Systems and methods for detecting particle generation at glass-to-glass contacts

Abstract

A particle detection system and method for glass articles is provided. The system includes a light source that emits a light beam, where the light beam is formed into a light sheet and directed toward an area below the glass article, and a camera for capturing an image of the inspection area within the light sheet. The inspection area may be located below the glass article. The system may include optics for shaping the light beam into the light sheet. The light source may be a laser light source. Particles falling through the light sheet in the inspection area are illuminated, and their images are captured in a time-resolved manner by the camera.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority under 35 U.S.C. § 119 to U.S. Provisional Application No. 63 / 428,244, filed November 28, 2022, the contents of which are relied upon and incorporated herein by reference in their entirety. [Technical Field]

[0002] This specification relates generally to detecting particles from glass containers, and more specifically to detecting particles generated during manufacturing, shipping, packaging, or filling of containers used to store pharmaceutical formulations due to contact between the container and other containers or processing equipment. [Background technology]

[0003] Historically, glass has been used as a preferred material for packaging pharmaceuticals due to its hermeticity, optical clarity, and superior chemical durability compared to other materials. Specifically, glass used in pharmaceutical packaging must have adequate chemical durability so as not to affect the stability of the pharmaceutical formulations contained therein. Glasses with suitable chemical durability include those glass compositions within the ASTM standard "Type IA" and "Type IB" glass compositions, which have a proven track record of chemical durability.

[0004] Type IA and Type IB glass compositions are commonly used in pharmaceutical packaging, but suffer from several deficiencies, including the tendency of the interior surface of the pharmaceutical package to shed glass particles or "delaminate" after exposure to pharmaceutical solutions.

[0005] In addition, the use of glass in pharmaceutical packaging can also be limited by the mechanical performance of the glass. Specifically, the high processing speeds utilized in the manufacture and filling of glass pharmaceutical packages can result in mechanical damage, such as abrasion, to the surface of the package when the package comes into contact with processing equipment, handling equipment, and / or other packages. This mechanical damage significantly reduces the strength of the glass pharmaceutical package, resulting in an increased likelihood of cracks in the glass, potentially compromising the sterility of the pharmaceutical contained in the package or causing complete failure of the package.

[0006] In addition, contact between the package and other packages and / or processing and handling equipment can create scratches on the surface of the glass package, which not only affects the mechanical durability and sterility of the scratched package but can also create glass particles. These glass particles can then be deposited on the glass package itself or on processing lines, potentially creating a hazardous situation in the manufacturing or processing environment. The presence of these particles can also require regular cleaning of facilities that process these packages, which can hinder productivity by increasing downtime of processing equipment. These defects and the resulting particles can contaminate pharmaceutical products contained in pharmaceutical vials or syringes and even be injected into the human body. Such defects can result in recalls from the Food and Drug Administration or other regulatory agencies and are a significant source of lot yield loss in the industry.

[0007] Therefore, there is a need for systems and methods for detecting particle production to address these issues. In addition, there is a need for a better understanding of how such particles are produced, which could be gained from improved particle monitoring systems and methods. Summary of the Invention

[0008] According to an embodiment, a particle detection system for a glass article is provided. The particle detection system includes a light source configured to emit a light beam, where the light beam is formed into a light sheet and directed toward an area below the glass article, and a camera configured to capture an image of an inspection area within the light sheet, where the inspection area is below the glass article. The system may further include an optical system configured to shape the light beam into the light sheet, the optical system being disposed in an optical path of the light beam between the light source and the inspection area. The light source may be a laser light source. In one aspect of the embodiment, the system includes a holder for holding the glass article. The holder includes a support surface configured to support the glass article thereon. The support surface has an open or porous structure configured to allow particles generated by the glass article to fall through the support surface into the inspection area. The inspection area is disposed below the support surface and is disposed at a position where particles generated by the glass article can fall. The system may further include an actuator configured to move the glass article. The actuator may be coupled to the holder. The particle detection system may further include a computing device communicatively coupled to the camera, the computing device including at least one processor and at least one memory storing computer-readable and executable instructions that, when executed by the at least one processor, cause the computing device to determine whether particles are present within the inspection area.

