عملکرد در برابر آتش کامپوزیت پلی‌یورتان گرمانرم با تاخیرانداز شعله-تورمی و نانوسیلیکا: مطالعه هم‌افزایی

نوع مقاله : پژوهشی

نویسندگان

1 تهران، دانشگاه علم و صنعت ایران، دانشکده شیمی، کد پستی 13114-16846

2 تهران، پژوهشگاه پلیمر و پتروشیمی ایران، پژوهشکده فرایند، گروه پلاستیک، صندوق پستی 115-14975

چکیده

فرضیه‌: هدف از این پژوهش، بهبود رفتار در برابر آتش گرمانرم پلی‌یورتان (TPU) با افزودنی‌های تأخیرانداز شعله-تورمی (IFR) و نانوذره سیلیکا به‌عنوان عامل هم‌افزاست. 
روش‌ها: سامانه شعله-تورمی متشکل از آمونیوم پلی‌فسفات (APP)، ملامین پلی‌فسفات (MPP) و پنتااریتریتول (PER) با روش اختلاط مذاب به TPU افزوده شد. اشتعال‌پذیری کامپوزیت با آزمون سوختن عمودی UL94 و کارایی نانوسیلیکا با آزمون گرماسنجی مخروطی ارزیابی شد. سپس، نانوسیلیکا با درصد وزنی بسیار کم به‌عنوان هم‌افزا به کامپوزیت TPU-IFR افزوده و خواص آتش بررسی شد. پایداری گرمایی و ساختار زغال پس از سوختن به‌ترتیب با تجزیه گرماوزن‌سنجی (TGA) و میکروسکوپ الکترونی (FE-SEM) بررسی شد. 
یافته‌ها: نتایج آزمون‌ها، اثربخشی سامانه IFR را با کاهش شایان توجه حداکثر شدت تولید دود و شدت رهایش گرما (PHRR)(PSPR) به‌ترتیب 58.3 و %62.6 نشان داد. افزودن %0.5 وزنی نانوسیلیکا به‌عنوان عامل هم‌افزا به سامانه IFR-TPU، سبب کاهش %75 در PHRR و %79.2 در PSPR نسبت به TPU مرجع و حذف شره مذاب شد. این نتیجه، هم‌افزایی مؤثر نانوسیلیکا را در تقویت  خواص نانوسیلیکای TPU تأیید کرد. هر دو کامپوزیت در آزمون UL-94 به درجه V0 دست یافتند. بازده زغال از %6 در TPU به %31.2 در TPU-IFR و %58.9 در  نانوکامپوزیت TPU افزایش یافت. بررسی ساختار زغال با میکروسکوپی الکترونی پویشی گسیل میدانی (FE-SEM)، وجود ساختار فشرده و یکپارچه را در نانوکامپوزیت TPU نشان داد، در حالی که زغال حاصل از سوختن TPU-IFR، ساختاری حفره‌دار داشت. تجزیه گرماوزنی (TGA) افزایش پایداری گرمایی در هر دو کامپوزیت TPU را با تشکیل زغال به‌عنوان سد گرمایی تأیید کرد. پژوهش حاضر، سامانه نانوسیلیکای شعله-تورمی کارآمدی را در بهبود رفتار TPU در برابر آتش معرفی می‌کند که با افزودن مقدار بسیار کم نانوسیلیکا به‌عنوان هم‌افزا، ایمنی آن در برابر آتش به‌طور شایان توجهی افزایش می‌یابد. 

