EP4655442A1 - Covered shape-memory polymeric fibers for textile applications - Google Patents
Covered shape-memory polymeric fibers for textile applicationsInfo
- Publication number
- EP4655442A1 EP4655442A1 EP24705986.8A EP24705986A EP4655442A1 EP 4655442 A1 EP4655442 A1 EP 4655442A1 EP 24705986 A EP24705986 A EP 24705986A EP 4655442 A1 EP4655442 A1 EP 4655442A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- shape
- memory
- fiber
- covered
- polymer
- 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.)
- Granted
Links
Classifications
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/38—Threads in which fibres, filaments, or yarns are wound with other yarns or filaments, e.g. wrap yarns, i.e. strands of filaments or staple fibres are wrapped by a helically wound binder yarn
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
-
- 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
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/36—Cored or coated yarns or threads
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/04—Heat-responsive characteristics
- D10B2401/046—Shape recovering or form memory
Definitions
- the present invention is in the field of shape-memory fibers and discloses a covered shape- memory polymeric fiber, a method of making the same, and a shape-memory fabric and shape-memory textile comprising the same.
- the present invention relates to the field of textiles, in particular shape-memory polymeric fibers and was partly developed under the EU project expGrowBot - Towards a new generation of plant-inspired growing artefacts“ (Grant Agreement 824074).
- SMPs Shape-Memory Polymers
- SMPs are an emerging class of smart materials which are able to modify their size and shape in response to external stimuli such as heat, electric current, and electro-magnetic field, water or light.
- Typical SMPs have the ability to memorize their original shape after deformation such as stretching. They maintain the deformed state in the absence of the stimulus, and recover their original shape after application of the external stimulus.
- SMPs have been increasingly investigated for biomedical applications. From a structural view point, SMPs can be classified as three-dimensional systems, such as shape memory blocks or shape memory foams, two-dimensional systems, such as shape memory films, and one-dimensional systems such as shape memory fibers, where shape memory fibers have drawn the most attention.
- shape memory fibers can be converted into two-dimensional and/or three-dimensional systems.
- SMPs in the form of fibers are generating great interest in structural and functional applications because of their flexibility, anisotropic properties and their capability of being converted into two-dimensional and/or three-dimensional systems.
- Known shape memory fibers have been produced from polyurethane block copolymers or from multiblock copolymers comprising poly( ⁇ -pentadecalactone) hard segments (PPDL) and poly( ⁇ - caprolactone) switching segments (PCL) via electrospinning methods as disclosed in F. Zhang et al.
- Shape memory polymer nanofibers and their composites electrospinning, structure, performance, and applications” Frontiers in Materials, October 2015, Vol.2, Article 62, or from poly(ethylene-co-vinyl acetate) random copolymers, as disclosed in K. Wang et al. “The Thermal and Mechanical Properties of Poly(ethylene-co-vinyl acetate) Random Copolymers (PEVA) and its Covalently Crosslinked Analogues (cPEVA)”, Polymers 2019, 11, pages 1055 (2019) via extrusion. white ip
- Patent Application Chinese patent application CN 1706997 A discloses a shape memory fiber prepared from shape memory polyurethane and its preparation method and Chinese utility model CN 201553838 U discloses a heat-sensitive shape memory polyurethane covered yarn (shape- memory polymeric fibers, cSMPF) and a method of producing it. Also related to this disclosure is the Chinese utility model application CN 201545991 U, in which a central shape-memory yarn coated by an external lapping yarn coated on the surface of the central yarn, featuring the effect of a soft hand feeling and anti-wrinkle capacity. Said cSMPF can be programmed by stretching at various temperatures before or after covering with conventional yarns in textile industry such cotton, nylon, and polyester etc.
- thermosensitive shape memory polyurethane disclosed here had stronger fabric wrinkling prevention capability with better elasticity and was easy to be recovered to permanent initial shape. This covering is not only necessary to overcome the processing related technical constraints, but also they are sometime necessary for comfort and due to regulatory requirements where the direct contact of such fibers to the body of the wearer can be avoided.
- thermosensitive shape memory polyurethane disclosed in CN 201553838 U is stated to have improved fabric wrinkling prevention capability and improved elasticity.
- the diameter ratio between the covering yarn and core yarn is reported as ranging from 0.1 to 1.0.
- WO 2012/045427 A1 discloses medical aids, in particular body support bandages and orthotics, comprising at least one element which generates or delivers a supporting force, compression or introduction of pressure, and which comprises shape memory material or consists thereof.
- the programmed shape memory transition of the medical aid is triggered by body heat whereby the stretched form of the medical aid, which facilitates application to the body, changes into a contracted form conveying the supporting and/or compression effect of the medical aid.
- the shape memory material according to this disclosure is a composite material, a mixture, an alloy, or a composite material having different shape memory effects.
- WO2000038531A1 discloses a tubular casing for use with food products having circumferential threads comprising elastic thread having a predetermined elastic limit so that below said elastic limit, said threads are elastically extensible and that at said elastic limit said threads become inextensible.
- This example from the food industry teaches that threats with a defined elastic limit can be used to limit the expansion of a tubular thread covering used with food-products.
- An example in connection with the elastic limit or the rupture point of elastic rubbers is described in US 1679822 A.
- the object of the present invention is to address and overcome a major shortcoming in the field of shape-memory fibers as observed in the prior art.
- Conventional shape-memory polymeric fibers (SMPF) while exhibiting remarkable shape memory properties, are limited by their susceptibility to being stretched beyond their recoverable shape-memory programming range. This limitation often results in a loss of shape-memory functionality, making the fibers less effective or even unusable for their intended applications, especially reducing important properties like the shape recovery ratio and shape recovery fixity. Once the fibers are stretched beyond a certain point, their ability to return to their pre-programmed shape is impaired.
- SMPF shape-memory polymeric fibers
- the invention aims to expand the functional scope and durability of shape memory materials and make them suitable for a wider range of practical applications that were previously limited due to the mechanical degradation of the shape-memory properties of earlier fibers.
- SOLUTION The problem is solved by a covered shape-memory polymeric fiber (cSMPF) with the features of claim 1.
- cSMPF covered shape-memory polymeric fiber
- the invention further discloses a method of making the same as well as a shape-memory textile comprising the same, a shape-memory fabric comprising the same and uses thereof. Further advantageous embodiments and further developments are shown in the subclaims and in the description with reference to the figures. white ip
- the covered shape-memory polymeric fiber of the invention solves the mechanical problems associated with shape-memory effects of previous shape-memory fibers, such as shape recovery ratios, encountered in practical textile applications, particularly in functional clothing and garments used in medical, recreational and technical applications, by covering the shape-memory polymer of the core fiber with a substantially unstretchable covering yarn wound around the core fiber in a manner that the maximum engineering strain of the core fiber is reduced to at most the strain at the yield point of the uncovered core fiber.
- This enables the application of shape-memory materials in textiles, fabrics, which are required to be fabricated into garments, which may be used in medical, leisure, and technical applications.
- cSMPFs of this disclosure are their ability to maintain consistent shape fixity and recovery across multiple shape-memory cycles. This is crucial in medical applications where precise and reliable performance is required. Furthermore, this design limits the maximum extension of the core fiber to a predetermined strain, preventing overstretching and potential structural damage. This limitation is particularly advantageous in medical textiles where controlled compression and consistent support are critical for therapeutic effectiveness, especially when constant and reproducible pressures are needed for effective treatment.
- the covering yarn not only limits the stretchability of the core fiber, but also adds an extra layer of protection. This additional layer helps in safeguarding the core fiber from environmental factors and mechanical wear, thereby enhancing the overall durability and longevity of the fiber and the textile products made from it.
- the present invention relates to a covered shape-memory polymeric fiber (cSMPF) having a core fiber, and a substantially unstretchable covering yarn wound around the core fiber in a manner that the maximum engineering strain of the core fiber is reduced to at most the strain at the yield point of the uncovered core fiber.
- cSMPF covered shape-memory polymeric fiber
- white ip Patent & Legal HELM-0001-P-EPWO 23.01.2024
- “have/having” may be used synonymously or interchangeably with the terms “comprising” or “consisting of” and means that a feature comprises or consists of a particular sub-feature.
- the invention relates to a covered shape-memory polymeric fiber (cSMPF) (1) comprising or consisting of at least - a core fiber (10), comprising or consisting of a shape-memory polymer (SMP), and - a substantially unstretchable covering yarn (20), wherein the substantially unstretchable covering yarn (20) is wound around the core fiber (10) in a manner that the maximum engineering strain of the core fiber (10) comprised by the covered shape-memory polymeric fiber (1) is reduced to at most the strain at the yield point of the uncovered core fiber (10).
- cSMPF covered shape-memory polymeric fiber
- the invention comprises a covered shape-memory polymeric fiber (cSMPF) (1) comprising or consisting of at least - a core fiber (10), comprising or consisting of a shape-memory polymer, and - a substantially unstretchable covering yarn (20) wound around the core fiber (10), wherein the maximum engineering strain ( ⁇ max ) of the core fiber (10) comprised by the covered shape-memory polymeric fiber (1) is limited to at most the strain at the yield point ( ⁇ yield ) of the uncovered core fiber (10), preferably determined at 25 °C, wherein the strain at the yield point ( ⁇ yield ) is preferably in the range between 10 % and 100 %, more preferably between 15 % and 70 %, most preferably between 20 % and 60 %
- cSMPFs exhibit consistent shape stability and recovery over multiple shape memory cycles and ensure a wide stretchability range while maintaining shape memory properties.
- the maximum engineering strain ( ⁇ max) of the core fiber (10) comprised by the covered shape-memory polymeric fiber (1) is limited to at most the strain at the yield point ( ⁇ yield) of the uncovered core fiber (10), preferably determined at 25 °C, wherein the strain at the yield point ( ⁇ yield) is in the numerical range obtained by combining any two of the following end point values: 10 %, 12 %, 14 %, 16 %, 18 %, 20 %, white ip
- a “core fiber (10)” (also referred to as “core shape-memory fiber (10)”) in the context of the current invention comprises or consists of a shape-memory polymer and may be covered by a substantially unstretchable covering yarn (20) wound around the core fiber (10).
- the maximum engineering strain ( ⁇ max ) of the core fiber (10) is equivalent to the maximum engineering strain ( ⁇ max ) of the covered shape-memory polymeric fiber (cSMPF) comprising the core fiber (10).
- An “uncovered core fiber (10)” (sometimes referred to as “core fiber (10)”) in the context of the current invention comprises or consists of a shape-memory polymer without a substantially unstretchable covering yarn (20) wound around the core fiber (10). Therefore the strain at the yield point ( ⁇ yield ) of the uncovered core fiber (10) is equivalent to the yield point of the core fiber (10) of a covered shape-memory polymeric fiber (cSMPF) without a substantially unstretchable covering yarn (20).
