FR2781366A1 - Yttrium-stabilized zirconium dioxide ceramic composition for dental prostheses is colored with a pigment blend of iron oxide, bismuth oxide and cerium oxide - Google Patents

Yttrium-stabilized zirconium dioxide ceramic composition for dental prostheses is colored with a pigment blend of iron oxide, bismuth oxide and cerium oxide Download PDF

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FR2781366A1
FR2781366A1 FR9809402A FR9809402A FR2781366A1 FR 2781366 A1 FR2781366 A1 FR 2781366A1 FR 9809402 A FR9809402 A FR 9809402A FR 9809402 A FR9809402 A FR 9809402A FR 2781366 A1 FR2781366 A1 FR 2781366A1
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cerium oxide
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Bernard Cales
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Norton Desmarquest Fine Ceramics SA
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    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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    • A61K6/00—Preparations for dentistry
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    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
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Abstract

The coloration of ceramic products for dental use comprises zirconium dioxide with a tetragonal microstructure stabilized with yttrium oxide, using a pigment blend of iron oxide, bismuth oxide and cerium oxide. A ceramic composition for dental applications consists of: (1) zirconium dioxide with a tetragonal microstructure, stabilized with yttrium oxide; (2) a colorant combination comprising iron oxide (0-1 wt. %), bismuth oxide (0-0.02 wt. %) and cerium oxide (0-5 wt. %) cerium oxide; and (3) impurities.

Description

L'invention concerne une composition céramique pour applicationsThe invention relates to a ceramic composition for applications.

dentaires, qui est a base de zircone et dont la microstructure (tétragonale) est stabilisée à l'oxyde d'yttrium. On parle couramment, en abrégé, de zircone  dental, which is based on zirconia and whose microstructure (tetragonal) is stabilized with yttrium oxide. We commonly speak, for short, of zirconia

stabilisée à l'oxyde d'yttrium (voire " stabilisée à l'yttrium ").  stabilized with yttrium oxide (or even "stabilized with yttrium").

La zircone stabilisée à l'oxyde d'yttrium est utilisée depuis une dizaine d'années comme matériau pour implant biomédical, notamment pour la réalisation de têtes de prothèses de hanche. Ce matériau présente une excellente biocompatibilité in vitro et in vivo, que ce soit à court terme ou à long terme, et présente des propriétés mécaniques très supérieures à l'alumine, autre céramique structurale utilisée dans le domaine biomédical. A titre d'exemple, la résistance à la rupture en flexion d'une zircone stabilisée à l'oxyde d'yttrium et frittée sous haute pression ( frittage " HIP ") peut dépasser 1500 MPa (elle dépasse 900 MPa en cas de frittage sans pression) alors que  Zirconia stabilized with yttrium oxide has been used for ten years as a material for a biomedical implant, in particular for the production of hip prosthesis heads. This material has excellent in vitro and in vivo biocompatibility, whether short or long term, and has mechanical properties far superior to alumina, another structural ceramic used in the biomedical field. For example, the flexural breaking strength of a zirconia stabilized with yttrium oxide and sintered under high pressure ("HIP" sintering) can exceed 1500 MPa (it exceeds 900 MPa in the event of sintering without pressure) while

celle des autres céramiques est généralement comprise entre 150 et 500 MPa).  that of other ceramics is generally between 150 and 500 MPa).

Dans le domaine dentaire, la zircone stabilisée à l'oxyde d'yttrium est déjà utilisée pour un certain nombre d'applications, comme les tenons dentaires  In the dental field, zirconia stabilized with yttrium oxide is already used for a certain number of applications, such as dental posts.

ou les implants intra-osseux. Ce matériau donne alors toute satisfaction.  or intraosseous implants. This material then gives all satisfaction.

En revanche, un certain nombre d'applications dentaires, dans lesquelles le matériau est visible de l'extérieur de la bouche, impose une condition esthétique, consistant à simuler au mieux la couleur de l'émail dentaire des autres dents de l'utilisateur. De ce point de vue, la zircone stabilisée à l'oxyde d'yttrium n'est pas directement utilisable car elle est  On the other hand, a certain number of dental applications, in which the material is visible from the outside of the mouth, imposes an aesthetic condition, consisting in simulating the color of the dental enamel of the other teeth of the user as well as possible. From this point of view, the zirconia stabilized with yttrium oxide is not directly usable because it is

naturellement blanche.naturally white.

