composite filament, and more partic ularly to a method for manufacturing the composite filament.
  • Clay is a widely investigated and commercially high demand filler in the polymer industry.
  • Polymer/clay nanocomposites are capable of having superior properties compared to conventional filled polymers even at a very low fraction of filler addition.
  • the easy availability, processability, low cost, and nontoxicity of clay and the advancements in the processing of clay nanocomposites have raised com dismissal interest in these materials.
  • the value-added properties enhanced without sacrificing of pure polymer properties make the clays important in the modern pol ymer industry.
  • Possible applications of polymer/clay nanocomposites range from household items to aerospace and medicine.
  • a composite filament contain ing
  • a method of manufacturing the composite filament comprises melt mixing components of the filament together in one or more processing steps to obtain a composition; and subjecting the composition thereby obtained to a further processing step to form the filament.
  • the composite filament is used for ad ditive manufacturing of a part.
  • Stiffness represents a material sample’s resistance to deformation, i.e. how it behaves under the application of external loading. Young's modulus, also known as the elastic modulus, is used as a measure of the stiffness of solid material.
  • the mechanical properties of plastic materials depend on the strain (rate) and tem perature. At low strain, the deformation is elastic, and after removal of the deform ing load the plastic returns to its original size and shape ln this regime, the stress (s) is proportional to the strain (e), i.e.
  • E the tensile (or Young's) modulus of the plastic, which is a measure of the stiffness of the material lt means that when a plastic sample is pulled at a (constant) strain rate the applied stress (or load) is directly proportional to the observed strain (or elongation) lf the plas tic material is loaded beyond its elastic limit, it does not return to its original shape and size, i.e. a permanent deformation occurs.
  • the stiffness means the rigidity of an object; the extent to which it resists deformation in response to an applied force.
  • the complementary concept is flexibility or pliability: the more flex ible an object is, the less stiff it is.
  • Polylactic acid, or polylactide is a biodegradable thermoplastic ali phatic polyester derived from renewable resources, such as corn starch, cassava roots, chips or starch, or sugarcane. Alternatively polylactide may be totally syn thetic.
  • Plain polylactide (PLA) is a brittle and stiff polymer ln an embodiment, PLA is modified so that the toughness and/or impact resistance of PLA is remarkably increased while the stiffness remains on a range comparable to that of plain un modified PLA.
  • a composite PLA filament is manufactured from PLA-based poly- mer matrix which is toughened by using nanosized reinforcement filler, such as nanoclay, and other additives as described below.
  • nanosized reinforcement filler such as nanoclay
  • An exemplary composition of the composite filament contains PLA- based polymer as a matrix in which nanoscale filler, such as nanoclay, is melt mixed with the matrix polymer.
  • the nanoclay in the composite filament acts as a na- noscale reinforcement thereby increasing the strength and stiffness of the compo site structure of the filament.
  • the filament may also include other additive(s), such as impact modifier(s), colorant(s), plasticizer(s), fire retardant(s), etc.
  • the nanoclay and the additive (s) may be added to the composite material in separate processing steps.
  • the stiffness of such material is comparable to plain PLA while its toughness is superior to PLA. Additionally other properties of such material may be superior to plain PLA, depending on chosen additives.
  • An exemplary composition further includes additive(s) which increases the crystallinity of the material(s).
  • additive(s) serve as a nucleating agent in- creasing the degree of crystallinity, which increases the strength and temperature resistance of the material.
  • aromatic sulfonate derivative(s) such as LAK 301
  • LAK 301 may be used as an additive that increases the crystallinity of the mate rials), thereby increasing the strength and temperature resistance of the material.
  • the stiffness of such material is comparable to plain PLA while its toughness and heat deflection temperature, i.e. heat resistance, is superior to PLA. Additionally other properties of such material may be superior to plain PLA, depending on cho sen additives.
