PROTECTIVE FABRIC RESISTANT TO MOLTEN METAL SPLASH
20230045496 · 2023-02-09
Assignee
Inventors
Cpc classification
D03D15/283
TEXTILES; PAPER
D03D13/004
TEXTILES; PAPER
International classification
D03D15/283
TEXTILES; PAPER
Abstract
Flame resistant fabrics are provided that exhibit improved protection from molten metal spills, metal splatter, electric arc, and related thermal hazards illustratively including open flame and radiant heat. The flame resistant fabrics are made from a combination of cellulosic fibers and thermoplastic fibers, where the flame resistant fabric forms a char layer that does not become brittle when contacted by molten metal, metal splatter, electric arc, and related thermal hazards. By not becoming brittle the likelihood of break out of the fabric is minimized, thereby improving the level of protection to the user. As a result, the flame resistant fabric retains the desirable properties of fibers formed of organic materials in terms of comfort, weight, and durability.
Claims
1. A flame resistant fabric comprising: a combination of cellulosic fibers and thermoplastic fibers having an adherent char layer thereon.
2. The fabric of claim 1 wherein the thermoplastic fiber and the cellulosic fiber are in direct contact between adjacent fibers thereof or the thermoplastic fiber and the cellulosic fiber are separated by a distance of 1 to 3 fiber diameters therebetween.
3. The fabric of claim 1 wherein the thermoplastic fiber and the cellulosic fiber are spun together to form a yarn woven into the form of the fabric.
4. The fabric of claim 1 wherein the fabric is devoid of wool.
5. The fabric of claim 1 wherein the char is adherent per ASTM D3359 - 09 Method B.
6. The fabric of claim 1 wherein the cellulosic fibers are formed of at least one of cotton, linen, rayon, bamboo, hemp, sisal, jute, or a cellulose ether reaction product of any of the aforementioned.
7. The fabric of claim 6 wherein the cellulose ether reaction product is one of methylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose, or bcarboxymethylcellulose (CMC).
8. The fabric of claim 1 wherein the thermoplastic fiber and the cellulosic fiber are present in adjacent layers.
9. The fabric of claim 8 wherein the cellulosic fiber is in an outer layer of the adjacent layers as measured by the direction of melt exposure.
10. The fabric of claim 1 wherein the thermoplastic fiber and the cellulosic fiber independently have fiber diameters of 1.5 denier.
11. The fabric of claim 10 wherein a number average fiber diameter ratio of the thermoplastic fiber to the cellulosic fiber is between 0.8:1 to 1.2:1.
12. A process of protecting a volume from a melt comprising: forming an article from a fabric of claim 1; and exposing the article to a melt, an electric arc, or a combination thereof to form an adherent char on an outer surface of the article.
13. The process of claim 12 wherein the volume defines equipment and the article is a shield or cover.
14. The process of claim 12 wherein the outer surface is enriched in cellulosics relative to an inner surface.
15. The process of claim 12 wherein the melt is molten glass or molten rock.
16. (canceled)
17. The process of claim 12 further comprising inverting the article to form an inverted article and then exposing the inverted article to a melt, an electric arc, or a combination thereof.
18. The process of claim 12 wherein the article is one of an apron, a cape, a sleeve, a bib, a chap, a coat, a coverall, a glove, a hood, a neck guard, pants, a sleeve, or spats.
19. The process claim 12 wherein the article has an arc rating of at least 8.5 cal/cm2 and an arc flash personal protection equipment category rating of 2 per standard NFPA70E Edition 2015 Table 130.7(C)(16).
