Impression materials Pavel Bradna Institute of Dental Research Purpose To prepare accurate and true replicas of oral structures (teeth, mucosa) The replica is prepared in 2 steps: Step 1. Making a negative (impression) Step 2. Prepare a model or a cast accurate positive (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 1 Requirements 1. Capable of plastic to rigid body transformation 2. Acceptable for a patient - non-toxic, non-irritant, tasteless, reasonable setting time up to 5-7 min 3. Good handling properties – easy to prepare/mix plastic before set, but viscous enough not to flow out of a tray (thixotropic), adequate working and setting times After being set: 4. Accuracy and detail reproduction (25-50µm), 5. Dimensionally stable 6. Resistant to mechanical stress - elastic and rigid 7. Compatible with model materials 8. Resistant to disinfectant solutions 9. Cost effective Important terms • Elastic/plastic deformations • Strength • Pseudoplastic/thixotropic • Hydrophilic/hydrophobic • Working time • Setting time (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 2 Elasticity/plasticity elastic/plastic deformation Describes behaviour of material under load stress (force/m2) Region of elastic deformations, Hook‘s law applies Region of plastic deformations Maximum load at fracture – ultimate strength Slope – Young‘s modulus, modulus of elasticity Deformation Proportional limit Mechanical model of elastic behaviour Deformation A spring – ideally elastic behaviour (Hook‘s law) No load 5N Loaded Deformation Unloaded When unloaded !fully recovers! t1 t2 loaded unloaded (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 3 Mechanical model of plastic behaviour A dashpot – ideally plastic behaviour permanent/irreversible deformation When unloaded !No recovery! Deformation Plastic = Permanent deformation t1 t2 loaded unloaded Recovery from deformation combination of a spring and a dashpot – a model of viscoelasticity Loaded for a long time deformation Loaded for a short time Plastic/permanent deformation Pouring after material relaxation t1 < t2 Time (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 4 Deformation The effect of recovery from deformation on the accuracy of a model 99% % Recovery from deformation 95% Time Plastic deformation Pseudoplasticity/thixotropy of fluids Slopeviscosity Stress τ Gradually loaded Gradually unloaded Thixotropic (structure is „broken“ under shear Gradually unloaded Pseudoplastic . τ = ηγ . Rate of deformation γ (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 5 Hydrophilic/hydrophobic Contact angle Hydrophilic material Hydrophobic material (α>90o) unable to wet humid surfaces able to wet humid surfaces Does not copy the wet surface Examples of clinical significance of pseudoplastic properties, hydrophilicity and high mechanical resistance (tear strength) of impression materials Impression material Prepared tooth Compromised flow in small details - too high viscosity and hydrophobicity Fracture and lost detail due to low strength (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 6 Working time – a period from the start of mixing to the final time at which the impression can be seated in the mouth without its distorsion Setting time – a period from the start of mixing till the impression becomes elastic enough to resist deformation during its withdrawal from the mouth Classification of impression materials Irreversible Reversible Inelastic/rigid ZnO-eugenol (ZOE) Impression comImpression plaster pounds Elastic Alginate Elastomeric: Polysulfide Polyether Silicone Agar hydrocolloid (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 7 Inelastic/rigid impression materials A. Irreversible 1. Zinc-oxide eugenol impression pastes (ZOE) Main indications: impression of edentulous ridges, surgical dressing Setting reaction: -OH and methoxy groups chelate structure A two-paste system composed of: Paste A – ZnO/mineral or vegetable oil as a plasticizer Paste B – oil of cloves with app. 85 % of eugenol or pure eugenol, resins and fillers, accelerators H2O, acetic acid, Zn acetate (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 8 Comparison of viscosity changes during ZOE setting Silicone impression materials Low viscosity of ZOE impression pastes – enables mucostatic impressions Edentulous ridges - low viscosity is favourable to avoid displacement of tissues rigidity ZOE Silicone Advantages: 1. Low viscosity – no compression of soft tissues 2. Dimensional stability (shrinkage less than 0.1 %) 3. Good surface detail reproduction 4. Low price Disadvantages: 1. Cannot be used in deep undercuts 2. Eugenol allergy in some patients (o-ethoxy benzoic acid [EBA] to replace eugenol) (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 9 2. Impression plaster Main indication: impression of edentulous ridges Setting reaction: CaSO4.0.5H2O + 1.5H2O CaSO4.2H2O + heat +expansion Composition: app. 0.1 lin % CaSO4 . 