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Open AccessOpen Access JUSTC Engineering & Materials /Chemistry 11 May 2022

Alginate-sepiolite-ammonium polyphosphate ternary hybrid gels for firefighting in grain and cotton reserves

  • State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei 230027, China

Cite this:
https://doi.org/10.52396/JUSTC-2021-0181
More Information
  • Author Bio:

    Chenyu Wang is currently a PhD candidate under the supervision of Professor Yuan Hu at the University of Science and Technology of China. His research interests focus on synthesis and application of environmental-friendly hybrid flame retardant materials

    Hu Shi is currently a PhD candidate under the tutelage of Professor Yuan Hu at the University of Science and Technology of China. He is mainly engaged in the preparation and application of hybrid gel materials for firefighting and fire prevention

    Xin Wang received his PhD degree in Safety Science and Engineering from the University of Science and Technology of China (USTC) in 2013. He is currently employed as an associate professor in the State Key Laboratory of Fire Science, USTC. His research interests focus on synthesis and application of bio-based flame retardants and functionalization of nanomaterials and their use in flame retardant polymer nanocomposites

    Yuan Hu obtained his PhD degree in Engineering Thermophysics from the University of Science and Technology of China (USTC) in 1997. He is currently employed as a professor in the State Key Laboratory of Fire Science, USTC. His main research areas include polymer/inorganic compound nanocomposites, new flame retardants and their flame retardant polymers, synthesis and properties of inorganic nanomaterials, combustion, and decomposition mechanism of polymers

  • Corresponding author: E-mail: wxcmx@ustc.edu.cn; E-mail: yuanhu@ustc.edu.cn
  • Received Date: 10 August 2021
  • Accepted Date: 03 January 2022
    • Available Online: 11 May 2022
    Abstract

  • Abstract

    An eco-friendly and bio-based ternary hybrid gel consisting of alginate, sepiolite, and ammonium polyphosphate (APP) was fabricated via a facile one-pot method. Rheological tests showed that this ternary hybrid hydrogel exhibited shear-thinning behavior. Firefighting experiments showed that a burning cotton bale extinguished by using water re-ignited, whereas the ternary hybrid gel effectively prevented smoldering and re-ignition of the cotton bale because of the firm adhesion of the hybrid gel to the surface of the cotton bale. Firefighting experiments also showed that the hybrid gel only covered the upper layer of a rice pile after firefighting efforts, whereas water ruined the grains completely, making them inedible and suitable for use only as a feed or for discard with the burnt grains. The firefighting mechanism of this hybrid gel involved multiple modes of action: volatilization of the large amount of water in the gel absorbed much heat (cooling the combustion zone), APP decomposed into non-flammable ammonia when heated (dilution of flammable volatiles and oxygen), and APP and sepiolite were conducive to forming a continuous and dense char layer (insulation of the exchange of combustible gas, heat, and oxygen). This work provides an environmentally friendly, cost-effective, and bio-based hybrid gel for firefighting in grain and cotton reserves.

    Graphical abstract

      The alginate-sepiolite-ammonium polyphosphate ternary hybrid gels showed high firefighting efficiency, because of their multiple modes of action.

    Abstract

    An eco-friendly and bio-based ternary hybrid gel consisting of alginate, sepiolite, and ammonium polyphosphate (APP) was fabricated via a facile one-pot method. Rheological tests showed that this ternary hybrid hydrogel exhibited shear-thinning behavior. Firefighting experiments showed that a burning cotton bale extinguished by using water re-ignited, whereas the ternary hybrid gel effectively prevented smoldering and re-ignition of the cotton bale because of the firm adhesion of the hybrid gel to the surface of the cotton bale. Firefighting experiments also showed that the hybrid gel only covered the upper layer of a rice pile after firefighting efforts, whereas water ruined the grains completely, making them inedible and suitable for use only as a feed or for discard with the burnt grains. The firefighting mechanism of this hybrid gel involved multiple modes of action: volatilization of the large amount of water in the gel absorbed much heat (cooling the combustion zone), APP decomposed into non-flammable ammonia when heated (dilution of flammable volatiles and oxygen), and APP and sepiolite were conducive to forming a continuous and dense char layer (insulation of the exchange of combustible gas, heat, and oxygen). This work provides an environmentally friendly, cost-effective, and bio-based hybrid gel for firefighting in grain and cotton reserves.