Il faut rappeler ici que la couleur de l'émail des dents varie avec l'âge et avec les habitudes alimentaires et d'hygiène buccale (notamment pour les fumeurs), et une gamme de teintes dites dentaires a été définie, regroupant les  It should be remembered here that the color of the tooth enamel varies with age and with eating habits and oral hygiene (especially for smokers), and a range of so-called dental shades has been defined, grouping together

diverses teintes que peut prendre l'émail dentaire dans diverses conditions.  various shades that dental enamel can take under various conditions.

Plusieurs nuanciers ont ainsi été définis, mais dans leur ensemble ils couvrent sensiblement la même gamme de teinte, allant d'une teinte crème très claire proche du blanc jusqu'à une teinte ivoire foncé. Il existe en particulier un nuancier connu sous la désignation de "VITA " (Société VITA à Bad Sâckingen, Allemagne) qui comporte 16 nuances notées A1, A2, A3, A3,5, A4, B1 à B4, Cl à C4 et D2 à D4 (les nuances A2 et A3,5 sont classiques pour des patients de 25 à 40 ans, tandis que les nuances B2, C2, C3 et D3  Several color charts have thus been defined, but as a whole they cover substantially the same range of shade, going from a very light cream shade close to white to a dark ivory shade. There is in particular a color chart known under the designation of "VITA" (VITA company in Bad Sâckingen, Germany) which comprises 16 nuances noted A1, A2, A3, A3,5, A4, B1 to B4, Cl to C4 and D2 to D4 (shades A2 and A3.5 are standard for patients aged 25 to 40, while shades B2, C2, C3 and D3

correspondent plutôt à des patients plus âgés).  rather correspond to older patients).

Il est donc apparu utile de développer des compositions céramiques, essentiellement constituées de zircone stabilisée à l'oxyde d'yttrium, pouvant avoir une quelconque teinte voulue au sein de la gamme dentaire, mais ayant des propriétés mécaniques très proches de la zircone stabilisée à l'oxyde  It therefore appeared useful to develop ceramic compositions, essentially consisting of zirconia stabilized with yttrium oxide, which may have any desired shade within the dental range, but having mechanical properties very close to zirconia stabilized at l 'oxide

d'yttrium sensiblement pur.substantially pure yttrium.

C'est l'objet que s'est fixé l'invention.  This is the object of the invention.

Celle-ci propose à cet effet une composition céramique dentaire essentiellement constituée ò de zircone de microstructure tétragonale, stabilisée à l'oxyde d'yttrium, ò d'une charge colorante et À d'impuretés, cette charge colorante étant constituée, en pourcentage en poids, - de 0% à 1% d'oxyde de fer Fe203, - de 0% à 0,2% d'oxyde de bismuth Bi203 et  To this end, it offers a dental ceramic composition essentially consisting of ò of zirconia of tetragonal microstructure, stabilized with yttrium oxide, ò of a coloring charge and of impurities, this coloring charge being constituted, in percentage in weight, - from 0% to 1% of iron oxide Fe203, - from 0% to 0.2% of bismuth oxide Bi203 and

- de 0% à 5% d'oxyde de cérium CeO2.  - from 0% to 5% of cerium oxide CeO2.

De préférence la concentration en oxyde de fer est au plus égale à 0, 2%, voire même au plus égale à 0,1%; cette teneur est de préférence non nulle, au moins égale à 0,01%. Elle est avantageusement comprise entre  Preferably the concentration of iron oxide is at most equal to 0.2%, or even at most equal to 0.1%; this content is preferably not zero, at least equal to 0.01%. It is advantageously between

0,03% et 0,1%.0.03% and 0.1%.

De même la teneur en oxyde de bismuth est avantageusement non nulle, au moins égale à 0,01%; elle est de préférence comprise entre 0,05% et 0,2%. De manière similaire, la teneur en oxyde de cérium est avantageusement non nulle, au moins égale à 0,1%, de préférence au moins  Similarly, the content of bismuth oxide is advantageously not zero, at least equal to 0.01%; it is preferably between 0.05% and 0.2%. Similarly, the content of cerium oxide is advantageously not zero, at least equal to 0.1%, preferably at least

égale à 0,5%. Elle est de manière préférée au plus égale à 1%.  equal to 0.5%. It is preferably at most equal to 1%.

