Patent Application
20080095875
UHMWPE: ultra-high molecular weight polyethylene
PB: polypyridobisimidazole, represented by the formula:
wherein N is a nitrogen atom, H is a hydrogen atom, and O is an oxgyen atom. The number of repeating units, n, is not critical. Preferably, each polymer chain has from 10 to 25,000 repeating units, n.
dpf: denier per filament
Da: Dalton, unit of molecular weight
For purposes herein, the term “filament” is defined as a relatively flexible, macroscopically homogeneous body having a high ratio of length to width across its cross-sectional area perpendicular to its length. The filament cross section can be any shape, but is typically circular. Herein, the term “fibre” is used interchangeably with the term “filament”.
The expressions “larger”, “smaller”, “largest”, “smallest” and “medium” in relation to a filament or plurality of filaments refers to the average diameter or linear density of the filament or plurality of filaments.
“Diameter” in reference to a filament is the diameter of the smallest circle that can be drawn to circumscribe the entire cross-section of the filament. In reference to a hole in a spinneret, it refers to the smallest circle that can be drawn to circumscribe the hole.
“Denier” the weight in grams per 9,000 m length of filament or yarn.
“Tex” the weight in grams of one kilometre of filament or yarn.
“Decitex” one tenth of a Tex.
The expressions “capillary” and “extrusion hole” are used interchangeably to mean the holes through which polymer is extruded in the formation of filaments.
The yarns produced from the spinnerets of the invention, having mixed average diameter filaments, show increased cut- and abrasion-resistance, as compared to conventional yarns comprising filaments of a single average diameter. It is believed that the mixed diameter arrangement has excellent cut- and abrasion-resistance for two main reasons:
The inventors have chosen to refer to these yarns as being made of filaments having different average diameters. The expression “average diameter” can be replaced with the expression “linear density” for an alternate definition of the yarns. It is equally possible to refer to the yarns as being made up of filaments having different linear densities. The yarns may be referred to as “mixed filament yarns”, “mixed denier yarns” and/or “mixed dtex yarns”.
For p-aramid (e.g., Kevlar®), average diameter of a filament can be converted to linear density approximately as shown below:
The yarns made with the spinnerets of the present invention may be made with filaments made from any polymer that produces a high-strength fibre, including, for example, polyamides, polyolefins, polyazoles, and mixtures of these.
When the polymer is polyamide, aramid is preferred. By aramid is meant a polyamide wherein at least 85% of the amide (—CONH—) linkages are attached directly to two aromatic rings. Suitable aramid fibres are described in Man-Made Fibres—Science and Technology, Volume 2, Section titled Fibre-Forming Aromatic Polyamides, page 297, W. Black et al., Interscience Publishers, 1968. Aramid fibres and their production are, also, disclosed in U.S. Pat. Nos. 4,172,938; 3,869,429; 3,819,587; 3,673,143; 3,354,127; and 3,094,511.
The preferred aramid is a para-aramid. The preferred para-aramid is poly(p-phenylene terephthalamide) which is called PPD-T. By PPD-T is meant the homopolymer resulting from mole-for-mole polymerization of p-phenylene diamine and terephthaloyl chloride and, also, copolymers resulting from incorporation of small amounts of other diamines with the p-phenylene diamine and of small amounts of other diacid chlorides with the terephthaloyl chloride. As a general rule, other diamines and other diacid chlorides can be used in amounts up to as much as about 10 mole percent of the p-phenylene diamine or the terephthaloyl chloride, or perhaps slightly higher, provided only that the other diamines and diacid chlorides have no reactive groups which interfere with the polymerization reaction. PPD-T, also, means copolymers resulting from incorporation of other aromatic diamines and other aromatic diacid chlorides such as, for example, 2,6-naphthaloyl chloride or chloro- or dichloroterephthaloyl chloride or 3,4′-diaminodiphenylether.
Additives can be used with the aramid and it has been found that up to as much as 10 percent or more, by weight, of other polymeric material can be blended with the aramid. Copolymers can be used having as much as 10 percent or more of other diamine substituted for the diamine of the aramid or as much as 10 percent or more of other diacid chloride substituted for the diacid chloride or the aramid.
