# US 10,441,391 B2 · Method to manufacture a colored blank, and blank

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- Number: US 10,441,391 B2
- Document ID: US10441391B2
- Status: Granted
- Kind: B2
- Application number: 15/464,316
- Filed: 2017-03-20
- Published: 2017-09-28
- Granted: 2019-10-15
- Earliest claimed: 2016-03-23
- Assignees: DENTSPLY SIRONA Inc.
- Applicants: DENTSPLY SIRONA Inc.
- Inventors: Lothar Volkl; Stefan Fecher; Martin Kutzner; Tanja Oefner
- Web page: https://patentgrep.com/patent/US10441391B2

## CPC

- A61C 13/0022: {Blanks or green, unfinished dental restoration parts}
- A61C 13/082: {Cosmetic aspects, e.g. inlays; Determination of the colour (A61C19/10 takes precedence)}
- A61C 13/083: Porcelain or ceramic teeth {(A61C13/081 takes precedence; preparations A61K6/80)}
- A61C 13/09: {Composite teeth, e.g. front and back section (A61C13/0835, A61C13/1023 take precedence)}; Multilayer teeth
- A61K 6/15: Compositions characterised by their physical properties
- A61K 6/78: Pigments
- A61K 6/818: comprising zirconium oxide
- A61K 6/822: comprising rare earth metal oxides
- A61K 6/824: comprising transition metal oxides
- A61K 6/84: comprising metals or alloys
- B32B 18/00: Layered products essentially comprising ceramics, e.g. refractory products
- C04B 35/48: based on zirconium or hafnium oxides, zirconates, {zircon} or hafnates
- C04B 35/486: Fine ceramics
- C04B 2235/3224: Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B 2235/3225: Yttrium oxide or oxide-forming salts thereof
- C04B 2235/3244: Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
- C04B 2235/3275: Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
- C04B 2235/40: Metallic constituents or additives not added as binding phase
- C04B 2235/608: Green bodies or pre-forms with well-defined density
- C04B 2235/612: Machining
- C04B 2235/72: Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
- C04B 2235/728: Silicon content
- C04B 2235/75: Products with a concentration gradient
- C04B 2235/945: Products containing grooves, cuts, recesses or protusions
- C04B 2235/96: Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B 2235/9607: Thermal properties, e.g. thermal expansion coefficient
- C04B 2235/9646: Optical properties
- C04B 2235/9653: Translucent or transparent ceramics other than alumina
- C04B 2235/9661: Colour
- C04B 2237/348: Zirconia, hafnia, zirconates or hafnates
- A61C: DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE (non-driven toothbrushes A46B; {tongue scrapers A61B17/24;} preparations for dentistry A61K6/00; preparations for cleaning the teeth or mouth A61K8/00, A61Q11/00)
- A61K: PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES (devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms A61J3/00; chemical aspects of, or use of materials for deodorisation of air, for disinfection or sterilisation, or for bandages, dressings, absorbent pads or surgical articles A61L; soap compositions C11D)
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE

## Abstract

The invention relates to a method for manufacturing a colored blank, which contains zirconium dioxide and is intended for the manufacture of a dental restoration, whereby raw materials in powder form, at least some of which contain one coloring substance each, are mixed with, zirconium dioxide as the main ingredient, the resulting mixture is pressed and subsequently subjected to at least one thermal treatment. To generate the desired fluorescence, it is intended that in the raw materials in powder form one uses as coloring substances at least terbium, erbium, cobalt, as well as one substance that generates a fluorescence effect in the dental restoration, however not iron, aside from naturally occurring impurities.

## Claims

### Claim 1

A method for manufacturing a colored blank comprising zirconium dioxide that is intended for the production of a dental restoration, the method comprising the steps of:
introducing into a mold a layer of a first ceramic material, which includes at least one coloring element, with zirconium dioxide as the main constitute to form a first mixture, wherein a first open cavity is formed in the layer;
introducing at least into the first open cavity a second ceramic material define a second layer, which includes a second mixture with a composition that is different from that of the first mixture;
pressing the first mixture and the second mixture, and subsequently subject the pressed first and second mixtures to at least one thermal treatment,
wherein the at least one coloring element in the raw materials in powder form is selected from the group consisting of terbium, erbium, cobalt, one element that generates a fluorescent effect in the dental restoration, and mixtures thereof,
wherein iron, apart from natural impurities, is not present.

### Claim 2 (depends on 1)

The method of claim 1, wherein bismuth is used as the element that generates the fluorescent effect.

### Claim 3 (depends on 1)

The method of claim 1, wherein disregarding naturally occurring impurities, the raw materials include at least one of the following:
a first raw material in powder form that includes bismuth as the element that generates the fluorescent effect;
a second raw material in powder form that includes exclusively terbium, or terbium and praseodymium;
a third raw material in powder form that includes exclusively erbium;
a fourth raw material in powder form that includes exclusively cobalt, or cobalt and manganese, and/or cerium; and
combination thereof.

### Claim 4 (depends on 1)

The method of claim 1, wherein one of the raw materials in powder form is free of coloring elements, apart from natural impurities.

