ABS (Polymer)
= Acrylonitril Butadiene Styrene
strong physical bonds: hetero atoms -> Nitrogen
strain hardeing via stretching of polymers -> long chains
Heterogeneity
long elongation at break: due to relativ movement of polymer chains in respect to each other
Toughening Mechanisms
strong physical bonds
internal crystal structure
heterogenity
strain hardening
Thermoplasts
linear / branched macromolecules
Semicrystalline: soft -> hard, tough (plastic flow), opaque due to scattering at inner interface
Solvent: swellable, soluble at higher T°C
Amorphous: hard & brittle, transparent
Solvent: easily soluble after previous svelling (in certain organics)
Heat: softening, become clear, weldable
Thermosets
tightly crosslined macromolecules
hard & brittle
transparent when not filled
Heat: remain hard, maintain shape until T°C of decomposition
Solvent: insoluble, almost no swelling
Elastomers
(mostly) loosely crosslinked
soft & flexible
Heat: flexible -> no plastic flow until T°C of decomposition
Solvent: insoluble -> swellable due to loose network
Chain growth polymersiation
Addition to monomer to growing chain with reactive terminus = growth at end of chain
Decrease of monomer concentration with increasing reaction time
Increase of Molar mass doesnt change with reaction procedure
after termination = chains arent active
Initiator required
Step growth Polymerisation
Reaction can occur between any pair of molecular species = growth troughout the matrix
rapid loss of monomers in favor of low oligomers
Takes a long time to get long chain
living polymer = end remain active
no initiator required
Diffusion Coefficient
Change of: dc sinkt
molar mass
cross link density
stiffness
molecule interactions
crystalinity
Change of: dc steigt
Plasticizer content
Filler content
Drug delivery system
= Device that enables introduction of therapeutic substance into body -> controlls rate, time & place of release
Concept: controlled release
Result: equal level in plasma & tissue over defined period
Drug delivery system - Membrane / Diffusion Controlled
transdermal therapeutic system
reactive agent in reservoir surrounded by polymer membrane
release by diffusion through rate controlling membrane (
Drug delivery system - Osmotic Controlled
strong water permeable membrane
flexible membrean (impermeable for water & drug)
due to contact to body fluid = water diffusion trough strong membrane
due to higher salt concentration in device
pressure increase in reservoir = drug release
Drug delivery system - Chemically Controlled
Carrier system
Backbones with pendant drug - degradable system
main chain bound active agents
side chain bound active agents
Sterilisation Method
1)Hot:
steam
dry heat
2)Cold:
gas: EO / Formaldehyd
gasplasma
chemical: more like desinfection
irradiation: e-beam, gamma radiation
Filtration: Retention of microorgs in membrane surface -> liquids & gas
Gas plasma sterilisation
Plasma = 4. state of matter, created when gas is heated / exposed to strong electromagnetic field
at low T°C: 37-60 °C
hydrogen peroxid vapors generates free radicals that interact with molecules
Vorteil:
for heat & moist sensitive devices
no toxic residues
shoert aberation time
Nachteil:
free radicals = influence on molecular structure of polymer
Titanium + Alloys
low weight
high strength + stiffness
biocompatability (TiO2 coating on surface)
pure Ti = hexagonal crystal structure = low ductility
sentitive to oxygen, hydrogen, nitrogen = difficult to process
= CP-Ti instead of Ti-6Al-4V:
Biocompatability (minimal alloying elements = lower risk of toxicity)
nearly 100% pure: softer & more ductile
Corrosion resistance
How to obtain high strength in ceramics
small grain size: nano scale powders
incoorporation of crack stoppers: fibers
low porosity: by high sintering temperature
transformation strengthening / toughening
Biodegradation
cleavage of covalent bonds (chemical)
by macrophages (natural)
Degradation Mechanisms (Polymers)
Polymer dissolution: cleavage of covalent bonds - thermal / mechnical processes - destruction of entire backbone
Hydrolysis: due to hydrolytic instable bond (amide, ester), reversed polycondensation
Enzymatic degradation: at specific groups identified by enzymes - hydrolytic, oxidative, chain scission
Dissociation of PPC: via salvation of macromolecular components - until: gain of free energy > than energy of intermolecular cooperative interaction between 2 polymers
Wound healing phases
1) Haemostasis (Clotting):
vasoconstriction
platelet aggregation + fibrin formation
2) Inflammation (Phagocytosis):
Differentiation of macrophages: Infiltration of: lymphozytes, neutrophiles, Monocytes
3) Proliferation (Wound closure):
Angiogensis
Collagen synthesis
Re-epithelialisation
4) Remodelling (development of tensile strength):
collagen modelling + vascular maturation
Wound dressing
give protection
assist in healing
restore skin integrity
Alignate
haemostatic properties - release of calcium ions
debridment of slough
highly absorbant (20x own weigth)
Hydrocolloids
moist wound healing
occlusive & waterproof
low to medium exudate wounds
for non infected wounds
Foam
highly absorbant
non adherent/adherent wound contact layer - hydrocellular foam - waterproof outer layer (silicone, polyurethane)
??
