{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,30]],"date-time":"2026-09-30T14:31:49Z","timestamp":1790778709771,"version":"4.1.0"},"reference-count":43,"publisher":"MDPI AG","issue":"1","license":[{"start":{"date-parts":[[2019,1,21]],"date-time":"2019-01-21T00:00:00Z","timestamp":1548028800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"European Commission\u2019s Erasmus Mundus joint doctorate program","award":["Sustainable Management & Design for Textiles (SMDTex)"],"award-info":[{"award-number":["Sustainable Management & Design for Textiles (SMDTex)"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Polymers"],"abstract":"<jats:p>In this study, two different types of industrial lignin (i.e., lignosulphonate lignin (LL) and kraft lignin (DL)) were exploited as charring agents with phosphorus-based flame retardants for polyamide 11 (PA11). The effect of lignins on the thermal stability and fire behavior of PA11 combined with phosphinate additives (namely, aluminum phosphinate (AlP) and zinc phosphinate (ZnP)) has been studied by thermogravimetric analysis (TGA), UL 94 vertical flame spread, and cone calorimetry tests. Various blends of flame retarded PA11 were prepared by melt process using a twin-screw extruder. Thermogravimetric analyses showed that the LL containing ternary blends are able to provide higher thermal stability, as well as a developed char residue. The decomposition of the phosphinates led to the formation of phosphate compounds in the condensed phase, which promotes the formation of a stable char. Flammability tests showed that LL\/ZnP ternary blends were able to achieve self-extinction and V-1 classification; the other formulations showed a strong melt dripping and higher burning. In addition to this, cone calorimetry results showed that the most enhanced behavior was found when 10 wt % of LL and AlP were combined, which strongly reduced PHRR (\u221274%) and THR (\u221222%), due to the interaction between LL and AlP, which not only promotes char formation but also confers the stability to char in the condensed phase.<\/jats:p>","DOI":"10.3390\/polym11010180","type":"journal-article","created":{"date-parts":[[2019,1,22]],"date-time":"2019-01-22T03:08:22Z","timestamp":1548126502000},"page":"180","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":29,"title":["Valorization of Industrial Lignin as Biobased Carbon Source in Fire Retardant System for Polyamide 11 Blends"],"prefix":"10.3390","volume":"11","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-9463-026X","authenticated-orcid":false,"given":"Neeraj","family":"Mandlekar","sequence":"first","affiliation":[{"name":"Politecnico di Torino, Dept. of Applied Science and Technology, 15121 Alessandria, Italy"},{"name":"ENSAIT, GEMTEX-Laboratoire de G\u00e9nie et Mat\u00e9riaux Textiles, F-59000 Lille, France"},{"name":"College of Textile and Clothing Engineering, Soochow University, Suzhou 215123, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5031-3396","authenticated-orcid":false,"given":"Aur\u00e9lie","family":"Cayla","sequence":"additional","affiliation":[{"name":"ENSAIT, GEMTEX-Laboratoire de G\u00e9nie et Mat\u00e9riaux Textiles, F-59000 Lille, France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0495-2047","authenticated-orcid":false,"given":"Fran\u00e7ois","family":"Rault","sequence":"additional","affiliation":[{"name":"ENSAIT, GEMTEX-Laboratoire de G\u00e9nie et Mat\u00e9riaux Textiles, F-59000 Lille, France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0712-6250","authenticated-orcid":false,"given":"St\u00e9phane","family":"Giraud","sequence":"additional","affiliation":[{"name":"ENSAIT, GEMTEX-Laboratoire de G\u00e9nie et Mat\u00e9riaux Textiles, F-59000 Lille, France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1405-4830","authenticated-orcid":false,"given":"Fabien","family":"Sala\u00fcn","sequence":"additional","affiliation":[{"name":"ENSAIT, GEMTEX-Laboratoire de G\u00e9nie et Mat\u00e9riaux Textiles, F-59000 Lille, France"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jinping","family":"Guan","sequence":"additional","affiliation":[{"name":"College of Textile and Clothing Engineering, Soochow University, Suzhou 215123, China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2019,1,21]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","unstructured":"Morgan, A.B., and Wilkie, C.A. (2014). Non-Halogenated Flame Retardant Handbook, Scrivener Publishing.","DOI":"10.1002\/9781118939239"},{"key":"ref_2","unstructured":"(2012). Rilsan\u00ae PA11: Created from a Renewable Source, Arkema Inc."