REFRACTORY MATERIALS

Dr Khushboo Racca I MDS

CONTENTS
y Introduction y Refractory materials - Properties y Investment materials 1. Gypsum bonded investment - Classification - Composition - Properties 2. High temperature investments i. Phosphate bonded investments - for all ceramic restorations - for titanium based alloys ii. Silica bonded investments y Divestments y Soldering investments y Dental ceramics

y Conclusion

INTRODUCTION Refractory materialsThis material is usually a form of silicon dioxide, such as Quartz, Tridymite, Cristobalite, or a mixture of these. Refractory materials are contained in all dental investments, whether for casting gold or high melting point alloys Recently Magnesia, Alumina, Zirconia are also added in the list of refractory materials The main properties due to which they are known as refractory materials 1. Poor thermal conductors & high heat capacity 2. Change in crystalline structure on heating which decreases density & increases volume without breakage of bonds Example1. Quartz when heated at 575 C (1067 F), form gets converted to form 2. Cristobalite when heated at 200-270 C (392-518 F), crystalline form gets converted to crystalline form 3. Tridymite undergoes inversions over a range of temperature.Two inversions at 117 C & 163 C 4. Fused quartz does not undergo inversion at any temperature. Also it has low co-efficient of thermal expansion Materials that utilizes refractory materials1. Investment materials 2. Divestment 3. Soldering investment

4. Dental ceramics INVESTMENT MATERIALS These are the materials in which the wax patterns are casted. They should posses the following requirements- Sufficient mold expansion to compensate casting shrinkage - Fine particle size for smooth surface - Easy manipulation - Smooth consisting on mixing - Porous for gas escape - Must not decompose on high temperature - Adequate strength - Casting temperature should not be critical - Should break easily on casting - Should not react with metal - Economical Composition Refractory materialIt constitutes 60-65% of the investment material. It withstands high temperature without decomposition. It resists heat to which it is subjected and force applied during casting. It compensates casting shrinkage Binder It constitutes 20-30% of the investment material. It helps forming a coherent solid mass. Calcium sulfate hemihydrate, Sodium silicate, Ethyl silicate, Ammonium sulfate, Sodium phosphate acts as binder

Other Chemicals It constitutes 5% of the total mass.Sodium chloride, boric acid, potassium sulphate, graphite, copper powder etc are added to modify physical properties CLASSIFICATION A. BASED ON PROCESSING TEMPERATURE 1. High Temperature - Phosphate Bonded Investment - Silica Bonded Investment 2. Low Temperature - Gypsum Bonded Investment B. BASED ON REFRACTORY MATERIAL 1. Quartz Investment 2. Cristoballite Investment C. BASED ON TYPE OF BINDER USED 1. Gypsum bonded investments 2. Phosphate bonded investments 3. Silicate bonded investments GYPSUM BONDED INVESTMENTS ADA Specification No.2 for casting investments for dental gold alloys encompasses three types of investments 1. TYPE 1 for Inlays or crowns. Undergoes thermal expansion 2. TYPE 2 - for Inlays or crowns. Undergoes hygroscopic expansion 3. TYPE 3 - Fixed Partial Dentures with Gold alloys

Composition 1. Refractory material It constitutes about 60-65%.Silica is used in the form of Quartz/ Cristobalite. It regulates thermal expansion and also provides mold expansion 2. hemihydrate/ dental stone It is 30-35% in the investment. It acts as a Binder. Imparts strength to the material. It Contributes to mold expansion by setting expansion 0.06-0.5%. if it is heated above 700 C, disintegrates into Sulphur di oxide and Sulphur tri oxide

3. Modifiers 5% Carbon added acts as a reducing agent by providing a non oxidizing atmosphere. Coloring agent is added in the form of powdered Copper.Boric acid, NaCl regulates setting expansion and setting time. It prevents most of the shrinkage when gypsum heated above 300C Setting time A.D.A specification no 2 states that for inlay casting investments setting time should not be less than 5 min & not more than 25 min. Modern inlay investments should have setting time of 9-18 min Effect of temperature on investment 1. On heatingQuartz expands to 1.4% at 600 C. Pure Cristobalite expands to 1.6% at 250 C. Expansion of Tridymite at 600 C is less than 1%. form stable at room temperature while form stable on heating. All three forms of silica expand on heating.

