Image writing on ceramics

Abstract: The present invention relates to writing and marking images on ceramic surfaces in a reversible fashion. The images are marked using a laser. The images are erased by heating the ceramic surfaces to a temperature of approximately 200°C or using a CO 2 laser. The ceramic has a surface with a first contrast and consists essentially of zirconia and a dopant selected from the group of rare earth oxides and oxides of calcium, magnesium, yttrium, scandium and cerium wherein the ceramic has a molar ratio of dopant to zirconia of from about 0.5:99.5 to about 25:75, the ceramic having an essentially crystal phase grain, wherein the surface is imaged by focusing a laser beam having a diameter of 5 µm or greater on the surface for a time sufficient to change the first contrast by reducing the doped zirconia to produce an image.

Description: Field of the Invention The present invention relates to writing, marking or decorating ceramic surfaces in a reversible fashion using lasers. These writings, markings, images and imprintings are due to the photo-assisted reduction of oxide ceramics and their erasure is due to thermal assisted reoxidation. Background of the Invention Writing or decorating ceramic surfaces, particularly on zirconia ceramics or oxide ceramics is not easy due to complexities of thermal glazing processes. In such thermal glazing processes, finer details of an image are not normally reproduced on ceramic surfaces. Writing on glass can be accomplished through acid (hydrofluoric) etching. Ceramics are typically decorated through screen printing or hand painting of various features. China and coffee mugs are examples of these technologies. The features imprinted on these objects are then fired at high temperatures to make them permanent and this process is called enameling. There exists a need for reversibly transferring images onto ceramic surfaces. The present invention is not only capable of finer writing or decorating on the surface of the ceramics, it is also compatible with digital transfer of electronically captured images. The digitally captured images can be imprinted on the ceramic surfaces through use of laser systems. The reversible nature of this image transfer process is one of the most important features of the invention. The erasure of the laser written images can be accomplished in a simple and cost effective manner. Brief Description of the Drawing Figure 1 shows an enlarged photograph of a laser written zirconia ceramic.. Figure 2 shows an enlarged photograph of a laser written zirconia ceramic. For a better understanding of the present invention, together with other advantages and capabilities thereof, reference is made to the following detailed description and appended claims in connection with the preceding drawings and description of some aspects of the invention. Summary of the Invention The present invention is a method of reversibly transferring images to a ceramic surface. It includes providing a ceramic having a surface, having an image due to a color difference, the ceramic consisting essentially of zirconium oxide (zirconia) and a dopant selected from the group of rare earth oxides and oxides of calcium, magnesium, yttrium, scandium and cerium wherein the ceramic has a molar ratio of dopant to zirconium oxide of from about 0.5:99.5 to about 25:75, depending on the dopant species. For yttria (yttrium oxide) as the dopant, the preferred molar range of yttria to zirconia is from about 0.5:99.5 to about 5.0:95.0. The crystal grain structure of the zirconia doped ceramic is essentially tetragonal in nature. A laser beam is focused on the ceramic surface, the laser beam having a diameter of 5 µm or greater, for a time sufficient to change the color difference of the surface by reducing the doped zirconia and produce an image. The method of the present invention is reversible in that the image can subsequently be erased. The present invention also includes an image element comprising a ceramic surface having a first color difference, the ceramic surface consisting essentially of tetragonal zirconia and a dopant selected from the group of rare earth oxides and oxides of calcium, magnesium, yttrium, scandium and cerium wherein the ceramic has a molar ratio of dopant to zirconia of from about 0.5:99.5 to about 25:75, depending on the dopant species, the ceramic having an essentially crystal phase grain. For yttria as the dopant, the preferred molar range of yttria to zirconia is from about 0.5:99.5 to about 5.0:95.0. The crystal structure of the zirconia doped ceramic is essentially tetragonal in nature. The surface is imaged by focusing a laser beam having a diameter 5 µm or greater on the surface for a time sufficient to change the first color difference by reducing the doped zirconia to produce an image. The image on the surface can be erased either through thermal heating or through CO 2 laser-assisted heating. In the present invention, the image quality that can be produced on the ceramic surface is of a much finer quality because grain size of the writing media can be made very small. In addition, the images can be electronically captured and digitally transferred to the media through lasers and the spot size of the lasers can be varied using appropriate optics. Other important advantages of this invention include faster image transference, image erasure, elimination of pretreatments and posttreatments