Patent Application
20240368833
The present invention concerns a composite elongated body. The present invention further concerns a lengthy body comprising the composite elongated body according to the invention. It also relates to a method of manufacturing the composite elongated body and a method of manufacturing the lengthy body. The present invention also relates to an article comprising the composite elongated body and/or the lengthy body according to the invention and to a method of manufacturing such article. A crane comprising a sheave and a rope comprising the composite elongated body are also part of the invention. The invention further relates to a method of lifting and/or placement of an object and to a use of a polymeric composition.
In many applications, ropes and belts are repeatedly subjected to friction and deformation when in contact with a counter surface. During use a rope is frequently pulled over fairleads, bollards, drums, flanges, pulleys, sheaves, etc., amongst others resulting in abrasion and bending of the rope. When exposed to such frequent abrasion and bending, a rope may fail due to rope, strand and/or filament damage; fatigue failure is often referred to as abrasive wear or bend fatigue.
HPPE (High Performance Poly Ethylene) fibre ropes with improved bending fatigue have been described in for example WO2007/062803 and WO2011/015485. WO2007/062803 describes a rope constructed from high performance polyethylene fibres and polytetrafluoroethylene fibres. These ropes can contain 3-18 mass % of liquid polyorganosiloxanes. WO2011/015485 describes ropes comprising HPPE fibres coated with a cross-linked silicone rubber. Thus, in the prior art it has been suggested to use silicone compositions alone or in combination with low friction fibres such as PTFE, to reduce the frictional behaviour of the HPPE fibres during bending applications. Especially WO2011/015485 describes a technology that has become established in the field of high end bending applications.
WO 2017/060461 concerns a method for producing a lengthy body comprising high performance polyethylene fibres and a polymeric resin and such composite lengthy body.
It is noted that US 2007/202329 relates to improvements in ropes, and in particular to high tenacity synthetic ropes suitable for use in marine applications.
It is noted that GB 1 405 551 relates to a size composition, and more particularly to a size composition for application to glass fibers to improve the processing and performance characteristics of glass fibers in glass fiber textiles, in the manufacture of glass fiber-reinforced elastomeric products and in the manufacture of glass fiber-reinforced plastics.
The present invention sets out to provide an improved lengthy body such as an improved synthetic rope. In particular an improved rope comprising HPPE filaments, such as a rope constructed from HPPE filaments. A lengthy body according to the invention, such as a rope according to the invention, comprises a composite elongated body according to the invention.
The present invention provides a composite elongated body, comprising high performance polyethylene HPPE filaments having a tenacity of at least 0.6 N/tex and a polymeric composition throughout the composite elongated body, wherein the polymeric composition comprises
A rope comprising the composite elongated body according to the invention demonstrates an improved abrasion performance. In an aspect this is demonstrated by an improved wear resistance against a static contra-surface, such as a fairlead.
This improved wear resistance against a static contra-surface may also be referred to as an improved external abrasion. External refers to the outer surface of the rope, the part that is visible to the human eye, or the part that if the rope is held in the hand or is touched by hand is in contact with the hand. This improvement is demonstrated herein for the rope as such without the use of a cover around the outer surface of the rope. The inventors found that the abrasion properties came combined with other improved mechanical properties. Said improvement may be seen for example in an improved repeated bending performance, or coefficient of friction. In particular in an improved Cyclic Bending Over Sheave (CBOS) performance.
The composite elongated body according to the invention is a composite material. A composite material is a material made from two or more constituent materials with significantly different physical and/or chemical properties that, when combined, produce a material with characteristics different from the individual components. The individual components remain separate and distinct within the finished structure.
In its simplest form the composite elongated body comprises 2 or more filaments lying side by side without being twisted about each other. The filaments will substantially be oriented in a single direction, the length direction of the composite elongated body.
By fibre is herein understood an elongated body, the length dimension of which is much greater than the transverse dimensions of width and thickness. The term fibre herein includes a filament, such filament may have a regular or irregular cross-section.
A filament is an elongated body, the length dimension of which is much greater than the transverse dimensions of width and thickness. Fibres may have continuous lengths, known in the art as filaments or continuous filaments, or discontinuous lengths, known in the art as staple fibres.
A yarn for the purpose of the invention is an elongated body comprising at least two filaments. In an aspect the yarn comprises at least at least 20 filaments, preferably at least 100 filaments, more preferably at least 400 filaments. The yarn comprises typically at most 10.000 filaments. In an aspect the yarn comprises at most 5000 filaments. The filaments in the yarn may be twisted or untwisted, preferably the filaments of a yarn are untwisted. During coating it is beneficial to have the filaments in the yarn untwisted to improve coating penetration/wetting on the surface on the filaments.
By elongated herein is understood the length dimension being much greater than the transverse dimensions of width and thickness. Preferably said length dimension is at least 10 times, more preferably at least 20 times even more preferably at least 50 times and most preferably at least 100 times greater than the width or thickness dimension whichever is larger. In an aspect the length dimension is from 20 to 1×1010 times greater than the width or thickness dimension whichever is larger.
A lengthy body herein is herein understood an elongated body, the length dimension of which is much greater than the transverse dimensions of width and thickness or diameter. Preferably said length dimension is at least 10 times, more preferably at least 20 times even more preferably at least 50 times and most preferably at least 100 times greater than the width or thickness dimension whichever is larger. In an aspect the length dimension of the elongated body is from 20 to 1×1010 times greater than the width or thickness dimension whichever is larger.
The present invention further provides a composite elongated body, comprising high performance polyethylene HPPE filaments having a tenacity of at least 0.6 N/tex and a polymeric composition throughout the composite elongated body, wherein the polymeric composition comprises:
In an aspect of the present invention the length dimension of the composite elongated body is at least 100, preferably at least 500 times greater than the width or thickness dimension of the composite elongated body, whichever is larger. In an aspect the length dimension of the composite elongated body is from 20 to 1×1010 times greater than the width or thickness dimension whichever is larger.
In a further aspect the ratio, on solid content basis, of the thermoplastic ethylene copolymer and the lubricant is from 1:1 to 1:10, preferably from 1:1 to 1:5, more preferably from 1:1.5 to 1:4, most preferably from 1:2 to 1:1.35. In an aspect the ratio, on solid content basis, of the thermoplastic ethylene copolymer and the lubricant is 1:1; 1:1.1; 1:1.2; 1:1.3; 1:1.4; 1:1.5; 1:1.6; 1:1.7; 1:1.8; 1:1.9; 1:2; 1:2.1; 1:2.2; 1:2.3; 1:2.4; 1:2.5; 1:2.6; 1:2.7; 1:2.8; 1:2.9; 1:3.0; 1:3.1; 1:3.2; 1:3.3; 1:3.4; 1:3.5; 1:3.6; 1:3.7; 1:3.8; 1:3.9; 1:4.0; 1:4.1; 1:4.2; 1:4.3; 1:4.4; 1:4.5; 1:4.6; 1:4.7; 1:4.8; 1:4.9; 1:5; 1:5.1; 1:5.2; 1:5.3; 1:5.4:1:5.5; 1:5.6; 1:5.7; 1:5.8; 1:5.9; 1:6; 1:6.1; 1:6.2; 1:6.3; 1:6.4:1:6.5; 1:6.6; 1:6.7; 1:6.8; 1:6.9; 1:7; 1:7.1; 1:7.2; 1:7.3; 1:7.4:1:7.5; 1:7.6; 1:7.7; 1:7.8; 1:7.9; 1:8; 1:8.1; 1:8.2; 1:8.3; 1:8.4:1:8.5; 1:8.6; 1:8.7; 1:8.8; 1:8.9; 1:9; 1:9.1; 1:9.2; 1:9.3; 1:9.4:1:9.5; 1:9.6; 1:9.7; 1:9.8; 1:9.9; or 1:10.
In an aspect of the invention the lubricant includes one or more of the following, including derivatives of these lubricants: a synthetic wax such as PE and/or PP wax; an animal wax such as beeswax; a plant wax such as carnauba wax; a synthetic grease or synthetic oil; a mineral grease or mineral oil; an inorganic solid such as graphite or molybdenum disulfide; a ceramic such as a ceramic lubricant or ceramic coating; a PUR; an acrylic; a hybrid of PUR and acrylic; or any combination thereof.
