LEE- Tekstil Mühendisliği Lisansüstü Programı
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ÖgeAkrilik filament ipliğin tekstüre edilmesi(Lisansüstü Eğitim Enstitüsü, 2021) Mutlu, Aras ; Demir, Ali ; 709844 ; Tekstil MühendisliğiAkrilik elyaf, en eski sentetik tekstil elyaflarından biridir. 2000 yılında dünya elyaf kullanımının yaklaşık %5'lik kısmını akrilik elyaf oluştururken bu oran 2020 yılında %1 mertebesine gerilemiştir. Üstelik birçok elyafın kullanım miktarı artmakta olmasına rağmen akrilik elyafta düşüş trendi devam etmektedir. Tüm bu akrilik elyaf tüketimi elyaf (kesikli lif) formundadır. Filament formunda akrilik ipliğin tarihçesinin 1950'li yıllara kadar dayanmasına ve birçok üreticinin akrilik filament iplik üretimine başlamış olmasına rağmen çeşitli nedenlerle ticari olarak yaygınlaşması yakın zamana kadar mümkün olmamıştır. Bu nedenle, akrilik filament ipliğin tekstüre edilmesi üzerine yaygın bir bilimsel literatür ya da ticari bilgi bulunmamaktadır. Aslında akrilik elyaf üretimi esnasında uygulanan "kıvırcıklandırma" işlemi, termomekanik tekstüre yöntemlerinin tüm temel aşamalarına sahiptir. Tüm dünyada kişi başına düşen elyaf tüketimi artarken filament iplik üretiminde de önemli artış yaşanmaktadır. Yıllık filament iplik üretimi çok daha hızlı bir artış göstermektedir ve 2013 yılından itibaren kesik elyaftan üretilen ipliklerin üretim miktarını da geçmiştir. Filament iplik, enerji ve iş gücü yoğun, detaylı ve uzun süren iplik eğirme proseslerini ortadan kaldırmasının yanı sıra final ürüne kazandırılan mükemmel fiziksel özellikler ile de hem düşük maliyetli hem de yüksek performanslı ürünler elde edilebilmesine olanak sağlamaktadır. Ancak filament ipliklerin en önemli dezavantajlarından biri düz ve bükümlü formda parlak ve suni bir görüntüye sahip olmasıdır. Bu haliyle birçok kullanım alanı için kabul görmeyen bir ürün halindedir. Tekstüre işlemi, filament ipliklerin daha doğal görünüm ve tutuma sahip hale getirilmesi için uygulanan bir prosestir. Tarih boyunca gerçek büküm-büküm açma, yalancı-büküm, bıçak sırtı, dişli çark, örme-sökme, yığma kutusu gibi termomekanik, hava-jeti gibi mekanik ve bunların yanı sıra bikomponent, kimyasal ile tekstüre gibi yöntemler çalışılmış olsa da günümüzde en yaygın olarak kullanılan iki yöntem yalancı-büküm ve hava-jeti ile tekstüre yöntemleridir. Polyester, poliamid, polipropilen gibi termoplastik liflerin tekstüre edilmesine yönelik yaygın literatür bulunmaktadır. Akrilik filament iplik ise fiziksel, kimyasal ve termal özellikler açısından bahsi geçen termoplastik liflere göre ayrıştığı için bu malzemenin tekstüre edilmesine yönelik özel araştırmaların gerçekleştirilmesi önem kazanmaktadır. Akrilik filament iplik, diğer sentetik ipliklere kıyasla ultraviyole ışınlarına, kimyasallara ve mikroorganizmalara karşı daha iyi bir dayanım gösterirken, yüksek ışık ve hava şartlarına karşı renk haslığı, rezilyans, boyutsal kararlılık gibi özellikleriyle de ön plana çıkmaktadır. Ayrıca akrilik kesik elyaftan üretilen ipliklere göre daha yüksek mukavemet ve kumaşa dönüştürüldükten sonra daha yüksek aşınma dayanımı ve boncuklanma özelliklerine sahip olacaktır. Akrilik filament iplik halihazırda kullanıldığı bükümlü haliyle kendisine tente, halı, dikiş ipliği gibi kullanım alanları bulabilse de tekstüre edilmemiş filament ipliklere özgü suni görüntüsü nedeniyle potansiyelinin altında bir kullanımı olduğu değerlendirilmektedir. Bu iplik için uygun tekstüre proses şartlarının belirlenerek sonraki tekstil proseslerinde işlenebilir ve kabul edilebilir fiziksel özelliklere sahip akrilik filament tekstüre iplikler elde edildiğinde çok daha yaygın bir şekilde kullanımı mümkün olacaktır. Bu çalışma kapsamında, gerçek büküm-büküm açma, yalancı-büküm, örme-sökme, sıcak hava-jeti, soğuk hava-jeti ile tekstüre yöntemleri incelenmiş, tüm yöntemlerle ilgili kritik noktalar belirlendiği gibi yalancı-büküm tekstüre ve hava-jeti ile tekstüre yöntemlerinde yürütülen deney tasarımı ve sonrasında gerçekleştirilen istatistiksel analiz ile optimum proses şartları belirlenmeye çalışılmıştır. Elde edilen sonuçlar, akrilik filament iplikten yeni ticari ürünler oluşturulmasına yardımcı olacağı gibi bu iplik için zayıf olan literatür bilgisinin genişletilmesinde ve potansiyel yeni çalışmalara temel oluşturulmasında yararlı olacaktır.
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ÖgeBimodal fonksiyonel dokusuz hava filtrelerinin üretimi ve geçirgenlik özelliklerinin karakterizasyonu(Lisansüstü Eğitim Enstitüsü, 2023-12-14) Toptaş, Ali ; Kılıç, Ali ; 503192806 ; Tekstil MühendisliğiNüfus artışı ve hızlı sanayi gelişimi nedeniyle temiz havaya olan ihtiyaç artmaktadır. Katı partikül maddeler, organik maddeler ve salgın hastalıklara yol açan ajanları (mikrop, virüs vb) içinde barındıran kirli hava, insan sağlığı için önemli bir tehdit oluşturmaktadır. Mikro ve nano ölçekteki PM10, PM2.5, PM1.0 ve PM0.3 olarak kategorize edilen Partikül Maddeler (PM), hava kirliğinin kaynaklarıdır. Partikül maddeler solunum sisteminde alveollere kadar nüfuz edebildikleri için kanser dahil çeşitli hastalıklara yol açabilmektedir. Dünya Sağlık Örgütü'ne (DSÖ) göre, her yıl 10 mikrometreden daha küçük parçacıkları içeren kirli havaya uzun süre maruz kalan 4 milyondan fazla kişi hayatını kaybetmektedir. Bu nedenle, bu parçacıkların havadan uzaklaştırılması/filtrelenmesi gerekmektedir. Filtreleme işlemi, havanın, nano- veya mikrogözeneklere sahip filtre yüzeylerinden geçirilerek, partikül maddelerin ayrıştırılma süreci ile tanımlanmaktadır. Özellikle hastanelerdeki yoğun bakım üniteleri, ameliyathaneler ve hastaların bulunduğu tüm ortamlarda havayı filtrelemek için HEPA veya ULPA filtreler kullanılmaktadır. Bunun yanında, yüksek seviyede PM bulunan ortamlarda çalışan kişilerin yüz maskelerini kullanmaları büyük önem arz etmektedir. Nano- ve mikro gözenekli dokusuz yüzeyler, solunan havanın zararlı etkilerini en aza indirmek için filtreler ve yüz maskeleri gibi filtrasyon yüzeylerinin üretiminde kullanılmaktadır. Nanolifli yüzeylerdeki gözenek boyutları da nano seviyelerdedir, dolayısıyla bu tür filtrelerle nano boyuttaki PM'leri filtrelemek mümkündür. Bu nedenle, hava filtrelemesi için nanolifli filtreler, mikrolifli filtrelere göre daha yüksek filtrasyon verimliliği (ղ) sunarlar. Çok ince nanoliflerden (65 nm'nin altında) meydana gelen filtre yüzeyleri, nanoliflerin yoğun bir şekilde paketlenmesi ile yüksek katılık değerine ulaşabilmektedir. Bu durum, havanın filtre yüzeyinden geçmesini zorlaştıraraak basınç düşüşü değerini artırıp, filtre yüzeyinin hızla tıkanmasına ve partiküllerin etkili bir şekilde filtrelenmesine engel olmaktadır. Bu durum, filtre yüzeyinin hızla tıkanarak havanın filtre yüzeyinden kolay bir şekilde geçmesine engel olur. Filtre yüzeylerinin hızlı bir şekilde tıkanmasını ve yüksek basınç düşüşü değerleri göstermesini engellemek için, nano- ve mikroliflerin biraraya gelerek oluşturduğu bimodal (Tez başlığında yer alan bu terim tüm çalışma boyunca yaygın kullanılacak bir terimdir. Filtre yüzeyinde iki farklı ortalama kalınlığa (çapa) sahip liflerin mevcut olduğunu ifade eder.) filtre yüzeyleri ön plana çıkmaktadır. Bimodal filtre yüzeylerinin yapısında nano- ve mikroliflerin birlikte bulunmasından dolayı, hava akış değerleri geniş bir Knudsen aralığında yer almaktadır. Bu sayede filtre yüzeyinden hava akışı daha kolay gerçekleşir. Filtre yüzeyinde mukavemeti daha yüksek olan mikroliflerin varlığı filtre yüzeyinin mekanik dayanıklılığını artırmaktadır. Bimodal yapıdaki yüzeyler kullanılarak, yüksek ղ, düşük basınç düşüşü (∆P) ve yüksek mekanik dayanıklılığa sahip filtre yapıları elde edilir. Literatürdeki bimodal filtre yapısı