Specialist firefighting composition

Abstract

A fire extinguishing composition useful for lithium-ion battery fires, comprising: an alkyl sulphate anionic surfactant, an alkyl polyglucoside and / or an alkyl sorbitan non-ionic surfactant, and water

Description

The present invention relates to a specialist firefighting composition for addressing changing threats of fires. Background The fighting of fires requires specific, impactful and decisive action in a short timeframe. This is dealt with often by preplanned courses of action, extensive training, along with defined protocols and firefighting compositions. In particular, firefighting compositions and equipment are often pre-installed where possible. Current firefighting methodology is underpinned in several ways. A specific and fundamental understanding is the so-called fire triangle. Le. the interplay between fuel, oxygen and heat. The underlying logic being that the removal of one of these factors will extinguish a fire when started or serve to prevent a fire starting in the first place. However, a specific category of fire, which is becoming increasingly relevant, prevalent and often of significant intensity, are battery fires. The most common being a lithium ion battery fire. In this instance there is no necessity for heat, as such, to initiate fire. Specifically, a short-circuit will spontaneously create the necessary heat. Hence, removing heat from an environment or stopping heat being created externally is not as relevant. However, removing the heat when such a fire or potential fire is started is crucial. In other words, the underlying science remains the same, but the practical steps required are significantly different. Further, removing oxygen from a fire is not the same as removing oxidant, oxygen being a specific if prevalent oxidant. Battery fires, such as lithium ion battery fires provide both oxidant and reductant and through electrical discharge, heat. Hence all three components of the fire triangle are available in a lithium ion battery. Hence, current firefighting techniques, equipment and firefighting compositions are not optimised, and sometimes even detrimental in suppressing a lithium-ion battery fire. It is increasingly common with such fires that the emergency service’s primary role is for isolation, containment and simply waiting for the fire to burn out. However, this is inadequate as several examples have shown, such as multi-storey car parks, cargo ships and other instances where a number of large lithium batteries are present in proximity (principally from vehicles) which leads to a combustion cascade resulting in significant damage whilst responders wait for the fire to eventually burn out. A number of compositions have been proposed for the fighting of lithium ion battery fires. WO2023235168A1 to Tyco, discloses A firefighting composition includes a sugar component and a salt component, the salt component including potassium formate, potassium formate hydrate, potassium acetate, magnesium sulfate, ammonium sulfate, sodium chloride, sodium sulfate, ammonium chloride, or a mixture thereof. WO2023235256A1 to Tyco, discloses a firefighting composition comprising an inorganic clay in particular inorganic clay component comprises a silicate, phyllosilicate, synthetically modified phyllosilicate, colloidal silica, fumed silica, mica, a micaceous clay, kaolin, a kaolin-serpentine clay, pyrophyllite talc, smectite, or a combination thereof. WO2023235454A1 to Tyco, discloses a firefighting composition comprising a glycol ether, water, and mixture comprising two or more selected from the group consisting of a glycol, an ethoxylated acetylenic diol surfactant, a quaternary silicone surfactant, and an ethoxylated polydimethylsiloxane and claims the composition provides highspeed wetting. WO2012107382A1 to Bosch, discloses a firefighting composition comprising a swellable carboxylate polymer for the purposes of neutralising hydrogen fluoride and phosphorus oxide acidic smoke components associated with lithium ion fires. WO2012107384A1 to Bosch, discloses a firefighting composition