The disclosure relates to glass articles comprising opaque layers that are selectively patterned to provide regions of relatively high optical transmission at a sensing wavelength associated with a sensor, and display systems comprising the same.
In various applications involving displays, it is desirable to employ an ambient light sensor to provide various inputs that may be used to control operation of the display. When an amount of ambient light detected by the ambient light sensor increases, for example, a display may be operated with increased brightness to improve the visibility of the image. One context where such ambient light sensors may find use is for automotive interiors, where ambient lighting conditions can vary dramatically depending on location and time of day.
It is generally beneficial to position an ambient light sensor near a display that is controlled by the ambient light sensor so that the sensor measures an accurate representation of the lighting conditions encountered by the display. For example, it may be beneficial to position an ambient light sensor behind a cover glass associated with the display. While beneficial from a display control perspective, such positioning of the ambient light sensor may adversely affect the appearance of the display. For example, the ambient light sensor may be visible to viewers when positioned behind the cover glass if additional measures are not taken to conceal the appearance of the sensor. Existing approaches for concealing sensors may employ a semi-transparent ink layer that is screen printed onto the cover glass. The semi-transparent ink layer may reduce the optical transmission of the cover glass to a great enough extent to conceal visibility of the ambient light sensor, while still having a high enough transmittance to facilitate operation of the ambient light sensor. However, such semi-transparent ink layers are generally screen printed onto the cover glass, which adds complexity and cost to the manufacturing process.
Accordingly, an alternative process for concealing sensors used with displays is desired.
An aspect (1) of the present disclosure pertains to a glass article comprising: a glass substrate having a first major surface and a second major surface, the second major surface being opposite the first major surface; and an opaque layer disposed on the second major surface, wherein: the opaque layer comprises an optical density of greater than 3.0 such that portions of the glass substrate covered by the opaque layer comprise an average optical transmission of less than or equal to 0.5% for light from 400 nm to 700 nm, within a sensor region of the glass article, the opaque layer comprises a plurality of ablated portions, and an average optical transmission of the glass article within the sensor region is greater than or equal 1.0% for the light from 400 nm to 700 nm as a result of the plurality of ablated portions.
An aspect (2) of the present disclosure pertains to a glass article according to the aspect (1), wherein the average optical transmission of the glass article within the sensor region is greater than or equal to 1.0% and less than or equal to 20% for the light from 400 nm to 700 nm.
An aspect (3) of the present disclosure pertains to a glass article according to any of the aspects (1)-(2), wherein each of the plurality ablated portions is completely devoid of material making up a remainder of the opaque layer.
An aspect (4) of the present disclosure pertains to a glass article according to any of the aspects (1)-(2), wherein, within each of the plurality of ablated portions, a material of the opaque layer is only partially removed such that the opaque layer comprises at least some of the material in each of the plurality of ablated portions.
An aspect (5) of the present disclosure pertains to a glass article according to any of the aspects (1)-(4), wherein each of the plurality of ablated portions comprises a maximum horizontal dimension, measured in a direction parallel to the second major surface, that is less than or equal to 100 μm.
An aspect (6) of the present disclosure pertains to a glass article according to the aspect (5), wherein the maximum horizontal dimension is less than or equal to 70 μm.
An aspect (7) of the present disclosure pertains to a glass article according to any of the aspects (5)-(6), wherein the ablated portions of the plurality of ablated portions are separated from one another by a minimum edge-to-edge separation distance that is greater than or equal to the maximum horizontal dimension.
An aspect (8) of the present disclosure pertains to a glass article according to the aspect (7), wherein the plurality of ablated portions comprises a plurality of separate holes formed in the opaque layer.
An aspect (9) of the present disclosure pertains to a glass article according to any of the aspects (1)-(8), wherein a combined surface area of the plurality of ablated portions constitutes no more than 50% of a total surface area of the sensor region.
An aspect (10) of the present disclosure pertains to a glass article according to the aspect (9), wherein the combined surface area of the plurality of ablated portions constitutes no more than 25% of the total surface area of the sensor region.
An aspect (11) of the present disclosure pertains to a glass article according to any of the aspects (1)-(10), wherein the opaque layer comprises a curable ink and comprises a thickness of less than or equal to 25 μm.
An aspect (12) of the present disclosure pertains to a glass article according to any of the aspects (1)-(11), wherein: the opaque layer comprises an edge that delineates a boundary between an image region that is not covered by the opaque layer and a peripheral region of the glass article that is covered by the opaque layer, and the sensor region comprises a sub-region of the peripheral region.
An aspect (13) of the present disclosure pertains to a display for a vehicle interior system, the display comprising: a glass substrate comprising a first major surface and a second major surface, the second major surface being opposite the first major surface; an opaque layer disposed on the second major surface; and a sensor positioned behind the glass substrate such that light initially incident on the first major surface propagates through the glass substrate and opaque layer prior to being incident on the sensor, wherein: the sensor is configured to detect light within a wavelength range of interest, within a sensor region of the glass article, the opaque layer comprises a plurality of ablated portions positioned along an optical path including the sensor such that the light initially incident on the first major surface propagates through one of the plurality of ablated portions onto the sensor, material of the opaque layer comprises an average optical transmission of less than 0.5% for light in the wavelength range of interest, and as a result of the ablated portions, the sensor region comprises an average optical transmission of greater than or equal to 1.0% for light in the wavelength range of interest.
An aspect (14) of the present disclosure pertains to a display according to the aspect (13), wherein the sensor region comprises an average optical transmission of greater than or equal to 5.0% and less than or equal to 20% for light in the wavelength range of interest.
An aspect (15) of the present disclosure pertains to a display according to any of the aspects (13)-(14), wherein the wavelength range of interest is from 400 nm to 700 nm.
An aspect (16) of the present disclosure pertains to a display according to any of the aspects (13)-(15), wherein, within each of the plurality of ablated portions, the material of the opaque layer is at least partially removed.
An aspect (17) of the present disclosure pertains to a display according to any of the aspects (13)-(16), wherein each of the plurality of ablated portions comprises a maximum horizontal dimension, measured in a direction parallel to the second major surface, that is less than or equal to 100 μm.
An aspect (18) of the present disclosure pertains to a display according to any of the aspects (13)-(17), wherein a combined surface area of the plurality of ablated portions constitutes no more than 50% of a total surface area of the sensor region.
An aspect (19) of the present disclosure pertains to a method of fabricating a glass article, the method comprising: forming a plurality of ablated portions in a sensor region of an opaque layer disposed on a major surface of the glass substrate by exposing the opaque layer to a laser beam to ablate material of the opaque layer, wherein: the opaque layer comprises an optical density of greater than 3.0 such that portions of the glass substrate covered by the opaque layer comprise an average optical transmission of less than or equal to 0.5% for light from 400 nm to 700 nm, and an average optical transmission of the glass article within the sensor region is greater than or equal 1.0% for the light from 400 nm to 700 nm as a result of the plurality of ablated portions.
An aspect (20) of the present disclosure pertains to a method according to the aspect (19), further comprising generating the laser beam with a laser source, wherein the laser source comprises a CO2 laser, an ultraviolet laser, or an infrared laser.
An aspect (21) of the present disclosure pertains to a method according to any of the aspects (19)-(20), wherein the forming the plurality of ablated portions comprises scanning the laser beam in a scanning pattern over the sensor region.
An aspect (22) of the present disclosure pertains to a method according to the aspect (21), wherein the laser beam is moved relative to the glass substrate during the formation of a single one of the plurality of ablated portions.
