Poly(glycerol sebacate) Thermal Properties Quiz
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Questions and Answers

What does the broad sigmoidal transition between -30 and -10 °C in the DSC curve for PGS indicate?

  • The glass transition temperature of the amorphous PGS polymer. (correct)
  • The degradation temperature of the PGS polymer.
  • The crystallization temperature of the PGS polymer.
  • The melting point of the PGS polymer.
  • According to the DSC results, what is the glass transition temperature (Tg) of the Poly(glycerol sebacate) (PGS) polymer?

  • -30°C
  • 5°C
  • -10°C
  • -23°C (correct)
  • What thermal behavior is evident from the mention of an exothermic peak at -20°C during cooling and an endothermic peak between -10 and 10°C during heating?

  • PGS has no phase transitions below 10°C.
  • PGS is a purely amorphous material at room temperature.
  • PGS is a semicrystalline polymer at room temperature. (correct)
  • PGS is a purely crystalline material at room temperature.
  • What does the melting temperature (Tm) of 5°C for PGS relate to?

    <p>The temperature at which the crystalline regions of the polymer melt. (B)</p> Signup and view all the answers

    What is the primary method used in the text to quantify the degradation of the PGS material?

    <p>Measuring the mass loss in 12PBS. (D)</p> Signup and view all the answers

    According to the lecture plan, which topic is covered on November 19th, 2024?

    <p>Biomedical hydrogels (C)</p> Signup and view all the answers

    Which of the following materials is classified as a non-degradable polymer according to the provided information?

    <p>Polyethers (C)</p> Signup and view all the answers

    Which of the following is NOT a non-degradable polymer?

    <p>Poly(esters) (C)</p> Signup and view all the answers

    Which of the following polymers are discussed in the lecture on November 5th?

    <p>Both resorbable and permanent polymers (A)</p> Signup and view all the answers

    What is the topic being covered on December 3rd, 2024?

    <p>Protein adsorption on surfaces (C)</p> Signup and view all the answers

    Which type of polymer is NOT mentioned in the context of hydrolytic degradation rates?

    <p>Polysaccharides (B)</p> Signup and view all the answers

    Which property is NOT explicitly mentioned as being of relevance for biomedical applications in the context of polymer materials?

    <p>Mechanical properties (B)</p> Signup and view all the answers

    Who is the lecturer for the topic 'Immune response to biomaterials'?

    <p>Trujillo (B)</p> Signup and view all the answers

    Which of the following forces are polyurethanes (PUs) known to resist?

    <p>Tension forces (B)</p> Signup and view all the answers

    What is a significant property of polyurethanes (PUs) that makes them suitable for certain applications?

    <p>Transparency (D)</p> Signup and view all the answers

    What is the primary focus of the lecture on October 22nd, 2024?

    <p>Physicochemical properties of polymer materials (C)</p> Signup and view all the answers

    According to the lecture plan, when are the student presentations?

    <p>February 4th, 11th and 18th, 2025 (A)</p> Signup and view all the answers

    Which property allows polyurethanes to be used in applications where friction reduction is needed?

    <p>Lubricity (C)</p> Signup and view all the answers

    What aspect of polyurethanes (PUs) can be specifically adjusted by modifying their composition?

    <p>Degradability (C)</p> Signup and view all the answers

    Which chemical linkage is formed when isocyanates react with hydroxyl-functional molecules in polyurethane synthesis?

    <p>Urethane linkage (C)</p> Signup and view all the answers

    What is a key characteristic of aliphatic polyesters used in biomedical applications?

    <p>Tunable physicochemical properties via monomer composition. (B)</p> Signup and view all the answers

    In the synthesis of thermoplastic polyester-urethane-ureas (TPEUU), what type of molecules react with isocyanates to form urea linkages?

    <p>Amines (B)</p> Signup and view all the answers

    Which statement accurately reflects the general properties of aliphatic polyesters?

    <p>They are generally thermoplastic and easily processed as melts. (A)</p> Signup and view all the answers

    What significant issue led to the retraction of some polyurethane applications from the market in the 1980s?

    <p>Failures in long-term implants (D)</p> Signup and view all the answers

    What are the typical monomers used in the synthesis of Poly(glycerol sebacate) (PGS)?

