COATINGS FOR GLASS SHAPING MOLDS AND MOLDS COMPRISING THE SAME

Abstract

Precision glass molds are described, which are formed by coating a mold made from high purity, fine grain sized graphite, with a coating including titanium. In various implementations, the titanium coating is overcoated with yttria (Y.sub.2O.sub.3) to provide a high precision glass mold of superior performance character. The resultant glass molds can be used to form glass articles having a highly smooth finish, for high precision applications such as consumer electronic device applications, medical instruments, and optical devices. The use of high purity, fine grain size graphite allows molds to be machined at low cost, thereby eliminating the need to fabricate a metal mold that must be coated with multiple layers including metal diffusion barrier layers to meet operational requirements for such precision applications.

Claims

1. A precision glass mold comprising: a fine grained graphite mold body having one or more mold features; an encapsulating coating atop the graphite mold body and the one or more mold features, the encapsulating coating has a coefficient of thermal expansion that is within 1 part per million/? C. of the coefficient of thermal expansion of the graphite mold body, the encapsulating coating comprising titanium and carbon.

2. The precision glass mold of claim 1 where the graphite grain size is 10 microns or less than 10 microns.

3. (canceled)

4. The precision glass mold of claim 1, in which the encapsulating coating comprising titanium and carbon is a titanium carbide.

5. The precision glass mold of claim 1, further comprising a titanium region atop the encapsulating coating comprising titanium and carbon.

6. The precision glass mold of claim 1, further comprising a glass contacting region that is an oxide of titanium.

7. The precision glass mold of claim 1, that is free of surface discontinuities that are greater than about 25 microns from the average surface plane of the article.

8. A method of making a precision glass mold comprising: forming an encapsulating coating comprising titanium and carbon atop a fine grain graphite mold body having one or more mold features, the encapsulating coating has a coefficient of thermal expansion that is within 1 part per million/? C. of the coefficient of thermal expansion of the graphite mold body.

9-12. (canceled)

13. A glass mold comprising a fine grain graphite body and a coating thereon comprising titanium and yttria.

14. The glass mold of claim 13, wherein the graphite body comprises mold feature(s) including forming surface on which the titanium and yttria coating is coated so that the resultant coated forming surface is configured for shaping glass in contact therewith during glass molding operation.

15. The glass mold of claim 13, wherein the graphite body is at least partially encapsulated with the titanium and yttria coating, including the forming surface of the graphite body.

16. (canceled)

17. The glass mold of claim 13, wherein the titanium and yttria coating comprises titanium on the graphite body, and an outer region comprising yttria.

18-21. (canceled)

22. The glass mold of claim 13, wherein the titanium and yttria coating includes titanium carbide on the graphite body, on which in turn is a layer or region of titanium metal, on which in turn is a layer or region of yttria.

23. The glass mold of claim 13, wherein the titanium and yttria coating includes titanium carbide on the graphite body, on which in turn is a layer or region of titanium metal, on which in turn is a layer or region of titanium oxide, on which in turn is a layer or region of yttria.

24. The glass mold of claim 13, wherein the titanium and yttria coating includes titanium carbide on the graphite body, on which in turn is a layer or region of titanium oxide, on which in turn is a layer or region of yttria.

25. The glass mold of claim 13, wherein the titanium and yttria coating includes an inner layer of titanium carbide, an intermediate layer including titanium metal, titanium oxide, or both titanium metal and titanium oxide, and an outer layer including yttria.

26. The glass mold of claim 13, comprising a pyrolyzed carbon layer or region in or under the titanium and yttria coating.

27. The glass mold of claim 13, wherein the titanium and yttria coating as a thickness in a range of from 10 nm to 500,000 nm.

28. (canceled)

29. The glass mold of claim 13, wherein the fine-grained graphite body has a coefficient of thermal expansion in a range of from 7 to 9 parts per million/? C.

30-32. (canceled)

33. A method of making a glass mold according to claim 13, comprising depositing the titanium and yttria coating, or one or more components thereof, over the fine-grained graphite body by a vapor deposition process.

34. The method of claim 33, wherein the vapor deposition process comprises a process selected from the group consisting of chemical vapor deposition (CVD), pulsed CVD, plasma-assisted CVD, physical vapor deposition (PVD), atomic layer deposition (ALD), sputtering, and evaporative deposition.