üzerine yapılan ilk çalışmalar genellikle simülasyon veya teorik hesaplamalara dayanmaktadır. Bimodal lif üretimine yönelik ilk çalışmalar, eriyikten üfleme (MB) yöntemi kullanılarak elde edilmiştir. Eriyikten üfleme yöntemini kullanan çalışmalarda, farklı erime sıcaklıklarına ve molekül ağırlıklarına sahip iki farklı polimerin ayrı ayrı ekstrüderlerden, tek bir ekstrüderden veya iki polimerin düze deliğinde buluşmasıyla elde edilen denizde adacık (Island in the sea) tipi liflerden oluşan yüzeylerin elde edildiği gösterilmiştir. Ayrıca literatürde, bimodal yapıların, kalın lif katmanları ve ince lif katmanlarının tabakalı bir şekilde oluşturulduğu çalışmalar da bulunmaktadır. Bu konudaki en dikkat çekici olan çalışmalar, yapısında nanonet içeren çalışmalardır. Bunlara ek olarak, literatürde elektro-üretim ve melt-blowing (MB) yöntemlerinin kombinasyonuyla filtre yüzeyi oluşturan bimodal çalışmalar da bulunmaktadır. Bu çalışmalarda çeşitli polimerler kullanılmaktadır. Çözeltiden üretilen lifli yüzeyler, genellikle poliviniliden florür (PVDF), poliakrilonitril (PAN), termoplastik poliüretan (TPU), poliamid-6 (PA-6), poliamid-6.6 (PA-6.6), polivinil alkol (PVA), politetrafloroetilen (PTFE) gibi sentetik polimerlerden veya jelatin, kolajen, kitosan, karboksimetil selüloz gibi doğal kökenli polimerik malzemelerden elde edilebilir. MB yöntemi kullanılarak eriyikten elde edilen lifli yüzeyler ise polyester (PET), polipropilen (PP), polibütilen tereftalat (PBT), polilaktik asit (PLA) gibi çeşitli termoplastik polimerlerden veya cam yünü gibi doğal kökenli malzemelerden elde edilebilir. Bu çalışma kapsamında öncelikle PVDF'ten üretilen nanoliflerin malzeme ve üretim sistemi parametrelerinin optimizasyonu üzerinde durulmuş ve PVDF bazlı elektret (Bu çalışma kapsamında elektret kelimesi yaygın kullanılmaktadır. Bu terim polimerlerin yüzeylerine uygulanan harici etkenler nedeniyle polimer zincirindeki serbest uçların polimer yüzeyine yönlenmesiyle oluşan negatif veya pozitif yüklerle yüklenmesini ifade eder.) nanolifli yüzeylerin elektro-üfleme yöntemi ile üretimi optimize edilmiştir. Deneysel parametreler, Taguchi üç düzeyli L9 ortogonal tasarımı kullanılarak sistemli bir şekilde oluşturulmuş ve ANOVA ile istatistiksel olarak analiz edilmiştir. Bu bağlamda, incelenen parametreler çözelti konsantrasyonu, hava basıncı ve elektrik alan olmuştur. Bu parametreler arasında, lif çaplarını en çok etkileyen faktörlerin çözelti konsantrasyonu ve elektrik voltajı olduğu belirlenmiştir. En ince nanolifli filtre yüzeyini (124±71 nm) üreten optimum parametreler, sırasıyla %9 çözelti konsantrasyonu, 2 bar hava basıncı ve 30 kV elektrik voltajıdır. Ayrıca, numunelere uygulanan korona deşarj işlemi, kalite faktörlerinde %70'in üzerinde bir iyileşmeye neden olmuştur. Elektret filtre üretimine yöntelik araştırmalarımızda korona deşarjı ile polarizasyonunun oluşum mekanizmasını çözümlemek amacıyla yapılan bir başka çalışmada PVDF bazlı nanolif nanojeneratörler, elektro-üfleme (EB) yöntemi kullanılarak üretilmiştir. Bu çalışmada uygulanan elektrik voltajı ve hava basıncının, lif morfolojisi ve piezoelektrik özellikleri üzerindeki etkileri araştırılmıştır. 2 bar basınç altında üretilen numuneler, 3 bar basınç altında üretilen numunelerden daha ince lif çaplarına sahip olmuştur. Ayrıca, β-faz yüzdesi, uygulanan voltajın artmasıyla artmıştır. En yüksek β-faz yüzdesi, 2 bar hava basıncı ve 30 kV ile üretilmiş numunede gözlemlenmiştir. En yüksek piezoelektrik etki, 224±60 nm ortalama lif çapına sahip numuneden elde edilmiş, β-faz içeriği %88 olmuştur. Sonuç olarak elektro-üfleme yöntemi ile üretilen PVDF nanoliflerin β-faz ve piezoelektrik etkisini maksimize etmek için polarizasyonun en etkin mekanizma olduğu belirlenmiştir. Bu tez kapsamında yapılan, farklı oranlarda PVDF ve polietilen glikol (PEG) polimerlerini içeren çözeltilerden elektro-üfleme yöntemi ile nanolif/nanonet yapılı filtrelerin üretildiği bir başka çalışmada, çözelti içeriğindeki suda çözünebilir, düşük molekül ağırlıklı PEG içeriğinin artırılması ve üretilen yüzeylere, bu tez kapsamında özgün olarak tasarlanan, su banyosu işlemi uygulanarak yapıdaki PEG'in uzaklaştırılmasıyla, lif çapları azaltılmış ve daha gözenekli yapılar elde edilmiştir. En yüksek PEG içeriğine sahip PVDF:PEG (3:7) numunesi, 170 nm ve 50 nm civarında ortalama çaplara sahip öbekler halinde nanolif/nanonet benzeri yapılar sergilemiştir. Geliştirilen bu numunenin ղ değerinde, korona deşarj işlemi sonrasında %3.6'lık bir artış, kalite faktöründe ise %60'lık bir iyileşme gözlemlenmiştir. Sonuç olarak, PVDF:PEG (3:7) numunesi, çok yüksek bir ղ değeri (%99.57), oldukça düşük bir ∆P (158 Pa) ve bu sayede tercih edilen bir kalite faktörü (QF) 0.0345 sunan nanolif yapılı filtrelerin başarılı bir şekilde üretilebileceğini göstermiştir. Tez kapsamında filtre yüzeyinde nano- ve mikroliflerin homojen dağılımı veya katmanlı kullanımı yoluyla bimodal filtreler elde edilmiştir. Çalışmada, bimodal yapısal tasarımın etkisi, eriyikten üfleme (MB), çözeltiden üfleme (SB) ve elektro-üfleme (EB) yöntemleriyle üretilen çeşitli katman konfigürasyonlarında ve farklı çaplardaki liflerden oluşan yüzeylerin filtrasyon performansları karşılaştırılmıştır. Filtre numunelerinin gramajı 30 gsm olarak korunurken, 4 katmanlı filtre (4L) yapılarının kullanılması, tek katmanlı numunelere (L) kıyasla hava geçirgenliğinin artmasıyla sonuçlanmıştır. Bu şekilde oluşturulan 4L numunesi 148 Pa basınç düşüşü değeri ve en yüksek filtrasyon verimliliğine (%99,52) sahip olmuştur. Ayrıca 4L yapısındaki MB katmanının, SB nanoliflerinin MB'ye homojen bir şekilde dahil edilmesiyle elde edilen bimodal yüzeyler (BM) katmanı ile değiştirilmesi, filtrasyon verimliliğini %99,61'e yükseltmiş ve ΔP neredeyse aynı kalmıştır. PVDF:PP masterbatch kullanılarak eriyikten üfleme yöntemi ile üretilen filtre yüzeyine uygulanan korona deşarj işlemi ile, işlemi ile elde edilen bimodal yapıdaki 4BML numunesinde en yüksek filtrasyon verimliliği (%99,99) elde edilmiştir. Bu numunelerde bir ay sonrasında dahi filtrasyon verimliliği %99,90 olarak korunmuş; bu durum, elektret filtrelerinde bimodal lif dağılımının en yüksek avantaj sağladığını göstermiştir. PVDF nanoliflerin yapısına eklenen katkı malzemelerinin filtre yüzeyinin morfolojik yapısına etkisinin incelendiği çalışmada, Al(NO3)3.9H2O, NaCl, LiCl, KCl gibi katkı maddelerinin PVDF çözeltisine %1 ağırlık oranında ilave edildiği çözeltilerden nanolifli yüzeyler üretilmiştir. Al(NO3)3.9H2O katkı malzemeli numuneden en ince lif çapı ve en düzgün lif morfolojisi elde edilmiştir. Ayrıca, korona deşarjı işleminden sonra %99,95 ղ değeri ve 195 Pa ∆P değerleri elde edilmiştir. Tüm bu ölçümler sonucunda, Al(NO3)3.9H2O numunesinin ince lif çapı ve yüksek filtrasyon verimliliği ile PVDF için uygun bir katkı malzemesi olduğuna karar verilmiştir. Farklı triboelektrik serilerde yer alan PVDF ve PA-6 polimerlerinden üretilen nanoliflerinden elde edilen katmanlı yapıların incelendiği diğer bir çalışmada, triboelektrik etki ile birlikte bimodal etkinin filtrasyon performansına etkileri incelenmiştir. Ortalama 60 nm çapındaki PA-6 nanolifleri ile 176 nm çapındaki PVDF nanoliflerinden elde edilen bimodal filtre yapıları, korona deşarjı sonrasında %99,997 ղ değeri ve 193 Pa basınç düşüşü değerine ulaşmıştır. Dört hafta sonra İPA yöntemi ile deşarj işlemine tabi tutulan numuneler, filtrasyon testi sonrasında hem 0.26 kV yüzey potansiyeli hem de %99,829 ղ değeri ile yüksek filtrasyon ve yüksek triboelektrik özelliğini muhafaza ettiği kanıtlanmıştır. Erişilen bu filtrasyon değerleri tez kapsamında elde edilen ticari olarak değerlendirilebilecek en önemli çıktıyı oluşturmaktadır.