0.5H2O β-hemihydrate Potassium sulfate – to reduce expansion but accelerates setting Borax – a retarder to prolonge setting time Diatomaceous earth, quartz, lime - to make the plaster more brittle Advantages: 1. Cheap and long shelf life, easy to prepare 2. Very good surface detail reproduction 3. Excellent dimensional stability Disadvantages: 1. Very rigid – often need to be fractured when removed from the mouth 2. Fractures if undercuts are present 3. Non-toxic but may dry soft tissues - unpleasant to patients Old fashioned – not frequently used (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 10 B. Reversible 3. Impression compounds (Kerr‘s, Stent‘s impression compounds) Thermoplastic material (softens when heated to 50oC and hardens on cooling) for making impressions of edentulous ridge, tooth impressions in a copper band Composition: 1. Resins (wax, shellac, guttapercha) 2. Filler (talc) 3. Lubricants (stearic acid, stearin) Advantages: 1. Can be reused, easy to use 2. Non-irritant and non-toxic Disadvantages 1. Poor dimensional stability 2. Easy to distort when withdrawn from the mouth Old fashioned – not frequently used (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 11 Elastic impression materials A. Hydrocolloid impression materials B. Elastomeric impression materials Irreversible Hydrocolloid Reversible Polysulfide Elastomeric (non-aqueous) (irreversible) Silicone - condensation - addition Polyethers A. Hydrocolloid impression materials Hydrocolloid – a colloidal system (particle size up to app. 0.5 µm) with water as a dispersion medium so called HYDROCOLLOID SOL that can be tranformed to a semisolid GEL Setting reaction reversible/agar sol irreversible/alginate sol Cooling Heating Coagulation gel gel (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 12 B. Irreversible hydrocolloid Alginate impression materials (Irreversible hydrocolloid impression material, preliminary, orthodontic impressions etc.) Based on natural polysaccharide – Na+, K+, triethanol amine alginate salts (isolated from brown seaweeds) Constituent units Alginate chains M = 30 – 150 000 Form viscous sols and gels after addition of Ca+2 ions Setting/gelation reaction: NanAlg + CaSO4 powder H2O nNa2SO4 + CanAlg2 gel Egg-box structure Cross-linked structure of alginate gels (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 13 Composition: 1. Na/K alginate 2. Calcium sulfate (CaSO4.2H2O, CaSO4.1/2 H2O) 3. Diatomaceous earth (amorphous SiO2) 4. Retarder – phosphates prolonge working time 2Na3PO4 + 3CaSO4 3Na2SO4 + Ca3(PO4)2 5. Setting accelerator - K2TiF6 (makes also stone surface hard) 6. Additives – glycol, paraffin oils – to agglomerate particles and make material „dustless“ Mixing ratio powder/water app. 10 g/20 mL Properties: 1. Set after mixing with water 2. Shrink due to loss of water by Syneresis – expression of water from the surface of impression (if contains Na2SO4 – decreased quality of stone surface); by Evaporation of water from the surface 3. Imbibition – sorption of water causing a dimensional change 4. Chromatic phase indicator may be incorporated to signal the impression setting (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 14 Store in a closed container with a towel saturated with water Dimensional changes of a cast prepared from alginate impression stored in various environments Phillips‘ Science of Dental materials Dimensional changes of a cast prepared from various alginate materials with storage time RH=100 %/23oC Dimensional changes lin % 1.00 Ypeen Premium Ypeen Phase 0.80 Hydrogum Elastic Standard types 0.60 0.40 Prolonged pouring time 0.20 0.00 0 5 10 15 20 25 Time /hours (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 15 Dependence of pH and rigidity on time 8.5 150 Blue - violet White 6.5 100 r ig id ity Pink 7.5 pH Setting 50 5.5 4.5 0 0:00 2:00 4:00 6:00 8:00 time [min] 10:00 