20. The process of claim 12 wherein the melt is molten metal.
21. The process of claim 20 wherein the molten metal is iron or aluminum.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] The subject matter that is regarded as the invention is particularly pointed out and distinctly claimed in the claims at the conclusion of the specification. The foregoing and other objects, features, and advantages of the invention are apparent from the following detailed description taken in conjunction with the accompanying drawings in which:
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DETAILED DESCRIPTION OF THE INVENTION
[0027] The present invention has utility as flame resistant fabrics that provide improved protection from molten metal spills, metal splatter, electric arc, and related thermal hazards illustratively including open flame and radiant heat. Embodiments of the inventive fabric are made from a combination of cellulosic fibers and thermoplastic fibers. Embodiments of the inventive flame resistant fabric form a char layer that does not become brittle when contacted by molten metal, metal splatter, electric arc, and related thermal hazards. By not becoming brittle the likelihood of break out of the fabric is minimized, thereby improving the level of protection to the user. As a result, embodiments of the inventive fabric retain the desirable properties of fibers formed of organic materials in terms of comfort, weight, and durability.
[0028] As a general rule it has been found that fabric weight influences performance. Traditionally, the heavier the fabric, the better the performance. Yet embodiments of the present invention afford a lightweight, durable multi-hazard fabric that can be laundered in an Industrial laundry and is comfortable to wear. Preferred embodiments of the present invention are a wool free blend of fibers.
[0029] It is to be understood that in instances where a range of values are provided that the range is intended to encompass not only the end point values of the range but also intermediate values of the range as explicitly being included within the range and varying by the last significant figure of the range. By way of example, a recited range of from 1 to 4 is intended to include 1-2, 1-3, 2-4, 3-4, and 1-4.
[0030] It has been surprisingly found that by comingling a cellulosic fiber with a thermoplastic fiber upon exposure to a melt, electric arc, and related thermal hazards that the comingled fiber forms a char that is sufficiently adherent to pass ASTM D3359 - 09 Method B testing, in contrast to prior art fire resistant fabrics that upon exposure to a melt, electric arc, and related thermal hazards simply fuse and/or burn to compromise the protective nature of the fabric. It has been found that the formation of an adherent char layer upon contact with molten metal makes the molten metal shed off the surface of embodiments of the inventive fabric with no penetration, breakthrough, or holes in the fabric, where embodiments of the fabric are light-weight and are a multi-hazard fabric.
[0031] As used herein, a melt is defined as a droplets or a pool of a metal, metal alloy, glass, or rock, having a melt temperature of from 190° C. to 2150° C.
[0032] An inventive char layer is formed from thermoplastic fiber proximal to cellulosic fiber in various relative configurations. Thermoplastic fibers operative herein illustratively include disparpolypropylenes, polyamides, polyesters, polyether ether ketones, polybenzobisoxazoles, polyphenylene sulfide; block copolymers containing at least of one of the aforementioned constituting at least 40 percent by weight of the copolymer; and blends thereof.
[0033] Cellulosic fibers, synonymously referred to herein as cellulosics, operative herein include cotton, linen, rayon, bamboo, hemp, sisal, jute, and celluolose ether reaction products of any of the aforementioned. As used herein cellulose ethers include methylcellulose (MC), hydroxypropylmethylcellulose (HPMC), hydroxyethylcellulose (HEC) and carboxymethylcellulose (CMC). Suitable cellulosic fibers, include, but are not limited to, natural and synthetic cellulosic fibers (e.g., cotton, rayon, acetate, triacetate, and lyocell, as well as their flame resistant counterparts FR cotton, FR rayon, FR acetate, FR triacetate, and FR lyocell). Examples of rayon fibers include Viscose™ and Modal™ by Lenzing, available from Lenzing Fibers Corporation. An example of an FR rayon material is Lenzing FR™, also available from Lenzing Fibers Corporation, and VISIL™, available from Sateri. Examples of lyocell fibers include TENCEL™, TENCEL G100™ and TENCEL A100™, all available from Lenzing Fibers Corporation. Examples of vinal fibers include Kuralon™ fibers available from Kuraray. The synthesis of cellulose ethers from cellulose is known to the art as detailed in P. Nasatto et al., "Methylcellulose, a Cellulose Derivative with Original Physical Properties and Extended Applications “Polymers 2015, 7, 777-803.
