Note: Descriptions are shown in the official language in which they were submitted.
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COMPOSITE ELONGATED BODY
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 W02007/062803 and
W02011/015485. W02007/062803 describes a rope constructed from high
performance polyethylene fibres and polytetrafluoroethylene fibres. These
ropes can
contain 3-18 mass% of liquid polyorganosiloxanes. W02011/015485 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 W02011/015485 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
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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) a thermoplastic ethylene copolymer as described herein and
b) a lubricant as described herein;
and wherein the thermoplastic ethylene copolymer is a copolymer of ethylene
and
wherein said polymeric composition has a peak melting temperature in the range
from
40 to 140 C, measured in accordance with ASTM E794-06.
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.
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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 1x101 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 1x101
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
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0.6 N/tex and a polymeric composition throughout the composite elongated body,
wherein the polymeric composition comprises:
a) a thermoplastic ethylene copolymer; and
b) a lubricant;
and wherein the thermoplastic ethylene copolymer is a copolymer of ethylene
and
wherein said polymeric composition has a peak melting temperature in the range
from
40 to 140 C, measured in accordance with ASTM E794-06.
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 20t0
1x101
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 1:1.5t0 1:4, most preferably from 1:2t0
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.
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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
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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%),
w-
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: II 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
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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
a) a thermoplastic ethylene copolymer and
b) a wax selected from a polyethylene wax, a polypropylene wax,
beeswax, carnauba wax, a Fischer-Tropsch wax and any combination
thereof;
and wherein the thermoplastic ethylene copolymer is a copolymer of ethylene
and
wherein said polymeric composition has a peak melting temperature in the range
from
40 to 140 C, measured in accordance with ASTM E794-06.
In a further aspect the ratio, on solid content basis, of the thermoplastic
ethylene
copolymer and the wax is from 11:1 to 1:10, preferably from 1:1 to 1:5, more
preferably
from 1:1.5 to 1:4, most preferably from 1:2t0 1:1.35.
In a further aspect the ratio, on solid content basis, of the thermoplastic
ethylene
copolymer and the wax is from 10:1 to 1:10, preferably from 5:1 to 1:5, more
preferably
from 4:1 to 1:4, most preferably from 3:1 to 1:3.
In a further aspect the ratio, on solid content basis, of the thermoplastic
ethylene
copolymer and the wax 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 1:2t0 1:1.35.
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;
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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 a-olefin and cyclic olefin copolymers, or
blends
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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 IS01183-04 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 IS01183-04. 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.
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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
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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:
a) 55-95 mass% of high-performance polyethylene filaments;
b) 5-45 mass% of the thermoplastic ethylene copolymer having a peak
melting temperature measured according to ASTM E794-06 of 40-140 C;
c) 5-45 mass% lubricant; and
d) 0-5.0 mass% of additives;
wherein the sum of components a)-d) is 100 mass%.
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In an aspect the composite elongated body according to the invention
comprises:
a) 70-85 mass% of high-performance polyethylene filaments
b) 7.5-30 mass% of the thermoplastic ethylene copolymer having a peak
melting temperature measured according to ASTM E794-06 of 40-140 C;
c) 7.5-25 mass% lubricant; and
d) 0-5.0 mass% of additives;
wherein the sum of components a)-d) is 100 mass%.
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 3x 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 figure 11)
The polymeric composition has a density as measured according to
IS01183-04 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 IS01183-04. 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.
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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
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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 1x109 (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 1x107 (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-C2o-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
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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 Al. 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.
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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
short chain branches per thousand total carbon atoms.
5 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
10 most 1 x 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 x 10-6 % per second,
preferably at most 2 x 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 x 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:
a) providing a coating composition, wherein the composition comprises
= a thermoplastic ethylene copolymer; and
= a lubricant;
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b) providing a yarn comprising at least two HPPE filaments having a
tenacity of at least 0.6 N/tex;
c) applying the coating composition to the yarn to obtain a coated yarn;
and
d) elevating the temperature of the coated yarn to obtain the composite
elongated body,
wherein the high molecular weight thermoplastic ethylene copolymer is a
copolymer of
ethylene and wherein said thermoplastic ethylene copolymer has a peak melting
temperature in the range from 40 to 140 C, measured in accordance with ASTM
E794-
06.
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
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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
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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
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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.
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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
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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.
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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 4Ø
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.
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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
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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
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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. Figure 8a shows as an example a part of such a knitted knotless net,
having
hexagonal meshes and joints formed by intermingled cords. In an aspect the net
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comprises cords joined in a net mesh, wherein each cord comprises one or more
composite elongated bodies according to the invention. In another embodiment,
the net
according to the invention is a Raschel net, comprising at least one cord, the
cord
comprising at least one composite elongated body according to the invention,
preferably one, two or three composite elongated bodies. In another
embodiment, the
net according to the invention is a Raschel net, comprising at least two
cords, each
cord comprising one, two or three composite elongated bodies, for example at
least
one cord as the warp yarn and at least one cord as the weft yarn. In another
embodiment, the net is a knitted knotless net made from three composite
elongated
bodies. A practical upper limit of the number of composite elongated bodies
per cord is
three. If the cords in a Raschel net, comprise more than on composite
elongated body,
such cord usually comprises parallel composite elongated bodies.
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
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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.
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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:
a) providing a rope, a chain or a belt according to the invention;
b) connecting the rope, the chain or the belt to the object to be lifted; and
c) using the rope, the chain or the belt to lift and/or place the object.
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
a) providing a rope as defined herein;
b) connecting the rope to the object to be lifted; and
c) using the rope to lift and/or place the object.
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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.
Embodiments:
1. A composite elongated body (3), comprising high performance polyethylene
(HPPE) filaments (2) having a tenacity of at least 0.6 N/tex and a polymeric
composition throughout (10) the composite elongated body, wherein the
polymeric composition comprises:
i. a thermoplastic ethylene copolymer and
ii. a lubricant;
and wherein the thermoplastic ethylene copolymer is a copolymer of
ethylene and wherein said polymeric composition 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.
2. A composite elongated body (3), comprising
- a yarn (1), said yarn comprising at least two high performance polyethylene
HPPE filaments (2) having a tenacity of at least 0.6 N/tex; and
- a polymeric composition (10) throughout the composite elongated body,
wherein
the polymeric composition comprises
i. a thermoplastic ethylene copolymer and
ii. a lubricant;
and wherein the thermoplastic ethylene copolymer is a copolymer of ethylene
and
wherein said polymeric composition has a peak melting temperature in the range
from 40 to 140 C.
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3. A composite elongated body, according to any preceding embodiment, wherein
said polymeric composition has a density as measured according to IS01183-04
in the range from 860 to 970 kg/m3.
4. A composite elongated body, according to any preceding embodiment, wherein
said polymeric composition has a heat of fusion of at least 5 J/g.
5. The composite elongated body according to any preceding embodiment, wherein
said polymeric composition has a peak melting temperature in the range from 50
to 120 C.