    <p>Glycerol and sebacic acid (D)</p> Signup and view all the answers

    Which of the following is NOT a typical processing method for polyurethanes?

    <p>Sintering (B)</p> Signup and view all the answers

    What is the typical range for the Young's Modulus of PGS?

    <p>0.01 - 1.5 MPa (A)</p> Signup and view all the answers

    What is the typical degradation time frame for PGS in biomedical applications?

    <p>Months to 2 years (A)</p> Signup and view all the answers

    What is the ultimate tensile strength range of PGS?

    <p>0.4 - 0.7 MPa (C)</p> Signup and view all the answers

    What type of polymer is PGS characterized as?

    <p>An elastomer (A)</p> Signup and view all the answers

    What are the two main steps involved in the synthesis of PGS?

    <p>Polycondensation and crosslinking (C)</p> Signup and view all the answers

    What atmospheric condition is typically used for the prepolymerization step of PGS synthesis?

    <p>Nitrogen atmosphere (B)</p> Signup and view all the answers

    What environment is preferred for the crosslinking step of PGS synthesis?

    <p>Vacuum environment (D)</p> Signup and view all the answers

    What structural feature is primarily responsible for the phase segregation observed in thermoplastic polyurethanes (TPUs)?

    <p>Hydrogen bonding between urethane groups. (B)</p> Signup and view all the answers

    Which of the following best describes the behavior of the soft segments at typical application temperatures?

    <p>They exhibit rubbery and amorphous characteristics. (D)</p> Signup and view all the answers

    What is the main function of the ordered hard domains in thermoplastic polyurethanes?

    <p>To act as physical cross-links providing elastomeric behavior. (C)</p> Signup and view all the answers

    Which process disrupts the physical cross-links in TPUs to enable polymer processing?

    <p>Heating the material above the hard segment melting transition. (D)</p> Signup and view all the answers

    In the synthesis of TPUs, what is the role of the diisocyanate?

    <p>It reacts with a polyol to form NCO-terminated prepolymers. (B)</p> Signup and view all the answers

    What is the primary structural difference between thermoplastic polyurethanes (TPUs) and thermoset polyurethanes?

    <p>TPUs have a linear and uncrosslinked structure, while thermosets have a chemically crosslinked 3D network. (B)</p> Signup and view all the answers

    What is a key process step in producing thermoplastic polyurethanes (TPUs)?

    <p>Creating a prepolymer with –NCO ending chains using excess diisocyanate. (B)</p> Signup and view all the answers

    Which statement accurately describes the reprocessability of thermoplastic and thermoset polyurethanes?

    <p>TPUs can be thermo-reprocessed, while thermosets cannot. (D)</p> Signup and view all the answers

    What is a chain extender, as described in the context of thermoplastic polyurethane synthesis?

    <p>A short diol, such as 1,4 butanediol (BDO), used to link prepolymers. (C)</p> Signup and view all the answers

    What characterizes the 'hard segment' in thermoplastic polyurethanes (TPUs)?

    <p>It is derived from rigid diisocyanates and chain extenders. (B)</p> Signup and view all the answers

    Which of these is true about thermoset polyurethanes?

    <p>They are prepared by mixing polyols and polyisocyanates with at least one monomer with functionality &gt; 4. (A)</p> Signup and view all the answers

    What is the main reason that thermoset polyurethanes cannot be thermo-reprocessed?

    <p>They have a chemically crosslinked 3D network structure. (A)</p> Signup and view all the answers

    In TPU synthesis, what is the purpose of the prepolymer intermediate?

    <p>To have –NCO ending chains, which then react further. (C)</p> Signup and view all the answers

    Flashcards

    Resorbable Polymers

    Polymers that break down over time in the body, often used for temporary implants or drug delivery.

    Permanent Polymers

    Polymers that remain stable in the body for extended periods, suitable for long-term medical devices.

    Hydrolytic Degradation

    A breakdown mechanism where water molecules break down the polymer chain through chemical reactions, leading to smaller fragments.

    Hydrolytically Degradable Polymers

    Polymers that undergo a chemical reaction with water molecules, leading to their gradual breakdown in the body.

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    Non-degradable Polymers

    Polymers that resist degradation in the body, preserving their original structure over time.

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    Synthetic Polymers

    Polymers derived from petroleum and other natural sources, often used for various applications.