An aspect (23) of the present disclosure pertains to a method according to any of the aspects (19)-(22), wherein the glass substrate is stationary during the formation of the plurality of ablated portions.
An aspect (24) of the present disclosure pertains to a method according to any of the aspects (19)-(22), wherein the glass substrate is moving during the formation of the plurality of ablated portions.
It is to be understood that both the foregoing general description and the following detailed description are merely exemplary, and are intended to provide an overview or framework to understanding the nature and character of the claims. The accompanying drawings are comprised to provide a further understanding, and are incorporated in and constitute a part of this specification. The drawings illustrate one or more embodiment(s), and together with the description serve to explain principles and operation of the various embodiments.
The accompanying drawings incorporated in and forming a part of the specification illustrate several aspects of the present invention and, together with the description, serve to explain the principles of the invention. In the drawings:
Referring generally to the figures, described herein are embodiments of glass articles comprising opaque layers that are selectively ablated to include an array of ablated portions that are regions of elevated optical transmission of the glass article. In the regions of elevated optical transmission, the glass article may transmit light in a wavelength range of interest associated with a sensor positioned proximate to the glass article. For example, in embodiments, the regions of elevated optical transmission may provide an average optical transmission of greater than or equal to 1% (e.g., greater than or equal to 5% greater than or equal to 10%, greater than or equal to 15%, greater than 20%) over the visible spectrum (e.g., from 400 nm to 700 nm) such that the sensor can detect a relative intensity of visible light incident on the glass article (e.g., when the sensor is an ambient light sensor). In embodiments, the opaque layer may comprise a relatively high optical density (e.g., greater than 3.0 or greater than or equal to 4.0 or greater than or equal to 5.0) and therefore substantially block visible light from propagating through the glass article. The opaque layer may be used to conceal various components associated with the glass article from view, while the array of ablated portions permits a sufficient amount of light through the glass article to permit detection by the sensor.
In aspects, the array of ablated portions may be structured to conceal the appearance of the sensor, while still providing sufficient optical transmittance to facilitate operation of the sensor. In embodiments, for example, the array of ablated portions extends over a sensor region of the glass article that overlaps the sensor. In embodiments, when the array of ablated portions comprises a plurality of ablated portions (i.e., more than or ablated portion), the array of ablated portions is structured (e.g., arranged, spaced, sized) such that at least 50% (e.g., at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%) of the glass substrate in the sensor region is still covered by the opaque layer. Put differently, within the sensor region, less than or equal to 50% (e.g., less than or equal to 45%, less than or equal to 40%, less than or equal to 35%, less than or equal to 30%, less than or equal to 25%, less than or equal to 20%) of the opaque layer is ablated via the processes described herein. The ablated portions may also be sized to have a maximum horizontal dimension (measured in a direction parallel to a major surface of the glass substrate) that is less than or equal to 100 μm (e.g., less than or equal to 90 μm, less than or equal to 80 μm, less than or equal to 70 μm, less than or equal to 60 μm, less than or equal to 50 μm, less than or equal to 40 μm, less than or equal to 35 μm). The array of ablated portions may also comprise a minimum edge-to-edge separation distance separating adjacent ablated portions that is greater than (e.g., at least 1.25 times greater than, at least 1.5 times greater than, at least 2.0 times greater than, at least 2.5 times greater than, at least 3.0 times greater than) the maximum horizontal dimension of the ablated portions. Such limited size of the ablated portions, in conjunction with the spacing therebetween, aids in concealing the sensor via the remaining opaque layer contained in the sensor region.
In aspects, the array of ablated portions in the opaque layer described herein may be formed using any suitable laser process. In embodiments, the opaque layer is absorptive of light ranging from the ultraviolet (“UV”) to (“IR”) spectra. For example, in embodiments, the opaque layers described herein may be formed of a suitable epoxy, acrylic, polyurethane, or latex paint or ink. As such, any suitable laser source emitting light in that wavelength range may be used to ablate the opaque layer by selectively heating portions of the opaque layer to a great enough extent to remove material of the opaque layer from select regions of the glass article. Any laser source (e.g., pulsed laser source, continuous wave laser source) capable of generating light above the material of the opaque layer's ablation threshold may be used. Moreover, various suitable mechanisms for providing relative movement between the glass article and laser beam (e.g., movement of the glass substrate relative to the laser source, a scanning optical system for moving the laser beam relative to the glass substrate, or a combination thereof) are contemplated and within the scope of the present disclosure. Existing laser marking systems may be employed to create the array of ablated portions. As such, the array of ablated portions described herein facilitates operation of sensors (e.g., ambient wavelength sensors) from behind the glass articles, while still concealing the sensors from view, without the use of additional semitransparent films or ink layers. The glass articles of the present disclosure facilitate sensor incorporation with minimal impact on the appearance of the display.
As used herein, the terms “optical transmission” and “percent transmission” or “transmittance” are used interchangeably and refer to a percentage of light transmitted through an article over a wavelength range of interest. An “average optical transmission” for light in a particular wavelength range is determined by averaging a measured optical transmission at all of the whole number wavelengths within that wavelength range. Unless otherwise noted herein, average optical transmission values are for ambient light incident on the entire article, which may be approximated with a CIE D65 illuminant.
As used herein, unless otherwise stated, the term “visible spectrum” refers to a wavelength range of 400 nm to 700 nm.
In embodiments, the vehicle display system 100 can be integrated with the electronics system of the vehicle, or the vehicle display system 100 may be separate therefrom. The display 110 may be manufactured as part of the vehicle or may be retrofitted. In embodiments, the display 110 is attached to a suitable support structure that is mounted on the vehicle base 105. In embodiments, a rear surface of the display 110 may be in contact with the support structure such that a front, user-facing surface of the display 110 (e.g., corresponding to the first major surface 470 described herein) faces the vehicle interior so that an image on the display 110 can be viewed by vehicle occupants. In embodiments, the display 110 may be positioned so as to form a portion of the vehicle base 105 and may follow the shape and contour thereof.
A variety of constructions of the display 110 are contemplated and within the scope of the present disclosure. As shown in
As shown in
In embodiments, the sensor 150 detects light in a suitable wavelength range of interest to determine the ambient light state. For example, in embodiments, the sensor 150 may measure light throughout the visible spectrum (e.g., from 400 nm to 700 nm) to determine whether the ambient light conditions are likely to generate glare on the display 110. Embodiments where the sensor 150 generates signals responsive to light in other wavelength ranges of interest (e.g., detects light outside of the visible spectrum) are also contemplated and within the scope of the present disclosure. Moreover, while the example of a photodetector has been described herein, the sensor 150 may be employed in a variety of forms (e.g., a location detector, a camera, a proximity sensor). While the depicted example only includes a single sensor 150, embodiments are also contemplated that incorporate more than one sensor.
In embodiments, the sensor 150 is positioned behind a cover glass associated with the display 110. For example,
The sensor 150 is shown to be disposed behind the glass article 400 and proximate to the display module 540. Such a structure is beneficial in that the sensor 150 is able to detect environmental conditions that accurately represent what the display 110 is exposed to (see
As shown in
In embodiments, the substrate 450 is a glass substrate that is optionally chemically strengthened and comprises a thickness of from 0.05 to 2.0 mm. More detail on the construction of such a glass substrate will be provided herein with respect to
In embodiments, the glass article 400 comprises a functional surface layer 490. The functional surface layer 490 can be configured to provide one or more of a variety of functions. For example, the functional surface layer 490 may be optical coating configured to provide easy-to-clean performance, anti-glare properties, antireflection properties, and/or half-mirror coating. Such optical coatings can be created using single layers or multiple layers. In the case of anti-reflection functional surface layers, such layers may be formed using multiple layers having alternating high refractive index and low refractive index. Non-limiting examples of low refractive index films include SiO2, MgF2, and Al2O3, and non-limiting examples of high refractive index films include Nb2O5, TiO2, ZrO2, HfO2, and Y2O3. In embodiments, the total thickness of such an optical coating (which may be disposed over an anti-glare surface or a smooth substrate surface) is from 5 nm to 750 nm. Additionally, in embodiments, the functional surface layer 490 that provides easy-to-clean performance also provides enhanced feel for touch screens and/or coating/treatments to reduce fingerprints. In some embodiments, functional surface layer 490 is integral to the first surface of the substrate. For example, such functional surface layers can include an etched surface in the first surface of the substrate 450 providing an anti-glare surface (or haze of from, e.g., 2% to 20%).
