{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,7,22]],"date-time":"2026-07-22T08:40:30Z","timestamp":1784709630791,"version":"3.55.0"},"reference-count":42,"publisher":"MDPI AG","issue":"5","license":[{"start":{"date-parts":[[2024,2,27]],"date-time":"2024-02-27T00:00:00Z","timestamp":1708992000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"National Centre for Research and Development","award":["01.01.01-00-0238\/21"],"award-info":[{"award-number":["01.01.01-00-0238\/21"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Polymers"],"abstract":"<jats:p>Polyurethane (PUR), as an engineering polymer, is widely used in many sectors of industries. However, the high fire risks associated with PUR, including the smoke density, a high heat release rate, and the toxicity of combustion products limit its applications in many fields. This paper presents the influence of silsesquioxane fillers, alone and in a synergistic system with halogen-free flame-retardant compounds, on reducing the fire hazard of polyurethane foams. The flammability of PUR composites was determined with the use of a pyrolysis combustion flow calorimeter (PCFC) and a cone calorimeter. The flammability results were supplemented with smoke emission values obtained with the use of a smoke density chamber (SDC) and toxicometric indexes. Toxicometric indexes were determined with the use of an innovative method consisting of a thermo-balance connected to a gas analyzer with the use of a heated transfer line. The obtained test results clearly indicate that the used silsesquioxane compounds, especially in combination with organic phosphorus compounds, reduced the fire risk, as expressed by parameters such as the maximum heat release rate (HRRmax), the total heat release rate (THR), and the maximum smoke density (SDmax). The flame-retardant non-halogen system also reduced the amounts of toxic gases emitted during the decomposition of PUR, especially NOx, HCN, NH3, CO and CO2. According to the literature review, complex studies on the fire hazard of a system of POSS\u2013phosphorus compounds in the PUR matrix have not been published yet. This article presents the complex results of studies, indicating that the POSS\u2013phosphorous compound system can be treated as an alternative to toxic halogen flame-retardant compounds in order to decrease the fire hazard of PUR foam.<\/jats:p>","DOI":"10.3390\/polym16050645","type":"journal-article","created":{"date-parts":[[2024,2,28]],"date-time":"2024-02-28T03:37:57Z","timestamp":1709091477000},"page":"645","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":11,"title":["Cage Nanofillers\u2019 Influence on Fire Hazard and Toxic Gases Emitted during Thermal Decomposition of Polyurethane Foam"],"prefix":"10.3390","volume":"16","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-6003-6940","authenticated-orcid":false,"given":"Arkadiusz","family":"G\u0142owacki","sequence":"first","affiliation":[{"name":"Institute of Chemistry, The Jan Kochanowski University, 25-406 Kielce, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5131-0699","authenticated-orcid":false,"given":"Przemys\u0142aw","family":"Rybi\u0144ski","sequence":"additional","affiliation":[{"name":"Institute of Chemistry, The Jan Kochanowski University, 25-406 Kielce, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Monika","family":"\u017belezik","sequence":"additional","affiliation":[{"name":"Institute of Geography and Environmental Sciences, Jan Kochanowski University, 25-406 Kielce, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ulugbek Zakirovich","family":"Mirkhodjaev","sequence":"additional","affiliation":[{"name":"Department of Biophysics, National University of Uzbekistan, Tashkent 100095, Uzbekistan"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2024,2,27]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"114","DOI":"10.1016\/j.jhazmat.2013.12.025","article-title":"Smoke suppression properties of ferrite yellow on flame retardant thermoplastic polyurethane based on ammonium polyphosphate","volume":"266","author":"Chen","year":"2014","journal-title":"J. Hazard. Mater."