6. The composite elongated body according to any preceding embodiment, wherein
the peak melting temperature is the melting temperature of highest melting
peak.
7. The composite elongated body according to any preceding embodiment, wherein
the thermoplastic ethylene copolymer comprises an ethylene-propylene co-
polymer.
8. The composite elongated body according to any preceding embodiment, wherein
the thermoplastic ethylene copolymer comprises an ethylene copolymer with co-
monomers such as 1-butene, isobutylene.
9. The composite elongated body according to any preceding embodiment, wherein
the thermoplastic ethylene copolymer comprises an ethylene copolymer with co-
monomers which contain at least one hetero atom such as acrylic acid,
methacrylic acid, vinyl acetate, maleic anhydride, ethyl acrylate, methyl
acrylate.
10. The composite elongated body according to any preceding embodiment,
wherein
the thermoplastic ethylene copolymer comprises an a-olefin copolymer or a
cyclic
olefin copolymer, or a blend thereof.
11. The composite elongated body according to any preceding embodiment,
wherein
the thermoplastic ethylene copolymer comprises a copolymer of ethylene and
contains as co-monomers one or more olefins having 2 to 12 C-atoms, preferably
ethylene, propylene, isobutene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-
octene, acrylic acid, methacrylic acid or vinyl acetate.
12. The composite elongated body according to any preceding embodiment,
wherein
the thermoplastic ethylene copolymer is an ethylene-propylene co-polymer.
13. The composite elongated body according to any preceding embodiment,
wherein
the thermoplastic ethylene copolymer is an ethylene copolymer with co-
monomers such as 1-butene, isobutylene.
14. The composite elongated body according to any preceding embodiment,
wherein
the thermoplastic ethylene copolymer is an ethylene copolymer with co-
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monomers which contain at least one hetero atom such as acrylic acid,
methacrylic acid, vinyl acetate, maleic anhydride, ethyl acrylate, methyl
acrylate.
15. The composite elongated body according to any preceding embodiment,
wherein
the thermoplastic ethylene copolymer is an a-olefin copolymer or a cyclic
olefin
copolymer, or a blend thereof.
16. The composite elongated body according to any preceding embodiment,
wherein
the thermoplastic ethylene copolymer is a copolymer of ethylene and contains
as
co-monomers one or more olefins having 2 to 12 C-atoms, preferably ethylene,
propylene, isobutene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene,
acrylic
acid, methacrylic acid or vinyl acetate.
17. The composite elongated body according to any preceding embodiment,
wherein
thermoplastic ethylene copolymer is made via copolymerization of ethylene with
ethylenically unsaturated monomers.
18. The composite elongated body according to any preceding embodiment,
wherein
the ethylenically unsaturated monomer comprises oxygen and/or nitrogen atoms.
19. The composite elongated body according to any preceding embodiment,
wherein
the ethylenically unsaturated monomer comprises a carboxylic acid group or
derivatives thereof resulting in an acylated polymer.
20. The composite elongated body according to any preceding embodiment,
wherein
the density of the thermoplastic ethylene copolymer is in the range from 860
to
970 kg/m3 as measured according to IS01183-04.
21. The composite elongated body according to any preceding embodiment,
wherein
the density of the thermoplastic ethylene copolymer is in the range from 870
to
930 kg/m3 as measured according to IS01183-04.
22. The composite elongated body according to any preceding embodiment,
wherein
the density of the thermoplastic ethylene copolymer is in the range from 870
to
920 kg/m3 as measured according to IS01183-04
23. The composite elongated body according to any preceding embodiment,
wherein
the density of the thermoplastic ethylene copolymer is in the range from 875
to
910 kg/m3 as measured according to IS01183-04.
24. The composite elongated body according to any preceding embodiment,
wherein
the density of the thermoplastic ethylene copolymer is in the range from 875
to
900 kg/m3 as measured according to IS01183-04.
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25. The composite elongated body according to any preceding embodiment,
wherein
the density of the polymeric composition is in the range from 870 to 930 kg/m3
as
measured according to IS01183-04.
26. The composite elongated body according to any preceding embodiment,
wherein
the density of the polymeric composition is in the range from 870 to 920 kg/m3
as
measured according to IS01183-04.
27. The composite elongated body according to any preceding embodiment,
wherein
the density of the polymeric composition is in the range from 875 to 910 kg/m3
as
measured according to IS01183-04.
28. The composite elongated body according to any preceding embodiment,
wherein
the density of the polymeric composition is in the range from 875 to 900 kg/m3
as
measured according to IS01183-04.
29. The composite elongated body according to any preceding embodiment,
wherein
the lubricant comprises: a wax including a synthetic wax such as PE and PP
wax,
an animal wax such as beeswax, a plant wax such as carnauba wax; a synthetic
grease or oils; a mineral grease or oils; 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.
30. The composite elongated body according to any preceding embodiment,
wherein
the composite elongated body comprises:
a) 55-95 mass% of high-performance polyethylene filaments;
b) 5-45 mass% of the thermoplastic ethylene copolymer having a peak
melting temperature measured according to ASTM E794-06 of 40-140 C;
c) 5-45 mass% lubricant; and
d) 0-5.0 mass% of additives;
wherein the sum of components a)-d) is 100 mass%.
31. The composite elongated body according to any preceding embodiment,
wherein
the composite elongated body comprises:
a) 70-85 mass% of high-performance polyethylene filaments;
b) 7.5-30 mass% of the thermoplastic ethylene copolymer having a peak
melting temperature measured according to ASTM E794-06 of 40-140 C;
c) 7.5-25 mass% lubricant; and
d) 0-5.0 mass% of additives;
wherein the sum of components a)-d) is 100 mass%.
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32. The composite elongated body according to any preceding embodiment,
wherein
ratio of component b) and c) in the coating composition, on solid content
basis, is
from 1:1 to 1:10, preferably from 1:1 to 1:5.
33. The composite elongated body according to any preceding embodiment,
wherein
ratio of component b) and c) in the coating composition, on solid content
basis, is
from 1:1 to 1:5.
34. The composite elongated body according to any preceding embodiment,
wherein
ratio of component b) and c) in the coating composition, on solid content
basis, is
from 1:1.5 to 1:4.
35. The composite elongated body according to any preceding embodiment,
wherein
ratio of component b) and c) in the coating composition, on solid content
basis, is
from 1:2 to 1:1.35.
36. The composite elongated body according to any preceding embodiment,
wherein
the peak melting temperature of the polymeric composition is in the range from
50
to 130 C, preferably wherein the peak melting temperature is in the range from
60
to 120 C.
37. The composite elongated body according to any preceding embodiment wherein
the heat of fusion of the polymeric composition is at least 10 J/g.
38. The composite elongated body according to any preceding embodiment wherein
the heat of fusion of the polymeric composition is at least 15 J/g, preferably
the
heat of fusion is at least 20 J/g.