In an embodiment of the composite elongated body according to the invention the lubricant comprises a wax.
In an aspect of the composite elongated body according to the invention the lubricant is a wax.
Waxes are organic compounds that characteristically consist of long aliphatic alkyl chains, although aromatic compounds may also be present. Typically aliphatic alkyl chains are C20 to C40 alkyl chains. Natural waxes may contain unsaturated bonds and include various functional groups such as fatty acids, primary and secondary alcohols, ketones, aldehydes and fatty acid esters. Synthetic waxes often consist of homologous series of long-chain aliphatic hydrocarbons (alkanes or paraffins) that lack functional groups.
Suitable waxes may include synthetic waxes or a natural waxes. Suitable waxes may include, but are not limited to: animal waxes such as beeswax, Chinese wax, spermaceti and wool wax; alant waxes such as wood wax, bayberry wax, candelilla wax, carnauba wax, castor wax, grass wax, japan wax, Jojoba oil wax, rice bran wax and soy wax; mineral waxes, such as ceresin waxes, montan wax, ozocerite wax and peat waxes; petroleum waxes, such as paraffin wax and microcrystalline wax; and synthetic waxes such as Fischer-tropsch wax, polyolefin waxes, including polyethylene homopolymer waxes, oxidized polyethylene wax, polypropylene wax, stearamide wax, substituted amide wax, ethylene-acrylic acid copolymer wax, ethylene-vinyl acetate copolymer waxes, oxidized ethylene-vinyl acetate copolymer wax, ethylene-maleic anhydride graft copolymer, a propylene-maleic anhydride graft copolymer wax, wax and other chemically modified waxes.
A suitable wax may include a wax with a melting point from 39 to 45.0° C. This melting point range may improve lubricating properties and improve performance during use. Preferably, the wax is a polyethylene wax, a polypropylene wax, beeswax, carnauba wax or a Fischer-Tropsch wax. More preferably it is carnauba wax.
Carnauba wax typically has a melting point of 82-86° C. (180-187° F.). Such melting point range may be beneficial in applications where the temperature may rise during use. Carnauba wax (INCI name: Copernicia cerifera (carnauba) wax) consists mostly of aliphatic esters (40 wt %), diesters of 4-hydroxycinnamic acid (21.0 wt %), w-hydroxycarboxylic acids (13.0 wt %), and fatty alcohols (12 wt %). The compounds are predominantly derived from acids and alcohols in the C26-C30 range. It is distinctive for its high content of diesters and its methoxycinnamic acid. Among the hardest of natural waxes and is practically insoluble in water or ethyl alcohol, it is soluble by heating in ethyl acetate or xylene. Solid carnauba wax is a hard wax scraped from the leaves and leaf strams of carnauba palms, Copernicia cerifera. The carnauba wax comprises esters of C18-C32 fatty acids, and C28-C34 alcohols, also containing high amounts of hydroxy acid esters and melting points around 80 and 86° C. Additionally, the solid carnauba wax usually comprises from about 80% by weight to about 85% by weight of fatty esters, from about 1% by weight to about 5% by weight of alcohols, from about 1% by weight to about 5% by weight of hydrocarbons, from about 1% by weight to about 5% by weight of free acids, from about 1% by weight to about 6% by weight of resins, from about 1% by weight to about 5% by weight of lactic components and from about 0.1% by weight to about 2% by weight of humidity. Carnauba wax is mainly produced by mechanically recovering the coating from the leaves of a variety of palm trees that almost executively grow in northeastern Brazil. The composition of this wax was reported by Vandenburg et al., “The Structural Constituents of Carnauba Wax,” J. Am. Oil Chem. Soc. 47:514-518 (1970) as follows: hydrocarbon (0.3-1%), aliphatic esters (38-40%), monohydric alcohols (10-12%), ω-hydroxy aliphatic esters (12-14%), p-methoxycinnamic aliphatic diesters (5-7%), p-hydroxycinnamic aliphatic diesters (20-23%), a triterpene type of diol (0.4%), and free fatty acids and other unknown constituents (5-7%). The esters have carbon numbers between 44 and 66 (Basson et al., “An Investigation of the Structures and Molecular Dynamics of Natural Waxes: Il Carnauba Wax,” J. Phys. D: Appl. Phys. 21:1429 (1988)), and the alkanes have carbon numbers between 16 and 34 (Vandenburg et al., “The Structural Constituents of Carnauba Wax,” J. Am. Oil Chem. Soc. 47:514-518 (1970)). The presence of long chain esters is believed to contribute to the high melting point and hardness of carnauba wax.
The thermoplastic ethylene copolymer and the lubricant, such as the wax, may be separated by a preparative fractionation method. Typically this could be a separation of components based on molar mass, e.g. using size exclusion chromatography or based on crystallinity e.g. using Temperature Rising Elution Fractionation. The factions thus obtained may then be analysed using for example IR and/or NMR technique(s). The type of lubricant may for example be determined using GC-MS and comparing the retention time and molar mass and compare the fingerprint with a date base. The skilled person will be able to select, depending on the sample to be tested, suitable sample preparation technique and method. The skilled person would know that if he/she is faced with a finished product, he/she needs to obtain the polymeric composition before doing the density measurement. It is part of the skills of the skilled person to, depending on what the finished product looks like, determine how to obtain and prepare a sample of the polymeric composition and thereafter based on what the sample looks like select the appropriate way to measure the density. For example the polymeric composition may be scraped off from the composite elongated body and analysed. For example the polymeric composition may be scraped off from the lengthy body according to the invention and analysed.
An example of a commercially available carnauba wax is Aquacer 2650, available from BYK Netherlands B.V. An example of a Fischer-Tropsch wax is Aquacer 2700, available from BYK Netherlands B.V.
In an aspect, the lubricant is a polymeric dispersion. Typically, the polymeric dispersion is a dispersion of a polyurethane or an acrylic, or a hybrid of a polyurethane and an acrylic. An example of a polyurethane dispersion is NeoRez R-2180, available from DSM Coating Resins B.V. An example of a dispersion of an acrylic is NeoCryl A-668, available from DSM Coating Resins B.V.
In an aspect the present invention provides a composite elongated body, comprising high performance polyethylene HPPE filaments having a tenacity of at least 0.6 N/tex and a polymeric composition throughout the composite elongated body, wherein the polymeric composition comprises
In an aspect the ratio, on solid content basis, of the thermoplastic ethylene copolymer and the wax is 1:1; 1:1.1; 1:1.2; 1:1.3; 1:1.4; 1:1.5; 1:1.6; 1:1.7; 1:1.8; 1:1.9; 1:2; 1:2.1; 1:2.2; 1:2.3; 1:2.4; 1:2.5; 1:2.6; 1:2.7; 1:2.8; 1:2.9; 1:3.0; 1:3.1; 1:3.2; 1:3.3; 1:3.4; 1:3.5; 1:3.6; 1:3.7; 1:3.8; 1:3.9; 1:4.0; 1:4.1; 1:4.2; 1:4.3; 1:4.4; 1:4.5; 1:4.6; 1:4.7; 1:4.8; 1:4.9; 1:5; 1:5.1; 1:5.2; 1:5.3; 1:5.4:1:5.5; 1:5.6; 1:5.7; 1:5.8; 1:5.9; 1:6; 1:6.1; 1:6.2; 1:6.3; 1:6.4:1:6.5; 1:6.6; 1:6.7; 1:6.8; 1:6.9; 1:7; 1:7.1; 1:7.2; 1:7.3; 1:7.4:1:7.5; 1:7.6; 1:7.7; 1:7.8; 1:7.9; 1:8; 1:8.1; 1:8.2; 1:8.3; 1:8.4:1:8.5; 1:8.6; 1:8.7; 1:8.8; 1:8.9; 1:9; 1:9.1; 1:9.2; 1:9.3; 1:9.4:1:9.5; 1:9.6; 1:9.7; 1:9.8; 1:9.9; or 1:10.