کلیدواژه‌ها

عنوان مقاله [English]

Fire Performance of Intumescent Flame Retardant/Nanosilica/Thermoplastic Polyurethane Composite: A Study on Synergism

نویسندگان [English]

  • Leila Taghi Akbari 1
  • Mohammad Reza Naimi - Jamal 1
  • Shervin Ahmadi 2
1 Department of Chemistry, Organic Chemistry, Iran University of Science and Technology, Postal Code, 1674613114, Tehran, Iran
2 IPlastic Processing and Engineering Department, Faculty of Processing, Iran Polymer and Petrochemical Institute, P.O. Box: 14975-112, Tehran, Iran
چکیده [English]

Hypothesis: The aim of this research is to improve the fire behavior of thermoplastic polyurethane (TPU) using an intumescent flame retardant system (IFR) and nanosilica as a synergistic agent 
Methods: A three-component IFR system consisting of ammonium polyphosphate (APP), melamine polyphosphate (MPP), and pentaerythritol (PER) was added to TPU by melt mixing. The flammability of the TPU-IFR was evaluated by UL94 vertical burning test and the efficiency of the IFR was investigated by cone calorimeter test (CCT). A nanosilica as a synergist with low loading was added to the TPU-IFR composite, and fire properties were investigated. Thermal stability and char morphology were investigated by thermal analysis and scanning electron microscopy, respectively.
Findings: The results show that the IFR system is effective with a significant decrease of 62.6% in peak heat release rate (PHRR) and 58.3% in peak smoke production (pSPR). By incorporation of 0.5% (by wt) nanosilica into TPU-IFR, there are decreases in PHRR and pSPR by 75.0% and 79.2%, respectively, compared to the original TPU, while the dripping is removed. This has confirmed the effective synergism of nanosilica in enhancing the flame retardancy of TPU-IFR. Further, the amount of residual char has reached 31.2% and 58.9% for TPU-IFR and TPU-IFR-nanosilica, respectively, compared to 6.2% in a neat TPU. Both TPU composites have reached V0 grade in UL-94 test. FESEM shows an integrated compact char in IFR-TPU-nanosilica, while there are small holes in the char structure of IFR-TPU. Thermal analysis (TGA) has shown enhanced thermal stability in the two TPU composites by formation of a carbon layer as a thermal barrier during burning. This work introduces an efficient intumescent flame retardant system for improving the fire behavior of TPU which can significantly enhance the fire safety of TPU by a low loading of nanosilica as a synergist. 

کلیدواژه‌ها [English]

  • Intumescent Flame retardant
  • Nanosilica
  • Synergistic agent
  • Thermoplastic Polyurethane
  • Cone calorimeter

