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CEVİZ KABUĞU VE KAOLİN KATKILI POLİPROPİLEN KOMPOZİTLERİN TERMAL KARAKTERİZASYONU

Yıl 2026, Cilt: 14 Sayı: 1, 1 - 10, 20.03.2026
https://doi.org/10.21923/jesd.1639744
https://izlik.org/JA95LK85PM

Öz

Doğal esaslı organik ve inorganik dolgu malzemeleri için kompozit malzemeler son yıllarda dikkat çeken yenilikçi bir malzeme sınıfı haline gelmiştir. Gelişmiş mekanik özellikleri, kimyasal dirençleri ve işlenebilirlik avantajları nedeniyle geniş bir kullanım alanına sahip olan termoplastiklerin başında gelen Polipropilen (PP) polimerinin sahip olduğu özellikleri daha da iyileştirmek, petrol esaslı polimerlerin kullanım oranlarını ve çevresel etkilerini azaltmak gibi amaçlar, doğal esaslı dolgu maddelerinin kullanımlarının giderek artmasına sebep olmuştur. Bu çalışmada tarımsal bir atık olan ceviz kabuğunun (W) doğal bir kil minerali olan kaolin (K) ile birlikte PP matrisinde kullanılabilirliği incelenmiş, doğal ve inorganik iki dolgu maddesinin sinerjik etkileri termal analizler ile karakterize edilmiştir. Diferansiyel taramalı kalorimetrik analiz (DSC) sonuçları, kaolinin etkili bir çekirdeklenme ajanı olarak hareket ettiğini, PP'nin kristalleşme sıcaklığını 115,7 °C'den 122,2 °C'ye yükselttiğini ve kristallik derecesini %48,2'den %53,7'ye yükselttiğini, erime sıcaklığının ise tüm bileşimler için neredeyse sabit kaldığını (165–167 °C) ortaya koymuştur. Termogravimetrik (TGA) ve termomekanik analizler, hibrit W/K dolgulu PP kompozitlerin gelişmiş termal ve boyutsal stabilite sergilediğini, en yüksek termal bozunma başlangıç sıcaklığının 426,1 °C'ye ulaştığını ve doğrusal ısıl genleşme katsayısı (CLTE) değerlerinin 86,6 µm/m·K'ye düştüğünü göstermiştir. Bu da dolgu hibridizasyonunun termal direnç ve viskoelastik performans üzerinde sinerjik etkileri olduğunu göstermektedir. Kullanılan iki doğal esaslı dolgu malzemesinin PP ile kombinasyonunun, kompozitlerin termal özelliklerini geliştirebildiği, aynı zamanda çevre üzerindeki olumsuz etkilerini de azaltabilme potansiyeline sahip olduğu görülmüştür.