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"289","DOI":"10.1177\/073490418700500501","article-title":"Fire Hazard and Toxic Potency of the Smoke from Burning Materials","volume":"5","author":"Hirschler","year":"1987","journal-title":"J. Fire Sci."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1080\/00222338208056462","article-title":"Smoke and Toxic Gas Production from Burning Polymers","volume":"17","author":"Woolley","year":"1982","journal-title":"J. Macromol. Sci. Part A\u2014Chem."},{"key":"ref_4","doi-asserted-by":"crossref","unstructured":"Krawiec, P., Wargu\u0142a, \u0141., Ma\u0142ozi\u0119\u0107, D., Kaczmarzyk, P., Dziechciarz, A., and Czarnecka-Komorowska, D. (2020). The Toxicological Testing and Thermal Decomposition of Drive and Transport Belts Madeof Thermoplastic Multilayer Polymer Materials. Polymers, 12.","DOI":"10.3390\/polym12102232"},{"key":"ref_5","doi-asserted-by":"crossref","unstructured":"Rybi\u0144ski, P., Syrek, B., \u017bukowski, W., and Brad\u0142o, D. (2019). Impact of Basalt Filler and Ceramizable Additives on the Toxicity of Gaseous Products Emitted from Thermal Decomposition of Silicone Rubber Composites. Materials, 12.","DOI":"10.3390\/ma12213478"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"1994","DOI":"10.1038\/s41598-021-81537-5","article-title":"Experimental study on thermal effect and gas release laws of coal-polyurethane cooperative spontaneous combustion","volume":"11","author":"Wang","year":"2021","journal-title":"Sci. Rep."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"103895","DOI":"10.1016\/j.firesaf.2023.103895","article-title":"Modelling carbon monoxide transport and hazard from smouldering for building fire safety design analysis","volume":"140","author":"Cheung","year":"2023","journal-title":"Fire Saf. J."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"3","DOI":"10.1186\/s40038-016-0012-3","article-title":"The fire toxicity of polyurethane foams","volume":"5","author":"McKenna","year":"2016","journal-title":"Fire Sci. Rev."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"2687","DOI":"10.1016\/j.polymdegradstab.2013.09.032","article-title":"Thermal degradation characteristics of rigid polyurethane foam and the volatile products analysis with TG-FTIR-MS","volume":"98","author":"Jiao","year":"2013","journal-title":"Polym. Degrad. Stab."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"131","DOI":"10.1007\/s10973-017-6294-4","article-title":"Analysis of flammability and smoke emission of rigid polyurethane foams modified with nanoparticles and halogen-free fire retardants","volume":"130","author":"Salasinska","year":"2017","journal-title":"J. Therm. Anal. Calorim."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"2375","DOI":"10.2147\/IJN.S15586","article-title":"Manufacturing of biodegradable polyurethane scaffolds based on polycaprolactone using a phase separation method: Physical properties and in vitro assay","volume":"2375","author":"Asefnejad","year":"2011","journal-title":"Int. J. Nanomed."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"995","DOI":"10.1016\/j.conbuildmat.2018.09.166","article-title":"The use of polyurethane for structural and infrastructural engineering applications: A state-of-the-art review","volume":"190","author":"Somarathna","year":"2018","journal-title":"Constr. Build. Mater."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"493","DOI":"10.1016\/S0141-3910(01)00177-X","article-title":"Thermal degradation of polyurethane and polyurethane\/expandable graphite coatings","volume":"74","author":"Duquesne","year":"2001","journal-title":"Polym. Degrad. Stab."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"195","DOI":"10.1016\/S0141-3910(02)00034-4","article-title":"Expandable graphite as an intumescent flame retardant in polyisocyanurate\u2013polyurethane foams","volume":"77","author":"Modesti","year":"2002","journal-title":"Polym. Degrad. Stab."},{"key":"ref_15","doi-asserted-by":"crossref","unstructured":"Chen, Y., Luo, Y., Guo, X., Chen, L., Xu, T., and Jia, D. (2019). Structure and Flame-Retardant Actions of Rigid Polyurethane Foams with Expandable Graphite. Polymers, 11.","DOI":"10.3390\/polym11040686"},{"key":"ref_16","doi-asserted-by":"crossref","unstructured":"Acu\u00f1a, P., Li, Z., Santiago-Calvo, M., Villafa\u00f1e, F., Rodr\u00edguez-Perez, M., and Wang, D.