In embodiments, the opaque layer 500 is printed onto the second major surface 480 of the substrate 450. The opaque layer 500 may be constructed of a suitable ink (e.g., photocurable ink a thermally curable ink), such that the opaque layer 500 possesses a relatively high optical density (e.g., an optical density of greater than 3 or greater than or equal to 4), in order to block light transmittance. In embodiments, the opaque layer 500 is constructed of a suitable ink comprising a pigment dispersion (e.g., containing a suitable colorant such as carbon black and monomers) and binder solution. Various commercially available photocurable and radiation-curable inks are contemplated and within the scope of the present disclosure. The ink used to form the opaque layer 500 may generally absorb radiation from the UV spectrum through the infrared spectrum.
In embodiments, the opaque layer 500 is used to block light from transmitting through certain regions of the glass article 400. In embodiments, the opaque layer 500 obscures functional or non-decorative elements provided for the operation of the glass article 400. In embodiments, the opaque layer 500 is provided to outline backlit icons and/or other graphics (not depicted) so as to increase the contrast at the edges of such icons and/or graphics. The opaque layer 500 can be any color; in particular embodiments, though, the opaque layer 500 is black or gray. In embodiments, the opaque layer 500 is applied via a suitable application technique (e.g., inkjet printing, screen printing) over the second major surface 480 of the substrate 450. Generally, the thickness of the opaque layer 500 is less than or equal to 25 μm (e.g., greater than or equal to 1.0 μm and less than or equal to 25.0 μm, greater than or equal to 5.0 μm and less than or equal to 25.0 μm, greater than or equal to 5.0 μm and less than or equal to 20.0 μm, greater than or equal to 5.0 μm and less than or equal to 10.0 μm).
In embodiments, the opaque layer 500 is directly deposited onto the second major surface 480. In embodiments, prior to deposition of the opaque layer 500, the second major surface 480 may be primed using a suitable primer (e.g., an acryloxy silane primer) to facilitate adhesion of the opaque layer 500 to the substrate 450. Any suitable treatment to the second major surface 480 may be used to facilitate adhesion of the opaque layer 500 to the substrate 450.
In embodiments, the high optical density of the opaque layer 500 causes the areas of the glass article 400 incorporating the opaque layer 500 to have relatively low average optical transmission (e.g., an average transmittance of less than or equal to 0.5% or less than or equal to 0.1%) in the visible spectrum. Accordingly, the boundaries of the opaque layer 500 may define an image region 520, where the glass article 400 can exhibit a relatively high optical transmission (e.g., greater than or equal to 50%, 60%, 70%, 80%, or 90%, averaged over the visible spectrum) to facilitate visibility of the light generated by the display module 540, and a peripheral region 530, where the glass article 400 generally exhibits a lower optical transmission than in the image region 520 to facilitate concealment of various components. In the depicted embodiment, the opaque layer 500 covers the edges 550 of the display module 540 to hide the edges 550 from view through the first major surface 470. The opaque layer 500 may also be used to obscure various other components from view (e.g., electrical connections, mechanical housings, and the like). The opaque layer 500 generally facilitates a desired portion of the display module 540 being viewable by users viewing the first major surface 470.
Referring still to
In embodiments, the plurality of ablated portions 562 in the opaque layer 500 contain less of the material that tends to absorb optical radiation in the wavelength range of interest associated with the sensor 150 that makes up a remainder of the opaque layer 500. As a result, within the plurality of ablated portions 562, the glass article 400 comprises a higher optical transmission within the wavelength range of interest than in other portions of the glass article 400 where the opaque layer 500 comprises a full thickness. The plurality of ablated portions 562 comprise regions of elevated optical transmission in the wavelength range of interest, thereby allowing a detectable amount of radiation to propagate through the glass article 400 within the sensor region 560 to reach the sensor 150 to generate a sensor signal that can be used to estimate the ambient light state of the display 110 and control the display module 540 accordingly.
In the depicted embodiment, the sensor region 560 is contained in the peripheral region 530. The sensor region 560 corresponds to the smallest shape extending tangent to all of the outermost ablated portions in the plurality of ablated portions 562. The outermost ablated portions comprise geometric centers that are the greatest radial distance from the geometric center of the plurality of ablated portions 562 when viewed as a whole (e.g., a geometric center of the array of ablated portions 564, see
In embodiments, the plurality of ablated portions 562 comprises at least 1 (e.g., at least 2, at least 3, at least 4, at least 6, at least 6, at least 7, at least 8, at least 9, at least 10, at least 12, at least 14, at least 16, at least 18, at least 20, at least 22, at least 24, at least 26, at least 28, at least 30, at least 40, at least 50) separate ablated portions of the opaque layer 500. The plurality of ablated portions 562 are generally arranged in an array of ablated portions 564. The array of ablated portions 564 may contain any suitable arrangement of ablated portions. For example, in the depicted embodiment, the array of ablated portions 564 comprises a plurality of equally spaced rows of ablated portions, with each row of ablated portions comprising a plurality of equally spaced ablated portions. Such an arrangement uniformly distributes the ablated portions over the sensor region 560 and may facilitate consistent measurements by the sensor 150. Other arrangements, where the ablated portions are distributed non-uniformly or in other patterns, are also contemplated and within the scope of the present disclosure. In embodiments, for example, the array of ablated portions 564 is arranged in an alternating row arrangement, where every other row of ablated portions is aligned in a direction extending perpendicular to the row direction, but adjacent rows are offset from one another along the row direction. Any suitable pattern of ablated portions is possible and may be fabricated in accordance with the method described herein.
The array of ablated portions 564 is constructed so that, within the sensor region 560, the glass article 400 comprises an average optical transmission of greater than or equal to 0.5% (e.g., greater than or equal to 1.0%, greater than or equal to 1.5%, greater than or equal to 2.0%, greater than or equal to 2.5%, greater than or equal to 3.0%, greater than or equal to 3.5%, greater than or equal to 4.0%, greater than or equal to 4.5%, greater than or equal to 5.0%, greater than or equal to 6.0%, greater than or equal to 7.0%, greater than or equal to 8.0%, greater than or equal to 9.0%, greater than or equal to 10%, greater than or equal to 12%, greater than or equal to 14%, greater than or equal to 16%, greater than or equal to 18%, greater than or equal to 19%) in the wavelength range of interest associated with the sensor 150. Such an optical transmission allows the sensor 150 to provide usable detection signals (e.g., above a signal-to-noise ratio associated with the sensor 150) from light propagating through the glass article 400. In embodiments, the array of ablated portions 564 is constructed so that, within the sensor region 560, the glass article 400 comprises an optical average transmission of less than or equal to 25% (e.g., less than or equal to 24%, less than or equal to 23%, less than or equal to 22%, less than or equal to 21%, less than or equal to 20%, less than or equal to 19%, less than or equal to 18%, less than or equal to 17%, less than or equal to 15%, less than or equal to 14%, less than or equal to 13%, less than or equal to 12%, less than or equal to 11%, less than or equal to 10%) in the visible spectrum to aid in concealing the sensor 150 from view. As such, in embodiments, within the sensor region 460, the glass article 400 may comprise an average optical transmission in the visible spectrum (e.g., from 400 nm to 700 nm) that is greater than or equal to 0.5% and less than or equal to 25% (e.g., greater than or equal to 1% and less than or equal to 20%, greater than or equal to 2% and less than or equal to 20%, greater than or equal to 3% and less than or equal to 20%, greater than or equal to 4% and less than or equal to 20%, greater than or equal to 5% and less than or equal to 20%). Such an optical transmission facilitates operation of the sensor 150 while still concealing the sensor 150 from view when the display 110 is viewed from the interior of the vehicle.