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"627","DOI":"10.14314\/polimery.2012.627","article-title":"Polyamides from renewable sources as matrices of short fiber reinforced biocomposites","volume":"57","author":"Kuciel","year":"2012","journal-title":"Polimery"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"80","DOI":"10.1007\/s11837-006-0234-2","article-title":"Natural-Fiber-Reinforced Polymer Composites in Automotive Applications","volume":"58","author":"Holbery","year":"2006","journal-title":"JOM"},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"255","DOI":"10.5028\/jatm.2012.040303912","article-title":"A review of welding technologies for thermoplastic composites in aerospace applications","volume":"4","author":"Botelho","year":"2012","journal-title":"J. Aerosp. Technol. Manag."},{"key":"ref_6","unstructured":"(2017). Lignin Products Global Market Size, Sales Data 2017\u20132022, Reuters. Available online: https:\/\/www.reuters.com\/brandfeatures\/venture-capital\/article?id=4789."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"1266","DOI":"10.1016\/j.progpolymsci.2013.11.004","article-title":"Chemical modification of lignins: Towards biobased polymers","volume":"39","author":"Laurichesse","year":"2014","journal-title":"Prog. Polym. Sci."},{"key":"ref_8","doi-asserted-by":"crossref","unstructured":"Polat, Y., Stojanovska, E., and Negawo, T.A. (2017). Lignin as an Additive for Advanced Composites. Green Biocompos., 71\u201389.","DOI":"10.1007\/978-3-319-46610-1_4"},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"515","DOI":"10.1007\/s10973-017-6253-0","article-title":"Polylactide\/lignin blends: Effects of processing conditions on structure and thermo-mechanical properties","volume":"130","author":"Cicala","year":"2017","journal-title":"J. Therm. Anal. Calorim."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"1072","DOI":"10.1021\/sc500087z","article-title":"Progress in Green Polymer Composites from Lignin for Multifunctional Applications: A Review","volume":"2","author":"Thakur","year":"2014","journal-title":"ACS Sustain. Chem. Eng."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"1192","DOI":"10.1016\/j.polymdegradstab.2005.05.024","article-title":"Thermal and photochemical stability of poly(vinyl alcohol)\/modified lignin blends","volume":"91","author":"Fernandes","year":"2006","journal-title":"Polym. Degrad. Stab."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"656","DOI":"10.1016\/j.indcrop.2010.08.001","article-title":"Thermal stability and miscibility of poly(hydroxybutyrate) and soda lignin blends","volume":"32","author":"Mousavioun","year":"2010","journal-title":"Ind. Crops Prod."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"147","DOI":"10.1007\/s10973-016-5596-2","article-title":"Thermal characterization of a series of lignin-based polypropylene blends","volume":"127","author":"Blanco","year":"2017","journal-title":"J. Therm. Anal. Calorim."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"628","DOI":"10.1002\/pat.1130","article-title":"Flammability properties of intumescent PLA including starch and lignin","volume":"19","author":"Casetta","year":"2008","journal-title":"Polym. Adv. Technol."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"287","DOI":"10.1007\/s10086-018-1701-4","article-title":"Lignosulfonate\/APP IFR and its flame retardancy in lignosulfonate-based rigid polyurethane foams","volume":"64","author":"Lu","year":"2018","journal-title":"J. Wood Sci."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"13704","DOI":"10.1021\/acs.iecr.7b03085","article-title":"Thermal Stability and Fire Retardant Properties of Polyamide 11 Microcomposites Containing Different Lignins","volume":"56","author":"Mandlekar","year":"2017","journal-title":"Ind. Eng. Chem. Res."