Modified basalt/hydrogel composite coating study on the influence of flame retardancy of wood

WANG Chi; LIU Jing; ZHANG Mengying; YUAN Guangming; GE Hailin

doi:10.13801/j.cnki.fhclxb.20240701.003

Volume 42 Issue 4

Apr. 2025

Turn off MathJax

Article Contents

Abstract

References

Supplements

Acta Materiae Compositae Sinica > 2025 > 42(4): 2191-2200. > DOI: 10.13801/j.cnki.fhclxb.20240701.003

WANG Chi, LIU Jing, ZHANG Mengying, et al. Modified basalt/hydrogel composite coating study on the influence of flame retardancy of wood[J]. Acta Materiae Compositae Sinica, 2025, 42(4): 2191-2200. DOI: 10.13801/j.cnki.fhclxb.20240701.003

Citation:

PDF (5557 KB)

Modified basalt/hydrogel composite coating study on the influence of flame retardancy of wood

1.
College of Materials Science and Engineering, Central South University of Forestry and Technology, Changsha 410004, China
2.
Sunon Technology Co., Ltd., Hangzhou 311215, China

Funds: National Natural Science Foundation of China (32171708; 31770606); National Key Research and Development Program of China (2019YFE0114600)

More Information

Received Date: April 25, 2024
Revised Date: June 14, 2024
Accepted Date: June 20, 2024
Available Online: July 02, 2024
Published Date: June 30, 2024

Abstract

Abstract

BS-PA-Al, BS-PA-Ni and BS-PA-Zn hydrogel flame retardant coating materials were prepared respectively using polyvinyl alcohol (PVA)/chitosan (CS) including aluminum hypophosphite (AHP) as hydrogel matrix, and employing basalt (BS) after NaOH pretreatment, KH550 grafting modification and phytic acid co-precipitation act as flame retardant filler. The effects of modified basalt/hydrogel composite coating on flame retarding and mechanical properties of wood were analyzed by thermogravimetric test, cone calorimetric test and vertical combustion test after coating on wood surface respectively. The results show that, due to the dilution of combustible gas and the increase of carbon layer density, the flame retardant properties of BS-PA-Al, BS-PA-Ni and BS-PA-Zn hydrogel flame retardant coated wood have been significantly improved. Among them, the flame retardant properties and mechanical properties of BS-PA-Ni have reached the best, and its UL-94 test has reached V-0 level. The residual carbon rate increased to 27.3%, while the peak heat release rate (pHRR), total heat release (THR) and total smoke release (TSR) decreased by 64.2%, 32.7% and 51.3%, respectively. In addition, when the thickness of the coating is 300 μm, the mechanical properties (tensile strength) of BS-PA-Ni enhanced to 80.4%, and the adhesion strength of the hydrogel on the wood reaches 3.4 MPa.
- hydrogel coating,
- flame retardant,
- basalt,
- aluminum hypophosphite,
- wood