39. The composite elongated body according to any preceding embodiment,
preferably wherein the heat of fusion of the polymeric composition is at least
30
J/g, preferably at least 50 J/g.
40. The composite elongated body according to any preceding embodiment wherein
the heat of fusion of the polymeric composition is at most 280 J/g, preferably
at
most 200 J/g.
41. The composite elongated body according to any preceding embodiment,
wherein
the thermoplastic ethylene copolymer is a semi-crystalline polyolefin having a
peak melting temperature in the range from 40 to 140 C and a heat of fusion of
at
least 5 J/g, measured in accordance with ASTM E794-06 and ASTM E793-85,
respectively, considering the second heating curve at a heating rate of 10
K/min,
on a dry sample.
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42. The composite elongated body according to any preceding embodiment,
wherein
the molecular weight of the thermoplastic ethylene copolymer is 6000 Dalton or
more, preferably 8000 Dalton or more, as measured using SEC-MALS.
43. The composite elongated body according to any preceding embodiment,
wherein
the composite elongated body comprises an amount of polymeric composition in
the range of from 5 mass% to 45 mass% matrix based on the total weight of the
composite elongated body.
44. The composite elongated body according to any preceding embodiment,
wherein
the composite elongated body 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.
45. The composite elongated body according to any preceding embodiment,
wherein
the composite elongated body comprises at least two filaments.
46. The composite elongated body according to any preceding embodiment,
wherein
the composite elongated body comprises at least at least 20 filaments.
47. The composite elongated body according to any preceding embodiment,
wherein
the composite elongated body comprises at least at least 100 filaments,
preferably the composite elongated body comprises at least 200 filaments.
48. The composite elongated body according to any preceding embodiment,
wherein
the composite elongated body comprises at least 400 filaments, preferably the
composite elongated body comprises at least 800 filaments.
49. The composite elongated body according to any preceding embodiment,
wherein
the composite elongated body comprises at most 1500 filaments, preferably at
most 1200 filaments, more preferably at most 5000 filaments.
50. The composite elongated body according to any preceding embodiment,
wherein
the yarn comprises at least two HPPE filaments.
51. The composite elongated body according to any preceding embodiment,
wherein
the yarn comprises at least at least 20 filaments.
52. The composite elongated body according to any preceding embodiment,
wherein
the yarn comprises at least at least 100 filaments, preferably the yarn
comprises
at least 200 filaments.
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53. The composite elongated body according to any preceding embodiment,
wherein
the yarn comprises at least 400 filaments, preferably the composite elongated
body comprises at least 800 filaments.
54. The composite elongated body according to any preceding embodiment,
wherein
the yarn comprises at most 1500 filaments, preferably at most 1200 filaments,
more preferably at most 5000 filaments.
55. The composite elongated body according to any preceding embodiment,
wherein
the tenacity of the HPPE filaments is at least 1.0 N/tex
56. The composite elongated body according to any preceding embodiment,
wherein
the tenacity of the HPPE filaments is at least 1.5 N/tex, preferably at least
1.8
N/tex.
57. The composite elongated body according to any preceding embodiment,
wherein
the tenacity of the HPPE filaments is at least 2 N/tex, preferably at least 3
N/tex.
58. The composite elongated body according to any preceding embodiment,
wherein
the tenacity of the HPPE filaments is at least 3.5 N/tex, preferably at least
4 N/tex.
59. The composite elongated body according to any preceding embodiment,
wherein
the tenacity of the HPPE filaments is at least 2.8 N/tex, preferably at least
3.2
N/tex and more preferably at least 3.5 N/tex.
60. The composite elongated body according to any preceding embodiment,
wherein
the tenacity of the HPPE filaments is at most 6.0 N/tex, preferably at most
5.5
N/tex and more preferably at most 5.0 N/tex.
61. The composite elongated body according to any preceding embodiment,
wherein
the HPPE filaments comprise ultrahigh molecular weight (UHMWPE).
62. The composite elongated body according to any preceding embodiment,
wherein
the HPPE filaments are ultrahigh molecular weight (UHMWPE) filaments.
63. The composite elongated body according to any preceding embodiment,
wherein
the UHMWPE has an IV between 4 and 40 dL/g, preferably between 6 and 30
dL/g and most preferably between 8 and 25 dL/g.
64. The composite elongated body according to any preceding embodiment,
wherein
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.
65. The composite elongated body according to any preceding embodiment,
wherein
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
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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.
66. The composite elongated body according to any preceding embodiment,
wherein
the SCB are C1-C2o-hydrocarbyl groups, preferably the C1-C2o-hydrocarbyl group
is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl,
hexyl,
octyl and cyclohexyl, isomers thereof and mixtures thereof.
67. The composite elongated body according to any preceding embodiment,
wherein the composite elongated body comprises at least 70 mass% UHMWPE,
based on the total weight of the composite elongated body.
68. The composite elongated body according to any preceding embodiment,
wherein
the composite elongated body comprises at least 75 mass% of UHMWPE, based
on the total weight of the composite elongated body, preferably at least
80 mass% of UHMWPE, based on the total weight of the composite elongated
body.
69. The composite elongated body according to any preceding embodiment,
wherein
the composite elongated body comprises at least 85 mass% of UHMWPE, based
on the total weight of the composite elongated body, preferably at least
90 mass% of UHMWPE, based on the total weight of the composite elongated
body.
70. The composite elongated body according to any preceding embodiment,
wherein
a minimum creep rate of a multifilament HPPE yarn, comprising the high
performance polyethylene HPPE filaments of at least 0.6 N/tex, determined as
described in the METHOD section is at most 1 x 10-5 % per second as measured
at a tension of 900 MPa and a temperature of 30 C.
71. The composite elongated body according to any preceding embodiment,
wherein
the minimum creep rate is at most 4 x 10-6 % per second, preferably at most 2
x
10-6% per second, measured at a tension of 900 MPa and a temperature of
C.
72. The composite elongated body according to any preceding embodiment,
wherein
30 the minimum creep rate is at least about 1 x 10-10 % per second as
measured at a
tension of 900 MPa and a temperature of 30 C.
73. The composite elongated body according to any preceding embodiment,
wherein
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
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microscopy, such as a SEM (Scanning Electron Microscopy), analysis of the
surface and/or of a cross section of the composite elongated body.
74. The composite elongated body according to any preceding embodiment,
wherein
the polymeric composition covers at least 70% of the total surface of the HPPE
filaments of the composite elongated body.
75. The composite elongated body according to any preceding embodiment,
wherein
the polymeric composition covers at least 80% of the total surface of the HPPE
filaments of the composite elongated body, preferably at least 90% of the
total
surface of the HPPE filaments of the composite elongated body.
76. The composite elongated body according to any preceding embodiment wherein
the elongated body has a length dimension (Ld) which is much greater than a
transverse dimension (Td) of width and of thickness.
77. The composite elongated body according to any preceding embodiment wherein
the 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 500 times
greater
than the width or thickness dimension of the composite elongated body,
whichever is larger.