Kaynakça

  • Albatrni, H., Qiblawey, H., Al-Marri, M.J., 2022. Walnut shell based adsorbents: A review study on preparation, mechanism, and application. Journal of Water Process Engineering 45, 102527.
  • Atagür, M., Kaya, N., Uysalman, T., Durmuşkahya, C., Sarikanat, M., Sever, K., Seki, Y., 2022. A detailed characterization of sandalwood-filled high-density polyethylene composites. Journal of Thermoplastic Composite Materials 35, 1903–1920.
  • Çelik, Y.H., Yalcin, R., Topkaya, T., Başaran, E., Kilickap, E., 2021. Characterization of hazelnut, pistachio, and apricot kernel shell particles and analysis of their composite properties. Journal of Natural Fibers 18, 1054–1068.
  • Çevik, B., Avşar, Y., 2024. Production and characterization of waste walnut shell powder that can be used as a sustainable eco-friendly reinforcement in biocomposites. Materials Testing.
  • Chaka, K.T., Fambri, L., Govindan, N., 2017. Kaolinite/polypropylene nanocomposites. part 1: compounding. Int Res J Eng Technol 4.
  • Dey, T.K., Tripathi, M., 2010. Thermal properties of silicon powder filled high-density polyethylene composites. Thermochimica Acta 502, 35–42.
  • Etcheverry, M., Ferreira, M.L., Capiati, N., Barbosa, S., 2013. Chemical anchorage of polypropylene onto glass fibers: Effect on adhesion and mechanical properties of their composites. International Journal of Adhesion and Adhesives 43, 26–31.
  • Feng, Y., Hao, H., Lu, H., Chow, C.L., Lau, D., 2024. Exploring the development and applications of sustainable natural fiber composites: A review from a nanoscale perspective. Composites Part B: Engineering 111369.
  • García-Martínez, J.-M., Collar, E.P., 2022. The Variance of the Polypropylene α Relaxation Temperature in iPP/a-PP-p PBMA/Mica Composites. Journal of Composites Science 6, 57.
  • Guessoum, M., Nekkaa, S., Fenouillot-Rimlinger, F., Haddaoui, N., 2012. Effects of kaolin surface treatments on the thermomechanical properties and on the degradation of polypropylene. International Journal of Polymer Science 2012, 549154.
  • Hansen, B., Borsoi, C., Júnior, M.A.D., Catto, A.L., 2019. Thermal and thermo-mechanical properties of polypropylene composites using yerba mate residues as reinforcing filler. Industrial crops and products 140, 111696.
  • Hasegawa, N., Kawasumi, M., Kato, M., Usuki, A., Okada, A., 1998. Preparation and mechanical properties of polypropylene‐clay hybrids using a maleic anhydride‐modified polypropylene oligomer. Journal of applied polymer science 67, 87–92.
  • Idumah, C.I., Hassan, A., 2016. Characterization and preparation of conductive exfoliated graphene nanoplatelets kenaf fibre hybrid polypropylene composites. Synthetic Metals 212, 91–104.
  • Jakubowska, P., Klozinski, A., 2015. The use of thermovision technique to estimate the properties of highly filled polyolefins composites with calcium carbonate, in: AIP Conference Proceedings. AIP Publishing.
  • Jikan, S.S., Ariff, Z.M., Ariffin, A., 2010. Influence of filler content and processing parameter on the crystallization behaviour of PP/kaolin composites. Journal of thermal analysis and calorimetry 102, 1011–1017.
  • Joseph, K., Thomas, S., Pavithran, C., 1992. Viscoelastic properties of short-sisal-fiber-filled low-density polyethylene composites: effect of fiber length and orientation. Materials Letters 15, 224–228.
  • Karagöz, İ., Mutlu, D., Çavuşoğlu, A., Çelebi, M., Ceylan, Ö., 2024. A comprehensive study on the effect of small rates of walnut shell and talc fillers on the thermal, mechanical, and morphological properties of epoxy hybrid composites. Biomass Conversion and Biorefinery 1–12.
  • Karian, H., 2003. Handbook of polypropylene and polypropylene composites, revised and expanded. CRC press.
  • Kuram, E., 2022. Advances in development of green composites based on natural fibers: A review. Emergent Materials 5, 811–831.
  • Leong, Y.W., Abu Bakar, M.B., Ishak, Z.A.M., Ariffin, A., Pukanszky, B., 2004. Comparison of the mechanical properties and interfacial interactions between talc, kaolin, and calcium carbonate filled polypropylene composites. Journal of Applied Polymer Science 91, 3315–3326.
  • Li, M., Chen, Y., Wu, L., Zhang, Z., Mai, K., 2019. A novel polypropylene composite filled by kaolin particles with β-nucleation. Journal of Thermal Analysis and Calorimetry 135, 2137–2145.