When the polymer is polyolefin, polyethylene or polypropylene are preferred. By polyethylene is meant a predominantly linear polyethylene material of preferably more than one million molecular weight that may contain minor amounts of chain branching or comonomers not exceeding 5 modifying units per 100 main chain carbon atoms, and that may also contain admixed therewith not more than about 50 weight percent of one or more polymeric additives such as alkene-1-polymers, in particular low density polyethylene, propylene, and the like, or low molecular weight additives such as anti-oxidants, lubricants, ultra-violet screening agents, colorants and the like which are commonly incorporated. Such is commonly known as extended chain polyethylene (ECPE) or ultra high molecular weight polyethylene (UHMWPE). Preparation of polyethylene fibers is discussed in U.S. Pat. Nos. 4,478,083, 4,228,118, 4,276,348 and Japanese Patents 60-047,922, 64-008,732. High molecular weight linear polyolefin fibres are commercially available. Preparation of polyolefin fibres is discussed in U.S. Pat. No. 4,457,985.
When the polymer is polyazole, suitable polyazoles are polybenzazoles, polypyridazoles and polyoxadiaoles. Suitable polyazoles include homopolymers and, also, copolymers. Additives can be used with the polyazoles and up to as much as 10 percent, by weight, of other polymeric material can be blended with the polyazoles. Also copolymers can be used having as much as 10 percent or more of other monomer substituted for a monomer of the polyazoles. Suitable polyazole homopolymers and copolymers can be made by known procedures, such as those described in U.S. Pat. No. 4,533,693 (to Wolfe, et al., on Aug. 6, 1985), U.S. Pat. No. 4,703,103 (to Wolfe, et al., on Oct. 27, 1987), U.S. Pat. No. 5,089,591 (to Gregory, et al., on Feb. 18, 1992), U.S. Pat. No. 4,772,678 (Sybert, et al., on Sep. 20, 1988), U.S. Pat. No. 4,847,350 (to Harris, et al., on Aug. 11, 1992), and U.S. Pat. No. 5,276,128 (to Rosenberg, et al., on Jan. 4, 1994).
Preferred polybenzazoles are polyzimidazoles, polybenxothiazoles, and polybenzoxazoles. If the polybenzazole is a polyzimidazoles, preferably it is poly[5,5′-bi-1H-benzimidazole]-2,2′-diyl-1,3-phenylene which is called PBI. If the polybenzazole is a polybenxothiazole, preferably it is a polybenxobisthiazole and more preferably it is poly(benxo[1,2-d:4,5-d′]bisthiazole-2,6-diyl-1,4-phene which is called PBT. If the polybenzazole is a polybenzoxazole, preferably it is a polybenzobisoxazole and more preferably it is poly(benzo[1,2-d:4,5-d′]bisoxazole-2,6-diyl-1,4-phenylene which is called PBO.
Preferred polypyridazoles are rigid rod polypyridobisazoles including poly(pyridobisimidazole), poly(pyridobisthiazole), and poly(pyridobisozazole). The preferred poly(pyridobisozazole) is poly(1,4-(2,5-dihydroxy)phenylene-2,6-pyrido[2,3-d:5,6-d′]bisimidazole which is called PB. Suitable polypyridobisazoles can be made by known procedures, such as those described in U.S. Pat. No. 5,674,969.
Preferred polyoxadiaoles include polyoxadizaole homopolymers and copolymers in which at least 50% on a molar basis of the chemical units between coupling functional groups are cyclic aromatic or heterocyclic aromatic ring units. A preferred polyoxadizaole is Oxalon®.
Although mixed dtex yarns can be made by “off-line assembly”, that is, the different denier filaments can be assembled after spinning, a continuous filament yarn produced by direct spinning (i.e., using a spinneret having different size holes to produce directly a yarn having mixed dtex filaments) is preferred. Off-line assembly is less preferred than direct spinning since it can lead to segregation of the filaments of different diameters, resulting in a non-homogeneous yarn which has less resistance to attacking forces.
The continuous filament mixed diameter yarns are made using a spinneret having holes of different diameters. Holes of smaller diameter will yield lower diameter filaments, and holes of larger diameter will yield larger diameter filaments. The arrangement of the larger holes with respect to the smaller holes in the spinneret is not of particular importance, however, it is advantageous to have smaller diameter filaments sandwiched between larger diameter filaments, as this maximizes rolling action of the filaments. In a preferred arrangement, the arrangement of holes in the spinneret is in the form of concentric circles, the whole forming a large circular array of holes. The holes toward the centre of the array are the smaller diameter holes, and those towards the circumference of the array are the larger diameter holes. Examples of different kinds of spinneret hole arrangements are shown in
The cross-section of the filaments used in mixed dtex yarns may be, for example, circular, elliptical, multi-lobed, “star-shaped” (refers to an irregular shape having a plurality of arms coming off a central body), and trapezoidal. The holes in the spinneret are chosen according to the desired filament diameter and cross-section.