Hydrogel
high water content: 96%
can absorb a lot without dissolving
good compatability with skin
can be loaded with therapeutics
needs secondary protective layer
help in debridment
Dressings
antimicrobial agents
Iodosorb, Aquacel AG
Sutures
Needles + Threads
FBR: Foreign Body Reaction
1) Blood Biomaterial Interaction:
Proteins (from blood & tissue = albumin, fibrinogen) adsorb onto surfce
2) Acute Inflammation:
Formation of Temporary Matrix (Wound healing steps)
Infiltration of: PMN & host cells = wound healig: defense against pathogens
3) Chronic Inflammation:
Phagozytosis: Macrophages + Monocytes
M1: pro inflammatory
M2: pro healing
exhibit high plasticity: can switch between: polarization / activation = perform different functions
4) Foreign Body Giant Cell Formation:
Fibroplasts: deposit collagen
Endothelial cells: angiogenesis -> Formation of granulation tissue = new tissue during healing phase
5) Encapsulation:
“walls off” material = isolating it
can cause functional issues around medical implant
Influence FBR (+)
Hydrophylic Implant surface
attracks water molecules = wettable surface
in FBR:
lower protein absorption
reduced cell adhesion
weaker inflammatory response
zB:
Hydrogels
Material coated by polar Molecules
Lattice Structure of Metals
1) FCC: Face centered cubic:
8 atoms in corner & 1 on each side
Kaltverformbarkeit: sehr gut & good ductility
betaFe, Al, Cu, Pb
2) BCC: Body centered cubic:
8 atoms in corner & 1 in middle
Kaltverformbarkeit: gut
alphaFe, Cr, Mo, V
3) HCP: Hexagonal close packed:
atoms arranged in hexagonal pattern: stacked ABAB sequence
Kaltformbarkeit: gering & low ductility
Mg, Zn, Ti
Stents: endovascular prothesis
1) Alloy, stainless steel:
Nickel, Chromium, Molybdenum, Iron
Gut:
austensite = primary structure = good corrosion resistance
Schlecht:
elastic deformation limited to 1%
Behandelt: Retenosis due to inflammation of tissue
smooth muscles proliferate = closing stent
corrosion = release of ions = retenosis
2) Nitinol:
hyperelastic
shape memory
biocompatability
corrosion resistance
for: stents, tools minimal invasive surgery, orthodontic wires
Surface preparation: Electropolishing!
3) Drug eluting stent:
antiproliferative agent
Drug: sirolimus & paclitaxel
Composition: stainless steel + polymer coating (non degradable)
4th generation: fully degradable polymer stent
temporary mechanical support, decrease risk of long term complication
Composition: Metal + Polyester
Stress induced phase transformation: Nitinol
Austenite Phase under Low Stress:
Austenite phase behaves = elastically
Martensitic Transformation under Higher Stress:
stress increases = austenite phase begins to convert into martensite.
more strain without permanent damage = superelasticity.