35-40. (canceled)

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0020] FIG. 1 is a schematic illustration of a glass mold structure according to one embodiment of the disclosure.

[0021] FIG. 2 is schematic illustration of a glass mold structure according to another embodiment of the disclosure.

[0022] FIG. 3 is a set of photographs of yttria coated graphite coupons, at 1 ?m average grain size (upper photograph) and 5 ?m average grain size (lower photograph), compare a sample with no heat treatment (sample on left in each photograph) and a sample with 60 minutes of heat treatment (sample on right in each photograph).

[0023] FIG. 4 is a photograph of 2 inch square samples of titanium coatings on graphite coupons, in which three samples were heat-treated to 800? C., 850? C., and 900? C., respectively, for one hour, and a fourth sample was a TiC sample with no heat treatment.

[0024] FIG. 5 is a photograph of 2 inch square samples of titanium and yttria coatings (comprising a titanium carbide layer formed on the graphite body of the coupon, and yttria coated on the titanium carbide) on graphite coupons, in which three samples were heat-treated to 800? C., 850? C., and 900? C., respectively, for one hour, and the fourth sample was a TiC/yttria sample with no heat treatment.

[0025] FIG. 6 is an SEM image of a cross-section of a graphite sample coated with TiC and further coated with 0.5 ?m of yttria.

DETAILED DESCRIPTION

[0026] The present disclosure relates to precision glass molds made from coated graphite mold bodies, to coatings applied to such graphite mold bodies, and to methods of making and using the coated graphite mold bodies in glass manufacturing operations.

[0027] As used herein, including in the appended claims, the singular forms a, an, and the include plural reference unless the context clearly dictates otherwise. Thus, for example, reference to a mold feature is a reference to one or more mold features and equivalents thereof known to those skilled in the art, and so forth.

[0028] Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art. Methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the present disclosure. All publications mentioned herein are incorporated by reference in their entirety. Nothing herein is to be construed as an admission that any invention of the present application is not entitled to antedate such disclosure by virtue of prior invention.

[0029] As used herein, the terms optional or optionally means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

[0030] All numeric values herein can be modified by the term about, whether or not explicitly indicated. The term about generally refers to a range of numbers that one of skill in the art would consider equivalent to the recited value (i.e., having the same function or result). In some embodiments the term about refers to ?10% of the stated value, in other embodiments the term about refers to ?2% of the stated value.

[0031] While compositions and methods are described in terms of comprising various components or steps (interpreted as meaning including, but not limited to), the compositions and methods can also consist essentially of or consist of the various components and steps, and such terminology should be interpreted as defining essentially closed or closed member groups.

[0032] Although the disclosure is shown and described herein with respect to one or more particular implementations, equivalent alterations and modifications will occur to others skilled in the art based upon a reading and understanding of this specification and the annexed drawings. The invention includes all such modifications and alterations and is limited only by the scope of the following claims. In addition, while a particular feature or aspect of the invention may have been disclosed with respect to only one of several implementations, such feature or aspect may be combined with one or more other features or aspects of the other implementations as may be desired and advantageous for any given or particular application.

[0033] To the extent that the terms includes, having, has, with, or variants thereof are used herein in either the detailed description or the claims, such terms are intended to be inclusive in a manner similar to the term comprising.

[0034] As used herein, the term exemplary is merely meant to mean an example, rather than the best.

[0035] It is to be appreciated that features, layers and/or elements depicted herein are illustrated with particular dimensions and/or orientations relative to one another for purposes of simplicity and ease of understanding, and that the actual dimensions and/or orientations may differ substantially from that illustrated herein.

[0036] The term region as used herein can refer to encapsulating coatings that may not have a distinct layer structure and wherein the composition of the coating may vary across the thickness of the coating and/or include non-stoichiometric compositions. For example, where a metal like titanium is vapor deposited on graphite, the deposited titanium material in the region closest to the graphite may be carbon rich and metal deficient. As vapor deposition of the metal continues a region that may be near stoichiometric titanium carbide can be formed. As vapor deposition continues further still, a region that may be titanium metal can be formed. The term layer as used herein may be employed to refer to encapsulating coatings that have a more distinct layer structure and composition as opposed to those characterized as being a region. Layer and region can be used to describe the structure of different embodiments of encapsulating coatings atop the graphite mold body.