[0009] According to an embodiment, a method for detecting particles generated from the impact of a glass article is provided. The method includes directing a light beam to an area below one or more glass articles, capturing an image of the inspection area within the light beam below the one or more glass articles with a camera, and determining whether particles are present in the image. The method may further include forming the light beam into a light sheet such that the inspection area is within the light sheet. The method may further include accelerating the one or more glass articles to cause the glass article impact, and the inspection area is imaged by the camera while accelerating the one or more glass articles.

[0010] Additional features and advantages of the particle monitoring system and method embodiments described herein are set forth in the detailed description that follows, and in part will be readily apparent to those skilled in the art from the description or may be learned by practicing the embodiments described herein, including the detailed description that follows, the claims, and the accompanying drawings.

[0011] It is to be understood that both the foregoing general description and the following detailed description are intended to describe various embodiments and provide an overview or framework for understanding the nature and features of the claimed subject matter. The accompanying drawings are included to provide a further understanding of the various embodiments, and are incorporated into and constitute a part of this specification. The drawings illustrate various embodiments described herein and, together with the description, serve to explain the principles and operation of the claimed subject matter. [Brief explanation of the drawings]

[0012] [Figure 1] 1 is a photograph of a scratched or damaged area on a glass container. [Figure 2A] 2 is a magnified image of area A on the glass container in FIG. 1. [Figure 2B] 3 is a further enlarged image of area A from FIGS. 1 and 2. FIG. [Figure 3]1 schematically depicts a glass particle detection system according to an embodiment of the present disclosure. [Figure 4] FIG. 4 is a close-up view of area B of FIG. 3 according to an embodiment of the present disclosure. [Figure 5] 1 is a depiction of an exemplary glass particle detection system, according to an embodiment of the present disclosure. [Figure 6A] 1 is an image captured by a glass particle detection system according to an embodiment of the present disclosure. [Figure 6B] 6B is a processed version of the image of FIG. 6A after performing an object identification routine, according to an embodiment of the present disclosure. [Figure 7A] 10 is a plot illustrating acceleration versus frequency for a first vibration pattern from an accelerator table running a vibration program, according to an embodiment. [Figure 7B] 10 is a plot illustrating acceleration versus frequency of a second vibration pattern from an accelerator table implementing a vibration program, according to an embodiment. [Figure 7C] 10 is a plot illustrating acceleration versus frequency for a third vibration pattern from an accelerator table implementing a vibration program, according to an embodiment. [Figure 8A] 10 is a plot showing particle generation for an uncoated container in terms of particle number versus time based on an acceleration of 1 G, according to an embodiment. [Figure 8B] 10 is a plot showing particle generation for an uncoated container in terms of particle number versus time based on 2G acceleration, according to an embodiment. [Figure 8C] 10 is a plot showing particle generation for an uncoated container in terms of particle count versus time based on 3G acceleration, according to an embodiment. [Figure 9A] 10 is a plot showing particle generation of a coated container in terms of particle number versus time based on an acceleration of 1 G, according to an embodiment. [Figure 9B] 10 is a plot showing particle generation of a coated container in terms of particle number versus time based on an acceleration of 2 G, according to an embodiment. [Figure 9C] 10 is a plot showing particle generation of a coated container in terms of particle count versus time based on 3G acceleration, according to an embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0013] Reference will now be made in detail to various embodiments of systems and methods for detecting particles generated from the collision of a glass article with another glass article or other surface. The embodiments include systems and methods for detecting particles emitted from the surface of a glass article in a time-resolved manner. The glass article may include glass containers, particularly pharmaceutical or parenteral packaging (e.g., vials, syringes, tubes, etc.), although the embodiments are not limited to any particular type of glass container or article. When uncoated glass articles are scratched against each other, the resulting interaction causes glass damage and the generation of glass particles. An example of such damage is shown in FIG. 1, where a glass surface 100 from an uncoated glass vial exhibits a scratch 102 after being rubbed against another glass vial with a normal force of 1-30 N. FIG. 2A shows a magnified view of area A from the photograph of FIG. 1, and FIG. 2B shows an even more magnified view of the glass particles generated. The damage shown in FIGS. 1-2B is the result of a laboratory scratch test, but similar results can be obtained with simple glass-to-glass contact. In manufacturing and production environments, these glass particles can detach from the glass articles and deposit on other glass articles or processing equipment in the surrounding environment (e.g., conveyors, work areas, and other equipment). In practice, routine cleaning must be performed to remove glass particles from production machines or conveying lines. For example, in the case of pharmaceutical vials or syringes, glass particles are typically removed from the production line after each vial filling campaign, and sometimes frequently during the campaign.