The “linear density” of the filament is determined by the rate (mass/time) at which polymer is extruded through a spinneret hole vs. the rate (speed, or linear distance/time) at which the filament is produced. The size (diameter) of the filament is a function of the polymer density and the fiber “linear density”. The number of holes in a spinneret (or section of a spinneret) is determined by the number of filaments desired in the final fiber bundle (“linear density” of which is the sum of the individual filaments contained therein). The size and shape of each hole in the spinneret is influenced by the pressure-drop, shear, spin-stretch, and orientation needed to produce the desired filament diameter. In a preferred embodiment of the p-aramid spinneret, the smaller holes have a diameter of between at or about 35-65 microns, more preferably at or about 50 microns, and the larger holes have a diameter between at or about 60 to 90 microns, more preferably at or about 64 microns. Preferably the ratio between the diameter of the larger holes to that of the smaller holes is at or about 1.2 to at or about 3, more preferably at or about 1.3 to 2.5. To make a yarn having three different diameter filaments, a spinneret may be used, for example, in which the holes are in the following ranges: smallest 35 to 65 microns (preferably 45-55 microns), medium 64-80 microns, largest 75 to 90 microns.
The spinneret is made of material suited to the polymer or polymer solution or suspension that will be spun. For p-aramid spun from concentrated H2SO4, preferred material are tantalum, tantalum-tungsten alloys, and gold-platinum (rhodium) alloys. Other materials which may be used include high grade stainless steels [i.e., with a high chromium (>15 wt %) and/or nickel (>30 wt %) content], such as Hastelloy® C-276, ceramics and nanostructures made with ceramics. p-Aramid spinnerets may also be made from mixed materials, such as pure tantalum clad on a tantalum-tungsten alloy. Materials other than tantalum can be used for the cladding layer so long as they have the required corrosion resistance and annealed yield strengths of less than 30,000 psi (2,110 kg/cm2). Among such suitable materials, listed in order of increasing hardness, are gold, M-metal (90% gold/10% rhodium by weight), C-metal (69.5% gold/30% platinum/0.5% rhodium by weight), D-metal (59.9% gold/40.0% platinum/0.1% rhenium by weight), and Z-metal (50.0% gold/49.0% platinum/1.0% rhodium by weight). The latter was substantially the same hardness as tantalum. Also suitable is a 75% gold/25% platinum alloy. All of these metals are, however, much more expensive than tantalum. All but Z-metal are much more easily damaged in use than tantalum. Softer materials are advantageous, however, when capillaries of quite high L/D ratio (e.g., greater than 3.5) are to be formed.
The polymer is extruded, either as a solution, suspension or melt, through the spinneret, and the resulting filaments are spun into yarn and treated in a manner suitable for the particular polymer.
A group of filaments may be classified as having the same average diameter if the deviation of the average diameter of any filament in the group from the average is less than at or about 0.4 micron.
In a preferred embodiment, two sizes of filaments make up the yarn. In this case, it is preferred that the smaller filaments have an average diameter in the range of at or about 8 to 22 microns, and the larger filaments have an average diameter in the range of at or about 16 to 32 microns. Although these ranges overlap, it is understood that the smaller and larger filaments are chosen to have different average diameters, such that the average diameter of the smaller filaments is smaller than the average diameter of the larger filaments. For example, included in the invention is a yarn having smaller filaments with average diameter of at or about 8 microns together with larger filaments having average diameter of at or about 16 microns, and a yarn having smaller filaments with average diameter of at or about 22 microns together with larger filaments having average diameter of at or about 32 microns.
In yarns consisting of two sizes of filaments, it is preferred that the smaller filaments not differ from the larger filaments by more than a factor of at or about 2, more preferably not more than a factor of at or about 1.5. If the filaments differ too much in size, segregation can occur, leading to nonhomogeneity and reduced cut-resistance. Preferably the ratio of the diameter of the larger filaments to the smaller filaments is at or about 1.3-1.5.
In those embodiments in which the yarn is made up of filaments having two different average diameters, the second plurality of filaments (i.e., larger average diameter) make up from at or about 20 to 60% (by number) of the filaments in the yarn, and the first plurality of filaments (i.e., smaller diameter) make up from at or about 40 to 80% (by number) of the filaments in the yarn. More preferably the larger diameter filaments make up from at or about 45 to 55% (by number) of the filaments in the yarn, and the smaller diameter filaments make up from at or about 45 to 55% (by number) of the filaments in the yarn.