},{"key":"ref_17","doi-asserted-by":"crossref","unstructured":"H\u00f6rold, S. (2014). Phosphorus-based and Intumescent Flame Retardants. Polymer Green Flame Retardants, Elsevier.","DOI":"10.1016\/B978-0-444-53808-6.00006-8"},{"key":"ref_18","unstructured":"Kleiner, H.-J., Budzinsky, W., and Kirsch, G. (1998). Low-Flammability Polyamide Molding Materials. (US5773556A), Available online: https:\/\/patents.google.com\/patent\/US5773556A."},{"key":"ref_19","doi-asserted-by":"crossref","unstructured":"Braun, U., Bahr, H., and Schartel, B. (2010). Fire retardancy effect of aluminium phosphinate and melamine polyphosphate in glass fibre reinforced polyamide 6. E-Polymers, 10.","DOI":"10.1515\/epoly.2010.10.1.443"},{"key":"ref_20","unstructured":"Jenewein, E., and Kleiner, H.-J. (1997). Synergistic Flame Protection Agent Combination for Thermoplastic Polymers. (EP0892829B1), Available online: https:\/\/patents.google.com\/patents\/EP0892829B1."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"1528","DOI":"10.1016\/j.polymdegradstab.2007.05.007","article-title":"Flame retardancy mechanisms of aluminium phosphinate in combination with melamine polyphosphate and zinc borate in glass-fibre reinforced polyamide 6,6","volume":"92","author":"Braun","year":"2007","journal-title":"Polym. Degrad. Stab."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"879","DOI":"10.1016\/j.polymdegradstab.2012.03.038","article-title":"Development of fire resistant PET fibrous structures based on phosphinate-POSS blends","volume":"97","author":"Didane","year":"2012","journal-title":"Polym. Degrad. Stab."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"63","DOI":"10.1016\/j.polymdegradstab.2018.04.019","article-title":"Fire retardant action of zinc phosphinate and polyamide 11 blend containing lignin as a carbon source","volume":"153","author":"Mandlekar","year":"2018","journal-title":"Polym. Degrad. Stab."},{"key":"ref_24","doi-asserted-by":"crossref","unstructured":"Troitzsch, J. (2004). Plastics Flammability Handbook: Principles, Regulations, Testing, and Approval, Hanser.","DOI":"10.3139\/9783446436695.fm"},{"key":"ref_25","unstructured":"ISO 5660 (2002). Fire Test, Reaction to Fire, Rate of Heat Release (Cone Calorimeter Method), International Organization for Standardization."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"59","DOI":"10.1016\/j.tca.2011.02.007","article-title":"Thermal degradation and flame retardancy properties of ABS\/lignin: Effects of lignin content and reactive compatibilization","volume":"518","author":"Song","year":"2011","journal-title":"Thermochim. Acta"},{"key":"ref_27","unstructured":"Sicken, M., Schlosser, E., Wanzke, W., and Burghardt, D. (2004). Fusible Zinc Phosphinate. (US20040176506A1)."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"39424","DOI":"10.1039\/C5RA04149J","article-title":"Bulk vs. surface flame retardancy of fully bio-based polyamide 10,10","volume":"5","author":"Battegazzore","year":"2015","journal-title":"RSC Adv."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"155","DOI":"10.1016\/j.tca.2009.06.013","article-title":"Investigation of the thermal degradation of PET, zinc phosphinate, OMPOSS and their blends\u2014Identification of the formed species","volume":"495","author":"Vannier","year":"2009","journal-title":"Thermochim. Acta"},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"74","DOI":"10.1016\/j.tca.2016.08.004","article-title":"Aluminium diethylphosphinate versus ammonium polyphosphate: A comprehensive comparison of the chemical interactions during pyrolysis in flame-retarded polyolefine\/poly(phenylene oxide)","volume":"640","author":"Sut","year":"2016","journal-title":"Thermochim. Acta"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"79","DOI":"10.1016\/j.jaap.2008.10.024","article-title":"Role of methoxyl group in char formation from lignin-related compounds","volume":"84","author":"Hosoya","year":"2009","journal-title":"J. Anal. Appl. Pyrolysis"},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"680","DOI":"10.1002\/pat.1147","article-title":"Flame retardancy mechanisms of metal phosphinates in combination with melamine cyanurate in glass-fiber reinforced poly (1,4-butylene terephthalate): The influence of metal cation","volume":"19","author":"Braun","year":"2008","journal-title":"Polym. Adv. Technol."