[0037] As used herein, a graphite mold body having one or more mold features refers to any shaped mold made of fine grained graphite that can be used to repeatedly form a three dimensional article from molten glass that is pressed into the mold. The mold feature can be a cavity, a cavity including protrusions, combinations of these, or other features used to form shaped glass articles.

[0038] As used herein, the term fine grain graphite means graphite stock or ingot comprising graphite particles (grains) with sizes that do not exceed 10 microns. In some embodiments the graphite particle sizes (grain sizes) of the graphite comprising the mold may be on the order of 1 micron in size. In other embodiments, the graphite particle (grain) sizes comprising the mold may be on the order of 5 microns in size, and in still other embodiments, the graphite particle (grain) sizes of the graphite particles (grains) comprising the mold may be on the order of 10 microns. It will be recognized that in various embodiments, the grain size of the graphite may comprise a grain size distribution, e.g., in a range of from 1 to 10 microns, or a range of from 2 to 10 microns, 2 to 8 microns, 1.5 to 6.5 microns, or other suitable range, although it is preferred in practice to utilize graphite stock or ingot having a uniform or substantially uniform grain size, so that the CTE and other performance characteristics of the graphite body of the mold are as isotropic and homogeneous as possible. The graphite particle size for a mold or stock piece can be prepared by sieving graphite particles using standard sieves to achieve the desired particle size. A non-limiting example of a graphite with a fine grain size of about 10 microns or less and a CTE comparable to titanium is commercially available from Poco Graphite, Decatur, Tex., USA under the trademark Glassmate-LT?.

[0039] The present disclosure relates to precision glass molds for shaping molten glass into articles. The glass mold is made of a graphite body with one or more mold features and a coating encapsulating the graphite mold body and the one or more mold features.

[0040] The coating in various embodiments has a coefficient of thermal expansion that differs from the coefficient of thermal expansion (CTE) of the graphite forming the mold body by an amount that does not exceed one part per million/? C. of CTE of the graphite, wherein both the CTE of the coating and the CTE of the graphite forming the mold body are measured by the same technique in the same units. Such CTE differential of one part per million/? C. or less ensures that the coating will not be susceptible to differential thermal expansion and contraction effects that would otherwise render the coating susceptible to delamination from the graphite forming the mold body, at a larger CTE differential between the coating and the graphite forming the mold body.

[0041] In various embodiments, the coating atop the graphite mold body and the one or more mold features is a composition comprising titanium and carbon. In other embodiments, the coating atop the graphite comprises a titanium carbide region or layer. In still other embodiments the coating atop the graphite mold body and the one or more mold features comprises a titanium carbide region or layer and optionally a titanium metal region or layer overtop of the region containing titanium and carbon.

[0042] The glass molds of the present disclosure can be used for precision molding of glass articles that are free of wrinkles, dimples, cavities, protrusions, and other surface discontinuities and asperities. The articles formed by the glass mold in embodiments described herein can be used in consumer electronic devices, medical instruments, optical devices, and other applications requiring precision-molded glass articles.

[0043] In various embodiments, the glass mold has a titanium carbide layer, a titanium layer, and a titanium oxide layer on a graphite substrate, wherein the CTE of these materials is comparable to titanium and the underlying graphite. The titanium carbide, titanium, and titanium oxide layers of the coating encapsulate the graphite mold and features, thereby reducing or eliminating any oxidation of the glass mold surface. This allows a glass mold to be made from inexpensively machined graphite, but having the benefit of a hard, non-stick coating. Conventional graphite cannot be used for the glass mold surface because the CTE is too small and a titanium coating cracks and peels off when the coated mold is cooled.

[0044] Accordingly, it is critical that the coating on the graphite mold body have a close match of CTE values with the graphite mold body so that the coating retains good adhesion characteristics to the graphite mold body in use, since the mold will be subject to thermal swings when the molding surface(s) of the mold contact the molten or otherwise soft formable glass and when the mold is subsequently relieved of the formed glass article and the mold surfaces are exposed to the ambient environment before receiving a next-succeeding charge of formable glass at elevated temperature.

[0045] The surface finish or smoothness of a mold surface of a mold of the present disclosure can be measured mechanically with commercially available profilometers or laser devices. The mold surface can also be indirectly evaluated by examining light-scattering characteristics of surfaces of pressed glass elements produced by the mold.