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ÖgeComposite nanofiber patches for topical drug delivery systems(Graduate School, 2021-04-19) Barbak, Zarife ; Karakaş, Hale ; 503122805 ; Textile Engineering ; Tekstil MühendisliğiNanofibers are ultrafine, continuous, solid state textile fibers that have diameters less than 1 micrometre. Nanofibers possess remarkable properties such as high interconnected porosity, specific surface area, ability to imitate the Extra Cellular Matrix (ECM) and potential carrier for drug delivery. Due to these fascinating properties, nanofibers are attractive candidates for medical applications for instance wound dressings, tissue scaffolds and artificial blood vessels. Electrospinning is the simplest and most practical among all methods to produce fine fibers with diameters ranging from micrometres to nanometres. Basic electrospinning equipment includes a high voltage source, a solution feeding unit, a syringe with a tip and a collector. At first, high voltage is applied to the polymer solution to produce an electrical field between the tip and the collector to shape the droplet on the tip as Taylor Cone. When the electrostatic force is higher than the surface tension of the polymer solution, polymer jet is ejected from the tip to the collector. Then, polymer jet reaches to collector following a spiral way by getting longer and thinner. Finally, nanoscale fibers are obtained on the collector. Topical drug delivery systems are composed of a formulation that applied to the skin directly to heal disorders or disease of the skin which guide/target pharmacological effect of the drug to the skin surface. Different pharmaceutical dosage forms can be used in topical drug delivery such as gels, creams, ointment, liquid preparation, sprays and solid powders. Electrospun nanofibers are excellent materials for drug delivery systems due to high interconnected porosity, high surface area, ability to imitate the Extra Cellular Matrix (ECM), potential carrier for drug delivery. Utilization of nanofibers in drug delivery systems is based on the principle that the high surface area of the nanofibrous formulation increases the dissolution rate of the drug. Compared with other dosage forms such as; liposomes, micelles and hydrogels, major advantages of nanofibers are increment in drug loading efficiency and loading capacity, low systemic toxicity and excellent stability. Furthermore, several drugs can be carried within nanofibers with high local drug concentration due to their excellent targeting and drug transportation ability in a safe way. Electrospinning offers the opportunity for direct loading of drugs or biological agents for instance antibacterial molecules, antibiotics, enzymes, growth factors, proteins, peptides, vitamins, DNA into the electrospun nanofibers. Poly (ε-caprolactone) (PCL), Poly Lactic Acid (PLA) and Poly (ethylene oxide) (PEO) were used as carrier polymers for drug delivery. PEO is a highly aqueous soluble polymer, that interacts with the body fluid quickly due to its hydrophilicity resulting in dissolution. PEO is widely used in the polymer matrix to enhance bioavailability and solubility of drugs because of its high aqueous solubility and unique properties in drug delivery applications. The compatibility of PCL and PLA with different types of drugs enables uniform drug distribution in the polymer matrix and the slow degradation rate makes them favourable for prolonged drug delivery systems. In recent years, various studies were reported on the fabrication of drug delivery systems, generated by electrospinning of PCL, PEO, PLA and their blends. PCL, PEO, PLA nanofibers or their blends were loaded with different drugs and biological agents such as; Niclosamide, Silver nanoparticles, Vitamin B12, Curcumin, Lysozyme, AgNO3, Metronidazole (MNA). Polymer blending is an effective approach to prepare functional nanofibers by incorporating the favourable properties of the component polymers. Furthermore, polymer blending facilitates the manipulation of physical, mechanical or biochemical properties of nanofibers. Hydrophilic/hydrophobic polymer blends have been electrospun into nanofibers to fabricate controlled DDS. The hydrophobic polymer forms the backbone structure and it degrades slowly, creating a long term but steady-state drug release. On the other hand, the hydrophilic polymer degrades with a more rapid process, faster than hydrophobic, which accelerates the drug release. In this study, hydrophilic water-soluble PEO was selected for the polymer matrix to enhance the solubility and bioavailability of insoluble SSD. The hydrophobic character of PCL and PLA offers a long period SSD release therefore hydrophilic PEO was blended with hydrophobic PCL and PLA. Thus, PCL/ PEO and PLA/PEO composite polymer matrix was used to provide both increased solubility and controlled release of SSD. Silver sulfadiazine (SSD) is a non-ionized, water-insoluble, topical agent with a wide range of antimicrobial activity that is affected both on bacteria and fungi. SSD is a sulfonamide based drug that is formed by the reaction of sulfadiazine with silver nitrate to form complex silver salt. SSD is used extensively in the topical treatment of infected burns. Silver sulfadiazine provides a long-term release of silver ions, whereas in the case of other silver salts, such as silver nitrate, large amounts of silver ions are released all at once. Thus, the use of SSD decreases the need for frequent application. This makes SSD a desirable and favourable agent since the frequent application is not always practical or possible for patients. However, the low aqueous solubility (3.4 mg/l at pH = 6.8) restricts the drug efficiency, bioavailability and potential antimicrobial activity of SSD thus its applications are limited. Drug solubility is an important issue since efficient drug release and antimicrobial efficiency is contributed just by decomposition of SSD to sulfadiazine and silver ions. Also, the solubility problem of SSD makes it difficult to be stabilized and incorporated into the polymer matrix. The aim of the thesis is to produce a novel SSD loaded topical drug delivery system by using advantages of electrospun nanofibers. Also, a new buffer, Water/Propylene Glycol/ Phosphoric Acid (82:16:2) was utilized to investigate the dissolution and release behaviour of SSD. Thereby SSD containing PCL/PEO and PLA/PEO composite nanofiber carriers were electrospun to achieve the enhancement in solubility, effective drug release and efficient drug loading of SSD. For this purpose, initially, the water-insoluble SSD was incorporated into highly aqueous soluble PEO to increase the solubility. Afterwards, the PEO+SSD solution was blended with PCL and PLA solution to produce composite PCL/(PEO+SSD) and PLA/(PEO+SSD) nanofibers and PCL/(PEO+SSD) casting films for topical drug delivery. SEM method was used to enable the observations of fiber defects and irregularities in the nanofibers structures and to measure the average fiber diameters of the nanofibers. The morphological characterization of the casting films was carried out by SEM and Optical Profilometer. Energy dispersive spectra (EDS) analysis was performed to confirm that the composite nanofibers and casting film which contain SSD, by detecting the Silver (Ag), Nitrogen (N), Sulphur (S) content of the nanofibers. Moreover, EDS-Mapping was carried out to show the distributions of these elements in the composite nanofibers and casting films. The stability of SSD in the fiber structure and the molecular interactions in the drug-free and drug loaded nanofibers were examined by Attenuated Total Reflectance Infrared (FTIR-ATR) Spectroscopy. The crystalline structure of the SSD loaded composite electrospun nanofibers were investigated with X-ray diffraction (XRD) analysis. Atomic Force Microscopy (AFM) was used to determine the surface roughness of the composite nanofibers. 3D AFM Images show the roughness structure of nanofibers. Water contact angle measurements were performed to evaluate the wettability properties of the fabricated nanofibers and casting films surfaces. In vitro drug release media and release conditions were optimized and the controlled drug release profile was obtained for 24 hours. Drug loading efficiency of the nanofiber formulations and casting film were calculated. To understand the SSD drug release mechanisms from SSD loaded formulations; Zero Order, First Order, Higuchi, Hixon Crowell and Korsmeyer-Peppas kinetics models were applied in the drug release profiles of the formulations. Drug release studies were also verified with conductivity measurement due to the conductive nature of SSD. Antibacterial activities of the composite nanofibers against gram-positive Staphylococcus aureus (S. aureus) and gram negative Pseudomonas Aeruginosa (P. aeruginosa) Escherichia coli (E. Coli) bacteria were performed for the period of 24, 48 and 72 hours according to disc diffusion test method. Also, the antibacterial activity of commercial SSD cream was tested for comparison with nanofiber formulations. Furthermore, antibacterial activity of the SSD loaded PCL/PEO and PLA/PEO nanofibers were examined with determining MIC and MBC values. Stability studies of the composite nanofibers were done for 3 and 6 months periods. Nanofiber samples were kept both at refrigerator conditions (+4ºC) and room conditions (25ºC ±2 and 65 % ±2ºC relative humidity) to evaluate stability of nanofiber patches. Stability tests were performed with calculating drug loading amount, cumulative drug release by UV absorption measurements and analysing surface morphology by SEM analysis. Finally, the cytotoxicity studies of the drug loaded and drug-free PCL/PEO and PLA/PEO nanofiber patches were done with using the cell viability assay (MTT assay).
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ÖgeDevelopment of ensete fiber based composites and their characterization(Graduate School, 2021-09-07) Negawo, Tolera Aderia ; Kılıç, Ali ; 503152802 ; Textile EngineeringComposite materials are developed from two or more components having dissimilar properties to create the desired materials' physical, chemical, and mechanical properties. The main constituents of composite materials formulations include matrices, fibers, and additives or fillers. When composite matrices are from polymers, it is considered polymer composite. Fibrous materials from different sources classified as synthetic and natural fibers are used to reinforce the polymeric matrices. The composites from renewable raw material sources either bio-based polymers or natural fibers have been given attention by recent research works. Due to increasing environmental awareness and concern about sustainability, the academic and industrial sectors have started to focus on greener technologies, a major part of which is played by material development. This thesis aims to develop ensete fiber-based composite materials by characterizing their properties. Ensete fiber is extracted by decortication of pseudostem and leaf parts of the Ensete plant as a by-product. Ensete plant known as ensete ventricosum (scientific name) is a perennial plant that has leaves, a large underground corm, pseudostem, and one of the main food plants grown for traditional diet in East Africa especially in Ethiopia. Besides its abundance, Ensete fiber has a tensile strength of 513 MPa, fracture strain of 3.2%, fineness of 8-16tex, crystallinity index of 64.9%, and moisture content of 12.2%. Ensete fiber chemical composition is from 56% of cellulose, 24% of hemicellulose, 2.2% of lignin, and 17.8 % of other extractives, wax, and ashes. These properties of ensete fiber indicate its competitive candidate to make natural fiber-based biocomposites. The novelty of this research contributed to academic literature through its first extensive work on the effects of ensete fiber surface modification and grafting of compatibilizers to polymers on developed composites properties. Additionally, the effects of hybridization and stacking sequences on composite structures and properties; the extraction of micro cellulose crystals from ensete fibers were investigated. The nanocomposite developed from nano cellulose fibrils filled thermoset resin was also characterized for its thermal stability improvements and dynamic mechanical properties. The outcomes of this study have been given in the form of research articles published in high-impact factor journals such as Composite Structures and Composite Science and Technology. The methodology used to develop ensete fiber-based composites includes manufacturing techniques such as vacuum-assisted resin transfer moulding (VARTM), carding of fiber webs, twin-screw melt compounding and granulating, hot press moulding, and liquid cast moulding of composites. The design of experiments was prepared for each research article to address specific objectives and to contribute to the purpose of the thesis in general. Surface modification of ensete fiber by varying alkali concentration was investigated for its effects on the fiber properties and ensete fiber-based unsaturated polyester (UP) composite physical, mechanical, dynamic mechanical, and morphological properties. Mechanical test results revealed that 5.0 wt% alkali treated Ensete fibers and unsaturated polyester composites showed 14.5% and 43.5% increase in flexural strength and Young's modulus respectively when compared with untreated fiber composite. A positive shift in glass transition temperature (Tg) of composites after alkali treatment and tensile fracture surface morphology and roughness of ensete fiber SEM images indicates better interfacial interaction in treated ensete fibers and UP composites. The hybrid composites developed from carded ensete fiber webs and woven glass fiber fabrics reinforcing unsaturated polyester were characterized for the effects of stacking sequences. A hybrid composite GGEE and GEEG showed improvement in tensile properties when compared to polyester composites from pure ensete fiber in its carded web form. The composites stacked as glass-ensete-glass (GEEG) showed higher storage modulus as compared to glass-ensete (GGEE) composites whereas the loss modulus of the composites reinforced with glass fiber exhibited the maximum value of 407 MPa and the height of the damping curve decreased in the GEEG composite. As observed from fracture surfaces, a more extensive fiber pullout was observed for the GEEG sample compared to the only ensete fiber composite sample. Tg of composites was increased for ensete-glass hybrid composites which might be related to more restrictions and a higher degree of reinforcements in hybrid composites. The ensete/glass fiber hybrid polyester composites can be used as load-bearing structures and components where high resistance to deformations and thermal stability is necessary. Ensete fiber and high-density polyethylene (HDPE) composites were developed in the presence of maleic anhydride grafted polyethylene (Ma-g-PE) as a compatibilizer. The grafting process was done by optimized maleic anhydride concentration of 1.5% by weight fraction and 0.5% of reaction initiator called dicumyl peroxide (DCP) and the rest 98% of HDPE polymer. The formulated and premixed composite constituents (chopped ensete fiber, MA-g-PE, and HDPE) were melt compounded by twin-screw extrusion, granulated, and then composite plates were molded using a hot press machine. Increasing the ensete fiber loading from 15 wt.% to 30 wt.% has resulted in the composites being stiffer and harder leading to a decrease in elongation at the break of the composites. The physical properties such as density and water absorption % increased with fiber loading increments while melt flow index reduced. The addition of 5wt% compatibilizer into 25wt% ensete fiber-filled HDPE improved the fiber-matrix adhesion. Its tensile strength, flexural strength, and impact absorption energy increased by nearly 43%, 46%, and 56% respectively when compared to composites with the same fiber loading and without compatibilizer. Morphological analysis on micrograph images taken by SEM confirmed the failure mechanism of the composites. The results of the study show that ensete fiber-HDPE composite could be commercialized in the industry for construction and building, low-density furniture, and moldable structures in need of design flexibility. The micro or nanometer cellulose fillers extracted from green material sources such as ensete fiber are needed to be utilized to develop biocomposites. The study focused on the extraction of micro cellulose crystals from lignocellulosic ensete fiber and additions of nano cellulose fibrils to epoxy resin were investigated. The process of isolating micro cellulose includes chemical and mechanical methods. Lignin and hemicellulose of ensete fibers were removed by soaking chopped short fibers in an alkali solution (17.5 wt% NaOH concentration) for 4 hr. at room temperature. The alkali treated fibers were washed with deionized water several times to keep PH value at 7; filtered to remove lignin and hemicellulose, and dried at 80 ℃ for 24 hr. Acid hydrolysis by 1M hydrochloric acid was done at 80 ± 5 ℃ for 2 hr. to remove hemicelluloses, pectin, and some of the suspended cellulose amorphous, and then fibrils of cellulose were mechanically ball milled to micro cellulose crystals. The analysis from FTIR measurements, x-ray diffraction, optic microscope, and SEM images revealed the removal of lignin, hemicelluloses, pectin, wax, and also hydrolysis of amorphous cellulose parts during the chemical process. The diameters of extracted MCC were ranging from 1-10µm. The epoxy resin filled with varying weight fractions of cellulose nanofibrils was moulded and cured by liquid cast moulding techniques. The effects of incorporating nano cellulose fibrils filler into epoxy at different loading (1wt%, 3wt%, and 5wt%) were investigated. The results of thermal properties from DSC, TGA, and DMA discussed thermal stability and stiffness of epoxy nanocomposites. From DMA test results, the reduction in tan delta peak height of nanocomposites with the increase in NCF loading shows increments of stiffness imparted by fillers. The glass transition temperature of nanocomposites shifted to a higher temperature as the filler loading and uniform dispersion were attained. The thermal stability of CNF filled nanocomposites can be compared from TGA results. The temperature where maximum weight loss happened is shifted to a higher temperature when compared with pure epoxy polymer. CNF fillers acted as a thermal insulating barrier to the epoxy polymer and resulted in less thermal degradation of nanocomposites relatively. From overall test results, 3wt% CNF is the optimized cellulose nanofibrils filler loading for better thermal properties and modulus of the epoxy-based nanocomposites. In conclusion, based on currently available technologies the utilization of an ensete fiber which is from renewable sources to be used as reinforcements of polymeric matrices and alternative new green composite products were able to be developed for desired engineering applications as recommended in each specific study done.
