In this study, organic-inorganic hybrid materials were prepared from polyurethane and boehmite. It was achieved by polymerizing monomers in the presence of functional nano-particles of boehmite with cyanate groups. The produced polyurethane organic-inorganic hybrid materials with enhanced mechanical properties were used for coating applications. Plate-like boehmite nano-particles were produced by hydrothermal process from aluminum hydroxide which was first ground in a high energy ball-mill, and then, processed hydrothermally under pressure and high temperature in a reactor. The surface morphology and crystal structure of boehmite were investigated by Scanning Electron Microscopy and X-Ray Diffraction analyses, respectively. The molecular structures of boehmite particles were investigated by Fourier Transform infrared spectroscopy. Furthermore, Brunauer-Emmett-Teller analysis and Photon Correlation Spectroscopy analysis were carried out to determine the surface area and the size of particles. Then, plate-like boehmite nano-particles were functionalized by the reaction of their hydroxyl groups with 1,6-hexamethylene diisocyanate and 4,4&rsquo / -methylene diphenyl diisocyanate. Scanning Electron Microscopy, Fourier Transform Infrared Spectroscopy, Differential Thermal Analysis-Thermal Gravimetric Analysis, and elemental analysis were performed for both functionalized and non-functionalized particles to confirm the functionalization of the particles. The polyester polyol used in the production of polyurethane was synthesized from 1,4-butanediol and adipic acid (PE-PO-1), and phthalic anhydride (PE-PO-2). Molecular structure of the polyester polyols was confirmed by Fourier Transform Infrared Spectroscopy analysis and molecular weight of the polymers were determined by end group analysis. Then, the produced functionalized nano-particles and polyester polyols were used for producing polyurethane organic-inorganic hybrid materials. Furthermore, polyurethane polymer and polymer-nonfunctionalized boehmite organic-inorganic hybrids were also synthesized for property comparison. Hardness, impact resistance, scratch resistance, abrasion resistance, and gloss property of the samples were determined. It was observed that mechanical properties of organic-inorganic hybrid materials improved significantly. The hardness of the PU produced with PE-PO-1 increased from 82 to 98 Persoz, and the hardness of the PU produced with PE-PO-2 increased from 52 to 78 Persoz when one weight percentage functionalized boehmite was used. The impact resistance of the coatings was found to depend on the type of the polyols used in PU but not in the inorganic component. Therefore PE-PO-2 used PU has higher impact resistance than PE-PO-1 used PU. Scratch resistance of the coatings improved from 2B to 2H when using functionalized boehmite. Abrasion resistance of PUs produced with PE-PO-1 increased from 2 to 10 l/micrometer and abrasion resistance of PUs produced with PE-PO-2 increased from 12 to 20 l/micrometer by addition of functionalized boehmite.

During last decade, polyurethanes (PUs) which are able to degrade into harmless molecules upon implantation have received a significant level of attention as a biomaterial in tissue engineering applications. Many studies are focused especially on development of PUs based on amino acid derivatives / however, there are only few applications of amino acid based PUs in tissue engineering. In this study, a biocompatible and biodegradable thermoplastic poly(ester-urethane) (PEU) based on L-lysine diisocyanate (LDI) and polycaprolactone diol (PCL) was synthesized and used for the preparation of two dimensional (2D) films and three dimensional (3D) scaffolds. The resulting polymer was casted as 2D films for full characterization purpose and it was found that it is highly elastic with modulus of elasticity ~12 MPa. Surfaces of 2Ds were modified via micropatterning and fibrinogen coating to check the material-cell interaction. The 3D scaffolds were obtained by salt leaching and rapid prototyping (bioplotting) techniques. The 3D scaffolds had various pore size and porosity with different mechanical strength. The bioplotted scaffolds had uniform pore size of ~450 &micro / m and exhibited higher compressive modulus (~4.7 MPa) compared to those obtained by salt leaching (~147 kPa). Salt leached 3D scaffolds had inhomogenous pore size distribution in the range of 5 &micro / m - 350 &micro / m and demonstrated greatest degradation profile compared to 2D films and 3D bioplotted samples under enzymatic condition. Rat bone marrow stem cells (BMSCs) were used to investigate the biocompatibility of the polymer and suitability of fabricated scaffolds for osteogenesis. Presence of micropatterns on 2D matrices did not show any influence on osteoblastic function, but presence of fibrinogen enhanced cell attachment and proliferation. All of the fabricated 3D PEU matrices supported proliferation, osteoblastic differentiation and extracellular matrix (ECM) deposition with highest osteoblastic activity on bioplotted scaffolds which confirmed by von Kossa staining and EDX analysis. The results indicated that the synthesized PEU based scaffolds were able to induce osteoblastic differentiation and mineralization of BMSC and therefore these scaffolds can be good candidates to be used in bone tissue engineering