78. The composite elongated body according to any preceding embodiment wherein
the composite elongated body has cross section having a rectangular shape, an
oval shape, a circular shape, a hexagonal or an octagonal shape.
79. A lengthy body comprising the composite elongated body according to any
preceding embodiments.
80. The lengthy body according to any preceding embodiment wherein the lengthy
body is selected from a strand, a cable, a cord, a rope, a belt, a strip, a
hose and
a tube.
81. A rope comprising at least three composite elongated bodies according to
any
preceding embodiment.
82. The rope according to any preceding embodiment demonstrating an improved
bending performance as compared with a reference rope, preferably wherein the
reference rope is a rope without the polymeric composition as defined in any
preceding embodiment.
83. The rope according to any preceding embodiment demonstrating 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
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preceding embodiment and lacking the lubricant as defined in any preceding
embodiment.
84. A belt comprising at least three composite elongated bodies according to
any
preceding embodiment.
85. The belt according to any preceding embodiment demonstrating an improved
bending performance as compared with a reference belt, preferably wherein the
reference belt is a belt without the polymeric composition as defined in any
preceding embodiment.
86. The belt according to any preceding embodiment demonstrating 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 in any preceding
embodiment.
87. An article comprising at least one lengthy body according to any preceding
embodiment.
88. An article comprising at least one composite elongated body according to
any
preceding embodiment.
89. The article according to any preceding embodiment wherein the article is a
net,
for example a fishing net or an aquaculture net (typically to grow fish); a
sling; a
synthetic chain link; a synthetic chain or a tendon.
90. The article according to any preceding embodiment wherein the article is a
personal protection item (such as a helmet or a body panel) or a knitted glove
comprising at least one composite elongated body as described herein.
91. A lift system or crane comprising a sheave and the lengthy body according
to any
preceding embodiment.
92. A lift system or crane comprising a winch and the lengthy body according
to any
preceding embodiment.
93. A lift system or crane comprising a sheave and the belt according to any
preceding embodiment.
94. A lift system or crane comprising a winch and the belt according to any
preceding
embodiment.
95. A lift system or crane comprising a sheave and the rope according to any
preceding embodiment.
96. A lift system or crane comprising a winch and the rope according to any
preceding embodiment.
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97. A method of manufacturing a composite elongated body comprising the steps:
a) providing a coating composition, wherein the composition comprises
i. a thermoplastic ethylene copolymer as defined in any preceding
embodiment; and
ii. a lubricant as defined in any preceding embodiment;
b) providing a yarn comprising at least two HPPE filaments as defined in
any
preceding embodiments;
c) applying the coating composition to the yarn to obtain a coated yarn;
and
d) exposing the coated yarn to elevated temperature obtain the composite
elongated body;
wherein the high molecular weight thermoplastic ethylene copolymer is a
copolymer of ethylene and wherein said thermoplastic ethylene copolymer has a
peak melting temperature in the range from 40 to 140 C.
98. The method of manufacturing a composite elongated body according to any
preceding embodiment wherein in step d) the coating composition is dried and
the thermoplastic ethylene copolymer melts.
99. The method of manufacturing a composite elongated body according to any
preceding embodiment, wherein the temperature in step d) is in the range from
the melting temperature of the thermoplastic ethylene copolymer to 153 C to at
least partially melt the thermoplastic ethylene copolymer.
100.The method of manufacturing a composite elongated body according to any
preceding embodiment, wherein upon completion of steps a), b), c) and d) the
polymeric composition is present throughout the composite elongated body.
101.The method of manufacturing a composite elongated body according to any
preceding embodiment, wherein upon completion of steps a), b), c) and d) the
thermoplastic ethylene copolymer and the lubricant are present throughout the
composite elongated body.
102.The method of manufacturing a composite elongated body according to any
preceding embodiment, wherein the process comprises an additional step: e)
shaping the composite elongated body by transporting it at the end of the oven
through a die having a shape, to obtain the composite elongated body having a
cross-sectional shape corresponding to the shape of the die.
103.The method of manufacturing a composite elongated body according to any
preceding embodiment, wherein the method comprises a drying step before step
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d) and wherein the drying conditions in this step include temperatures of from
40
to 130 C, preferably from 50t0 120 C.
104.The method of manufacturing a composite elongated body according to any
preceding embodiment, wherein the temperature in step d) is at least 2 C above
the peak melting temperature of the thermoplastic ethylene copolymer.
105.The method of manufacturing a composite elongated body according to any
preceding embodiment, wherein the temperature in step d) is at least 5 C above
the peak melting temperature of the thermoplastic ethylene copolymer.
106.The method of manufacturing a composite elongated body according to any
preceding embodiment, wherein the temperature in step d) is at most 150 C.
107.The method of manufacturing a composite elongated body according to any
preceding embodiment wherein the temperature in step d) is at least 5 C above
the peak melting temperature of the thermoplastic ethylene copolymer and at
most 145 C.
108.The method of manufacturing a composite elongated body according to any
preceding embodiment wherein the temperature in step d) is at least 10 C above
the peak melting temperature of the thermoplastic ethylene copolymer and at
most 140 C.
109.The method of manufacturing a composite elongated body according to any
preceding embodiment, wherein step d) is combined with the drying step.
110.The method of manufacturing a composite elongated body according to any
preceding embodiment, wherein in step d) a temperature gradient is applied to
the coated yarn whereby the temperature is raised from about room temperature
to the maximum temperature this step.
111.The method of manufacturing a composite elongated body according to any
preceding embodiment, wherein in step d) the yarn is kept in an oven for from
2
to 100 seconds, preferably from 3 to 60 seconds, more preferably from 4 to 30
seconds.
112.The method of manufacturing a composite elongated body according to any
preceding embodiment, wherein 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.
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113.The method of manufacturing a composite elongated body according to any
preceding embodiment, wherein the HPPE filaments are prepared by a melt
spinning process or a gel spinning process.
114.The method of manufacturing a composite elongated body according to any
preceding embodiment, wherein the concentration of thermoplastic ethylene
copolymer in the coating composition is between 5 and 50 mass%, whereby the
weight percentage is the weight of thermoplastic ethylene copolymer in the
total
weight of the coating composition, preferably concentration of thermoplastic
ethylene copolymer in the coating composition is between 6 and 40 mass%,
whereby the weight percentage is the weight of thermoplastic ethylene
copolymer
in the total weight of the coating composition.
115.The method of manufacturing a composite elongated body according to any
preceding embodiment, wherein the high performance polyethylene (HPPE)
filaments have a tenacity of at least 1.0 N/tex.
116.The method of manufacturing a composite elongated body according to any
preceding embodiment, wherein the HPPE filaments have a tenacity of 1.5 N/tex,
preferably have a tenacity of at least 1.8 N/tex, preferably at least 2.5
N/tex and
more preferably at least 3.5 N/tex.