Martensite Reversion:
stress is removed = martensite transforms back into austenite = material returns to its original shape.
Glass Ceramic
hybrid material -> glass & crystalline phase
Glass
amorphous
Bioactive Glass
specific type of glass that interacts with biological tissue
Zirkonia
high strength
fracture toughness
for crwon coppings, bridge frameworks, abutments
by CAD, CAM, AMT
Transformation strengthening:
Tetragonal -> Monoclin = Increase in Volume = closes cracks (controlled by heterogenousf nucleation)
Stiffness
resistance against elastic deformation (reversible)
Strength
resistance against plastic deformation, fracture (irreversible)
Hardness
Resistance against plastic deformation by indentation
Toughness
Resistance against crack growth
Hydrogel*
3D network of hydrophilic polymers by:
covalent bonds
physical cross links through entanglments
ionic interaction
cant dissolve!
Process:
Polymer selection
Crosslinking
Gelation
Stress shielding
biomechanical phenomenon where implant bears a disproportionate load
= leading to reduced stress on surrounding bone
Mechanism:
remodelling follows Wolfs Law:
bone grows in response to mechanical stress
if implant is too stiff = absorbs all the stress
reduced bone stimulation
bone resorption
Lösung:
Materials with E-Modul close to natural bone (Ti-alloys, porous ceramics)
design implant with: tailored geometires, surface treatments to support osseointegration
Metal Ductility
ability to undergo plastic deformation before fracture
allows material to be stretched / to be shaped)
Characteristics:
Deformation without fracture
high tensile strain
Factors:
crystal structure (hexagonal = low ductility)
T°C
Impurities & Alloys
Grain size
Toughnening Mechanisms (all materials)
heterogeneity
Strengthening of Metals
cold working
grain refinement
solut solution strengthening
precipitation strengthening
CoCrMo-alloy
gut:
high strenght
weat & corrosion resistance
durability
schlecht:
brittleness
alloy melted at 1350-1450°C, poured & pressurized into ceramic molds of desired shape
zB: femoral stems, oral implants, cardiac stent
Mg + alloys
biodegradable & bioabsorbable!
temporary application
corrosion products = biocompatible (Mg in human body)
high specific strength & elastic modulus wie knochen
low corrosion resistance
formation of hydrogen: bubbles around implant = delay of healing
low ductility
ISO 10993-5 Cytotoxicity
to assess compatability of Material through use of isolated cells in vitro
direct contact procedure
indirect contace procedure
extract test
ISO 10993-10 Irritation & Skin sensitization
to determine wheter material contains chemicals that cause local / systemic effects after repeated / prolonged exposure
intracutaneous test
primary skin irritation test
murine local lymph node assay
ISO 10993-11 Acute systemic toxicity
to evaluate materials potential to cause pyrogenic repsonse / fever
pyrogenic = substance that can cause fever when in body / blood (injections)
in vitro
in vivo - rabbit pyrogen test
ISO 10993- xx (sub-) chronic toxicity
to determine potentially harmfull effects from longer term / multiple exposure
test during in life phase
hematology
clinical chemistry
ISO 10993-3 Genotoxicity
to detect mutagens
can cause cancer
Mutagenicity & Carciagenicity
in vivo / vitro
ISO 10993-6 Implantation test
to evaluate interaction between MD & living tissue
cellular & immunologic response
ISO 10993-4 Hemacompatability
Materials used in blood containing devices must be assest for blood compatability
Hemolysis assay
coagulation assay
complement activation
ISO 10993-16 Pharmacokinetics
to investigate metabolic processes of: absorption, distribution, etc of toxic leachables from test materials
for: bioabsorbable material, durg-device combination
ISO 10993- xx Reproductive & Development Toxicity
to asses pot. effects of material on fertility / reproductive function
weil: oft permanent contact with internal tissue
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