Patent Application
20060037514
The present invention relates to a system for chemically bonded ceramic (CBC) materials, and a composite biomaterial for preferably dental and/or orthopaedic applications. The CBC-system includes a binding (chemical cement) phase and inert phases with specified geometry providing the biomaterial defect tolerance through an improved fracture toughness. The invention also relates to the powdered materials and the hydration liquid, respectively, as well as the formed ceramic material.
For materials to be used as filling materials, dental fillings or bone void fillers, which have to interact with human tissue it is advantageous to make the biomaterials as biocompatible and bioactive as possible. These and other properties required for dental and orthopaedic materials are easy handling, good mouldability, hardening and curing within a short time period to make the material useful as soon as possible, high hardness and strength, corrosion resistant, ability to close gaps between the injected material and the host tissue and exhibit radio opacity. These as well as other property aspects of chemically bonded ceramics (initial moulding ability, initial strength, heat evolved and early colour/transmittance development as well as high general strength), are dealt with in SE 463 493, SE 502 987, SE 519 990, SE 519 991, SE522 510, SE 522 511, SE522 512 SE 523 671, SE Patent application 0203910-5, approved 30 Jun. 2004, WO 00/21489, WO 01/76534 and WO 01/76535.
The present invention relates to binding systems of the hydrating cement system type, in particular cement-based systems that comprise chemically bonded ceramics in the group that consists of aluminates, silicates, phosphates, carbonates, sulphates and combinations thereof, having calcium as the major cation, and in addition to the said system at least one second phase contributing to an increased defect tolerance. The invention has been especially developed for biomaterials for dental and orthopaedic applications, but can also be used as filler materials in industrial applications in electronics, micro-mechanics etc., or in the construction field.
The present invention specifically relates to the problems of remaining larger defects originating from pores, bubbles, insufficient mixing, a somewhat in-diligent handling, larger inhomogeneities origination from the raw materials, non-dispersed regions etc. These defects often determine the actual strength of the material and not the general microstructure of the same material. To assure the material some kind of threshold value as far as strength is concerned, it is important to find a means of demasking/removing the influence from these defects. To avoid these defects or to remove them totally by even more careful raw materials handling, develop operator's skill etc. are probably not doable. The present invention provides a tool that diminishes the harmful effect of these occasionally occurring defects by hindering or reducing the stress concentration around these defects. This is achieved by introducing fibers and (whisker or platelets) of specified sizes related to the defect size of possible defects discussed above. The fiber size is chosen so as to have the ability of shielding the defect but at the same time not working as a new defect. The proper choice of sizes is related to the basic fracture mechanics equation, described in more details below.
As distinguished from the survey article on strong and safe brittle ceramics “Strong and safe brittle ceramics—Materials aspects of design with structural ceramics”, by L. Hermansson”, in Advanced Ceramics for Structural and Tribological Applications, ed. Hawthorne and Troczynski, 1995, the present invention does not deal with the general microstructure of a material and the related strength, but with the practical strength of a material with remaining unpurposely introduced larger inhomogeneities. From the basic fracture mechanics equation
KIC=Yσc1/2, where
Another aspect can be understood from the level of KIC-values. In materials for use as dental filling materials or as bone void fillers, strength levels of more than 50 MPa are required with respect to bending strength. This also indicates that shield materials need to be 20-80 micrometer in length. Fibers of a length above this interval will need too high fracture toughness values to be used, or will constitute strength-controlling defects.
Accordingly, the present invention aims at providing a system for materials, preferably biomaterials, having a second phase as a shield or barrier with a length of at least 25 micrometer but not more than 80 micrometer.
The use of fibers and similar shield materials in the range of 25-80 micrometer does not exclude the use of fibers or whiskers with different sizes, especially not those with a length <25 micrometer. However, the range of 25-80 micrometer is the crucial range for threshold values based on the risk of fractures for biomaterials.
These and other objectives are attained by the system, the powdered material, the hydration liquid and the ceramic material according to the invention, as defined in the claims.
Thus, CBC-materials with the binding phases mentioned and the shield-giving additives function so as to achieve high performance features related to biomechanical properties.
The binding particles in the present invention are composed of chemically bonded ceramics, preferably Ca-aluminates, preferably CA=(CaO)(Al2O3), C12A7=(CaO)12(Al2O3)7) and C3A=(CaO)3(Al2O3), and in addition inert phases including glass, e.g. a phosphorous-containing glass. The inert filler (stable glass particles or oxides) is essential for the general end-product microstructure. Its effect concerns a lowered expansion, increased radio-opacity and favoured mechanical properties, especially hardness and the general microstructurally related strength.
Concerning calcium aluminate phases it is preferable to use CA, C12A7 and C3A, which yield good initial strength. The addition of an accelerator is dependant upon the selection of the Ca-aluminate phase. Low concentrations of lithium ions increase the reaction rate for CA. For C12A7 and C3A the effect of an accelerator is more complex.