117.The method of manufacturing a composite elongated body according to any
preceding embodiment, wherein the amount of thermoplastic ethylene copolymer
in the composite elongated body is from 1 to 25 mass%, whereby the weight
percentage is the weight of thermoplastic ethylene copolymer in the total
weight
of the composite elongated body.
118.The method of manufacturing a composite elongated body according to any
preceding embodiment, wherein the amount of thermoplastic ethylene copolymer
in the composite elongated body is from 2 to 20 mass%, preferably from 4 to
18 mass%, whereby the weight percentage is the weight of thermoplastic
ethylene copolymer in the total weight of the composite elongated body.
119.The method of manufacturing a composite elongated body according to any
preceding embodiment wherein the density of the thermoplastic ethylene
copolymer is in the range from 870 to 930 kg/m3
120.The method of manufacturing a composite elongated body according to any
preceding embodiment wherein the density of the thermoplastic ethylene
copolymer is in the range from 875 to 900 kg/m3.
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121.The method of manufacturing a composite elongated body according to any
preceding embodiment wherein the thermoplastic ethylene copolymer has a heat
of fusion of at least 5 J/g.
122.The method of manufacturing a composite elongated body according to any
preceding embodiment wherein the peak melting temperature of the
thermoplastic ethylene copolymer is in the range from 50 to 130 C, preferably
in
the range from 60 to 120 C.
123.The method of manufacturing a composite elongated body according to any
preceding embodiment the peak melting temperature is the melting temperature
of highest melting peak.
124.The method of manufacturing a composite elongated body according to any
preceding embodiment wherein the heat of fusion of the thermoplastic ethylene
copolymer is at least 10 J/g.
125.The method of manufacturing a composite elongated body according to any
preceding embodiment wherein the heat of fusion of the thermoplastic ethylene
copolymer is at least 15 J/g, preferably the heat of fusion is at least 20
J/g.
126.The method of manufacturing a composite elongated body according to any
preceding embodiment wherein the heat of fusion of the thermoplastic ethylene
copolymer is at most 280 J/g, preferably at most 200 J/g.
127.The method of manufacturing a composite elongated body according to any
preceding embodiment wherein the coating composition is applied to the
filaments by spraying, dipping, brushing or transfer rolling.
128.The method of manufacturing a composite elongated body according to any
preceding embodiment, wherein the coating composition is an aqueous
composition comprising at least 40 mass% water,
129.The method of manufacturing a composite elongated body according to any
preceding embodiment, wherein the coating composition is an aqueous
composition comprising at least 50 mass%, preferably at least 60 mass% water.
130.The method of manufacturing a composite elongated body according to any
preceding embodiment, wherein the coating composition is an aqueous
composition comprising at least 70 mass%, preferably at least 80 mass%, most
preferably at least 90 mass% water.
131. The method of manufacturing a composite elongated body according to any
preceding embodiment, wherein the coating composition is an aqueous
composition as described herein.
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132.The method of manufacturing a composite elongated body according to any
preceding embodiment wherein the coating composition is an aqueous
suspension or aqueous dispersion.
133.The method of manufacturing a composite elongated body according to any
preceding embodiment, wherein the coating composition is a solvent based
composition, preferably comprising toluene, hexane, heptane or a mixture
thereof.
134.A composite elongated body obtainable by the method according to any of
the
preceding embodiments comprising HPPE filaments as defined in any of the
preceding embodiments, and a polymeric composition as defined in any
preceding embodiment throughout the composite elongated body.
135.A method of manufacturing a lengthy body comprising the step of assembling
at
least two composite elongated bodies according to any preceding embodiment to
form the lengthy body.
136.The method of manufacturing a lengthy body according to any preceding
embodiment, wherein the lengthy body is a strand, a cable, a cord, a rope, a
belt,
a strip, a hose or a tube.
137.A method of manufacturing an article comprising the step of providing the
lengthy
body according to any preceding embodiment and generating the article.
138.A method of manufacturing an article comprising the step of providing the
composite elongated body according to any preceding embodiment and
generating the article.
139.The method of manufacturing an article according to any preceding
embodiment,
wherein the article is a net, for example a fishing net or an aquaculture net
(typically to grow fish); a round sling; a synthetic chain link; a synthetic
chain; or a
tendon.
140.The method of manufacturing an article according to any preceding
embodiment,
wherein the article is a personal protection item (such as a helmet or a body
panel) or a glove.
141.A method of lifting and / or placement of an object comprising the steps
a) providing a rope according to any preceding embodiment;
b) connecting the rope to the object to be lifted; and
c) using the rope to lift and/or place the object.
142.A method of lifting and / or placement of an object comprising the steps
a) providing a sling according to any preceding embodiment;
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b) connecting the sling to the object to be lifted; and
c) using the sling to lift and/or place the object.
143.A method of lifting and / or placement of an object comprising the steps
a) providing a chain according to any preceding embodiment;
b) connecting the chain to the object to be lifted; and
c) using the chain to lift and/or place the object.
144. Use of the coating composition as defined in any one of the preceding
embodiments to improve bending performance of a rope or belt.
145. Use of the polymeric composition as defined in any one of the preceding
embodiments to improve bending performance of a rope or belt compared to a
rope of belt without such polymeric composition.
146. Use of the coating composition as defined in any one of the preceding
embodiments to improve fairlead abrasion of a rope or belt.
147. Use of the coating composition as defined in any one of the preceding
embodiments to improve abrasion performance of a rope or belt.
148. Use of the polymeric composition as defined in any one of the preceding
embodiments to reduce abrasion of a rope or belt compared to a rope of belt
without such polymeric composition.
FIGURE DESCRIPTION
Figure la schematically depicts a cross section of a yarn (1)
comprising high performance polyethylene HPPE filaments (2) having a tenacity
of at
least 0.6 N/tex.
Figure lb schematically depicts a yarn (1) comprising high
performance polyethylene HPPE filaments (2) having a tenacity of at least 0.6
N/tex
having a length dimension (Ld) which is much greater than a transverse
dimension (Td)
of width and of thickness.
Figure lc schematically depicts a cross section of a composite
elongated body according to the invention comprising high performance
polyethylene
HPPE filaments (2) having a tenacity of at least 0.6 N/tex and a polymeric
composition
throughout (10) the composite elongated body. The composite elongated body
comprises said polymeric composition, more specifically the polymeric
composition is
present in between the filaments of the composite elongated body.
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The polymeric composition is present throughout the cross-section of the
composite
elongated body and in intimate contact with the at least one filament, i.e.
with the individual filaments. In an even more preferred embodiment the
polymeric
composition impregnates the filaments; in other words: the polymeric
composition is
present throughout the cross-section of the composite elongated body. Hereby
is
understood that the polymeric composition is present in between substantially
all the
filaments of the composite elongated body. Preferably at least 50% of the
surface of
the filaments of the composite elongated body in contact with the polymeric
composition, more preferably at least 70% and most preferably 90% of the
filament
surface is in contact with the polymeric composition. A way to look at this
may be via a
microscopic image of a cross section of the composite elongated body and see
which % of the filament surface is in contact with the polymeric composition.
