ENHANCED FABRIC
20190031882 ยท 2019-01-31
Inventors
Cpc classification
D06M23/06
TEXTILES; PAPER
D06M23/08
TEXTILES; PAPER
C03C25/47
CHEMISTRY; METALLURGY
C09D1/00
CHEMISTRY; METALLURGY
D06M11/46
TEXTILES; PAPER
D06M23/10
TEXTILES; PAPER
International classification
C09D1/00
CHEMISTRY; METALLURGY
D06M11/46
TEXTILES; PAPER
D06M23/08
TEXTILES; PAPER
C03C25/47
CHEMISTRY; METALLURGY
Abstract
A method is disclosed for treating a fabric (107) to improve its mechanical properties, comprising coating the fabric (107) with a liquid suspension of particles (102), and then drying the fabric (108). A fabric (108) comprising a woven or knitted arrangement of fibres (105) is disclosed, at least some of the fibres (105) being coated with particles (102), wherein the particles (102) comprise a surface treatment (103) to make the particles (102) hydrophobic.
Claims
1-40. (canceled)
41. A method of treating a fabric to improve its properties, comprising coating the fabric with a liquid suspension of particles, and then drying the fabric, wherein the liquid suspension comprises an organic non-polar solvent, and the particles comprise a surface treatment to make the particles hydrophobic.
42. The method of claim 41, wherein coating the fabric comprises one of: (i) spray coating the fabric with the liquid suspension; and (ii) depositing between 0.1% and 10% by weight of the dry particles, as a fraction of the total fabric weight after treatment.
43. The method of any of claim 42, comprising applying a further surface coating to the treated fabric.
44. The method of claim 43, wherein the further surface coating comprises polymeric material and represents less than 5% of the total fabric by weight.
45. The method of claim 41, wherein the fabric comprises at least one of: aramid fibres, carbon fibres, ultra-high molecular weight polymer fibres, glass fibres, wool fibres, cotton fibres.
46. The method of claim 41, wherein the organic non-polar solvent comprises Xylene, Pentane, Cyclopentane, Hexane, Cyclohexane, Benzene, Toluene, 1,4-Dioxane, Chloroform, Diethyl ether, Dichloromethane.
47. The method of claim 41, wherein the surface treatment is derived from dodecenylsuccinic anhydride, DDSA.
48. The method of claim 41, comprising surface treating the particles to make them hydrophobic.
49. The method of claim 41, wherein the particles comprise at least one of: titanium dioxide, hydroxyapatite, silicon dioxide, ceria, zinc oxide, iron oxide, alumina, and tungsten oxide.
50. The method of claim 49, wherein the particles originate from an aqueous synthesis process comprising synthesising the particles with an aqueous synthesis process.
51. A method of preparing a liquid for treatment of a fabric, comprising: synthesising particles; and surface treating the particles to make the particles hydrophobic.
52. The method of claim 51, wherein synthesising the particles comprises synthesising the particle with an aqueous process using supercritical water.
53. The method of claim 52, further comprising extracting the hydrophobic particles into an organic non-polar solvent.
54. The method of claim 53, wherein surface treating the particles comprises adding a surface treatment composition comprising a carboxylic anhydride having a hydrophobic tail to an aqueous suspension of the particles.
55. The method of claim 54, wherein the surface treatment composition is dissolved in a solvent before being added to the suspension and wherein the solvent comprises toluene.
56. The method of claim 52, wherein surface treating the particles comprises heating the aqueous suspension to at least 120 C. so produce carboxyl groups that bond with the particles.
57. The method of claim 41, further comprising making a garment using the treated fabric and wherein the garment comprises personal protective equipment.
58. The method of claim 51, wherein the fabric comprises fibres with a diameter of between 5 and 20 microns, and the particles have a median diameter that is selected to be less than half the diameter of the fibres.
59. A liquid for spray treating fabric to enhance the mechanical properties thereof, comprising a liquid suspension of particles, wherein the liquid suspension comprises an organic non-polar solvent, and the particles comprise a surface treatment to make them hydrophobic and wherein the particles comprise at least one of titanium dioxide, hydroxyapatite, silicon dioxide, ceria, zinc oxide, iron oxide(s) alumina, and tungsten oxide, and wherein the organic non-polar solvent comprises Xylene, Pentane, Cyclopentane, Hexane, Cyclohexane, Benzene, Toluene, 1,4-Dioxane, Chloroform, Diethyl ether, Dichloromethane.