In an aspect of the composite elongated body according to the invention the wax includes a synthetic wax such as PE or PP wax; an animal wax such as beeswax; a plant wax such as carnauba wax; or any combination thereof.
The thermoplastic ethylene copolymer herein is a semi-crystalline polymer has a peak melting temperature in the range from 40 to 140° C., measured in accordance with ASTM E794-06, considering the second heating curve at a heating rate of 10 K/min, on a dry sample. In an embodiment, the peak melting temperature of the thermoplastic ethylene copolymer is at least 50 or 60° C. and at most 130 or 120° C. In an embodiment, the peak melting temperature of the thermoplastic ethylene copolymer is at least 50° C. and at most 130° C. In an embodiment, the peak melting temperature of the thermoplastic ethylene copolymer is at least 60° C. and at most 130° C. In an embodiment, the peak melting temperature of the thermoplastic ethylene copolymer is at least 60° C. and at most 120° C. In an embodiment, the peak melting temperature of the thermoplastic ethylene copolymer is in the range from 50 to 120° C. In an embodiment, the peak melting temperature of the thermoplastic ethylene copolymer is in the range from 50° C. to 120° C. Such peak melting temperatures allow making the composite elongated body with the polymer composition melting and impregnating filaments without negatively affecting the mechanical properties of the high performance polyethylene filaments. The thermoplastic ethylene copolymer may have more than one peak melting temperature. In such case at least the highest melting peak of said melting temperatures falls within the above ranges. A second and/or further peak melting temperature of the copolymer may fall within or outside, preferably below, the temperature ranges. Multiple melting peak may be observed for example if the thermoplastic ethylene copolymer is a blend of different polymers.
In an aspect of the invention the thermoplastic ethylene copolymer comprises an ethylene-propylene co-polymer.
The thermoplastic ethylene copolymer may comprise the various forms of ethylene-propylene co-polymers, other ethylene copolymers with co-monomers such as 1-butene, isobutylene, as well as with hetero atom containing monomers such as acrylic acid, methacrylic acid, vinyl acetate, maleic anhydride, ethyl acrylate, methyl acrylate; generally α-olefin and cyclic olefin copolymers, or blends thereof. Preferably the thermoplastic ethylene copolymer is a copolymer of ethylene which may contain as co-monomers one or more olefins having 2 to 12 C-atoms, in particular propylene, isobutene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, acrylic acid, methacrylic acid and vinyl acetate.
Furthermore, the thermoplastic ethylene copolymer may be a functionalized polyethylene or alternatively the thermoplastic ethylene copolymer may comprise a functionalized polymer. Such functionalized polymers are often referred to as functional copolymers or grafted polymers, whereby the grafting refers to the chemical modification of the polymer backbone mainly with ethylenically unsaturated monomers comprising heteroatoms whereas functional copolymers refer to the copolymerization of ethylene with ethylenically unsaturated monomers. Preferably the ethylenically unsaturated monomer comprises oxygen and/or nitrogen atoms. Most preferably the ethylenically unsaturated monomer comprises a carboxylic acid group or derivatives thereof resulting in an acylated polymer, specifically in an acetylated polyethylene. Preferably, the carboxylic reactants are selected from the group consisting of acrylic, methacrylic, cinnamic, crotonic, and maleic, fumaric, and itaconic reactants. Said functionalized polymers typically comprise between 1 and 10 mass % of carboxylic reactant or more. The presence of such functionalization in the thermoplastic ethylene copolymer may substantially enhance the dispersability of the thermoplastic ethylene copolymer and/or allow a reduction of additives present for that purpose such as surfactants. Such composition may also be referred to as solvent-free. By solvent is herein understood a liquid in which at room temperature the thermoplastic ethylene copolymer is soluble in an amount of more than 1 mass % whereas a non-solvent is understood a liquid in which at room temperature the thermoplastic ethylene copolymer is soluble in an amount of less than 0.1 mass %.
The thermoplastic ethylene copolymer has a density as measured according to ISO1183-04 in the range from 860 to 970 kg/m3, preferably from 870 to 930 kg/m3, more preferably from 870 to 920 kg/m3, most preferably from 875 to 910 kg/m3. In an aspect the density of the thermoplastic ethylene copolymer is in the range from 875 to 900 kg/m3 as measured according to ISO1183-04. The inventors identified that thermoplastic ethylene copolymer with densities within said preferred ranges provide an improved balance between the mechanical properties of the composite elongated body and the processability of the coating composition, especially the dried coating composition during the process of the invention.
The thermoplastic ethylene copolymer is a semi-crystalline polymer having a peak melting temperature in the range from 40° C. to 140° C. and typically a heat of fusion of at least 5 J/g, measured in accordance with ASTM E794-06 considering the second heating curve at a heating rate of 10 K/min, on a dry sample and ASTM E793-85, respectively. The thermoplastic ethylene copolymer is a semi-crystalline polyolefin having a peak melting temperature in the range from 40 to 140° C. and typically a heat of fusion of at least 5 J/g, measured in accordance with ASTM E794-06 considering the second heating curve at a heating rate of 10 K/min, on a dry sample and ASTM E793-85, respectively. In a preferred embodiment of the present invention the thermoplastic ethylene copolymer has a heat of fusion of at least 10 J/g, preferably at least 15 J/g, more preferably at least 20 J/g, even more preferably at least 30 J/g and most preferably at least 50 J/g. The inventors surprisingly found that with the increase heat of fusion the composite elongated body showed improved monofilament like character. The heat of fusion of the thermoplastic ethylene copolymer is not specifically limited by an upper value, other than the theoretical maximum heat of fusion for a fully crystalline polyethylene or polypropylene of about 300 J/g. The thermoplastic ethylene copolymer is a semi-crystalline product with a peak melting temperature in the specified ranges. Accordingly a reasonable upper limit for the thermoplastic ethylene copolymer heat of fusion is at most 200 J/g, preferably at most 150 J/g. In another embodiment the thermoplastic ethylene copolymer has a peak melting temperature in the range from 50 to 130° C., preferably in the range from 60 to 120° C., measured in accordance with ASTM E794-06, considering the second heating curve at a heating rate of 10 K/min, on a dry sample. Such preferred peak melting temperatures provide a more robust processing method to produce the composite elongated body in that the conditions for drying of the composite elongated body do need less attention while composite elongated bodies with good properties are produced. The thermoplastic ethylene copolymer may have more than one peak melting temperature. In such case at least the highest melting peak of said melting temperatures falls within the above ranges. A second and/or further peak melting temperature of the thermoplastic ethylene copolymer may fall within or outside the temperature ranges. Such may for example be the case when the thermoplastic ethylene copolymer is a blend of polymers.
The thermoplastic ethylene copolymer may have a modulus that may vary in wide ranges. A low modulus thermoplastic ethylene copolymer with for example a modulus of about 50 MPa, will provide very flexible composite elongated bodies with good strength properties. A high modulus thermoplastic ethylene copolymer with for example a modulus of about 500 MPa may provide composite elongated bodies such as monofilaments with improved structural appearance. Each application may have an optimum modulus for the thermoplastic ethylene copolymer, related to the specific demands during the use of the application. The modulus mat be determined as described in the METHODS herein.
The amount of polymeric composition present in the composite elongated body (coating percentage) may vary widely in function of the intended application of the composite elongated body and may be adjusted by the employed method of applying. The amount of polymeric composition in the composite elongated body according to the invention may be determined as described in the METHOD section herein. In an aspect of the invention the composite elongated body comprises an amount of polymeric composition in the range of from 5 mass % to 45 mass % based on the total weight of the composite elongated body. In another aspect of the invention comprises an amount of polymeric composition in the range of from 8 mass % to 25 mass % based on the total weight of the composite elongated body, preferably the composite elongated body comprises an amount of polymeric composition in the range of from 12 mass % to 20 mass % based on the total weight of the composite elongated body.