In another preferred embodiment, three sizes of filaments make up the yarn. In this case, it is preferred that the smallest filaments have an average diameter in the range of at or about 4 to 10 microns (more preferably at or about 6 to 9 microns), the medium filaments have an average diameter in the range of at or about 10 to 13 microns, and the largest filaments have an average diameter in the range of at or about 14 to 18 microns. For example, an advantageous result is obtained with a yarn made up of filaments having the following average diameters: 8, 12 and 16 microns. In those yarns having three sizes of filaments, preferably the ratio of the average diameter of smallest:medium:largest is at or about 2:6:8, more preferably at or about 2:3:4.
In those embodiments in which the yarn is made up of filaments having three different average diameters (linear densities), the third plurality of filaments (i.e. the largest) make up at or about 15 to 35% (by number) of the filaments in the yarn, the second plurality of filaments (i.e., the medium) make up at or about 30 to 45% (by number) of the filaments in the yarn, and the first plurality of filaments (i.e., the smallest) make up from at or about 30 to 45% (by number) of the filaments in the yarn.
In other preferred embodiments, the yarn is made up of four, five, six or more sizes of filaments.
In a further embodiment, referred to as “continuous”, the yarn consists of a largest filament or group of filaments (e.g., average diameter of at or about 15-40 microns) and a smallest filament or group of filaments (e.g. average diameter of at or about 4-25 microns) wherein the largest filament (or group of filaments) and the smallest filament (or group of filaments) have different average diameters, and a plurality of filaments having average diameters distributed between the average diameter of the largest filament and the smallest filament. With such an arrangement, very high packing densities (>90%) can be obtained, resulting in highly cut-resistant yarns.
The size of the holes in the spinneret influences the average diameter of the extruded filaments. The tension used to draw the filaments (drawing) also influences the average diameter of the filaments and the characteristics of the finished yarn. Drawing reduces the average diameter of the filaments.
By adjusting the velocity of the fibre as it leaves the coagulating bath to higher than the velocity of the polymer as it emerges from the spinning holes one can adjust various physical properties of the filament such as its tenacity, modulus and elongation, and also its diameter. The ratio of the two speeds here referred to, is called spin-stretch in p-aramids in which the filament is set in the coagulation batch and drawing ratio when referring to a fiber such as UHMWPE which is extended substantially after the fiber is quenched. High drawing ratio achievable with UHMWPE can reach up to 50-100 times. With p-aramid a typical spin-stretch ratio is approximately 2 to 14.
The filaments making up the mixed dtex yarns may have a substantially circular cross-section. A circular cross-section maximizes the “rolling” of the filaments with respect to each other, thus maximizing cut-resistance. A circular cross-section also maximizes the packing density, also beneficial for cut-resistance. In alternative embodiments, the cross-section of the filaments may be elliptical. It is also possible for the smaller filaments to be circular in cross-section and the large filaments to be elliptical in cross-section, or vice versa. The cross-section of the filaments is influenced by the shape of the holes in the spinneret, with round holes resulting in a circular cross-section, and elliptical holes resulting in an elliptical cross-section. It is also influenced by the internal capillary shape, grooves and channels parallel or helicoidally arranged. Further, it is influenced by the coagulation process; for instance, m-aramid (e.g., Nomex®) filaments typically have a two-lobe “dog-bone” shape when dry spun, or are multi-lobed, or “star shaped” when wet spun, since the skin is solidified before the solvent is extracted from the core, and the contracted area does not “fill” the perimeter.
The yarn preferably has a tenacity of at or about 15 to 40 g/denier, more preferably at or about 25 to 35 g/denier.
The yarn of the invention preferably has an elongation at break of at or about 1.5 to 15%, more preferably at or about 2 to 4%.
The yarn preferably has a modulus of elasticity of at or about 5 to 450 N/tex, more preferably at or about 50 to 400 N/tex.
In a preferred embodiment, the yarn has a tenacity of at or about 25 to 35 g/denier, an elongation at break of from at or about 2 to 4%, and a modulus of elasticity of from at or about 50 to 400 N/tex.
The number of filaments making up the yarn is not limited, and depends on the end-use, and the linear density required in the final yarn. Typical yarns comprise from 16 to 1500 total filaments. In a preferred embodiment, the total number of filaments in the yarn is 276, of which 45-55% (in number) are the smaller filaments and 45-55% (in number) are the larger filaments.
In yarns of the invention having a third plurality of filaments, with greater average diameter than the first and second plurality of filaments, an example would be 276 total filaments in the yarn, with 25-50% (by number) being the smallest filaments, 25-50% (by number) being the medium filaments and 15-35% (by number) being the largest filaments.