    • Public Summary

    • An eco-friendly, cost-effective and bio-based hybrid gels was developed for the firefighting of grain and cotton reserves.
    • The ternary hybrid gel effectively prevented the cotton bale from smoldering and re-ignition.
    • The firefighting mechanism involved multiple modes of action, including cooling, dilution of flammable volatiles, and insulation of heat and oxygen.

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    • References(20)
  • [1]
    Ren X, Hu X, Cheng W, et al. Study of resource utilization and fire prevention characteristics of a novel gel formulated from coal mine sludge (MS). Fuel, 2020, 267: 117261. doi: 10.1016/j.fuel.2020.117261
    [2]
    He F, Wang L, Yang S, et al. Highly stretchable and tough alginate-based cyclodextrin/Azo-polyacrylamide interpenetrating network hydrogel with self-healing properties. Carbohyd. Polym., 2021, 256: 117595. doi: 10.1016/j.carbpol.2020.117595
    [3]
    Vincent T, Dumazert L, Dufourg L, et al. New alginate foams: Box-Behnken design of their manufacturing; fire retardant and thermal insulating properties. J. Appl. Polym. Sci., 2018, 135 (7): 45868. doi: 10.1002/app.45868
    [4]
    Cheng W M, Hu X M, Xie J, et al. An intelligent gel designed to control the spontaneous combustion of coal: Fire prevention and extinguishing properties. Fuel, 2017, 210: 826–835. doi: 10.1016/j.fuel.2017.09.007
    [5]
    Zhou C S, Tang Y B. A novel sodium carboxymethyl cellulose/aluminium citrate gel for extinguishing spontaneous fire in coal mines. Fire Mater., 2018, 42 (7): 760–769. doi: 10.1002/fam.2631
    [6]
    Liu Y, Zhang C J, Zhao J C, et al. Bio-based barium alginate film: Preparation, flame retardancy and thermal degradation behavior. Carbohyd. Polym., 2016, 139: 106–114. doi: 10.1016/j.carbpol.2015.12.044
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    [10]
    Li X L, Wang Q P, Li H L, et al. Effect of sepiolite fiber on the structure and properties of the sepiolite/silica aerogel composite. J. Sol-Gel Sci. Techn., 2013, 67 (3): 646–653. doi: 10.1007/s10971-013-3124-4
    [11]
    Nasution D A, Ismail H, Wirjosentono B, et al. The effect of sepiolite loading on curing and tensile properties of sepiolite filled natural rubber/styrene-butadiene rubber (SMR L/SBR) blends. Aip. Conf. Proc., 2020, 2267 (1): 020057. doi: 10.1063/5.0015958
    [12]
    Chen S S, Li X, Li Y, et al. Intumescent flame-retardant and self-healing superhydrophobic coatings on cotton fabric. ACS Nano, 2015, 9 (4): 4070–4076. doi: 10.1021/acsnano.5b00121
    [13]
    Hanna A A, Nour M A, Elsherief M A, et al. Fire performance of polypropylene treated with ammonium polyphosphate and kaolin. Egypt. J. Chem., 2017, 60 (5): 937–944. doi: 10.21608/ejchem.2017.1509.1110
    [14]
    Huang Z, Ruan B, Wu J, et al. High-efficiency ammonium polyphosphate intumescent encapsulated polypropylene flame retardant. J. Appl. Polym. Sci., 2021, 138 (20): 50413. doi: 10.1002/app.50413
    [15]
    Xiao Y, Jin Z, He L, et al. Synthesis of a novel graphene conjugated covalent organic framework nanohybrid for enhancing the flame retardancy and mechanical properties of epoxy resins through synergistic effect. Compos. Part B:Eng., 2020, 182: 107616. doi: 10.1016/j.compositesb.2019.107616
    [16]
    Xiao Y, Mu X, Wang B, et al. A novel phosphorous-containing polymeric compatibilizer: Effective reinforcement and flame retardancy in glass fiber reinforced polyamide 6 composites. Compos. Part B: Eng., 2021, 205: 108536. doi: 10.1016/j.compositesb.2020.108536
    [17]
    Wang J, Zhang D, Zhang Y, et al. Construction of multifunctional boron nitride nanosheet towards reducing toxic volatiles (CO and HCN) generation and fire hazard of thermoplastic polyurethane. J. Hazard. Mater., 2019, 362: 482–494. doi: 10.1016/j.jhazmat.2018.09.009
    [18]
    Wang J L, Ma C, Mu X W, et al. Designing 3D ternary-structure based on SnO2 nanoparticles anchored hollow polypyrrole microspheres interconnected with N, S co-doped graphene towards high-performance polymer composite. Chem. Eng. J., 2020, 402: 126221. doi: 10.1016/j.cej.2020.126221
    [19]
    Wang X, Zhou S, Xing W, et al. Self-assembly of Ni-Fe layered double hydroxide/graphene hybrids for reducing fire hazard in epoxy composites. J. Mater. Chem. A, 2013, 1 (13): 4383–4390. doi: 10.1039/c3ta00035d
    [20]
    Song L, He Q L, Hu Y, et al. Study on thermal degradation and combustion behaviors of PC/POSS hybrids. Polym. Degrad. Stabil., 2008, 93 (3): 627–639. doi: 10.1016/j.polymdegradstab.2008.01.014
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    Figure  1.  Digital photographs of the gels with different (a) sodium alginate and (b) sepiolite concentrations.