In the composite elongated body the surface of the HPPE filaments is substantially (in an aspect at least 50%, at least 60%, at least 70%, at least 90%, at least 95%, or at least 98%) coated (i.e. covered) with the polymeric composition. In an aspect of the composite elongated body the surface of the HPPE filaments is from 70% to 100% coated (i.e. covered) with the polymeric composition. Alternatively one may say the polymeric composition in the composite elongated body is present as a sizer on substantially the entire surface of the HPPE filament.
In an aspect the composite elongated body according to the invention comprises:
In an aspect the composite elongated body according to the invention comprises:
In an aspect the polymeric composition forms a uniform film on the surface of the HPPE filaments. This may be observed via visual analysis e.g. by using SEM on a cross section of the composite elongated body and determining which % of the surface is covered with the coating composition, while using a SEM measurement window of at least 3× the diameter of the filament. Alternatively by making a SEM at 10 locations (evenly distributed over the cross section) to determine which % of the surface is covered with the coating composition.
In an aspect the polymeric composition forms a uniform film on the surface of the HPPE filaments. This may be further be observed via visual analysis e.g. by using SEM on the outer surface of the composite elongated body (this is illustrated in
The polymeric composition has a density as measured according to ISO1183-04 in the range from 860 to 970 kg/m3, preferably from 870 to 930 kg/m3, more preferably from 870 to 920 kg/m3, most preferably from 875 to 910 kg/m3. In an embodiment the density of the polymeric composition is in the range from 875 to 900 kg/m3 as measured according to ISO1183-04. The inventors identified that a polymeric composition with a density within said ranges provide a good balance between the mechanical properties of the composite elongated body and the processability of the coating composition comprising the thermoplastic ethylene copolymer and the lubricant during manufacturing the composite elongated body of the invention.
In an embodiment the composite elongated body according to according to the invention the lubricant is as described herein.
In the context of the present invention HPPE filaments are understood to be polyethylene filaments with improved mechanical properties such as tenacity. In a preferred embodiment the high performance polyethylene filaments are polyethylene filaments with a tenacity of at least 0.6 N/tex, preferably at least 1.0 N/tex, more preferably at least 1.5 N/tex, more preferably at least 1.8 N/tex, even more preferably at least 2.5 N/tex and most preferably at least 3.5 N/tex. In a preferred embodiment the high performance polyethylene filaments are polyethylene filaments with a tenacity of at most 6.0 N/tex, preferably at most 5.5 N/tex and more preferably at most 5.0 N/tex Preferred polyethylene is high molecular weight (HMWPE) or ultrahigh molecular weight polyethylene (UHMWPE). Best results were obtained when the high performance polyethylene filaments comprise ultra-high molecular weight polyethylene (UHMWPE) and have a tenacity of at least 2.0 N/tex, more preferably at least 3.0 N/tex. In an aspect the high performance polyethylene filaments are ultra-high molecular weight polyethylene (UHMWPE) filaments having a tenacity in the range from 2.0 to 6.0 N/tex. In an aspect the high performance polyethylene filaments are ultra-high molecular weight polyethylene (UHMWPE) filaments having a tenacity in the range from 2.5 to 5.0 N/tex.
Preferably the composite elongated body of the present invention comprises HPPE filaments comprising high molecular weight polyethylene (HMWPE) or ultra-high molecular weight polyethylene (UHMWPE) or a combination thereof, preferably the HPPE filaments substantially consist of HMWPE and/or UHMWPE.
In the context of the present invention the expression ‘substantially consisting of HMWPE and/or UHMWPE’ has the meaning of ‘may comprise a minor amount of further species’ wherein minor is up to 5 mass %, preferably of up to 2 mass % of said further species or in other words ‘comprising more than 95 mass % of preferably ‘comprising more than 98 mass % of’ HMWPE and/or UHMWPE based on the filaments.
In an aspect the composite elongated body of the present invention comprises high molecular weight polyethylene (HMWPE) filaments with a tenacity of at least 0.6 N/tex, preferably at least 1.0 N/tex, more preferably at least 1.5 N/tex, more preferably at least 1.8 N/tex, even more preferably at least 2.5 N/tex and most preferably at least 3.5 N/tex. Best results were obtained when the high performance polyethylene filaments comprise ultra-high molecular weight polyethylene (UHMWPE) and have a tenacity of at least 2.0 N/tex, more preferably at least 3.0 N/tex. In an aspect the composite elongated body of the present invention comprises high molecular weight polyethylene (HMWPE) filaments with a tenacity in the range from 2.0 to 5.5 N/tex. In an aspect the composite elongated body of the present invention comprises high molecular weight polyethylene (HMWPE) filaments with a tenacity in the range from 2.0 to 5.0 N/tex.
In an embodiment the composite elongated body according to the invention comprises at least two filaments. In an embodiment the composite elongated body according to the invention comprises at least at least 20 filaments, preferably at least at least 100 filaments, more preferably at least 200 filaments. In an embodiment the composite elongated body according to the invention comprises at most 1500 filaments, preferably at most 1200 filaments, more preferably at most 5000 filaments.
In an aspect the composite elongated body according to the inventions comprises from 2 to 1×109 (UHMWPE) filaments having a tenacity in the range from 2.0 to 5.0 N/tex. In an aspect the composite elongated body according to the inventions comprises from 2 to 1×107 (UHMWPE) filaments having a tenacity in the range from 2.0 to 5.0 N/tex.
In the context of the present invention the polyethylene (PE) of the filament may be linear or branched, whereby linear polyethylene is preferred. Linear polyethylene is herein understood to mean polyethylene with less than 1 side chain per 100 carbon atoms, and preferably with less than 1 side chain per 300 carbon atoms; a side chain or branch generally containing at least 10 carbon atoms. Side chains may suitably be measured by FTIR.
The PE of the filament is preferably of high molecular weight with an intrinsic viscosity (IV) of at least 2 dl/g; more preferably of at least 4 dl/g, most preferably of at least 8 dl/g. Such polyethylene with IV exceeding 4 dl/g are also referred to as ultra-high molecular weight polyethylene (UHMWPE). Intrinsic viscosity is a measure for molecular weight that can more easily be determined than actual molar mass parameters like number and weigh average molecular weights (Mn and Mw). Typically the IV of the PE of the filament is at most 50 dl/g.
In an aspect of the present invention the UHMWPE has an intrinsic viscosity (IV) of at least 4 dL/g and comprises at least 0.3 short chain branches (SCB) per thousand total carbon atoms. In a further aspect the short chain branches (SCB) originate from a co-monomer in the UHMWPE wherein the co-monomer is selected from the group consisting of alpha-olefins with at least 3 carbon atoms, cyclic olefins having 5 to 20 carbon atoms and linear, branched or cyclic dienes having 4 to 20 carbon atoms. In an aspect of the present invention the SCB are C1-C20-hydrocarbyl groups, preferably the C1-C20-hydrocarbyl group is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl and cyclohexyl, isomers thereof and mixtures thereof. In an aspect of the present invention the short chain branches (SCB) originate from a co-monomer in the UHMWPE wherein the co-monomer is selected from the group consisting of alpha-olefins with at least 3 carbon atoms, cyclic olefins having 5 to 20 carbon atoms and linear, branched or cyclic dienes having 4 to 20 carbon atoms. In an aspect of the present invention the SCB are C1-C20-hydrocarbyl groups, preferably the C1-C20-hydrocarbyl group is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl and cyclohexyl, isomers thereof and mixtures thereof.
The HPPE filaments in the present invention may be obtained by various processes, for example by a melt spinning process, a gel spinning process or a solid state powder compaction process. A preferred method for the production of the filaments used in the invention comprises melt spinning which includes feeding the polyethylene to an extruder, extruding a molded article at a temperature above the melting point thereof and drawing the extruded filaments below its melting temperature. If desired, prior to feeding the polymer to the extruder, the polymer may be mixed with a suitable liquid compound, for instance to form a gel, such as is preferably the case when using ultra high molecular weight polyethylene. In a method for the production of the filaments used in the invention the filaments used in the invention are prepared by a gel spinning process. A suitable gel spinning process is described in for example GB-A-2042414, GB-A-2051667, EP 0205960 A and WO 01/73173 A1. In short, the gel spinning process comprises preparing a solution of a polyethylene of high intrinsic viscosity, extruding the solution into a solution-filaments at a temperature above the dissolving temperature, cooling down the solution-filaments below the gelling temperature, thereby at least partly gelling the polyethylene of the filaments, and drawing the filaments before, during and/or after at least partial removal of the solvent.