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ÖgeDevelopment of stretchable conductive fabric through different metals coating approach for e-textile applications(Graduate School, 2022-07-25) Hassan, Zuhaib ; Kalaoğlu, Fatma ; 503122807 ; Textile EngineeringThis study aims to manufacture and characterize various types of conductive (cotton knitted and polyester knitted) fabrics. The fabrics were prepared through the electro-less copper metal coating approach. The effect of copper electroleess plating on different types of fabric structures and on different crossections of yarns was also observed. The main response of prepared fabric was electrical conductivity, EMI shielding and their durability against washing and rubbing. The current research activity has multiple benefits considering extensive comparison with other studies. Previously electroless plating has been performed by different salts and reducing agents' combinations over different fibres. However, there were no study available to metallize the fabric structures having different GSM and different cross section of fibres. Secondly, we have also studied the effect of different fibrous cross-section (round, hollow round, W shape and octolobel) against copper electroless plating. At first, nine-combed cotton knitted fabric samples with different yarn fineness and elastane percentage were selected in order to see effect of these parameters on electrical conductivity and physical properties of samples such as an increase in weight and thickness, impact of washing cycles and abrasion resistance on the electrical conductivity of the fabric sample. The surface morphology of all the knitted cotton fabric samples were also explored before and after the coating method via scanning electron microscope (SEM) and it showed a remarkably uniform deposition of copper on the fabric surface. the energy dispersive spectroscopy (SEM-EDX) was performed to determine the coated material content on the surface of the fabric after the metal coating process. The utility of conductive fabrics was analyzed for electromagnetic shielding ability over frequency range of 30 MHz to 1.5 GHz. The electrical conductivity and amount of metal deposition was found to be higher for the fabric samples having less GSM and higher cotton percentages in their structures. The results revealed that knitted cotton fabric of 5% elastane with the finer yarn count (Ne=40/1) showed lowest resistivity (3.24 Ω.cm) as compared to the other knitted cotton fabric of 10% elastane with a finer count (Ne=40/1) or 5% elastane with coarser (Ne=30/1). The increase in elastane content into fabric structure also influences the fabric stretchability. The objectives of second part of the study were, to carry out research with the best performing three samples obtained from the first part of the study and three single jersey knitted cotton fabric samples were selected. The selected fabric samples with GSM (136, 154 and 176 GSM) out of nine fabric samples were used in this part. These fabric samples provided the lowest value of electrical resistivity coupled with high EMI shielding and more contents of metal particles. Thereafter, the selected samples were pre-treated with laser to enhance the surface roughness, then electroless plating was performed in order to see the impact of roughness on copper deposition. This section of the research work addresses the development and characterization of conductive cotton fabrics treated with lasers in context of copper (Cu) metallization methodologies. The abrasion resistance, thickness, and durability of the laser-treated knitted cotton fabric samples were investigated. Additionally, samples exhibited exceptionally consistent deposition of Cu nanoparticles on the surface of cotton fabric when the surface morphology of the laser-treated surfaces was examined by employing the scanning electron microscope (SEM) both before and after the coating procedure. To assess the elemental analysis on the surface of the treated samples following the electroless metallization process, an energy dispersing spectroscopy (SEM-EDX) examination was performed. This section of the study indicated that fabric samples that had been laser-treated outperformed untreated fabric samples in terms of wear resistance. Abrasion resistance being one of the significant features in electric textile applications, laser-treated samples might thereby be the best options. The third part of the study was the development and characterization of conductive textured and non-textured polyester fabrics with different cross-sections. The electroless copper plating method was selected to impart conductivity on fabric structures. The deposition of copper nanoparticles on textured and non-textured polyester fabrics was characterized by electrical conductivity, electron scanning microscopy (SEM), microscopic morphology, and energy dispersive X-ray spectroscopy (EDX). SEM images revealed a uniform copper nanoparticle coating of a thin film on textured and non-textured polyester fabrics. The properties of conductive textured polyester fabrics were compared in terms of electrical conductivity, wear resistance, thickness and durability with non-textured conductive polyester fabrics. Structural studies showed that the crystalline surface of the textured and non-textured polyester fabric structure is not affected by electroless metallization. Conductivity studies have shown that textured (lowest resistivity 2.18 Ω.cm) and non-textured (lowest resistivity 76.39 Ω.cm) polyester fabrics have good electrical conductivity. When the durability of conductive textured and non-textured polyester fabrics was examined against washing and rubbing fastness, the textured polyester fabrics showed good retention of copper nanoparticles by maintaining their electrical conductivity level after 250 abrasion cycles. Furthermore, resistivity analysis was also carried to study the effect of copper metallization and conductivity against different morphological structures of fibres. It was observed that there are lower values of electrical resistivity for each coated sample. The resistivity was found to be lowest for hollow round coated fibres (either textured or non-textured). The behaviour of metal deposition for hollow round fibers and electrical conductivity was further justified from the SEM analysis. The W shape fibers showed less amount of metal deposition and higher electrical resistivity values as compared to all. The final applications of developed copper plated fabrics are in the field of smart textiles, sensors, stretchable actuators, EMI shielded panels and stretchable electrodes. Keywords: Conductive textiles, Electroless plating, Copper coating, Electromagnetic interference shielding, sensors and actuators, Stretchable conductive fabrics, Smart textiles, metal coatings, textured polyester fabrics, Metal coated, Cross-sectional fiber.
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ÖgeDevelopment of structural health monitoring system for fiber reinforced polymer composites(Lisansüstü Eğitim Enstitüsü, 2021) Shahrukh, Shahbaz ; Berkalp, Ömer Berk ; 692349 ; Tekstil MühendisliğiFiber Reinforced Polymer (FRP) composites have emerged as a promising structural material for high-end applications. Their advantage of tailored properties according to specific requirements of desired applications has enabled them to achieve a preferred position above conventional metals. Glass Fiber Reinforced Polymer (GFRP) composites have gained a huge market in advanced engineering applications, among which aerospace and automotive industries are significant. The advancements in technologies have enabled the industries to commercialize large-scale composite architectures with higher productivities. Although composites have been offering reliable performance for large-scale and complex architectures, their maintenance is necessary for safety reasons and prolonging the service life with the least costs involved. The anisotropic nature of composites makes the detection of damage and failure very complicated in real-time. Therefore, various Structural Health Monitoring (SHM) techniques are being studied widely to monitor structural integrity in real-time. Focusing on this issue, piezoresistive strain sensors have been investigated in this study which has the potential to offer real-time information about structural integrity. The primary aim of this study is to sense induced strains and damages in the composite structures in real-time for which three major categories of strain sensors have been developed and analyzed. To support the simultaneous multichannel electrical signal acquisition, an Arduino microcontroller setup was developed to offer customized electrical measurements. The setup was successfully designed and implemented to record real-time electrical measurements from the embedded sensors in composite specimens. Carbon fiber based strain sensors were utilized to detect induced strains during tensile and flexural loadings by coupled electrical measurements. The experimental results showed that carbon fiber rovings were highly sensitive to low strains in composites during tensile and flexural loadings. The dual assembly of strain sensors revealed that the piezoresistive behavior of carbon fiber strain sensors is opposite for compressive strain and tensile strain during flexural loading. Temperature cycles from -10 oC to 80 oC influenced the resistance of carbon fibers up to 7.29%. Multi-Walled Carbon Nanotubes (MWCNTs) based strain sensors were developed and embedded in GFRP composites to analyze their piezoresistive behavior. Carboxy and amide functionalized MWCNTs were used to develop CNT-enabled E-Glass fiber strain sensors. FTIR spectroscopy confirmed the interactions between MWCNTs and glass fiber surfaces. The electromechanical test results indicated that MWCNT coated sensors in GFRP composites show promising piezoresistive sensing characteristics with good cyclic reproducibility that is significant for in-situ strain monitoring and damage detection. The experimental results showed that amide functionalized MWCNT sensors had higher strain sensitivity to flexural strains, whereas higher sensitivity to tensile loading was noticed with carboxy functionalized sensors. However, more linear piezoresistive behavior was found with amide functionalized sensors. A significant reproducible behavior with -8% relative resistance change was noticed as an electrical response to temperature cycles in the range of -10 oC to 80 oC. The development of carbon fiber thin films as strain sensors using a facile method was experimented. Thin films having conductive properties were developed in six different formulations with casting techniques to analyze their piezoresistive behavior for strain sensing in FRP composites. Higher concentrations of short carbon fibers encouraged higher conductivities in thin films. The electromechanical testing in a three-point bending configuration showed that the higher concentration of short carbon fibers influenced the sensitivity of sensors positively in the elastic region. Moreover, higher reproducibility during cyclic loading was also achieved with high concentrations of carbon fibers. Temperature cycles from -10 oC to 80 oC affected the resistance of the sensors with a negative temperature coefficient of resistance. Overall, the studied sensors had more sensitivity to tensile strains as compared to flexural strains. However, carbon fiber thin films showed the highest sensitivity to the induced flexural strains. Further work may improve the efficiency of sensing various types of damages using these sensors.