comprising a carboxylate polymer calcium salt. WO2023089108A1 to Lifesafe discloses a firefighting composition comprising one or more of a phosphate, a hydrogen phosphate, a dihydrogen phosphate or polyphosphate salt; a carbonate or hydrogen carbonate salt; a sulphate salt; and an intumescent component. WO2024056202A1 to Lifesafe discloses a firefighting composition comprising a phosphate, hydrogen phosphate or dihydrogen phosphate salt. And contains no, or substantially no, sulphate or more hydrogen carbonate salts. There is a need for improved firefighting compositions particularly suitable for battery and particularly lithium-ion battery fires. The present invention The present invention in its various aspects is as set out in the appended claims. The fire extinguishing composition of the present invention comprises: a. an alkyl sulphate anionic surfactant and an b. an alkyl poly glucoside and / or an alkyl sorbitan nonionic surfactant c. water. The composition of the present invention is preferably an aqueous composition. However, it may be provided in concentrated form for dilution upon application. This composition provides a low foaming fire extinguisher composition. This is counterintuitive to current technology where high levels of foam are preferred to blanket a fire and exclude oxygen. However, this is not helpful for lithium-ion fires as the foam acts as an insulator and serves to intensify the fire which is self-sustaining. Additionally, the present invention is particularly advantageous in enabling water to extract heat from a combusting surface. Whilst not wishing to be bound by theory, the high specific heat capacity of water and the specific heat capacity of boiling is the same across compositions the effectiveness of utilisation of that the capacity can vary markedly between compositions. Specifically, the degree of physical contact between a hot surface and water determines the extent to which the water can extract heat, whether by simply heating up or by boiling in the time that it is in contact with the surface. A specific characteristic is the Leidenfrost point where water can ‘float’ as droplets over a hot surface and have minimal contact with it. The reader may be familiar with this effect if having seen droplets of water splashed on to a flat hot metal surface. Droplets of water will ‘skate’ over the surface with minimal contact. The composition of the present invention has been found to optimise the heat removal from the surface, this is essential in lithium-ion fires. It has been found that a fire extinguishing composition of the present invention demonstrates better fire extinguishing results than known compositions in specific respects. Preferably the alkyl sulphate is the tri ethyl amine salt. This reduces foam production and thereby reduces the insulation of a surface being contacted with the composition and hence assists in treating fires to remove heat, particularly important in lithium-ion battery fires. Preferably the alkyl poly glucoside and an alkyl sorbitan nonionic surfactant are both present. This mixture of surfactants has been found to optimise heat transfer and reduce forming. Preferably the anionic to non-ionic surfactant is present in a 1: 1 to a 10:1 weight ratio. Preferably the weight ratio is 1:3 to 1: 7, most preferably the way ratio is a 5 : 1 weight ratio. This has been found to maximise heat transfer and minimise foaming. The anionic may be a C8; C10; C12 (Dodecyl); C14 (Tetradecyl); C16 (Hexadecyl or Cetyl); C18 (Octadecyl or Stearyl) alkyl. Preferably the anionic is a C10 to C16 alkyl sulphate. In the present invention the generation of foam is preferably limited or avoided. In this respect at first you the use of C8 and C 10 alkyl sulphate would be counterintuitive as these are high forming, however they have low foam stability and in between antifoam generation and impinging upon a fire the composition may effectively de-foam. The mid-range C 12 to C14 alkyl compositions are less preferred as they are foaming and provide relatively stable forms. The higher alkyl C16 and C 18 can also be preferable in some