Creep is a parameter known in the art and it typically depends on the tension and the temperature applied on a material. Under constant loading HPPE filaments show an irreversible deformation (creep) behavior that is strongly dependent upon load and temperature. High tension and high temperature values typically promote fast creep behavior. The creep may be (partially) reversible or irreversible on unloading. The rate of time dependent deformation is called creep rate and is a measure of how fast the filaments are undergoing said deformation. The initial creep rate may be high but the creep deformation may decrease during constant loading to a final creep rate that may be negligible (e.g. close to zero value).
In an embodiment of the composite elongated body according to the invention the HPPE filaments comprise ultrahigh molecular weight (UHMWPE) having an intrinsic viscosity (IV) of at least 4 dL/g and comprising at least 0.3 short chain branches per thousand total carbon atoms.
In an embodiment of the composite elongated body according to the invention the HPPE filaments comprise ultrahigh molecular weight (UHMWPE) having an intrinsic viscosity (IV) in the range from 4 dL/g to 50 dL/g and comprising from 0.3 to 10 short chain branches per thousand total carbon atoms.
In an embodiment the high performance polyethylene HPPE filaments are provided as a yarn, said yarn comprising at least two HPPE filaments having a tenacity of at least 0.6 N/tex. In an embodiment the composite elongated body comprises a yarn comprising high performance polyethylene HPPE filaments having a tenacity of at least 0.6 N/tex, and wherein the yarn has a minimum creep rate of at most 1×10−5% per second as measured at a tension of 900 MPa and a temperature of 30° C. as described in the METHOD section herein.
In an embodiment of the composite elongated body according to the invention the yarn has a minimum creep rate of at most 4×10−6% per second, preferably at most 2×10−6% per second, measured at a tension of 900 MPa and a temperature of 30° C. as described in the METHOD section herein.
In an embodiment of the composite elongated body according to the invention the yarn has a minimum creep rate is at least about 1×10−10% per second as measured at a tension of 900 MPa and a temperature of 30° C. as described in the METHOD section herein.
In an embodiment of the composite elongated body according to the invention the polymeric composition covers at least 50% of the total surface of the HPPE filaments of the composite elongated body, preferably by making an electron microscopy, such as a SEM (Scanning Electron Microscopy), analysis of the surface and/or of a cross section of the composite elongated body. Preferably the polymeric composition covers at least 70% of the total surface of the HPPE filaments of the composite elongated body. In an aspect the polymeric composition covers at least 80% of the total surface of the HPPE filaments of the composite elongated body. In a further aspect at least 90% of the total surface of the HPPE filaments of the composite elongated body is covered by the polymeric composition.
The present invention further provides a method of manufacturing a composite elongated body comprising the steps:
In one embodiment in step d) elevating the temperature causes the coating composition to dry and the thermoplastic ethylene copolymer to melt.
In an embodiment the coating composition herein, is an aqueous polymeric dispersion. By aqueous dispersion is understood that particles of the polymeric composition are dispersed in water, water is acting as non-solvent. The thermoplastic ethylene copolymer present in the applied coating composition, such as an aqueous dispersion, and ultimately present in the obtained composite elongated body of the present invention is a copolymer of ethylene, as described herein.
The concentration of thermoplastic ethylene copolymer in the coating composition may widely vary and is mainly limited by the capability to formulate a stable dispersion of the thermoplastic ethylene copolymer in water. A typical range of concentration is from 2 to 80 mass % of thermoplastic ethylene copolymer in water, whereby the weight percentage is the weight of thermoplastic ethylene copolymer in the total weight of aqueous dispersion. Preferred concentrations are from 4 to 60 mass %, more preferably from 5 to 50 mass %, most preferably from 6 to 40 mass %. Another preferred concentration of the thermoplastic ethylene copolymer in the dispersion is at least 15 mass %, preferably at least 18 mass % and even more preferably at least 20 mass %. In another preferred embodiment the concentration of the thermoplastic ethylene copolymer in the coating composition is from 10 to 50 mass %, preferably from 15 to 40 mass %, most preferably from 18 mass % to 30 mass %. Such preferred higher concentrations of thermoplastic ethylene copolymer may have the advantage of a providing a composite elongated body with higher concentration while reducing the time and energy required for the removal of the water. For some applications a low concentration coating composition, having from 2 to 10 mass % of the thermoplastic ethylene copolymer in the dispersion, may be advantageous for example to increase the wetting and impregnation speed with low viscous suspensions. Last but not least the coating composition concentration and quantity should be chosen to provide a composite elongated body with the required amounts of polymeric composition present in said body.
The coating composition may further comprise additives such as ionic or non-ionic surfactants, tackyfying resins, stabilizers, anti-oxidants, colorants or other additives modifying the properties of the polymeric composition or of the prepared composite elongated body.
The application of the coating composition to a yarn comprising the HPPE filaments may be done by methods known in the art and may depend amongst others on the moment the composition is added to the yarn, the nature of the filaments, the concentration and viscosity of the coating composition. The coating composition may for example be applied to the yarn by spraying, dipping, brushing, transfer rolling or the like, especially depending on the intended amount of coating polymeric composition present in the composite elongated body of the invention.
Once the coating composition is applied to the yarn comprising at least two HPPE filaments, the coated yarn is exposed to elevated temperature, for example a hot air oven. In an aspect the coated yarn is at least partially dried at elevated temperature, for example a hot air oven.
In an embodiment of the method of manufacturing a composite elongated body according to the invention during step d) the thermoplastic ethylene copolymer melts.
In an embodiment of the method of manufacturing a composite elongated body according to the invention exposing the coated yarn to elevated temperature in step d) causes the coating composition to dry and the thermoplastic ethylene copolymer to melt.
In an embodiment of the method of manufacturing a composite elongated body according to the invention during step d) the coating composition is dried and the thermoplastic ethylene copolymer melts.
Drying involves the removal, e.g. the evaporation, of at least a fraction of the water present in the coated yarn. Preferably the majority, more preferably essentially all water is removed during the drying, optionally in combination with other components. Drying, i.e. the removal of water, may be done by methods known in the art. Typically the evaporation of water involves an increase of the temperatures of the coated yarn up to or above the boiling point of water. The temperature increase may be assisted or substituted by a reduction of the pressure and or combined with a continuous refreshment of the surrounding atmosphere. Typical drying conditions are temperatures of between 40 and 130° C., preferably 50 and 120° C.
The step d) of exposing the coated yarn to elevated temperature in method of the invention may comprise heating the filaments comprising the coating composition to a temperature in the range from the peak melting temperature of the thermoplastic ethylene copolymer to 153° C. Such heating may be performed before, during and/or after the partially drying the coating composition. Typically heating the filaments comprising the coating composition to a temperature in the range from the peak melting temperature of the thermoplastic ethylene copolymer to 153° C. is done during and/or after at least partially drying the coating composition. In an aspect this heating is done after at least partially drying the coating composition. Heating may be carried out by keeping the coated yarn for a dwell time in an oven set at an elevated temperature, subjecting the impregnated filaments to heat radiation or contacting the body with a heating medium such as a heating fluid, a heated gas stream or a heated surface. In an aspect heating is done in a hot air oven. Preferably, the elevated temperature is at least 2° C., preferably at least 5° C., most preferably at least 10° C. above the peak melting temperature of the thermoplastic ethylene copolymer. In an aspect the elevated temperature is from 2° C. to 100° C. above the peak melting temperature of the thermoplastic ethylene copolymer. At such temperature the thermoplastic ethylene copolymer melts and can adhere to the filaments and fuse the filaments together in a monofilament-like structure, and the composite elongated body is be obtained. In an aspect the elevated temperature is at most 153° C., preferably at most 150° C., more preferably at most 145° C. and most preferably at most 140° C. This upper limit is also referred to herein as maximum temperature. In an aspect the dwell time is preferably between 2 and 100 seconds, more preferably between 3 and 60 seconds, most preferably between 4 and 30 seconds.