- a ”fiber” in the context of this invention is a single continuous strand of a material, a form in which it is much longer in one axial direction than in 2 others comparably small directions.
- a “filament” according to the current invention may be a monofilament, which corresponds to a “fiber” in the spirit of the current invention, or a multifilament, which comprises at least a “fiber” in the spirit of the current invention.
- a multifilament is a bundle of co-directed fibers that in some preferred embodiments are filament fibers, i.e. fibers whose length is comparable to the length of the multifilament (common example rope, cable, synthetic textile yarns), or in another preferred embodiment are staple fibers, i.e.
- the present invention relates to a covered shape-memory polymeric fiber (cSMPF) having a core fiber of semi-crystalline polymer fibers and a substantially unstretchable covering yarn wound around the core fiber in a manner that the maximum engineering strain ( ⁇ max) of the core shape-memory fiber is reduced to at most the strain at the yield point ( ⁇ yield) of the uncovered core fiber.
- cSMPF covered shape-memory polymeric fiber
- the covering yarn is used to limit the stretchability or deformation of the core shape-memory fibers during programming so as to ensure maximum recoverable strain.
- Patent Application yarn can be influenced by the density of entwining (also preferably referred to as density of covering) ( ⁇ 0) of the core fiber in the unstretched state, i.e. by the number of twists per meter of the covering yarn when the core fiber is in the unstretched state, and the length (l) and diameter (d) of the covering yarn, all in relation to the diameter of the core fiber (D0) in the unstretched state.
- the strain ( ⁇ ) of the core fiber is given by the following formula: ⁇ wherein ⁇ 1 is the strain, L1 is the length of the core fiber at said stress, L0 is the length of the core fiber in the unstretched state.
- stress and “strain” can be used interchangeably, because the deformation of the SMPF is limited to its yield point and/or elastic limit. In this ranges, each strain value may correspond to one stress value. This is why each point on the stress- strain curve of SMPF may be used to unambiguously defined with either stress or strain value.
- Stretching (elongation) of the core fiber having the covering yarn wound around it causes the pitch (r), i.e. the distance between two loops of the twist, of the covering yarn around the core fiber to increase from r 0 to r 1 , whereby the density of entwining ( ⁇ 1 ) decreases.
- the covering yarn is not stretched until up to a maximum strain ( ⁇ max ) of the core fiber. Further stretching of the core fiber beyond the maximum strain ( ⁇ max ) would require stretching of the covering yarn as well.
- this point of maximum strain ( ⁇ max ) of the core fiber should be chosen so as to not exceed the strain at the yield point ( ⁇ yield ) of the core fiber.
- the point of maximum strain ( ⁇ max ) is independent of the material of the covering yarn, and solely dependent on the diameter (D 0 ) of the shape-memory white ip
- Patent & Legal HELM-0001-P-EPWO 23.01.2024 Int. Patent Application polymeric core fiber (cSMPF), the diameter of the covering yarn (d) and the density of entwining ( ⁇ 0), wherein the density of entwining ( ⁇ 0) is defined as: n ⁇ 0 0 L 0 wherein ⁇ 0 is the density of entwining, L0 is the length of the core fiber in the unstretched state and n0 is the number of windings of the covering yarn around the core fiber in the unstretched state.
- the strain at the yield point of the shape-memory polymeric core fiber is dependent on the material of the core fiber, particularly the shape-memory-polymer comprised by the core fiber, and the diameter (D0) of the core fiber, while being limited by accordingly selecting the diameter of the covering yarn (d) and the density of entwining ( ⁇ 0) and the material of the covering yarn so that the maximum strain ( ⁇ max) of the core fiber, determined by the material and diameter of the core fiber, should be chosen so as to not exceed the strain at the yield point ( ⁇ yield) of the core fiber.
- the length of the covering yarn, dependent on the length of the core fiber, required to achieve that the maximum engineering strain ( ⁇ max ) of the core shape-memory fiber is reduced to at most the strain at the yield point ( ⁇ yield ) of the uncovered core fiber can be determined according to the following equation: ⁇ 2 ⁇ 2 D2 ⁇ ⁇ (1 + 0 0 ) ⁇ 2 + 2 ⁇ ⁇ 2 ⁇ 2 d ⁇ ⁇ 2 ⁇ 2 D 2 ⁇ + 1 + 2 2 D + d 2 4 max ( 0 0 0 ) max ( ⁇ ⁇ 0 ( ) ) wherein L0 is the length of the core fiber in the unstretched state, D0 is the diameter of the core fiber in the unstretched state, ⁇ 0 is the density of entwining in the unstretched state, d is the diameter of the covering yarn, and ⁇ max is the strain of the core fiber at its yield point.
- the covering yarn may be wound around the core fiber as single or double, covering with S or Z-directional twists.
- the twist density is preferably in a range of 750 to 3000 twists per meter.
- the yield point is the point on a stress-strain curve that indicates the limit of elastic behavior.
- the engineering strain at the yield point ( ⁇ yield) is the strain (elongation) the core fiber white ip
- the yield point is a material characteristic value and can be determined according to ISO 527.
- the “yield point” is corresponding to the “elastic limit”, which is the point on a stress-strain curve that indicates the limit of elastic behavior.
- the engineering strain at the yield point ( ⁇ yield ) is limited to the strain at the elastic limit.
- the elastic limit especially in the context of the shape-memory polymers comprised by the core fiber of the cSMPF of the current invention may be determined by thermomechanical analysis using a tensile testing machine, for example a MTS 858 testing machine equipped with an appropriate indirect temperature measurement system, preferably a IR camera, for example a ThermaCam TM Phoenix.
- the yield point closely related to the elastic limit, marks the transition from elastic to plastic behavior, indicating the maximum strain the SMP can withstand without undergoing permanent deformation.
- Limiting the engineering strain ( ⁇ max ) to the yield point ( ⁇ yield ) or to the elastic limit is therefore important for ensuring a high shape recovery ratio and the mechanical stability of the shape-memory effect against strain.
- Elastic limit can be determined with a step-cycle test described and performed in ” Strain recovery and stress relaxation behaviour of multiblock copolymer blends physically cross- linked with PLA stereocomplexation” Izraylit, V., Heuchel, M., Gould, O. E., Kratz, K., & Lendlein, A. (2020). Polymer, 209, 122984.
- the elastic limit is determined with a step-cycle test. A sample was stretched to a certain strain ⁇ with a constant extension rate. Then, the stress was removed to 0 at the same contraction rate. At each following step the sample was elongated to a higher strain than at the previous one. The cycles were continued until sample rupture. The recovered strain is considered to be the elastic component ⁇ e of the deformation, while remaining is the plastic component ⁇ p of the deformation. Elastic limit can be determined a point of sharp increase of the tangent of the ⁇ p( ⁇ ) where ⁇ is the stress value at the stress-strain curve at deformation ⁇ related to ⁇ p in the particular step in the step-cycle experiment.
- the yield point is defined as a point of the maximum curvature of the stress-strain curve white ip
- the expression “substantially unstretchable” means that the covering yarn is stiffer in relation to the core fiber. This ratio can be quantified with Young’s modulus. Young’s modulus is a mechanical property that measures the compressive stiffness, in this context particularly tensile stiffness, of a solid material when force is applied lengthwise. In an embodiment of the invention, the covering yarn has higher Young’s modulus than the core fiber.
- the Young’s modulus of the covering yarn is at least twice, preferably at least three times, most preferably at least five times of the Young’s modulus of the of the core fiber.
- the ratio of the diameter of the core fiber D 0 , the diameter of the covering yarn d, and the density of entwining ⁇ 0 are defined in a way that during the stretching of cSMPF exists ⁇ onset , at which stretching of covering yarn 20 onsets and the slope of tangent of a stress-strain curve increases in a leap.
- L 0 defines the length of the core fiber in an unstretched state and L 1 defines the length of the core fiber 10 in a stretched state.
- D 0 defines the diameter of the core fiber 10 in an unstretched state and D 1 defines the diameter of the core fiber 10 in a stretched state.
- the Poisson’s rate ⁇ of the core fiber 10 is defined as: ⁇
- the formula of the Poisson’s rate ⁇ of the core fiber 10 can be rewritten as white ip
- ⁇ 1 2 ⁇ 2 ⁇ 2( D 1 + ⁇ )2 + ⁇ 1 2 ⁇ 2
- ⁇ 1 2 ⁇ 2 0 ⁇ 0 2 ⁇ 2( ⁇ 0 ( 1 ⁇ ⁇ ⁇ ) + ⁇ )2 + ⁇ 2 1
- ⁇ 1 2 ⁇ 2 0 ⁇ 0 2 ⁇ 2 ( ⁇ 0 2 ⁇ 2 ⁇ 0 2 ⁇ ⁇ + ⁇ 0 2 ⁇ 2 ⁇ 3 + 2 ⁇ 0 ⁇ ⁇ 2 ⁇ 0 ⁇ ⁇ + ⁇ 2 ) + ⁇ 2 0 + 2 ⁇ ⁇ 2 0 + ⁇ 2 ⁇ 2 0 white ip
- Patent Application ⁇ 2 0 ((1 + ⁇ 2 ⁇ 2 ⁇ 0 2 ⁇ 0 2 ) ⁇ 2 + (2 ⁇ 2 ⁇ 2 ⁇ ⁇ 0 2 ⁇ 0 ⁇ ⁇ 2 ⁇ 2 ⁇ ⁇ 0 2 ⁇ 0 2 ) ⁇ + (1 + ⁇ 2 ⁇ 0 2 ( ⁇ 0 + ⁇ ) 2 ))
- the covering yarn 20 is wound around the core fiber 10 in a manner that after stretching to a defined engineering strain ( ⁇ max ), the covering fiber will be so deformed that further stretching of cSMPF will cause axial stretching of the covering yarn.
- a defined engineering strain ⁇ max
- the core fiber (10) is selected from a shape-memory polymer (SMP), wherein the shape-memory polymer is a thermally programmable shape-memory polymer SMP, preferably with a crystalline rigid segment and a switching segment, wherein the thermally programmable shape-memory polymer has a programming temperature (Tprog) between 40 and 80 °C, more preferably between 40 and 70 °C, as determined with Differential Scanning Calorimetry (DSC).
- SMP shape-memory polymer
- Tprog programming temperature
- DSC Differential Scanning Calorimetry
- cSMPF covered shape-memory polymeric fibers
- the shape fixity (R f ) and shape recovery (R r ) in a cycle (N) can be calculated from applied deformation ( ⁇ m ) during programming, fixed strain in the temporary shape ( ⁇ u ) after removing stress in the programming step and recovered strain ( ⁇ p ) in the recovery cycle using following equations.
- the shape-recovery ratio for the covered fibers, especially the covered shape-memory polymeric fibers is between 80 % and 100 % more preferably between 92.5 % and 100 %, especially preferably between 95 % and 100 %. This allows for repeated use in the disclosed applications.