The multi-dtex yarn made from the spinnerets of the invention preferably has a maximum possible packing density of at or about 80 to 95%, more preferably at or about 90 to 95%. Cross section and packing density can be measured by immobilizing the fibre under a relatively small tension in an epoxy resin placed in a cylindrical mould perforated at the bottom to allow passage of the fibre flow of the resin. The molded sample is then cured at room temperature for 12 hours. The sample is then frozen in liquid nitrogen for one minute and a cut transverse to the fibre axis is made to realize image analysis and diameter measurement and void ratio evaluation under SEM microscope enlargement. The sample preparation used is well know for scanning microscopy except that polishing is avoided.
Packing density is influenced by the relative diameters (i.e., linear density) of the filaments, and the ratio of the number of first plurality of filaments (i.e., smaller) to the number of the second plurality of filaments (i.e., larger). Yarns having a ratio of first plurality of filaments to second plurality of filaments of at or about 0.5 (i.e., 50% by number smaller filaments and 50% by number larger filaments), and a large difference in average diameter between the filaments (large:small at or about 2) will typically have a high packing density (e.g. preferably greater than 90%, typically 90 to 95%). In addition, yarns made in the “continuous” embodiment also have high packing densities.
With a filament mix comprising 57 filaments of 12 micron in the centre, 115 filaments of 8 micron concentrically positioned around the first layer, then another 58 filaments of 12 micron concentrically positioned around the second layer and 46 filaments of 16 micron externally positioned around the third layer, one can obtained a packing density of approximately 90%.
The multi-dtex yarn is particularly suited to making cut-, abrasion- and penetration-resistant fabrics, having excellent comfort characteristics. Such fabrics may be made by braiding, knitting or weaving techniques known in the art. Fabrics made from the yarns of the invention may be used for making cut-, abrasion- and penetration-resistant garments, for example, gloves, footwear, coveralls, trousers and shirts, as well as parts of garments that require particular cut-, abrasion- and penetration-resistance, such as the palms of gloves, cuffs of trousers, coveralls or shirts. Such articles may be coated with various resins and elastomers.
Additionally, multi-dtex yarns may be incorporated in unidirectional protective structures, in which largely unidirectional (parallel) yarns are imbedded or partially imbedded in an immobilizing medium, such as a resin and elastomers.
Temperature: All temperatures are measured in degrees Celsius (° C).
Denier is determined according to ASTM D 1577 and is the linear density of a fibre as expressed as weight in grams of 9000 meters of fibre. The denier can be measured on a Vibroscope from Textechno of Munich, Germany. Denier times (10/9) is equal to decitex (dtex).
Referring to
After the polymer solution batch was made, a 5 cm3 meter pump (16) was used to transfer the solution through a flow plate (22) and a screen pack (20), shown in
Referring to
The inventive sample was made from a yarn of 400 denier out of a spinneret as depicted in
The yarn was knitted to yield a sample of areal density of about 400 g/m2.
The control sample was made using yarn made exactly as specified above, but the spinneret had only one size hole and yielded only 1.5 dpf (about 12 micron in diameter) filaments. The resulting yarn was 400 denier and consisted exclusively of 1.5 dpf filaments. The yarn was knitted to yield a sample of areal density of about 400 g/m2.
The abrasive cut testing procedure was based on the EN388:1994 (Protective gloves against mechanical risks) current procedure, which was modified in terms of the weight force applied onto the circular blade, i.e., instead of a 5N equivalent force a 2.9N equivalent force was applied, thereby permitting an increased number of cut cycles, which promotes abrasion.
The procedure is described in the EN document. It can be summarized as follows:
Two layers of a rectangular shaped sample (approx. 80 by 100 mm), one on the top of the other, were tested simultaneously. A load of 2.9N instead of 5N was positioned in its dedicated position. The test specimen sat on a support covered by a conductive rubber. The horizontal movement of the circular rotating blade was 50 mm long. The resulting linear peripheral speed was 10 cm/s. The cut tester was equipped with an automated electro-conductive system, which detected cuts throughout the specimen.
The blade sharpness was checked at the beginning and between each sample testing using a cotton standard fabric as per specification of EN388-1994 procedure.
Based on the number of cycles and a proposed calculation, provided in the EN388-1994, a cut level was computed, whereby a cut level between 0 to 5 was determined, 0 being the lowest achievable cut protection level, and 5 being the highest.
The inventive sample required more than 300 cycles to cut through, whereas the control one made of 100% identical filaments required less than 150 cycles to cut through.