مراجع

  1. Finnigan B., Martin D., Halley P., Truss R., and Campbell K., Morphology and Properties of Thermoplastic Polyurethane Nanocomposites Incorporating Hydrophilic Layered Silicates, Polymer, 45, 2249-2260, 2004.
  2. Chen X., Ma C., and Jiao C., Enhancement of Flame-Retardant Performance of Thermoplastic Polyurethane with the Incorporation of Aluminum Hypophosphite and Iron-Graphene, Polym. Degrad. Stab., 129, 275-285, 2016.
  3. Zhao X., Chen C., and Chen X., Effects of Carbon Fibers on the Flammability and Smoke Emission Characteristics of Halogen-Free Thermoplastic Polyurethane/Ammonium Polyphosphate, J. Mater. Sci., 51, 3762-3771, 2016.
  4. Sut A., Metzsch-Zilligen E., Großhauser M., Pfaendner R., and Schartel B., Synergy between Melamine Cyanurate, Melamine Polyphosphate and Aluminum Diethylphosphinate in Flame Retarded Thermoplastic Polyurethane, Polym. Test., 74, 96-204, 2019.
  5. Lu S., Shi H., Shen B., Hong W., Yu D., and Chen X., Polypyrrole-Functionalized g-C3N4 for Rheological, Combustion and Self-Healing Properties of Thermoplastic Polyurethane, J. Polym. Res., 29, 263, 2022.
  6. Chen L. and Wang Y., A Review on Flame Retardant Technology in China. Part I: Development of Flame Retardants, Polym. Adv. Technol., 21, 1-26, 2010.
  7. Morgan A.B., A Review of Transition Metal-Based Flame Retardants: Transition Metal Oxide/Salts, and Complexes, Fire and Polymers, ACS Symposium Series, 1013, 312-328, 2010.
  8. Laoutid F., Bonnaud L., Alexandre M., Lopez-Cuesta J.M., and Dubois P., New Prospects in Flame Retardant Polymer Materials: From Fundamentals to Nanocomposites, Mater. Sci. Eng. R: Rep., 63, 100-125, 2009.
  9. Qu H., Wu W., Xie J., and Xu J., A Novel Intumescent Flame Retardant and Smoke Suppression System for Flexible PVC, Polym. Adv. Technol., 22, 1174-1181, 2011.
  10. Chen Y., Zhan J., Zhang P., Nie S., Lu H., Song L., and Hu Y., Preparation of Intumescent Flame Retardant Poly(butylene succinate) Using Fumed Silica as Synergistic Agent., Ind. Eng. Chem. Prod. Res., 1, 8200-8208, 2010.
  11. Toldy A., Szolnoki B., and Zimonyi E., Flame Retardancy of Thermoplastics Polyurethanes, Polym. Degrad. Stab., 97, 2524-2530, 2012.
  12. Chen X.L., Jiao C.M., and Zhang J., Microencapsulation of Ammonium Polyphosphate with Hydroxyl Silicone Oil and Its Flame Retardance in Thermoplastic Polyurethane, J. Therm. Anal. Calorim., 104, 1037-1043, 2011.
  13. Wang W., Chen X., Gu Y., and Jiao C., Synergistic Fire Safety Effect between Nano-CuO and Ammonium Polyphosphate in Thermoplastic Polyurethane Elastomer, J. Therm. Anal. Calorim., 131, 3175-3183, 2018.
  14. Liu L., Xu Y., Li S., Xu M., He Y., Shi Z., and Li B., A Novel Strategy for Simultaneously Improving the Fire Safety, Water Resistance and Compatibility of Thermoplastic Polyurethane Composites through the Construction of Biomimetic Hydrophobic Structure of Intumescent Flame Retardant Synergistic System, Composites: Part B, 176,107218, 2019.
  15. Ye L., Wu Q.H., and Qu B.J., Synergistic Effects of Fumed Silica on Intumescent Flame-Retardant Polypropylene, J. Appl. Polym. Sci.,115, 3508-3515, 2010.
  16. Jiao C.M. and Chen X., Influence of Fumed Silica on the Flame-Retardant Properties of Ethylene Vinyl Acetate/Aluminum Hydroxide Composites, J. Appl. Polym. Sci., 120, 1285-1289, 2011.
  17. Wang X.Y., Li Y., Liao W.W., Gu J., and Li D., A New Intumescent Flame-Retardant: Preparation, Surface Modification, and Its Application in Polypropylene, Polym. Adv. Technol., 19, 1055-1061, 2008.
  18. Fanglong Z., Qun X., Qianqian F., Rangtong L., and Kejing L.I., Influence of Nano-silica on Flame Resistance Behavior of Intumescent Flame Retardant Cellulosic Textiles: Remarkable Synergistic Effect? Surf. Coat. Technol., 294, 90-94, 2016.