- the shape- recovery ratio for the covered fibers is above 95 % to meet the demand of the RAL-387 standard for medical compression garments, especially preferably the class 1 range with a pressure range between 2.4 and 2.8 kPa.
- a test with ⁇ 100 shape-memory cycles was performed which showed identical results for shape- recovery and lower shape fixity ratios over the course of 100 cycles.
- the heating and cooling rates were 10°C ⁇ min -1 here and equilibration times were reduced to 1 min.
- the thermic programming process comprising a) An initial programming step, comprising controlled heating of the covered shape- memory polymeric fiber to a specific programming temperature (T prog ) while stretching the fiber at a controlled rate, preferably ⁇ 10 mm/min, to a predefined programming strain ( ⁇ prog ) below maximum engineering strain, then b) An equilibration step, comprising holding the stretched state for an equilibration time, preferably between 1 and 10 minutes, followed by c) A cooling step, comprising cooling the covered shape-memory polymeric fiber to a temperature below its crystallization point, preferably ⁇ 35 °C while under predefined programming strain ( ⁇ prog ).
- the stretching with the programming strain ( ⁇ prog) aligns the polymer chains in the direction of the force applied.
- the programming temperature may be in the numerical range obtained by combining any two of the following end point values: 40 °C, 42 °C, 44 °C, 46 °C, 48 °C, 50 °C, 52 °C, 54 °C, 56 °C, 58 °C, 60 °C, 62 °C, 64 °C, 66 °C, 68 °C, 70 °C, 75 °C, or 80 °C.
- the programming temperature is in the range between 40°C and 70 °C, or may alternatively be in the numerical range obtained by combining any two of the following end point values: 40 °C, 42 °C, 44 °C, 46 °C, 48 °C, 50 °C, 52 °C, 54 °C, 56 °C, 58 °C, 60 °C, 62 °C, 64 °C, 66 °C,68 °C, or 70 °C.
- the temperature range is chosen so that the programming and/or shape-recovery can be executed directly on the subject’s body. This may advantageously allow the thermal programming and recovery of the covered shape-memory polymeric fiber and/or shape- memory textile and/or shape-memory fabric comprising the same directly to the shape of the subject and realize an optimal force distribution.
- the shape-memory textile or fabric is programmed according to the contours of a patient’s body. This means that the shape-memory textile or fabric is initially set to conform to the patient's specific body shape. After wearing and removal, the programmed shape can be restored. This is particularly useful in medical garments where a custom fit is essential for therapeutic effectiveness.
- An alternate embodiment involves programming the permanent shape of the shape-memory textile or shape-memory fabric at higher temperatures, beyond the typical range of environmental or body temperatures. This ensures that the programmed shape is not inadvertently altered or distorted through everyday activities, such as washing or drying. In this case, the patient does not play a role in the programming process.
- a garment comprising a cSMPF or a shape-memory textile or shape-memory fabric is designed to maintain its therapeutic shape and function regardless of routine handling, ensuring consistency and reliability in medical applications.
- a thermally programmable shape-memory polymer may also be a semi-crystalline shape- memory polymer and vice versa. These two designations refer to two different but related properties of a shape-memory polymer and are not mutually exclusive.
- a shape-memory polymer is a thermally programmable semi-crystalline shape- memory polymer.
- a shape-memory polymer comprised by the core fiber of the covered shape-memory polymeric fiber is a semi-crystalline shape-memory polymer (SSMP) with a degree of crystallinity between 3 % and 70 %, which is thermally programmable and has a programming temperature (Tprog) between 40 and 80 °C, which white ip
- the crystalline properties which are preferably controlled by the method for making a cSMPF according to the present disclosure and which have a profound effect on the programming temperature, strain, and other parameters of the core fiber, can be modified to achieve the desired programming temperatures essential for use of the cSMPF in garments, shape-memory fabrics and shape-memory textiles, particularly those suitable for thermal programming and recovery on the body of a subject.
- the nature of the covering yarn ranges from yarns of natural fibers, such as cotton, wool, etc., to semi-synthetic or synthetic yarns, such as viscose, acrylic, nylon, polyester, etc.
- the covering yarn is selected from cotton, wool, silk, linen, viscose, acrylic, nylon and polyester.
- the covering yarn is wound around the core fiber as single or double covering with S or Z direction twists.
- the diameter ratio between the covering yarn and core fiber may preferably range from 1:1 to 1:20.
- the diameter ratio between the covering yarn and core fiber lies preferably within 1:1 to 1:20. A smaller diameter ratio ensures adequate coverage and protection of the core fiber by the covering yarn, while larger ratios allow for greater flexibility and adaptability of the core fiber within the covering.
- the diameter of the core fiber in the cSMPF lies within 50-500 ⁇ m.
- the diameter of the core fiber lies within 50-500 ⁇ m.
- the covering yarn may be a multifilament or a monofilament yarn. However, monofilament yarns are preferred.
- the covering yarn is a monofilament yarn.
- the core fiber (10) is a multifilament fiber, preferably with a linear fiber density value between 15 and 1000 dtex, more preferably between 35 and 600 dtex.
- a multifilament fiber consists of many fine individual filaments that are collected as a single fiber.
- linear fiber density of the core fiber in the cSMPF is within the numerical range obtained by combining any two of the following end point values: 15 dtex, 20 dtex, 25 dtex, 30 dtex, 35 dtex, 40 dtex, 45 dtex, 50 dtex, 75 dtex, 100 dtex, 150 dtex, 200 dtex, 250 dtex, 300 dtex, 350 dtex, 400 dtex, 450 dtex, 500 dtex, 550 dtex, 600 dtex, 650 dtex, 700 dtex, 750 dtex, 800 dtex, 850 dtex, 900 dtex, 950 dtex, and 1000 dtex.
- the core fiber comprised by the cSMPF is a multifilament fiber with a linear fiber density value between 15 and 75 dtex, more preferably between 20 and 50 dtex. Because of the high density of the cSMPF in a shape- memory fabric according to the current intention, the linear fiber density of the comprised cSMPF is chosen from this range as higher linear fiber densities would lead to a rigid fabric for the uses disclosed herein.
- the core fiber comprised by the cSMPF comprised by the shape-memory textile is a multifilament fiber with a linear fiber density value between 250 and 750 dtex, more preferably between 300 and 600 dtex. Because of the lower amount of the cSMPF fibers in a shape-memory textile according to the current intention, the linear fiber density of the comprised cSMPF is chosen from this range as lower linear fiber densities would lead to a textile with a weak shape-memory effect.
- dtex stands for "decitex” and is a unit of measurement used to express the linear density or fineness of a fiber.
- the covered shape-memory polymeric fiber according to any one of the previous claims wherein the covering yarn (20) is wound around the core fiber (10) with a rate of 500 to 6000 twists per meter, preferably 750 to 3000 twists per meter. A higher twist rate ensures that the covering yarn is securely wound around the core fiber, providing stability and protection. At the same time, maintaining the twist rate within this range prevents over- constriction of the core fiber, which could otherwise impede its shape-memory functionality.
- the covered shape-memory polymeric fiber according to any one of the previous claims wherein the covered shape-memory polymeric fiber has a stretchability from 30 to 1000%, preferably 50 to 900%.
- the fiber can be used in settings that require either moderate or significant elongation, catering to various functional needs. For instance, higher stretchability might be desired in textiles for sports and leisure, white ip
- the elongation at break ( ⁇ break) with error margins is in a range between 500 ⁇ 150 % and 1150 ⁇ 150 %, preferably between 600 ⁇ 150 % and 1000 ⁇ 150 %. This allows a large safety margin after stretching the fiber beyond the intended engineering strain according to the invention.
- a “shape-memory polymer” in accordance with the current invention is preferably a semi- crystalline polymer with a rigid segment and a switching segment.
- the rigid segment also referred to as the hard segment, is the part of the shape-memory polymer that defines the permanent shape of the material by establishing intermolecular interactions. This segment enables the polymer to retain the information of its original shape under various conditions and/or after deformation.
- the rigid segment can be presented by covalent bonds, molecular entanglement, crystallites, or other molecular interactions.
- the switching segment of the shape-memory polymer is responsible for the shape-memory behavior of the material. This segment is designed to be responsive to external stimuli, such as temperature changes.
- the switching segment When exposed to a specific temperature, also referred to as programming temperature, associated with a phase transition, preferably the glass transition and/or melting temperature, the switching segment becomes flexible, allowing the shape-memory polymer to be temporarily reshaped under a certain programming strain ( ⁇ prog ) at programming temperature (T prog ) followed by a defined equilibration time. Upon removal of the stimulus, the segment returns to its original state, governed by the rigid segment, thus reverting the material to its predefined shape.
- the switching segment can be presented by crystallites, glassy amorphous segments, or other reversible molecular interactions.
- the shape-memory polymer is a semi-crystalline shape-memory polymer (SSMP) with a degree of crystallinity between 3 % and 70 %, more preferably with a degree of crystallinity between 5 % and 60 %, as determined with wide angle x-ray scattering (WAXS), also referred to as X-ray diffraction spectroscopy (XRD).
- WAXS wide angle x-ray scattering
- XRD X-ray diffraction spectroscopy
- the degree of crystallinity may be determined with DSC.
- the degree of crystallinity is an attribute that significantly influences the performance and application of the shape-memory polymer fibers according to the current invention.
- a semi-crystalline shape-memory polymer is also thermally programmable with degree of crystallinity as an indicator of the molecular structure, more specific content of the switching segment in shape-memory polymer, which influence the phase transition temperature and shape fixity associated with the thermal programming of the shape-memory polymer and its shape- memory performance.
- degree of crystallinity in the context of this invention is defined as the proportion of the polymer's structure in the core fiber that is in a crystalline state. This crystalline state is characterized by a well-ordered and tightly packed molecular arrangement, which contrasts with the less ordered structure of the amorphous regions.
- the degree of crystallinity impacts crucial properties of the SMP, such as its thermal responsiveness, mechanical strength, flexibility, and the efficacy of its shape-memory effect.
- the degree of crystallinity can be quantitatively determined and is typically expressed as a percentage. This percentage reflects the ratio of the crystalline portion to the total volume of the polymer, encompassing both crystalline and amorphous areas.
- the invention specifically focuses on polymers with a degree of crystallinity between 3 % and 70 %, more preferably between 3% and 60 %, most preferably between 3 and 50 %, and may have a degree of crystallinity in the numerical range obtained by combining any two of the following end point values: 3 %, 4 %, 5 %, 6 %, 7 %, 8%, 9 %, 10 %, 11 %, 13 %, 15 %, 17 %, 19 %, 21 %, 23 %, 25 %, 27 %, 29 %, 31 %, 33 %, 35 %, 37 %, 39 %, 41 %, 43 %, 45 %, 47 %, 49 %, 51 %, 53 %, 55 %, 57 %, 59 %, 61 %, 63 %, 65 %, 67 %, 69 %, or 70 %.