  • Li, Y., Yu, Q., Chang, Y., Shi, Y., 2024. Preparation and Characterization of Magnetic Walnut Shell Adsorbents. Water, Air, & Soil Pollution 235, 312.
  • Mittal, P., Naresh, S., Luthra, P., Singh, A., Dhaliwal, J.S., Kapur, G.S., 2019. Polypropylene composites reinforced with hybrid inorganic fillers: Morphological, mechanical, and rheological properties. Journal of Thermoplastic Composite Materials 32, 848–864.
  • Orue, A., Eceiza, A., Arbelaiz, A., 2020. The use of alkali treated walnut shells as filler in plasticized poly (lactic acid) matrix composites. Industrial Crops and Products 145, 111993.
  • Pirayesh, H., Khazaeian, A., Tabarsa, T., 2012. The potential for using walnut (Juglans regia L.) shell as a raw material for wood-based particleboard manufacturing. Composites Part B: Engineering 43, 3276–3280.
  • Prakash, A., Sarkhel, G., Kumar, K., 2015. Strength optimization for kaolin reinforced epoxy composite using taguchi method. Materials Today: Proceedings 2, 2380–2388.
  • Prasad, M.S., Reid, K.J., Murray, H.H., 1991. Kaolin: processing, properties and applications. Applied clay science 6, 87–119.
  • Pritchard, G., 2004. Two technologies merge: wood plastic composites. Plastics, Additives and Compounding 6, 18–21.
  • Ptáček, P., Kubátová, D., Havlica, J., Brandštetr, J., Šoukal, F., Opravil, T., 2010. Isothermal kinetic analysis of the thermal decomposition of kaolinite: the thermogravimetric study. Thermochimica Acta 501, 24–29.
  • Ptáček, P., Šoukal, F., Opravil, T., Havlica, J., Brandštetr, J., 2011. The kinetic analysis of the thermal decomposition of kaolinite by DTG technique. Powder Technology 208, 20–25.
  • Rukmini, K., Ramaraj, B., Shetty, S.K., Taraiya, A., Bandyopadhyay, S., Siddaramaiah, 2013. Development of Eco‐Friendly Cotton Fabric Reinforced Polypropylene Composites: Mechanical, Thermal, and Morphological Properties. Advances in Polymer Technology 32.
  • Salasinska, K., Barczewski, M., Górny, R., Kloziński, A., 2018. Evaluation of highly filled epoxy composites modified with walnut shell waste filler. Polymer Bulletin 75, 2511–2528.
  • Şen, İ., 2024. Structure, performance, and crystallization behavior of Turkey leonardite and raw kaolin added polylactic acid composite films. Journal of Composite Materials 58, 1303–1316.
  • Şen, İ., Tuna, S., Kurtlu, M.A., 2024. Evaluation of the use and performance of natural filler based polypropylene/leonardite composites. Journal of Cleaner Production 480, 144105.
  • Sever, K., 2020. Influence of wollastonite hybridization on the properties of artichoke-filled polypropylene composites. Emerging Materials Research 9, 302–307.
  • Singh, M.K., Mohanty, A.K., Misra, M., 2023. Upcycling of waste polyolefins in natural fiber and sustainable filler-based biocomposites: A study on recent developments and future perspectives. Composites Part B: Engineering 263, 110852.
  • Singha, A.S., Thakur, V.K., 2009. Synthesis and characterizations of silane treated Grewia optiva fibers. International Journal of Polymer Analysis and Characterization 14, 301–321.
  • Tuna, S., Akkoyun Kurtlu, M., 2024. Effect of coupling agent on polylactic acid/polypropylene and polylactic acid/polyamide 6 foam composites. Journal of Applied Polymer Science 141, e54849.
  • Venkatesan, R., Alagumalai, K., Kim, S.-C., 2023. Preparation and antimicrobial characterization of poly (butylene adipate-co-terephthalate)/kaolin clay biocomposites. Polymers 15, 1710.
  • Wang, J., Kazemi, Y., Wang, S., Hamidinejad, M., Mahmud, M.B., Pötschke, P., Park, C.B., 2020. Enhancing the electrical conductivity of PP/CNT nanocomposites through crystal-induced volume exclusion effect with a slow cooling rate. Composites Part B: Engineering 183, 107663.
  • Wang, K., Bahlouli, N., Addiego, F., Ahzi, S., Rémond, Y., Ruch, D., Muller, R., 2013. Effect of talc content on the degradation of re-extruded polypropylene/talc composites. Polymer degradation and stability 98, 1275–1286.
  • Zhou, Y., Rangari, V., Mahfuz, H., Jeelani, S., Mallick, P.K., 2005. Experimental study on thermal and mechanical behavior of polypropylene, talc/polypropylene and polypropylene/clay nanocomposites. Materials Science and Engineering: A 402, 109–117.
  • Zhuang, Z., Liu, Y., Wei, W., Shi, J., Jin, H., 2024. Preparation of biochar adsorption material from walnut shell by supercritical CO2 pretreatment. Biochar 6, 11.