60. The liquid of claim 59, wherein the particles comprise at least 50% by volume of: platelet shaped particles; spherical particles; or rod shaped particles.
61. The liquid of claim 60, wherein at least 50% by volume of the particles comprise rod or plate shaped particles with an aspect ratio of at least 5.
62. A fabric comprising a woven or knitted arrangement of fibres, at least some of the fibres being coated with particles, wherein the particles comprise a surface treatment to make the particles hydrophobic and comprising a loading of particles of between 0.1% and 10% by weight, and wherein the particles comprise titania and/or hydroxyapetite, and wherein the surface treatment comprises a polymer coating, disposed over the particles on the fabric.
63. The fabric of claim 62, wherein the surface treatment comprises at least 50% by weight of a molecule having at least one carboxylic acid group at one end, and a hydrophobic tail at the other, and wherein the molecule is derived from DDSA.
Description
[0058] Embodiments of the invention will now be described, purely by way of example, with reference to the accompanying drawings, in which:
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[0071] Particles for treating the fabric may be sourced from any suitable process. Preferably, the particles have a well-controlled morphology and size distribution, so that the performance of the treatment be maximised for a particular fabric. One process that is suitable is hydrothermal synthesis using supercritical water, and a process of this type was used to synthesise the particles in the below embodiments.
[0072] The reactor used to synthesise the particles may be a counter-flow reactor, in which superheated water is introduced in a downward direction into an upward counter current of a second aqueous reagent (such as a metal salt). To synthesise HA, an ammonium phosphate solution may be introduced as a heated flow from the top of the reactor and a calcium nitrate solution from the bottom. This allows the modification of the pH of the ammonium phosphate solution without altering the other precursor before the reaction point, leading to instant production of single phase, stoichiometric HA. The particle morphology depends on the pH conditions used, with plates being formed with a down-flow of pH 8 and rods with a downflow of pH 10.
[0073] For synthesis of titania particles, a single precursor (e.g. a titanium salt) may be introduced from the bottom of the reactor and mixed against a down-flow of supercritical water.
[0074] In order to apply the particles to untreated aramid fibres (e.g. Kevlar) in a way that results in the particles both being well dispersed and adhered, the particles may be surface modified to make them hydrophobic, and dispersed in a non-polar organic solvent.
[0075] In general, this can be achieved by introducing a surface treatment dissolved in a non-polar organic solvent to the flow within the reactor, before or after synthesis of the particles. The surface treatment functionalises the surface of the particles to make them hydrophobic, and the successfully treated particles are naturally extracted into the non-polar organic solvent. If the non-polar organic solvent is non-miscible with water, it is straightforward to separate it from the aqueous component of the output of the reactor, which can be discarded.
[0076] For example, the hydrophobic surface treatment may be formed by introducing dodecenylsuccinic anhydride (DDSA) following synthesis of the particles. DDSA may be delivered dissolved in toluene, mixing with the product stream after the reaction point and first cooler, but still within the pressurised system.
[0077] As shown in
[0078] Examples of suitable particles produced by the above process are shown in
[0079] The hydrophobic particles (with DDSA derived hydrophobic surface treatment) will naturally extract from the water in which they were synthesised into the non-polar toluene. Since toluene is immiscible with water, the final product naturally separates into two layers, with the organic phase containing the successfully hydrophobically functionalised particles.
[0080] After washing and drying, thermal analysis of particles showed DDSA contents of about 40.7, 24.2 and 12.3% wt. for HA plates, HA rods and titania nanoparticles respectively. Although the TiO.sub.2 nanoparticles have an increased specific surface area (200 m.sup.2g.sup.1 compared with around 20 m.sup.2g.sup.1 and 30 m.sup.2g.sup.1 for the HA plates and rods previously described), the HA particles showed higher loadings, which may be due to a greater tendency for covalent bonding with OH on the surface of HA.
[0081] The fabric may comprise aramid fibres such as Kevlar, or may comprise graphite/carbon fibres, high (or ultra-high) molecular weight polymer (such as polyethylene) fibres, or glass fibres. In the example embodiment, the untreated fabric comprised clean Kevlar fibres arranged in bundles to form yarns, the yarns being woven to define the fabric. In other embodiments the fabric may be knitted.