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    Degradation Rate

    The rate at which a polymer breaks down in the body, influenced by its chemical composition.

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    Polymer Backbone

    The backbone of a polymer is the central chain of repeating units that forms the basis of its structure.

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    Chemistry of Backbone

    The chemical structure of the repeating units that make up a polymer, determining its properties and degradation rate.

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    Degradation of Polymers

    The process of breaking down a polymer into smaller fragments, typically through chemical reactions.

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    Degradation

    A material's resistance to breaking down or decomposing over time, often measured by mass loss.

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    Poly(glycerol sebacate) (PGS)

    A polymer made from glycerol and sebacic acid. Known for its flexibility and biocompatibility.

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    Glass transition temperature (Tg)

    The temperature at which a material transitions from a rigid, glassy state to a more flexible, rubbery state.

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    Differential Scanning Calorimetry (DSC)

    A technique used to measure the thermal properties of materials, showing how they behave when heated or cooled.

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    Semicrystalline polymer

    A material that exhibits both crystalline and amorphous regions, meaning it has ordered and disordered structures.

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    Hard Segment in TPU

    A region within a thermoplastic polyurethane (TPU) where polymer chains are tightly packed due to hydrogen bonding between urethane and urea groups. These domains act as physical cross-links that resist deformation under stress.

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    Soft Segment in TPU

    Regions in a thermoplastic polyurethane (TPU) that are primarily made up of flexible chains, often with lower glass transition temperatures (Tg). They provide elasticity and flexibility to the material.

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    Hydrogen Bonding in TPUs

    These are interactions between molecules where a hydrogen atom is shared between two electronegative atoms, such as oxygen or nitrogen. In TPUs, this occurs between urethane and urea groups, creating strong intermolecular forces that lead to the formation of hard segments.

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    Processing of TPUs

    A process that involves heating a thermoplastic polyurethane (TPU) above its hard segment melting transition temperature. This breaks the physical cross-links in the hard segments, making the polymer more fluid and allowing it to be processed (e.g., molded or extruded).

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    Segment Ratio and TPU Properties

    The relative amounts of hard and soft segments in a thermoplastic polyurethane (TPU) directly influence its mechanical properties. A higher proportion of hard segments results in a stiffer and stronger material, while a higher proportion of soft segments provides greater elasticity and flexibility.

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    Tension Resistance

    The ability of a material to resist stretching or elongation under tensile forces. It is a measure of how much force is required to deform the material.

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    Compression Resistance

    The ability of a material to resist compression forces, or being squeezed or pushed together. It's how much force is needed to change its volume.

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    Fatigue Resistance

    The ability of a material to withstand repeated cycles of loading and unloading without breaking. It's how many times it can be stressed before it fails.

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    Circumferential Stress Resistance

    The strength of a material in resisting forces acting perpendicular to a surface. Imagine a rope tied around a post, pulling on it.

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    Shear Stress Resistance

    The ability of a material to resist forces that tend to cause it to slide or deform in parallel directions. It's how much force it takes to make the material slip.

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    Friction and Wear Resistance

    The ability of a material to resist wear and tear from rubbing or sliding against another surface. Think of the friction between your shoes and the floor.

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    Transparency

    The ability of a material to allow light to pass through it. Think of a window letting sunlight in.

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    Lubricity

    The ability of a material to reduce friction between moving surfaces. Think of oil in an engine, preventing parts from rubbing together.

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    What is PGS?

    Poly(glycerol sebacate) is a biodegradable, biocompatible, and resorbable polyester used in various biomedical applications.

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    How is PGS synthesized?

    PGS is synthesized through a two-step process involving polycondensation followed by crosslinking.

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    What monomers are used to synthesize PGS?

    Glycerol and sebacic acid are the monomers used in the synthesis of PGS. These monomers are derived from plant sources.

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    What is the first step in PGS synthesis?

    Polycondensation is the first step in PGS synthesis. It involves the reaction of glycerol and sebacic acid to form a prepolymer.

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    What is the second step in PGS synthesis?

    Crosslinking is the second step in PGS synthesis. It involves the formation of a 3D network structure by the reaction of prepolymer chains.

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    Why is crosslinking done in vacuum?

    The crosslinking step is performed in vacuum to remove water molecules and promote the formation of a strong network structure.