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ÖgeDevelopment of textile based temperature sensor for wearable electronics(Graduate School, 2021-09-30) Arman Kuzubaşoğlu, Burcu ; Kurşun Bahadır, Senem ; 503122802 ; Textile EngineeringDue to their compressibility, bendability, and compatibility with irregular and curvilinear surfaces, flexible and stretchable devices are attracting attention and have a wide range of applications. The increasing number of publications in this field demonstrates the growing popularity of flexible sensors. Flexible sensors provide mechanical robustness, biocompatibility, multifunctionality, and comfort when compared to conventional rigid sensors. For this reason, next-generation wearable technologies are expected to be driven by interest in flexible, stretchable, and soft devices. Textiles, in addition to their protective and aesthetic functions, provide an exceptional flexible platform for providing sensing functions and comfort to the wearer with diverse range of fibers, yarns, and fabric structures. New developments in printed electronics enable mass production of sensors using efficient printing processes by considerably minimizing costs and enhancing the potential of large-scale production. In this thesis, at first, the capabilities of temperature sensors, their sensing method, and previous research that has been conducted on them are presented. Additionally, the techniques and uses of inkjet printing are examined in detail. A comprehensive explanation of inkjet printing technology and printing challenges are issued. Dispersion is required for the development of inks that include carbon nanotubes. Due to the hydrophobic nature of carbon nanotubes, they must be distributed using a combination of mechanical and chemical methods. Numerous methods, including ultrasonication, non-covalent and covalent alterations, were used to disperse nanotubes. The use of various types of carbon nanotubes in CNT ink formulations is also studied. The development of conductive inks formulations containing CNT, PEDOT:PSS and CNT/PEDOT:PSS with a proper evaluation guideline is studied. Moreover, the concepts and properties of functional materials, as well as the critical additives used during the printing process that can have a significant influence on the printing process of conductive inks are discussed. The physical, structural, morphological, and electrical properties of the materials are investigated using various techniques (UV-Vis, FTIR, optical profilometer, SEM, AFM, optic microscope, multimeter, etc.). With relevant to print quality, the textile basis material should be dependable, maintaining a level surface and good uniformity during the printing process. In order to create conductive material sensors for temperature measurement, the inkjet printing process was used, which has the advantage of reducing ink waste while also being a low-cost and simple method. Following the procurement of CNT-based inkjet suitable dispersion, a PEDOT:PSS/CNT composite ink and a PEDOT:PSS inkjet appropriate dispersion are manufactured for temperature sensing. Appropriate ink formulations have been developed to produce high-quality inkjet-printed sensors, which are typically characterized by low imperfection points throughout the surface of the printing material. The sensor manufacturing process is then completed by including silver yarn, followed by the application of silver based conductive glue and an encapsulating operation. Spectrophotometer studies were conducted to determine the qualities of carbon nanotube printing when many print passes are used, as well as the color characteristics of the produced specimens. The properties of CNT based, PEDOT:PSS based and CNT/PEDOT:PSS composite based sensors are compared to investigate their temperature sensing performance. Hence, proper ink formulations with appropriate physical and chemical properties that typically affects homogeneous printing surface characteristics and sensing properties, were successfully developed by analysing their morphologies and printing parameters. It was determined whether the printed temperature sensors performed properly by subjecting them to a temperature range ranging from 25 to 50 degrees Celsius. Furthermore, wear and performance tests, such as durability against bending, folding, humidity, rubbing, washing, light, and human sweat, were carried out with the help of some characterization methodologies in order to investigate the sensor's reliability and durability under unfavorable situations. The sensor real time measurement using of a mannequin and human gloved hand are reported with discussions. As a result, during our proof-of-concept inquiry, our newly designed temperature sensor was placed to a mannequin's skin and human body on a gloved hand for temperature monitoring. Our developed wearable sensor provides highly accurate temperature monitoring. Lastly, the application based on artificial intelligence for the modeling of wearable sensors in various temperature and humidity conditions is described. Artificial neural networks (ANN) are used to model wearable sensors in various temperature and humidity conditions. The relationship between temperature, humidity, and electrical resistance is presented with the use of ANN. This innovative wearable temperature sensor development process is expected to aid development of smart wearable technologies. The developed sensor with its good mechanical properties and excellent sensing performance is believed to be useful for use in the textile products. Moreover, this developed sensor also offers the opportunity to be directly included in wearable smart systems in industrial production. In addition to the lack of standardized and consistent manufacturing techniques, there are unfortunately not yet any regular and comparable tests that can be used for the development and implementation of wearable e-textile sensors. Hence, this study will pave a way for development phases and implemenation of wearable e-textile sensors, in particular, contribute to industrialization in this area. To conclude, the developed textile-based sensor might be a solution instead of rigid device components for human body temperature monitoring and it can be directly utilized by sticking the sensor on various garment types while maintaining the user's comfort. Hence, it reveals a strong potential for use in wearable healthcare and biomedical applications.
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ÖgeElectrospun composite nanofibers with metal/metal oxidenanoparticles(Graduate School, 2021-04-21) Başkan, Havva ; Karakaş, Hale ; 503142809 ; Textile Engineering ; Tekstil MühendisliğiFunctional materials have taken great interest due to their superior physical and chemical features which allow them to be succesfully used in a wide range of engineering applications. Nanomaterials, specifically nanofibers are regarded as functional materials due the their high surface area to volume ratio, high pore interconnectivity, small pore dimensions and superior chemical and mechanical features. Nanofibers are produced by mainly electrospinning which is a simple and inexpensive technique. Moreover, many types of polymers or polymer blends can be converted to nanofibers by electrospinning. Combination of two or more materials in a nanofibrous structure can result in functional materials. In this thesis, the goal was obtaining functional nanofibrous materials by incorporating a noble metal (silver) and metal oxides (iron III oxide (Fe3O4) and aluminum oxide (Al2O3)) in novel polymeric nanofiber structures and evaluate the biological features of the samples for medical applications. First of all, a novel Poly (acrylonitrile-co-itaconic acid) (P (AN-co-IA)) copolymer was synthesized by emulsion polymerization. In the literature, copolymerization of itaconic acid (IA) with acrylonitrile (AN) was performed for decreasing the cyclization temperature of polyacrylonitrile (PAN) homopolymer and consuming less energy for carbon fiber production. However, in the scope of the thesis, it was aimed to enhance the application areas of IA by integration of metals and metal oxides. Since Fe3O4 nanoparticles and Al2O3 nanoparticles play an imperative role in many biomedical applications, they were utilized together with P (AN-co-IA) copolymer. It was very difficult to study with metal oxide nanoparticles due to their tendency to agglomeration. For that reason, the appropriate amount of metal oxide nanoparticles was determined first by using polyacrylonitrile /N,N Dimethylformamide (PAN/DMF) solutions. Afterwards, the optimized amout of Fe3O4/ Al2O3 nanoparticles were added into P (AN-co-IA)/DMF polymer solutions and the solutions were subjected to electrospinning to obtain a nanofibrous structure. In addition to conventional electrospinning, coaxial electrospinning was also performed for metal oxide nanoparticle incorporation. Detailed morphologic and spectroscopic characterizations of the obtained nanofibers were performed. Thermal features of the resultant nanofibers were also analyzed by Differential Scanning Calorimety (DSC) and Thermogravimetric Analysis (TGA). It was captured from the characterization results that addition of metal oxide nanoparticles to P (AN-co-IA) copolymer structure altered the features of the plain P (AN-co-IA) nanofibers. Even using very small amount (1 wt %) of Al2O3 caused improvements in thermal stability of the nanofibers. On the other side, silver nanoparticles (AgNPs) formation and integration to polymer structures were achieved by different chemical and physical methods. By the assistance of P (AN-co-IA) polymer and DMF, AgNPs were formed in-situ in polymer solution and then the polymer solution was electrospun for nanofiber production. The novelty of the method was related to the decreased reduction duration of silver nitrate (AgNO3) by using P (AN-co-IA) polymer. The method was compared with the literature studies on the utilization of PAN polymer for reduction of AgNO3. P (ANco-IA) polymer allowed to obtain AgNPs from the precursor AgNO3 two times faster than PAN. Moreover, it was understood that P(AN-co-IA)/Ag nanofibers had high electrical conductivity, enhanced thermal stability and satisfying nanofiber morphologies. Besides conventional electrospinning, AgNPs were introduced into P(AN-co-IA) polymer structure via coaxial electrospinning. In the process, AgNO3/DMF solution was prepared to be used as a shell solution and P (AN-co- IA)/DMF solution was prepared as a core solution. Since the most important point in coaxial electrospinning is the feed-rate of core and shell solutions, a set of experimental study was performed for the optimization of flow-rate (0.2 ml/h) of shell solution. After coaxial electrospinning, P(AN-co-IA)(core)/ AgNO3 (shell) nanofibers were subjected to UV-irradiation to generate AgNPs by the reduction of AgNO3. UVirradiation duration was optimized as 3 hours by using PAN(core)/ AgNO3 (shell) nanofibers. In addition to P (AN-co-IA) and PAN polymers, biodegradable and biocompatible poly (3-hydroxybutyrate) P (3HB) and poly (3-hydroxyoctanoate-3 hydroxydecanoate)(P (3HO-3HD)) polymers were also utilized for the combination of AgNPs. To this end, nanofibers of P (3HB)/P (3HO-3HD) were collected via conventional electrospinning and by dip-coating they were coated with AgNPs. As in the nanofibers including metal oxide nanoparticles, detailed morphologic, spectroscopic and thermal characterizations of the resultant nanofibers were performed by Scanning Electron Microscope –Energy Dispersive Spectroscopy (SEM-EDS), Ultra Violet-Visible (UV-Visible) and Fourier Transform Infrared-Attenuated Total Reflectance (FTIR-ATR) spectroscopy, and DSC. Most importantly, antimicrobial activity studies of P(AN-co-IA)/Ag nanofibers (obtained via conventional electrospinning) against S. aureus, E.coli, P. aeruginosa and C. albicans and immunomodulatory properties of P (3HB)/P (3HO-HD)/Ag nanofibers against special cytokines (IL-1 (α and β), IL-6, IL-8, TNF-α, TGF-β and HBD-2) were evaluated. Related to the antimicrobial activity results of P (AN-co-IA)/Ag nanofibers, it was observed that the nanofibers produced inhibition zones against the studied microorganisms. That was also proved by susceptibility testing. According to time-kill analysis, without silver nanoparticles, either PAN or P (AN-co-IA) nanofibers did not show any antimicrobial activity against any microorganisms. However, bacteriostatic/fungistatic activity was observed for all nanofiber samples which include AgNPs at almost all time points. Bactericidal activity was started from 24-48 hours and lasted until 120 hours at 10x Minimum Inhibitory Concentration (MIC) whereas fungicidal activity was observed between 120 and 168 hours at 10xMIC. Based on the real-time reverse transcriptase polymer chain reaction (RT-PCR) tests of P (3HB)/P (3HO-3HD)/Ag nanofibers, it was understood that while plain P(3HB)/P(3HO-3HD) nanofibers did not show any difference in the basal production of these molecules by HaCaT cells in culture, AgNP-containing P(3HB)/P(3HO-3HD) nanofibers upregulated the studied proinflammatory cytokines which were IL-1(α and β), IL-6 and IL-8 after 6 hours to start the healing process. Those findings of AgNPs containing P (AN-co-IA) and P (3HB)/P (3HO-3HD) nanofibers revealed that they could be used in wound dressing or tissue engineering applications effectively. Polypyrrole (PPy) is popular with its conductivity, but it can also be used in biological applications such as biosensors and drug delivery. However, due to the problems in processing with PPy, it is very difficult to obtain PPy nanofibers. In this thesis, it wasaimed to combine PPy with AgNPs to be used in biological applications and also converting it to a nanofibrous web structure by the help of P (AN-co-IA). Since it was difficult to electrospin P (AN-co-IA), PPy and AgNPs in a single step, AgPPy was synthesized via chemical oxidation polymerization first. Then AgPPy and P (AN-co-IA) was gathered in a nanofiber structure via coaxial electrospinning. AgPPy/DMF solution was prepared as shell solution and P (AN-co-IA) /DMF was prepared as core solution. It can be fairly said that the same protocol of the abovementioned coaxial electrospinning was performed for coaxial electrospinning of P (AN-co-IA) (core)/AgPPy (shell) nanofibers. Bead-free and continuous nanofiber morphologies with fine nanofiber diameters could be obtained. As a conclusion, in the scope of this thesis, functional nanofibers were achieved by incorporating metal/metal oxide nanoparticles into polymeric nanofiber structures with various experimental procedures. The obtained nanofibers are good candidates for medical applications where conductivity and antimicrobial activity are desired.