[0046] An encapsulated mold surface having a surface roughness (e.g., pit or dimple) not exceeding about 25 microns deviation from the average surface plane of the mold can be a precision glass mold in various embodiments of the disclosure. In other embodiments, an encapsulated mold surface having a surface roughness (e.g., a pit or dimple) not exceeding about 15 microns deviation from the average surface plane can be a precision glass mold.

[0047] For precision molding, the mold surface finish is sufficiently smooth that the molten glass does not stick to the mold surface during processing, and this characteristic results in a molded glass article that can used to make the cover glass for various consumer electronic devices such as cellular phones, medical instruments, optical devices, etc.

[0048] In various embodiments, precision molded glass articles are free of wrinkles, dimples, or other surface discontinuities and surface asperities that are greater than about 25 microns in dimensional deviation from the average surface plane of the article. In other embodiments, precision molded glass articles are free of wrinkles, dimples, or other surface discontinuities and surface asperities that are greater than about 15 microns in dimensional deviation from the average surface plane of the article. It will be appreciated that the surface of the mold may be characterized in other manners, e.g., with reference to root mean square roughness or other parameterizing characteristics, to specify the product mold article of the present disclosure as having desirably smooth molding surface(s).

[0049] In various embodiments, the coating encapsulates the graphite mold body and the one or more mold features. The encapsulating coating prevents oxidation or substantially reduces the oxidation of the underlying graphite mold body during glass molding, as compared to an uncoated graphite mold. The coating provides a release, or non-stick, surface and molten glass does not stick to the mold, thereby avoiding the creation of defects in the molded glass articles produced by the mold during glass molding and release operations, such as otherwise would otherwise occur if the formed glass were prone to stick to the molding surface of the coated mold article.

[0050] As indicated, the coating atop the graphite desirably has a coefficient of thermal expansion that differs from the coefficient of thermal expansion of the graphite body by an amount of 1 part per million/? C. or less, based on the graphite CTE, wherein both CTE values, of the coating and of the graphite, are measured by the same techniques and measured in the same units of measurement.

[0051] The coating on the graphite mold surfaces can be formed from metal that is deposited on top of the graphite mold surfaces and features. The metal can be deposited by physical, chemical, or physicochemical methods, including, without limitation, physical vapor deposition (PVD), chemical vapor deposition (CVD), evaporation of metal source material, or any other suitable techniques or processes. The metal can form an encapsulating layer or region atop the graphite that is a composition that contains or includes the metal and carbon.

[0052] In some embodiments, the encapsulating layer or region atop the graphite mold surfaces includes metal carbide, which can be stoichiometric or non-stoichiometric in composition. Continued deposition of the metal can form a layer or region of metal atop the metal carbide or a metal layer or region atop the composition that includes metal and carbon. For example, in the case of vapor-deposited titanium metal, the encapsulating coating on the graphite mold surfaces forms a layer or region of titanium carbide atop the graphite and then a layer or region of titanium atop the titanium carbide. The surface of the titanium that is exposed to air forms a layer or region containing oxides of titanium and in some embodiments a layer or region containing titanium, oxygen and carbon.

[0053] In some embodiments the thickness of the coating is chosen to reduce oxidation of the underlying graphite. In various embodiments, the thickness of the coating can be greater than or equal to 10 nanometers and less than or equal to 500,000 nanometers, i.e., 10 nm<t<500,000 nm, where t is the coating thickness, in nanometers. Any other coating thicknesses can be employed, as suitable to encapsulate the graphite body, or selected part(s) thereof, and to prevent oxidation of the carbon body.

[0054] The coating deposited on top of the graphite in various embodiments is free of electroless or electroplated metal coatings directly atop the graphite, i.e., in direct contact with the graphite surface.

[0055] The carbon of the graphite body can be purified to reduce contaminants and form a high purity graphite body, as disclosed in U.S. Pat. No. 3,848,739, where a graphite mold body or graphite stock body is placed within a purification furnace in which it is contacted by a halogen-containing gas for a period of time and at a temperature sufficient to permit penetration of the halogen into the graphite body, to cause the halogen to react with and volatilize the inorganic impurities, and to expel such impurities from the graphite.

[0056] Advantageously, the titanium coated graphite glass molds described herein allow for glass molds to be machined at relatively low cost, as compared to stainless steel or titanium molds, while providing a mold that resists oxidation at the mold surface. Using a graphite mold coated as described herein allows the graphite-based mold to be used during the entire service life of a mobile device or other molded glass containing article, thereby reducing the overall costs to manufacture shaped glass.