- Such specified ranges of crystallinity are crucial for achieving the desired balance of material properties such as rigidity, flexibility, and phase transition temperature, ensuring optimal shape- memory function and mechanical performance for various applications.
- the degree of crystallinity is precisely determined using wide-angle X-ray scattering (WAXS). This technique involves analyzing the diffraction patterns obtained from the polymer to distinguish between the crystalline and amorphous regions.
- WAXS wide-angle X-ray scattering
- Such measurements can be performed using a white ip
- the beam can be focused and the geometric properties adjusted using standard means and methods known from the state of the art, e.g. a graphite monochromator and a pinhole collimator with an aperture of 0.8 mm.
- the samples must be illuminated for a suitable time, e.g.60 s in transmission geometry, and the diffraction images can be recorded at a distance of 15 cm between the sample and the detector.
- the measurements can be performed at room temperature and the diffraction images were taken from 8 to 42 of scattering angle.
- the two-dimensional diffraction images can be integrated to obtain plots of intensity versus diffraction angle.
- These profiles can be analyzed using suitable software known to the skilled person, e.g. Bruker's TOPAS software, to determine the degree of crystallinity (DOC), which is the ratio of the area of the crystalline peaks to the total area under the diffraction curve (area of the crystalline peaks plus area of the amorphous halo).
- DOC degree of crystallinity
- the semi-crystalline shape-memory polymer is selected from the list comprising or consisting of semi-crystalline polyesters, such as polycaprolactone, ethylene-co-monomer-polymers, such as poly[ethylene-co-vinyl acetate] (PEVA), poly(ethylene-1-octene), poly[ethylene-co-ethyl acrylate-co-maleic anhydride] (PEEAMA), poly[ethylene-co-(methyl acrylate)-co-(glycidyl methacrylate)] (PEMAGMA), di- or multi-block-co-polymers, such as amorphous multi block cycloaliphatic polyetherurethane (PEU) consisting of poly(tetramethylene glycol) (PTMEG), 1,4 butanediol (1,4-BD) and methylene bis(p-cyclohexyl isocyanate) (H12MDI), or semi-crystalline ionomers, such as perfluo
- the semi-crystalline core fiber is selected from shape-memory polymers selected from the group of polycaprolactone, poly[ethylene-co-vinyl acetate] (PEVA), poly(ethylene-1- octene), polycyclooctene containing trans-polyocentamer (PCO/TOR), poly[ethylene-co-ethyl white ip
- PEEAMA Patent Application acrylate-co-maleic anhydride]
- PEMAGMA poly[ethylene-co-(methyl acrylate)-co-(glycidyl methacrylate)]
- PFSA perfluorosulphonic acid ionomer
- PEU amorphous multi block cycloaliphatic polyetherurethane consisting of poly(tetramethylene glycol) (PTMEG), 1,4 butanediol (1,4-BD) and methylene bis(p-cyclohexyl isocyanate) (H12MDI)
- the semi-crystalline core fiber is of a poly[ethylene-co-vinyl acetate] (PEVA) polymer.
- the core fiber is selected from shape-memory polymers selected from the group of polycaprolactone, poly[ethylene-co-vinyl acetate] (PEVA), poly(ethylene-1-octene), polycyclooctene containing trans-polyocentamer (PCO/TOR), poly[ethylene-co-ethyl acrylate-co-maleic anhydride] (PEEAMA), poly[ethylene-co-(methyl acrylate)-co-(glycidyl methacrylate)] (PEMAGMA), perfluorosulphonic acid ionomer (PFSA), amorphous multi block cycloaliphatic polyetherurethane (PEU) consisting of poly(tetramethylene glycol) (PTMEG), 1,4 butanediol (1,4-BD) and methylene bis(p-cyclohexyl isocyanate) (H12MDI).
- PTMEG poly(tetramethylene glycol)
- 1,4-BD 1,4 butane
- the shape-memory polymer comprises poly[ethylene-co-vinyl acetate] (PEVA), wherein poly[ethylene-co-vinyl acetate] is formed from a poly[ethylene-co- vinyl acetate] polymer (PEVAP), preferably comprising a cross-linker and/or an initiator, for example by curing which preferably takes place under UV, beta or gamma radiation.
- PEVA poly[ethylene-co-vinyl acetate]
- PEVAP poly[ethylene-co- vinyl acetate] polymer
- a shape-memory polymeric fiber may be a “cross-linked shape-memory polymeric fiber”. This fiber is characterized by its enhanced structural integrity and improved shape-memory properties due to the cross-linking process.
- a cross-linked shape-memory polymeric fiber may preferably be a covalently cross-linked polymeric fiber.
- the cross-linked shape-memory polymeric fiber may exhibit superior mechanical strength and shape recovery compared to its non-cross-linked counterparts. This is a result of the cross-links acting as junction points within the polymer matrix, influencing the reordering process, and crystallinity of the bulk material.
- the cross-linking grade is carefully controlled to balance flexibility and rigidity, ensuring that the fiber can be deformed to a temporary shape and then recover its original shape upon exposure to a specific stimulus, typically a change in temperature.
- a specific stimulus typically a change in temperature.
- the cross-linking can be induced by a cross-linker or cross-linking agent.
- PEVA may be prepared by blending different poly[ethylene-co-vinyl acetate] polymers, for example PEVAPs with a different vinyl acetate content, and cross- linked by adding cross-linking agents and/or initiators and/or by curing.
- the vinyl acetate content in the poly[ethylene-co-vinyl acetate] polymer is between 5 % and 50 % of the total weight of the polymer.
- the vinyl acetate content in poly[ethylene-co-vinyl acetate] is between 3 wt% and 45 wt% of the total weight, alternatively preferably may have a degree of crystallinity in the numerical range obtained by combining any two of the following end point values: 3 %, 5 %, 7 %, 9 %, 11 %, 13 %, 15 %, 17 %, 19 %, 21 %, 23 %, 25 %, 27 %, 29 %, 31 %, 33 %, 35 %, 37 %, 39 %, 41 %, 43 %, or 45 %.
- VA content significantly influences the properties of the PEVA, such as its flexibility, thermal behavior, and shape-memory characteristics.
- An increase in VA content is associated with a decrease in degree of crystallinity.
- the vinyl acetate content (VA-content) of PEVA and PEVAP in the context of this invention can be preferably determined with derivative thermogravimetric (DTG) analysis. Two decomposition stages of PEVA and PEVAP can be observed, which are associated with the formation of volatile products.
- the first peak of the DTG curves occurs in the temperature range from 300 °C to 410 °C, which can be attributed to the deacetylation of VA segments, while at higher temperatures around 420 °C to 510 °C the second peak for the decomposition of the residues occurs, which is caused by the breaking of the C-C bond along the main chains.
- the composition of cPEVA could be determined based on the weight loss of the acetic acid groups, according to: ⁇ ⁇ 100 %, white ip
- the poly[ethylene-co-vinyl acetate] polymer comprises a cross-linker and/or an initiator.
- Comprising in this context is preferably realized by blending one, preferably at least two, poly[ethylene-co-vinyl acetate] polymer(s) with different vinyl actetate contents, with a cross-linker, preferably TAIC and an initator, preferably BP, before the cross- linking initiated with irradiation (curing), yielding PEVA, preferably covalently cross-linked PEVA.
- a cross-linker preferably TAIC and an initator, preferably BP
- An exemplary method for conducting DSC measurements is outlined as follows: DSC measurements were carried out using a DSC 204 Phoenix (NETZSCH, Selb, Germany). This involved a comprehensive heating-cooling-heating cycle to accurately characterize the thermal properties of PEVAP and PEVA shape-memory polymers according to the current invention.
- the procedure began with the first heating process, which ramped up from ambient temperature to 200 °C at a heating rate of 20 °C per minute. This step was crucial for determining the material's behavior upon heating.
- the sample After reaching 200 °C, the sample underwent a cooling phase down to -100 °C. This cooling was conducted at varied rates, including 100 °C/min, 50 °C/min, 20 °C/min, 10 °C/min, 5 °C/min, and 1 °C/min. These varying rates were employed to precisely determine the temperature at which crystallization of the material occurred, an essential factor for understanding the material's thermal behavior and stability. Following the cooling phase, a second heating run was performed.
- This stage involved heating the sample from -100 °C back up to 200 °C.
- critical thermal transition temperatures of the PEVAP and PEVA shape-memory polymers specifically the melting temperature and the glass transition temperature, were accurately measured.
- the crystallinity index ( ⁇ ⁇ ) of the PE segments in PEVAP and PEVA shape- memory polymers can be calculated from the exothermic curves obtained during the DSC analysis.
- the crystallinity index is a crucial parameter indicating the degree of crystallinity within the polymer structure, which impacts the material's mechanical and thermal properties. The calculation is based on the following Equation: white ip
- ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ 100
- ⁇ ⁇ ⁇ represents the integrated melting enthalpy, corresponding to the area under the melting peak in the DSC curve.
- ⁇ ⁇ 100 is the specific melting enthalpy for a 100% crystalline PE segment, which in this example is 287.3 J/g. This calculation allows for determination of the crystalline structure within PEVAP and PEVA shape-memory polymers.
- This DSC method provides a comprehensive thermal analysis, ensuring that the shape-memory polymers used in the invention meet the required specifications for optimal performance in covered shape-memory polymeric fiber (cSMPF) of the invention and/or shape-memory textile and/or shape-memory fabric comprising the same.
- cSMPF covered shape-memory polymeric fiber
- the cross-linker is triallyl isocyanorate (TAIC).
- TAIC triallyl isocyanorate
- the amount of cross-linking agent and initiator in the poly[ethylene-co-vinyl acetate] polymer ranges from 1.0% to 2.0% by weight.
- the cross-linking agent is benzophenone (BP).
- the polymers are optionally present as a blend, wherein the content of each polymer in the blend is at least 10 wt%.
- the content of each shape-memory polymer in the blend may be in the numerical range obtained by combining any two of the following end point values: 1 wt%, 3 wt%, 5 wt%, 7 wt%, 9 wt%, 11 wt%, 13 wt%, 15 wt%, 17 wt%, 19 wt%, 21 wt%, 23 wt%, 25 wt%, 27 wt%, 29 wt%, 31 wt%, 33 wt%, 35 wt%, 37 wt%, 39 wt%, 41 wt%, 43 wt%, 45 wt%, 47 wt%, 49 wt%, 51 wt%, 53 wt%, 55 wt%, 57 wt%, 59
- the hard segment content such as (H12MDI)/(1,4-BD), polyethylene co-monomer content, trans-double-bond content may preferably vary between 40% and 95% in the polymers.