In a preferred embodiment of the method of manufacturing a composite elongated body, the heating of the coated yarn overlaps, more preferably is combined with the drying step of the coating composition. It may prove to be practical to apply a temperature gradient in step d) to the coated yarn whereby the temperature is raised from about room temperature to the maximum temperature of the heating step over a period of time during which the coated yarn will undergo a continuous process from drying of the coating composition to at least partially melting of the thermoplastic ethylene copolymer. In an aspect of the method of manufacturing a composite elongated body in step d) the coated yarn undergoes a continuous process from drying of the coating composition to at least partial melting of the thermoplastic ethylene copolymer. In an aspect of this method in step d) the elevated temperature is a temperature gradient with an increasing temperature that falls in the range from 20° C. to a temperature at least 2° C., preferably at least 5° C., most preferably at least 10° C. above the peak melting temperature of the thermoplastic ethylene copolymer. In an aspect of this method in step d) the elevated temperature is a temperature gradient having a temperature that increases from a starting temperature in the range from 20° C. to 153° C. to a higher end temperature in the range from 20° C. to 153° C.
In a preferred embodiment of the method of manufacturing a composite elongated body upon completion of steps a), b), c) and d) the polymeric composition is present throughout the composite elongated body. In a preferred embodiment of the method of manufacturing a composite elongated body upon completion of steps a), b), c) and d) the thermoplastic ethylene copolymer and the lubricant are present throughout the composite elongated body. In a preferred embodiment of the method of manufacturing a composite elongated body upon completion of steps a), b), c) and d) the thermoplastic ethylene copolymer and the wax are present throughout the composite elongated body.
In an aspect the composite elongated body a composite elongated body contains more than 50 mass % UHMWPE as described herein. In an aspect the composite elongated body a composite elongated body comprises from 55 to 95 mass % UHMWPE as described herein. A preferred embodiment of the present invention concerns a composite elongated body containing more than 70 mass % UHMWPE as described herein, preferably 80 mass % of UHMWPE, preferably more than 90 mass % of UHMWPE, whereby the mass % are expressed as mass of UHMWPE to the total mass of the composite elongated body. In a yet preferred embodiment, the UHMWPE present in the composite elongated body is comprised in the HPPE filaments of said composite elongated body. In an embodiment the composite elongated body a composite elongated body comprises from 55 to 95 mass % UHMWPE in the form of HPPE filaments. In an embodiment the composite elongated body according to the invention, said composite elongated body comprises at least 80 mass % UHMWPE present in the form of HPPE filaments. In an embodiment the composite elongated body according to the invention, said composite elongated body comprises at least 85 mass % UHMWPE present in the form of HPPE filaments. In an embodiment the composite elongated body according to the invention, said composite elongated body comprises from 85 mass % to 95 mass % UHMWPE present in the form of HPPE filaments.
The present invention also relates to the composite elongated body produced with the method of manufacturing a composite elongated body according to the invention. Such composite elongated body comprises HPPE filaments as defined herein and a polymeric composition comprising a thermoplastic ethylene copolymer and a lubricant as defined herein, wherein the thermoplastic ethylene copolymer is a copolymer of ethylene as defined herein. Such composite elongated body is subject to the preferred embodiments and potential advantages as discussed above or below in respect of the present inventive method, whereas the preferred embodiments for the composite elongated body potentially apply vice versa for the inventive method of manufacturing the composite elongated body.
The present invention further relates to a lengthy body comprising the composite elongated body according to the invention as described herein. The term lengthy body includes but is not limited to a strand, a cable, a cord, a rope, a belt, a strip, a hose and a tube. In an aspect the lengthy body comprises from 2 to 100.000 composite elongated bodies according to the invention. In an aspect the lengthy body comprises from 3 to 10.000 composite elongated bodies according to the invention. In an aspect the lengthy body comprises from 5 to 1000 composite elongated bodies according to the invention. A lengthy body herein is herein understood an elongated body, the length dimension of which is much greater than the transverse dimensions of width and thickness or diameter. Preferably said length dimension is at least 10 times, more preferably at least 20 times even more preferably at least 50 times and most preferably at least 100 times greater than the width or thickness dimension of the lengthy body, whichever is larger. The cross-sectional shape of the lengthy body may be from round or almost round, oblong or rectangular shape.
In its simplest form the lengthy body comprises 2 or more composite elongated bodies lying side by side without being twisted about each other. Such thread of untwisted composite elongated bodies may also be called a bundle and as elaborated above may have a variety of cross-sectional shapes. The composite elongated bodies in a bundle will substantially be oriented in a single direction, the length direction of the lengthy body. Furthermore, a thread may be comprised of two or more twisted composite elongated bodies. The lengthy body according to the invention typically demonstrates an improved abrasion resistance. An improved abrasion resistance may be demonstrated in a fairlead abrasion test, such as the fairlead test described in the METHOD section herein. The lengthy body according to the invention typically demonstrates an improved bending performance. An improved bending performance may be demonstrated in a Cyclic Bending Over Sheave (CBOS) test, such as a CBOS test described in THE METHODS herein.
The present invention relates to a method of manufacturing a lengthy body comprising the step of assembling at least two composite elongated bodies as defined herein to form the lengthy body, preferably the lengthy body is a rope, such as a laid or braided rope.
The present invention relates to a rope comprising at least three composite elongated bodies according to the invention. In an aspect the rope comprises from 3 to 1000 composite elongated bodies according to the invention. In an aspect the rope comprises from 3 to 10.000 composite elongated bodies according to the invention. In an aspect the rope comprises from 3 to 100.000 composite elongated bodies according to the invention. The rope according to the invention demonstrates an improved abrasion resistance. An improved abrasion resistance may be demonstrated in a fairlead abrasion test, such as the fairlead test described in the METHOD section herein. In an aspect the rope according to the invention demonstrates an improved abrasion resistance as compared with a reference rope, preferably wherein the reference rope is a rope without the polymeric composition as defined herein. In an aspect the rope according to the invention demonstrates an improved abrasion resistance as compared with a reference rope wherein the reference rope is a rope comprising a thermoplastic ethylene copolymer as defined in any preceding embodiment and lacking the lubricant as defined herein.
The rope according to the invention typically demonstrates an improved bending performance. An improved bending performance may be demonstrated in a Cyclic Bending Over Sheave (CBOS) test, such as a CBOS test described in THE METHODS herein. In an aspect the rope according to the invention demonstrates an improved bending performance as compared with a reference rope, preferably wherein the reference rope is a rope without the polymeric composition as defined herein. In an aspect the rope according to the invention demonstrates an improved bending performance as compared with a reference rope wherein the reference rope is a rope comprising a thermoplastic ethylene copolymer as defined in any preceding embodiment and lacking the lubricant as defined herein.
In an embodiment the rope according to the invention comprises the composite elongated body according to the invention in an amount in the range from 80 mass % to 100 mass % based on the total weight of the rope. In a preferred aspect 90 mass % to 100 mass % based on the total weight of the rope. The total weight of the rope here refers to the weight of the rope without a cover if any. In an aspect the rope consists of assembled composite elongated bodies according to the invention.
In a preferred embodiment of the rope according to the invention, the rope comprises ultra-high molecular weight polyethylene (UHMWPE) filaments, more preferably gel spun UHMWPE filaments. In a further aspect, at least 50 mass %, more preferably at least 80 mass % and even more preferably at least 90 mass % and most preferably all of the high performance polyethylene filaments present in the rope are UHMWPE filaments.
The rope according to the invention may be of various constructions, including laid, braided, parallel, and wire rope-like constructed ropes. In general a rope is composed of strands, typically laid or braided strands. The number of strands in the rope may also vary widely, but is generally at least 3 and preferably at most 16, to arrive at a combination of good performance and ease of manufacture. The number of strands in a braided rope according to the invention is preferably at least 3. There is no upper limit to the number of strands, although in practice ropes will generally have no more than 32 strands. Particularly suitable are ropes of an 8- or 12-strand braided construction. Such ropes provide a favourable combination of tenacity and resistance to bend fatigue, and may be made economically on relatively simple machines.