[0057] In another aspect, the disclosure relates to a glass mold comprising a fine grain graphite body and a coating thereon comprising titanium and yttria. The graphite body comprises mold feature(s) including forming surface on which the titanium and yttria coating is coated so that the resultant coated forming surface is configured for shaping glass in contact therewith during glass molding operation. The graphite body is at least partially encapsulated with the titanium and yttria coating, including the forming surface of the graphite body, and preferably is the graphite body is fully encapsulated by the titanium and yttria coating.

[0058] The titanium and yttria coating may be constituted in any compositional form providing enhancement of oxidation resistance of the fine grain graphite body. In various embodiments, the coating includes titanium on the graphite body, and such titanium may be in a form of titanium carbide on the graphite body, e.g., at the interface of the graphite body and the coating, or otherwise in contact with the graphite body, and with an outer region of the coating including yttria. In various embodiments, the coating intermediate the titanium carbide and the yttria may include titanium in a form of titanium metal. In various embodiments, the coating intermediate the titanium carbide and the yttria may include titanium oxide. In any of such embodiments, the titanium carbide, yttria, and when present, titanium oxide, may independently be of stoichiometric or non-stoichiometric character.

[0059] Accordingly, the titanium and yttria coating in specific implementations may include titanium carbide on the graphite body, on which in turn is a layer or region of titanium metal, on which in turn is a layer or region of yttria. In other implementations, the titanium and yttria coating may include titanium carbide on the graphite body, on which in turn is a layer or region of titanium metal, on which in turn is a layer or region of titanium oxide, on which in turn is a layer or region of yttria. In still other implementations, the titanium and yttria coating may include titanium carbide on the graphite body, on which in turn is a layer or region of titanium oxide, on which in turn is a layer or region of yttria.

[0060] It will therefore be appreciated that the titanium and yttria coating may be constituted in any of a variety of compositional forms, as comprising an inner layer or region of titanium carbide on the graphite body, and an outer layer or region of yttria.

[0061] The titanium and yttria coating thus in various embodiments may include an inner layer of titanium carbide, an intermediate layer including titanium metal, titanium oxide, or both titanium metal and titanium oxide, and an outer layer including yttria. The titanium and yttria coating may also contain other coating components and/or layers, as may be necessary or desirable in specific applications of the glass mold article.

[0062] The respective components of the titanium and yttria coating may be incorporated in the coating by any suitable coating formation techniques, by which the coating of desired character and composition may be achieved.

[0063] For example, titanium may be deposited on the graphite body by any of various suitable vapor deposition techniques or processes, e.g., chemical vapor deposition (CVD), pulsed CVD, plasma-assisted CVD, physical vapor deposition (PVD), atomic layer deposition (ALD), sputtering, evaporative deposition, etc., using appropriate titanium source material, as for example an organotitanium source reagent such as titanium tetraisopropoxide (TTIP), Ti[OCH(CH.sub.3).sub.2].sub.4 for CVD.

[0064] The titanium may be deposited on the graphite body in any suitable ambient deposition environment. The titanium will interact with the graphite body to form titanium carbide at the surface of the graphite body. Such deposition of titanium may be continued to form titanium metal over the titanium carbide or to form titanium oxide over the titanium carbide if the titanium metal is exposed to oxygen, or to form titanium metal over the titanium carbide and titanium oxide over the titanium metal, or to form titanium oxide over the titanium carbide, and any of these various deposition schemes may be carried out in continuous or otherwise consecutive deposition operations to constitute the respective regions or layers of the coating.

[0065] Subsequently, the titanium-based coating of a type as described above may be overcoated with yttria to complete the titanium and yttria coating on the graphite body. Such over-coating with yttria may be effected in any suitable manner. For example, yttrium may be deposited by any of the previously described vapor deposition techniques or processes, as conducted in an oxygen-containing ambient environment, or otherwise with deposited yttrium being exposed to oxygen to form yttria as an outermost layer or region of the titanium and yttria coating.