THERMAL CHARACTERIZATION OF WALNUT SHELL AND KAOLIN ENHANCED POLYPROPYLENE COMPOSITES

Yıl 2026, Cilt: 14 Sayı: 1, 1 - 10, 20.03.2026
https://doi.org/10.21923/jesd.1639744
https://izlik.org/JA95LK85PM

Öz

Composite materials for natural-based organic and inorganic fillers have become an innovative class of materials that have attracted attention in recent years. Improving the properties of Polypropylene (PP), which is one of the most widely used thermoplastics due to its advanced mechanical properties, chemical resistance and processability advantages, and reducing the usage rates and environmental impacts of petroleum-based polymers have led to the increasing use of natural-based fillers. In this study, the applicability of walnut shell (W), an agricultural waste, together with kaolin (K), a natural clay mineral, in PP matrix was investigated and the synergistic effects of natural and inorganic fillers were characterised by thermal analyses. Differential scanning calorimetry (DSC) results revealed that kaolin acted as an effective nucleating agent, increasing the crystallization temperature of PP from 115.7 °C to 122.2 °C and enhancing the degree of crystallinity from 48.2% to 53.7%, while the melting temperature remained nearly constant (165–167 °C) for all compositions. Thermogravimetric analysis (TGA) and thermomechanical test results showed that hybrid W/K filled PP composites exhibited improved thermal and dimensional stability, with the highest thermal onset temperature reaching 426.1 °C and reduced coefficient of linear thermal expansion (CLTE) values down to 86.6 µm/m·K, indicating synergistic effects of filler hybridization on thermal resistance and viscoelastic performance. It was observed that the combination of two natural-based fillers with PP can improve the thermal properties of the composites and also has the potential to reduce the negative impact on the environment.