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    What is the DE in PGS synthesis?

    The degree of esterification (DE) is a measure of the extent of the reaction between glycerol and sebacic acid during PGS synthesis.

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    How does the DE change during PGS synthesis?

    DE increases during the polycondensation step and reaches a plateau during the crosslinking step.

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    How does temperature affect the DE and PGS properties?

    The temperature and time of the polycondensation step influence the DE and the properties of the final PGS material.

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    How does PGS degrade?

    PGS is a biodegradable polymer that degrades in the body through hydrolysis, breaking down into monomers that are then absorbed and metabolized.

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    What are the two main types of polyurethanes?

    Polyurethanes (PUs) are materials that can be classified into two main categories: thermosets and thermoplastics. They are typically formed through the reaction of polyols and polyisocyanates.

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    What makes thermoplastic PUs unique?

    Thermoplastic PUs (TPUs) are linear, uncrosslinked structures that can be melted and reshaped without degrading. They are usually made by a two-step process involving prepolymer synthesis and chain extension.

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    What distinguishes thermoset PUs?

    Thermoset PUs are characterized by their 3D crosslinked network structure. This makes them strong and rigid, but also unable to be melted or reshaped.

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    Describe the prepolymer synthesis step in TPU production.

    Prepolymer synthesis involves reacting a polydiol with an excess of diisocyanate, resulting in a molecule with –NCO groups at its ends. This prepolymer is then further extended with a chain extender.

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    What happens in the chain extension step of TPU production?

    The final stage of TPU production involves adding a chain extender, such as 1,4 Butanediol (BDO), to the prepolymer. This creates longer, linear chains, contributing to the TPU's flexibility.

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    How are thermoset PUs typically prepared?

    Thermoset PUs are typically produced by mixing polyols and polyisocyanates in a single step, leading to the formation of a 3D crosslinked network. This process often includes the use of surfactants and blowing agents for foam formation.

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    What is the purpose of the hard segment in TPUs?

    The hard segment in TPUs is typically composed of a rigid diisocyanate and a chain extender. This segment contributes to the material's stiffness and strength.

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    What is the role of the soft segment in TPUs?

    The soft segment of TPUs is mainly composed of a flexible and long diol. This segment contributes to the material's flexibility and elasticity.

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    Study Notes

    Lecture Plan

    • Dates and topics for various lectures on biomedical materials
    • Speakers assigned to specific lecture topics
    • Topics include fundamentals of biomedical materials, selection criteria for biomaterials used in medical devices, physicochemical properties of polymer materials, synthetic biomedical polymers (resorbable and permanent), biomedical hydrogels, additive manufacturing of biomedical polymers, protein adsorption on surfaces and more.
    • Dates for presentations by students also included

    Biomedical Polymers

    • Lecture 4: Synthetic, resorbable biomedical polymers (II)
    • Lecture 4: Synthetic, permanent biomedical polymers (I)

    Hydrolytic Degradation Rates

    • Chart depicting hydrolytic degradation rates of biomedical polymers based on the chemistry of the polymer backbone.
    • Time scales for degradation are shown (days, weeks, months, years)
    • Examples of degradable and non-degradable polymers are listed
    • Data included for the degradation rate coefficient in s⁻¹

    Outline

    • Outline of topics covered in the lecture series
    • Specific topics for each session (e.g., other resorbable polymers, permanent biomedical polymers).

    General Properties of Aliphatic Polyesters

    • Summary of properties of aliphatic polyesters for biomedical applications
    • Hydrophobic character mentioned
    • Tunable physicochemical properties, including the ability to adjust mechanical properties (through monomer composition, copolymerization, and blending).
    • Easy processability as melts, allowing sterilization
    • Low price

    Degradable Aliphatic Polyesters

    • List of degradable aliphatic polyesters including: Polyglycolide (PGA), Polylactide (PLA), Polyhydroxybutyrate (PHB), Poly(lactide-co-glycolide) (PLGA), Poly(hydroxyvalerate-co-hydroxybutyrate) (PHBV), Polycaprolactone (PCL).Poly(propylene fumarate) (PPF), Poly(glycerol sebacate) (PGS) and Poly(glycerol sebacate) (PGS).
    • Chart to show the approximate time for degradation and rate of degradation coefficient.