situations as they are lower forming even if the foam is relatively stable. These are preferable where the application of the composition to a fire involves relatively little physical agitation to enable the entrainment of air. Preferably the alkyl poly glucoside non-ionic surfactant is a C 8 to C 10 alkyl poly glucoside. The composition of the present invention may be wherein the degree of polymerisation of the alkyl poly glucoside non-ionic surfactant is from 1.1 to 1.8. This 4 has been found to be the most synergistic with the alcohol sulphate in terms of the balance of desirable properties. The composition of the present invention may be wherein the alcohol sorbitan nonionic surfactant is a C 8 to C 18 alkyl sorbitan. The alkyl sorbitan may be C 14 to C 18 as this improves emulsion stability and can therefore provide a more stable product, particularly during storage. Preferably the alkyl sorbitan is a C 10 to C 14 alkyl sorbitan which gives a balance between foaming and stability. The present invention may further comprise one or more inorganic salts. The one or more inorganic salts are preferably salts of alkali metal or alkaline earth metals or ammonium salts. The one or more inorganic salts are preferably salts of sodium, potassium, calcium and ammonia. Those preferred are potassium and ammonia salts. These have excellent fire extinguishing properties and without wishing to be bound to theory, they liberate positive ions that arrest pyrolysis. Most preferred are the Ammonium salts which decompose into incombustable gases and the decomposion of these compounds is in addition endothermic. The one or more inorganic salts are preferably selected from one or more of a phosphate, hydrogen phosphate, dihydrogen phosphate, carbonate, hydrogen carbonate and sulphate salts. These components decompose into incombustable gases, the decomposion of these compounds is endothermic in addition to this Preferred inorganic phosphate salts include trisodium phosphate (Na3PO4); tripotassium phosphate (K3PO4).; triammonium phosphate (NH4)3PO4), disodium phosphate (Na2HPO4), dipotassium phosphate (K2HPO4) and diammonium hydrogen phosphate ((NH4)2HPO4), diammonium hydrogen phosphate ((NH4)2HPO4), monosodium phosphate (NaH2PO4), monopotassium phosphate (KH2PO4) and monoammonium phosphate ((NH4)H2PO4). The most preferred phosphate is ammonium phosphate, the most preferred ammonium phosphate is triammonium phosphate. Decompositon liberates Ammonium ions that arrest pyrolysis and Ammonium salts decompose into incombustable gases, the decomposion of these compounds is endothermic in addition to this Preferred (hydrogen) carbonate salts include, sodium carbonate (Na2CO3), potassium carbonate K2CO3, sodium hydrogen carbonate (NaHCO3), potassium hydrogen carbonate (KHCO3) and ammonium hydrogen carbonate ((NH4)HCO3). In some embodiments, the hydrogen carbonate salt is ammonium hydrogen carbonate ((NH4)HCO3). The most preferred carbonates are sodium, ammonium and potassium bicarbonate. These have excellent fire extinguishing properties and without wishing to be bound to theory, they liberate positive ions that arrest pyrolysis Preferred sulphate salts include, sulphate salt is selected from sodium sulphate (Na2SO4), potassium sulphate (K2SO4), ammonium sulphate ((NH4)2SO4). and ammonium sulphate ((NH4)2SO4). The most preferred sulphate is ammonium sulphate. These have excellent fire extinguishing properties and without wishing to be bound to theory, these decompose into incombustable gases It is important to note that whilst there is some technical underpinning for the choice of materials the particular blends of materials are themselves important and in particular in conjunction with the preferred surfactant composition. The combustion process is sufficiently complex that the process and effectiveness of for extinction compositions is not per se predictable. The composition of the present invention may include an organic carboxylic acid salt. The organic carboxylic acid salts may be sodium or potassium citrate. Preferred is potassium citrate. The organic carboxylic acid salt may be