-Y. (2019). Influence of the Characteristics of Expandable Graphite on the Morphology, Thermal Properties, Fire Behaviour and Compression Performance of a Rigid Polyurethane Foam. Polymers, 11.","DOI":"10.3390\/polym11010168"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"13","DOI":"10.1016\/j.ijmst.2013.01.003","article-title":"Synergistic effects of expandable graphite and dimethyl methyl phosphonate on the mechanical properties, fire behavior, and thermal stability of a polyisocyanurate\u2013polyurethane foam","volume":"23","author":"Hu","year":"2013","journal-title":"Int. J. Min. Sci. Technol."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"445","DOI":"10.3390\/nano2040445","article-title":"Polyhedral Oligomeric Silsesquioxane (POSS)-Containing Polymer Nanocomposites","volume":"2","author":"Ayandele","year":"2012","journal-title":"Nanomaterials"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"212","DOI":"10.1039\/C6QM00062B","article-title":"Polyhedral oligomeric silsesquioxane-based hybrid materials and their applications","volume":"1","author":"Zhou","year":"2017","journal-title":"Mater. Chem. Front."},{"key":"ref_20","doi-asserted-by":"crossref","unstructured":"Rybi\u0144ski, P., Syrek, B., Brad\u0142o, D., and \u017bukowski, W. (2018). Effect of POSS Particles and Synergism Action of POSS and Poly-(Melamine Phosphate) on the Thermal Properties and Flame Retardance of Silicone Rubber Composites. Materials, 11.","DOI":"10.3390\/ma11081298"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"106040","DOI":"10.1016\/j.polymertesting.2019.106040","article-title":"Determination of toxic products emissions of polymers thermal decomposition using fluidised bed reactor and FTIR analysis","volume":"79","author":"Syrek","year":"2019","journal-title":"Polym. Test."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"50","DOI":"10.1016\/j.polymdegradstab.2014.03.025","article-title":"Degradative and morphological characterization of POSS modified nanohybrid polyurethane elastomers","volume":"104","author":"Lewicki","year":"2014","journal-title":"Polym. Degrad. Stab."},{"key":"ref_23","unstructured":"(2010). Technical Terminology: Translation of Units of Measurement and Other Basic Physical Quantities. Standard No. PN-EN ISO 291:2010."},{"key":"ref_24","unstructured":"(2014). Standard Test Method for Determining Flammability Characteristics of Plastics and Other Solid Materials Using Microscale Combustion Calorimetry. Standard No. ASTM D7309-14."},{"key":"ref_25","unstructured":"(2017). Reaction-to-Fire Tests\u2014Heat Release, Smoke Production and Mass Loss Rate\u2014Part 1: Heat Release Rate (Cone Calorimeter Method with a Nominal Heat Flux of 50 kW\/m2). Standard No. PN-EN ISO 5660-1:2017."},{"key":"ref_26","unstructured":"(2012). Plastics\u2014Smoke Generation\u2014Part 2: Determination of Optical Density by a Single-Chamber Test. Standard No. PN-EN ISO 5659-2:2012."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"277","DOI":"10.1016\/B978-0-12-804065-2.00009-7","article-title":"Polyurethane Nanocomposite Foams","volume":"9","author":"Verdolotti","year":"2017","journal-title":"Polyurethane Polym."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"110370","DOI":"10.1016\/j.msec.2019.110370","article-title":"Examining the influence of functionalized POSS on the structure and bioactivity of flexible polyurethane foams","volume":"108","author":"Hebda","year":"2019","journal-title":"Mater. Sci. Eng. C"},{"key":"ref_29","doi-asserted-by":"crossref","unstructured":"Kwiatkowski, K., and Nachman, M. (2017). The Abrasive Wear Resistance of the Segmented Linear Polyurethane Elastomers Based on a Variety of Polyols as Soft Segments. Polymers, 9.","DOI":"10.3390\/polym9120705"},{"key":"ref_30","doi-asserted-by":"crossref","unstructured":"Cz\u0142onka, S., Str\u0105kowska, A., and Kairyt\u0117, A. (2020). Application of Walnut Shells-Derived Biopolyol in the Synthesis of Rigid Polyurethane Foams. Materials, 13.","DOI":"10.3390\/ma13122687"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"555","DOI":"10.1016\/j.polymdegradstab.2004.10.012","article-title":"FTIR analysis of thermally processed PU foam","volume":"87","author":"Hatchett","year":"2005","journal-title":"Polym. Degrad. Stab."