    Poly(glycerol sebacate) (PGS)

    • Monomer information (glycerol and sebacic acid)
    • Synthesis method (polycondensation and cross-linking)
    • Glass Transition Temperature (Tg): 23°C
    • Melting Temperature (Tm): 5°C
    • Degradation time: months to 2 years
    • Mechanical properties such as Young's modulus and elongation at break.
    • Categorization as an elastomer
    • Two synthesis steps shown

    Synthesis of PGS

    • Details of two-step synthesis: pre-polymerization using high temperature, pressure and microwave radiation and cross-linking through chemical agents..

    PGS Properties

    • Physical status (wax, viscous liquid, sticky elastomer, elastomer) depends on Degree of Esterification (DE) and temperature.

    PGS Mechanical Properties

    • Stress-strain curves of PGS specimens prepared at different temperatures & thermal treatments

    Properties of PGS

    • Degradation of PGS samples as a function of DE at 130°C over various time periods

    Poly(glycerol sebacate) (PGS) Thermal Properties

    • DSC curve for dry PGS and composites with Bioglass
    • Glass Transition Temperature (Tg): -23°C
    • Melting Temperature (Tm): 5°C
    • Crystallization Temperature (Tc): -18°C

    Derivatization of Poly(glycerol sebacate)

    • Discussion of derivatization of Poly(glycerol sebacate) (PGS) to polyurethane (PGSU) using Hydralese™ (Secant Group) for drug delivery applications (ocular implants).

    PGSU fibers

    • Applications of PGSU fibers in orthopedic medical textiles facilitating tissue ingrowth, and biological benefits for various loads

    Compilations of Relevant Polyester-Based Biomaterials

    • Table with numerous polymers, types, mechanical and degradation properties.
    • Properties of a number of biomaterials (e.g., Polylactic acid (PLA), poly(lactic-co-glycolic acid) (PLGA), Poly(L-lactic acid) (PLLA), poly(ɛ-caprolactone) (PCL) discussed
    • Data and specifics

    Exercise 1

    • Exercises on the functional requirements for composite dental crowns, silicone contact lenses, wound dressings, and cardiovascular stents
    • Include relevant factors regarding function, material characteristics

    Exercise 1

    • Types of stresses: tension, compression, fatigue, cyclical, circumferential, torque, shear, friction
    • Determining which tissues are affected by these mechanical stresses

    Exercise 1

    • Example of a medical device with specific functional requirements: resistance to tension, compression, cyclic stress, shear stress, friction and more

    Poly(urethanes)

    • Historical overview of polyurethane development including applications in coatings, cardiovascular devices, and breast implants

    Poly(urethanes) (PUs)

    • General Properties: tough, biocompatible, hemocompatible, processable by various methods (like extrusion), adjustable properties, and expensive

    Thermoplastic Polyester-Urethanes (TPEUs) and Thermoplastic Polyester-Urethane-Ureas (TPEUUs)

    • Synthesis details (polyaddition of macrodiols, diisocyanates, and chain extenders)
    • Urethane and urea linkage formation

    Classes of PUs

    • Classification into thermoplastic and thermosetting.

    Thermoplastic PUs

    • Detailed description of synthesis (pre-polymerization and chain extension)
    • Explanation of micro-segregation, hard and soft segments, the effect on properties and processability

    Thermoplastic PUs

    • Explanation of the properties of soft and hard segments, glass transition temperatures, and mechanical behavior

    Synthesis of TPUs

    • Detailed steps in the synthesis involved in the preparation of pre-polymers and chain extenders to form the material.

    Exercise synthesis PUs

    • Exercise questions on tuning mechanical properties and degradation rates of TPUs

    Polyisocyanate Intermediates

    • List and chemical structure of several types of isocyanates useful in synthesizing biodegradable PUR biomaterials.

    Polyol Intermediates

    • Chemical names and structures of common polyol intermediates (e.g., PEO, PPO, PCL, polylactide, glycolide).

    Mechanical Properties of Biomaterials

    • Data displaying mechanical properties in graphs of some relevant biomaterials (e.g., PLA, PGS, PHA, PU)

    PU foams (PUFs)

    • Synthesis of PUFs using polyisocyanates, polyols, water and blowing agents

    PU foams

    • Properties of flexible and rigid PUFs
    • Microscopic images displaying open and closed cellular structures.

