Fonksiyonelleştirilmiş Selüloz Katkısıyla Güçlendirilmiş CMC Esaslı Hidrojeller: NaOH-Üre Katalizli Oksidasyon ve Mekanik Ön işlem Uygulamaları, Sitrik asit ve Epiklorohidrin ile Çapraz Bağlanma ve Karakterizasyon

Year 2025, Volume: 26 Issue: 2, 290 - 301, 15.10.2025

Asena Damla Büyüküstün , Esat Gümüşkaya , Emir Erişir

https://doi.org/10.17474/artvinofd.1687370

Abstract

Düşük jel mukavemetine sahip karboksimetilselüloz (CMC) bazlı kopolimer hidrojelin performansını iyileştirmek için, doğal selüloz gibi katkı maddeleri yaygın olarak kullanılmaktadır, ancak bunların yapısal sınırlamaları, modifikasyon olmadan CMC bazlı hidrojellere başarılı bir şekilde entegre edilmesini engellemektedir. Bu çalışmada, katkı maddesi olarak işlenmiş ve işlenmemiş odun hamurunun hidrojel performansı üzerindeki etkileri incelenmiştir. Ön işlemler, NaOH-üre ile katalize edilen hidrojen peroksit oksidasyonunun yanı sıra mekanik ön işlem olarak PFI veya kolloid değirmenler kullanılarak gerçekleştirilmiştir. Bu yarı sentetik polimerlerin çapraz bağlanmasında, epiklorohidrin (ECH) veya sitrik asit (CIT) kullanılarak gerçekleştirilmiştir. Hidrojellerin kimyasal, fiziksel ve morfolojik özelliklerini analiz etmek için FTIR spektroskopisi, DSC ve elektron mikroskobu teknikleri ile şişme ve su emme testleri kullanılmıştır. Her iki ajanla çapraz bağlanmanın başarılı olduğu FTIR spektrumları ile doğrulanmıştır. Kullanılan çapraz bağlama maddesinden bağımsız olarak, tüm hidrojellerin alkali çözeltilerdeki şişme oranı, nötr ve asidik ortamlardakinden daha yüksekti. CIT ile çapraz bağlanmış hidrojeller, pH 7'de kontrol grubuna göre 16 kat daha fazla şişme oranı göstermiştir. Na⁺ ve K⁺ içeren çözeltilerde şişme performansı artmış, ancak Mg²⁺ ve NH₄⁺ varlığında hidrojellerin performansı %50-70 oranında azalmıştır. DSC eğrileri, alkali oksidasyon ön işlemleri nedeniyle kristallik azaldığını ve ECH çapraz bağlı hidrojelin termal stabilitesinin CIT'den %40 daha yüksek olduğunu göstermektedir. SEM görüntüleri, ECH numunelerinde farklı desenler ve kırıklar gösterirken, CIT numunelerinde daha pürüzsüz hidrojel yüzeyleri ve liflerin varlığı görülmektedir.

Keywords

CMC hidrojel , Selüloz takviyesi , NaOH-üre , Süpermasskolloider , PFI rafinasyonu

Ethical Statement

Bu makalenin orijinal bir çalışma olduğunu, daha önce herhangi bir yerde yayınlanmadığını, başka bir dergide değerlendirme sürecinde olmadığını ve tüm yazarların makalenin dergiye sunulan son halini okuyup onayladığını beyan ederiz. Yazarlar arasında herhangi bir çıkar çatışması bulunmamaktadır.

Supporting Institution

TÜBİTAK

Project Number

215O313

Thanks

Yazarlar, bu çalışmayı 1001 Bilimsel ve Teknolojik Araştırma Projeleri Fon Programı (hibe numarası 215O313) aracılığıyla finanse eden Türkiye Bilim ve Teknoloji Kurumu'na teşekkür eder.

Functionalized Cellulose-Reinforced CMC-Based Hydrogels: NaOH-Urea Catalyzed Oxidation and Mechanical Pretreatments, Crosslinking with Citric Acid and Epichlorohydrin, and Characterization

Abstract

To improve the performance of carboxymethylcellulose (CMC)-based copolymer hydrogels with low gel strength, additives like natural cellulose are extensively utilized but its structural limitations restrict successful integration into CMC-based hydrogels without modification. In this study, it was examined the effects of wood pulp with and without treatments as additives on the performance of hydrogels. Pretreatment of cellulose was carried out using hydrogen peroxide oxidation catalyzed by NaOH-urea, as well as mechanical pretreatment using PFI or colloid mills. In the cross-linking of these semi-synthetic polymers, either epichlorohydrin (ECH) or citric acid (CIT) were used. FTIR spectroscopy, DSC, and electron microscopy techniques, as well as swelling and water absorption tests, were used to analyze the chemical, physical, and morphological properties of hydrogels. The successful cross-linking by both agents was verified by FTIR spectra. For all hydrogel groups, regardless of the cross-linking agent used, the swelling ratio in alkaline solutions was higher than that in neutral and acidic environments. CIT-crosslinked hydrogels displayed a swelling rate 16 times greater at pH 7 than the control group. Enhanced swelling performance was observed in solutions with Na⁺ and K⁺, but hydrogels demonstrated a 50–70% reduction in performance in the presence of Mg²⁺ and NH₄⁺. DSC curves demonstrate that crystallinity diminished due to alkaline oxidation pretreatments, and the thermal stability of ECH-crosslinked hydrogels exceeds that of CIT by 40%. SEM images show different patterns and fractures in ECH samples, while CIT samples reveal smoother hydrogel surfaces and the presence of fibers.

Keywords

CMC hydrogel , Cellulose reinforcement , NaOH-urea , Supermasscolloider , PFI refining

Ethical Statement

We declare that this article is an original work, has not been published anywhere else, is not currently under review for publication in any other journal, and that all authors have read and approved the final version of the article submitted to the journal. There are no conflicts of interest among the authors.

Supporting Institution

TÜBİTAK

Project Number

215O313

Thanks

The authors would like to thank the Turkish Scientific and Technological Research Council for funding this work through the 1001 Scientific and Technological Research Projects Fund Program (grant number 215O313).

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