Summary

Summary

Objectives
Wood has been used for a long time in the field of construction and furniture because of its wide range of sources, excellent mechanical properties, and renewable. However, the flammability of wood limits its scope of application. Therefore, the modified basalt (BS) /hydrogel composite flame retardant coating was prepared by green degradable polyvinyl alcohol (PVA) /chitosan (CS) as film forming material and BS as filler, which the synergistic effect of formed flame retardant system on the flame retardant property and smoke suppression property of wood was studied.
Methods
The BS was first pretreated with sodium hydroxide (NaOH) and KH550 silane coupling agent. Zinc phytate, aluminum phytate and nickel phytate were deposited on the surface of the BS through co-precipitation method. In addition, the aluminum hypophosphite (AHP) was added to the PVA/CS hydrogel matrix and combined with the modified basalt to obtain the modified BS/hydrogel composite flame retardant coating. Scanning electron microscope (SEM) and energy dispersive spectrometer (EDS) were used to observe the changes of the morphology of BS after modifying, and the deposition of phytic acid metal salts on the surface of BS. The chemical structure of modified BS/hydrogel composite flame retardant coating was investigated by Fourier Transform Infrared Spectrometer (FTIR). The effect of flame retardant coating on the thermal stability of wood was analyzed by thermogravimetric (TG) test. The influence of composite coating on flame retardant property of wood was analyzed by cone calorimetry (CONE). Moreover, the UL-94 grade of coating applied to wood was tested by vertical combustion. The adhesion strength and tensile strength of coating were analyzed by mechanical test.
Results
The SEM results showed that the basalt surface became rougher after NaOH etching. In addition, it was observed from the EDS that phytic acid metal salts were successfully deposited on the BS surface. According to the results of FTIR, the modified BS by NaOH etching and the grafting of KH550 silane coupling agent has enhanced the corresponding -OH absorption peak at 3554 cm, and the -NH absorption peak appears at 1646 cm, indicating that KH550 has been successfully grafted to the basalt surface. The P-O vibration absorption peak appears at 1063 cm, which further proves that aluminum phytate, nickel phytate and zinc phytate were successfully deposited on the basalt surface. In addition, P-O vibration absorption peak appeared at 1063 cm, and a weaker absorption peak appeared at 1075-1125 cm, which can be attributed to O=P expansion vibration peak, further demonstrating that the phytate metal salt was deposited on the BS surface. In addition, as a result, the carbon residue rate of wood coated coating without AHP and modified BS hydrogel is 3.12%, while the carbon residue rate of wood coated coating with AHP and modified BS is increased, indicating that AHP and modified BS can effectively avert the degradation of the coating and improve the thermal stability of the coating. Among them, the carbon residue rate of composite coating contained nickel phytate up to 27.27%, possessed the most superior thermal stability, which due to the outstanding catalytic performance of Ni , which effectively improving the quality of carbon layer. Cone results showed that the peak heat release rate (pHHR), total heat release (THR) and total smoke release (TSR) of hydrogel-coated wood were lower than uncoated wood, and the highest reduction values were 64.15%, 32.67% and 55.28%, respectively. Furthermore, the composite flame retardant coating deposited with aluminum phytate and nickel phytate reached V-0 grade, suggesting that composite coating played a synergistic flame retardant role in physical and chemical aspects. In addition, in terms of mechanical properties, when the thickness of the coating is 300 m, the tensile strength of the wood with coating added with AHP and modified BS has hardly change compared to without AHP and modified BS, but its adhesion is reduced, which is owing to the pipe hole structure on the surface of the wood. The hydrogel coating permeates the wood surface, forming a gel network interlocking structure inside the wood after curing.Conclusions: The modified BS and hydrogel coating were combined to form a gas phase/condensate phase flame retardant system. In this flame retardant system, PVA enhanced the adhesion of hydrogel to wood, the non-flammable gas released by CS during combustion effectively reduces the concentration of combustible gas, and the addition of modified BS and AHP effectively improves the thermal stability of hydrogel coating, and the catalytic carbonization of nickel phytate endows with the composite flame retardant coating an excellent carbon residue rate. The composite flame retardant system effectively improves the flame retardancy and smoke suppression performance of wood. In addition, the tensile strength of composite flame retardant wood with AHP and modified BS has hardly change but the adhesion to wood decreased, which needs to be further studied.

Innovation Points

FullText(HTML)

References (30)