Kaynakça

  • Albatrni, H., Qiblawey, H., Al-Marri, M.J., 2022. Walnut shell based adsorbents: A review study on preparation, mechanism, and application. Journal of Water Process Engineering 45, 102527.
  • Atagür, M., Kaya, N., Uysalman, T., Durmuşkahya, C., Sarikanat, M., Sever, K., Seki, Y., 2022. A detailed characterization of sandalwood-filled high-density polyethylene composites. Journal of Thermoplastic Composite Materials 35, 1903–1920.
  • Çelik, Y.H., Yalcin, R., Topkaya, T., Başaran, E., Kilickap, E., 2021. Characterization of hazelnut, pistachio, and apricot kernel shell particles and analysis of their composite properties. Journal of Natural Fibers 18, 1054–1068.
  • Çevik, B., Avşar, Y., 2024. Production and characterization of waste walnut shell powder that can be used as a sustainable eco-friendly reinforcement in biocomposites. Materials Testing.
  • Chaka, K.T., Fambri, L., Govindan, N., 2017. Kaolinite/polypropylene nanocomposites. part 1: compounding. Int Res J Eng Technol 4.
  • Dey, T.K., Tripathi, M., 2010. Thermal properties of silicon powder filled high-density polyethylene composites. Thermochimica Acta 502, 35–42.
  • Etcheverry, M., Ferreira, M.L., Capiati, N., Barbosa, S., 2013. Chemical anchorage of polypropylene onto glass fibers: Effect on adhesion and mechanical properties of their composites. International Journal of Adhesion and Adhesives 43, 26–31.
  • Feng, Y., Hao, H., Lu, H., Chow, C.L., Lau, D., 2024. Exploring the development and applications of sustainable natural fiber composites: A review from a nanoscale perspective. Composites Part B: Engineering 111369.
  • García-Martínez, J.-M., Collar, E.P., 2022. The Variance of the Polypropylene α Relaxation Temperature in iPP/a-PP-p PBMA/Mica Composites. Journal of Composites Science 6, 57.
  • Guessoum, M., Nekkaa, S., Fenouillot-Rimlinger, F., Haddaoui, N., 2012. Effects of kaolin surface treatments on the thermomechanical properties and on the degradation of polypropylene. International Journal of Polymer Science 2012, 549154.
  • Hansen, B., Borsoi, C., Júnior, M.A.D., Catto, A.L., 2019. Thermal and thermo-mechanical properties of polypropylene composites using yerba mate residues as reinforcing filler. Industrial crops and products 140, 111696.
  • Hasegawa, N., Kawasumi, M., Kato, M., Usuki, A., Okada, A., 1998. Preparation and mechanical properties of polypropylene‐clay hybrids using a maleic anhydride‐modified polypropylene oligomer. Journal of applied polymer science 67, 87–92.
  • Idumah, C.I., Hassan, A., 2016. Characterization and preparation of conductive exfoliated graphene nanoplatelets kenaf fibre hybrid polypropylene composites. Synthetic Metals 212, 91–104.
  • Jakubowska, P., Klozinski, A., 2015. The use of thermovision technique to estimate the properties of highly filled polyolefins composites with calcium carbonate, in: AIP Conference Proceedings. AIP Publishing.
  • Jikan, S.S., Ariff, Z.M., Ariffin, A., 2010. Influence of filler content and processing parameter on the crystallization behaviour of PP/kaolin composites. Journal of thermal analysis and calorimetry 102, 1011–1017.
  • Joseph, K., Thomas, S., Pavithran, C., 1992. Viscoelastic properties of short-sisal-fiber-filled low-density polyethylene composites: effect of fiber length and orientation. Materials Letters 15, 224–228.
  • Karagöz, İ., Mutlu, D., Çavuşoğlu, A., Çelebi, M., Ceylan, Ö., 2024. A comprehensive study on the effect of small rates of walnut shell and talc fillers on the thermal, mechanical, and morphological properties of epoxy hybrid composites. Biomass Conversion and Biorefinery 1–12.
  • Karian, H., 2003. Handbook of polypropylene and polypropylene composites, revised and expanded. CRC press.
  • Kuram, E., 2022. Advances in development of green composites based on natural fibers: A review. Emergent Materials 5, 811–831.
  • Leong, Y.W., Abu Bakar, M.B., Ishak, Z.A.M., Ariffin, A., Pukanszky, B., 2004. Comparison of the mechanical properties and interfacial interactions between talc, kaolin, and calcium carbonate filled polypropylene composites. Journal of Applied Polymer Science 91, 3315–3326.
  • Li, M., Chen, Y., Wu, L., Zhang, Z., Mai, K., 2019. A novel polypropylene composite filled by kaolin particles with β-nucleation. Journal of Thermal Analysis and Calorimetry 135, 2137–2145.
  • Li, Y., Yu, Q., Chang, Y., Shi, Y., 2024. Preparation and Characterization of Magnetic Walnut Shell Adsorbents. Water, Air, & Soil Pollution 235, 312.
  • Mittal, P., Naresh, S., Luthra, P., Singh, A., Dhaliwal, J.S., Kapur, G.S., 2019. Polypropylene composites reinforced with hybrid inorganic fillers: Morphological, mechanical, and rheological properties. Journal of Thermoplastic Composite Materials 32, 848–864.