Highest expansion is shown by Cristobalite while the lowest by Tridymite 2. On cooling On cooling to room temperature, investment exhibits an overall contraction.On reheating, investment does not expand to the previous level. Reheating of investment causes internal cracks Expansion Expansion is needed for compensation of casting shrinkage of alloy .It is of 3 types : 1. Normal setting expansion. 2. Hygroscopic setting expansion 3. Thermal expansion Setting expansion Silica & gypsum results in greater setting expansion than gypsum alone. Silica helps in expansion by interfering with the intermesh creating outward thrust Hygroscopic expansion There are two ways of achieving hygroscopic expansion 1. Water immersion hygroscopic technique It is achieved when Investment mould is placed in water during initial set. It is five times the normal setting expansion. Certain investments are specially designed for hygroscopic expansion. According to ADA Specification, type II investments should have a minimum setting expansion of 1.2% & maximum permissible is 2.2%. Investments used in the hygroscopic technique usually contain Quartz or Tridymite which have lower thermal expansion but higher hygroscopic expansion

Factors Affecting hygroscopic Setting Expansion a) Effect of composition b) Water powder ratio c) Effect of temperature d) Effect of time of immersion e) Effect of spatulation f) Shelf life of investment g) Effect of confinement h) Effect of amount of added water 2. Water added technique In this, water is placed on the upper surface of the investment within the casting ring. It produces readily controlled expansion Thermal expansion It is directly related to the amount & type of Silica used. Contraction of gypsum is entirely balanced when Silica content is 75% . Investments containing Cristobalite expand earlier than those containing Quartz because of lower inversion temperature of Cristobalite compared to Quartz. For Type I investment thermal expansion should neither be less than 1% nor greater than 1.6%. If hygroscopic expansion is used, thermal expansion of 0.5-0.6% sufficient. If thermal expansion used with normal setting expansion, then thermal setting expansion should be 1-2%. Investments used in the thermal technique contains cristobalite which has a high thermal expansion. Factors affecting thermal expansion 1. water powder ratio 2. Effect of thermal modifiers

STRENGTH According to ADA Specification No 2, compressive strength for inlay investment should not be less than 2.5 MPa 2 hrs after testing. This is adequate to prevent fracture or chipping of mould during heating and casting of gold alloy HYGROSCOPIC- THERMAL INLAY CASTING INVESTMENT It is used for hygroscopic or thermal type of expansion. It consists of blend of Quartz & Cristobalite. For hygroscopic casting technique it is heated to 482 C while for thermal casting technique it is heated to 649 C

HIGH TEMPERATURE INVESTMENTS ISO classification Type 1- fabrication of inlays, crowns, & other fixed restoration Type 2- fabrication of partial dentures or other removable appliances Type 3- fabrication of casts for soldering, brazing & welding Type 4- for refractory dies PHOSPHATE BONDED INVESTMENTS It is the most common type of investment for casting high melting alloys TypesType I - Inlays, crowns & other fixed restoration Type II- Partial dentures & other cast removable restorations

Composition 1. Binder- 20% Acidic part is ammonium diacid phosphate while the basic part is magnesium oxide 2. Refractory- 80% Silica (Cristobalite or Quartz or mixture of two) also combination of different particle sizes are used. It provides high temperature thermal shock resistance & thermal expansion at high temperature 3. Modifiers- Carbon acts as reducing agent. It is added when the casting alloy is gold. It is not used for Silver-palladium alloys, base metal alloys. Carbon crucible should also be avoided when these metals needs to be casted. Gold alloys used with porcelain are not premelted in presence of carbon. 4. Colloidal solution of silica preferred over water due to dual effect of increasing setting expansion & strengthening the set material. SETTING & THERMAL EXPANSION Phosphate bonded investments when mixed with water exhibit shrinkage between 2000C to 4000C. Colloidal silica when used for mixing replaces this contraction. Predominantly for base metal alloys, 33% dilution of colloidal solution is used. Early thermal shrinkage of phosphate bonded investments is because of decomposition of binder and is accompanied by evolution of ammonia Setting & working timeWorking time - 2 minutes Setting Time - 1 hour

Warmer the mix, faster it sets.Increasing mixing time, fastens the setting reaction. Increasing L/P ratio, increases working time Advantages 1. High green strength. It is the prefired strength of an investment acquired through some chemical reaction at or near room temperature. It is compared with fired strength. 2. High firing strength. Hence less mold cracking and few fins on casting 3. Can withstand temperature up to 1000C for short period of time Disadvantages 1. When temperature is raised to 1375C, mold breaks down producing roughen surface of casting 2. Special liquid that is used for mixing produces less porous mold which leads to incomplete casting 3. Produces oxides that is difficult to remove from castings INVESTMENTS FOR ALL CERAMIC RESTORATION Two types of investment are used 1. For cast glass technique It is provided by the manufacturer & it utilizes phosphate bonded refractories 2. Refractory die It is obtained by pouring the investment in the impression directly. Die ovtained is then heated to remove gasses. These materials must accurately produce the details, remain undamaged during firing & have a thermal expansion compatible with ceramic. These materials are also phosphate bonded & they generally contain fine grained refractory fillers.