- the hard segment content trans-1,4 butadiene monomer block content in 1,4 butanediol (1,4-BD) and methylene bis(p-cyclohexyl isocyanate) (H12MDI) may preferably vary between 1 and 50 mol% in the polymers.
- the vinyl acetate in the poly[ethylene-co-vinyl acetate] polymer may preferably vary between 5% and 50% of the total weight of the polymer.
- the poly[ethylene-co-vinyl acetate] polymer comprises a cross-linker such as triallyl isocyanorate (TAIC) and/or an initiator such as benzophenone (BP).
- TAIC triallyl isocyanorate
- BP benzophenone
- the amount of cross-linking agent and initiator in the poly[ethylene-co-vinyl acetate] polymer ranges from 0.5% to 5.0% by weight, such as from 1.0% to 2.0% by weight.
- cross-linker crosslinker
- crosslinker crosslinker
- cross-linking agent are synonymous and describe chemical compounds employed to establish cross-links within a polymer matrix.
- cross-linkers act by creating reactive sites directly on the polymer chains. These sites subsequently react with each other, facilitating cross-linking.
- This type of cross-linking typically involves the use of strong acids or peroxides.
- the proportion of the cross-linker falls within the range of 0.05 wt% to 5 wt%. More specifically, an optimal range for enhanced efficacy and balance in the properties of the resulting polymer is between 0.1 wt% and 2.5 wt%. This proportion is critical in influencing the final properties of the shape-memory polymer, particularly in terms of its cross-linking density, mechanical strength, and thermal responsiveness. In the context of shape-memory polymers the level of cross-linking, also referred to as “cross-linking grade” holds particular significance.
- a higher cross-linking grade typically correlates with reduced crystallinity, in particular reduced degree of crystallinity, within the polymer. This relationship is of paramount importance in the design of shape-memory polymers.
- the crystallinity level directly affects the transition temperatures of these semi- crystalline polymers, which is a crucial aspect in tailoring their thermal-responsive behavior to meet the specific requirements of the current invention. Therefore, the selection and concentration of cross-linkers must be carefully considered to achieve the desired balance between cross-linking grade and crystallinity, ensuring the optimal performance of the shape- memory polymers in their intended applications.
- cross-linkers are preferably substances with at least two, more preferably between 2 and 4 alkene functional groups, preferably allyl or vinyl groups. These cross-linkers can react with radicals generated on a polymer, preferably a shape-memory polymer within the meaning of the present invention, by irradiation and/or an initiator, preferably a photoinitiator, such as benzophenone (BP).
- BP benzophenone
- the gel content in a polymer and its cross-linking grade are closely related concepts in polymer chemistry.
- a shape-memory polymer which is preferably a cross-linked shape-memory polymer and most preferably a covalently cross-linked shape-memory polymer, is characterized by a gel content ranging white ip
- This embodiment is particularly significant for ensuring the desired physical and mechanical properties of the shape-memory polymers used in various applications.
- the gel content a shape-memory polymer may be in the numerical range obtained by combining any two of the following end point values: 60 %, 65 %, 70 %, 75 %, 80 %, 85 %, 90 %, 95 %, 97 %, 98 %, 99 %, and 100%.
- the polymers constituting the core fibers, or their blends, in this embodiment can undergo cross-linking through different mechanisms, including covalent bonds, ionic interactions, or crystallite formation.
- the emphasis in this embodiment is on covalently cross-linked polymer networks, which are known for their robustness and stability.
- these covalently cross-linked polymers exhibit a gel content ranging from 60 to 100%.
- G gel content of the cross-linked core fibers, specifically the cross-linked shape-memory polymers within these fibers
- a solvent extraction method is employed. This involves immersing the polymer sample in solvents like toluene or xylene at a constant temperature of 110°C or lower. The extraction process lasts for 24 hours, followed by an additional 24 hours of solvent evaporation in a vacuum oven set at 45°C.
- the gel content is then calculated using the following equation: ⁇ ⁇
- ⁇ ⁇ represents the dry weight of the sample after extraction
- ⁇ ⁇ ⁇ ⁇ is the isolated weight of the sample before extraction.
- the elastic modulus (E), also referred to as Young’s modulus is between 1.0 ⁇ 0.5 and 15.0 ⁇ 0.5 MPa, preferably between 2.0 ⁇ 0.5 and 10.0 ⁇ 0.5 MPa. This allows for a broad range of applications were different stress and strains are required.
- the current invention furthermore is related to a method for producing the covered shape- memory polymeric fiber as disclosed herein including the steps of extruding a core fiber of a poly[ethylene-co-vinyl acetate] polymer, optionally together with a cross-linker or cross- linking agent, optionally curing the extruded fibers for covalent cross-linking and winding a covering yarn around the core fiber.
- the curing takes place under UV, beta or gamma radiation.
- the present invention relates to a method for manufacturing the covered shape-memory polymeric fiber (cSMPF).
- the method includes the steps of extruding a core fiber of a poly[ethylene-co-vinyl acetate] polymer, optionally together with a cross-linker or cross-linking agent, optionally curing the extruded fibers for covalent crosslinking, preferably by applying radiation such as UV, beta or gamma radiation, and winding a covering yarn around the core fiber.
- cross-linking can be performed by heating to temperatures below melting temperature of specific polymer defined by ISO 11357, while stretching of the core fibers after extrusion can be performed up to 10 times comparing to unstretched extruded fiber. This is preferably done by pulling the fibers through a cooling bath and winding them around a bobbin with a defined tension or force.
- the invention furthermore relates to a method for producing the covered shape-memory polymeric fiber (cSMPF) as claimed in any one of the previous claims including the steps of a) extruding a core fiber (10), of a core fiber precursor for a shape-memory polymer according to the invention, preferably with a cross-linker or cross- linking agent, more preferably of a poly[ethylene-co-vinyl acetate] polymer, optionally together with a cross-linker or cross-linking agent, then b) curing the extruded fiber, preferably under UV, beta or gamma radiation for covalent cross-linking, then white ip
- “Curing” in the context of the present invention refers to the process of inducing cross-linking within the shape-memory polymer, typically aiming for covalent cross-linking. This step stabilizes the polymer structure, significantly influencing its mechanical, thermal, and most importantly shape-memory properties.
- the curing can involve direct radical cross-linking. This is often achieved using peroxides and/or photoinitiators, such as benzophenone, as initiators, and preferably a cross-linker, such as TAIC.
- the initiators decompose under specific conditions, such as thermic activation or irradiation with electromagnetic radiation, to generate free radicals, which facilitate the formation of covalent bonds between polymer chains.
- This initial step involves the extrusion of a core fiber precursor, which is formulated to become a shape-memory polymer.
- the precursor is poly[ethylene-co-vinyl acetate] polymer (PEVAP).
- PEVAP poly[ethylene-co-vinyl acetate] polymer
- a cross-linker or cross-linking agent is included in the mixture. The presence of a cross-linker is crucial when enhanced structural integrity or specific mechanical properties, including shape-memory properties, are desired in the final cSMPF.
- curing can be carried out using irradiation methods, such as UV, beta, or gamma radiation in combination with an initiator, and optionally a cross-linker.
- irradiation methods such as UV, beta, or gamma radiation in combination with an initiator, and optionally a cross-linker.
- UV, beta, or gamma radiation in combination with an initiator, and optionally a cross-linker.
- Irradiation provides a controlled way to achieve cross-linking, allowing for precise manipulation of the polymer's properties.
- a covering yarn is wound around the core fiber. This yarn is typically substantially unstretchable, providing additional structural support and protection to the core fiber.
- the shape-memory polymer precursor is provided before step a), which is prepared through a comprehensive compounding process.
- This process involves several carefully controlled steps to ensure the optimal blending of the polymer(s) and reagents, preferably initiator and cross-linker.
- a 50:50 mixture of initiator and cross-linker preferably BP and TAIC is prepared.
- this mixture is manually blended with the shape-memory white ip
- Patent Application polymer precursor for example PEVAP (poly[ethylene-co-vinyl acetate]) polymer granulates.
- PEVAP poly[ethylene-co-vinyl acetate]
- the extruder is set to a specific temperature profile: 25°C in the feeding zone, gradually increasing to 80°C, and then maintaining 110°C across the melting and mixing zones, before finally reaching 100°C at the die.
- the screw rotation speed is preferably between 30-60 rpm, more preferably between 45 and 55 rpm.
- This controlled environment ensures thorough mixing and melting of the components, leading to a homogenous blend.
- the continuous filament may be cut into granulates.
- This palletizing step transforms the extruded blend into manageable granules, facilitating further processing and handling.
- this blend may be advantageously stored under controlled conditions for further processing.
- the shape memory polymer precursor may be pelletized and extruded multiple times to achieve a more uniform distribution.
- the granulates are dried overnight at a temperature of 30 to 80 °C, preferably 35 to 55 °C. This drying step is crucial to remove any residual moisture, which could potentially interfere with the subsequent curing process of the polymer.
- the shape-memory polymeric fibers before curing are provided as monofilaments with diameters ranging from 0.05 mm to 0.5 mm. This diameter range is chosen to provide a balance between the mechanical strength of the fibers and their flexibility.
- the mixture is fed into a single screw extruder for extrusion. The extruder is equipped with filament dies of various diameters to produce monofilaments with the desired thickness as disclosed herein.
- the feeding zone may be maintained at 20°C to prevent premature melting of the mixture.
- the temperature may then increased to 80°C, followed by a consistent temperature of 110°C across the melting zones.
- the temperature at the die is set to 100°C.
- This controlled temperature profile is crucial for achieving uniform melting and smooth flow of the polymer through the dies.
- the screw rotation speed during extrusion is kept between 5 and 20 rpm. This range of rotation speeds allows for careful control over the extrusion process, ensuring that the monofilaments are extruded at a consistent rate and with uniform diameter.
- the shape-memory polymeric fibers before curing are provided as multifilament with a linear density of 40 to 500 dtex.
- This may be achieved through melt-spinning, which involves an extrusion-like setup but is distinct in its use of a spinneret at the end.
- the spinneret contains multiple holes, preferably between 20 to 200, more preferably between 36 to 150 through which multiple filaments are extruded.
- the filaments are extruded simultaneously and collected as one continuous filament. This process allows for the production of a bundle of filaments, which can then be used in various textile applications.
- the shape memory polymer fibers have been cured by in- line UV irradiation, which is integrated into the fiber extrusion process.
- This method allows for immediate cross-linking of the fibers during their manufacture, streamlining the manufacturing process.
- cross-linking can also be carried out as a post- processing step. This can be done by UV irradiation or electron beam irradiation. Irradiation with electron beams can advantageously be carried out with different doses, preferably between 50 and 200 kGy, particularly preferably between 90 and 170 kGy, whereby different degrees of crosslinking can be achieved depending on the specific requirements of the application.