To provide such an optical transmission, the ablated portions in the opaque layer 500 may be constructed with a size and spacing such that a majority of the surface area of the opaque layer 500 in the sensor region 560 does not contain an ablated portion. In embodiments, when, for example, the array of ablated portions 564 comprises more than one ablated portion, a combined surface area of the plurality of ablated portions 562 makes up less than 50% (e.g., less than 45%, less than 40%, less than 35%, less than 30%, less than 25%, less than 10%) of the surface area of the sensor region 560, measured in a direction extending parallel to the second major surface 480 of the glass substrate 450 (see
In the depicted embodiment, each ablated portion in the plurality of ablated portions 562 is substantially circular in shape. The shape of the ablated portions may generally correspond in shape to the spatial intensity density distribution of a laser beam that is used to form the plurality of ablated portions 562. The shape of the spatial intensity distribution at which the laser beam possesses an intensity above the material of the opaque layer 500's ablation threshold generally determines the shape and size of the ablated portions. As may be appreciated, the actual shape of the ablated portions may vary somewhat from being precisely circular due to laser variations and the ablation process. In embodiments, each ablated portion of the plurality of ablated portions 562 comprises a maximum horizontal dimension 565, measured in a direction extending parallel to the second major surface 480 of the glass substrate 450 (see
As shown in
While the array of ablated portions 564 comprises a rectangular peripheral shape of evenly spaced rows of ablated portions, it should be understood that a variety of arrangements of ablated portions are contemplated and within the scope of the present disclosure. Any suitable combination of ablated portions, having any suitable size or peripheral shapes, are contemplated and within the scope of the present disclosure. Since the ablated portions described herein may be formed through laser ablation of the opaque layer 500, the arrangement of ablated portions can be tailored specifically to use case needs through manipulation of laser parameters.
At block 602, the glass substrate 450 is provided with the opaque layer 500 disposed thereon. The glass substrate 450 may be fabricated via any suitable method (e.g., float method, down-draw method) or purchased commercially. The opaque layer 500 may be formed by depositing a suitable curable ink (e.g., a thermally cured ink or radiation-curable ink) comprising, for example, a pigment dispersion, binder system, and photoinitiator. The pigment dispersion may contain a suitable colorant (e.g., carbon black) at a relatively high weight percentage (e.g., at least 10 wt %, at least 20 wt %, at least 30 wt %) such that the ink, once cured, provides an optical density of greater than or equal to 3 or greater than or equal to 4. The ink may be deposited onto the second major surface 480 (or a primer layer or other coating disposed thereon) using a suitable deposition process (e.g., inkjet printing or screen printing). After curing via a suitable curing method, the opaque layer 500 may comprise an average optical transmission of less than or equal to 1% (e.g., less than or equal to 0.5%, less than or equal to 0.1%) for light from 400 nm to 700 nm.
At block 604, the opaque layer 500 is exposed to light from a light source to selectively remove the opaque layer in a pattern to form transmissive regions in the opaque layer 500. In embodiments, portions of the opaque layer 500 are selectively exposed to a laser beam such that the laser beam heats the material of the opaque layer 500 to ablate the material and form the plurality of ablated portions 562.
A variety of approaches for forming the array of ablated portions 564 is contemplated. For example, in embodiments, the base 614 is stationary. As a result, the glass substrate 450, when placed on the base 614, may remain stationary upon exposure to the laser beam 616. Accordingly, to form ablated portions in a desired pattern, the laser beam 616 may be scanned over the opaque layer 500 such that various regions thereof are exposed to the laser beam 616 for a sufficient period to cause ablation of the material of the opaque layer 500. In this regard, the apparatus 610 may include an optical system 618. The optical system 618 may include one or more optical elements (e.g., lenses, mirrors, etc.) to manipulate the laser beam 616 and scan the opaque layer 500 in a desired pattern to form the array of ablated portions 564. For example, in embodiments, the optical system 618 comprises a galvanometric scanner (e.g., a 1D optical scanner, a 2D optical scanner) that alters the propagation direction of the laser beam 616 to change the point of incidence of the laser beam 616 on the opaque layer 500. In embodiments, for example, the laser beam 616 may initially be incident on a first portion of the opaque layer 500. The opaque layer 500 may be exposed to the laser beam 616 for an exposure period to cause sufficient heating to ablate the material of the opaque layer 500. After the exposure period, the galvanometric scanner may alter configurations to change the point of incidence of the laser beam 616 to form another ablated portion. Such a process may repeat until a desired pattern of ablated portions is formed.
In embodiments, the base 614 is in motion while the glass substrate 450 is exposed to the laser beam 616. For example, the base 614 may be (or disposed on) a conveyor belt that moves the glass substrate 450 in a conveyor direction 620. In such embodiments, a controller (not depicted) may detect the position of the glass substrate 450 and fire the laser source 612 to remove portions of the opaque layer 500 as described above. The scanning patterns of the laser beam 616 may be modified based on the movement rate and direction of the glass substrate 450. Such an “on the fly” approach beneficially improves operating efficiencies by avoiding stoppages of the glass substrate 450.
In embodiments, the optical system 618 also includes beam conditioning optics that may manipulate the spatial intensity distribution of the laser beam 616 when the laser beam 616 is incident on the opaque layer 500. For example, the optical system 618 may focus the laser beam 616 to cause at least a portion of the beam to have an intensity above an ablation threshold of the material of the opaque layer 500. The optical system 618 may also partially determine the shape of the ablated portions my manipulating the shape of the intensity distribution of the laser beam 616.
In embodiments, the optical system 618 may manipulate the laser beam 616 during the formation of a single one of the plurality of ablated portions 562. That is, during the formation of a single ablated portion, the optical system 618 may alter a point of incidence of the laser beam 616 on the opaque layer 500, such that each individual of ablated portion is formed by scanning the laser beam 616 in a scanning pattern. Such an approach provides flexibility in the shape and size of the ablated portion that may be formed, as the scanning pattern used may alter the precise portion of the opaque layer 500 that is exposed to enough radiation to cause ablation. Using such an approach, a wide variety of ablated portions, that may vary in shape from a spatial intensity distribution of the laser beam 616, may be formed. Ablated portions of circular, elliptical, and parallelepiped-shaped cross-sections are contemplated and within the scope of the present disclosure.
In embodiments, the optical system 618 can comprise one or more diffractive optical elements. For example, in embodiments, the diffractive optical element is a one-dimensional or two-dimensional diffractive beam splitter that can diffract the laser beam 616 into a plurality of diffractive beams that are each capable of ablating the material of the opaque layer 500. This way, a pattern of ablated regions can be formed via diffraction and without scanning the laser beam 616. In embodiments, the optical system 618 can include a micro lens array for focusing the laser beam 616 into a plurality of focal spots on the opaque layer 500 to form the array of ablated portions 652 without moving. Each focal spot may have a circular or non-circular spatial power distribution to facilitate forming ablated portions of a desired shape.