Typically a rope has a cross-section that is about circular or round, but also a rope having an oblong cross-section, meaning that the cross-section of a tensioned rope shows a flattened, oval, or even (depending on the number of primary strands) an almost rectangular form, is known. Such oblong cross-section preferably has an aspect ratio, i.e. the ratio of the larger to the smaller diameter (or width to thickness ratio), in the range of from 1.2 to 4.0.
A preferred embodiment of the present invention concerns a lengthy body comprising the composite elongated body according to the invention and containing more than 70 mass % UHMWPE as described herein, preferably 80 mass % of UHMWPE, preferably more than 90 mass % of UHMWPE, whereby the mass % are expressed as mass of UHMWPE to the total mass of the lengthy body. In a yet preferred embodiment, the UHMWPE present in the lengthy body is comprised in the HPPE filaments of said composite elongated body.
In an embodiment the lengthy body according to the invention is constructed from composite elongated bodies according to the invention.
The composite elongated body according to the invention may for example be used in the manufacture of a lengthy body such as a rope. The composite elongated body according to the invention may for example be used in the manufacture of an article such as a net, for example a fishing net or an aquaculture net (typically to grow fish); a sling, such as a round sling, a webbing sling or a rope sling; a synthetic chain link; a synthetic chain or a tendon.
Therefore an aspect of the present invention includes an article according to the invention comprising the composite elongated body according to the invention, such as a net (for example a fishing net or an aquaculture net comprising the composite elongated body), a sling, a synthetic chain or a tendon comprising the composite elongated body according to the invention. The article according to the invention typically demonstrates an improved abrasion resistance and/or an improved overall durability. The article according to the invention may comprise from 2 to 100.000 composite elongated bodies according to the invention.
In an embodiment of the present invention the article according to the invention comprises the composite elongated body according to the invention and contains more than 70 mass % UHMWPE, preferably 80 mass % of UHMWPE, preferably more than 90 mass % of UHMWPE, whereby the mass % are expressed as mass of UHMWPE to the total mass of the article. In a yet preferred embodiment, the UHMWPE present in the article is comprised in the HPPE filaments of said article. In an embodiment the article is constructed from composite elongated bodies.
A synthetic chain link according to the invention comprises at least one composite elongated body according to the invention. In an embodiment the synthetic chain link according to the invention comprises from 2 to 10.000 composite elongated bodies according to the invention.
A synthetic chain according to the invention comprises at least one composite elongated body according to the invention. In an embodiment the synthetic chain according to the invention comprises at least two interconnected synthetic chain links according to the invention. In an embodiment the synthetic chain according to the invention comprises from 2 to 10.000 interconnected synthetic chain links according to the invention. In an embodiment the synthetic chain according to the invention comprises from 2 to 1000 interconnected synthetic chain links according to the invention. In an embodiment the synthetic chain according to the invention comprises at least two interconnected synthetic chain links wherein at least a part of the links comprise the composite elongated body according to the invention. In an embodiment the synthetic chain according to the invention comprises a plurality of interconnected chain links wherein at least a part of the links comprise the composite elongated body according to the invention. In an embodiment the synthetic chain according to the invention comprises a plurality of interconnected chain links wherein each link comprises the composite elongated body according to the invention. The chain according to the invention is typically suitable to moor or anchor boats, to lash cargo in road, rail, water and air transportation and suitable for conveying, hoisting, suspending and lifting applications. The synthetic chain according to the invention according to the invention may have an improved resistance to particle ingress, resistance to abrasion resistance and/or an improved overall durability.
In an aspect the article according to the invention is a personal protection item (such as a helmet, a body panel) or a glove comprising at least one composite elongated body as described herein.
The present invention further relates to a belt comprising at least three composite elongated bodies according to the invention. A belt is a loop of flexible material generally used to link two or more rotating shafts mechanically, most often parallel. Belts may be used as a source of motion, to transmit power efficiently or to track relative movement. In an aspect the belt according to the invention demonstrates an improved bending performance as compared with a reference belt, preferably wherein the reference belt is a belt without the polymeric composition as defined herein. In an aspect the belt according to the invention demonstrates an improved bending performance as compared with a reference belt wherein the reference belt is a belt comprising a thermoplastic ethylene copolymer as defined in any preceding embodiment and lacking the lubricant as defined herein. In an aspect the article according to the invention is a personal protection item (such as a helmet, a body panel) or a glove comprising from 1 to 5.000 composite elongated bodies as described herein. In an aspect the article according to the invention is a personal protection item (such as a helmet, a body panel) or a glove comprising from 1 to 10.000 composite elongated bodies as described herein.
The present invention further relates to a net, such as a net for fishing or fish farming, comprising at least one composite elongated body as described herein. The present invention further relates to a net comprising at least three composite elongated bodies according to the invention. The net may comprise up to 1000 composite elongated bodies according to the invention. A practical upper limit of the number of composite elongated bodies in the net is eight, preferably seven, six or five. A net herein may comprise 1, 2, 3, 4, 5, 6, 7 or 8 composite elongated bodies according to the invention.
A benefit of a lubricant in the polymeric composition may include improvement in long term use of nets comprising the composite elongated body, when used in an aquatic environment. Without wishing to be bound to any theory, enhanced durability may be caused by reduced abrasion between filaments and composite elongated bodies in the at least one cord or between cords of the net.
In embodiments of present disclosure, the net is to be applied in fish farming, and is also called an aquaculture net. Such nets are known to the skilled person, and may have widely varying dimensions, mass, construction, and number and type of cords. The cords of present net can be joined by techniques such as knots or clamps, but the joints may also be made as integral part of the process of net making from cords. Typically, the net will have a mesh size of at least 8 mm, preferably at least 10, at least 12, at least 14 or at least 16 mm. The maximum mesh size of the net of the present disclosure is not particularly limited, and may be at most 500 mm, preferably at most 400, at most 300, at most 200, at most 100, at most 90, at most 80, at most 70, or at most 60 mm depending for example on the type of fish and conditions of use. Mesh size of a knotted net is generally determined as the full mesh knot to knot distance, i.e. the distance from center to center of 2 adjacent knots of a mesh. In case of a knotless net, e.g. made using interbraiding, the mesh size is the distance between two joints as measured across the space of a mesh taking the distance between two opposite joints as further described in the METHODS.
The construction of the cords of the nets of the invention are not specifically limited and may be amongst others braided, laid or parallel arrangements of a single or multiple composite elongated bodies.
In an embodiment, the net according to the invention is a knitted knotless net, often referred to as Raschel net, comprising at least one composite elongated body according to the invention. In an embodiment, the net according to the invention is a knitted knotless net, often referred to as Raschel net, comprising from 1 to 1000 composite elongated body according to the invention. In such embodiment, the knotless net is made by a knitting technique, such as by warp knitting using a Raschel frame.
In embodiments the net is a braided net, preferably a braided knotless net, wherein the cords comprise at least one composite elongated body, such as 1 composite elongated body or 2 or 3 composite elongated bodies as described herein. In embodiments the net is a braided net, preferably a braided knotless net, wherein the cords have 4 composite elongated bodies, or 8, 12, 16, 20 or 24 composite elongated bodies.
In one embodiment, the net construction comprises cords that are braids comprising at least three composite elongated bodies. Braids and braiding processes are well known. Commonly a braid is formed by crossing over a number of elongated bodies diagonally so that each elongated body passes alternately over and under one or more of the other elongated bodies to form a coherent cord.
An alternative but also beneficial net construction, the construction comprises twisted cords instead of braided cords, in which two composite elongated bodies are twisted together to form a cord.
The cords of the net of the invention can be joined by standard techniques such as knots, shackles or interbraiding. It is preferred that the net of the invention is a knotless net. A knotless construction of the net typically results in a further improvement of the net robustness against pressure washing and especially retention of the mesh breaking strength as compared to a construction in which the cords are joint by other means such as knots or shackles.