- the invention relates to a shape-memory fabric, comprising or consisting of a covered shape-memory polymeric fiber (cSMPF) comprising a core fiber (10), and a substantially unstretchable covering yarn (20) according to the invention, wherein the covered shape-memory polymeric fiber (cSMPF) is arranged in a) a shape-memory mesh network of interwoven or intertwined, preferably by techniques such as knitting, weaving, crotcheting, brainding, cSMPFs, forming an operatively connected structure, and/or b) a shape-memory inlay, arranged in a second fabric, preferably non-shape- memory fabric, wherein the maximum engineering strain of the core fiber (10), is reduced to at most the strain at
- a “non-shape-memory fabric” is any fabric that doesn’t comprise or consist of a covered shape-memory polymeric fiber (cSMPF) according to the invention. Common fabrics are known to the person skilled in the art.
- a further and/or a second fabric is a non- shape-memory fabric.
- interwoven in the spirit of the invention refers to the method of arranging covered shape-memory polymeric fibers (cSMPFs) by systematically crossing them over and under each other. This weaving process, for example as defined by ISO 3572:1976, creates a fabric or mesh network where the cSMPFs intersect at regular intervals, forming a grid-like structure. In an interwoven design, the cSMPFs can be aligned in perpendicular or other angular arrangements to create various weave patterns.
- cSMPFs ensures a uniform distribution of the shape-memory effect throughout the fabric, allowing for consistent performance and functionality.
- Intertwining involves twisting or entangling cSMPFs together without following the systematic over-and-under pattern of weaving. This method results in a more flexible and potentially less structured arrangement of fibers.
- Intertwined cSMPFs create a fabric where the fibers are looped or knotted around each other, forming a network that retains the shape-memory properties while allowing for more flexibility and adaptability in the textile's design. In both interwoven and intertwined arrangements, the cSMPFs form an operatively connected structure.
- This structure is akin to a mesh network or fabric, where each individual fiber contributes to the overall shape-memory functionality of the textile.
- the operative connection means that the movement or deformation of one fiber affects and is coordinated with the surrounding fibers, enabling the entire textile to exhibit the desired shape-memory properties uniformly.
- a person skilled in the art of textile manufacturing would understand various methods of arranging fibers to create these operatively connected structures. Techniques such as knitting, weaving, braiding, and knotting can be employed to form shape-memory fabrics. white ip
- Patent Application The choice of technique depends on the desired properties of the final product, such as flexibility, stretchability, strength, and the specific shape-memory characteristics required. Additionally, the invention encompasses the concept of a shape-memory inlay. This involves embedding or integrating the cSMPF within a second fabric, preferably a non-shape-memory fabric.
- the inlay technique allows for the incorporation of shape-memory properties into conventional fabrics, enhancing their functionality without altering their fundamental characteristics. This integration can be achieved in a specific knitting process as well as through sewing, adhesive bonding, or other methods known to those skilled in the art.
- the present invention relates to a shape-memory textile comprising a covered shape-memory polymeric fiber (cSMPF) according to the current invention and at least a further fabric, preferably non-shape-memory fabric, and/or a further fiber, preferably non-shape-memory fiber, wherein the cSMPF is arranged in and/or on the shape-memory textile by knitting, preferably circular knitting or flat knitting or jacquard knitting, weaving, preferably inlay weaving or layered weaving, braiding, embroidery, composite techniques or as 3D textile structure, wherein the maximum engineering strain of the core fiber (10), is reduced to at most the strain at the yield point of the uncovered core fiber (10).
- cSMPF covered shape-memory polymeric fiber
- cSMPF covered shape-memory polymeric fibers
- This technique involves interlocking loops of yarn to create a fabric, which can be executed in various forms.
- Circular knitting is the preferred method for producing seamless, tubular structures, whereby the knitting is done in a continuous circular motion. This technique is ideal for the production of items such as socks, tubulars and other circular garments.
- the integration of cSMPFs into circular knitting can lead to innovative applications such as tubular compression garments with shape-memory properties.
- Flat knitting involves knitting back and forth in rows, allowing for more intricate designs and patterns.
- Flat knitting is suitable for the production of larger, flat pieces of fabric that can be cut and sewed into specific garments.
- the use of cSMPFs in flat knitting can result in shape-memory fabrics with complex geometries and detailed designs.
- Jacquard knitting allows for the creation of multi- colored and complex patterns.
- the use of cSMPFs in Jacquard knitting not only adds white ip
- Embroidery involves the decorative stitching of covered shape- memory polymeric fibers (cSMPFs) onto a base fabric.
- cSMPFs covered shape- memory polymeric fibers
- This technique allows for precise placement of cSMPFs, enabling the addition of shape-memory functionalities in specific patterns or designs.
- Embroidery can be used to create localized regions of shape-memory properties, which can add functional value, such as adaptive fit or dynamic structural support in specific areas of the textile, for example in sport and leisure garments as well as specialised medical applications, for example individual burn and scar dressing.
- Composite techniques refer to the combination of cSMPFs with other materials to form a composite textile. This approach can involve layering, bonding, or embedding cSMPFs with other fabrics or materials to enhance the overall properties of the textile.
- the result is a synergistic combination where the shape-memory properties of the cSMPFs are integrated with the structural, thermal, or other characteristics of different materials.
- Composite techniques are particularly useful in applications requiring a balance of flexibility, strength, and adaptive shape-memory functions. Braiding involves intertwining multiple strands of cSMPFs, and possibly other types of fibers, in a systematic pattern. This method provides a unique way to create strong, flexible, and durable textiles with shape-memory properties. Braided structures are particularly suited for applications requiring high tensile strength and resilience, such as in medical devices, protective clothing, or in structural applications where the shape-memory effect can be utilized for dynamic functionality.
- the braiding process allows for the creation of complex, three-dimensional textile structures with enhanced shape-memory characteristics.
- the present invention relates to a method for preparing a shape-memory textile and/or a shape-memory fabric, comprising the steps of a) Providing covered shape-memory polymeric fiber (cSMPF), then b) Arranging the covered shape-memory polymeric fiber (cSMPF) into and/or onto a textile or fabric, preferably by knitting, particularly preferably circular knitting or flat knitting or jacquard knitting, weaving, particularly preferably inlay weaving or layered weaving, braiding, embroidery, composite techniques, or 3D textile structuring.
- cSMPF covered shape-memory polymeric fiber
- cSMPF covered shape-memory polymeric fiber
- this method of preparing a shape-memory textile or fabric is characterized by its versatility and adaptability.
- cSMPFs which are the basic building blocks of shape-memory textiles or fabrics.
- These fibers are characterized by a core of shape memory polymer, which is then covered with a non-stretchable yarn. The composition, thickness and properties of these fibers are selected based on the desired properties of the final textile or fabric.
- the present invention relates to a use of the covered shape-memory polymeric fiber (cSMPF).
- cSMPF covered shape-memory polymeric fiber
- the cSMPF can be used for example for compression garments, orthopedic bandages, orthoses, posture correction garments, push-up garments, corsets and corsages, and sports garments.
- One embodiment of the current invention relates to the field of textiles, in particular shape- memory polymeric fibers (SMPF) for textile applications or medical applications where shape fixity and recovery can be kept constant over multiple shape-memory cycles.
- the present invention provides a covered shape-memory polymeric fiber (cSMPF) having a core fiber of semi-crystalline polymer fibers and a substantially unstretchable covering yarn wound around the core fiber in a manner that the maximum engineering strain ( ⁇ max) of the core shape- memory fiber is reduced to at most the strain at the yield point ( ⁇ yield) of the uncovered core fiber.
- the covering yarn is used to limit the stretchability or deformation of the core shape-memory fibers during programming so as to ensure maximum recoverable strain.
- a use of the covered shape-memory polymeric fiber in a fabric preferably a shape-memory fabric, such as a technical, medical, orthopedic, industrial, sports or leisure fabric.
- a use of the shape-memory textile according or a shape-memory fabric according as a medical, orthopedic and/or compression garment preferably repeatedly thermally programmable by heating between 40 and 70°C on a subject’s body. This increases comfort and effectiveness without risking burns to the subject's body.
- a use of the shape-memory textile according or a shape-memory fabric according as a sport or leisure garment preferably repeatedly thermally programmable by heating between 40 and 70°C on a subject’s body.
- the shape-memory textile and/or shape-memory fabric is specifically tailored for individuals within the age range of 50 to 90 years.
- This embodiment is designed to address age-related conditions such as poor circulation, edema, varicose veins, and support during post-surgical recovery.
- the garment features graduated compression to enhance blood flow, normalize blood backflow, reduce swelling, and improve overall comfort, making it especially suitable for daily wear and enhancing mobility in this age group.
- Another embodiment is focused on athletes and sports enthusiasts aged between 15 and 50 years.
- This version of the shape-memory textile and/or shape-memory fabric is engineered to support muscle recovery, reduce fatigue, and enhance athletic performance. It incorporates materials and designs suitable for high-intensity activities and endurance sports.
- Patent Application garment is optimized for activities such as running, cycling, and team sports, where muscle exertion and the need for support are significant.
- Another embodiment of shape-memory textile and/or shape-memory fabric is applications of compression therapy where highly individualized garments and/or bandages are required for each individual case. In this applications, deformation of the patient’s body or prescribed therapy demand individual fit and/or compression profile, for example in treatment of burns, scars, or ulcers.
- a dedicated embodiment of the shape-memory textile and/or shape-memory fabric is designed for pregnant women. This garment is tailored to accommodate the changing body during pregnancy, providing support and comfort while managing symptoms like leg swelling.
- the design ensures safety and ease of use, making it a practical solution for everyday wear during pregnancy.
- One embodiment of the current invention is specifically crafted for individuals suffering from lymphatic disorders such as lymphedema.
- the shape-memory textile and/or shape-memory fabric is designed to promote lymphatic fluid circulation, helping to reduce swelling and discomfort associated with lymphatic accumulation. Its unique construction is aimed at providing targeted support in affected areas.
- the shape-memory effect and the thermally programmable nature allow a customizable solution for the subject.
- a further embodiment addresses the needs of individuals, whose condition limits their mobility and/or who faces particular difficulties with pulling compression garments on and off.
- the shape-memory textile and/or shape-memory fabric can simplify this with a procedure based on shape-memory effect that allows for easier pulling the compression garments on with subsequent adjustment to required fit and compression as well as easier pulling compression garments off without significant irreversible damaging of their therapeutic properties.
- a preferred embodiment addresses the needs of individuals with postural issues or those leading a sedentary lifestyle.
- the shape-memory textile and/or shape-memory fabric provides postural support, particularly for those who spend extended periods sitting or have occupation-related postural challenges. Its design focuses on promoting correct posture and reducing strain on the back and legs. white ip
- Patent Application A specialized embodiment is developed for long-distance travelers, particularly those undertaking extended flights.