    Effect of Composition on PU Foams

    • Factors affecting the properties of PU foams (such as type of polyol/polyisocyanates, cross-linker, water content, additives)

    Medical Polyurethanes

    • Overview of a broad and versatile medical polyurethane portfolio, including biostability, durability, customizability, performance, and combination with other materials.

    Bionate

    • Description of aromatic polycarbonate-based thermoplastic polyurethane for load-bearing and articulating implants.
    • Excellent oxidative and ablation resistance

    Biomerix

    • Unique scaffold with open-cell, porous structure made from aromatic polycarbonate-based thermoset polyurethane (PCPU)
    • High void content.

    Elasthane

    • Durable and abrasion-resistant aromatic polyether-based thermoplastic polyurethane (TPU)
    • Ideal use for chronic implants and insulating sheathing in pacing leads (CRM)

    Biospan (SPU)

    • Segmented polyether polyurethane delivered in dimethylacetamide solution.
    • Enhanced flexibility and durability. Applications include cardiovascular implants, artificial hearts, and balloon catheters.

    PurSil (TSPU)

    • Combining the best properties of silicone and aromatic polyether-based TPU with high flexibility and oxidative stability.
    • Applications in ophthalmic and continuous glucose monitoring.

    New Class of PUs: Thermosetting PU Vitrimers

    • Introduction of new method employing dynamic covalent bonds for processability in PU vitrimers with limited properties loss..

    Degradability of PUs

    • Degradation mechanisms dependent on factors such as diol/isocyanate type, and rigid/soft segments.
    • Categorization as polyester- or polyether-based urethane, degradation rates and environmental consideration.

    Degradability of PUs

    • Various possible degradation mechanisms in PUs (hydrolysis, oxidation and enzymatic degradation)
    • Detailing various environmental issues and concerns.

    PU Biomedical Devices

    • Hollow-fiber membranes used in dialysis, oxygenators

    PU based hollow fiber membranes

    • Description of the synthesis procedure.

    PU-based biomedical devices (Degradable)

    • NovoSorb is a biodegradable, matrix, indicated for burns, and partial thickness wounds

    PU-based biomedical devices (Degradable)

    • Details on the structure and properties of NovoSorb, a bioabsorbable material for wound healing applications

    PU-based biomedical devices (Degradable)

    • Description of Nasopore, its application for nasal dressings, functions (to absorb drainage, reduce adhesions), and its handling aspects.

    PU-based biomedical devices (Degradable)

    • Detailed description and use of OtoPore, bioabsorbable polyurethane dressing

    PU-based biomedical devices (permanent)

    • Overview and details of the polyurethane ureteral catheter, BD product- including its function, flexibility, color-coding, sterilization..

    Permanent polymeric biomaterials

    • Summary of various permanent polymers like polyolefins, halogenated biomaterials (e.g., PVC, PTFE), poly(ethers), poly(acrylates)(e.g.PET), and polyamides

    Polyolefins (Poly(ethylene), Poly(propylene))

    • General properties: hydrophobic, chemically inert, oil/fat resistant, superior mechanical properties, low friction coefficient, and wear resistance

    Poly(ethylene)

    • Properties of the material, including different types of densities and their applications(packaging and implants).

    Poly(ethylene)

    • Stress-strain curve including regions (regions of initiation, cold drawing, hardening, and fracture)
    • Comparison of LDPE and UHMWPE mechanical properties in terms of various tensile strength

    Poly(ethylene)

    • Detailed look at synthesis of LDPE via free radicals and LLDPE/HDPE via coordination polymerization.

    Porous PE for Craniomaxillofacial Surgery

    • Description of MEDPOR's use and characteristics for reconstruction and augmentation in craniomaxillofacial surgeries.

    UHMWPE for Joint Prostheses

    • Application of UHMWPE for total hip and knee replacements.
    • Structure and components of UHMWPE articulating and lining prostheses.

    Studying That Suits You

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    Description

    Test your knowledge on the thermal properties and characteristics of Poly(glycerol sebacate) (PGS) based on various questions related to Differential Scanning Calorimetry (DSC) results. The quiz covers topics such as glass transition temperature, melting temperature, and degradation methods. Perfect for students studying polymer science or materials engineering.

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