[0014] Some glass articles are coated with coatings that reduce the coefficient of friction of the glass article's surface, mitigating the effects of glass-to-glass contact or contact between the glass article and other surfaces. Corning®'s Valor® glass vial is one example of a coated glass article. The Valor® vial's coating prevents damage to the glass upon contact, and no glass particles are generated. However, with coated glass articles, concerns about coating-generated particles may still exist. Therefore, a system and method for evaluating any glass article (e.g., a vial, syringe, tube, or other container) for particles, whether coated or uncoated, would be desirable. However, such a solution remains elusive, especially given the complexities associated with providing a practical solution within the desired environment. For example, mechanical measurements are often performed in controlled conditions. While this is useful for damage characterization, there remains an unmet need to be able to simulate the multiple, variable forces that vials experience while being processed on a production or filling line. Previous laboratory-scale measurements of vials contacting mock-up accelerator tables have shown little to no glass particles, and potentially no coating particles, generated as a result of the vial contact. However, previously used detection methods require particles to be delivered a significant distance from the device to be detected via a particle counter wafer plate. Such methods likely measure only a minority of the particles generated. In addition, this type of setup using a particle wafer plate cannot record when particles are captured, making the detector non-time-resolved and the cumulative particle count a time integral.There are other methods in the industrial powder industry that capture and characterize the size and quantity of a small portion of a powder distribution, such as static light scattering (SLS) / laser diffraction particle size distribution analysis by Horiba Scientific (https: / / www.horiba.com / gbr / scientific / technologies / static-light-scattering-sls-laser-diffraction-particle-size-distribution-analysis / static-light-scattering-sls-laser-diffraction-particle-size-distribution-analysis / ). However, these methods require large amounts of particles, which may not be present in all applications. Therefore, there remains a need for a method to simulate the various accelerations experienced in manufacturing, processing, or filling lines and measure the particles generated when glass articles (e.g., vials, tubes, syringes) come into contact with each other.

[0015] Embodiments of the present disclosure provide systems and methods that overcome the above-mentioned shortcomings of existing methods. In particular, embodiments include systems and methods for measuring particles generated from glass articles (e.g., glass containers, vials, or pharmaceutical packaging) due to item-to-item contact within the contacted area in a time-resolved manner, thereby providing a means to capture a higher percentage or majority of particles generated due to contact. The detected particles may be generated due to item-to-item contact or may be generated due to contact between the article and another surface, such as part of a manufacturing or filling line. The results of these types of particle detection measurements apply to manufacturing, processing, and filling lines, as well as packaging and shipping processes, including internal shipping containers.