  • Stiffness of the composite filament may be also improved (i.e. in creased) by using talc (i.e. magnesium silicate) as mineral filler.
  • the mineral filler such as talc, which may be of nanoscale or of submicron scale, has a physical rein forcement capability and simultaneously a positive effect to the crystallization rate, thereby enhancing the reinforcing of the material and the crystallization rate of the material.
  • Particle size (gm) and load-% of the mineral filler may be adjusted ac cording to need.
  • the particle size may be from 0.5 gm (500 nm) to 30 gm (30 000 nm) and the load may be from 1% to 10%.
  • the stiffness and toughness of the composite may be adjusted. Specifically, by adjusting the ar omatic sulfonate derivative/talc mineral ratio in the composition, the stiffness and toughness of the composite may be adjusted. Measurements show that increasing filler load from 5% to 13% lead to 48% increase in flexural modulus.
  • An exemplary composition may also include at least one impact modi bomb as an additive.
  • the impact modifier is a compound that improves the impact strength of the polymer.
  • the impact modifier forms entanglements in the matrix polymer, thereby resulting in improved impact strength properties.
  • the impact strength is improved so that the composition containing at least one impact modi bomb has a better (i.e. increased) shock absorption capability.
  • the entanglements may be formed when the components of the composite filament are melt mixed, or during the crystallization process of matrix polymer.
  • MBS metalhacry late butadiene styrene
  • MBS metalhacry late butadiene styrene
  • An exemplary composition of the composite filament contains or con sists of:
  • nanosized reinforcement such as Cloisite 20a nanoclay, in an amount of 0.1 wt-% - 20 wt-%, preferably 0.5 wt-% - wt-1.5%; and optionally one or more of:
  • nucleating agent such as LAK 301, in an amount of 0.1 wt-% - 20 wt-%, preferably 0.5 wt-% - 1.5 wt-%;
  • impact modifier such as MBS, in an amount of 0.1 wt-% - 30 wt-%, preferably 5 wt-% - 15 wt-%;
  • talc Mg silicate having an average particle size of 0.5 gm (500 nm) to 30 gm (30 000 nm), in an amount of 1 wt-% - 20 wt-%, preferably 3 wt-% - 10 wt-%.
  • poly-alpha-hydroxyacid based polymer such as PLA is used as the polymer matrix in the filament.
  • Nanoclay such as Cloisite 20a is used as the nanosized reinforcement that increases the impact strength of the filament.
  • Nucleating agent such as LAK 301 may be used to increase the degree of crystallin ity of the polymer matrix, enabling increased strength and temperature resistance of the filament lmpact modifier such as MBS may be used to improve the impact resistance of the filament.
  • Talc may be used to improve stiffness and degree of crys tallinity of the filament.
  • An exemplary method for manufacturing the composite filament com prises mixing components of the filament together in one or more processing steps, and subjecting the composition thereby obtained to heat and pressure to form the filament.
  • the method may comprise mixing components of the filament together by using melt mixing, such as twin screw melt extrusion and/or compounding, to obtain the composite filament.
  • the composite filament may be used for additive manufacturing (i.e. 3D printing) of a part.
  • the additive manufacturing may comprise fused filament fabrication (FFF).
  • FFF fused filament fabrication
  • a 3D printed part pre pared by fused filament fabrication, by using the composite filament as raw mate rial.
  • the feasibility of a composite filament on 3D printing was studied by using PLA (HP2500) in which 1% of nanoclay was melt mixed to form a mixture.
  • Other additives in the mixture included 1 wt-% of LAK and 10 wt-% of MBS.
  • the amount of PLA in the mixture was thus 88 wt-%.
  • the obtained mixture was melt processed into a form of a continuous filament having a diameter of 1.75 mm.
  • the obtained continuous filament was used as a raw material in 3D printing by means of fused filament fabrication (FFF).
  • FFF fused filament fabrication
  • the stiffness of 3D printed part (standard dog bone test bar) thus obtained was similar as plain PLA (manual measurement ac cording to how the material feels on hand while bending), but the toughness was superior to plain PLA.
  • Toughness of the 3D printed part was observed manually by bending the formed part and by comparing the results to a part 3D printed from plain non-reinforced PLA material. Both parts were bent to 90 degrees angle from the middle.
  • the part manufactured from plain PLA broke in two parts, while the part manufactured from the material according to an embodiment of the present invention showed no visual signs of a fracture.