References

[1]	YAN L, XU Z S, DENG N. Synthesis of organophosphate-functionalized graphene oxide for enhancing the flame retardancy and smoke suppression properties of transparent fire-retardant coatings[J]. Polymer Degradation and Stability, 2020, 172: 109064. DOI: 10.1016/j.polymdegradstab.2019.109064
[2]	BERGLUND L A, BURGERT I. Bioinspired wood nanotechnology for functional materials[J]. Advanced Materials, 2018, 30(19): 1704285. DOI: 10.1002/adma.201704285
[3]	WIMMERS G. Wood: A construction material for tall buildings[J]. Nature Reviews Materials, 2017, 2(12): 17051. DOI: 10.1038/natrevmats.2017.51
[4]	LI S, WANG X H, XU M J, et al. Effect of a biomass based waterborne fire retardant coating on the flame retardancy for wood[J]. Polymers for Advanced Technologies, 2021, 32(12): 4805-4814. DOI: 10.1002/pat.5472
[5]	XIE H L, LAI X J, LI H Q, et al. A highly efficient flame retardant nacre-inspired nanocoating with ultrasensitive fire-warning and self-healing capabilities[J]. Chemical Engineering Journal, 2019, 369: 8-17. DOI: 10.1016/j.cej.2019.03.045
[6]	韦嘉盛, 戴磊, 贺瓶. 基于纤维素及其衍生物的凝胶材料设计[J]. 复合材料学报, 2022, 39(7): 3084-3103. WEI Jiasheng, DAI Lei, HE Ping. Design of gel materials with cellulose and its derivatives[J]. Acta Materiae Compositae Sinica, 2022, 39(7): 3084-3103(in Chinese).
[7]	CUI X F, ZHENG W J, ZOU W, et al. Water-retaining, tough and self-healing hydrogels and their uses as fire-resistant materials[J]. Polymer Chemistry, 2019, 10(37): 5151-5158. DOI: 10.1039/C9PY01015G
[8]	CHEN X X, LIU J H, KURNIAWAN A, et al. Inclusion of organic species in exfoliated montmorillonite nanolayers towards hierarchical functional inorganic-organic nanostructures[J]. Soft Matter, 2021, 17(43): 9819-9841. DOI: 10.1039/D1SM00975C
[9]	ZHANG L, HUANG Y B, SUN P, et al. A self-healing, recyclable, and degradable fire-retardant gelatin-based biogel coating for green buildings[J]. Soft Matter, 2021, 17(20): 5231-5239. DOI: 10.1039/D1SM00435B
[10]	ZHAO X J, LIANG Z W, HUANG Y B, et al. Influence of phytic acid on flame retardancy and adhesion performance enhancement of poly (vinyl alcohol) hydrogel coating to wood substrate[J]. Progress In Organic Coatings, 2021, 161: 106453. DOI: 10.1016/j.porgcoat.2021.106453
[11]	WANG Q Y, GUO J H, XU D F, et al. Facile construction of cellulose/montmorillonite nanocomposite biobased plastics with flame retardant and gas barrier properties[J]. Cellulose, 2015, 22(6): 3799-3810. DOI: 10.1007/s10570-015-0758-0
[12]	CHEN Q, CUI X F, ZHENG W J, et al. Hydrogels containing modified ammonium polyphosphate for fireproof materials[J]. Journal of Applied Polymer Science, 2021, 138(39): e51007. DOI: 10.1002/app.51007
[13]	ZHAO P P, GUO C G, LI L P. Exploring the effect of melamine pyrophosphate and aluminum hypophosphite on flame retardant wood flour/polypropylene composites[J]. Construction and Building Materials, 2018, 170: 193-199. DOI: 10.1016/j.conbuildmat.2018.03.074
[14]	YUAN B H, BAO C L, GUO Y Q, et al. Preparation and characterization of flame-retardant aluminum hypophosphite/poly(vinyl alcohol) composite[J]. Industrial & Engineering Chemistry Research, 2012, 51(43): 14065-14075.
[15]	LIU X D, SUN J, ZHANG S, et al. Effects of carboxymethyl chitosan microencapsulated melamine polyphosphate on the flame retardancy and water resistance of thermoplastic polyurethane[J]. Polymer Degradation and Stability, 2019, 160: 168-176. DOI: 10.1016/j.polymdegradstab.2018.12.019
[16]	WEN P Y, WANG D, LIU J J, et al. Organically modified montmorillonite as a synergist for intumescent flame retardant against the flammable polypropylene[J]. Polymers for Advanced Technologies, 2017, 28(6): 679-685. DOI: 10.1002/pat.3967