In embodiments, the optical system 618 can comprise of a geometrical phase hologram, a spatial light modulator, or other suitable beam manipulation device. In embodiments, for example, the hologram or spatial light modulator may be used in combination with a suitable optical system (e.g., lens system) to generate a desired pattern on the opaque layer 500 to form a pattern of ablated regions without any moving parts. Embodiments are also envisioned where the spatial light modulator, hologram, diffractive optical element(s), or micro lens array may be used in combination with a scanner to provide further flexibility in pattern generation.
Referring generally to
Referring again to
It should be appreciated that display articles in accordance with the present disclosure may include any number of sensor regions. In embodiments, each of such sensor regions comprises a different array of ablated portions of the opaque layer 500. The arrays of ablated portions may vary depending on the sensors that each sensor region is disposed in front of. Embodiments are also envisioned where a single sensor region is placed in front of multiple sensors. A single array of ablated portions may be used to facilitate operation of a plurality of sensors while hiding the sensors from view.
Embodiments of the present disclosure may be further understood in view of the following examples.
In the following examples, an opaque layer of a commercially available ink was disposed on a glass substrate and exposed to various lasers to form ablated portions as shown. In the examples, an acrylic opaque layer within the thickness ranges described herein was disposed on a glass substrate and subjected to exposure from various laser sources to generate the depicted ablated regions.
In a first example, a CO2 laser operating at a 9.3 μm wavelength having an effective power of 4 W was scanned over the opaque layer and used to generate circle-shaped holes in the opaque layer in a grid-like pattern (uniform spacing). The laser had a Gaussian intensity distribution and was focused onto the opaque layer with a spot size of about 80 μm. The laser was operated as a quasi-cw source with an on-time of 0.1 ms per ablated portion. Such an approach successfully generated ablated portions where the opaque layer was fully removed. The holes were 60 μm in diameter and a 20×20 grid was generated in less than 0.5 seconds.
Referring to
In various embodiments, thickness t is 2 mm or less. In particular, the thickness t is from 0.30 mm to 2.0 mm. For example, thickness t may be in a range from about 0.30 mm to about 2.0 mm, from about 0.40 mm to about 2.0 mm, from about 0.50 mm to about 2.0 mm, from about 0.60 mm to about 2.0 mm, from about 0.70 mm to about 2.0 mm, from about 0.80 mm to about 2.0 mm, from about 0.90 mm to about 2.0 mm, from about 1.0 mm to about 2.0 mm, from about 1.1 mm to about 2.0 mm, from about 1.2 mm to about 2.0 mm, from about 1.3 mm to about 2.0 mm, from about 1.4 mm to about 2.0 mm, from about 1.5 mm to about 2.0 mm, from about 0.30 mm to about 1.9 mm, from about 0.30 mm to about 1.8 mm, from about 0.30 mm to about 1.7 mm, from about 0.30 mm to about 1.6 mm, from about 0.30 mm to about 1.5 mm, from about 0.30 mm to about 1.4 mm, from about 0.30 mm to about 1.4 mm, from about 0.30 mm to about 1.3 mm, from about 0.30 mm to about 1.2 mm, from about 0.30 mm to about 1.1 mm, from about 0.30 mm to about 1.0 mm, from about 0.30 mm to about 0.90 mm, from about 0.30 mm to about 0.80 mm, from about 0.30 mm to about 0.70 mm, from about 0.30 mm to about 0.60 mm, or from about 0.30 mm to about 0.40 mm. In other embodiments, the t falls within any one of the exact numerical ranges set forth in this paragraph.
In various embodiments, width W is in a range from 5 cm to 250 cm, from about 10 cm to about 250 cm, from about 15 cm to about 250 cm, from about 20 cm to about 250 cm, from about 25 cm to about 250 cm, from about 30 cm to about 250 cm, from about 35 cm to about 250 cm, from about 40 cm to about 250 cm, from about 45 cm to about 250 cm, from about 50 cm to about 250 cm, from about 55 cm to about 250 cm, from about 60 cm to about 250 cm, from about 65 cm to about 250 cm, from about 70 cm to about 250 cm, from about 75 cm to about 250 cm, from about 80 cm to about 250 cm, from about 85 cm to about 250 cm, from about 90 cm to about 250 cm, from about 95 cm to about 250 cm, from about 100 cm to about 250 cm, from about 110 cm to about 250 cm, from about 120 cm to about 250 cm, from about 130 cm to about 250 cm, from about 140 cm to about 250 cm, from about 150 cm to about 250 cm, from about 5 cm to about 240 cm, from about 5 cm to about 230 cm, from about 5 cm to about 220 cm, from about 5 cm to about 210 cm, from about 5 cm to about 200 cm, from about 5 cm to about 190 cm, from about 5 cm to about 180 cm, from about 5 cm to about 170 cm, from about 5 cm to about 160 cm, from about 5 cm to about 150 cm, from about 5 cm to about 140 cm, from about 5 cm to about 130 cm, from about 5 cm to about 120 cm, from about 5 cm to about 110 cm, from about 5 cm to about 110 cm, from about 5 cm to about 100 cm, from about 5 cm to about 90 cm, from about 5 cm to about 80 cm, or from about 5 cm to about 75 cm. In other embodiments, W falls within any one of the exact numerical ranges set forth in this paragraph.
In various embodiments, length L is in a range from about 5 cm to about 2500 cm, from about 5 cm to about 2000 cm, from about 4 to about 1500 cm, from about 50 cm to about 1500 cm, from about 100 cm to about 1500 cm, from about 150 cm to about 1500 cm, from about 200 cm to about 1500 cm, from about 250 cm to about 1500 cm, from about 300 cm to about 1500 cm, from about 350 cm to about 1500 cm, from about 400 cm to about 1500 cm, from about 450 cm to about 1500 cm, from about 500 cm to about 1500 cm, from about 550 cm to about 1500 cm, from about 600 cm to about 1500 cm, from about 650 cm to about 1500 cm, from about 650 cm to about 1500 cm, from about 700 cm to about 1500 cm, from about 750 cm to about 1500 cm, from about 800 cm to about 1500 cm, from about 850 cm to about 1500 cm, from about 900 cm to about 1500 cm, from about 950 cm to about 1500 cm, from about 1000 cm to about 1500 cm, from about 1050 cm to about 1500 cm, from about 1100 cm to about 1500 cm, from about 1150 cm to about 1500 cm, from about 1200 cm to about 1500 cm, from about 1250 cm to about 1500 cm, from about 1300 cm to about 1500 cm, from about 1350 cm to about 1500 cm, from about 1400 cm to about 1500 cm, or from about 1450 cm to about 1500 cm. In other embodiments, L falls within any one of the exact numerical ranges set forth in this paragraph.
In embodiments, the substrate 450, may be formed from any suitable glass composition comprising soda lime glass, aluminosilicate glass, borosilicate glass, boroaluminosilicate glass, alkali-containing aluminosilicate glass, alkali-containing borosilicate glass, and alkali-containing boroaluminosilicate glass.
Unless otherwise specified, the glass compositions disclosed herein are described in mole percent (mol %) as analyzed on an oxide basis.