[0016] An example of an embodiment of the present disclosure is a glass particle detection system 200, schematically depicted in FIG. 3 . The glass particle detection system 200 may include a light source 202 capable of emitting a light beam 203. The light beam 203 is directed toward an area below one or more glass articles 214 on a support surface 212. The support surface 212 may be the bottom of a shipping container, a processing line or conveyor, a basket or box, or other surface for holding, storing, processing, transporting, or testing the glass articles 214. In some embodiments, the support surface 212 has a porous or partially open surface to allow particles generated from the glass articles 214 to fall through the support surface 212. In embodiments, the support surface 212 may be part of or attached to an accelerator table used to accelerate the glass articles 214, which may be used to generate particles in a laboratory environment to better understand the particle generation behavior of the glass articles 214. The accelerator table can be programmed (e.g., by programming the magnitude, frequency, and timing of the oscillations from the accelerator table) to replicate the type of acceleration that the glass article 214 may experience in a particular environment.

[0017] Particle detection system 200 is positioned such that light beam 212 forms a light sheet 210 below support surface 212. The shaping of light beam 212 into a thin light sheet 210 with high irradiance allows the particle detection system to visualize micro-airborne particles through one or more imaging or detection techniques, including both geometric and Mie scattering processes (size-dependent) with a reasonable signal-to-noise ratio. FIG. 4 shows a close-up view of area B below support surface 212, including a falling particle 232 and a particle 234 illuminated as it falls through light sheet 210. Light source 202 can be a laser that emits light beam 203. Light beam 203 can be a line of light. Light source 202 can be a diode laser, including an array of laser diodes that projects a line of light. Light source 202 can project light sheet 210, or light sheet 210 can be formed using optical system 208. Optical system 208 may include one or more lenses and / or other optics for manipulating light beam 203 into light sheet 210. In embodiments, light sheet 210 may be formed by rapid movement or oscillation of light source 202. In some embodiments, light source 202 is a light source other than a laser, such as an LED light source, a visible light source, and an infrared light source.

[0018] Particle detection system 200 also includes camera 218. Camera 218 is used to capture images of particles as they fall through and are illuminated by light sheet 210 within inspection area 230. One or more optical components or mirrors (220) may be positioned to direct images of particles within inspection area 230 toward camera 218. Camera 218 may be any device having an array of sensing devices capable of detecting radiation in the ultraviolet, visible, or infrared wavelength bands. Camera 218 may have a focal plane located at inspection area 230. Camera 218 may include an optical lens. Camera 218 may capture images of light sheet 210, including any illuminated particles 234 within light sheet 230.

[0019] The camera 218 may communicate with the computing device 219 via a communication path 221. The computing device 219 may include one or more processors and a memory module. Each of the one or more processors may be any device capable of executing machine-readable instructions. Accordingly, each of the one or more processors may be a controller, an integrated circuit, a microchip, a computer, or any other computing device. The one or more processors are coupled to the communication path 221 for communication with the camera 218. The camera 218 may transmit captured images of the light sheet 210 in the inspection area 230 to the processor of the computing device 219 via the communication path 221. In some embodiments, the camera 218 may include one or more processors and a memory module. In some such embodiments, the camera 218 may capture images of the light sheet 210 and / or the illuminated particles 234, process the images with one or more processors, and store the processed images in a memory module or transmit the processed images to the computing device 219.

[0020] Communication path 221 may be formed from any medium capable of transmitting a signal, such as, for example, a conductive wire, a conductive trace, an optical waveguide, etc. In some embodiments, communication path 221 may facilitate the transmission of wireless signals, such as WiFi, Bluetooth, near field communication (NFC), etc. Furthermore, communication path 221 may be formed from a combination of media capable of transmitting a signal. In one embodiment, communication path 221 comprises a combination of conductive traces, conductive wires, connectors, and buses that cooperate to enable the transmission of electrical data signals to components such as processors, memories, sensors, input devices, output devices, and communication devices. Thus, communication path 221 may comprise, for example, a vehicle bus such as a LIN bus, a CAN bus, a VAN bus, etc. Additionally, it should be noted that the term “signal” refers to a waveform (e.g., electrical, optical, magnetic, mechanical, or electromagnetic) that can travel through a medium, such as DC, AC, sine wave, triangular wave, square wave, vibration, etc.