partially neutralised, as in mono or disodium citrate. The organic carboxylic salt may preferably be a polymeric organic carboxylic acid. This may be in the form of a copolymer. A suitable polymeric organic carboxylic acid is poly methacrylic acid or poly acrylic acid. The presence of an organic acid can be beneficial for the purposes of neutralising gaseous components such as HF during the combustion of lithium ion batteries. A polymeric carboxylic acid may also be helpful as a thickening agent for the composition. This reduces the rate of run-off of composition and hence increases the duration in which the fire extinguishing composition may remain in physical proximity to the fire. Citrates can help to buffer and neutralise the acidic combustion products, also sequestering buffers The composition of the present invention may include a polymeric thickener. The composition of the present invention may be wherein the polymeric thickener is xanthan gum, carboxymethyl cellulose, hydroxy ethyl cellulose or Hydroxypropyl Methylcellulose. The use of the polymeric thickener enables the composition to be more stable upon storage with a reduction in separation of components particularly on long-term storage and freeze thaw stability. Without being bound by theory these specific polymers add beneficial surface associations and viscosity, maximising agent effectiveness. The composition of the present invention may comprise between 10 and 50% water. This level of water represents a concentrated composition particularly suitable for use in dilution upon application. The composition of the present invention may comprise between 51 and 99% water. The composition of any one of claims 1 to 18 further comprising an anti-foam. An antifoam or defoamer is advantageous in that it can be used to suppress from production of the composition and hence reduce the insulating effect that a phone may have another fire. Furthermore, a non-foamed composition has a higher density (as air is not entrained) and therefore has a higher specific a pre-heat capacity for removing heat from the fire per unit volume. The use of an antifoam is preferred. The composition of the present invention may be wherein the antifoam is selected from one or more of Silicone-based Defoamer; Mineral Oil-based Defoamer; Polyether-based Defoamer; Alkylbenzene-based Defoamer; Fatty Acid-based Defoamer; Alcohol-based Defoamer; Silica-based Defoamer; Propylene Glycol-based Defoamer; Organic Ester-based Defoamer; Natural Oil-based Defoamer; Amide-based Defoamer and fluorocarbon particulates. The preferred defoamer is a silicon-based defoamer, such as based upon poly dimethyl siloxane. Without wishing to be bound to theory this is preferred because the siloxane is highly stable and less likely to decompose during fire extinguishing An example of a Silicone-based Defoamer is Polydimethylsiloxane (PDMS), Silicone emulsions. An example of a Mineral Oil-based Defoamer is White mineral oils. An example of a Polyether-based Defoamer is Polyethylene glycol (PEG), Polypropylene glycol (PPG). An example of a Fatty Acid-based Defoamer is Stearic acid, Oleic acid. An example of an Alcohol-based Defoamer is Higher molecular weight alcohol such as octanol and decanol. An example of a Silica-based Defoamer is Hydrophobic silica. An example of an Organic Ester-based Defoamer is Esters of fatty acids. An example of a Natural Oil-based Defoamer is Vegetable oils like soybean oil. An example of an Amide-based Defoamer is an Alkanolamide. The present invention includes a method of suppressing fire comprising contacting the fire with a composition of the present invention. The composition of the present invention may preferably be diluted with further water before being projected onto a fire. The present invention includes a fire extinguishing device charged with the composition of the present invention. Currently fire extinguishers are categorised as carbon dioxide, which is relatively low he capacity; water, which is effective in some situations but not optimal for enabling the water per se to extract heat; and foambased compositions