12:00 14:00 Acid-base colour indicators (phenolftalein/thymolphtalein) 5 sec 35 sec 1 min 30 sec 2 min (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 16 Most frequently used impression material Advantages: 1. Very good biological tolerance 2. Easy to use and mix 3. Fast setting 4. Low price Disadvantages: 1. Poor dimensional stability 2. Setting dependent on water temperature and water hardness 3. Although 100 h pouring time is also recommended they should be poured as soon as possible 4. Sometimes problems with a model stone compatibility B. Reversible hydrocolloid Agar impression materials (Reversible hydrocolloid impression material) Based on thermoreversible gelation of natural polysaccharide – agar (isolated from red algae/seaweeds) Agarose, is a strongly gelling, non-ionic polysaccharide Agaropectin, is more complex polysaccharide having sulfate groups 1,3- linked β-D-galactopyranose and 1,4-linked 3,6-anhydro-α-L-galactopyranose units (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 17 Gelation: Agar sols form gels upon cooling of a hot solution to (30 – 40)°C Agar gels melt to sols upon heating to (90 – 95)°C Sol random coils Gelation II aggregation of helices Gelation I Double helices Composition: 1. Agar 2. Borax to increase the gel strength 3. Potassium sulfate as a gypsum hardener 4. Water – dispersion medium Supplied in two forms – in tubes and cartridges Tray material Filled tray (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 18 100oC Material in syringes applied to teeth Advantages: 65oC 45oC Compartments for liquefying 100oC, storage 65oC and tempering the material in a tray at 45oC 1. Very good biological properties 2. Excellent surface detail reproduction Disadvantages: 1. Need special equipment (water bath) and special technique 2. Dimensionally instable - evaporation or imbibition 3. Low strength and poor tear resistance 4. Slow setting time Other applications of hydrocolloid materials Reversible hydrocolloid impression materials are used as duplicating materials to prepare dental cast models (gypsum or from investment materials) (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 19 C. Elastomeric (non-aqueous) impression materials Synthetic polymers with rubber properties after setting Polysulfide Elastomeric (non-aqueous) (irreversible) Silicone - condensation - addition Polyethers Main indications · impressions for partial prostheses (removable) · impressions for crowns and bridges (fixed) · impressions for implantology Polymerization shrinkage of elastomers is usually compensated for using a combination of: 1. Highly filled-viscous material „Putty“ for preliminary impression (low polymer content - of low shrinkage) 2. Low filled-low viscosity „wash“ or „light“ impression material (high polymer content - higher elasticity but higher shrinkage) (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 20 Polysulfide impression materials (Thiokol rubbers, mercaptan rubbers) The very first elastomeric impression material Based on reaction between polymer with free mercaptan (-SH) groups and oxidizing agent PbO2 which lenghtens and cross-links chains via reaction of terminal and pendant -SH groups) Setting reaction: Linear polysulfide polymer HS SH HS HS O SH HS SH HS SH HS SH HS Catalyst PbO2 -H2O PbO + O Water released increases contraction -S – S- Cross-linked polymer (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 21 Composition: Supplied in a two-paste system Base paste: polysulfide polymer, filler, plasticizer Catalyst paste: lead dioxide, sulfur, inert oil Volume mixing ratio 1:1 Advantages: 1. Low price 2. Long working time Disadvantages: 1. 2. 3. 4. 5. Should be poured within 0.5 – 1 hour Lead oxide may cause toxic effects Unpleasant mercaptane smell Long setting time app. to 10 min Poor elastic recovery – prone to plastic deformation Old fashioned – not frequently used (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 22 Polyether impression materials Based on cross-linking of polyether chains via cationic polymerization of aziridine rings using a aromatic sulfonate ester as an initiator Initiation: + SO3R R+ SO3- Propagation: Linear polymer Hydrophilic part (ethylene oxide units) CH3-CH-CO-O-[CHR-(CH2)n –O]m-O-CO-CH-CH3 Ring opening N CH2 CH2 N CH2 aziridine rings - N + CH2 +CH 2 + R+ CH2 N-R CH2 CH2 Cross-linked structure (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 23 Composition: Supplied in a two-paste system Base paste: • • Polyether Filler, plasticizer Catalyst paste: • Sulphonic acid ester • Inert oil • Filler Advantages: 1. 