[0034] An inventive fabric relies on a char layer being generated that is protective of the thermoplastic fibers relative to the challenge of a contact with a melt, an electric arc, and related thermal hazards. Without intending to be bound to a particular mechanism, it is believed that the cellulosic fiber material combusts with kinetic rapidity relative to the thermoplastic fiber content to generate a char residue that deposits on proximal thermoplastic. The alteration of the surface energy of the fabric with a fluorocarbon finish, minimizes the contact time a molten metal drop will have on the surface, thereby causing the molten metal to roll off the surface, and charring the fabric where the molten metal makes contact. The char being flexible and adherent per ASTM D3359 - 09 Method B, and either being thermally insulative or having a surface energy that precludes melt wetting of the char thereby causing the melt to run off the fabric before fabric integrity is compromised.
[0035] Proximity of thermoplastic fiber to cellulosic fiber is achieved by direct contact between adjacent fibers, or such fibers are separated by a distance of 1 to 3 fiber diameters therebetween. Fibers are in intimate contact given the length of the fibers and the blending process, some portion of cellulosic fibers will always make contact with the thermoplastic fibers. This proximity is achieved through conventional textile manufacture techniques using a yarn that include both thermoplastic fiber and cellulosic fiber content. In an alternative inventive embodiment, a cellulosic fabric layer is provided outward relative to a direction of melt exposure and a thermoplastic fiber layer or mixed thermoplastic-cellulosic layer to create the critical char at the interface between the layers. However, this construction is much harder to achieve as described. In most cases, fabrics are woven fabrics formed from the yarns described. In an inventive embodiment, the blended yarn is used in both the warp and fill direction in the fabric. In some embodiments, only the yarn containing a cellulosic component will be oriented in the warp direction and only the second group of yarns containing the thermoplastic component will be oriented in the fill direction. In this way, the fibers on the face side of the fabric will predominantly include those of the first group of cellulosic yarns and the fibers on the body side of the fabric will predominantly include those of the second group of thermoplastic yarns.
[0036] Typical fiber diameters according to the present invention are independent for each of the thermoplastic fiber and cellulosic fiber. It is appreciated that a variety of fiber diameters are readily spun together to form a yarn. Textile fibers are reported in denier (indirect measure of diameter). The denier of fibers used for both cellulosic and thermoplastic is roughly 1.5 denier. In inventive embodiments, the average fiber (based on number average) diameter ratio of the thermoplastic fiber:cellulosic fiber is 1:1, however the ratio may range from 0.8:1 to 1.2:1.
[0037] Referring now to the figures,
[0038] Stretch fiber yarns may be used to form stretch protective garments such as stretch trousers and shirts that can protect against hazards as described herein. For example, a spandex/lycra core yarn with a blend of cellulosic and thermoplastic fibers (with an adherent char layer) as the wrapper may be used to form a stretchable garment construction.
[0039] It is a appreciated that outer layer 22 may also be in the form of a unitary sheet as opposed to a fabric (not shown). In inventive embodiments the inventive fabric is a woven or a knit fabric. The fabric may be constructed with the first and second groups of yarns in a variety of ways, including but not limited to, one or more of twill weave (2x1, 3x1, etc.), satin weave (4x1, 5x1, etc.), sateen weave, and double-cloth constructions, or any other weave where yarn is predominantly more on one side of the fabric than the other side of the fabric. A person skilled in the art would be familiar with and could utilize suitable fabric constructions. Embodiments of the fabric may also be a circular or a jersey knit fabric using the yarns described in the invention.