L'invention couvre également des prothèses dentaires ayant une composition céramique à base de zircone stabilisée à l'oxyde d'yttrium du type précité. En fait l'utilisation en soi de l'oxyde de fer, ou de l'oxyde de cérdum ou de l'oxyde de bismuth avait déjà été proposée comme agent colorant. A titre d'exemple, le document US - 5,387, 558 (GROSSMAN) indique que l'on peut colorer en jaune une vitro- céramique en utilisant en combinaison de l'oxyde de vanadium, de l'oxyde de cérium et de l'oxyde de terbium dans des  The invention also covers dental prostheses having a ceramic composition based on zirconia stabilized with yttrium oxide of the aforementioned type. In fact, the use per se of iron oxide, or cerum oxide or bismuth oxide had already been proposed as a coloring agent. For example, document US Pat. No. 5,387,558 (GROSSMAN) indicates that a ceramic glass can be colored in yellow by using in combination vanadium oxide, cerium oxide and terbium oxide in

concentrations respectives minimales comprises entre 0,05% et 0,1% en poids.  respective minimum concentrations between 0.05% and 0.1% by weight.

Par ailleurs le document US - 5,125,970 (KLEPACKI) rapporte que de très nombreux oxydes peuvent être utilisés (les oxydes de fer et de bismuth sont cités parmi une vingtaine d'oxydes possibles), par agglomération puis introduction dans une pâte de restauration dentaire (par exemple à la faveur de rainures), pour colorer de manière appropriée des prothèses dentaires. Quant aux documents US - 5,219,805 ou US - 5,263, 858 (HOYA Corp), ils divulguent des zircones stabilisées (à l'oxyde d'yttrium, de cérium, de calcium ou de magnésium) dont la teinte est dans les tons ivoire grâce à la présence, en  Furthermore, the document US Pat. No. 5,125,970 (KLEPACKI) reports that a very large number of oxides can be used (iron and bismuth oxides are cited from around twenty possible oxides), by agglomeration then introduction into a dental restoration paste (by example using grooves), to properly color dentures. As for documents US - 5,219,805 or US - 5,263, 858 (HOYA Corp), they disclose stabilized zirconia (with yttrium, cerium, calcium or magnesium oxide) whose color is in ivory tones thanks to the presence, in

combinaison, d'oxydes de praséodyme, de fer, et de zinc, voire d'erbium.  combination of praseodymium oxides, iron, and zinc, or even erbium.

Ainsi, s'il avait déjà été proposé divers types de colorants pour la zircone stabilisée à l'oxyde d'yttrium ou pour des matériaux de restauration dentaire, il n'avait pas été proposé de choisir exclusivement comme oxydes colorants l'oxyde de fer, l'oxyde de bismuth et l'oxyde de cérium, seuls ou en combinaison. Il faut préciser à ce propos que la connaissance de la fonction colorante d'un oxyde dans un matériau donné ne permet pas d'en déduire que cette fonction colorante sera obtenue dans un autre matériau, et ce sans dégradation des autres propriétés notamment mécaniques. En particulier il faut noter que le changement de matériau se traduit souvent pour les ions colorants un changement d'environnement cristallographique, ce qui laisse prévoir des changements d'effet. C'est ainsi par exemple qu'il a été constaté que l'utilisation comme agent colorant dans de la zircone stabilisée a l'oxyde d'yttrium de l'oxyde de vanadium donnait une coloration orange et conduisait à une microfissuration rédhibitoire, tandis que la présence d'oxyde de zinc induisait une transformation de phase cristalline, également inacceptable. L'oxyde d'erbium donnait une coloration rose, I'oxyde de manganèse donnait une coloration noire rédhibitoire et l'oxyde de praséodyme donnait une coloration  Thus, if various types of dyes had already been proposed for zirconia stabilized with yttrium oxide or for dental restorative materials, it had not been proposed to choose exclusively as coloring oxides iron oxide , bismuth oxide and cerium oxide, alone or in combination. It should be noted in this connection that knowledge of the coloring function of an oxide in a given material does not allow it to be deduced that this coloring function will be obtained in another material, and this without degradation of the other properties, in particular mechanical properties. In particular, it should be noted that the change in material often results in a change in the crystallographic environment for the coloring ions, which suggests changes in effect. Thus, for example, it has been found that the use as a coloring agent in zirconia stabilized with yttrium oxide of vanadium oxide gives an orange coloration and leads to an unacceptable inhibiting microcracking, while the presence of zinc oxide induced a crystal phase transformation, also unacceptable. Erbium oxide gave a pink color, manganese oxide gave an unacceptable black color and praseodymium oxide gave a color

jaune foncé.dark yellow.