  • Orue, A., Eceiza, A., Arbelaiz, A., 2020. The use of alkali treated walnut shells as filler in plasticized poly (lactic acid) matrix composites. Industrial Crops and Products 145, 111993.
  • Pirayesh, H., Khazaeian, A., Tabarsa, T., 2012. The potential for using walnut (Juglans regia L.) shell as a raw material for wood-based particleboard manufacturing. Composites Part B: Engineering 43, 3276–3280.
  • Prakash, A., Sarkhel, G., Kumar, K., 2015. Strength optimization for kaolin reinforced epoxy composite using taguchi method. Materials Today: Proceedings 2, 2380–2388.
  • Prasad, M.S., Reid, K.J., Murray, H.H., 1991. Kaolin: processing, properties and applications. Applied clay science 6, 87–119.
  • Pritchard, G., 2004. Two technologies merge: wood plastic composites. Plastics, Additives and Compounding 6, 18–21.
  • Ptáček, P., Kubátová, D., Havlica, J., Brandštetr, J., Šoukal, F., Opravil, T., 2010. Isothermal kinetic analysis of the thermal decomposition of kaolinite: the thermogravimetric study. Thermochimica Acta 501, 24–29.
  • Ptáček, P., Šoukal, F., Opravil, T., Havlica, J., Brandštetr, J., 2011. The kinetic analysis of the thermal decomposition of kaolinite by DTG technique. Powder Technology 208, 20–25.
  • Rukmini, K., Ramaraj, B., Shetty, S.K., Taraiya, A., Bandyopadhyay, S., Siddaramaiah, 2013. Development of Eco‐Friendly Cotton Fabric Reinforced Polypropylene Composites: Mechanical, Thermal, and Morphological Properties. Advances in Polymer Technology 32.
  • Salasinska, K., Barczewski, M., Górny, R., Kloziński, A., 2018. Evaluation of highly filled epoxy composites modified with walnut shell waste filler. Polymer Bulletin 75, 2511–2528.
  • Şen, İ., 2024. Structure, performance, and crystallization behavior of Turkey leonardite and raw kaolin added polylactic acid composite films. Journal of Composite Materials 58, 1303–1316.
  • Şen, İ., Tuna, S., Kurtlu, M.A., 2024. Evaluation of the use and performance of natural filler based polypropylene/leonardite composites. Journal of Cleaner Production 480, 144105.
  • Sever, K., 2020. Influence of wollastonite hybridization on the properties of artichoke-filled polypropylene composites. Emerging Materials Research 9, 302–307.
  • Singh, M.K., Mohanty, A.K., Misra, M., 2023. Upcycling of waste polyolefins in natural fiber and sustainable filler-based biocomposites: A study on recent developments and future perspectives. Composites Part B: Engineering 263, 110852.
  • Singha, A.S., Thakur, V.K., 2009. Synthesis and characterizations of silane treated Grewia optiva fibers. International Journal of Polymer Analysis and Characterization 14, 301–321.
  • Tuna, S., Akkoyun Kurtlu, M., 2024. Effect of coupling agent on polylactic acid/polypropylene and polylactic acid/polyamide 6 foam composites. Journal of Applied Polymer Science 141, e54849.
  • Venkatesan, R., Alagumalai, K., Kim, S.-C., 2023. Preparation and antimicrobial characterization of poly (butylene adipate-co-terephthalate)/kaolin clay biocomposites. Polymers 15, 1710.
  • Wang, J., Kazemi, Y., Wang, S., Hamidinejad, M., Mahmud, M.B., Pötschke, P., Park, C.B., 2020. Enhancing the electrical conductivity of PP/CNT nanocomposites through crystal-induced volume exclusion effect with a slow cooling rate. Composites Part B: Engineering 183, 107663.
  • Wang, K., Bahlouli, N., Addiego, F., Ahzi, S., Rémond, Y., Ruch, D., Muller, R., 2013. Effect of talc content on the degradation of re-extruded polypropylene/talc composites. Polymer degradation and stability 98, 1275–1286.
  • Zhou, Y., Rangari, V., Mahfuz, H., Jeelani, S., Mallick, P.K., 2005. Experimental study on thermal and mechanical behavior of polypropylene, talc/polypropylene and polypropylene/clay nanocomposites. Materials Science and Engineering: A 402, 109–117.
  • Zhuang, Z., Liu, Y., Wei, W., Shi, J., Jin, H., 2024. Preparation of biochar adsorption material from walnut shell by supercritical CO2 pretreatment. Biochar 6, 11.
Toplam 43 adet kaynakça vardır.

Ayrıntılar

Birincil Dil İngilizce
Konular Malzeme Bilimi ve Teknolojileri, Polimer Bilimi ve Teknolojileri
Bölüm Araştırma Makalesi
Yazarlar

İbrahim Şen 0000-0003-2733-7191

Sibel Tuna 0000-0002-4406-9048

Gönderilme Tarihi 14 Şubat 2025
Kabul Tarihi 23 Şubat 2026
Yayımlanma Tarihi 20 Mart 2026
DOI https://doi.org/10.21923/jesd.1639744
IZ https://izlik.org/JA95LK85PM
Yayımlandığı Sayı Yıl 2026 Cilt: 14 Sayı: 1

Kaynak Göster

APA Şen, İ., & Tuna, S. (2026). THERMAL CHARACTERIZATION OF WALNUT SHELL AND KAOLIN ENHANCED POLYPROPYLENE COMPOSITES. Mühendislik Bilimleri ve Tasarım Dergisi, 14(1), 1-10. https://doi.org/10.21923/jesd.1639744