In one or more embodiments, the glass composition may comprise SiO2 in an amount in a range from about 66 mol % to about 80 mol %, from about 67 mol % to about 80 mol %, from about 68 mol % to about 80 mol %, from about 69 mol % to about 80 mol %, from about 70 mol % to about 80 mol %, from about 72 mol % to about 80 mol %, from about 65 mol % to about 78 mol %, from about 65 mol % to about 76 mol %, from about 65 mol % to about 75 mol %, from about 65 mol % to about 74 mol %, from about 65 mol % to about 72 mol %, or from about 65 mol % to about 70 mol %, and all ranges and sub-ranges therebetween.
In one or more embodiments, the glass composition comprises Al2O3 in an amount greater than about 4 mol %, or greater than about 5 mol %. In one or more embodiments, the glass composition comprises Al2O3 in a range from greater than about 7 mol % to about 15 mol %, from greater than about 7 mol % to about 14 mol %, from about 7 mol % to about 13 mol %, from about 4 mol % to about 12 mol %, from about 7 mol % to about 11 mol %, from about 8 mol % to about 15 mol %, from 9 mol % to about 15 mol %, from about 9 mol % to about 15 mol %, from about 10 mol % to about 15 mol %, from about 11 mol % to about 15 mol %, or from about 12 mol % to about 15 mol %, and all ranges and sub-ranges therebetween. In one or more embodiments, the upper limit of Al2O3 may be about 14 mol %, 14.2 mol %, 14.4 mol %, 14.6 mol %, or 14.8 mol %.
In one or more embodiments, glass layer(s) herein are described as an aluminosilicate glass article or comprising an aluminosilicate glass composition. In such embodiments, the glass composition or article formed therefrom comprises SiO2 and Al2O3 and is not a soda lime silicate glass. In this regard, the glass composition or article formed therefrom comprises Al2O3 in an amount of about 2 mol % or greater, 2.25 mol % or greater, 2.5 mol % or greater, about 2.75 mol % or greater, about 3 mol % or greater.
In one or more embodiments, the glass composition comprises B2O3 (e.g., about 0.01 mol % or greater). In one or more embodiments, the glass composition comprises B2O3 in an amount in a range from about 0 mol % to about 5 mol %, from about 0 mol % to about 4 mol %, from about 0 mol % to about 3 mol %, from about 0 mol % to about 2 mol %, from about 0 mol % to about 1 mol %, from about 0 mol % to about 0.5 mol %, from about 0.1 mol % to about 5 mol %, from about 0.1 mol % to about 4 mol %, from about 0.1 mol % to about 3 mol %, from about 0.1 mol % to about 2 mol %, from about 0.1 mol % to about 1 mol %, from about 0.1 mol % to about 0.5 mol %, and all ranges and sub-ranges therebetween. In one or more embodiments, the glass composition is substantially free of B2O3.
As used herein, the phrase “substantially free” with respect to the components of the composition means that the component is not actively or intentionally added to the composition during initial batching, but may be present as an impurity in an amount less than about 0.001 mol %.
In one or more embodiments, the glass composition optionally comprises P2O5 (e.g., about 0.01 mol % or greater). In one or more embodiments, the glass composition comprises a non-zero amount of P2O5 up to and comprising 2 mol %, 1.5 mol %, 1 mol %, or 0.5 mol %. In one or more embodiments, the glass composition is substantially free of P2O5.
In one or more embodiments, the glass composition may comprise a total amount of R2O (which is the total amount of alkali metal oxide such as Li2O, Na2O, K2O, Rb2O, and Cs2O) that is greater than or equal to about 8 mol %, greater than or equal to about 10 mol %, or greater than or equal to about 12 mol %. In some embodiments, the glass composition comprises a total amount of R2O in a range from about 8 mol % to about 20 mol %, from about 8 mol % to about 18 mol %, from about 8 mol % to about 16 mol %, from about 8 mol % to about 14 mol %, from about 8 mol % to about 12 mol %, from about 9 mol % to about 20 mol %, from about 10 mol % to about 20 mol %, from about 11 mol % to about 20 mol %, from about 12 mol % to about 20 mol %, from about 13 mol % to about 20 mol %, from about 10 mol % to about 14 mol %, or from 11 mol % to about 13 mol %, and all ranges and sub-ranges therebetween. In one or more embodiments, the glass composition may be substantially free of Rb2O, Cs2O or both Rb2O and Cs2O. In one or more embodiments, the R2O may comprise the total amount of Li2O, Na2O and K2O only. In one or more embodiments, the glass composition may comprise at least one alkali metal oxide selected from Li2O, Na2O and K2O, wherein the alkali metal oxide is present in an amount greater than about 8 mol % or greater.
In one or more embodiments, the glass composition comprises Na2O in an amount greater than or equal to about 8 mol %, greater than or equal to about 10 mol %, or greater than or equal to about 12 mol %. In one or more embodiments, the composition comprises Na2O in a range from about from about 8 mol % to about 20 mol %, from about 8 mol % to about 18 mol %, from about 8 mol % to about 16 mol %, from about 8 mol % to about 14 mol %, from about 8 mol % to about 12 mol %, from about 9 mol % to about 20 mol %, from about 10 mol % to about 20 mol %, from about 11 mol % to about 20 mol %, from about 12 mol % to about 20 mol %, from about 13 mol % to about 20 mol %, from about 10 mol % to about 14 mol %, or from 11 mol % to about 16 mol %, and all ranges and sub-ranges therebetween.
In one or more embodiments, the glass composition comprises less than about 4 mol % K2O, less than about 3 mol % K2O, or less than about 1 mol % K2O. In some instances, the glass composition may comprise K2O in an amount in a range from about 0 mol % to about 4 mol %, from about 0 mol % to about 3.5 mol %, from about 0 mol % to about 3 mol %, from about 0 mol % to about 2.5 mol %, from about 0 mol % to about 2 mol %, from about 0 mol % to about 1.5 mol %, from about 0 mol % to about 1 mol %, from about 0 mol % to about 0.5 mol %, from about 0 mol % to about 0.2 mol %, from about 0 mol % to about 0.1 mol %, from about 0.5 mol % to about 4 mol %, from about 0.5 mol % to about 3.5 mol %, from about 0.5 mol % to about 3 mol %, from about 0.5 mol % to about 2.5 mol %, from about 0.5 mol % to about 2 mol %, from about 0.5 mol % to about 1.5 mol %, or from about 0.5 mol % to about 1 mol %, and all ranges and sub-ranges therebetween. In one or more embodiments, the glass composition may be substantially free of K2O.
In one or more embodiments, the glass composition is substantially free of Li2O.
In one or more embodiments, the amount of Na2O in the composition may be greater than the amount of Li2O. In some instances, the amount of Na2O may be greater than the combined amount of Li2O and K2O. In one or more alternative embodiments, the amount of Li2O in the composition may be greater than the amount of Na2O or the combined amount of Na2O and K2O.
In one or more embodiments, the glass composition may comprise a total amount of RO (which is the total amount of alkaline earth metal oxide such as CaO, MgO, BaO, ZnO and SrO) in a range from about 0 mol % to about 2 mol %. In some embodiments, the glass composition comprises a non-zero amount of RO up to about 2 mol %. In one or more embodiments, the glass composition comprises RO in an amount from about 0 mol % to about 1.8 mol %, from about 0 mol % to about 1.6 mol %, from about 0 mol % to about 1.5 mol %, from about 0 mol % to about 1.4 mol %, from about 0 mol % to about 1.2 mol %, from about 0 mol % to about 1 mol %, from about 0 mol % to about 0.8 mol %, from about 0 mol % to about 0.5 mol %, and all ranges and sub-ranges therebetween.