Rien ne permettait donc de déduire de l'état de la technique qu'il était possible d'obtenir sensiblement toutes les teintes nécessaires pour des applications dentaires en utilisant l'un ou plusieurs de trois oxydes, à savoir  Nothing therefore made it possible to deduce from the state of the art that it was possible to obtain substantially all the shades necessary for dental applications by using one or more of three oxides, namely

I'oxyde de fer, I'oxyde de cérium et l'oxyde de bismuth.  Iron oxide, cerium oxide and bismuth oxide.

En pratique il est apparu que l'oxyde de fer donne une teinte d'autant plus foncée que sa concentration est importante, dans la limite toutefois de 1% environ (au-delà la teinte obtenue est trop foncée compte tenu de l'application considérée); il est même apparu suffisant de mettre au plus 0,2%, voire même  In practice it appeared that iron oxide gives a shade all the darker as its concentration is important, within the limit however of approximately 1% (beyond the shade obtained is too dark taking into account the application considered ); it even appeared sufficient to put at most 0.2%, or even

0,1% en poids.0.1% by weight.

L'oxyde de cérium ainsi que l'oxyde de bismuth sont apparus avoir pour effet d'éclaircir la teinte normalement donnée par l'oxyde de fer. A l'état isolé chacun de ces oxydes de cérium ou de bismuth est apparu donner à la zircone une teinte crème plus ou moins légère. L'effet colorant de l'oxyde de cérium est apparu moins marqué que celui de l'oxyde de bismuth; son usage permet donc une plus grande précision dans la teinte atteinte. En fait, pour distinguer les effets de ces deux oxydes, on peut dire que: - I'oxyde de cérium donne une teinte plutôt crème,  Cerium oxide as well as bismuth oxide have appeared to have the effect of lightening the color normally given by iron oxide. In the isolated state each of these cerium or bismuth oxides appeared to give the zirconia a more or less light creamy hue. The coloring effect of cerium oxide appeared less marked than that of bismuth oxide; its use therefore allows greater precision in the shade achieved. In fact, to distinguish the effects of these two oxides, we can say that: - cerium oxide gives a rather creamy shade,

- alors que l'oxyde de bismuth donne une coloration plutôt jaune.  - while the bismuth oxide gives a rather yellow coloring.

Le tableau I donne les caractéristiques de plusieurs échantillons  Table I gives the characteristics of several samples

essentiellement constitués de zircone stabilisée à l'oxyde d'yttrium.  essentially made of zirconia stabilized with yttrium oxide.

Les échantillons ont été préparés à partir d'une poudre de zircone sensiblement pure contenant 3% (en mole) d'oxyde d'yttrium; on y a ajouté des charges colorantes (les oxydes étant introduits sous forme de nitrates). La poudre de mélange a été homogénéisée en jarre et broyée dans de l'alcool éthylique (35 à 40 litres pour une masse de zircone de 20 Kg), puis séchée à l'évaporateur rotatif (avec récupération de l'alcool dans un bain à 50 C sous vide), autoclave pendant 12 heures à 110 C et tamisage à 100 jzm. Des liants de pressage ont été ajoutés, en tant que de besoin, pendant l'opération d'homogénéisation en jarre. La poudre séchée a ensuite été pressée en  The samples were prepared from a substantially pure zirconia powder containing 3% (by mole) of yttrium oxide; coloring charges were added (the oxides being introduced in the form of nitrates). The mixing powder was homogenized in a jar and ground in ethyl alcohol (35 to 40 liters for a mass of zirconia of 20 Kg), then dried on a rotary evaporator (with recovery of the alcohol in a 50 C under vacuum), autoclave for 12 hours at 110 C and sieving at 100 dm. Press binders were added, as needed, during the jar homogenization operation. The dried powder was then pressed in

pastilles puis frittée sous air à 1500 C pendant environ 3 heures.  pellets then sintered in air at 1500 C for about 3 hours.