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ÖgeEv tipi yıkamalarda suyun tekrar kullanımı için yıkama atık suyundan renk giderme sisteminin geliştirilmesi(Lisansüstü Eğitim Enstitüsü, 2021-11-23) İlkiz Arslan, Başak ; İridağ Beceren, Yeşim ; Candan, Cevza ; 503062802 ; Tekstil MühendisliğiSon yıllarda temiz su kaynaklarının hızla kirlenmesi nedeniyle su geri kazanımının önemi günden güne daha da artmaktadır. Bu tez çalışması öncelikle su kaynaklarının sürdürülebilir olmasını desteklemek ve kullanılan atık suyu tekrar kullanabilmek amacıyla tetiklenmiştir. Pazarda yaygın bulunan yüksek kapasiteli ve önden yüklemeli ev tipi çamaşır makinelerinde her çevrimde yıkama ve durulama adımlarının tamamında minimum 50 L ve üzerinde su tüketimi gerçekleşmektedir. Sunulan tez çalışmasında, ozonlama yöntemi kullanılarak renkli çamaşırların yıkanmasıyla ortaya çıkan çamaşır makinesi atık sularındaki rengin giderilmesi ve rengi giderilen suyun bir sonraki yıkamada tekrar kullanılması hedeflenmiştir. Bu hedef doğrultusunda, çamaşır makinesi atık suyundaki boyarmadde konsantrasyonunu tahminleme, ozon ile renk giderme sistemine sahip makine prototipinin hazırlanması çalışmaları ve bu makinede renk giderme testleri yürütülmüştür. Çamaşır yıkama sonucunda oluşan atık su, gri su kategorisindedir, hanelerde evsel aktiviteler için kullanılan toplam su içerisinde yüksek bir paya sahip olup (%27) geri kazanım ve tekrar kullanım için potansiyel oluşturmaktadır. Günümüzde yaygın olarak tercih edilen pamuk içerikli tekstil ürünleri çamaşır makinelerinde sıklıkla yıkanmakta olup, bu ürünlerin renklendirilmesinde çoğunlukla reaktif boyarmaddeler kullanılmaktadır. Bu reaktif boyarmaddeler içerisinden azo ve antrakinon boyarmaddeler yaygınlık, suda yüksek çözünürlük göstermeleri, life fikse oranlarının düşük olması ve atık suda risk oluşturmaları nedeniyle tercih edilmiştir. Yıkamaya karşı renk haslığı düşük ve lekeleme konusunda problemli olarak bilinen kırmızı ve mavi renkler belirlenerek, bu renklerin elde edilmesi için azo boyarmadde sınıfından reaktif kırmızı 195 ve antrakinon boyarmadde sınıfından reaktif mavi 19 boyarmaddeleri seçilmiştir. Çalışmada yaygın kullanılan ve sık yıkama ihtiyacı bulunan örme kumaşlar tercih edilmiş ve ticari koşullarda üretilip boyanmıştır. Tekstil atık sularında organik kirleticilerin fazla bulunmasından dolayı, bu sulardan reaktif boyarmaddelerin giderilmesinde oksidasyon yöntemlerinden ozonlamanın ve ozon ile diğer yöntemlerin kombinasyonlarının sıklıkla tercih edildiği belirlenmiştir. Teknolojisinin olgunlaşmış olması, yan ürün açığa çıkarmaması, yerinde renk giderimini hızlı şekilde gerçekleştirebilmesinden dolayı çamaşır makinesi için ozonlama yöntemi tercih edilmiştir. Çamaşır makinesinde renk giderimi için yıkama çevrimindeki uygun yıkama adımının -hedef atık su çözeltisinin- belirlenmesi için yapılan deneysel çalışmada, yapılan ölçümlerde deterjan konsantrasyonu düşük olan ve yumuşatıcı içermeyen birinci durulama adımının renk giderim için daha uygun olduğuna karar verilmiştir. Literatür araştırması sırasında renk giderimi çalışmalarında çoğunlukla konsantrasyonu bilinen yapay çözeltiler ile çalışıldığı saptanmıştır. Oysa, çamaşır makinesinde yapılan yıkamalar sonunda ortaya çıkan atık suların içeriği farklı (lif, hav, deterjan vb.) ve oldukça kaotiktir. Literatürde rastlanmaması nedeniyle tezin yenilikçi yönü olarak yapay çözeltiler yerine "evsel çamaşır makinesi atık suları" ile çalışılmıştır. Ev tipi çamaşır makinesinden kaynaklı boyarmadde içeren atık suyun renginin giderilmesi için ozonlama ile renk giderme sistemi önerisi yapılmıştır. Yaşanan en büyük zorluk, yıkama sırasında boyalı kumaşlardan elde edilen atık suların boyarmadde konsantrasyonunun bilinememesidir. Bu atık suların boyarmadde konsantrasyonunun tahmin edilmesi için iteratif bir yaklaşım geliştirilmiştir. Boyarmadde konsantrasyonunun belirlenebilmesi için VIS spektrofotometre cihazı ile renkli atık su çözeltilerinin absorbans taraması yapılmış ve spektrumda maksimum absorbans değerini veren dalgaboyu tespit edilmiştir. Ancak, çamaşır makinesi atık suyunda yapılan ölçümlerde maksimum absorbans değeri elde edilememiştir. Boyarmadde konsantrasyonunun tahmin edilebilmesi için geliştirilen yaklaşımda, birinci adımda, saf su ile yapay olarak hazırlanan kontrol boya çözeltilerinin spektrum taramalarından maksimum absorbans değerlerinin elde edildiği dalgaboyları Reaktoset Red RFT (C.I. RR 195) için 540 nm, Reaktoset BRL Blue R Spec (C.I. RB 19) için 592 nm olarak belirlenmiştir. İkinci adımda, boya konsantrasyonları ve deterjan konsantrasyonları, sırasıyla, ana yıkama adımı için 10 –– 100 mg/L aralığında ve 4,6 g/L olarak; durulama adımı için 1 – 40 mg/L aralığında ve 0,5 g/L olarak hazırlanmış ve çözeltilerin absorbans ölçümlerinden kırmızı (RR 195) ve mavi (RB 19) boyalar için ana yıkama ve durulama kalibrasyon eğrisi denklemleri elde edilmiştir. Üçüncü adımda, renkli atık su çözeltileri tergotometer cihazında boyalı kumaşların yıkanması sonucunda elde edilmiştir. Bu çözeltiler ilgili dalgaboyunda net bir absorbans değeri vermediğinden, boyarmadde konsantrasyonunun hesaplanması için adım 2'de elde edilen kalibrasyon eğrilerine ait denklemlerin (kırmızı atık su için: A=0,0186C+0,0427, R² = 0,9997; mavi atık su için: A=0,0115C+0,0540, R² = 0,9966) kullanılmasına karar verilmiştir. Doğrulama testlerinde, denklemlerden hesaplanan boya konsantrasyonuna en yakın konsantrasyondaki deterjanlı yapay boya çözeltilerinin spektrumları ile renkli kumaşlardan elde edilen spektrumların karakteri farklı olmasına rağmen belirlenen dalgaboyunda üst üste çakıştığı saptanmıştır. Çamaşır makinesi ve tergotometer cihazından elde edilen atık su çözeltilerinin absorbans ve konsantrasyon değerleri arasında güçlü bir ilişki olduğu belirlenmiş ve tergotometer cihazının su ve kumaş sarfiyatını azaltmak amacıyla çamaşır makinesi yerine kullanılabileceği kanaatine varılmıştır. Renk giderme sistemine sahip makine prototipi için, bir ozon düzeneği kurularak çalışmalara başlanmıştır. Kurulan düzenekte hava kompresörü, hava kurutucu, akış ölçer, ozon jeneratörü, ventüri, su haznesi, iki adet su pompası ve debimetre yer almaktadır. Ozon düzeneğinde yapılan deney tasarımı sonucunda renk giderme etkinliği üzerinde en etkili faktörlerin sırasıyla %22,0 ile boyarmadde*ozon jeneratörü ikili etkileşimi, %15,4 ile ozon jeneratörü*ozonlama süresi ikili etkileşimi ve %14,8 ile tek başına ozon jeneratörü olduğu saptanmıştır. 500 mg/sa kapasiteli (500-B kodlu) ozon jeneratörü ile en yüksek renk giderme oranlarına ulaşıldığından bu ozon jeneratörünün kullanılmasına karar verilmiştir. Ventüri sistemi ve geri kazanılan suyun bulunacağı depoya sahip 9 kg kapasiteli çamaşır makinesi prototipi hazırlanmıştır. Sistemin çalışma prensibi şu şekildedir: Dışarıdan hava kompresörü yardımıyla çekilen ortam havası ozon jeneratöründen geçirilerek ozon üretilmekte ve ventüri elemanına taşınmaktadır. Pompalar yardımıyla ventüri elemanında renkli su ve ozon buluşmakta, belirli süre yapılan sirkülasyon sonrasında ozonlama yoluyla renksiz su elde edilmektedir. Önerilen denklemler kullanılarak boya konsantrasyonları hesaplandığında, renkli kumaşların farklı tüketici koşullarında yıkanması sonucu atık su boya konsantrasyonunun 15 mg/L ile 90 mg/L arasında değişkenlik gösterdiği saptanmıştır. Çamaşır makinesinde ozonlama testleri iki aşamada yürütülmüştür. Birinci aşamada, çamaşır makinesinde 14 L olarak deterjanlı, 20 – 40 – 60 – 80 mg/L boya konsantrasyonuna sahip yapay çözeltiler hazırlanmış ve ozonlanmıştır. İkinci aşamada, gerçek yıkama koşulunu temsilen ticari koşullarda üretilen kumaşların (1 kg) Beko 9 kg çamaşır makinesinde pamuklu 40 programında 52 g standart deterjan ile yıkanmasından elde edilen birinci durulama suları toplanarak ozonlanmıştır. Kırmızı ve mavi yapay boya çözeltilerinde renk giderme oranı %95 ve üzerinde gerçekleşmiştir, görsel olarak rengin tamamen giderildiği tespit edilmiştir. Renk giderimi etkinliğinin başlangıç boya konsantrasyonuna ve boyarmadde tipine bağlı olduğu belirlenmiştir. Boya konsantrasyonu arttıkça renk giderimi daha uzun sürede gerçekleşmiştir. Reaktif kırmızı 195 boyarmaddesi ile hazırlanan çözeltilerde renk gideriminin reaktif mavi boyarmadde ile hazırlanan çözeltilere göre daha uzun sürdüğü belirlenmiştir. Kırmızı ve mavi kumaşlardan elde edilen birinci durulamaya ait atık suların boya konsantrasyonu sırasıyla 35,1 mg/L ve 42,3 mg/L olarak belirlenmiştir ve kırmızı ve mavi renkli atık su çözeltilerinde %80 civarında renk giderimi sağlanmıştır. Renk giderimi mavi atık su çözeltisi için yaklaşık üç kat daha hızlıdır. Kırmızı renkli atık sularda 240 dakikada %76 oranında renk giderimi; mavi renkli atık sularda ise 70 dakikada %82 oranında renk giderimi gerçekleşmektedir. Ozonlama ile boyarmaddenin kromofor grubunun parçalanıp parçalanmadığının analizi için, 100 mg/L boya konsantrasyonuna sahip deterjansız çözeltiler ozonlanmış ve dondurularak kurutulmuştur. FTIR cihazı analizleri sonucunda, kırmızı çözeltilerde ozonlama etkisiyle 1540 cm-1 civarında görülen N = N bağının kırıldığı, dolayısıyla azo kromofor grubunun parçalandığı; mavi çözeltilerde ozonlama etkisiyle 1575 cm-1 civarında görülen kromofor grubu temsil eden antrakinon halkasına ait bağların kaybolduğu belirlenmiştir. Ozon ile rengi giderilen suyun kalitesi incelendiğinde, çıkış suyu parametrelerinin giriş suyu parametrelerine göre daha iyi seviyede olduğu saptanmıştır. AKM, bulanıklık, KOİ (%54 düşüş) ve TOK (%35 düşüş) parametrelerinde ozonlama işlemi etkisiyle belirgin düşüş sağlanmıştır. Hazırlanan prototip makinede geri dönüştürülen su bir sonraki çevrimin ana yıkama adımında kullanılmıştır. 10 çevrim süresince ozonlanmış su ile yıkanan çeşitli tekstil numunelerinde herhangi bir tekstil hasarlanma etkisi görülmemiştir. Geri kazanılmış su ve şebeke suyu ile yapılan yıkamaların yıkama performansı değerleri arasında belirgin bir fark tespit edilememiştir. Çamaşır makinesi ozon ile renk giderme sisteminin enerji tüketimi, mavi kumaştan elde edilen suyu ozonlamak için pamuklu 40 programının enerji tüketiminin yaklaşık beşte biri, kırmızı kumaştan elde edilen suyu ozonlamak için pamuklu 40 programının yaklaşık üçte ikisidir. Ozon ile renk giderme sistemine sahip çamaşır makinelerinin yaklaşık dörtte bir oranında su tasarrufu sağlayacağı tahmin edilmektedir. 8-9-10 kg kapasiteli çamaşır makinelerinde çevrim başı yaklaşık 14 L'lik su tasarrufunun bir yılda yaklaşık 1,24 hm3'lük su tasarrufu sağlaması beklenmektedir. Çamaşır makinesi ortamında atık suyun kendi kaynağında renginin giderilmesi, geri kazanımı ve tekrar kullanımı ile sürdürülebilir yaşam desteklenebilecektir. Geliştirilen ürünün hem ticari açıdan hem çevresel açıdan başarı potansiyeli bulunmakta hem de sürdürülebilir ürün gamında kalıcı bir yer edinmesi beklenmektedir.