### Claim 5 (depends on 1)

The method of claim 1, wherein raw materials in powder form includes yttrium-stabilized zirconium dioxide of the following composition:
HfO2<3.0% by wt;
Al2O3<0.3% by wt;
Unavoidable impurities due to technical limitations ≤0.2% by wt;
Y2O3 4.5 to 9.5% by wt;
ZrO2=100%−(Y2O3+Al2O3+HfO2+unavoidable impurities) % by wt.

### Claim 6 (depends on 1)

The method of claim 1, wherein after introduction of the second ceramic material, a second open cavity is created in the mold.

### Claim 7 (depends on 6)

The method of claim 6, wherein into the second open cavity is filled a third ceramic material, which possesses a composition that is different from those of the first and/or second ceramic material.

### Claim 8 (depends on 1)

The method of claim 1, wherein in the layer formed of the first ceramic material are formed several first open cavities and into these is filled the second ceramic material.

### Claim 9 (depends on 8)

The method of claim 8, wherein at least some of the several open first cavities possess differing inside geometries.

### Claim 10 (depends on 1)

The method of claim 1, wherein after sintering to full density, the second ceramic material possesses a thermal expansion coefficient that is 0.2 to 0.8 μm/m*K greater than that of the first ceramic material.

### Claim 11 (depends on 1)

The method of claim 1, wherein the interior geometry of the first open cavity is geometrically matched to the shape of a dental jaw region that is to be provided with a restoration or to that of an abutment originating from a jaw region.

### Claim 12 (depends on 1)

The method of claim 1, wherein when working the dental restoration out of the blank, a dentine region of the dental restoration is at least partially composed of the second ceramic material and an incisal region of the first ceramic material.

### Claim 13 (depends on 1)

The method of claim 1, wherein the yttrium oxide content in the first ceramic material is 7.0% by weight to 9.5% by weight; and/or the yttrium content in the second and/or third ceramic material is 4.5% by weight to 7.0% by weight, whereby the yttrium oxide content in the first ceramic material is higher than that of the second or third material.

### Claim 14 (depends on 1)

The method of claim 1, wherein in the first ceramic material or the second ceramic material, the quotient of the tetragonal crystal phase and the cubic crystal phase of the zirconium dioxide after pre-sintering is ≥1.

### Claim 15 (depends on 1)

A method for the manufacture of a blank of a ceramic material, whereby at least two layers are introduced by filling into a mold ceramic material, which includes mixtures that were created in accordance with claim 1 and possess different compositions, and that after introduction of the layers, these are pressed and subsequently sintered, after introduction of a first layer comprising of a first mixture, the surface of this layer is structured in such a way that the surface of the first layer, viewed along the surface, possesses regions of different heights, and subsequently a second layer comprising of a mixture with a composition different from that of the first mixture is filled into the mold, or in that after introduction of the first layer, a further layer is filled on top of it into the mold, which includes of a mixture that is different from that of the first layer, in that the material of the first layer is intermixed with the material of the further layers to form an intermediate layer, and that subsequently the second layer is filled into the mold.

### Claim 16 (depends on 15)

The method of claim 15, wherein the surface of the first layer is being structured in a way so that depressions and elevations are created whereby the latter confine the former.

### Claim 17 (depends on 15)

The method of claim 15, wherein in a top view of the surface the created structure has an annular pattern, which comprises the depressions and the elevations bordering them.

### Claim 18 (depends on 1)

The method of claim 1, wherein a structure is created by an element, which moves-relative to the first layer, and which structures a surface region of the first layer with a segment that is embodied with a wave-like, comb-like or serrated shape.

### Claim 19 (depends on 18)

The method of claim 18, wherein the structure is created by a pressure element that acts along a direction perpendicular to the surface region of the first layer.

### Claim 20 (depends on 19)

The method of claim 19, wherein the pressure element imprints into the surface region of the first layer elevations that extend concentrically or in parallel, and depressions extending in between the elevations.

### Claim 21 (depends on 15)

The method of claim 15, wherein the structure is formed in such a way that the volume of the elevations is equal or approximately equal to the volume of the depressions.

### Claim 22 (depends on 15)

The method of claim 15, wherein the material of the mixture of the additional layer is intermixed with the material of the mixture of the first layer downward from the free surface of the additional layer along a height that corresponds to twice or approximately twice the height of the additional layer.

### Claim 23 (depends on 22)

The method of claim 22, wherein the mixture used for the additional layer is identical to that of the second layer.

### Claim 24 (depends on 1)

The method of claim 1, wherein that contacting regions of the first layer and the second layer are mixed over a height that corresponds to ⅕ H to ¼ H, where H is the total height H of the first and second layer.

### Claim 25 (depends on 1)

The method of claim 1, wherein that the first layer in an unstructured state possesses a height that corresponds to half or approximately half the height of the total height H of the first and second layer.

### Claim 26 (depends on 1)

The method of claim 1, wherein the first and second ceramic mixtures used for the first layer and the second layer are such that the quotient of the tetragonal crystal phase to the cubic crystal phase of the zirconium dioxide in both the first layer and the second layer will be ≥1 after pre-sintering.