La couleur des échantillons a été observée sur une face préalablement polie de ceux-ci et comparée au nuancier VITA précité. La stabilité des céramiques a été vérifiée par diffraction aux rayons X avant et après maintien en autoclave à 134 C sous 2 bars pendant 5 heures (conditions censées simuler le vieillissement dans la bouche (salive à 37 C) pendant environ 20 années). La microstructure a été observée et la taille de grains a été mesurée au microscope électronique à balayage (" SEM ") sur des facettes  The color of the samples was observed on a previously polished face of these and compared with the aforementioned VITA color chart. The stability of the ceramics was checked by X-ray diffraction before and after autoclaving at 134 C at 2 bars for 5 hours (conditions supposed to simulate aging in the mouth (saliva at 37 C) for about 20 years). The microstructure was observed and the grain size was measured with a scanning electron microscope ("SEM") on facets

polies puis attaquées thermiquement.  polished then heat attacked.

Le tableau I donne pour chaque échantillon le nom (arbitraire) de celui-ci, les concentrations en chacun des oxydes de fer, de cérium et de bismuth, la couleur (en termes qualitatifs), la nuance selon l'échelle de VITA, la taille de grains en microns, le pourcentage de microstructure monoclinique constaté sur la facette polie considérée, avant autoclave (donc a l'état poli) et  Table I gives for each sample the (arbitrary) name of it, the concentrations in each of the oxides of iron, cerium and bismuth, the color (in qualitative terms), the shade according to the VITA scale, the grain size in microns, the percentage of monoclinic microstructure found on the polished facet considered, before autoclave (therefore in the polished state) and

après autoclave.after autoclave.

Il peut tout d'abord être constaté que tous les échantillons ont sensiblement la même taille de grains (à peu près égale à celle de la zircone stabilisée sans colorant - voir échantillon P00), et des proportions de microstructure monoclinique avant et après autoclave sensiblement égales. On peut en déduire que l'usage des oxydes choisis ne change pas de façon significative les propriétés physico-chimiques des zircones stabilisées à l'oxyde d'yttrium. En ce qui concerne les effets colorants, on peut notamment faire les observations suivantes: * I'oxyde de fer donne une teinte brunâtre qui est atténuée lorsque l'un et/ou l'autre des oxydes de cérium et de bismuth est présent (voir les échantillons P10, P17 et P18), * en addition à de l'oxyde de fer l'oxyde de bismuth a un effet atténuateur environ 10 fois plus marqué que l'oxyde de cérium (voir les échantillons précités), * à l'état isolé l'oxyde de cérium (1 %) donne une teinte crème un peu plus légère que l'oxyde de bismuth (0,1%), et l'addition d'1% d'oxyde de cérium à 0,1% d'oxyde de bismuth est sensiblement sans effet, * la combinaison des trois oxydes permet d'obtenir des tons très  It can first of all be observed that all the samples have substantially the same grain size (approximately equal to that of the stabilized zirconia without dye - see sample P00), and proportions of monoclinic microstructure before and after autoclave substantially equal. . It can be deduced therefrom that the use of the chosen oxides does not significantly change the physicochemical properties of the zirconia stabilized with yttrium oxide. With regard to the coloring effects, the following observations can be made in particular: * iron oxide gives a brownish tint which is attenuated when one and / or the other of the cerium and bismuth oxides is present (see samples P10, P17 and P18), * in addition to iron oxide bismuth oxide has an attenuating effect approximately 10 times more marked than cerium oxide (see the aforementioned samples), * to the isolated state cerium oxide (1%) gives a slightly lighter cream shade than bismuth oxide (0.1%), and the addition of 1% cerium oxide to 0.1% of bismuth oxide is substantially without effect, * the combination of the three oxides makes it possible to obtain very

voisins dans la gamme allant des teintes crème jusqu'au brun léger.  neighbors in the range from cream to light brown.

On peut en outre noter que les mots ne suffisent pas toujours pour distinguer certaines nuances très proches, ce qui explique que des expressions qualitatives identiques apparaissent en regard de nuances différentes selon  It can also be noted that the words are not always sufficient to distinguish certain very close nuances, which explains why identical qualitative expressions appear opposite different nuances according to

l'échelle de VITA.the VITA scale.