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ÖgeFabrication and characterization of biodegradable fibrous webs for vascular graft structures(Graduate School, 2022-01-10) Öztemur, Janset ; Eniş Yalçın, İpek ; 503181804 ; Textile Engineering ; Tekstil MühendisliğiCardiovascular diseases are among the most common types of non-infectious diseases, causing approximately 20 million deaths worldwide to date. Deaths caused by cardiovascular diseases, triggered by the increase in the stress level brought about by settling from rural to urban at the global level and the spread of unhealthy eating habits, increased by 21.1% between 2007 and 2017. According to the World Health Organization data, it is estimated that the annual incidence of cardiovascular disease-related mortality will increase to 23.6 million worldwide by 2030. On the other hand, while the Covid-19 pandemic, which affected the entire world, caused an unexpected increase in cardiovascular diseases, the fact that people with these types of diseases were among the ones defined as a high-risk group once again revealed the seriousness of the situation. Mild cardiovascular diseases are treated with dietary modification, lifestyle changes, and medications, while treatment options for more damaged blood vessels usually consist of bypassing a part of the autologous vessel to replace the diseased part. The use of autologous vessels requires an additional clinical procedure such as vascular integration to the damaged area, as well as taking veins from certain parts of the body such as leg vein, forearm artery, and thoracic artery for this procedure. In addition to the aforementioned risks, dimensional incompatibilities may also occur in some cases. For this reason, the necessity of finding alternative solutions in order to overcome these problems experienced in autologous vessels is among the prominent issues in recent years. Although allografts taken from donors or cadavers and xenografts procured from animals are alternatives, they cannot fully meet this need due to the lack of donor/incompatibility and their short lifespan. Replacing the damaged vessel with a vascular graft in the treatment of cardiovascular diseases is one of the preferred methods of recent times, but problems such as infection formation, risk of thrombosis, incompatibility in radial elasticity, inadequacy in cell development, especially in small-caliber vessel changes, limit surgical success. At this point, the search for new materials and constructions has come to the fore, and the design of biodegradable scaffolds that can be replaced by an autograft produced by the body over time has taken its place among the priority research topics. Although important findings have been obtained in the research that has accelerated in the last 10 years, there is no small-caliber biodegradable vascular graft that has achieved commercial success yet. In order to meet the need, it is expected from the vascular graft to provide structural support and encourage cellular activity for the body to produce its vessel. The most important step in approximating vascular grafts designs to native blood vessel structure is to optimize the surface morphology and develop a microenvironment in which cells can attach and proliferate. For this reason, the features of the graft surface should be well understood and morphological criteria should be determined. Within this thesis, a detailed literature review is realized to understand the native artery structure and an experimental study is carried in three parts including the selection of biopolymers, optimization of solution and production parameters, and morphological, structural, thermal, and chemical analyses of the structures. The first experimental part of the thesis is a preliminary study that includes the selection of biomaterials as well as optimization of solution parameters (polymer concentration and blend ratio) and production parameters (feed rate, voltage, and tip-collector distance). A literature review is performed for surfaces produced by electrospinning using low molecular weight polycaproclactone (PCL) and polylactic acid (PLA) polymers as part of this investigation. The affects of parameters like molecular weight, concentration, and blending ratio on surface morphology, smooth fiber production, and fiber diameter parameters are examined during the research work. Electrospinning parameters are systematically studied, and the influences of these parameters on fiber production are determined. Basic parameters such as voltage, feed rate, and tip-collector distance have been optimized in this context by considering the environment's temperature and humidity, as well as the characteristics of the polymer solution. In the first stage, PCL at 16, 18, and 20 % concentrations, PLA at 7, 8, and 9% concentrations and 12% concentration of PLA/PCL (25/75 and 50/50 ratios) are used for surface formation. In this context, a definite conclusion is reached about the polymers to be used in the thesis by evaluating the performances of the determined parameters in the fibrous surface formation process and the morphological properties analyzed by scanning electron microscopy (SEM); furthermore, polymer solution concentration ranges and blending ratio are determined. The results indicate that the spinnability of low molecular weight PCL (45,000 Mn) is insufficient since either bead formation or thick and discontinuous fiber-like forms are observed in all polymer concentrations while neat PLA and PLA/PCL blends have better spinnability, which allows smooth fiber production. In the second part of the thesis, higher molecular weight PCL (80,000 Mn) is introduced to the fibrous webs in order to take the advantage of its better mechanical properties and spinnability. Similar to the preliminary part, PCL, PLA and PCL/PLA blends are studied, but polymer concentration ranges are kept constant as 6, 8, and 10% for all polymeric structures. The morphologies of the electrospun webs are observed by SEM, also fiber diameter and porosity values are measured. Thus, the polymer concentration at which smooth and fine fibers are obtained is determined for neat PLA and PCL in addition to PLA/PCL blends. The hydrophobicity of the surfaces is evaluated by water contact angle analysis (WCA). Differential scanning calorimetry (DSC) is used to observe the thermal behavior of the surfaces during heating and cooling to investigate the crystallinity of the surfaces that provide insights about biodegradability processes. Although it is not possible to obtain fibers at low polymer concentrations on all polymeric surfaces, 8%, and 10% polymer concentration allow continuous fiber formation; moreover, an expected relationship between fiber diameter and porosity ratio is detected. Surfaces with the finest fibers are those with the highest porosity. On the other hand, the thermal behavior of the surfaces is in line with the literature and the highest crystallinity is that of PCL with about 40%. In the last and final part of the thesis, poly (L-lactide) (PLLA), a derivative of PLA, is also introduced in the study, and its effects on surface properties are investigated. Within the scope of developing the most suitable surface for vascular grafts, which is one of the major objectives of the study, different blending ratios for both PLA/PCL and PLLA/PCL are determined in detail. Similar to previous experimental parts, the structures are mainly subjected to SEM, Fourier-transform infrared spectroscopy (FTIR), and DSC analyses, and the effects of blend ratios on morphological, thermal, and chemical properties are investigated in details. It has been observed that the fiber diameter increases with the increase of the ratio of PLA, which has a high molecular weight, in the PCL structure, but the increase in the ratio of PLLA, which has a lower molecular weight than PCL, in the PCL structure causes a decrease in fiber diameter. It has been determined that the polymer ratio is very effective on the fiber diameter depending on the molecular weight of the polymers, and during the thermal analysis, it determines the characteristic curves in the heating and cooling processes. Selected samples of PLA100, PCL100, PLA20PCL80, PLA50PCL50, PLLA20PCL80, and PLLA50PCL50 are subjected to biodegradability analysis at 1st, 3rd, and 5th months. All samples except PLA20PCL80 showed an increase in degradation rate in consecutive months. It is thought that this exception ocuurs in the PLA20PCL80 because of the measurement accuracy. As expected and as seen in the literature research, the degradation rate of PLA (14.29% and 40%, respectively) at the end of the 3rd and 5th months is considerably higher than that of PCL (2.17% and 3.70%, respectively). On the other hand, it is observed that 50% PLA ratio in the blend considerably increases the weight loss of the surface. Moreover, the addition of PLLA on surfaces is also found to accelerate biodegradation, similar to PLA. Cell analysis (MTS) consists of the proliferation of fibroblast and human umbilical vessel endothelial cells (HUVECs), which are one of the basic cells of the native vascular structure. In the content of MTS cellular analysis, affirmative outcomes are obtained in both fibroblast cells and HUVECs compared to control samples, and it is observed that each surface is a suitable environment for cells to live. Besides, PLA appears to have a positive effect on cell viability on PCL up to 20%, and the highest cell proliferation occurred in the PLA20PCL80 sample. The findings of the experimental studies as detailed in the three stages above shed light on the best way to examine the morphological, chemical, thermal, and biological properties of a wide variety of surfaces produced from PLA, PLLA, and PCL polymers. Surfaces designed and fabricated according to the optimized parameters are promising for layered vascular graft structures. In the studies that will take place in the thesis' continuation, small-caliber vessel grafts will be designed and fabricated from these optimized surfaces with desired orientation levels, taking into account the mechanical properties of the vessels and advanced cell activities both in-vitro and in-vivo.