such as thermal treatments of the written surfaces, and no use of chemicals or corrosive acids. Description of the Preferred Embodiments The present invention is a method of reversibly transferring images to a ceramic surface and the resulting imaged ceramic article. The present invention includes the following features: the process to transfer the image is fast; the resolution of the final image is high; the process is easy to perform; the process is applicable to images that are electronically captured and digitally stored; and finally, the process is reversible in that the images can be erased from the ceramic surfaces either by low temperature (≈200°C) thermal oxidation or by laser assisted thermal oxidation. In the present invention the surface chosen for imaging is a zirconia doped ceramic wherein the zirconia is doped with a secondary oxide selected from the group of rare earth oxides and oxides of calcium, magnesium, yttrium, scandium and cerium wherein the ceramic has a molar ratio of dopant to zirconia of from about 0.5:99.5 to about 25:75, depending on the dopant species. Most preferably, the secondary oxide is yttria. For yttria as the dopant, the preferred molar range of yttria to zirconia is from about 0.5:99.5 to about 5.0:95.0. The crystal structure of the zirconia doped ceramic is essentially tetragonal in nature. The zirconia surfaces used in the present invention were either thermally or mechanically polished, or used as sintered. It is believed that resolution of laser written images on zirconia surfaces depends not only on the size of the laser spot but on the density and grain size of the zirconia being used. In U.S. Patents 5,290,332; 5,336,282 and 5,358,913 methods for manufacturing zirconia articles having very high densities (6.03 to 6.06 grams/ml) using very fine (0.1 to 0.6 µm grain size, average size being 0.3 µm) zirconia alloy powders are disclosed. These ceramics are ideal candidates for transferring images onto their polished or as sintered surfaces. The laser used for transferring the image onto the zirconia surfaces was a Nd:YAG laser, Q-switched, optically pumped with a krypton arc lamp. The wavelength of such a laser is approximately 1.06 X 10 -6 meters or 1.06 µm. The spot size or beam diameter of such a laser is approximately 100 µm in TEM∞ (low order mode). The spot size can be increased to 300 µm in MM (multimode) using a 163 mm focusing lens. The beam diameters of such lasers can be made as small as 5 µm by using appropriate lenses. However, it should be kept in mind that laser spot size is a function of the laser-material interaction. The laser spot size depends on the laser wavelength and the lens optics. Thus, the ultimate dot density is determined by the laser and ceramic. The focusing of the laser beam is determined by a digitized image converted to an appropriate dot density. The following parameters were used in the writing and image transfer of a laser onto a sintered ceramic surface of zirconia: Laser Power CW average - 2 to 40 watts Peak Power - 50 W to 5 kW (Q-switched) Pulse Rate Up to 50 kHz Pulse Width 100 to 150 ns Scan Field 114.3 x 114.3 mm Scan Velocity Up to 3 meters/second Repeatability: ± 25 µm The laser photo marking procedure used in the present invention is described below: The marking system accepts only vector coordinate instructions and these instructions are fed into the system in the form of a plot file. The plot files are loaded directly into the scanner driver electronics. The electronically stored photographic images are converted to a vector format using a number of commercially available software packages (e.g., Corel Draw, Envision-It by Envision Solutions Technology, CA). In the working example of this invention the images were captured electronically with a digital flat bed scanner or a Kodak photo CD. The captured images were converted to the appropriate dot density of approximately 600 dots/inch (240 dots/cm). These images were then reduced to two colors by dithering to half tones. A raster to vector conversion operation was then executed on the half toned images. The converted vector files in the form of plot files were saved and were laser scanned onto the ceramic surfaces. Typical examples of laser written, imprinted features on zirconia surfaces are shown in Figures 1 and 2. These Figures have been enlarged and the scale is shown for clarity. The laser written images can easily be erased from the zirconia surfaces by either heating the surfaces in air to around 200°C for about 10 minutes or by treating with a CO 2 laser operating with the following parameters: Wave Length 10.6 µm Peak Power 300 watts - operated at 20% duty cycle Average Power 70 watts Beam Size 500 µm and the beam width was pulse modulated The yttria doped-zirconia ceramic surfaces used in the present invention are an off-white color. The laser writing reduces the ceramic oxide and changes the off-white surface to black. This change in color difference from white to black produces the image. It is believed that dot densities of 1250 dots/inch (500 dots/cm) are possible with the present invention. While there has been shown and described what are at present considered to be the preferred embodiments of the invention, it will be obvious to those skilled in the art that various changes and modifications can be made herein without departing from the scope of the invention as defined by the appended claims.