échan- teneur teneur teneur couleur nuance taille de microstr. microstr.  sample content content color content grade microstr. microstr.

-tillon en en CeO2 en VITA grains monocl. monocl.  -complete in CeO2 in VITA single grain. monocl.

Fe203 Bi203 avant après autoclave autoclave P00 - blanc - 0,50 0,0 2,5 P10 0,1 brunâtre A4 0,48 0,0 2,4 Pli 0,1 crème A2 0,50 0,0 3,1 P14 1 crème B1 0,47 0,0 1,8 _______, 1 léger P16 1 0,1 crème A2 0,48 0,0 3,0 P17 0,1 0,1 crème A3,5 0,48 0,0 2,6 foncé P18 0,1 1 crème B3 0,49 0,0 2,2 foncé P19 0,05 - 0,1 brun C2 0,49 0,7 3,7 _ _ _ _ __i_ _ _ _ _ _ léger P20 0,05 1 crème B3 0,48 0,3 3,5 foncé P21 0,05 01 0,1 brun C3 0,52 0,0 1,9 léger P31 0, 03 0,5 0,1 crème B2 0,48 0,0 2,3 P32 0,03 0,5 - crème B2 0,41 0,1 2,1 P33 0,03 0,5 0,05 crème B2 0,47 0,1 2,4 P34 0,03 0,5 0,2 crème B1 0,44 0,1 2,4 Tableau I Echantillons de zircones colorées  Fe203 Bi203 before after autoclave autoclave P00 - white - 0.50 0.0 2.5 P10 0.1 brownish A4 0.48 0.0 2.4 Fold 0.1 cream A2 0.50 0.0 3.1 P14 1 cream B1 0.47 0.0 1.8 _______, 1 light P16 1 0.1 cream A2 0.48 0.0 3.0 P17 0.1 0.1 cream A3.5 0.48 0.0 2 , 6 dark P18 0.1 1 cream B3 0.49 0.0 2.2 dark P19 0.05 - 0.1 brown C2 0.49 0.7 3.7 _ _ _ _ __i_ _ _ _ _ _ light P20 0.05 1 cream B3 0.48 0.3 3.5 dark P21 0.05 01 0.1 brown C3 0.52 0.0 1.9 light P31 0, 03 0.5 0.1 cream B2 0 , 48 0.0 2.3 P32 0.03 0.5 - cream B2 0.41 0.1 2.1 P33 0.03 0.5 0.05 cream B2 0.47 0.1 2.4 P34 0 , 03 0.5 0.2 cream B1 0.44 0.1 2.4 Table I Colored zirconia samples

Claims (22)