Figure 2 schematically depicts a Cyclic bend-over-sheave (CBOS)
test set-up for a 5 mm rope. Details are given below in the METHODS. Fig 2B
depicts a
schematic "see through" of the inside of the schematic frame (24) in Fig. 2A.
F
represents the direction of the Tension (MPa).
Figure 3 schematically depicts a Cyclic bend-over-sheave (CBOS)
test set-up for a 21 mm rope. Details are given below in the METHODS.
Figure 4 schematically depicts a fairlead abrasion test set-up. Details
are given below in the METHODS.
Figure 5 schematically depicts a cross section of a composite
elongated body (53) according to the invention comprising high performance
polyethylene HPPE filaments (52) having a tenacity of at least 0.6 N/tex and a
polymeric composition throughout (50) the composite elongated body. In an
embodiment the composite elongated body may have cross section having a
rectangular shape (54), an oval shape (52), a circular shape (55), a hexagonal
(56) or
an octagonal shape.
Figure 6 schematically depicts an embodiments of a chain according
to the invention. The chain (60) comprises at least two interconnected chain
links (61).
The chain link comprises a strip (62). The strip is typically a narrow webbing
comprising
at least at least two composite elongated bodies (not shown in detail). The
strip of
material in this embodiment forms a plurality of convolutions of said strip,
the strip
having a longitudinal axis and each convolution of said strip comprising a
twist along
the longitudinal axis of said strip, said twist being an odd multiple of 180
degrees. Such
a chain link is described in the published patent application W02013186206,
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incorporated herein by reference. By a "convolution" of the strip is herein
understood a
loop thereof, also called a winding or a coiling, i.e. a length of said strip
starting at an
arbitrary plane perpendicular to the longitudinal axis of the strip and ending
in an
endless fashion at the same plane, thereby defining a loop of said strip. The
term
"plurality of convolutions" may also be understood herein as "coiled into a
plurality of
overlapping layers". Said overlapping layers of the strip are preferably
substantially
superimposed upon one another but may also present a lateral offset. The
convolutions
may be in direct contact to each other but may also be separated. Separation
between
the convolutions may for example be by a further strip of material, an
adhesive layer or
a coating. Preferably, the chain link in the chain according to the present
invention
comprises at least 2 convolutions of the strip of material, preferably at
least 3, more
preferably at least 4, most preferably at least 8 convolutions. The maximum
number of
convolutions is not specifically limited. For practical reasons 1000
convolutions may be
considered as an upper limit. Each convolution of the strip of material may
comprise a
twist of an odd multiple of 180 degrees along its longitudinal axis;
preferably the odd
multiple is one. Said twist of an odd multiple of 180 degrees will result in a
chain link
comprising a twist of an odd multiple of 180 degrees along its longitudinal
axis. The
presence of said twist in each convolution of the strip of material results in
a chain link
with a single outer surface. Another characteristic of said construction may
be that the
lateral surfaces of a first end of the strip of material are superimposed on
either side by
the convoluted strip of material. It was observed that said twist results in a
construction
such that the convolutions lock themselves against relative shifting.
Preferably, at least
2 convolutions of the strip of material are connected to each other by at
least one
fastening means.
Figure 7 schematically depicts an embodiment of a chain according to
the invention. The chain (70) comprises at least two interconnected chain
links (71).
The chain links comprise at least at least two composite elongated bodies (not
shown
in detail).
Figure 8a represents an example of a knotless warp-knitted net
(Raschel Knotless net) (80), comprising cords (81), each cord comprises a
single
composite elongated body (81), the cords form mesh legs (indicated with ovals
85) and
joints. The joints are formed from intermingled cords (indicated within ovals
82 and 83:
two mesh legs are formed into a joint). The mesh size (length) is indicated by
arrow
(84). In another embodiment the cord comprises at least two composite
elongated
bodies, typically 2 to 3 composite elongated bodies.
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Figure 8b shows schematically that mesh size (84) of a knotless net
is measured as the length between the 2 opposite joints of a stretched mesh.
Figure 9 schematically depicts a rope (90) according to the invention
comprising laid strands (91), the strands comprise at least three composite
elongated
bodies (not shown in detail) according to the invention. The outer surface of
the rope is
indicated with 92.
Figure 10 schematically depicts a rope (100) according to the
invention comprising twelve braided strands (101), the strands comprise the
composite
elongated body (not shown in detail) according to the invention. The outer
surface of
the rope is indicated with 102.
Figure 11 shows a SEM picture of a surface of a composite elongated
body.
Figure 12 is described in the METHODS under Tensile properties of
HPPE filaments.
Figure 13 is described in the METHODS under Coefficient of Friction.
METHODS
= Titer was measured by weighing an arbitrary length of yarn or filament,
respectively. The titer of the yarn or filament was calculated by dividing the
weight
by the length and is reported in either tex or dtex expressing the weight in
gram
per 100,000 m or 10,000 m respectively. The length of yarn or filament
measured
is typically 50 meters.
= Heat of fusion and peak melting temperature have been measured according
to
standard DSC methods ASTM E 793-85 and ASTM E 794-06, respectively, at a
heating rate of 10 K/min for the second heating curve and performed under
nitrogen on a dehydrated sample. In such DSC measurement a part of the full
composite elongated composition (including HPPE filaments) can be measured.
The peaks from HPPE and coating are sufficiently well separated so the Tm and
heat of fusion of coating can be determined directly.
= Coating percentage The amount of polymeric composition in the composite
elongated body according to the invention (coating percentage) may be
determined as follows.
A sample of 1.0 gram of composite elongated body is taken. The polymeric
composition in the sample is extracted from the composite elongated body via a
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warm Soxhlet extraction: refluxing with toluene containing 5% acetic acid (150
ml),
for 16 hours. After extraction the remainder of the sample is dried for 2.5
hours at
80 C in vacuum. By weighing the sample before and after the extraction
process,
the coating percentage can be calculated using the following formula:
Coating percentage = (1-(M_after_extraction/M_before_extraction))*100%
In which M_after_extraction is the mass of the sample after extraction and
drying
as described above and M_before_extraction is the mass of the sample before
extraction and drying as described above.
= Density The density of the polymeric composition is measured according to
ISO
1183-04. The density of the thermoplastic ethylene copolymer is measured
according to ISO 1183-04.
Immersion method (A) and more preferably density gradient column method (B)
are suitable for the present products. It is noted that ISO 1183-1:2004 covers
three
methods, and that 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
measured. Depending on what the scraped off product looks like, any of the
corresponding methods listed in the ISO 1183-2004 may be used.
It is noted that the density of the thermoplastic ethylene copolymer will
typically be
provided by the supplier will provide this information e.g. in the
specification of the
product.
= IV: the Intrinsic Viscosity is determined according to method ASTM
D1601(2004)
at 135 C in decalin, the dissolution time being 16 hours, with BHT (Butylated
Hydroxy Toluene) as anti-oxidant in an amount of 2 g/I solution, by
extrapolating
the viscosity as measured at different concentrations to zero concentration.