[0021] The one or more memory modules may comprise RAM, ROM, flash memory, a hard drive, or any device capable of storing machine-readable instructions such that the machine-readable instructions can be accessed by one or more processors. The one or more memory modules may store images captured by the camera 218. The captured images may be processed by one or more processors before being stored in the one or more memory modules. The machine-readable instructions may include, for example, logic or algorithm(s) written in any programming language of any generation (e.g., 1GL, 2GL, 3GL, 4GL, or 5GL) that can be directly executed by a processor, or that can be compiled or assembled into machine-readable instructions and stored on one or more memory modules, such as assembly language, object-oriented programming (OOP), scripting language, microcode, etc. Alternatively, the machine-readable instructions may be written in a hardware description language (HDL), such as logic implemented via a field-programmable gate array (FPGA) configuration or an application-specific integrated circuit (ASIC), or their equivalents. Thus, the systems and methods described herein can be implemented in any conventional computer programming language, as pre-programmed hardware elements, or as a combination of hardware and software components.

[0022] According to embodiments of the present disclosure, systems and methods are provided that allow for the detection and counting of a significant number, if not most or all, of the particles generated, rather than just the particles that are sent furthest by contact, a limitation of existing methods. Embodiments can also ensure that detected particles are time-resolved. This provides several previously unknown insights into particle generation, including understanding when particle generation occurred in time, understanding particle generation rates, and understanding any time-dependent nonlinear particle generation behavior. The systems and methods of the present disclosure also allow for the characterization of the force / acceleration required to generate particles on glass articles where small forces do not generate particles.

[0023] According to embodiments, the camera may transmit a captured image to one or more processors, which may perform image processing on the captured image to remove any lighting, noise, particles, etc. outside the region of interest. This processing removes particles or noise appearing in the camera's field of view outside the region of interest, while leaving particles within the region of interest. The one or more processors may then determine whether any particles are present within the region of interest on the processed image. If a particle is determined to be present within the region of interest on the processed image, the one or more processors may determine various characteristics of the particle (e.g., size, shape, location within the field of view, timing of particle generation, relationship to other detected particles, relationship of particle generation time to external conditions, etc.). Based on the determination, the one or more processors may indicate that the glass article should be rejected or that it is time for the area to be cleaned. The rejection indication may be stored in one or more memory modules along with the identification of the group or lot of glass articles. If a particle is determined to be absent within the region of interest on the processed image, the one or more processors may determine that no particles are present for glass vials present above the field of view when the image was captured. The determination, along with the identification of the glass article, may be stored in one or more memory modules.

[0024] In embodiments, various processing methods may be performed on the captured image to remove undesired data on the image. For example, a threshold filter may be applied to the captured image to remove most of the unwanted artifacts from the image. The processing may also convert the captured image into a binary image. For example, captured particles on the image may be converted to white dots, while the rest of the image may be converted to black dots or a black or blue background. A particle filter may be applied to the captured image to remove any artifacts that do not persist after image processing. The various processes may effectively remove features in the image that are too small to be actual particles.

[0025] For particles within the region of interest, the camera or one or more processors may process the image to affect the appearance of the detected particles. For example, processing may magnify the particles in the image relative to background structures or adjust the contrast, brightness, or another characteristic. Magnification is intentionally performed to increase the sensitivity of particle detection. The actual particle size may be determined by calibrating the image based on test samples of known particle size. [Example]