[0066] Although the foregoing discussion has been directed to techniques and processes for forming the titanium and yttria coating in consecutive regions and layers including an innermost region or layer of titanium carbide and then outermost region or layer of yttria, as successive discrete regions or layers, it will be appreciated that the coating may be constituted in a variety of other forms. For example, it may be desirable in some embodiments to dope the titanium carbide inner layer of the coating with yttrium, or additional titanium, or with other coating components. As another example, it may be desirable in other embodiments to utilize inter-layers between consecutive layers of the coating to enhance coating performance properties such as tribological properties, delamination resistance, or other properties. For example, it may be desirable in some embodiments to utilize a pyrolyzed carbon layer or region in or under the titanium and yttria coating.

[0067] In the titanium and yttria coating, the overall thickness of the coating may be of any suitable value that is effective to reduce oxidation of the underlying graphite body, and the titanium and yttria coating may for example in specific embodiments have a total thickness that is in a range of from 10 nm up to 500,000 nm or more. In other embodiments, the total film thickness may be in a range of from 5 to 15 mils (127 to 381 microns), or in a range of from 6 to 10 mils (152.4 to 254 microns), or in a range of from 6 to 8 mils (152.4 to 203.2 microns), or other suitable range. Yttria likewise may be present in the coating at any suitable thickness, e.g., a thickness of from 0.1 to 100 microns, a thickness of from 0.2 to 10 microns, a thickness of from 0.25 to 2 microns, a thickness of from 0.5 to 1 micron, or other appropriate thickness for the specific application.

[0068] The fine-grained graphite body utilized in making the glass molds of the present disclosure advantageously have a coefficient of thermal expansion (CTE) that is in a range of from 7 to 9 parts per million/? C., and difference between the respective CTE values of the coating and the graphite body should not exceed one part per million/? C., and preferably is less than one part per million (ppm)/? C., more preferably is less than 0.75 ppm/? C., and most preferably is less than 0.5 ppm/? C.

[0069] It is to be appreciated that the disclosure herein in respect of glass molds including fine-grained graphite bodies coated with titanium coatings is likewise applicable, to the extent compatible, to glass molds including fine-grained graphite bodies coated with titanium and yttria coatings, and that disclosure herein in respect of glass molds including fine-grained graphite bodies coated with titanium and yttria coatings is likewise applicable, to the extent compatible, to glass molds including fine-grained graphite bodies coated with titanium coatings without yttria therein.

[0070] The disclosure further contemplates glass molds in which the fine-grained graphite body comprises a dense pyrocarbon surface to which yttria is directly applied, without any titanium being present in the coating, but the resulting glass mold should be subsequently limited in glass forming applications to those applications in which temperature does not exceed 800? C., since the yttria coating in thermal cycles involving higher temperature conditions is susceptible to loss of adhesion of the yttria coating to the immediately underlying graphite body. The disclosures herein related to glass molds including titanium and yttria coatings, and the disclosures herein related to glass molds including titanium coatings without yttria therein, are likewise applicable, to the extent compatible, to glass molds in which the fine-grained graphite body comprises a dense pyrocarbon surface to which yttria is directly applied, without any titanium being present in the coating.

[0071] Accordingly, the coatings and the glass molds of the present disclosure achieve a substantial advance in the art, in providing glass molds with high oxidation resistance in which titanium coating, yttria coating, or titanium and yttria coating provides a smooth non-porous surface that improves the appearance of the form glass and requires less polishing of the glass after forming, in relation to graphite molds without a coating of the present disclosure.

[0072] The provision of titanium and yttria coating on the graphite body is particularly advantageous in molding alumino-silicate glasses, wherein yttria inhibits the oxidation of titanium carbide under the conditions required for molding such alumino-silicate glasses, so that the titanium and yttria coating provides a non-porous, non-stick and oxidation-resistant forming surface of the glass mold, in which the yttria forms a bond with the titanium-based material that increases the adhesion of the yttria.

[0073] Referring now to the drawings, FIG. 1 is a schematic illustration of a glass mold structure according to one embodiment of the disclosure. As shown, the glass mold structure includes a fine-grained graphite body, on which is formed a layer of titanium carbide in direct contact with the graphite body, and over which is an intermediate layer of the titanium metal, over which is an outer layer of titanium oxide.