In one or more embodiments, the glass composition comprises CaO in an amount less than about 1 mol %, less than about 0.8 mol %, or less than about 0.5 mol %. In one or more embodiments, the glass composition is substantially free of CaO. In some embodiments, the glass composition comprises MgO in an amount from about 0 mol % to about 7 mol %, from about 0 mol % to about 6 mol %, from about 0 mol % to about 5 mol %, from about 0 mol % to about 4 mol %, from about 0.1 mol % to about 7 mol %, from about 0.1 mol % to about 6 mol %, from about 0.1 mol % to about 5 mol %, from about 0.1 mol % to about 4 mol %, from about 1 mol % to about 7 mol %, from about 2 mol % to about 6 mol %, or from about 3 mol % to about 6 mol %, and all ranges and sub-ranges therebetween.
In one or more embodiments, the glass composition comprises ZrO2 in an amount equal to or less than about 0.2 mol %, less than about 0.18 mol %, less than about 0.16 mol %, less than about 0.15 mol %, less than about 0.14 mol %, less than about 0.12 mol %. In one or more embodiments, the glass composition comprises ZrO2 in a range from about 0.01 mol % to about 0.2 mol %, from about 0.01 mol % to about 0.18 mol %, from about 0.01 mol % to about 0.16 mol %, from about 0.01 mol % to about 0.15 mol %, from about 0.01 mol % to about 0.14 mol %, from about 0.01 mol % to about 0.12 mol %, or from about 0.01 mol % to about 0.10 mol %, and all ranges and sub-ranges therebetween.
In one or more embodiments, the glass composition comprises SnO2 in an amount equal to or less than about 0.2 mol %, less than about 0.18 mol %, less than about 0.16 mol %, less than about 0.15 mol %, less than about 0.14 mol %, less than about 0.12 mol %. In one or more embodiments, the glass composition comprises SnO2 in a range from about 0.01 mol % to about 0.2 mol %, from about 0.01 mol % to about 0.18 mol %, from about 0.01 mol % to about 0.16 mol %, from about 0.01 mol % to about 0.15 mol %, from about 0.01 mol % to about 0.14 mol %, from about 0.01 mol % to about 0.12 mol %, or from about 0.01 mol % to about 0.10 mol %, and all ranges and sub-ranges therebetween.
In one or more embodiments, the glass composition may comprise an oxide that imparts a color or tint to the glass articles. In some embodiments, the glass composition comprises an oxide that prevents discoloration of the glass article when the glass article is exposed to ultraviolet radiation. Examples of such oxides comprise, without limitation oxides of: Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ce, W, and Mo.
In one or more embodiments, the glass composition comprises Fe expressed as Fe2O3, wherein Fe is present in an amount up to (and comprising) about 1 mol %. In some embodiments, the glass composition is substantially free of Fe. In one or more embodiments, the glass composition comprises Fe2O3 in an amount equal to or less than about 0.2 mol %, less than about 0.18 mol %, less than about 0.16 mol %, less than about 0.15 mol %, less than about 0.14 mol %, less than about 0.12 mol %. In one or more embodiments, the glass composition comprises Fe2O3 in a range from about 0.01 mol % to about 0.2 mol %, from about 0.01 mol % to about 0.18 mol %, from about 0.01 mol % to about 0.16 mol %, from about 0.01 mol % to about 0.15 mol %, from about 0.01 mol % to about 0.14 mol %, from about 0.01 mol % to about 0.12 mol %, or from about 0.01 mol % to about 0.10 mol %, and all ranges and sub-ranges therebetween .
Where the glass composition comprises TiO2, TiO2 may be present in an amount of about 5 mol % or less, about 2.5 mol % or less, about 2 mol % or less or about 1 mol % or less. In one or more embodiments, the glass composition may be substantially free of TiO2.
An exemplary glass composition comprises SiO2 in an amount in a range from about 65 mol % to about 75 mol %, Al2O3 in an amount in a range from about 8 mol % to about 14 mol %, Na2O in an amount in a range from about 12 mol % to about 17 mol %, K2O in an amount in a range of about 0 mol % to about 0.2 mol %, and MgO in an amount in a range from about 1.5 mol % to about 6 mol %. Optionally, SnO2 may be comprised in the amounts otherwise disclosed herein.
In one or more embodiments, the glass substrate 450 discussed herein may be formed from a strengthened glass sheet or article. In one or more embodiments, the glass articles used to form the layer(s) of the decorated glass structures discussed herein may be strengthened to comprise compressive stress that extends from a surface to a depth of compression (DOC). The compressive stress regions are balanced by a central portion exhibiting a tensile stress. At the DOC, the stress crosses from a positive (compressive) stress to a negative (tensile) stress.
In one or more embodiments, the glass articles used to form the layer(s) of the decorated glass structures discussed herein may be strengthened mechanically by utilizing a mismatch of the coefficient of thermal expansion between portions of the glass to create a compressive stress region and a central region exhibiting a tensile stress. In some embodiments, the glass article may be strengthened thermally by heating the glass to a temperature above the glass transition point and then rapidly quenching.
In one or more embodiments, the glass articles used to form the layer(s) of the decorated glass structures discussed herein may be chemically strengthening by ion exchange. In the ion exchange process, ions at or near the surface of the glass article are replaced by—or exchanged with—larger ions having the same valence or oxidation state. In those embodiments in which the glass article comprises an alkali aluminosilicate glass, ions in the surface layer of the article and the larger ions are monovalent alkali metal cations, such as Li+, Na+, K+, Rb+, and Cs+. Alternatively, monovalent cations in the surface layer may be replaced with monovalent cations other than alkali metal cations, such as Ag+ or the like. In such embodiments, the monovalent ions (or cations) exchanged into the glass article generate a stress.
Ion exchange processes are typically carried out by immersing a glass article in a molten salt bath (or two or more molten salt baths) containing the larger ions to be exchanged with the smaller ions in the glass article. It should be noted that aqueous salt baths may also be utilized. In addition, the composition of the bath(s) may comprise more than one type of larger ion (e.g., Na+ and K+) or a single larger ion. It will be appreciated by those skilled in the art that parameters for the ion exchange process, comprising, but not limited to, bath composition and temperature, immersion time, the number of immersions of the glass article in a salt bath (or baths), use of multiple salt baths, additional steps such as annealing, washing and the like, are generally determined by the composition of the glass layer(s) of a decorated glass structure (comprising the structure of the article and any crystalline phases present) and the desired DOC and CS of the glass layer(s) of a decorated glass structure that results from strengthening.
Exemplary molten bath composition may comprise nitrates, sulfates, and chlorides of the larger alkali metal ion. Typical nitrates comprise KNO3, NaNO3, LiNO3, NaSO4 and combinations thereof. The temperature of the molten salt bath typically is in a range from about 380° C. up to about 450° C., while immersion times range from about 15 minutes up to about 100 hours depending on the glass thickness, bath temperature and glass (or monovalent ion) diffusivity. However, temperatures and immersion times different from those described above may also be used.
In one or more embodiments, the glass articles used to form the layer(s) of the decorated glass may be immersed in a molten salt bath of 100% NaNO3, 100% KNO3, or a combination of NaNO3 and KNO3 having a temperature from about 370° C. to about 480° C. In some embodiments, the glass layer(s) of a decorated glass may be immersed in a molten mixed salt bath comprising from about 5% to about 90% KNO3 and from about 10% to about 95% NaNO3. In one or more embodiments, the glass article may be immersed in a second bath, after immersion in a first bath. The first and second baths may have different compositions and/or temperatures from one another. The immersion times in the first and second baths may vary. For example, immersion in the first bath may be longer than the immersion in the second bath.