  19. Li H.L., Huo C., Miao P., Zhang T., and Wei H.L. Phenolic Foam Based the Influence of Intumescent Flame Retardancy System Ammonium Polyphosphate/Pentaerythritol/Melamine, International Conference on Manufacturing Engineering and Intelligent Materials (ICMEIM 2017), Atlantis, 654-661, 2017.
  20. Zhang H., Lu J., Yang H., Yang H., Lang J., and Zhang Q., Synergistic Flame-Retardant Mechanism of Dicyclohexenyl Aluminum Hypophosphite and Nano-silica, Polymers, 19, 1211, 2019.
  21. Bakhtiyari S., Taghi A L., and Barikani M., The Effective Parameters for Reaction-to-Fire Properties of Expanded Polystyrene Foams in Bench Scale, Iran. Polym. J., 19, 27-37, 2010.
  22. Babrauskas V., Development of the Cone Calorimeter-A Bench-Scale Heat ReleaseRate Apparatus Based on Oxygen Consumption, Fire Mater., 8, 81-95, 1983.
  23. Schartel B. and Hull TR., Development of Fire-Retarded Materials-Interpretation of Cone Calorimeter Data, Fire Mater., 31, 327-354, 2007.
  24. Liu L., Xu Y., He Y., Xu M., Shi Z., Hu H., Yang Z., and Li B., An Effective Mono-Component Intumescent Flame Retardant for the Enhancement of Water Resistance and Fire Safety of Thermoplastic Polyurethane Composites, Polym. Degrad. Stab., 167, 146-56, 2019.
  25. Babrauskas V. and Peacock R.D., Heat Release Rate: The Single Most Important Variable in Fire Hazard, Fire Saf. J., 18, 255-272, 1992.
  26. Chen X.L. and Jiao C.M., Flame Retardancy and Thermal Degradation of Intumescent Flame Retardant Polypropylene Material, Polym. Adv. Technol., 22, 817-821, 2011.
  27. Lin M., Li B., Li Q.F., Li S., and Zhang S.Q., Synergistic Effect of Metal Oxides on the Flame Retardancy and Thermal Degradation of Novel Intumescent Flame-Retardant Thermoplastic Polyurethanes, J. Appl. Polym. Sci., 121, 1951-1960, 2011.
  28. Chen X., Jiang Y., Liu J., Jiao C., Qian Y., and Li S., Smoke Suppression Properties of Fumed Silica on Flame-Retardant Thermoplastic Polyurethane Based on Ammonium Polyphosphate, J. Therm. Anal. Calorim., 120, 1493-1501, 2015.
  29. Alarifi A.A., Phylaktou H.N., and Andrews G.E., What Kills People in a Fire? Heat or Smoke? The 9th Saudi Students Conference, ICC, University of Birmingham, Birmingham, 13-14 February, 2016.
  30. Levchik S., Hirschler M., and Weil E., Practical Guide to Smoke and Combustion Products from Burning Polymers-Generation, Assessment and Control, 1st ed., Smithers Rapra, UK, 7, 167-211, 2011.
  31. Herrera M., Matuschek G., and Kettrup A., Thermal Degradation of Thermoplastic Polyurethane Elastomers (TPU) Based on MDI, Polym. Degrad. Stab., 78, 323-231, 2002.
  32. Liu X., Sun J., Zhang S., Guo J., Tang W., Li H., and Gu X., Effects of Carboxymethyl Chitosan Microencapsulated Melamine Polyphosphate on the Flame Retardancy and Water Resistance of Thermoplastic Polyurethane, Polym. Degrad. Stab., 1, 168-176, 2019.
  33. Cai C., Sun Q., Zhang K., Bai X., Liu P., Li A., LYu Z., and Li Q. Flame-Retardant Thermoplastic Polyurethane Based on Reactive Phosphonate Polyol, Fire Mater., 46,130-137, 2022.
  34. Chen K., Yang D., Shi Y., Feng Y., Fu L., Liu C., Chen M., and Yang F., Synergistic Function of N-P-Cu Containing Supermolecular Assembly Networks in Intumescent Flame Retardant Thermoplastic Polyurethane, Polym. Adv. Technol., 32, 4450-63, 2021.
  35. Levchik S.V. and Weil E.D., Thermal Decomposition, Combustion and Fire-Retardancy of Polyurethanes- A Review of the Recent Literature, Polym. Int., 53,1585-1610, 2004.
  36. Wilkie C.A., TGA/FTIR: An Extremely Useful Technique for Studying Polymer Degradation, Polym. Degrad. Stab., 66, 1-6, 1999.

 

مجله علوم و تکنولوژی پلیمر
دوره 36، شماره 1 - شماره پیاپی 183
فروردین و اردیبهشت 1402
صفحه 73-86

فایل ها

ارجاعات به این مقاله

هم رسانی

ارجاع به این مقاله

آمار