The desirable properties of polyurethanes (PUs) such as mechanical flexibility associated with chemical versatility make these polymers attractive in the development of biomedical devices. In this study, various segmented polyurethanes were synthesized through polymerization reactions between polycaprolactone (PCL) diol or triol and excess hexamethylene diisocyanate (HDI) with varying NCO/OH ratios and the effect of composition on the properties of the resultant polyurethane films were examined. Initially, isocyanate terminated prepolymers were synthesized through one-shot polymerization, and then these prepolymers were cured by introducing crosslinkages into the structure and thus PUs were obtained. In order to enhance biocompatibility and hydrophilicity of the resulting polymers, heparin was added into the prepolymer before the curing process. The influence of excess HDI as a crosslinker on the degree of H-bond formation between hard-hard segments or hard-soft segments was examined by using Fourier transform infrared-Attenuated total reflectance spectroscopy (FTIR-ATR). Also the effects of HDI content on the chemical, physical and mechanical properties of the polyurethanes were examined with differential scanning calorimetry (DSC), X-Ray diffraction spectroscopy (XRD), dynamic mechanical analyzer (DMA), mechanical tester and goniometer. FTIR- ATR, DSC and DMA analyses showed that use of triol resulted in better network formation and homogenous distribution of hard segments within soft segment matrix. Incorporation of heparin into the polymer matrix produced more hydrophilic films (water contact angle reduced from 80 to 60). Polyurethanes from PCL and HDI in the absence of any solvent, initiator, catalyst or chain extender were successfully synthesized and this kind of synthesis enhanced biocompatibility and increased the potential of polymers for use in biomedical applications.

A series of segmented poly (epsilon-caprolactone) polyurethane-ureas (PCLUUs) were prepared from poly (epsilon-caprolactone) (PCL) diol, different dissociates and chain extenders to improve the recovery stress of shape memory polymers. NMR and FT-IR were used to identify the structure of the synthesized shape memory polyurethane-ureas. Parameters such as soft segment content (molecular weight and content), chain extender and the rigidity of the main chain were investigated to understand the structure-property relationships of the shape memory polymer systems through DSC, DMA, physical property test, etc. Cyclic thermal mechanic tests were applied to measure the shape memory properties which showed that the recovery stress can be improved above 200% simply by modifying the chain extender. Meanwhile, the synthesis process was optimized to be similar to that of Spandex /LYCRA®. Continuous fibers were made from a wet spinning process, which indicated excellent spinnability of the polymer solution. Small angle neutron scattering (SANS) was used to study the morphology of the hard segment at different temperatures and stretch rates and found that the monodisperse rigid cylinder model fit the SANS data quite well. From the cylinder model, the radius of the cylinder increases with the increasing hard segment content. The SANS results revealed phase separation of hard and soft segments into nano scale domains.