Claims: A method of reversibly transferring images to a ceramic surface comprising: providing a ceramic having an image due to a color difference, the ceramic consisting essentially of zirconia and a dopant selected from the group consisting of rare earth oxides and oxides of calcium, magnesium, yttrium, scandium and cerium wherein the ceramic has a molar ratio of dopant to zirconia of from about 0.5:99.5 to about 25:75, the ceramic having an essentially tetragonal crystal grain; and focusing a laser beam having a diameter of 5 µm or greater on the surface for a time sufficient to change the color difference of the surface by reducing the doped zirconia to produce an image. A method according to claim 1 wherein the focusing of a laser beam is determined by a digitized image converted to an appropriate dot density. A method according to claim 2 wherein the dot density of the digitized image is approximately 1250 dots/inch (500 dots/cm). A method according to claim 3 wherein the dot density of the digitized image is approximately 600 dots/inch (240 dots/cm). A method according to claim 1 wherein the ceramic consists essentially of zirconia and yttria wherein the molar ratio of yttria to zirconia is from about 0.5:99.5 to about 5.0:95.0. An image element comprising: a ceramic surface having a first color difference, the ceramic consisting essentially of tetragonal zirconia and a dopant selected from the group of rare earth oxides and oxides of calcium, magnesium, yttrium, scandium and cerium wherein the ceramic has a molar ratio of dopant to zirconia of from about 0.5:99.5 to about 25:75, the ceramic having an essentially crystal phase grain, wherein the surface is imaged by focusing a laser beam having a diameter of 5 µm or greater on the surface for a time sufficient to change the first color difference by reducing the doped zirconia to produce an image. An element according to claim 6 wherein the ceramic consists essentially of zirconia and yttria wherein the molar ratio of yttria to zirconia is from about 0.5:99.5 to about 5.0:95.0. An image element according to either of claims 6 and 7 wherein the contrast of the surface can be returned to the first contrast by heating the writing surface to approximately 200°C. An image element according to either of claims 6 and 7 wherein the contrast of the surface can be returned to the first contrast by CO 2 treatment.

Inventors: CHATTERJEE DILIP K, GHOSH SYAMAL K, SHAFFER WAYNE K, VANKERHOVE ALAN P, CHATTERJEE, DILIP K., GHOSH, SYAMAL K., SHAFFER, WAYNE K., VANKERHOVE, ALAN P., Chatterjee, Dilip K., c/o Eastman Kodak Co., Ghosh, Syamal K., c/o Eastman Kodak Co., Shaffer, Wayne K., c/o Eastman Kodak Co., Vankerhove, Alan P., c/o Eastman Kodak Co.
Applicants: EASTMAN KODAK CO, EASTMAN KODAK COMPANY
Application year: 1996
Main classification: C04B41
IPC codes: B41M5, C04B41, C04B35, G03C5, G03C1, B41M1, B44C1