= Tensile properties of HPPE filaments: filament tenacity and filament
tensile
modulus:
Determination of filament linear density and mechanical properties is carried
out on
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a semiautomatic, microprocessor controlled tensile tester (Favimat, tester no.
37074, from Textechno Herbert Stein GmbH & Co. KG, Monchengladbach,
Germany) which works according to the principle of constant rate of extension
(DIN 51 221, DIN 53 816, ISO 5079) with integrated measuring head for linear
density measurement according to the vibroscopic testing principle using
constant
tensile force and gauge length and variable exciting frequency (ASTM D 1577).
The Favimat tester is equipped with a 1200 cN balance, no. 14408989. The
version number of the Favimat software: 3.2Ø
Clamp slippage during filament tensile testing, preventing filament fracture,
is
eliminated by adaption of the Favimat clamps of the Favimat according to
figure
12.
The upper clamp 121 is attached to the load cell (not shown). The lower clamp
122
moves in downward direction (D) with selected tensile testing speed during the
tensile test. The filament (125) to be tested, at each of the two clamps, is
clamped
between two jaw faces 123 (4x4x2 mm) made from Plexiglass and wrapped
three times over ceramic pins 124. Prior to tensile testing, the linear
density of the
filament length between the ceramic pins is determined vibroscopically.
Determination of filament linear density is carried out at a filament gauge
length (F)
of 50 mm (see figure 12), at a pretension of 2.50 cN/tex (using the expected
filament linear density calculated from yarn linear density and number of
filaments). Subsequently, the tensile test is performed at a test speed of the
lower
clamp of 25 mm/min with a pretension of 0.50 cN/tex, and the filament tenacity
is
calculated from the measured force at break and the vibroscopically determined
filament linear density. The elongational strain is determined by using the
whole
filament length between the upper and lower plexiglass jaw faces at the
defined
pretension of 0.50 cN/tex. The beginning of the stress-strain curve shows
generally
some slackness and therefore the modulus is calculated as a chord modulus
between two stress levels. The Chord Modulus between e.g. 10 and 15 cN/dtex is
given by equation (1):
Chord Modulus between 10 and 15 cN/dtex = CM(10 :15) = 50 (N/tex)
(1)
15 - 10
where:
Eio = elongational strain at a stress of 10 cN/dtex ( /0); and
15 = elongational strain at a stress of 15 cN/dtex ( /0).
The measured elongation at break is corrected for slackness as given by
equation
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(2):
50
EAB = EAB (measured) - (6, (2)
CM (5 : 10)
where:
EAB = the corrected elongation at break ( /0)
EAB (measured) = the measured elongation at break (%)
5 = elongational strain at a stress of 5 cN/dtex ( /0)
CM(5:10) = Chord Modulus between 5 and 10 cN/dtex (N/tex).
= Tensile properties of HPPE yarns: tensile strength (or tenacity) and
tensile
modulus (or modulus) of a yarn are defined and determined on multifilament
yarns
as specified in ASTM D885M (1995), using a nominal gauge length of the yarn of
500 mm, a crosshead speed of 50 %/min and lnstron 2714 clamps, of type "Fibre
Grip D5618C". On the basis of the measured stress-strain curve the modulus is
determined as the gradient between 0.3 and 1 % strain using a pretension of
0.2
cN/tex. For calculation of the modulus and strength, the tensile forces
measured
are divided by the titre, as determined above; values in GPa are calculated
assuming a density of 0.97 g/cm3 for the HPPE.
= Tensile strength and tensile modulus at break of the thermoplastic
ethylene
copolymer may be measured according ISO 527-2.
= Short chain branches per 1000 total carbon (SCB/1000TC):
is determined by NMR techniques and IR methods calibrated thereon. As an
example the amount of methyl, ethyl or butyl short side chains are identical
to the
amounts of methyl side groups per thousand carbon atoms contained by the
UHMWPE as determined by proton 1H liquid-NMR, hereafter for simplicity NMR,
as follows:
¨ 3 - 5 mg of UHMWPE are added to a 800 mg 1,1',2,2-tetracholoroethane-d2
(TCE) solution containing 0.04 mg 2,6-di-tert-butyl-paracresol (DBPC) per
gram TCE. The purity of TCE is > 99.5 % and of DBPC > 99 /0.
¨ The UHMWPE solution is placed in a standard 5 mm NMR tube which is then
heated in an oven at a temperature between 140 - 150 C while agitating until
the UHMWPE is dissolved.
¨ The NMR spectrum is recorded at 130 C e.g. with a high field 400 MHz NMR
spectrometer using an 5 mm inverse probehead and set up as follows: a
sample spinrate of between 10 - 15 Hz, the observed nucleus -1H, the lock
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nucleus - 2H, a pulse angle of 90 , a relaxation delay of 30 sec, the number
of
scans is set to 1000, a sweep width of 20 ppm, a digital resolution for the
NMR
spectrum of lower than 0.5, a total number of points in the acquired spectrum
of 64k and a line broadening of 0.3 Hz.
¨ The recorded signal intensity (arbitrary units) vs. the chemical shift
(ppm),
hereafter spectrum 1, is calibrated by setting the peak corresponding to TCE
at 5.91 ppm.
¨ After calibration, the two peaks (doublet) of about equal intensity are
used to
determine the amount of methyl side groups are the highest in the ppm range
between 0.8 and 0.9 ppm. The first peak should be positioned at about 0.85
ppm and the second at about 0.86 ppm.
¨ The deconvolution of the peaks is performed using a standard ACD software
produced by ACD/Labs;
¨ The accurate determination of the areas Al methyl side groups ,hereafter
Al of the
deconvoluted peaks used to determine the amount of methyl side groups, i.e.
Al = Al first peak + Al second peak is computed with the same software.
¨ The amounts of methyl side groups per thousand carbon atoms, is computed
as
follows:
1000 x Al
3 .
methyl side groups = 2><
Al + A2 + A3
¨ wherein A2 is the area of the three peaks of the methyl end groups which are
the second highest in the ppm range between 0.8 and 0.9 and are located
after the second peak of the methyl side groups towards increasing the ppm
range and wherein A3 is the area of the peak given by the CH2 groups of the
main UHMWPE chain, being the highest peak in the entire spectrum and
located in the ppm range of between 1.2 and 1.4.
= Minimum creep rate of yarns may be determined as described in the
published patent
application W02016001158. In particular as described in the section
"Stabilizing
creep and minimum creep rate in the fibers" of W02016001158. The minimum creep
rate of the yarns has been derived therein from a creep measurement applied on
multifilament yarns by applying ASTM D885M (1995) standard method under a
constant load of 900 MPa, at a temperature of 30 C and then measuring the
creep
response (i.e. strain elongation, /0) as a function of time. The minimum
creep rate
is determined by the first derivative of creep as function of time, at which
this first
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derivative has the lowest value (e.g. the creep rate [1/s] of the yarn is
plotted as
function of strain elongation [ /0] of the yarn in a so-called known Sherby
and Down
diagram.)