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[0083] In order to avoid the problems of with prior art dipping processes, a spray coating process may be used to add the particles to the fabric 107. Preferably, the hydrophobic functionalised particles are incorporated into an organic non-polar solvent (such as, Pentane, Cyclopentane, Hexane, Cyclohexane, Benzene, Toluene, 1,4-Dioxane, Chloroform, Diethyl ether, Dichloromethane), and then applied onto the fabric 107 (e.g. by spraying). The solvent is subsequently evaporated (e.g. in a drying process), leaving behind the particles. Non-polar solvents tend to wet the fibres of the fabric more readily, which results in a more uniform distribution of particles. The particles were found to adhere well to the aramid fabric used in the example embodiments, and it is expected that this will also apply for other types of fibre (e.g. carbon/graphite, glass, etc). The solvent in which the particles are suspended for spraying is preferably substantially non-toxic, so as to minimise the potential for any harmful residues.
[0084] In some embodiments, a polymer coating 104 may be applied to the fabric 108 after the particles 102 have been added.
[0085] In the example embodiments described below, shellac was used as a polymer coating, at loadings of up to 2.5% wt. with respect to the untreated fabric 107. The polymer coating process used preferably should be undertaken at room temperature, avoiding physical or chemical alteration of the fibres 105, with minimal diffusion of the polymer into the fabric.
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[0087] HA plates 102a were found to have a tendency to align on the surface, and form a crust-like coating. In contrast, HA rods 102b aligned substantially randomly across the surface of the yarns, while still being evenly distributed. Transmission electron microscopy (TEM) analysis of the particles showed that the titania particles were too small to be seen using a scanning electron microscope (SEM), at generally less than 20 nm in diameter. Samples that also included a polymer 104 did not show any visual difference with the polymer-free samples, which may indicate some degree of diffusion of the polymer into the layer of particles 102, or that the polymer coating was very thin and evenly distributed.
[0088] For the HA plates 102a, HA rods 102b and titania spheres 102c, an increase in material content led to two distinct types of coating: The ones with 0.1-0.5% wt increases, which seemed to be embedded onto the fibres' surface, somewhat like micro- or nano-texturing; and the samples with 2.5% loads (or higher), showing full coverage of the textile. All the samples that have been analysed using SEM were previously subject to cutting, bending and transport, and no cracks or peeling of the coatings was observed, indicating that the particles are well adhered.
[0089] One way to investigate the effect of the coatings on fabric performance is with a yarn pull-out test. Yarn pull-out is an important energy dissipation mechanism within fabrics where the yarns (e.g. tows) of bundled fibres are pulled through the yarn cross over points. For woven fabrics, the yarn pull-out is influenced by the yarn-to-yarn frictional properties. Increasing the inter-yarn friction (both static and dynamic) without premature yarn tensile failure is a feasible way to increase the total pull-out energy, enhancing the penetration and ballistic properties of a fabric.
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[0093] For the HA plates 102a, at the lowest loading (0.1% wt.) the particles 102a have little effect. The main increase in peak and plateau loads occurred for weight additions of 0.5% wt, wherein the peak load increased over 60% and the plateau load by over 90% (compared to 0.1% loading). The further increase to 2.5% loading only increased peak load by 19% and plateau load by 10% (compared to 0.5% loading). The less abrupt effect over frictional forces with loadings over 0.5% wt. are thought to be due to the tendency of the plates 102a to stack together flat on top of each other. This may mean that friction offered by the plates 102a results from the initial surface layer (in contact with the fibre 105), and is not improved by increased thickness of coating, as illustrated in
[0094] For the HA rod 102b treatment frictional improvements were almost linear with increasing particle load. A 0.5% loading of HA rods 102b resulted in a 23% increase in peak force (compared with uncoated Kelvar 210), and a 2.5% loading an increase of 134%. The enhanced yarn pull-out performance with rod particle morphology may be due to the random orientation of the rods at a microscopic level. As schematically illustrated in
[0095] The data (231-235, 243 and 263) for samples treated with titania particles shows a different character than the HA plates or HA rods. Even at the lowest weight increase of 0.1% wt there was a significant increase in peak and plateau loads, or 41% and 54% respectively (compared with uncoated Kelvar). This is due to the higher specific area of the titania particles, which provide more surface area to interact with the yarns 106 and fibres 105. A subsequent increase to 0.5% wt. loading did not show significant improvement in frictional forces, which could be due to frictional slippage between the particles of the coating. The overall friction in the 0.25% and 0.5% samples may come from the available surface of the TiO.sub.2 itself, which was similar independently of the coating content, but showed a shear thinning-like effect within the coating. Similar shear thinning behaviours have previously been observed for concentrated suspensions of spherical particles. At 1.25% and 2.5% wt titania, the yarn pull-out peak and plateau loads showed an abrupt increase (at 318% and 273% higher than uncoated Kevlar for the 2.5% wt. loading). This increase could have been because of shear thickening-like properties within the coating, where the TiO.sub.2 coatings comprising high specific surface area nano-particles thickened when stressed, as the individual particles clustered together, impeding the free movement of the translating yarn. This mechanism is schematically illustrated in
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[0098] For HA plates A), peak data for: no shellac 241, 0.1% shellac 244, 0.5% shellac 245 and 2.5% shellac 246 are shown, with uncoated Kevlar 240 as a reference point. HA plate plateau data are also shown for: no shellac 261, 0.1% shellac 264, 0.5% shellac 265 and 2.5% shellac 266, with uncoated Kevlar 260 as a reference point.