### Claim 27 (depends on 1)

A pre-sintered or fully sintered blank that is manufactured in accordance with claim 1.

### Claim 28 (depends on 1)

A pre-sintered or fully sintered blank to be used in the manufacture of a dental restoration, comprising a ceramic material that includes zirconium dioxide, and possesses regions of different compositions, whereby a first region includes a first ceramic material and at least a second region includes a second ceramic material of a different composition, and the regions adjoin each other, whereby in particular the first ceramic material and/or the second ceramic material include of a mixture according to claim 1, wherein the second region extends within the first region and possesses an outside geometry that narrows as the distance from a base region or base surface increases.

### Claim 29 (depends on 28)

The blank of claim 28, wherein the base region extends in the area of an outer surface of the first region, and merges flush with the outer surface.

### Claim 30 (depends on 28)

The blank of claim 28, wherein that the second region has a cavity that originates from its base region.

### Claim 31 (depends on 28)

The blank of claim 28, wherein the second region possesses a cone-like exterior geometry.

### Claim 32 (depends on 28)

The blank of claim 28, wherein within the second region extends a third region, which includes of a third ceramic material with a composition that is different from that of the first and/or second ceramic material.

### Claim 33 (depends on 28)

The blank of claim 28, wherein a first region includes a plurality of layers, the plurality of layers each differing by composition.

### Claim 34 (depends on 28)

The blank of claim 28, wherein at least a few of the plurality of layers have differing exterior geometries.

### Claim 35 (depends on 28)

The blank of claim 28, wherein the blank includes zirconium dioxide doped with yttrium oxide.

### Claim 36 (depends on 28)

The blank of claim 28, wherein the yttrium oxide content in the second ceramic material or the third ceramic material is between 4.5% by weight and 7.0% by weight, while the yttrium oxide content is between 7.0% by weight and 9.5% by weight in the first ceramic material, whereby the yttrium oxide content in the first ceramic material is greater than in the second ceramic material.

### Claim 37 (depends on 28)

The blank of claim 28, wherein the second ceramic material is colored differently from the first ceramic material.

### Claim 38 (depends on 28)

The blank of claim 28, wherein the amount of the element generating the fluorescent effect in the first ceramic material is different from that in the second ceramic material.

### Claim 39 (depends on 28)

The blank of claim 28, wherein after sintering to full density, the dental restoration produced from the blank possesses a higher strength on a dentine side than on an incisal side and/or a higher translucency on the incisal side than on the dentine side and/or in the dentine region a higher content of the element generating the fluorescence effect than in the incisal region.

### Claim 40 (depends on 28)

The blank of claim 28, wherein a thermal expansion coefficient of the first region is 0.2 μm/m*K to 0.8 μm/m*K lower than a thermal expansion coefficient of the second and/or third region.

### Claim 41 (depends on 28)

The blank of claim 28, wherein the blank comprises at least three layers, one of which is a middle layer, which extends over at least 1/10 H to ⅕ H of the total height H of the blank, and which includes a material of the first layer and the second layer.

### Claim 42 (depends on 41)

The blank of claim 41, wherein in the middle layer the fraction of the material of the first layer decreases along the direction from the first layer towards the second layer in a continuous or largely continuous manner.

### Claim 43 (depends on 41)

The blank of claim 41, wherein the yttrium oxide content in the middle layer increases from the first layer towards the second layer in a continuous or largely continuous manner.

### Claim 44 (depends on 41)

The blank of claim 41, wherein the first layer is colored differently than the second layer and/or includes different amounts of the element generating the fluorescent effect.

### Claim 45 (depends on 41)

The blank of claim 41, wherein after the sintering to completeness of the blank, the dental restoration produced from the former exhibits, viewed along the tooth axis, a higher rigidity on the root side than on the incisal side and/or exhibits a higher translucency on the incisal side than on the root side.

### Claim 46 (depends on 1)

A dental restoration, manufactured in accordance with claim 1, wherein the dental restoration is embodied monolithically and includes at least of a first layer, which includes of a first ceramic material and extends on the incisal side, and a second layer, which includes of a second ceramic material and extends on the dentine side, whereby the first layer possesses a higher translucency and/or lower rigidity and/or a lower degree of fluorescence than the second layer.

### Claim 47 (depends on 46)

The dental restoration of claim 46, wherein a thermal expansion coefficient of the first layer is 0.2 μm/m*K to 0.8 μm/m*K lower than a thermal expansion coefficient of the second layer.

### Claim 48 (depends on 28)

A dental restoration, produced from a blank of claim 28, wherein the dental restoration, viewed along the axial direction of the tooth, includes of at least a first layer extending on the root side, a second layer extending on the incisal side, and, extending in between these, a middle layer or intermediate layer, in which the strength decreases from the first layer towards the second layer in a continuous or largely continuous manner and/or in which the translucency increases continuously or largely continuously and/or in which the fluorescence characteristic decreases.