[0040] It is further appreciated that the constructs of
[0041] Embodiments of the inventive protective fabrics may be formed with spun yarns, filament yarns, stretch broken yarns, or combinations thereof. The yarns may include a single yarn or two or more individual yarns that are combined together in some form, including, but not limited to, twisting, plying, tacking, wrapping, covering, core-spinning (i.e., a filament or spun core at least partially surrounded by spun fibers or yarns), etc. Embodiments of fabrics disclosed herein are not laminated, or metallized such that the fibers of the yarns remain exposed on the fabric surfaces, however the fabrics may optionally be coated to alter the surface energy of the fabric.
[0042] A fabric is readily formed into a variety of articles of protective wear to protect a volume, the volume readily enclosing a person or equipment. Representative articles of protective wear include an apron, a cape, a sleeve, a bib, a chap, a coat, a coverall, a glove, a hood, a neck guard, pants, a sleeve, spats, and a combination thereof. It is further appreciated that the fabric is readily fashioned as a custom shaped shield or cover for a given piece of equipment.
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[0044] The test set up as shown in
[0045] The calorimeter/sensor board 34 to which the fabrics are attached may be constructed according to ASTM standard F955-15. The board has two 4 cm (1.57 inch) diameter, 0.158 cm (1 /16 inch) thick, copper disks that serve as part of the sensors 36. One copper disk is located under the point of molten metal impact, and the second copper disk is located 4 inches below the first.
[0046] Each copper disk calorimeter may have a single 30-gauge iron/constantan Type J thermocouple inserted into the back of the calorimeter. The thermocouple output from the calorimeter may be recorded with a high precision digital data acquisition system. The temperature rise for both calorimeters may be plotted for forty-five seconds for each fabric/metal combination. The total heat energy that flowed through the fabric may be calculated at each time step using the following formula:
where: [0047] Q = heat energy (J/cm2), [0048] m = mass of copper slug (g), [0049] Cp = average heat capacity of copper during the temperature rise (J/g°C), [0050] Temp.sub.final = final temperature of calorimeter at time.sub.final (°C), [0051] Temp.sub.initial = initial temperature of calorimeter at time.sub.initial (°C), [0052] Area = area of copper calorimeter.
[0053] This heat energy curve may be compared to an empirical predicted human second-degree skin burn injury model (Stoll Curve). The Stoll curve is calculated from the following formula.
where tj is the time after molten metal impact.
[0054] During a testing run, each fabric to be evaluated is placed on the calorimeter board 34 and held in place with clips along the upper edge. The preheated crucible ladle 32 is filled with molten aluminum from a resistance heat furnace held at a temperature of approximately 20° C. (68° F.) above the target temperature. The filled crucible ladle 32 is transferred to the ladle holder and metal temperature checked with a thermocouple. The metal weight is determined with an electronic balance and is maintained at 1 kg. ± 0.1 kg. The metal is poured from the ladle onto the fabric and the results are assessed.
[0055] In operation, a melt filled crucible ladle 32 is suspended in an upright position above a test fabric positioned under the pour arc of ladle 32 (not shown).
[0056] The visual appearance of the front (impact) surface of each experimental fabric tested with only a T-shirt backing (as best shown in
[0057] Metal adherence refers to the amount of metal sticking to the fabric, and the break out rating describes the extent of fabric destruction in terms of the size, number of holes created, and penetration of molten metal through the fabric. It is desirable to have no adherence and no breakout or penetration of molten metal through the fabric. The rating system described below uses numbers one through five as levels in each category, with “1” representing the best behavior and “5” representing poor behavior. Representative images of the charring, shrinkage, metal adherence, and break out levels are shown in
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[0082] The present invention is further detailed with respect to the following examples. These examples are illustrative of specific embodiments of the present invention and not intended to limit the scope of the appended claims.
EXAMPLES
Example 1
[0083] The visual ratings of embodiments of the inventive fire resistant fabric combination were tested with molten aluminum using the test set up of
[0084] The visual ratings of the Flame Pro™ fabric combination tested with molten aluminum is presented in Table 1.