which is made previously mentioned have insulating and no specific heat capacity per unit volume. The present invention provides an alternative approach using a surfactant-based water composition but with low forming and high surface contact. The fire extinguishing device is preferably a device that is progressively charged with the composition by means of introducing the composition into a stream of water. This is a preferred means of application as the final composition can be produced in situ preferably relatively high dilution as compositions of the present invention can be effective at levels as low as 0.2% by weight in water although the composition is preferably present in at least 1 % or preferably in the range 2 to 5% by weight. The weight is weight of nonaqueous components of the composition of the present invention is further diluted with water. The fire extinguishing device is preferably device were progressive charging takes 5 place by means of introducing the composition into water via a venturi inductor actuated by a stream of water. In particular advantageous use of the present invention is where the fire extinguishing device is configured for the dispensing of a fire foam. Whilst the present invention is specifically configured not for the generation of foam fire foam dispensing systems are widespread installations and these may be 10 suitably updated and improved by use of a composition of the present invention which suppresses the foam and enhances heat transfer characteristics. Most existing foam systems may be optimal for some fires situations where a lithium-ion fires may occur will greatly benefit from use of the present invention. 15 Currently there are limited number of standards for testing the efficiency of fire suppressant compositions with battery fires, such as lithium-ion battery fires. The current relevant standards are NTA 8133 and NFPA 18. Compositions of the present invention have been found to pass test NTA 8133. Examples The present invention will now be illustrated by means of the compositions shown in table 1. Compositions 1 to 9 are within the scope of the present invention. The further compositions are comparatives and are denoted by the suffix C 5 Table 1 Formulation => 1 2 3 4 5 6 7 8 9 10C 11C 12C 13C 14C Type Material Trade Alkyl + APG (10:1) Alkyl + APG (1:10) Alkyl + APG (1:1) Alkyl + Sorbitan 10:1 Alkyl + APG + Sorbitan Alkyl + APG + Sorbitan + Salt Alkyl + APG + Sorbitan + Alternate Salt Alkyl + APG + Sorbitan +salt + Antifoam Alkyl + APG + Sorbitan + Alternate salt + Antifoam Tween 20 Biosoft SBDS DK225 APG Competitor Lifesafe Competitor Corexit 9500 Anionic Benzenesulfonic acid, 4-C10-13-sec-alkyl derivs., compds. with 2-propanamine Abeson TEA 33.4 3.3 16.7 33.4 33.4 33.4 33.4 33.4 33.4 50 Sorbitan Sorbitan laurate C12 Surfacare S20 Veg FG 1 0.4 0.4 0.4 0.4 0.4 Polyoxyethylene (20) sorbitan monolaurate Tween 20 15 Formulation => 1 2 3 4 5 6 7 8 9 10C 11C 12C 13C 140 Apg Alkyl poly i glucoside C8-10 Glucopon 225 DK 1.42 14.2 7.14 0.85 0.85 0.85 0.85 0.85 22 1.42 q ,, Ammonium a Phosphate - 18 18 Ammonium bicarbonate 1.5 1.5 Ammonium sulfate - 5 5 Sodium bicarbonate 1 1 Potassium citrate B40 40 40 Potassium bicarbonate . 3.5 3.5 Promulgen D Antifoam Cetearyl Alcohol (and) Ceteareth-20 3 3 Summary Preffered Alkyl / APG ratio Inverted Alkyl / APG ratio Altered Alkyl / APG ratio Preffered Alkyl / Sorbitan ratio Preffered Alkyl / Sorbitan / APG ratio -sorbitan / APG blend more effective Preffered Alkyl / Sorbitan / APG ratio enhancing salt - Salts add additional cooling qualities to the Preffered Alkyl / Sorbitan / APG ratio + alternative enhancing salt Preffered Alkyl / Sorbitan / APG ratio + enhancing salt + Antifoam -Antifoam improves performance of the working fluid Preffered Alkyl / Sorbitan / APG ratio alternative enhancing salt + Antifoam Material only control Material only control Material only control Competitor lifesafe Competitor Corexlt 9500 Formulation => 10C I 11C i 12C i 13C i 14C working fluid The above compositions are presented as parts by weight. The compositions are made up to 97% by weight of