[0074] FIG. 2 is a schematic illustration of a glass mold structure according to another embodiment of the disclosure, in which the glass mold structure includes a fine-grained graphite body, on which is formed a layer of titanium carbide in direct contact with the graphite body, and over which is an intermediate layer that may comprise titanium metal and/or titanium oxide, over which is an outer layer of yttria. In the structure, the intermediate layer may comprise titanium metal alone, or alternatively the intermediate layer may comprise titanium oxide alone, or alternatively the intermediate layer may comprise a sublayer of titanium metal in direct contact with the titanium carbide and a sublayer of titanium oxide over and in direct contact with the sublayer of titanium metal, or alternatively the intermediate layer may comprise a heterogeneous combination of titanium metal and titanium oxide.

[0075] It will be appreciated that although the layer structures in FIGS. 1 and 2 have been shown as discrete consecutive layers, in the schematic depictions of the corresponding structures, the respective coatings may include layers or sub layers having compositional gradations at their respective interfaces between adjacent layers or sublayers.

[0076] The features and advantages of the coatings and glass molds of the present disclosure are further illustrated by the following non-limiting examples.

Example 1

[0077] One and five micron average grain size graphite coupons 0.25 inch (0.635 cm) thick and 2 inches?2 inches (5.08 cm?5.08 cm) in size were pyro-sealed (sealed with a pyrolyzed carbon coating) and coated with 400-500 nm thickness of yttria. The one micron average grain size samples were subjected to two 30 minutes runs at 800? C. and the five micron average grain size samples underwent one 60 minute cycle at 800? C. Weights were taken before and after each heat treatment and given below in Table 1. Weight loss after 60 minutes was the same for the 1 and 5 micron samples. The bottom sample in each case had less weight loss than the top sample since it had less exposure. Both samples showed delamination of the yttria coating. The one micron sample was more severe, likely due to the extra thermal cycle. Molding of potassium ion-exchange aluminosilicate glass, of a type commercially available under the trademark GORILLA GLASS (Corning Incorporated, Corning, N.Y., USA), was simulated with the samples. Glass sample pickup of some of the yttria coating was observed in each of the first cycles, and no transfer was observed on the second 30 minute run. The photographs of FIG. 3 compare a sample with no heat treatment and a sample with 60 minutes of heat treatment.

TABLE-US-00001 TABLE 1 1 micron base 2-Bot 3-Top Initial 36.628 36.183 30 @800? 36.619 36.170 % loss 0.025 0.036 30 @800? 36.610 36.156 T % loss 0.049 0.075 5 micron base 7-Bot 8-Top Initial 29.372 29.360 60 @800? 29.357 29.337 % loss 0.051 0.078

[0078] FIG. 4 is a photograph of 2 inch square (5.08 cm?5.08 cm) samples of titanium coatings on 0.25 inch (0.635 cm) thickness graphite coupons. Three samples were heat-treated to 800? C., 850? C., and 900? C., respectively, for one hour. The fourth sample is a TiC sample with no heat treatment. The non-heat-treated sample exhibited a reflective silver appearance, while the 3 heat-treated samples were white in color, indicative of titanium dioxide having been formed.

[0079] FIG. 5 is a photograph of 2 inch square (5.08 cm?5.08 cm) samples of titanium and yttria coatings (comprising a titanium carbide layer formed on the graphite body of the coupon, and yttria coated on the titanium carbide) on graphite coupons of 0.25 inch (0.635 cm) thickness. Three samples were heat-treated to 800? C., 850? C., and 900? C., respectively, for one hour. The fourth sample is a TiC/yttria sample with no heat treatment. The non-heat-treated sample exhibited a reflective deep purple appearance, while the three heat-treated samples had a reflective silver appearance. The partial dark squares in the heat-treated samples were an artifact of the glass samples that were molded during the heat treatment. No delamination of the titanium and yttria coatings was seen, and the titanium and yttria coatings were observed to fully retain the structural integrity and properties of the corresponding initially formed titanium and yttria coatings.

[0080] FIG. 6 is an SEM image of a cross-section of a graphite sample coated with TiC and further coated with 0.5 ?m of yttria.

[0081] Accordingly, while the disclosure has been has been set out herein in reference to specific aspects, features and illustrative embodiments, it will be appreciated that the utility of the disclosure is not thus limited, but rather extends to and encompasses numerous other variations, modifications and alternative embodiments, as will suggest themselves to those of ordinary skill in the field of the present disclosure, based on the description herein. Correspondingly, the invention as hereinafter claimed is intended to be broadly construed and interpreted, as including all such variations, modifications and alternative embodiments, within its spirit and scope.