TABLE-US-00001 Visual rating of fabrics exposed to molten aluminum - rating of outer (impacted) layer Fabric Number Fabric Name Backing Charring Shrinkage Adherence Break Out 1 Flame Pro™ T-Shirt 3 1 1 1 1 Flame Pro™ T-Shirt 3 1 1 1 1 Flame Pro™ T-Shirt 3 1 1 1
[0085] The calorimeter data, including the maximum calorimeter temperature rise within 30 seconds after molten aluminum impact and the time to second degree burn according to the Stoll curve, is given in Table 2.
TABLE-US-00002 Maximum calorimeter temperature rise during the first 30 seconds and time to second degree burn according to the Stoll curve after impact with Molten aluminum Fabric Number Fabric Name Backing Temperature Increase Top Calorimeter (°C) Temperature Increase Bottom Calorimeter (°C) Time to Second Degree Burn (sec) 1 Flame Pro™ T-Shirt 17.5 18.9 No Burn 1 Flame Pro™ T-Shirt 15.7 13.2 No Burn 1 Flame Pro™ T-Shirt 17.8 18.1 No Burn
Example 2
[0086] Test to determine effectiveness of embodiments of the inventive fire resistant fabric when the fabric is pre-treated prior to molten metal splash testing. Pre-treatment included washing and drying the fabric. A dry mass of the inventive fire resistant fabric weighing 0.36 Kg was put through five wash cycles at 60° C. with a counterweight mass weighing 1.65 Kg of polyester using a washing powder made of ECE detergent 98, sodium perborate, and TAED. The fabric was tumbled dried.
[0087] In a first test iron with a pouring temperature of 780±20° C. was poured at an angle of 60±1 at a pouring height of 225±5 mm. the results are shown in table 3.
TABLE-US-00003 Test results for treated material Mass of metal used (g) Mass of metal pouring (g) Ignition Puncture Metal adhered to fabric Assessment of PVC film 365 358 Yes Yes Yes Damaged 214 207 No No No Not Damaged 214 207 No No No Not Damaged 214 207 No No No Not Damaged 215 207 No No No Not Damaged
[0088] In a second test iron with a pouring temperature of 1400±20° C. was poured at an angle of 75±1 at a pouring height of 225±5 mm. the results are shown in table 4.
TABLE-US-00004 Test results for treated material Mass of metal used (g) Mass of metal pouring (g) Ignition Puncture Metal adhered to fabric Assessment of PVC film 204 204 No No No Not Damaged 204 204 No No No Not Damaged 204 204 No No No Not Damaged 207 207 No No No Not Damaged
Example 3
[0089] Electric Arc Exposure Test: Determination of the Arc Rating (APTV or E.sub.BT50) of Flame Resistant Materials for Clothing. Twenty one (21) individual panel arc trials were conducted with embodiments of the inventive fire resistant fabric combination in accordance with ASTM standard F1959/F1959M-14. The following test data was recorded for each trial: Arc exposure electrical conditions: arc trial number, RMS arc current, peak arc current, arc voltage, arc duration, energy dissipated in arc, plots of arc current and arc voltage; temperature rise response from two monitor sensors for each panel in each trial, plot of average responses from two monitor sensors, pictures after arc exposure. The graph entitled “Determination of APTV, 50% of Probablility of 2.sup.nd degree burn” shown in
[0090] Table 5 provides a summary of measured energy and subjective evaluation of each individual arc trial panel. As can be readily seen in Table 5, none of the 21 individual panel arc trials experienced break open, and trials 1-C through 2-C, 4-B, 5-B, 5-C, and 6A-7C were not burnt.