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"2423","DOI":"10.1007\/s00396-017-4218-2","article-title":"Effects of hydrophilic groups of curing agents on the properties of flame-retardant two-component waterborne coatings","volume":"295","author":"Yin","year":"2017","journal-title":"Colloid Polym. Sci."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"569","DOI":"10.1080\/1023666X.2017.1312754","article-title":"Structure analysis of polyether-based thermoplastic polyurethane elastomers by FTIR, 1H NMR and 13C NMR","volume":"22","author":"Tang","year":"2017","journal-title":"Int. J. Polym. Anal. Charact."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"3171","DOI":"10.1016\/j.eurpolymj.2013.06.009","article-title":"Influence of oxidation state of phosphorus on the thermal and flammability of polyurea and epoxy resin","volume":"49","author":"Mariappan","year":"2013","journal-title":"Eur. Polym. J."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"1230","DOI":"10.1016\/j.polymdegradstab.2009.04.016","article-title":"Polyhedral oligomeric silsesquioxane as flame retardant for thermoplastic polyurethane","volume":"94","author":"Bourbigot","year":"2009","journal-title":"Polym. Degrad. Stab."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"4365","DOI":"10.1023\/A:1004805023228","article-title":"Preparation of silicon carbide foams using polymeric precursor solutions","volume":"35","author":"Bao","year":"2000","journal-title":"J. Mater. Sci."},{"key":"ref_37","doi-asserted-by":"crossref","unstructured":"Ramgobin, A., Fontaine, G., Penverne, C., and Bourbigot, S. (2017). Thermal Stability and Fire Properties of Salen and Metallosalens as Fire Retardants in Thermoplastic Polyurethane (TPU). Materials, 10.","DOI":"10.3390\/ma10060665"},{"key":"ref_38","doi-asserted-by":"crossref","unstructured":"Rybi\u0144ski, P., Syrek, B., Marzec, A., Szadkowski, B., Ku\u015bmierek, M., \u015aliwka-Kaszy\u0144ska, M., and Mirkhodjaev, U.Z. (2021). Effects of Basalt and Carbon Fillers on Fire Hazard, Thermal, and Mechanical Properties of EPDM Rubber Composites. Materials, 14.","DOI":"10.3390\/ma14185245"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"7230","DOI":"10.1016\/j.polymer.2005.06.032","article-title":"Phase behavior and hydrogen bonding in biomembrane mimicing polyurethanes with long side chain fluorinated alkyl phosphatidylcholine polar head groups attached to hard block","volume":"46","author":"Tan","year":"2005","journal-title":"Polymer"},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"100608","DOI":"10.1016\/j.mser.2021.100608","article-title":"Structure-properties relationships of cellular materials from biobased polyurethane foams","volume":"145","author":"Peyrton","year":"2021","journal-title":"Mater. Sci. Eng. R Rep."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"149","DOI":"10.1023\/B:FIRE.0000016841.07530.64","article-title":"Generation and Transport of Smoke Components","volume":"40","author":"Butler","year":"2004","journal-title":"Fire Technol."},{"key":"ref_42","doi-asserted-by":"crossref","unstructured":"Rybi\u0144ski, P., Mirkhodjaev, U.Z., \u017bukowski, W., Brad\u0142o, D., Gawlik, A., Zamachowski, J., \u017belezik, M., Mas\u0142owski, M., and Miedzianowska, J. (2023). Effect of Hybrid Filler, Carbon Black\u2013Lignocellulose, on Fire Hazard Reduction, including PAHs and PCDDs\/Fs of Natural Rubber Composites. Polymers, 15.","DOI":"10.3390\/polym15081975"}],"container-title":["Polymers"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2073-4360\/16\/5\/645\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T14:05:57Z","timestamp":1760105157000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2073-4360\/16\/5\/645"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2024,2,27]]},"references-count":42,"journal-issue":{"issue":"5","published-online":{"date-parts":[[2024,3]]}},"alternative-id":["polym16050645"],"URL":"https:\/\/doi.org\/10.3390\/polym16050645","relation":{},"ISSN":["2073-4360"],"issn-type":[{"value":"2073-4360","type":"electronic"}],"subject":[],"published":{"date-parts":[[2024,2,27]]}}}