- This embodiment of the shape-memory textile and/or shape- memory fabric is designed to prevent circulation-related issues such as deep vein thrombosis (DVT). It features compression properties that promote blood flow in the lower extremities, making it an essential travel accessory for health-conscious travelers.
- an embodiment is designed for individuals in occupations requiring prolonged standing or heavy physical labor.
- This embodiment of the shape-memory textile and/or shape-memory fabric helps to reduce leg fatigue, support muscle endurance, and improve overall comfort during long hours of work. It is particularly beneficial for workers in sectors like healthcare, construction, and retail, where physical demand is a constant feature of the job.
- the invention also relates to a thermally programmable textile, such as a technical, medical, orthopedic, industrial, sports or leisure thermally programmable textile, comprising or consisting of the covered shape-memory polymeric fiber or the shape-memory fabric according to the current invention or the shape-memory textile, preferably with a compression force between 0.5 and 8.5 kPa.
- thermally programmable textile such as a technical, medical, orthopedic, industrial, sports or leisure thermally programmable textile, comprising or consisting of the covered shape-memory polymeric fiber or the shape-memory fabric according to the current invention or the shape-memory textile, preferably with a compression force between 0.5 and 8.5 kPa.
- These levels of compression are critical in medical applications for improving blood circulation, reducing swelling, and offering support to injured or weakened body parts.
- a further advantageous feature of these garments is their thermally programmable nature, with a range of 40 to 70°C, allowing for the compression level to be easily adjusted on the subject'
- the invention discloses a preferred use of the thermally programmable textile as a medical or orthopedic garment, preferably with a compression force between 0.5 and 8.5 kPa, preferably repeatedly thermally programmable by heating between 40 and 70°C on a subject’s body. Furthermore, the invention discloses a use of the thermally programmable textile as a sport or leisure garment, preferably with a compression force between 0.5 and 8.5 kPa, preferably repeatedly thermally programmable by heating between 40 and 70°C on a subject’s body.
- the invention relates to a thermally programmable fabric, such as a technical, medical, orthopedic, industrial, sports or leisure shape-memory fabric, comprising or consisting of the covered shape-memory polymeric fiber or the shape-memory fabric or white ip
- the invention discloses a preferred use of the thermally programmable fabric as a medical or orthopedic garment, preferably with a compression force between 0.5 and 8.5 kPa, preferably repeatedly thermally programmable by heating between 40 and 70°C on a subject’s body.
- the invention discloses a preferred use of a thermally programmable fabric as a sport or leisure garment, preferably with a compression force between 0.5 and 8.5 kPa, preferably repeatedly thermally programmable by heating between 40 and 70°C on a subject’s body.
- a thermally programmable fabric as a sport or leisure garment, preferably with a compression force between 0.5 and 8.5 kPa, preferably repeatedly thermally programmable by heating between 40 and 70°C on a subject’s body.
- Fig.1 shows a schematic view of the covered shape-memory polymeric fiber (cSMPF) according to the present invention in a state
- Fig.2A shows a schematic view of the covered shape-memory polymeric fiber (cSMPF) according to the present invention in a unstreteched state
- Fig.2B shows a schematic view of the covered shape-memory polymeric fiber (cSMPF) according to the present invention in a streteched state.
- Fig.3B shows a schematic representation of a curing process of PEVA polymer to PEVA (covalently cross-linked PEVA) by a initiator and a cross-linker, indicating some of the potential sites for covalent cross-linking according to the current invention white ip
- Patent Application Fig.4A shows an example for a thermally-programming in laboratory setting of a shape-memory textile, comprising a covered shape-memory polymeric fiber (cSMPF)
- Fig.4B shows an example of thermally-programming on the body of a subject of a shape-memory textile comprising a covering polymer shape-memory fiber (cSMPF)
- Figure 1 illustrates an exemplary embodiment of a covered shape-memory polymeric fiber (cSMPF) having a core fiber ( 10) and a substantially unstretchable covering yarn ( 20) wound around the core fiber (10).
- the covering yarn (20) is wound around the core fiber (10) in a manner that the maximum engineering strain ( ⁇ max ) of the core fiber ( 10) is reduced to at most the strain at the yield point ( ⁇ yield ) of the uncovered core fiber (10).
- the present invention defines a cSMPF structure, which has its purpose to prevent overstretching of the core fiber 10, causing its irreversible plastic deformation and deterioration of mechanical and shape-memory properties as well as shape.
- Figure 2A and 2B illustrate exemplary embodiments of two states of a covered shape- memory polymeric fiber. In both states the covered shape-memory polymeric fiber has a core fiber 10 and a substantially unstretchable covering yarn 20 wound around the core fiber 10.
- Figure 2A the core fiber 10 is in a unstretched state.
- Figure 2B shows the core fiber 10 in a stretched state.
- the change in coils/twists spacing of the covering yarn 20 upon mechanical deformation of the core fiber 10 during programming (from Figure 2A to Figure 2B) and recovery (from Figure 2B to Figure 2A) can be seen.
- Stretching (elongation) of the core fiber 10 having the covering yarn 20 wound around it causes the pitch, i.e. the distance between two loops of the twist, of the covering yarn 20 around the core fiber 10 to increase from r 0 to r 1 , whereby the density of entwining ( ⁇ 1 ) decreases.
- Figure 3A presents a schematic depiction of a representative semi-crystalline shape-memory polymer, demonstrating the curing process using irradiation.
- This process involves a phototinitiator and a tri-functional cross-linker, where each functional group (FG), such as an ethene group, actively participates in the cross-linking reaction.
- FG functional group
- the diagram highlights the molecular structure of the polymer before and after the cross-linking process. It shows how the functional groups of the cross-linker interact with the polymer chains, resulting in a network structure that imparts the shape-memory properties to the polymer.
- Patent Application Figure 3B offers a schematic representation of the curing process specifically for a PEVA polymer, transforming it into covalently cross-linked PEVA.
- This figure illustrates the various potential sites within the PEVA polymer that are susceptible to covalent cross-linking when exposed to an initiator and a cross-linker.
- the diagram details the structural changes at the molecular level, emphasizing the sites where cross-linking occurs, thereby enhancing the polymer's mechanical strength and shape-memory characteristics.
- Figure 4A and 4B demonstrate the shape-memory characteristics of a shape-memory textile according to the current invention.
- 4A shows a thermally-programming in the laboratory
- 4B demonstrates the ability to reprogram the fiber on the body surface of a subject, due to the insolating properties of the covering yarn and the further fabric comprised by the textile.
- Design examples With reference to the following figures and examples of embodiments, the present invention will be explained in more detail without limiting the invention thereto.
- the following tables list some preferred shape-memory polymers comprised by the core fiber, Sample-ID-Nos.: 1 to 20 list some preferred, but not limiting, examples of shape- memory polymers of the invention, each of which is another embodiment of the present invention.
- the shape-memory polymer according to the invention was prepared, first, a core fiber precursor was provided: Initially, a 50:50 mixture of initiator and cross-linker, in this case BP and TAIC is prepared. Then, this mixture is manually blended with PEVAP (poly[ethylene-co-vinyl acetate]) polymer granulates. This manual mixing ensures a preliminary and uniform distribution of the BP/TAIC mixture with the PEVA granulates. The manually mixed materials are then compounded in a twin-screw extruder (Euro Prism Lab, Thermo Fisher Scientific, Waltham, USA).
- BP and TAIC poly[ethylene-co-vinyl acetate]
- the extruder is set to a specific temperature profile: 25°C in the feeding zone, gradually increasing to 80°C, and then maintaining 110°C across the melting and mixing zones, before finally reaching 100°C at the die.
- the screw rotation speed is controlled at 30-50 rpm, with a preference for 50 rpm. This controlled environment ensures thorough mixing and melting of the components, leading to a homogenous blend.
- the continuous filament is cut into granulates.
- This palletizing step transforms the extruded blend into manageable granules, facilitating further processing and handling.
- the blend granulates (PEVAP+BP+TAIC) are then subjected to a second round of extrusion.
- This second extrusion utilizes the same temperature profile and screw rotation speed as the first, ensuring consistent and thorough mixing.
- the repeated extrusion process is critical to achieve an even distribution of the cross-linking agents within the polymer matrix.
- the extruded blend is again palletized into granulates after the second extrusion. Finally, the granulates are dried overnight at a temperature of 40°C. This drying step is crucial to remove any residual moisture, which could potentially interfere with the subsequent curing process of the polymer.
- the compounded mixture is then fed into a single screw extruder (Extrudex, Mühlacker, Germany) for extrusion.
- the extruder is equipped with filament dies of various diameters to produce monofilaments with the desired thickness.
- the monofilaments are extruded with diameters ranging from 0.05 mm to 0.5 mm. This diameter range is chosen to provide a balance between the mechanical strength of the fibers and their flexibility.
- the feeding zone is maintained at 20°C to prevent premature melting of the mixture.
- the temperature is then increased to 80°C, followed by a consistent temperature of 110°C across the melting zones. Finally, the temperature at the die is set to 100°C. This controlled temperature profile is crucial for achieving uniform melting and smooth flow of the polymer through the dies.
- the screw rotation speed during extrusion is kept between 5 and 20 rpm.
- the polymers in the core fiber or their blends can be cross-linked with covalent bonds, ionic interactions or crystallites.
- the shape-memory polymer fibers were cured through inline UV irradiation, which is integrated with the fiber extrusion process. This method allows for immediate cross-linking of the fibers as they are being produced, streamlining the manufacturing process.
- Covalently cross-linked polymer networks have a gel content of 60 -100% according to ASTM D2765 or ISO 10147.
- the gel content (G) of cross-linked core fibers was estimated by extraction in solvents such as toluene or xylene at constant temperature ⁇ 110°C. Extraction time was 24 h, with another 24 h for solvent evaporation in vacuum oven at 45 °C. G was calculated from the isolated weight miso of the sample and the dry weight md after extraction using the equation below. ⁇ ⁇ However, non-extracted fibers were used for covering and for investigations such as thermo- mechanical and shape-memory properties. Results of the gel content determination are listed in table 3 for different, exemplary shape-memory polymers in the spirit of the current invention.
- the selected shape-memory polymer comprised by the core fiber (10) was PEVA.
- Semi-crystalline cross-linked poly[ethylene-co-vinyl acetate] (cPEVA) fibers were covered with single or double covering of yarn with 750 to 3000 twists per meter. The number of twists were adjusted to allow certain deformation but to reduce the maximum engineering strain ( ⁇ max ) of the core shape-memory polymeric fiber to at most the strain at the yield point ( ⁇ yield ) of the uncovered core fiber. The effect of the twist density and angle of the covering yarn on the stretchability during programming and recovery of the SMP covered yarns was evaluated.