In one or more embodiments, the glass articles used to form the layer(s) of the decorated glass structures may be immersed in a molten, mixed salt bath comprising NaNO3 and KNO3 (e.g., 49%/51%, 50%/50%, 51%/49%) having a temperature less than about 420° C. (e.g., about 400° C. or about 380° C.). for less than about 5 hours, or even about 4 hours or less.
Ion exchange conditions can be tailored to provide a “spike” or to increase the slope of the stress profile at or near the surface of the resulting glass layer(s) of a decorated glass structure. The spike may result in a greater surface CS value. This spike can be achieved by single bath or multiple baths, with the bath(s) having a single composition or mixed composition, due to the unique properties of the glass compositions used in the glass layer(s) of a decorated glass structure described herein.
In one or more embodiments, where more than one monovalent ion is exchanged into the glass articles used to form the layer(s) of the decorated glass structures, the different monovalent ions may exchange to different depths within the glass layer (and generate different magnitudes stresses within the glass article at different depths). The resulting relative depths of the stress-generating ions can be determined and cause different characteristics of the stress profile.
CS is measured using those means known in the art, such as by surface stress meter (FSM) using commercially available instruments such as the FSM-6000, manufactured by Orihara Industrial Co., Ltd. (Japan). Surface stress measurements rely upon the accurate measurement of the stress optical coefficient (SOC), which is related to the birefringence of the glass. SOC in turn is measured by those methods that are known in the art, such as fiber and four point bend methods, both of which are described in ASTM standard C770-98 (2013), entitled “Standard Test Method for Measurement of Glass Stress-Optical Coefficient,” the contents of which are incorporated herein by reference in their entirety, and a bulk cylinder method. As used herein CS may be the “maximum compressive stress” which is the highest compressive stress value measured within the compressive stress layer. In some embodiments, the maximum compressive stress is located at the surface of the glass article. In other embodiments, the maximum compressive stress may occur at a depth below the surface, giving the compressive profile the appearance of a “buried peak.”
DOC may be measured by FSM or by a scattered light polariscope (SCALP) (such as the SCALP-04 scattered light polariscope available from Glasstress Ltd., located in Tallinn Estonia), depending on the strengthening method and conditions. When the glass article is chemically strengthened by an ion exchange treatment, FSM or SCALP may be used depending on which ion is exchanged into the glass article. Where the stress in the glass article is generated by exchanging potassium ions into the glass article, FSM is used to measure DOC. Where the stress is generated by exchanging sodium ions into the glass article, SCALP is used to measure DOC. Where the stress in the glass article is generated by exchanging both potassium and sodium ions into the glass, the DOC is measured by SCALP, since it is believed the exchange depth of sodium indicates the DOC and the exchange depth of potassium ions indicates a change in the magnitude of the compressive stress (but not the change in stress from compressive to tensile); the exchange depth of potassium ions in such glass articles is measured by FSM. Central tension or CT is the maximum tensile stress and is measured by SCALP.
In one or more embodiments, the glass articles used to form the layer(s) of the decorated glass structures maybe strengthened to exhibit a DOC that is described a fraction of the thickness t of the glass article (as described herein). For example, in one or more embodiments, the DOC may be equal to or greater than about 0.05 t, equal to or greater than about 0.1 t, equal to or greater than about 0.11 t, equal to or greater than about 0.12 t, equal to or greater than about 0.13 t, equal to or greater than about 0.14 t, equal to or greater than about 0.15 t, equal to or greater than about 0.16 t, equal to or greater than about 0.17 t, equal to or greater than about 0.18 t, equal to or greater than about 0.19 t, equal to or greater than about 0.2 t, equal to or greater than about 0.21 t. In some embodiments, The DOC may be in a range from about 0.08 t to about 0.25 t, from about 0.09 t to about 0.25 t, from about 0.18 t to about 0.25 t, from about 0.11 t to about 0.25 t, from about 0.12 t to about 0.25 t, from about 0.13 t to about 0.25 t, from about 0.14 t to about 0.25 t, from about 0.15 t to about 0.25 t, from about 0.08 t to about 0.24 t, from about 0.08 t to about 0.23 t, from about 0.08 t to about 0.22 t, from about 0.08 t to about 0.21 t, from about 0.08 t to about 0.2 t, from about 0.08 t to about 0.19 t, from about 0.08 t to about 0.18 t, from about 0.08 t to about 0.17 t, from about 0.08 t to about 0.16 t, or from about 0.08 t to about 0.15 t. In some instances, the DOC may be about 20 μm or less. In one or more embodiments, the DOC may be about 40 μm or greater (e.g., from about 40 μm to about 300 μm, from about 50 μm to about 300 μm, from about 60 μm to about 300 μm, from about 70 μm to about 300 μm, from about 80 μm to about 300 μm, from about 90 μm to about 300 μm, from about 100 μm to about 300 μm, from about 110 μm to about 300 μm, from about 120 μm to about 300 μm, from about 140 μm to about 300 μm, from about 150 μm to about 300 μm, from about 40 μm to about 290 μm, from about 40 μm to about 280 μm, from about 40 μm to about 260 μm, from about 40 μm to about 250 μm, from about 40 μm to about 240 μm, from about 40 μm to about 230 μm, from about 40 μm to about 220 μm, from about 40 μm to about 210 μm, from about 40 μm to about 200 μm, from about 40 μm to about 180 μm, from about 40 μm to about 160 μm, from about 40 μm to about 150 μm, from about 40 μm to about 140 μm, from about 40 μm to about 130 μm, from about 40 μm to about 120 μm, from about 40 μm to about 110 μm, or from about 40 μm to about 100 μm.
In one or more embodiments, the glass articles used to form the layer(s) of the decorated glass structures may have a CS (which may be found at the surface or a depth within the glass article) of about 200 MPa or greater, 300 MPa or greater, 400 MPa or greater, about 500 MPa or greater, about 600 MPa or greater, about 700 MPa or greater, about 800 MPa or greater, about 900 MPa or greater, about 930 MPa or greater, about 1000 MPa or greater, or about 1050 MPa or greater.
In one or more embodiments, the glass articles used to form the layer(s) of the decorated glass structures may have a maximum tensile stress or central tension (CT) of about 20 MPa or greater, about 30 MPa or greater, about 40 MPa or greater, about 45 MPa or greater, about 50 MPa or greater, about 60 MPa or greater, about 70 MPa or greater, about 75 MPa or greater, about 80 MPa or greater, or about 85 MPa or greater. In some embodiments, the maximum tensile stress or central tension (CT) may be in a range from about 40 MPa to about 100 MPa.
Unless otherwise expressly stated, it is in no way intended that any method set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not actually recite an order to be followed by its steps or it is not otherwise specifically stated in the claims or descriptions that the steps are to be limited to a specific order, it is in no way intended that any particular order be inferred. In addition, as used herein, the article “a” is intended to comprise one or more than one component or element, and is not intended to be construed as meaning only one.
It will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit or scope of the disclosed embodiments. Since modifications, combinations, sub-combinations and variations of the disclosed embodiments incorporating the spirit and substance of the embodiments may occur to persons skilled in the art, the disclosed embodiments should be construed to comprise everything within the scope of the appended claims and their equivalents.
This application claims the benefit of priority under 35 U.S.C. § 119 of U.S. Provisional Application Ser. No. 63/333,231 filed on Apr. 21, 2022, the content of which is relied upon and incorporated herein by reference in its entirety.
Number | Date | Country | |
---|---|---|---|
63333231 | Apr 2022 | US |