Cellulose nanowhisker (CNW) prepared by acid hydrolysis of softwood Kraft pulp was incorporated as nanofiller in rigid polyurethane (PU) foam synthesis. The density, morphology, chemical structure, mechanical properties and thermal behavior of the products were characterized. The nanocomposites exhibited better performance especially at high CNW¡¯s content which was probably due to the high specific strength and aspect ratio of CNW, the hydrogen bonding and crosslinking between CNW and polymer matrix, a higher crosslinking density compared to the control, and the function of CNW as an insulator and mass transfer insulator. Lignin polyol was synthesized through oxypropylation and used for rigid PU foam preparation. The density, morphology, chemical structure, compressive property and thermal behavior of the product were characterized. Lingin-based rigid PU foam showed improved compressive property compared to its commercial counterpart. Ethanol organosolv lignin-based PU showed a slightly stronger compressive property than Kraft lignin-based PU. The enhancement was primarily attributed to the rigid phenolic structure and the high hydroxyl functionality of lignin. Lignin-based PU generated more char than common PUs which was possibly related to the better flame retardant property. This study provided an alternative way to valorize the two most abundant biopolymers and resulted in relatively environmentally benign rigid PU nanocomposite foam.

Zugl.: Paderborn, Univ., Diss. M. Müller, 2009

The goal for this thesis was to apply electrospun biomimetic coatings on implantable glucose biosensors and test their efficacy as mass-transport limiting and tissue engineering membranes, with special focus on achieving reliable and long sensing life-time for biosensors when implanted in the body. The 3D structure of electrospun membranes provides the unique combination of extensively interconnected pores, large pore volumes and mechanical strength, which are anticipated to improving sensor sensitivity. Their structure also mimics the 3D architecture of natural extracellular matrix (ECM), which is exploited to engineer tissue responses to implants. A versatile vertical electrospinning setup was built in our workshop and used to electrospin single polymer - Selectophore™ polyurethane (PU) and two polymer (coaxial) – PU and gelatin (Ge) fibre membranes. Extensive studies involving optimization of electrospinning parameters (namely solvents, polymer solution concentration, applied electric potential, polymer solution feed flow rate, distance between spinneret and collector) were carried out to obtain electrospun membranes having tailorable fibre diameters, pore sizes and thickness. The morphology (scanning electron microscopy (SEM) and optical microscopy), fibre diameter (SEM), porosity (bubble point and gravimetry methods), hydrophilicity (contact angle), solute diffusion (biodialyzer) and uniaxial mechanical properties (tensile tester) were used to characterize certain shortlisted electrospun membranes. Static and dynamic collector configurations for electrospinning fibres directly on sensor surface were optimized of which the dynamic collections system helped achieve snugly fit membranes of uniform thickness on the entire surface of the sensor. The biocompatibility and the in vivo functional efficacy of electrospun membranes off and on glucose biosensors were evaluated in rat subcutaneous implantation model. Linear increase in thickness of electrospun membranes with increasing electrospinning time was observed. Further, the smaller the fibre diameter, smaller was the pore size and higher was the fibre density (predicted), the hydrophilicity and the mechanical strength. Very thin membranes showed zero-order (Fickian diffusion exponent ‘n’ ~ 1) permeability for glucose transport. Increasing membrane thickness lowered ‘n’ value through non-Fickian towards Fickian (‘n’ = 0.5) diffusion. Thin electrospun PU membranes (~10 μm thick) did not affect, while thicknesses between 20 and 140 μm all decreased sensitivity of glucose biosensor by about 20%. PU core - Ge shell coaxial fibre membranes caused decrease in ex vivo sensitivity by up to 40%. The membranes with sub-micron to micron sized pore sizes functioned as mass-transport limiting membranes; but were not permeable to host cells when implanted in the body. However, PU-Ge coaxial fibre membranes, having <2 μm pore sizes, were infiltrated with fibroblasts and deposition of collagen in their pores. Such tissue response prevented the formation of dense fibrous capsule around the implants, which helped improve the in vivo sensor sensitivity. To conclude, this study demonstrated that electrospun membrane having tailorable fibre diameters, porosity and thickness, while having mechanical strength similar to the natural soft tissues can be spun directly on sensor surfaces. The membranes can function as mass-transport limiting membranes, while causing minimal or no effect on sensor sensitivity. With the added bioactive Ge surfaces, evidence from this study indicates that reliable long-term in vivo sensor function can be achieved.