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"355","DOI":"10.1515\/hfsg.1991.45.5.355","article-title":"Thermogravimetry\/mass spectrometry of various lignosulfonates as well as of a kraft and acetosolv lignin","volume":"45","author":"Jakab","year":"1991","journal-title":"Holzforschung"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"1083","DOI":"10.1016\/j.polymdegradstab.2012.04.010","article-title":"Fire performances comparison of back coating and melt spinning approaches for PET covering textiles","volume":"97","author":"Didane","year":"2012","journal-title":"Polym. Degrad. Stab."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"2185","DOI":"10.1002\/macp.200400255","article-title":"Flame retardant mechanisms of red phosphorus and magnesium hydroxide in high impact polystyrene","volume":"205","author":"Braun","year":"2004","journal-title":"Macromol. Chem. Phys."},{"key":"ref_36","doi-asserted-by":"crossref","unstructured":"Lewin, M., and Weil, E. (2001). Mechanisms and Modes of Action in Flame Retardancy of Polymers, Woodhead Publishing Ltd.","DOI":"10.1533\/9781855737464.31"},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"1040","DOI":"10.1016\/j.compositesa.2005.01.030","article-title":"Heat release of polymer composites in fire","volume":"37","author":"Mouritz","year":"2006","journal-title":"Compos. Part A Appl. Sci. Manuf."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"327","DOI":"10.1002\/fam.949","article-title":"Development of fire-retarded materials\u2014Interpretation of cone calorimeter data","volume":"31","author":"Schartel","year":"2007","journal-title":"Fire Mater."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"135","DOI":"10.1016\/j.polymdegradstab.2014.12.015","article-title":"Chemical modification of lignin by phosphorus molecules to improve the fire behavior of polybutylene succinate","volume":"113","author":"Ferry","year":"2015","journal-title":"Polym. Degrad. Stab."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"1508","DOI":"10.1016\/j.polymdegradstab.2011.05.002","article-title":"Synthesis, application and flame retardancy mechanism of a novel flame retardant containing silicon and caged bicyclic phosphate for polyamide 6","volume":"96","author":"Chen","year":"2011","journal-title":"Polym. Degrad. Stab."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"5","DOI":"10.1177\/0734904105043451","article-title":"Effect of red phosphorus and melamine polyphosphate on the fire behavior of HIPS","volume":"23","author":"Braun","year":"2005","journal-title":"J. Fire Sci."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"26","DOI":"10.1016\/j.polymdegradstab.2018.01.008","article-title":"Highly efficient flame-retardant glass-fiber-reinforced polyamide 6T system based on a novel DOPO-based derivative: Flame retardancy, thermal decomposition, and pyrolysis behaviour","volume":"148","author":"Huang","year":"2018","journal-title":"Polym. Degrad. Stab."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"66","DOI":"10.1016\/j.polymdegradstab.2015.03.018","article-title":"Synergistic effects of sepiolite on the fl ame retardant properties and thermal degradation behaviors of polyamide 66\/aluminum diethylphosphinate composites","volume":"117","author":"Zhan","year":"2015","journal-title":"Polym. Degrad. Stab."}],"container-title":["Polymers"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2073-4360\/11\/1\/180\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T12:27:36Z","timestamp":1760185656000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2073-4360\/11\/1\/180"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2019,1,21]]},"references-count":43,"journal-issue":{"issue":"1","published-online":{"date-parts":[[2019,1]]}},"alternative-id":["polym11010180"],"URL":"https:\/\/doi.org\/10.3390\/polym11010180","relation":{},"ISSN":["2073-4360"],"issn-type":[{"value":"2073-4360","type":"electronic"}],"subject":[],"published":{"date-parts":[[2019,1,21]]}}}