[17]	LI Y, JIANG J C, CHEN Z Q, et al. Preparation and characterization of microencapsulated aluminum hypophosphite and its performance on the thermal, flame retardancy, and mechanical properties of epoxy resin[J]. Polymer Composites, 2021, 42(4): 1818-1834. DOI: 10.1002/pc.25937
[18]	ZHANG Z H, LI X J, MA Z Y, et al. A facile and green strategy to simultaneously enhance the flame retardant and mechanical properties of poly(vinyl alcohol) by introduction of a bio-based polyelectrolyte complex formed by chitosan and phytic acid[J]. Dalton Transactions, 2020, 49(32): 11226-11237. DOI: 10.1039/D0DT02019B
[19]	YANG W, JIA Z J, CHEN Y N, et al. Carbon nanotube reinforced polylactide/basalt fiber composites containing aluminium hypophosphite: Thermal degradation, flame retardancy and mechanical properties[J]. RSC Advances, 2015, 5(128): 105869-10579. DOI: 10.1039/C5RA18606D
[20]	NOVITSKII A G, EFREMOV M V. Technological aspects of the suitability of rocks from different deposits for the production of continuous basalt fiber[J]. Glass and Ceramics, 2013, 69(11-12): 409-412. DOI: 10.1007/s10717-013-9491-z
[21]	HE P, WANG J X, LU F Y, et al. Synergistic effect of polyaniline grafted basalt plates for enhanced corrosion protective performance of epoxy coatings[J]. Progress in Organic Coatings, 2017, 110: 1-9. DOI: 10.1016/j.porgcoat.2017.05.001
[22]	张招崇, MAHONEY J J, 王福生, 等. 峨眉山大火成岩省西部苦橄岩及其共生玄武岩的地球化学: 地幔柱头部熔融的证据[J]. 岩石学报, 2006(6): 1538-1552. DOI: 10.3321/j.issn:1000-0569.2006.06.012 ZHANG Zhaochong, MAHONEY J J, WANG Fusheng, et al. Geochemistry of picritic and associated basalt flows of the western Emeishan flood basalt province, China: Evidence for a plume-head origin[J]. Acta Petrologica Sinica, 2006(6): 1538-1552(in Chinese). DOI: 10.3321/j.issn:1000-0569.2006.06.012
[23]	中国国家标准化管理委员会. 塑料燃烧性能的测定水平法和垂直法: GB/T 2408—2008[S]. 北京: 中国标准出版社, 2008. Standardization Administration of the People's Pepublic of China. Plastics—Determination of burning characteristics—Horizontal and vertical test: GB/T 2408—2008[S]. Beijing: Standards Press of China, 2008(in Chinese).
[24]	ZHANG L, HUANG Y B, SUN P, et al. A self-healing, recyclable, and degradable fire-retardant gelatin-based biogel coating for green buildings[J]. Soft Matter, 2021, 20(17): 5231-5239.
[25]	ZHENG H P, LIU L, MENG F D, et al. Multifunctional superhydrophobic coatings fabricated from basalt scales on a fluorocarbon coating base[J]. Journal of Materials Science and Technology, 2021, 84: 86-96.
[26]	SHI H, HE Y, PAN Y, et al. A modified mussel-inspired method to fabricate TiO₂ decorated superhydrophilic PVDF membrane for oil/water separation[J]. Journal of Membrane Science, 2016, 506: 60-70. DOI: 10.1016/j.memsci.2016.01.053
[27]	GAO X, ZHAO C C, LU H F, et al. Influence of phytic acid on the corrosion behavior of iron under acidic and neutral conditions[J]. Electrochim Acta, 2014, 150: 188-196. DOI: 10.1016/j.electacta.2014.09.160
[28]	ZIEGLER-BOROWSKA M, CHELMINIAK D, KACZMAREK H, et al. Effect of side substituents on thermal stability of the modified chitosan and its nanocomposites with magnetite[J]. Journal of Thermal Analysis and Calorimetry, 2016, 124(3): 1267-1280. DOI: 10.1007/s10973-016-5260-x
[29]	ZHANG Z H, MA Z Y, LENG Q, et al. Eco-friendly flame retardant coating deposited on cotton fabrics from bio-based chitosan, phytic acid and divalent metal ions[J]. International Journal of Biological Macromolecules, 2019, 140: 303-310. DOI: 10.1016/j.ijbiomac.2019.08.049
[30]	罗吉. 植酸金属盐的制备及其协效IFR阻燃PLA的研究[D]. 上海: 华东理工大学, 2021. LUO Ji. Preparation of phytic acid metal salt and synergistic effect with IFR for the flame retartant performance control of PLA[D]. Shanghai: East China University of Science and Technology, 2021(in Chinese).