Šiame darbe nuodugniai ištirtos gamybinių polietilentereftalato (PET) atliekų susidarymo vietos, priežastys bei jų savybės. Pasiūlyti skirtingi cheminio perdirbimo būdai ir sąlygos kiekvienai gamybinių PET atliekų rūšiai. Vykdant gamybinių PET atliekų glikolizę etilenglikoliu, pasiekta didesnė negu 85 % bis(2-hidroksietilen)tereftalatо išeiga. Peresterinant gamybines PET atliekas dietilenglikoliu (DEG) ir naudojant funkcinius priedus glicerolį (GL) ir/arba adipo rūgštį (ADR), susintetinta serija aromatinių poliesterpoliolių (APP), besiskiriančių savo klampa ir kitomis savybėmis. Pirmą kartą nuodugniai ištirta ir matematiškai aprašyta peresterinimo reakcijos mišinyje esančių funkcinių priedų įtaka APP klampai. APP, susintetinti peresterinant gamybines PET atliekas DEG ir turintys ADR ir/arba GL fragmentų, yra mažai linkę kristalintis ir stabilūs saugant juos kambario temperatūroje. APP klampa mažai priklauso nuo metaloorganinio katalizatoriaus cheminės sudėties ir jo koncentracijos. Naudojant PET peresterinimo metu gautus APP ir diizocianato perteklių, susintetintos poliuretano-poliizocianurato (PU-PIR) putos. Putos, gautos iš APP, kuriuose yra GL ir/arba ADR fragmentų, pasižymi geromis fizikomechaninėmis savybėmis ir dideliu terminiu stabilumu, joms degant išsiskiria mažesnis šilumos ir dūmų kiekis. Atliekant degumo bandymus nustatyta, kad PU-PIR putos atitinka reikalavimus, taikomus Е klasės statybinėms konstrukcijoms ir elementams. / In this study, the generation points, reasons and properties of industrial PET waste were examined in detail. Different chemical recycling ways were suggested for each kind of industrial PET waste. Under glycolysis of industrial PET waste by ethylene glycol, the yield of the main product bis(2-hidroxyethylene) terephthalate was higher than 85 %. Several series of aromatic polyester polyols (APP) were synthesized by transesterification of industrial PET waste using diethyleneglycol (DEG) in the presence of functional additives glycerol (GL) or/and adipic acid (ADA). The effect of functional additives on transesterification process and viscosity of APP was thoroughly studied and mathematically described for the first time. APP synthesized by transesterification of industrial PET waste using DEG in the presence of ADA and/or GL fragments, had lower crystallinity and were much more stable during storage at room temperature. Viscosity of APP slightly depended on the catalyst type and its concentration. Polyurethane-polyisocyanurate (PU-PIR) foams were produced under the reaction of APP and an excess of diisocyanate. PU-PIR foams based on PET-waste-derived APP containing fragments of GL or/and ADA were characterized by excellent physical-mechanical properties, high thermal stability, low heat release and smoke production. The burning test confirmed that PU-PIR foams satisfied the requirements for class E of construction products and building elements.