- the mechanical properties of the covered and non-covered shape-memory polymeric fibers were tested by tensile testing at room as well as at elevated temperatures (below and within the broad melting transition ranges). These tensile tests were conducted on a Zwick/Roell machine Z005 (Zwick, Ulm, Germany) equipped with a thermo-chamber and temperature controller (Eurotherm Regler, Limburg, Germany) with a strain rate of 5 mm ⁇ min ⁇ 1 . The selected temperature for such measurements were 25°C, 37°C, 40°C, 50°C, 60°C, 70°C, 80°C and 90°C.
- cSMPF shape-memory polymeric fibers
- SMP-1 to SMP-8, SMP- 10, SMP-17 to SMP-20 (table 3) were determined.
- the elastic modulus (E) (at 25 °C) was between 2.49 ⁇ 0.1 and 9.07 ⁇ 0.3 MPa, the elongation at break ( ⁇ break) and stress at break ( ⁇ break) were obtained and analyzed.
- the range of elongation at break ( ⁇ break) was measured to be in a range between 730 ⁇ 130 % and 915 ⁇ 20 %.
- Shape-recovery ratio (after normal stretching to 50 %) in these specific examples was determined was measured between 97 % and 100 %.
- the strain at the yield point ( ⁇ yield) at 25°C was determined in a range of 24 ⁇ 0.2 % to 54 ⁇ 0.5 %.
- the shape-memory characteristic of the fibers were evaluated on a Zwick/Roell machine Z005 (Zwick, Ulm, Germany) equipped with a thermo-chamber and temperature controller (Eurotherm Regler, Limburg, Germany).
- Each shape-memory cycle within one experiment consisted of an initial programming step followed by a recovery step under stress-free conditions with heating and cooling rates ⁇ 10°C ⁇ min ⁇ 1 .
- Each shape-memory test consisted of at least three cycles.
- a single step programming procedure was applied, where the sample was stretched with a rate of ⁇ 10 mm ⁇ min ⁇ 1 to a certain programming strain ( ⁇ prog ) at programming temperature (T prog ) followed by an equilibration time of ⁇ 10 min and cooling below crystallization temperature ( ⁇ 25 °C) under constant strain. After another ⁇ 10 min equilibration time, the stress was released at this lower temperature and the sample was white ip
- T rec can be anywhere within the melting range of the polymer and can identical to T prog .
- the shape-fixity ratios and recovery ratio were calculated from second and third cycles and the results were analyzed.
- the shape-recovery ratio for the covered fibers were ⁇ 95%.
- a test with ⁇ 100 shape-memory cycles was performed which showed identical results for shape- recovery and lower shape fixity ratios over the course of 100 cycles.
- the heating and cooling rates were 10°C ⁇ min -1 here and equilibration times were reduced to 1 min.
- EXAMPLE 2 Shape-memory textile
- the thermal programming of a shape- memory textile incorporating covered shape-memory polymeric fibers is demonstrated using covered PEVA fibers. Initially, these fibers were programmed separately before their integration into the textile. An exemplary textile is shown in Figure 4A and 4B.
- the programming process involved heating the shape-memory textile to 60 °C and stretching them to a low programming strain of 50%, followed by cooling to approximately 25 °C.
- This step established the comprised shape-memory polymer fibers’ temporary shape.
- the integration of thermally-programmed covered shape-memory polymeric fibers into a knitted cotton textile, achieved through weaving, serves as a specific example of the broader applicability of the techniques disclosed in the present invention.
- the textile Upon exposure to a temperature of 60 °C, the textile underwent significant contraction, its diameter reducing from 14 cm to 10 cm. This change was driven by the activation of the shape recovery process in the SMP fibers within the covered shape-memory polymeric fibers. Demonstrating the versatility of this method, the shape-memory textile was subjected to a reprogramming phase. This process entailed reheating the textile to 60 °C, manually expanding it to its original diameter of 14 cm, and then cooling it to 25 °C. This procedure reset the covered shape-memory polymeric fibers to a new, temporarily held shape. When reheated to 60 °C, the textile consistently returned to a diameter of 10 cm.
- This cycle of reprogramming and recovery was successfully replicated five times, emphasizing the durability and reliability of the shape-memory effect in the textile.
- An important feature of this example is the insulating property of the textile's cotton component. This insulation ensures safe heating of the SMP fibers for shape recovery, maintaining safety even when the textile is worn.
- subsequent cycles involved reprogramming the entire textile, including the integrated SMP fibers. This highlights the flexibility of the programming process, which is effective both for individual covered shape-memory polymeric fibers and the composite shape-memory textile comprising the same.
- Patent Application REFERENCE LIST (1) Covered shape-memory polymeric fiber (cSMPF) (10) Core fiber (20) Unstretchable covering yarn (30) Semi-crystalline shape-memory polymer (31) Crystalline rigid segment (32) Switching segment (40) covalently cross-linked shape-memory polymer (50) radicals (60) Initiator (61) Cross-linker white ip
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP23152852.2A EP4403682A1 (en) | 2023-01-23 | 2023-01-23 | Covered shape-memory polymeric fibers for textile applications |
| PCT/EP2024/051570 WO2024156714A1 (en) | 2023-01-23 | 2024-01-23 | Covered shape-memory polymeric fibers for textile applications |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP4655442A1 true EP4655442A1 (en) | 2025-12-03 |
| EP4655442B1 EP4655442B1 (en) | 2026-04-29 |
Family
ID=85036142
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP23152852.2A Withdrawn EP4403682A1 (en) | 2023-01-23 | 2023-01-23 | Covered shape-memory polymeric fibers for textile applications |
| EP24705986.8A Active EP4655442B1 (en) | 2023-01-23 | 2024-01-23 | Covered shape-memory polymeric fibers for textile applications |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP23152852.2A Withdrawn EP4403682A1 (en) | 2023-01-23 | 2023-01-23 | Covered shape-memory polymeric fibers for textile applications |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20260117427A1 (en) |
| EP (2) | EP4403682A1 (en) |
| JP (1) | JP2026501901A (en) |
| KR (1) | KR20250136898A (en) |
| CN (1) | CN120769939A (en) |
| WO (1) | WO2024156714A1 (en) |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1679822A (en) * | 1927-02-28 | 1928-08-07 | Frank W Gorse Co | Short-stretch covered elastic thread |
| JPH0770859A (en) * | 1993-08-31 | 1995-03-14 | Nippon Ester Co Ltd | Conjugated yarn |
| AUPP790198A0 (en) * | 1998-12-23 | 1999-01-28 | Ennio Pty Ltd | A tubular product having a maximum extensible diameter |
| AU2003299049A1 (en) * | 2002-09-14 | 2004-04-08 | W. Zimmermann Gmbh And Co. Kg | Electrically conductive thread |
| CN1324174C (en) | 2004-06-09 | 2007-07-04 | 香港理工大学 | A kind of shape memory fiber prepared by shape memory polyurethane and its preparation method |
| CN201553838U (en) | 2009-10-29 | 2010-08-18 | 浙江省现代纺织工业研究院 | A thermosensitive shape memory polyurethane covered yarn |
| CN201545991U (en) * | 2009-10-29 | 2010-08-11 | 浙江省现代纺织工业研究院 | A shape memory polyurethane covered yarn |
| DE102010048083A1 (en) | 2010-10-04 | 2012-04-05 | Bauerfeind Ag | Shape memory elements for medical aids |
| CN103798977A (en) * | 2012-11-12 | 2014-05-21 | 江南大学 | Shape memory covering yarn silk stockings |
-
2023
- 2023-01-23 EP EP23152852.2A patent/EP4403682A1/en not_active Withdrawn
-
2024
- 2024-01-23 JP JP2025542277A patent/JP2026501901A/en active Pending
- 2024-01-23 CN CN202480014913.0A patent/CN120769939A/en active Pending
- 2024-01-23 US US19/150,158 patent/US20260117427A1/en active Pending
- 2024-01-23 WO PCT/EP2024/051570 patent/WO2024156714A1/en not_active Ceased
- 2024-01-23 KR KR1020257028010A patent/KR20250136898A/en active Pending
- 2024-01-23 EP EP24705986.8A patent/EP4655442B1/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2026501901A (en) | 2026-01-16 |
| US20260117427A1 (en) | 2026-04-30 |
| CN120769939A (en) | 2025-10-10 |
| EP4403682A1 (en) | 2024-07-24 |
| KR20250136898A (en) | 2025-09-16 |
| EP4655442B1 (en) | 2026-04-29 |
| WO2024156714A1 (en) | 2024-08-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105102703B (en) | Stretch knitted fabrics and garments | |
| TWI321172B (en) | Garment, composite elastic yarns and air-jet method for producing composite elastic yarns | |
| RU2582466C2 (en) | Stretchable knitted fabric and clothing | |
| JP5083561B2 (en) | Suspension knitted fabric product with wire prevention function | |
| Gupta | Manufacture, types and properties of biotextiles for medical applications | |
| CN102845841A (en) | Clothes with shape memory | |
| CA2614091A1 (en) | Bandage with lengthwise elasticity in warp direction | |
| Zhu et al. | Effect of steaming on shape memory polyurethane fibers with various hard segment contents | |
| JP5779341B2 (en) | Elastic warp knitted fabric | |
| EP4655442B1 (en) | Covered shape-memory polymeric fibers for textile applications | |
| TWI314170B (en) | Process for producing elastic cloth | |
| JP5896677B2 (en) | Knitted fabric | |
| JP6510337B2 (en) | Stretchable weft knit | |
| TW452612B (en) | Composition polyurethane elastic yarns and stretch woven fabrics | |
| KR101807000B1 (en) | High Gravity Polyester Composite Yarn and Fabric | |
| JP6368602B2 (en) | Leg wear | |
| US20250101642A1 (en) | Yarns of shape memory polymers and uses thereof | |
| Ali Shah et al. | Development of auxetic braided yarns and study the effects of braid angle and material modulus on the negative Poisson’s ratio | |
| JP6004624B2 (en) | Supporter | |
| KR101882308B1 (en) | Splint for orthopedics | |
| JP2015094044A (en) | Elastic knitted fabric and clothes | |
| Hu et al. | Functional shape memory textiles | |
| JP6315695B2 (en) | Leg clothing | |
| Meng | Studies of functional shape memory fibers | |
| JP2013072155A (en) | Exothermic supporter |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
| 17P | Request for examination filed |
Effective date: 20250821 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC ME MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
| DAV | Request for validation of the european patent (deleted) | ||
| DAX | Request for extension of the european patent (deleted) | ||
| INTG | Intention to grant announced |
Effective date: 20251120 |
|
| GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
| RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: IZRAYLIT, VICTOR Inventor name: FARHAN, MUHAMMAD |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC ME MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: F10 Free format text: ST27 STATUS EVENT CODE: U-0-0-F10-F00 (AS PROVIDED BY THE NATIONAL OFFICE) Effective date: 20260429 |