Abstract

L'invention concerne un filament composite, contenant un poly(acide lactique) et/ou un autre polymère, copolymère, terpolymère, mélange de polymères ou mélange de copolymères à base de poly-alpha-hydroxyacide, en tant que matrice polymère, et un renforcement à l'échelle nanométrique. Le filament composite contient éventuellement un additif choisi parmi l'un ou plusieurs d'un agent de nucléation, d'un modificateur d'impact et d'une charge. L'invention concerne également un procédé de fabrication du filament composite, comprenant le mélange à l'état fondu de constituants du filament ensemble dans une ou plusieurs étapes de traitement pour obtenir une composition et la soumission de la composition ainsi obtenue à une étape de traitement supplémentaire pour former le filament.
PCT/FI2018/050632 2018-09-06 2018-09-06 Filament composite WO2020049211A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/FI2018/050632 WO2020049211A1 (fr) 2018-09-06 2018-09-06 Filament composite

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/FI2018/050632 WO2020049211A1 (fr) 2018-09-06 2018-09-06 Filament composite

Publications (1)

Publication Number Publication Date
WO2020049211A1 true WO2020049211A1 (fr) 2020-03-12

Family

ID=69722883

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI2018/050632 WO2020049211A1 (fr) 2018-09-06 2018-09-06 Filament composite

Country Status (1)

Country Link
WO (1) WO2020049211A1 (fr)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103980683A (zh) * 2014-04-30 2014-08-13 中国科学院化学研究所 一种三维打印可生物降解聚乳酸材料及其制备方法
JP2016028887A (ja) * 2014-07-14 2016-03-03 学校法人同志社 熱溶解積層型３次元プリンタ用フィラメントおよびその製造方法
KR20160063877A (ko) * 2014-11-27 2016-06-07 재단법인 한국탄소융합기술원 3d 프린터용 필라멘트 제조방법 및 이에 의해 제조된 필라멘트
CN106380806A (zh) * 2016-09-28 2017-02-08 北京石油化工学院 用于热熔型3d打印的导电聚乳酸复合材料组合物及其制备方法
US20170088709A1 (en) * 2015-09-30 2017-03-30 Aspen Research Corporation Bio-alloy compositions
US20170130034A1 (en) * 2015-11-10 2017-05-11 Korea Institute Of Science And Technology High strength polymer filament for fdm 3d printer including graphene coated metal nanoparticles, nanocarbons for 3d printer, and preparation method of the same
CN107556768A (zh) * 2017-09-05 2018-01-09 广西丰达三维科技有限公司 一种高性能环保复合材料及其应用
US20180118936A1 (en) * 2016-10-28 2018-05-03 Clark Atlanta University Nanocellulose nucleating agents for crystallization of polylactides and other polymers
CN108485218A (zh) * 2018-04-10 2018-09-04 桂林航天工业学院 果壳粉增强聚乳酸丝材及其制备方法和3d打印

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103980683A (zh) * 2014-04-30 2014-08-13 中国科学院化学研究所 一种三维打印可生物降解聚乳酸材料及其制备方法
JP2016028887A (ja) * 2014-07-14 2016-03-03 学校法人同志社 熱溶解積層型３次元プリンタ用フィラメントおよびその製造方法
KR20160063877A (ko) * 2014-11-27 2016-06-07 재단법인 한국탄소융합기술원 3d 프린터용 필라멘트 제조방법 및 이에 의해 제조된 필라멘트
US20170088709A1 (en) * 2015-09-30 2017-03-30 Aspen Research Corporation Bio-alloy compositions
US20170130034A1 (en) * 2015-11-10 2017-05-11 Korea Institute Of Science And Technology High strength polymer filament for fdm 3d printer including graphene coated metal nanoparticles, nanocarbons for 3d printer, and preparation method of the same
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US20180118936A1 (en) * 2016-10-28 2018-05-03 Clark Atlanta University Nanocellulose nucleating agents for crystallization of polylactides and other polymers
CN107556768A (zh) * 2017-09-05 2018-01-09 广西丰达三维科技有限公司 一种高性能环保复合材料及其应用
CN108485218A (zh) * 2018-04-10 2018-09-04 桂林航天工业学院 果壳粉增强聚乳酸丝材及其制备方法和3d打印

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* Cited by examiner, † Cited by third party
Title
COPPOLA, B. ET AL.: "Layered Silicate Reinforced Polylactic Acid Filaments for 3D Printing of Polymer Nanocomposites", 2017 IEEE 3RD INTERNATIONAL FORUM ON RESEARCH AND TECHNOLOGIES FOR SOCIETY AND INDUSTRY (RTSI), 12 October 2017 (2017-10-12), pages 1 - 4, XP033163161 *

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