REVENDICATIONS 1. Composition céramique dentaire essentiellement constituée de zircone de microstructure tétragonale, stabilisée à l'oxyde d'yttrium, À d'une charge colorante et d'impuretés, cette charge colorante étant constituée, en pourcentage en poids, de 0% à 1% d'oxyde de fer, de 0% à 0,2% d'oxyde de bismuth et  1. Dental ceramic composition essentially consisting of zirconia of tetragonal microstructure, stabilized with yttrium oxide, with a coloring charge and of impurities, this coloring charge being constituted, in percentage by weight, from 0% to 1% iron oxide, 0% to 0.2% bismuth oxide and de 0% à 5% d'oxyde de cérium.from 0% to 5% of cerium oxide. 2. Composition selon la revendication 1, caractérisée en ce que la  2. Composition according to claim 1, characterized in that the concentration en oxyde de fer est au plus égale à 0,2%.  iron oxide concentration is at most equal to 0.2%. 3.Composition selon la revendication 1 ou la revendication 2, caractérisée en ce que la concentration en oxyde de fer est au plus égale à 0,1%.  3. Composition according to claim 1 or claim 2, characterized in that the concentration of iron oxide is at most equal to 0.1%. 4. Composition selon l'une quelconque des revendications 1 à 3,  4. Composition according to any one of claims 1 to 3, caractérisée en ce que la teneur en oxyde de fer est au moins égale à 0, 01%.  characterized in that the iron oxide content is at least 0.01%. 5. Composition selon la revendication 4, caractérisée en ce que la  5. Composition according to claim 4, characterized in that the teneur en fer est comprise entre 0,03% et 0,1%.  iron content is between 0.03% and 0.1%. 6. Composition selon la revendication 4 ou la revendication 5, caractérisée en ce que la teneur en oxyde de bismuth est au moins égale à  6. Composition according to claim 4 or claim 5, characterized in that the content of bismuth oxide is at least equal to 0,01%.0.01%. 7. Composition selon la revendication 6, caractérisée en ce que la  7. Composition according to claim 6, characterized in that the teneur en oxyde de bismuth est comprise entre 0,05% et 0,2%.  bismuth oxide content is between 0.05% and 0.2%. 8. Composition selon la revendication 6 ou la revendication 7, caractérisée en ce que la teneur en oxyde de cérium est au moins égale à 0,1%.  8. Composition according to claim 6 or claim 7, characterized in that the content of cerium oxide is at least equal to 0.1%. 9. Composition selon la revendication 8, caractérisée en ce que la9. Composition according to claim 8, characterized in that the teneur en oxyde de cérium est au moins égale à 0,5%.  cerium oxide content is at least 0.5%. 10. Composition selon la revendication 8 ou la revendication 9,  10. Composition according to claim 8 or claim 9, caractérisée en ce que la teneur en oxyde de cérium est au plus égale à 1%.  characterized in that the content of cerium oxide is at most equal to 1%. 11. Composition selon la revendication 4 ou la revendication 5, caractérisée en ce que la teneur en oxyde de cérium est au moins égale à 0,1%.  11. Composition according to claim 4 or claim 5, characterized in that the content of cerium oxide is at least equal to 0.1%. 12. Composition selon la revendication 11, caractérisée en ce que la teneur en oxyde de cérium est au moins égale à 0,5%.12. Composition according to claim 11, characterized in that the content of cerium oxide is at least equal to 0.5%. 13. Composition selon la revendication 11 ou la revendication 12,13. Composition according to claim 11 or claim 12, caractérisée en ce que la teneur en oxyde de cérium est au plus égale à 1%.  characterized in that the content of cerium oxide is at most equal to 1%. 14. Composition selon la revendication 1, caractérisée en ce que la  14. Composition according to claim 1, characterized in that the teneur en oxyde de bismuth est au moins égale à 0,01%.  bismuth oxide content is at least 0.01%. 15. Composition selon la revendication 14, caractérisée en ce que la  15. Composition according to claim 14, characterized in that the teneur en oxyde de bismuth est comprise entre 0,05% et 0,2%.  bismuth oxide content is between 0.05% and 0.2%. 16. Composition selon la revendication 14 ou la revendication 15, caractérisée en ce que la teneur en oxyde de cérium est au moins égale à 0,1%.  16. Composition according to claim 14 or claim 15, characterized in that the content of cerium oxide is at least equal to 0.1%. 17. Composition selon la revendication 16, caractérisée en ce que la17. Composition according to claim 16, characterized in that the teneur en oxyde de cérium est au moins égale à 0,5%.  cerium oxide content is at least 0.5%. 18. Composition selon la revendication 16 ou la revendication 17,  18. Composition according to claim 16 or claim 17, caractérisée en ce que la teneur en oxyde de cérium est au plus égale à 1%.  characterized in that the content of cerium oxide is at most equal to 1%. 19. Composition selon la revendication 1, caractérisée en ce que la  19. Composition according to claim 1, characterized in that the teneur en oxyde de cérium est au moins égale à 0,1%.  cerium oxide content is at least 0.1%. 20. Composition selon la revendication 19, caractérisée en ce que la  20. Composition according to claim 19, characterized in that the teneur en oxyde de cérium est au moins égale à 0,5%.  cerium oxide content is at least 0.5%. 21. Composition selon la revendication 19 ou la revendication 20,  21. Composition according to claim 19 or claim 20, caractérisée en ce que la teneur en oxyde de cérium est au plus égale à 1%.  characterized in that the content of cerium oxide is at most equal to 1%. 22. Prothèse dentaire ayant une composition selon l'une quelconque  22. Dental prosthesis having a composition according to any one des revendications 1 à 21.of claims 1 to 21.
FR9809402A 1998-07-23 1998-07-23 COLORED CERAMIC COMPOSITION BASED ON STABILIZED ZIRCONIA FOR DENTAL APPLICATIONS Expired - Fee Related FR2781366B1 (en)

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