INVESTMENTS FOR TITANIUM BASED ALLOYS Molten Titanium is highly reactive with Oxygen. It also reduces oxides in investments. It dissolves Oxygen, Nitrogen & Carbon present in investments which embrittles the casting. Hence conventional investments are not used for casting titanium alloys. CLASSIFICATION A. Phosphate bonded investments B. Ethyl silicate bonded investments C. Cemented investments Refractories used are Silica, Alumina, Magnesia, Zirconia Modifications in Phosphate bonded investments for titanium based alloys are1. Investment of Phosphate binder, Magnesia & Quartz. It provides little advantage of use of one form of silica over other. 2. Investment of Phosphate binder, Alumina & magnesiaThermal expansion provided by these oxides is low 3. Investment with Phosphate bonded investments that contains both Magnesia & Alumina. It attains large expansion by the spinal reaction (MgO+Al2O3---MgOAl2O3) at 1150-1200 C. Spinal forming temperature can be reduced by mixing with magnesia acetate

4. PBI with Spodumen ( LiO2-Al2O3-SiO2). Spodumen expands irreversibly from 900-1100 C

Ethyl- silicate bonded investments Reaction between these investments & liquid Titanium is less due to highly refractory oxides in the powder. It is not used due to complex procedure Cemented investments It includes Investment of Magnesia refractory bonded to Aluminous cement( CaO-Al2O3) with mass fraction of 5% Zirconia powder. Oxidation of Zirconia powder during burnout produces irreversible expansion. FEF (Gibbs free energy of formation of Zirconia is 728 kj & hence it does not contaminate Titanium SILICA BONDED INVESTMENTS These investment materials are being used since 1930 but are slowly loosing there popularity due to complicated and time consuming procedures involved COMPOSITION Binder ---- Sodium silicate, Colloidal silica & Ethyl silicate Refractory ---- Silica (80%) Additives---- Magnesium oxide Wetting agent Silica bonded investments are supplied in 2 bottlesOne bottle contains diluted water soluble silicate sol as sodium silicate, while the other contains diluted acid solution Green shrinkage During manufacturing, Polysilicic acid gel is dried at temperature less than 168 C. It Leads to volumetric contraction losing alcohol & water and this is known as green shrinkage.

DIVESTMENT It is a die stone-investment combination. Commercially obtained gypsum-bonded material is mixed with concentrated colloidal silica liquid to obtain divestment. Die preparation14-16ml liquid is mixed with 50 gm powder. It is used with Polysulphide or Silicone rubber impression material. Rigid impression tray is used & there should be adequate clearance between teeth & tray. Divestment is poured in the impression & it should be separated from Polysulphide impression within 3 hrs. Aerosol dry lubricant spray by Dupont- SLIP-SPRAY can be used for easy separation InvestmentEntire assembly (die and pattern) is invested in the divestment. The only concern is that of sprue attachment. It should be secured properly. Setting expansion is 0.9% . while thermal expansion is 0.6% on heating 677C Advantages Highly accurate technique Disadvantages Not recommended for high fusing alloys DIVESTMENT Divestment phosphate or DVP is a phosphate bonded investment that is used in the same manner for high fusing metal ceramic alloys

SOLDERING INVESTMENT It is used In the process of assembling parts of RPD ADA Specification No 93 (ISO 11244) for dental brazing investments defines 2 types:1. Type I- Gypsum bonded dental brazing investments 2. Type II- Phosphate bonded dental brazing investments For low melting alloys the investment is similar to casting investments containing Quartz & Calcium Sulphate hemihydrates. For high melting alloys, Phosphate bonded investments are used they are designed to have lower setting & thermal expansion to prevent shifting of assembled parts DENTAL CERAMICS Composition Feldspar- 60-80%- basic glass former Kaolin 3-5%- binder Quartz 15-25% - filler & refractory Alumina 8-20%- glass former Boric oxide 2-7%- glass former & flux Oxides of Na, K & Ca%- glass modifiers Metallic pigments Refractory material added to ceramic helps it in withstanding high temperature Conclusion Research is needed in laboratory material for casting procedure to help producing better fitting castings

Bibliography 1. Science of Dental Materials- Anusavice- 10th edition 2. Dental materials & their selection- William 0Brien 3. Restorative Dental Materials- Craig-12th edition 4. Clinical aspects of Dental Materials- Galdwin & Bagby 5. Operative dentistry, modern clinicals & practise- Marzouk 6. Applied Dental Materials- McCabe