    Figure  2.  Relationship between viscosity and shearing rate of gels with different (a) sodium alginate and (b) sepiolite concentrations.

    Figure  3.  TGA curves of gel A3 and hybrid gel C1.

    Figure  4.  Fire extinguishing test for cotton bale using water: (a) before ignition; (b) ignition; (c) spraying initiated; (d) 6 min after spraying.

    Figure  5.  Fire extinguishing test for cotton bale, using hybrid gel (C1): (a) before ignition; (b) ignition; (c) spraying initiated; (d) one-week after spraying.

    Figure  6.  Photographs of the immersion depth after spraying (a) water and (b) hybrid gel on the surface of rice.

    Figure  7.  SEM images and Raman spectra of pinewood residues of pine wood after extinguishing (a, d) by free burning; (b, e) with water; (c, f) with hybrid gel.

    Figure  8.  (a) XPS survey spectra of wood surface extinguished by C1; high-resolution C1s XPS profiles of (b) free burning, (c) water-extinguished and (d) hybrid gel(C1)-extinguished wood surface; (e) high-resolution P2p XPS profile of wood surface extinguished by hybrid gel (C1).

    Figure  9.  Schematic illustration of possible fire extinguishing mechanism for hybrid gel.

    [1]
    Ren X, Hu X, Cheng W, et al. Study of resource utilization and fire prevention characteristics of a novel gel formulated from coal mine sludge (MS). Fuel, 2020, 267: 117261. doi: 10.1016/j.fuel.2020.117261
    [2]
    He F, Wang L, Yang S, et al. Highly stretchable and tough alginate-based cyclodextrin/Azo-polyacrylamide interpenetrating network hydrogel with self-healing properties. Carbohyd. Polym., 2021, 256: 117595. doi: 10.1016/j.carbpol.2020.117595
    [3]
    Vincent T, Dumazert L, Dufourg L, et al. New alginate foams: Box-Behnken design of their manufacturing; fire retardant and thermal insulating properties. J. Appl. Polym. Sci., 2018, 135 (7): 45868. doi: 10.1002/app.45868
    [4]
    Cheng W M, Hu X M, Xie J, et al. An intelligent gel designed to control the spontaneous combustion of coal: Fire prevention and extinguishing properties. Fuel, 2017, 210: 826–835. doi: 10.1016/j.fuel.2017.09.007
    [5]
    Zhou C S, Tang Y B. A novel sodium carboxymethyl cellulose/aluminium citrate gel for extinguishing spontaneous fire in coal mines. Fire Mater., 2018, 42 (7): 760–769. doi: 10.1002/fam.2631
    [6]
    Liu Y, Zhang C J, Zhao J C, et al. Bio-based barium alginate film: Preparation, flame retardancy and thermal degradation behavior. Carbohyd. Polym., 2016, 139: 106–114. doi: 10.1016/j.carbpol.2015.12.044
    [7]
    Liu Y, Zhao J C, Zhang C J, et al. Effect of manganese and cobalt ions on flame retardancy and thermal degradation of bio-based alginate films. J. Mater. Sci., 2016, 51 (2): 1052–1065. doi: 10.1007/s10853-015-9435-9
    [8]
    Liu Y, Wang J S, Zhu P, et al. Thermal degradation properties of biobased iron alginate film. J. Anal. Appl. Pyrol., 2016, 119: 87–96. doi: 10.1016/j.jaap.2016.03.014