water before testing. Tests are all scored on a scale of 1 to 5 with the most desirable result, for the purposes of the present invention, being 1 and least desirable 5. ASTM D117 Ross miles foam test Formulations at 3% by volume were made up with water and the test carried out as in the standard ASTM D117. This is scored into our system by means of foam height, with 1 being the lowest foam volume observed and 5 being the greatest In summary, in the scoring system 1 has the Lowest foam volume, 5 has the highest foam volume. Heat transfer test. Test is adapted from the following paper; Enhancement of pool boiling heat transfer using innovative non-ionic surfactant on a wire heater 2017 Each formulation is formulation added to water at 3% by weight to make up 100ml of test solution agitated in a vortex mixer for 1 minute to provide the working fluid. Current is passed through a Nichrome wire immersed in a chamber filled with the working fluid, in this case, the formulations at use dilutions. This is scored into our system by measurement of a heat transfer coefficient versus degassed, de-ionised water. All results are compared to the water control and scored by order of magnitude of increased heat transfer. In summary, in the scoring system 1 has the highest heat transfer, 5 has the lowest heat transfer. Emulsification light absorbance test Each formulation is formulation added to water at 3% by weight to make up 100ml of test solution agitated in a vortex mixer for 1 minute with 24ml of 99.99% n-heptane. The emulsion is then characterised by looking at the change in backscattering of light over time using a Turbiscan TLAB spectrometer. This method can characterise; droplet size, migration velocity and emulsion stability globally and in a targeted area. In summary, in the scoring system 1 has the best emulsification, 5 has the lowest emulsification. NTA8133 Battery fire test A single test of the formulations 8 and 9 against the NTA 8133 battery fire test standard was carried out using six GNB 7000mAh 4S 70C LiPo Battery (Batch no. GNB70004S70A). 5 This is a pass or fail test as set out in NTA 8133. The results of the above tests are tabulated in table 2. Table 2 Formulation => 9 10C 11C 12C 13C 14C Foam test ASTM D1173 ross miles foam test 4 5 5 3 2 2 1 1 1 2 2 4 2 1 HTC test Simple paper summary of test Enhancement of pool boiling heat transfer using innovative non-ionic surfactant on a wire heater 2017 4 5 5 4 2 2 1 1 1 3 3 3 2 3 Emulsification test Simply summary of test Use Turbiscan data to predict 3 543222 1 2 2 1 3 4 2 NTA 8133 tested once against a recognised certification NTA 8133 - specify what battery is used, all details - NTA test replicated using our composition using ‘this battery’ M Pass Pass Fail* Fail* Estimated result. As can be seen the compositions of the present invention and in particular compositions 5,6,7,8 and 9 are low foaming. Comparative composition 10C, 11C and 14C is also low foaming but as this represents polysorbate surfactant, APG surfactant alone and a competitor formulation respectively, they are not an effective extinguishing composition. The compositions of the present invention provide a high heat transfer coefficient, in particular compositions 5,6,7,8 and 9. Comparative composition 13C also provides a high heat transfer coefficient, however this is not an effective emulsifying composition. The compositions of the present invention provide effective emulsification, in particular compositions 8, 9. Comparative formulation 11C also provides effective emulsification but as this represents Sodium benzyl sulphonate surfactant alone, this is not an effective extinguishing composition. Comparative composition 14C also provides a high heat transfer coefficient but is understood not to be suitable for treating lithium ion battery fires such as in test NTA 8133. The composition is directed towards oil spills. The compositions of the present invention, where they are not otherwise specified are made up to 100% using water. Temperatures relevant in the present invention, where they are not otherwise specified or implied are at 20°C.