It is preferred that the system comprises inert dental glass, as an additive in the powdered material, preferably at a content of 5-45 weight-%, more preferably 15-35%. The particle size is critical in establishing high homogeneity. It is preferred that the mean particle size is 0.1-5 μm, more preferably 0.2-2 μm, and most preferably 0.3-0.7 μm. The glass may contain low amounts of less stable glass or reactive glass, preferably below 5% of the glass content. These glasses can preferably contain fluorine and phosphorus to yield fluoride and phosphate ions, which contribute to F-apatite formation.
According to one aspect of the invention the inert filler particles are composed of prehydrated chemically bonded ceramics of the same composition or similar as that of the main binding phase. This improves the homogeneity of the microstructure and enhances the binding between reacting chemically bonded ceramics and the filler material.
According to another aspect of the present invention an additional system is included to improve the closure of pores initially, namely by introducing a system that works by pure water up-take, e.g. the semi-hydrate of CaSO4, gypsum. And a further system to solidify the total system initially, the combination of phosphoric acid and zinc oxide-forming Zn-phosphate. These phases will not contribute to the long-term properties but will enhance the initial pore closure and initial strength.
The system and material according to the invention have the advantages compared to systems/materials such as glass ionomer cements and pure Ca-aluminate based systems or monomer based filling materials, that it maintains its bioactivity, that it has improved initial strength and that it has long time stability regarding both dimensional aspects, strength and minimised deterioration and improved fracture toughness and able of shielding sparsely occurring large defect, making the materials according to the invention robust and defect tolerant. The introduction of glass fibers according to present invention reduces the geometrical change during curing to a minimum. The viscosity of the material can be controlled within wide frames, upon initial mixing of the powdered material and the hydration liquid, from moist granules to an injectable slurry. However it is preferable to decrease the water to cement (w/c) ratio as much as possible leaving an appropriate viscosity for given application. The w/c ratio should be <0.50, more preferably within the interval of 0.30-0.40. This is accomplished according to the present invention by using dispersing agents, preferably salts of polyacrylic acids.
In the table below is illustrated how the strength-controlling defect size is related to the actual strength for given fracture toughness levels in the interval 0.50-1.25 Mpam1/2. Y is 1.98.
As is clearly seen defects larger than 25 micrometer should be removed or shielded to avoid fracture at the given stress levels for typical fracture toughness levels for chemically bonded ceramics. For a Y-value of 1.7 the limit is approximately 30 micrometer.
Tests were performed to investigate the influence of shielding additives on the obtained flexural strength of material. The fracture toughness was also measured.
Description of Raw Materials
Calcium aluminate ((CaO)3(Al2O3), (CaO)(Al2O3), (CaO)12(Al2O3)7), dental glass filler (Schott), poly acid (Na-PAMA=poly(acrylic-co-maleic acid) sodium salt Mw=50,000 and glass fibers G1, G2 at different contents.
Glass fiber G1 had an average length:diameter ratio of 20, with an average diameter of 3 micrometer. Glass fiber G2 had an average length:diameter ratio of 40, with an average diameter of 1.5 micrometer. The fibers are based on Ca-silicate glasses.
As reference material a commercial glass ionomer cement (Dentsply) was used.
Description of Materials
Calcium aluminate was mixed with dental glass and poly(acrylic-co-maleic acid) sodium salt and the glass fibers. The calcium aluminate phases were synthesised via a sintering process where first CaO and Al2O3 were mixed to the desired composition and then sintered at elevated temperature for 6 hours. The formed calcium aluminate lumps were crushed and jetmilled to a mean grain size of 1.5 μm and a maximum grain size of 9 μm. The dental glass, calcium aluminate and poly acids were mixed with acetone and Si3N4 marbles for 14 hours to obtain the desired homogeneity. Formulations were made according to (in wt. %):
The formulations were placed in 5 ml jars and wet with liquid and blended in a “rotmix” (3M ESPE) for 15 seconds followed by centrifugation for 3 seconds. In addition 18 mM of LiCl was added to further increase the hydration speed.
Description of Tests
The flexural strength was measured according to ASTM F-394, KIC according to the single edge notch technique, and hardness according to Vickers indentation at 100 g for the eight formulations. All samples were stored at 37 degrees C. in phosphate buffer system 0.02 M (pH 7.4) for one week before testing.
Results
The results from the testing are presented in the table below.
The glass fiber addition increases the KIC essentially above that of the glass ionomer cement. The glass fiber with the larger surface contact area (G2) has a somewhat higher fracture toughness than that of the G1 formulation. The strength of the glass fiber-reinforced material is above 80 MPa.
The results show the fiber-reinforced material to have the potential to meet general mechanical requirements put on biomaterials for injectable dental and orthopaedic applications.
The system is not restricted to biomaterials application, and can favourably be used for industrial applications in electronics, micro-mechanics etc or in the construction field.