= Coefficient of friction The set-up of the equipment to measure the
coefficient of
friction is schematically depicted in Figure 13a. Figure 13b depicts a cross
section
of one of the sheaves from Figure 13a, the cross section is given along the X-
Y
area in Figure 13a. The coefficient of friction of a 5 mm diameter rope (131)
with
respect to metal was measured by running the rope in a machine over two
sheaves (132, 133) made from tool steel 1.2709 (roughness Ra 0.215 0.002
(n=3)), one of which was blocked (132) to prevent rotation (see Figure 13).
Water
of 23 C ran through the blocked sheave (132), the Relative Humidity in the
room
was 50%. Sheave diameter (D) of each of the sheaves (132, 133) was 99 mm. The
radius of the groove (136) of each of the sheaves was 3 mm. A force was
applied
between the two sheaves using two pneumatic cylinders (134, only one is shown)
both connected to opposite sides of the freely rotating sheave (133) such that
the
rope was loaded with a load of 3750 N. The rope was then moved over the
sheaves at a speed of 2750 mm/min by means of a slider (135) to which the rope
is connected, and which slider is moved along the Y-axis. The force required
to
move the rope was measured, and using Eq 1 the coefficient of friction was
calculated
1 Fbraid Fmeasured)
it
¨ ln(
Fbraid
Where pi. is the coefficient of friction, Fbraid is the force in the braid
(3750 N), and
Fmeasured is the measured force required to move the rope over the stationary
and
moving sheave at the defined speed.
Before measuring the coefficient of friction, the rope was loaded to 7750N for
60
seconds by means of increasing the pressure in the pneumatic cylinders and
subsequently unloaded by means of increasing and decreasing pressure in the
pneumatic cylinders to remove constructional elongation. Subsequently, the
measurement of the coefficient of friction was performed by moving the slider
(135)
350 mm down and thereafter 350 mm up. This is one cycle. For each rope 3
cycles
were measured. The average force during the second cycle was used to calculate
the coefficient of friction.
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= CBOS 5 mm test (test set-up is schematically depicted in Figure 2): 6
bends per
machine cycle, rope diameter 5 mm, D/d 10, Tension 510 MPa (Load: 30%
Minimum Breaking Load), in wet environment (water cooling: ambient temperature
water sprayed (Fig. 2a ¨ item 25) at bending zone area of the top sheave (21).
The cyclic bending over sheave (CBOS) performance was tested. Within this test
the rope (20) is bend over three rolling sheaves (21, 22, 23) each having a
diameter
of 50 mm. The three sheaves were positioned in an upside-down V-formation on a
frame (24). The rope was placed over the sheaves in such way that the rope has
a
bending zone at each of the sheaves. The rope was placed under a specific load
(30% MBL). The frame with the sheaves is cycled back and forth (indicated with
an
arrow (G)) during which the rope is exposed to cyclic bending over sheaves
until the rope reaches failure (= break). One machine cycle represents the
frame
with the sheaves going back and forth once. This means that one machine cycle
represents 6 bends (3 bends a time). The stroke length (L, see Fig 2c, is the
distance
from start(S) to end (E)) of the rope was 45 cm long. The cycling period was 5
seconds per machine cycle.
One machine cycle contains a straight bend (90 ) at A, reverse bend (180 ) at
B,
followed by straight bend (90 ) at C. Rope is alternately bend in opposite
directions,
one full cycle exists of 4 (90 ) straight bends and 2 (180 ) reverse bends.
One full
cycle is 2 stroke lengths long.
= Cyclic bend-over-sheave (CBOS) 21 mm-A test (test set-up is schematically
depicted in Figure 3): rope diameter 21 mm, D/d 20. CBOS test: the bend
fatigue
of the rope was tested by bending the rope over a sheave. This is
schematically
depicted in Figure 3. The test rope (30) was configured in an endless loop
construction, meaning both rope ends have been connected with use of a splice
termination. The loop had a circumference of about 6.5 m. The splice
termination
(often referred also to as a tucked splice) had an amount of tucks of 9 per
rope
side. Both splice-ends were not tapered. This loop was positioned over the
large
sheave on top (traction sheave (31)) and small bending sheave (32) in the
bottom
of the machine.
The rope was placed under load (Tension 280 MPa (this is 18% of the MBL)) and
cycled back and forward over the sheave, at a stroke speed of 210 m/min, until
the
rope reached failure. Each machine cycle produced two straight-bent-straight
bending cycles of the exposed rope section, the double bend zone. The double
bend zone was approximately 14 times the diameter of the rope. The bending
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cycle time was 12 seconds per machine cycle (1 cycle is back and forth) , in
dry
environment (no water cooling). The pause was 1 second between each cycle
reversal. The pre-load for bedding in the rope was 5 times 14.5 metric tons.
= Cyclic bend-over-sheave (CBOS) 21 mm-B test: the same as for CBOS 21mm-A
above but with Tension 370 MPa.
= Fairlead 10 mm test: rope diameter 10 mm, 2 abrasion cycles per machine
cycle,
36 seconds per machine cycle - C2 fairlead (DIN 81915) D/d 20, Tension 380 MPa
(Load: 25% MBL), in dry environment (no water cooling).
The fairlead abrasion performance was tested. This is schematically depicted
in
Figure 4. Within this test the rope (40) is moved under a specific load (1800
kg) over
a fairlead (41). One machine cycle represents the rope being pulled over the
surface
back and forth once. The rope was cycled back and forth until failure. The
cycling
period was 36 seconds per machine cycle. The stroke length of the rope was 56
cm
long.
EXPERIMENTS
The following examples are given by way of non-limiting reference only.
MATERIALS
ParameltTM 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 Michem prime 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.
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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.
Manufacturing of the coating compositions for Ex. 1-6
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.
Manufacturing of a composite elongated body
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 By, 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).
Manufacturing of a 5 mm rope
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.
Manufacturing of a 10 mm 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
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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.
Fairlead test
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.
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Table 1
Example No. Polyethylene Lubricant Solids Coefficient
Fairlead
copolymer base nnatrix:solids of friction
abrasion
matrix lubricant cycles
Comp. Ex. 1 X2050 None N/A 0.13 11.5
Ex. 1. X2050 Aquacer 1:1 0.10 25
2650
Ex. 2. X2050 NeoRez R- 3:7 0.13 26
2180
Ex. 3. X2050 NeoCryl A- 1:3 0.11 28
668
Ex. 4. X2050 NeoCryl A- 1:1 0.12 18
668
Comp. Ex. 2. MP2960 None N/A 0.13 23.5
Ex. 5. MP2960 Aquacer 1:1 0.12 48.3
2700
Ex. 6. MP2960 Aquacer 1:1 0.07 29
2650
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.