TABLE-US-00005 Summary of measured energy and subjective evaluation Test Time (ms) Cycles 50 Hz Ei cal/cm.sup.2 SCD cal/cm.sup.2 HAF % Burn Break Open 1-A 193,2 9,66 10,7 0,66 75,6 Y N 1-B 193,2 9,66 10,3 0,12 80,1 Y N 1-C 193,2 9,66 8,9 -0,02 79,0 N N 2-A 152,6 7,63 7,7 -0,22 80,3 N N 2-B 152,6 7,63 7,1 -0,25 78,2 N N 2-C 152,6 7,63 8,0 -0,21 80,8 N N 3-A 213,2 10,66 11,5 0,67 77,2 Y N 3-B 213,2 10,66 12,0 0,76 77,3 Y N 3-C 213,2 10,66 12,0 0,83 76,6 Y N 4-A 172,8 8,64 8,1 0,14 75,8 Y N 4-B 172,8 8,64 9,1 -0,12 80,2 N N 4-C 172,8 8,64 9,0 0,35 75,4 Y N 5-A 82,8 9,14 8,2 0,2 75,5 Y N 5-B 182,8 9,14 8,8 -0,09 79,4 N N 5-C 182,8 9,14 7,8 -0,12 79,7 N N 6-A 193,4 9,67 9,4 0,25 76,7 Y N 6-B 193,4 9,67 10,6 0,7 75,4 Y N 6-C 193,4 9,67 8,9 0,34 75,9 Y N 7-A 183 9,15 9,5 0,33 77,3 Y N 7-B 183 9,15 11,7 0,75 78,1 Y N 7-C 183 9,15 8,3 0,06 77,3 Y N
[0091] The Electric Arc Exposure Test determined that the inventive fire resistant fabric tested according to ASTM standard F1959/F1959M-14 has an Arc rating (ATPV) of 8.5 cal/cm.sup.2 and an Arc Flash Personal Protective Equipment (PPE) category rating of 2 (minimum arc rating of 8 cal/cm.sup.2) according to standard NFPA70E Edition 2015 Table 130.7(C)(16) - Personal Protective Equipment (PPE).
Example 4
[0092] A Ne. 28/2 yarn was spun using a standard ring-spinning machine using a blend containing 75% FR rayon fibers from Lenzing (1.5 denier) and 25% FR nylon fibers from Nexylon (1.5 denier). A woven fabric was produced using the above yarn in both the warp and weft direction, and the areal weight of the woven fabric was 290 gram/m2. The construction of the woven fabric was a ¼ sateen weave (36 warp/cm x 24 weft/cm). After dyeing and finishing the fabric, the weight of the fabric increased to 305 gram/m. A fluorocarbon finish, Rucostar TEE6 from Rudolf duraner, was applied to the fabric during the finishing process to alter the surface energy of the fabric to improve the shedding properties to molten metal. Table 6 shows the properties of the woven fabric formed with the Ne. 28/2 yarn.
TABLE-US-00006 Test results for the woven material formed with Ne. 28/2 yarn. Nature of test Methodology Woven article Abrasion Resistance EN ISO 12947-2:2016 100000 Pilling Resistance ISO 12945-2:2000 5000 rev 4 2000 rev 4 Pilling Resistance ASTM D 3512 (30,60,90,120 min) 30 min 4-5B 60 min 4F 90 min 4F 120imn 4F Dimensional Stability ISO 3759:2011 +/-3% Dimensional Stability AATCC 135 +/-3% Color Fastness to light ISO 105B (grade 5) 5 Color Fastness to XENON light AATCC16 3,5 Color Fastness to rubbing ISO 105-x12:2016 dry: 4-5 wet: 4 Crocking AATCC8 (wet&dry) dry 4,5 wet 4 Color fastness to washing ISO 105-C06:2010 4-5 Color fastness to perspiration EN ISO 105-E04:1996 4-5 Tensile Strength ISO 13934-1:2013 warp: 1200 N weft: 750 N Tear Strength ISO 13937-1:2000 warp: 38 N weft: 32 N
[0093] As a person skilled in the art will recognize from the previous detailed description and from the figures and claims, modifications and changes can be made to the preferred embodiments of the invention without departing from the scope of this invention defined in the following claims.