    [9]
    Jankovic-Castvan I, Lazarevic S, Stojanovic D, et al. PVB/sepiolite nanocomposites as reinforcement agents for paper. J. Serb. Chem. Soc., 2016, 81 (11): 1295–1305. doi: 10.2298/JSC160506067J
    [10]
    Li X L, Wang Q P, Li H L, et al. Effect of sepiolite fiber on the structure and properties of the sepiolite/silica aerogel composite. J. Sol-Gel Sci. Techn., 2013, 67 (3): 646–653. doi: 10.1007/s10971-013-3124-4
    [11]
    Nasution D A, Ismail H, Wirjosentono B, et al. The effect of sepiolite loading on curing and tensile properties of sepiolite filled natural rubber/styrene-butadiene rubber (SMR L/SBR) blends. Aip. Conf. Proc., 2020, 2267 (1): 020057. doi: 10.1063/5.0015958
    [12]
    Chen S S, Li X, Li Y, et al. Intumescent flame-retardant and self-healing superhydrophobic coatings on cotton fabric. ACS Nano, 2015, 9 (4): 4070–4076. doi: 10.1021/acsnano.5b00121
    [13]
    Hanna A A, Nour M A, Elsherief M A, et al. Fire performance of polypropylene treated with ammonium polyphosphate and kaolin. Egypt. J. Chem., 2017, 60 (5): 937–944. doi: 10.21608/ejchem.2017.1509.1110
    [14]
    Huang Z, Ruan B, Wu J, et al. High-efficiency ammonium polyphosphate intumescent encapsulated polypropylene flame retardant. J. Appl. Polym. Sci., 2021, 138 (20): 50413. doi: 10.1002/app.50413
    [15]
    Xiao Y, Jin Z, He L, et al. Synthesis of a novel graphene conjugated covalent organic framework nanohybrid for enhancing the flame retardancy and mechanical properties of epoxy resins through synergistic effect. Compos. Part B:Eng., 2020, 182: 107616. doi: 10.1016/j.compositesb.2019.107616
    [16]
    Xiao Y, Mu X, Wang B, et al. A novel phosphorous-containing polymeric compatibilizer: Effective reinforcement and flame retardancy in glass fiber reinforced polyamide 6 composites. Compos. Part B: Eng., 2021, 205: 108536. doi: 10.1016/j.compositesb.2020.108536
    [17]
    Wang J, Zhang D, Zhang Y, et al. Construction of multifunctional boron nitride nanosheet towards reducing toxic volatiles (CO and HCN) generation and fire hazard of thermoplastic polyurethane. J. Hazard. Mater., 2019, 362: 482–494. doi: 10.1016/j.jhazmat.2018.09.009
    [18]
    Wang J L, Ma C, Mu X W, et al. Designing 3D ternary-structure based on SnO2 nanoparticles anchored hollow polypyrrole microspheres interconnected with N, S co-doped graphene towards high-performance polymer composite. Chem. Eng. J., 2020, 402: 126221. doi: 10.1016/j.cej.2020.126221
    [19]
    Wang X, Zhou S, Xing W, et al. Self-assembly of Ni-Fe layered double hydroxide/graphene hybrids for reducing fire hazard in epoxy composites. J. Mater. Chem. A, 2013, 1 (13): 4383–4390. doi: 10.1039/c3ta00035d
    [20]
    Song L, He Q L, Hu Y, et al. Study on thermal degradation and combustion behaviors of PC/POSS hybrids. Polym. Degrad. Stabil., 2008, 93 (3): 627–639. doi: 10.1016/j.polymdegradstab.2008.01.014
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