[0099] As expected from the low content of plates, the increase in peak and plateau loads in all the polymer-composite samples with 0.1% wt and 0.5% wt plates came only from the shellac coating. When the content of plates was increased to 2.5% wt, the heavier polymer coatings (0.5% and 2.5% wt shellac) shielded any effects from the hydroxyapatite. In contrast, 2.5% wt plates with 0.1% shellac showed higher pull-out forces, up to 118% and 164% greater than uncoated Kevlar, and ca. 100% and 140% more than the 0.1% shellac-only coated sample for peak and plateau loads respectively. It was unclear whether the polymer had soaked into the plates, as the SEM images of these samples did not show any obvious difference with the shellac-free analogous. Coatings with 2.5% shellac were used with this morphology to show that high polymer loadings tend to stop the nanoparticles underneath having any effect on yarn pull-out forces (the results are similar to what would be obtained with shellac alone).
[0100] For HA rods B), peak data for: no shellac 242, 0.1% shellac 247, and 0.5% shellac 248 are shown, with uncoated Kevlar 240 as a reference point. HA rod plateau data are also shown for: no shellac 262, 0.1% shellac 267 and 0.5% shellac 268, with uncoated Kevlar 260 as a reference point.
[0101] Composite samples of rods (1st coating) with a top layer of 0.5% wt shellac showed no obvious improvement when compared to the nanomaterial-free analogues. An advantage of the rods (with no shellac), was that they increased the yarn-to-yarn friction through random interactions between them when in motion/stressed. At this shellac content (0.5% wt), the rods were prevented from moving when the yarn was being pulled, which decreased the overall forces within the sample at all particle loadings. In contrast, when shellac was added as a 0.1% wt top layer, the frictional effect of the rods was maximised at rod contents of 0.5% wt, but not at 2.5% weight. The 0.5% wt rods with 0.1% wt shellac, proved to be an almost ideal combination where the shellac content increased the effect of the rods rather than annulling it. The 1:5 shellac:HA-rods ratio may have modified the way the rods interacted with each other and with the yarn being pulled. The polymer content may be high enough for the rods to be immobilised, but sufficient to increase the friction between them, the overall viscosity within the coating or the binding with the Kevlar. In addition, both peak and plateau loads were maximised, giving performances 212% and 231% higher than uncoated Kevlar. For top layers of 0.1% wt shellac, when the content of rods was increased from 0.5 to 2.5% wt, the performance was compromised because of the excess of rods for the amount of shellac used. This minimised any effect from the polymer layer, as shown in
[0102] For samples coated with titania nanoparticles (with substantially spherical morphology), further addition of shellac had little beneficial effects on the overall yarn pull-out performance of the fabrics, as shown in
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[0104] The pull-out data showed that coatings according to embodiments are very promising, offering large increases in performance at relatively low particle loadings. Dramatic improvements in stab resistance are to be expected from fabrics treated according to embodiments. Embodiments of the present invention are also expected to improve UV degradation properties and flame resistance of fabric materials.
[0105] A number of modifications and variations will be apparent to the skilled person, and the above embodiments are not intended to limit the scope of the invention, which is determined only by the appended claims.