In this study, the generation points, reasons and properties of industrial PET waste were examined in detail. Different chemical recycling ways were suggested for each kind of industrial PET waste. Under glycolysis of industrial PET waste by ethylene glycol, the yield of the main product bis(2-hidroxyethylene) terephthalate was higher than 85 %. Several series of aromatic polyester polyols (APP) were synthesized by transesterification of industrial PET waste using diethyleneglycol (DEG) in the presence of functional additives glycerol (GL) or/and adipic acid (ADA). The effect of functional additives on transesterification process and viscosity of APP was thoroughly studied and mathematically described for the first time. APP synthesized by transesterification of industrial PET waste using DEG in the presence of ADA and/or GL fragments, had lower crystallinity and were much more stable during storage at room temperature. Viscosity of APP slightly depended on the catalyst type and its concentration. Polyurethane-polyisocyanurate (PU-PIR) foams were produced under the reaction of APP and an excess of diisocyanate. PU-PIR foams based on PET-waste-derived APP containing fragments of GL or/and ADA were characterized by excellent physical-mechanical properties, high thermal stability, low heat release and smoke production. The burning test confirmed that PU-PIR foams satisfied the requirements for class E of construction products and building elements. / Šiame darbe nuodugniai ištirtos gamybinių polietilentereftalato (PET) atliekų susidarymo vietos, priežastys bei jų savybės. Pasiūlyti skirtingi cheminio perdirbimo būdai ir sąlygos kiekvienai gamybinių PET atliekų rūšiai. Vykdant gamybinių PET atliekų glikolizę etilenglikoliu, pasiekta didesnė negu 85 % bis(2-hidroksietilen)tereftalatо išeiga. Peresterinant gamybines PET atliekas dietilenglikoliu (DEG) ir naudojant funkcinius priedus glicerolį (GL) ir/arba adipo rūgštį (ADR), susintetinta serija aromatinių poliesterpoliolių (APP), besiskiriančių savo klampa ir kitomis savybėmis. Pirmą kartą nuodugniai ištirta ir matematiškai aprašyta peresterinimo reakcijos mišinyje esančių funkcinių priedų įtaka APP klampai. APP, susintetinti peresterinant gamybines PET atliekas DEG ir turintys ADR ir/arba GL fragmentų, yra mažai linkę kristalintis ir stabilūs saugant juos kambario temperatūroje. APP klampa mažai priklauso nuo metaloorganinio katalizatoriaus cheminės sudėties ir jo koncentracijos. Naudojant PET peresterinimo metu gautus APP ir diizocianato perteklių, susintetintos poliuretano-poliizocianurato (PU-PIR) putos. Putos, gautos iš APP, kuriuose yra GL ir/arba ADR fragmentų, pasižymi geromis fizikomechaninėmis savybėmis ir dideliu terminiu stabilumu, joms degant išsiskiria mažesnis šilumos ir dūmų kiekis. Atliekant degumo bandymus nustatyta, kad PU-PIR putos atitinka reikalavimus, taikomus Е klasės statybinėms konstrukcijoms ir elementams.

Shape memory polymers (SMPs) are a relatively new class of active materials that can store a temporary shape and return to the original configuration upon application of a stimulus such as temperature. This shape changing ability has led to increased interest in their use for biomedical and aerospace applications. A major challenge, however, in the advancement of these applications is the ability to accurately predict the material behavior for complex geometries and boundary conditions. This work addresses this challenge by developing an experimentally calibrated and validated constitutive model that is implemented as a user material subroutine in Abaqus ? a commercially available finite element software package. The model is formulated in terms of finite deformations and assumes the SMP behaves as a thermoelastic material, for which the response is modeled using a compressible neo-Hookean constitutive equation. An internal state variable, the glassy volume fraction, is introduced to account for the phase transformation and associated stored deformation upon cooling from the rubbery phase to the glassy phase and subsequently recovered upon heating. The numerical implementation is performed such that a system of equations is solved using a Newton-Raphson method to find the updated stress in the material. The conductive heat transfer is incorporated through solving Fourier's law simultaneously with the constitutive equations. To calibrate and validate the model parameters, thermomechanical experiments are performed on an amorphous, thermosetting polyurethane shape memory polymer. Strains of 10-25% are applied and both free recovery (zero load) and constrained displacement recovery boundary conditions are considered for each value of applied strain. Using the uniaxial experimental data, the model is then calibrated and compared to the 1-D experimental results. The validated finite element analysis tool is then used to model biomedical devices, including cardiovascular tubes and thrombectomy devices, fabricated from shape memory polymers. The effects of heat transfer and complex thermal boundary conditions are evaluated using coupled thermal-displacement analysis, for which the thermal material properties were experimentally calibrated.