The present invention also relates to a crane. A crane is a type of machine, generally equipped with a rope or chain, and sheaves, that may be used both to lift and lower materials and to move them horizontally. It is mainly used for lifting heavy things and transporting them to other places. Cranes are commonly employed in the transport industry for the loading and unloading of freight, in the construction industry for the movement of materials, and in the manufacturing industry for the assembling of heavy equipment. The crane according to the invention comprises a sheave and the lengthy body according to the invention, such as a rope according to the invention. In an aspect the crane according to the invention comprises a sheave and the belt according to the invention. In an aspect the crane according to the invention comprises a sheave and the chain according to the invention. The crane according to the invention comprises a winch and the lengthy body according to the invention, such as the rope according to the invention.
A fairlead is a device to guide a line, rope or cable around an object, out of the way or to stop it from moving laterally. Typically a fairlead will be a ring or hook. The fairlead may be a separate piece of hardware, or it could be a hole in the structure. An additional use on boats is to keep a loose end of line from sliding around the deck. While fairleads are most frequently found in nautical applications, they may be found anywhere rigging is used. In off-roading, a fairlead is used to guide the winch cable and remove lateral strain from the winch.
The present invention also relates to a marine vessel, a sailing vessel, a boat, a ship or a marine platform comprising a fairlead and a rope according to the invention. The present invention also relates to a vehicle, such as a car, a truck, an aircraft, a train or a tram comprising a fairlead and the rope according to the invention. A boat is a watercraft of a large range of types and sizes, but generally smaller than a ship, which is distinguished by its larger size, shape, cargo or passenger capacity, or its ability to carry boats. A ship is a large watercraft that travels the world's oceans and other sufficiently deep waterways, carrying goods or passengers, or in support of specialized missions, such as defense, research and fishing. A marine platform herein includes without limitation an oil platform, offshore platform, and an offshore drilling rig.
The present invention further provides a method of manufacturing an article comprising the step of creating/producing the article from the lengthy body and/or the composite elongated body, preferably the article is a net, a synthetic chain, a personnel protection item or a glove.
The present invention further relates to the use of the coating composition as defined herein for improving bending performance of a lengthy body according to the invention.
The present invention further relates to the use of the coating composition as defined herein for improving abrasion performance, in particular an improved external abrasion fatigue of a lengthy body according to the invention.
The present invention further relates to the use of the coating composition as defined herein for improving bending performance of a rope.
The present invention further relates to the use of the coating composition as defined herein for improving abrasion performance, in particular an improved external abrasion fatigue of a rope.
In particular, the present invention provides a use of the polymeric composition as defined herein to reduce abrasion of a rope, a synthetic chain or a belt comprising such composition, wherein the rope, synthetic chain or belt comprises high performance polyethylene (HPPE) filaments having a tenacity of at least 0.6 N/tex. Abrasion may be measured as described herein. A typical method is the Fairlead abrasion performance test. For example the 10 mm rope fairlead abrasion performance test.
The present invention provides a use of the coating composition as defined herein to improve bending performance of a rope, a synthetic chain or a belt comprising such composition.
The present invention further relates to a method of lifting and/or placement of an object comprising the steps:
The method of lifting and/or placement according to the invention includes heavy lifting and mooring of objects onto a seabed. The method of lifting and/or placement according to the invention includes lifting and placement of objects, onto a ship, onto land or on land. Other applications include offshore oil and gas exploration, oceanographic, seismic and other industrial applications.
In one embodiment, the method of lifting and/or placement of an object comprises the steps
The invention will be further explained by the following embodiments and examples and comparative experiments.
Below also the methods used in determining the various parameters useful in defining the present invention are hereinafter presented.
The present invention includes without limitation the following embodiments. Features of any one embodiment may be combined with features of another embodiment. So for example features of a composite elongated body, may be combined with any features of lengthy body embodiments, method embodiments and/or use embodiments and vice versa.
The following examples are given by way of non-limiting reference only.
Paramelt™ Aquaseal X2050 (also referred to as X2050 herein) is a water based dispersion, formulated with unplasticized high molecular weight thermoplastic ethylene copolymers, which is totally solvent free. Solids content 44%, pH 11, a milky white liquid, with a Viscosity (Dynamic @ 20C) of 150 mPas. This thermoplastic ethylene copolymer has a melting peak at 76.7° C. and heat of fusion of 21.9 J/g. It was purchased from Paramelt Veendam B.V., Veendam The Netherlands.
Michelman® Michemprime MP2960 is a water-based copolymer dispersion having pH of 11-12 and a non-volatile content of 16.5-17.5%. It was purchased from Michelman SARL, Windhof, Luxembourg.
BYK® Aquacer® 2650 is a non-ionic emulsion of carnauba wax in water. It comprises 30% non-volatile matter and has a pH of 4.5. It was purchased from BYK Netherlands B.V.
BYK® Aquacer® 2700 is an emulsion comprising a Fischer-Tropsch wax at a pH of 9.5. It was purchased from BYK Netherlands B.V.
NeoCryl A-668 is an anionic acrylic styrene copolymer emulsion, supplied as 45% solids in water. It was purchased from BYK Netherlands B.V.
DSM NeoRez® R-2180 is an aliphatic, self-crosslinking polyurethane dispersion in water, having a pH of 7.3 and a solids content of 35%. It was acquired from DSM Coating Resins B.V. Waalwijk, Netherlands.
The thermoplastic ethylene copolymer and the lubricant were mixed by adding the lubricant to the ethylene copolymer at room temperature and stirring for 15 min.
Manufacturing of the Comparative Coating Compositions for Comp. Ex. 1 and Comp. Ex. 2
The comparative coating composition was prepared by diluting the ethylene copolymer by water in the amount of 1:1.
A HPPE yarn (Dyneema® 1760 SK78, yarn tenacity 34.5 cN/dtex, filament tenacity 37 cN/dtex, Modulus 1190 cN/dtex, from DSM Protective materials BV, The Netherlands) was impregnated by dipping in the coating composition. The wetted yarns were fed first through a die and then in seven passes through a hot air oven with a length of 6 meters with an inlet speed of 50 m/min and an outlet speed of 50 m/min. The oven temperature was set at 110° C. The obtained dried monofilament-like product each contained about 15 mass % polymeric composition and 85 mass % was fibrous material (filaments).
The composite elongated body was used to produce 5 mm ropes (rope having 5 mm diameter), each having 48 single yarns divided over 12 strands. The rope contained 12 strands, (round) braided in 6 clockwise oriented strands and 6 counter-clockwise oriented strands, each strand contained a 20 turns per meter twisted assembly of 4 monofilament-like products, braiding pitch was 7 times the diameter of the rope.
The composite elongated body was used to produce 10 mm ropes (10 mm diameter). Each rope contained 12 strands, (round) braided in 6 clockwise oriented strands and 6 counter-clockwise oriented strands, each strand contained 18 turns per meter twisted assembly of 20 monofilament-like products, braiding pitch was 7 times the diameter of the rope. This way Rope Examples 1 to 6 and Comparative Examples 1 and 2 were made.
The ropes from Rope Examples 1 to 6 and Comparative Examples 1 and 2 were subjected to the Fairlead 10 mm test as described above.
Table 1 reports the Fairlead test results.
The results indicate that presence of a lubricant together with a polyethylene copolymer base matrix leads to a reduction in the coefficient of friction. Further, the presence of a lubricant together with a polyethylene copolymer base matrix improves the abrasion resistance of a coated elongated body. Further, coating with MP2960 improves abrasion resistance more than coating with X2050. When the coating comprises a higher proportion of solids in the lubricant than solids in the matrix, the rope has a further improved abrasion resistance.
| Number | Date | Country | Kind |
|---|---|---|---|
| PCT/EP2021/074621 | Sep 2021 | WO | international |
| PCT/EP2021/074622 | Sep 2021 | WO | international |
| PCT/EP2021/074623 | Sep 2021 | WO | international |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/068794 | 7/6/2022 | WO |