2. 3. 4. 5. Naturally hydrophillic Accurate and high dimensional stability Good elastic recovery Low setting contraction Excellent surface detail reproduction Disadvantages: 1. Rather stiff when set material (difficult to remove from mouth) 2. Very expensive 3. May cause allergic reaction due to the sulphonic acid ester (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 24 Silicone impression materials C-silicone impression materials (condensation silicones) Based on cross-linking polycondensation reaction of hydroxy terminated polysiloxane prepolymer with tetra alkoxy silanes catalyzed by dibutyl-tin dilaurate (DBTD) Setting reaction - polycondensation DBTD O …..O Si O O O O O Si Si O O Si O … … … … O Linear polymer Si O HO Si …..O OH …..O …..O Si …..O + Si(OC2H5)4 O …..O O O 4C2H5OH …..O O HO Si OH … Si … … … O …..O Cross-linked polymer Alcohol releases from the reaction mixture and contributes to contraction/shrinkage of the impression (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 25 Composition: Supplied as a two-component system Base paste: • • Hydroxyterminated polysiloxane polymer Filler (cristobalite, talc, starch) Catalyst: Liquid catalyst: • Cross-linking agent (e.g tetraethoxy silane) + activator (dibutyl-tin dilaurate) Paste catalyst: • Cross-linking agent, activator, inert oil • Filler Advantages: 1. Accurate impressions when poured soon 2. Good elastic recovery 3. Lower price Disadvantages: 1. Hydrophobic 2. Shrinking of impression over time, pouring time till 4 h 3. Catalyst may cause allergic reaction 4. Difficult to dispense proper volumes of both components 5. Usually hand-mix version only (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 26 A-silicone impression materials (addition silicones, vinyl siloxane, poly(vinyl siloxane)) Impression material, duplicating material, relining material, bite registration material, root canal sealer Based on cross-linking polyaddition reaction of vinyl terminated polysiloxane polymer with methylhydrogen silicone cross-linking agent in the presence of platinium catalyst Setting reaction - polyaddition CH3 …..O Si CH=CH2 + CH3 H Si …..O CH3 CH3 O CH3 Si O CH3 …..O CH3 O Si CH=CH2 + H Si H + CH3 O CH3 CH3 Si O CH2=CH Si CH3 CH3 CH3 Vinyl polymer Pt Crosslinking agent …..O O Si CH2-CH2 Si CH3 CH3 CH2-CH2 Si CH3 Si CH2-CH2 Si CH3 CH3 Cross-linked polymer Pt may release H2 from water or –OH groups from the reaction mixture causing bubbles on a gypsum model (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 27 Composition: Supplied as a two-component 1:1 system Base paste: 1. 2. 3. 4. Vinyl terminated polysiloxane polymer Pt catalyst Filler (cristobalite, talc) Surfactant (hydrophilic agent) Catalyst: 1. Vinyl terminated polysiloxane polymer 2. Cross-linking agent 3. Filler, silicone oil (adjust viscosity of duplicating materials) Advantages: 1. Accurate impressions, very low shrinkage 2. Very good surface detail 3. Highly elastic 4. Perfect elastic recovery 5. Dimensionally stable 6. Non-toxic and non-irritant Disadvantages: 1. Hydrophobic – necessary to add a surfactant 2. Setting inhibited by latex gloves or some adstringents (sulfur, heavy metals) 3. Hydrogen release – surface bubbles – pouring time 1 h after removal from the mouth 4. High price (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 28 Typical properties of elastic impression materials Property No of components Algi- Agar nate 1 Polysulfide Polyether C-silicone A-silicone 1 2 pastes 2 pastes 2 pastes 2 pastes powder Working time [min] 1.5 - 4-7 2-3 2-4 2-4 Setting time [min] 3-4 3-5 7-10 5-6 5-8 4-7 Contraction [lin %] after 24 h 0.5 0.01 0.4-0.5 0.2-0.3 0.2-1.0 0.01-0.2 Recovery from deformation [%] 96 98.8 94.5-96.9 98.3-99.0 97.2-99.6 99.0-99.9 Detail reproduction [µm] 50 25 25 25 25 25 Hydrogen release N N N N N Y Contact angle [o] Very low Very low 82 50-60 98 70*-80 Relative cost Very low high low Very high lower high *Hydrophilic types Partly from Phillips‘ Science of dental materials Examples of typical packages of impression materials Putty Light Light (C) Institute of Medical Biochemistry, 1st Fac. Med., Charles University, and Institute of Dental Research in Prague 29
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