Claims

1. A fire extinguishing composition comprising:a. an alkyl sulphate anionic surfactant and anb. an alkyl poly glucoside and an alkyl sorbitan nonionic surfactantc. waterwherein the anionic to non-ionic surfactant is present in a 1:3 to 1: 7 weight ratio andwherein the alkyl sorbitan non-ionic surfactant is a C 10 to C 14 alkyl sorbitan.

2. The composition of claim 1 wherein the alkyl sulphate is the tri ethyl amine salt.

3. The composition of any preceding claim wherein the anionic is a C10 to C16 alkyl sulphate.

4. The composition of any preceding claim wherein the alkyl poly glucoside non-ionic surfactant is a C8 to C10 alkyl poly glucoside.

5. The composition of any preceding claim wherein the degree of polarisation of the alkyl poly glucoside non-ionic surfactant is from 1.1 to 1.8.

6. The composition of any preceding claim further comprising an alkali metal salts.

7. The composition of any preceding claim further comprising one or more of a phosphate, hydrogen phosphate, dihydrogen phosphate or polyphosphate salt.

8. The composition of any preceding claim further comprising a carbonate or a hydrogen carbonate.29 04 259. The composition of any preceding claim further comprising one or more cosolvent selected from glycols, diols and polyethers.

10. The composition of claim 9 when co-solvent is ethylene glycol or propylene glycol.

11. The composition of any preceding claim further comprising polymeric thickener selected from one or more of Guar Gum; Xanthan Gum; Carboxymethyl Cellulose (CMC); Hydroxyethyl Cellulose (HEC); Hydroxypropyl Methylcellulose (HPMC); Agar-Agar; Pectin; Carrageenan; Alginate; Starch and Modified Starches; Chitosan.

12. The composition of claim 11 wherein the polymeric thickener is xanthan gum, carboxymethyl cellulose, hydroxy ethyl cellulose or Hydroxypropyl Methylcellulose.

13. The composition of any preceding claim comprising between 10% and 50% water.

14. The composition of any of claims 1 to 12 comprising between 51 and 99% water.

15. The composition of any one of claims 1 to 14 further comprising an anti-foam.

16. The composition of claim 15 when the antifoam is selected from one or moreof Silicone-based Defoamer; Mineral Oil-based Defoamer; Polyether-based Defoamer; Alkylbenzene-based Defoamer; Fatty Acid-based Defoamer; Alcohol-based Defoamer; Silica-based Defoamer; Propylene Glycol-based Defoamer; Organic Ester-based Defoamer; Natural Oil-based Defoamer; Amide-based Defoamer17. A method of suppressing fire comprising contacting a fire with a composition of any one of claims 1 to 16.

18. A fire extinguishing device charged with the composition of any one of claims 1 to 16.

19. The fire extinguishing device of claim 18 when the device is progressively charged with the composition by means of introducing the composition into a stream of water.

20. The fire extinguishing device of claim 19 with the progressive charging takes place by means of introducing the composition into a venturi nozzle actuated by a stream of water.

21. The firing extinguishing device of claim 19 wherein the fire extinguishing device is configured for the dispensing of a fire foam.29 04 25Application No: GB2410687.4Examiner: Hannah SamuelClaims searched: 1-25Date of search: 10 December 2024Patents Act 1977: Search Report under Section 17Documents considered to be relevant:Category Relevant to claims Identity of document and passage or figure of particular relevance X 1,5-7,12- US 2016 / 0023032 Al 17,21,22, 25 (BOWEN) See especially example 1, and paragraphs 0008 and 0054. X 1,2,5,6,9, US 2024 / 0226632 Al 12- (MONFILS et al.) See especially table 1, formulation A, and paragraphs 16,18,21- 23,25 0062 and 0065. X 1,2,5,6,9, US 2011 / 0240309 Al 12- 16,18,21- 23,25 (KINGMA) See table 2 and paragraph 0179. X 1,5,9,12- WO 2023 / 177688 Al 15,17,21- (KINETIC FOAM ENGINEERING INTERNATIONAL) See table 1 25 example 1, and paragraph 0062. X 1,3,5,6,12 CN 107890620 A ,17,21-23 (SHANGHAI INST TECH) See WPI abstract, Accession No. 2018-31928P, paragraph 0029 embodiment 1, and claim 10. X 1,3,5,6,9- CN 107744635 A 16,18 (ZHEJIANG) See WPI abstract, Accession No. 2018-189647, and example 9. A - US 2023 / 0166148 Al (PARK MYUNG KYUN) See paragraphs 0035-0036. A - JP 2001046546 A (KUWANO) See paragraph 0012.Categories:X Document indicating lack of novelty or inventive step A Document indicating technological background and / or state of the art. Y Document indicating lack of inventive step if P Document published on or after the declared priority date but combined with one or more other documents of same category'. before the filing date of this invention. & Member of the same patent family E Patent document published on or after, but with priority date earlier than, the filing date of this application.Field of Search:International Classification:Subclass Subgroup Valid From A62D 0001 / 00 01 / 01 / 2006