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ÖgeImproving the comfort properties of spacer fabrics for sportswear applications(Graduate School, 2022) Karabulut, Ayşe Berna ; Nergis, Fatma Banu ; 779370 ; Department of Textile EngineeringSportswear is the clothing including footwear, worn during sports or physical exercise and has an increasing demand due to lifestyle changes, increasing both sports organizations and health consciousness of people. The global sports apparel market is estimated to witness a Compound Annual Growth Rate (CAGR) of greater than 7% during the forecast period of 2022 to 2027. Bearing that into mind, it is no surprise to observe that the sports apparel with improved comfort properties have become more popular than ever. As is well known, comfort perception has four different aspects, such as thermo physiological, psychological, sensorial and wear comfort. In general, optimum thermal and moisture regulation, good air and water vapor permeability, rapid moisture absorption wicking and drying property, soft and pleasant touch are the most common characteristics sought in sportswear for satisfactory comfort properties. Enhancing the wearer's comfort is possible by engineering fabric structures by incorporating suitable fibers. For doing so, in this study, bilayered spacer fabric samples were produced with two different materials, on a Mayer & Cie Relanit 28 fine circular interlock knitting machine (30 inches in diameter and 92 feeders). 78/60x1 dtex S and Z twisted Recycle PA66 textured yarn (P) and 78/72 dtex S and Z twisted PA6-Umorfil textured yarn (U) together with 44 dtex Elastane were used for knitting both or one of the sides of the spacer samples. 22/1 dtex PA6 FDY monofilament yarn was employed as the spacer yarn. The samples were tested both in greige and dyed state and were conditioned under the standard atmosphere conditions (20 0C ±2, 65 % ±5%) before testing. Yarn and fabric tests, such as thickness, air permeability, stiffness, contact angle, water vapor permeability, wicking, drying rate, were conducted in accordance with the relevant standards. Comfort properties of fibers can be used in different parts of the garments depending on the intended use and purposes. Making the inner side of fabric as rcy-PA66 and the outer side of fabric as Umorfil gives cost saving production with improved comfort properties.
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ÖgeSynthesis of bleach activators for textile industry(Graduate School, 2021-06-29) Altay, Pelin ; Gürsoy, Nevin Çiğdem ; 503132801 ; Textile EngineeringCotton fiber, is the most widely used natural fiber worldwide, contains undesired natural yellowish-brown coloring matters that hinder absorbency (wetting), reduce the natural whiteness of the fibers. These coloring impurities, which may cause poor dyeing quality, poor finishing performance and end product defects, must be removed by bleaching process to prepare the textile materials for dyeing and finishing. Hydrogen peroxide (H2O2), a universal and environment-friendly bleaching agent, is widely used for cotton and cotton blends. Conventional hot hydrogen peroxide bleaching is conducted under alkaline medium (pH 10.5–12) at high temperatures near boiling (at around 98 °C), leading extensive use of energy and severe chemical damage to textiles. Increasing demands for textile bleaching include reduction in processing costs (energy and water consumption), reduction in environmental impact and improvement in quality. Since energy is one of the main cost factors in textile industry, there has been considerable interest in recent years in ''low temperature'' bleaching. Activated peroxide systems have been investigated as an alternative approach to cotton bleaching at lower temperatures. Although there have been many reports on the use of cationic bleach activators for cotton bleaching, yet it has never reached the commercial success due to either production cost on a large scale, environmental concerns and/ or activity. This study focuses on the development and synthesis of novel, sustainable based on aliphatic acid chloride and more cost-effective cationic bleach activators, with the aim of reduced production cost, improved affinity and bleaching performance, reduced fiber damage for low temperature cotton bleaching to overcome the drawbacks of conventional hot hydrogen peroxide bleaching and other cationic bleach activators based on aromatic acid chloride. Compared to conventional peroxide bleaching, using a bleach activator in a peroxide bleaching bath is an effective and kinetically more potent oxidation generating highly reactive peracid in situ, providing low-temperature bleaching. Activated bleach systems have the potential to produce more efficient kinetically potent bleaching systems through increased oxidation rates with reducing energy cost, saving time and, hence, causing less cellulose polymer chains damage or degradation than conventional hot peroxide bleaching. Cationic bleach activators have been investigated as the next generation bleach activators with inherent substantivity towards cellulosic fibers. In this study, facile synthesis of more sustainable and cost-effective bleach activators (N-[4-(N,N,N)-triethylammoniumchloride- butyryl] caprolactam, TBUCC, and N-[4- (N,N,N)-triethylammoniumchloride- butanoyl] butyrolactam, TBUCB, based on an aliphatic acyl chloride (4- chlorobutyryl chloride), was reported. Fourier transform infrared and high resolution mass spectrometry and 1HNMR confirmed the molecular structure of the synthesized bleach activator. Bleaching performance of newly- synthesized bleached activators was evaluated in terms of whiteness index, water absorbency and fiber damage (degree of polymerization) and compared with conventional peroxide system. Central composite design (CCD) (orthogonal blocks) was used to establish an optimized TBUCB-activated hot peroxide-cotton bleaching system at lower temperature for providing reduced energy cost and maintaining the integrity of cellulose polymer chains. The significance of the process parameters (independent variables) and their interactions were statistically evaluated using Minitab. First principles density functional theory (DFT) calculations were performed to elucidate the reaction mechanism via identifying plausible transition state(s) of the nucleophilic attack of perhydroxyl anion (HOO-) with different carbonyl carbons and identifying the advantages and limitations of TBUCB activator for hydrogen peroxide bleaching for cotton. The synthesis of bleach activators was conducted using a two-step reaction procedure. In the first step, intermediate product was synthesized by condensation reaction of 4- chlorobutyryl chloride with lactam leaving groups (caprolactam and butyrolactam). In the second step, quaternization step was performed to obtain the cationic bleach activators. Experimental results show that, in TBUCC-H2O2 system, the whiteness index (WI) of bleached samples improved when 1:8 and 1:10 molar ratio of TBUCC: H2O2 was used at 60 °C for 30 min. Using 1:8 molar ratio of TBUCC: H2O2 at 36.7 mmol/L activator provided a WI of 70. As the temperature increased from 60 to 70 °C, WI increased to 75.72 and 78.97 at 1:10 and 1:12 molar ratio of TBUCC to H2O2, respectively. The optimum pH was found to be 11.5 for effective bleaching performance. It was concluded that the effective concentration of generated PAA depends on the concentration of H2O2 up to a certain level. Based on the results of the experimental design and statistical analysis, a WI higher than 70 was achieved for TBUCB-activated bleach system at 9.47 g /L (29.7 mmol/L) and higher activator concentrations and at a molar ratio of 1:6-1:10 activator: H2O2. WI higher than 80 can be achieved between 11.7 g/L (36.7 mmol/L) and 13.93 g/L (43.7 mmol/L) of activator concentrations at a temperature of 80 0C. Considering the significance of the process parameters (independent variables) and their interactions, temperature (D) followed by molar ratio of activator: H2O2 (B) and concentration of activator (A), respectively, have the highest statistical relevance on whiteness index. On the other hand, it was revealed that the two-way interaction between the concentration of activator (A) and the molar ratio of activator: H2O2 (B) is greater than the other two-way interactions. When the bleached samples with similar whiteness values were compared (WI= ~ 75) in terms of fiber damage for conventional and activated peroxide bleaching systems, a 19.5% decrease in the average degree of polymerization (DP) was observed in conventional peroxide bleaching, while a decrease of 11.4% and 9.8% was observed in the TBUCC and TBUCB activated peroxide bleach systems, respectively. All these results show that whiteness index greater than 80 for cotton can be achieved by using TBUCC and TBUCB activated peroxide bleaching systems at lower temperature, providing reduced energy cost while maintaining the integrity of cellulose polymer chains. Density functional theory calculations were performed to elucidate the reaction mechanism of the bleach activator with cellulose and rationalize the superior efficiency of the bleach activator while maintaining the integrity of cellulose polymer chains compared to conventional hydrogen peroxide bleaching. DFT calculations elucidated the reaction mechanism, reactivity and peroxide bleaching reaction pathway of the perhydroxyl anion attack at carbonyl group of the butanoyl segment not at the carbonyl carbon of the butyrolactam, which is consistent with the experimental results. Reactions were found to follow two step mechanisms, which are perhydroxyl anion attack at the carbonyl carbon and the peracid formation. Reaction barrier for the perhydroxyl anion attack at the carbonyl carbon was calculated by using sum of electronic and thermal free energies at 70 ̊C under water solvation effect and determined as 12.55 kcal/mol. For perhydroxyl anion attack, TBUCB was found to have a lower reaction barrier and higher solubility than TAED, which was determined as 13.72 kcal/mol. These newly developed and synthesized aliphatic acid chloride-based cationic bleach activators, which are more cost-effective, sustainable and highly reactive compared to other aromatic based cationic bleach activators, enable peroxide bleaching possible at lower temperature (70 0C) compared to conventional hot peroxide bleaching (98 0C). With a sustainable production approach, using these novel cationic bleach activators in hot peroxide bleaching bath provides many advantages such as energy savings, reduced production cost, improved affinity and bleaching efficiency (whiteness index), and less fiber damage. This study provides key fundamental science principles and suggestions at the molecular level of novel and sustainable bleach activators for cotton using a combined experimental and first principles DFT calculations. This study is expected to provide a great contribution to the commercialization of these novel, more sustainable and effective cationic bleach activators for cellulose and cellulosic materials and to the future development of cost-effective industrial bleach activators and sustainable bleaching systems.