[0026] FIG. 5 depicts the experimental setup of a particle detection system 300 according to an embodiment of the present disclosure. The particle detection system 300 was used to measure particles generated by a glass pharmaceutical vial 314. The test conditions, image capture and processing, and results are shown in FIGS. 6A-9C. The particle detection system 300 includes a laser source 302, sheet-forming optics 308, a mirror 309, an accelerator table 306, a vial basket 312 for holding vials 314, a mirror 320, and a camera 318. The laser source 302 and optics 308 are supported on an optical breadboard 304, and the camera 318 and mirror 320 are mounted on a tripod 322. Laser sheet imaging was selected as the illumination and imaging strategy. The shaping of the laser beam 303 into a thin laser sheet 310 with high irradiance allows for visualization of small airborne particles through both geometric and size-dependent Mie scattering processes with a reasonable signal-to-noise ratio. Light source 302 offers more spatial control and particle detection capabilities than traditional high-power LEDs or flashlights. A continuous-wave Nd:YAG laser producing 532 nm laser light was selected as light source 302. It was mounted on an optical breadboard 304 located next to accelerator table system 306. The beam was collimated into a horizontal laser sheet 310 using a cylindrical lens 308. The shaper of laser sheet 310 was approximately 20 mm wide and 3 mm thick. Laser sheet 310 was positioned to pass 20 mm below vial basket 312 (containing vials 314) and collected in beam dump 316. The exact arrangement of components is exemplary of an embodiment of the present disclosure. As will be understood by those skilled in the art, some components are for convenience, practicality, or compactness of system 300, and some components are optional or can be rearranged as needed.

[0027] For camera 318, a Basler acA640-750um USB camera 318 (from Basler AG) was used to image and detect particles as they crossed the laser sheet 310. Due to physical constraints, camera 318 imaged the underside of the vial basket through an aluminum mirror 320 mounted at a 45-degree angle. The camera 318 and mirror 320 were attached to a photographic tripod 322 using a mounting rod 324 to isolate them from the accelerator table 306. The camera operated at 100 Hz with a 1 ms exposure time. For each test condition, the recording time was 15 minutes. The camera's relatively high frame rate, compared to the thickness of the laser sheet, facilitated time-resolved detection methods. The relatively short exposure time minimized collected background light, increasing the particle signal-to-noise ratio and facilitating subsequent particle identification through software processing via thresholding.

[0028] The accelerator table used to move the vials was configured via a Telcordia GR-63 profile. It is designed to simulate vibrations experienced during shipping and handling. It is a random vibration profile with a frequency range of 10-2000 Hz and 3.21 G. This vibration profile is used for testing and illustrative purposes only; embodiments of the present disclosure are not limited to any particular vibration profile or application. For example, a vibration profile can be programmed to simulate the acceleration experienced by pharmaceutical vials on a manufacturing or filling line. The same break table profile was tested at 1 G, 2 G, and 3 G as a step stress event for particle generation. Table 1 shows the reference breakpoint values. [Table 1]

[0029] Figure 6A shows an example image captured by the camera 318 during this experiment, showing light reflected from particles 600 in the inspection area. While the vials 314 in the basket 312 were accelerating, the room lights were turned off so that only light reflected from particles within the field of view was observed. The recorded data was processed using a purpose-written Matlab algorithm. Each raw image in the sequence (e.g., Figure 6A) was converted into a binary mask by setting all pixels below a certain threshold equal to 0 and all pixels above it equal to 1, resulting in the binary mark shown in Figure 6B. The threshold was chosen to be the chip saturation value (based on 255 counts). Once the captured image was converted into a binary mask, an object identification routine was performed to count all detected particles and the value stored in the array. Additional image processing, including, for example, processing to remove any lighting, noise, particles, etc. within the image or to the side of the region of interest within the image, can be performed by the camera or a computing device external to the camera.

[0030] As mentioned above, the acceleration table was operated at different levels. Figure 7A shows a plot of acceleration 700 at 1G, plotting acceleration level versus frequency. The acceleration table was designed to randomly access all frequencies within the cyan limit range 702, 704, as demonstrated in the image above. Similar plots are shown below in Figures 7B and 7C for accelerations of 2G and 3G, respectively.

[0031] Experiments were conducted using Corning® Valor® pharmaceutical vials, with some runs using coated Valor® vials and some using uncoated Valor® vials. Processing data can be used to compare the coated vials to uncoated vials. Embodiments are not limited to these specific vials; other glass articles, including those that are borosilicate or other compositions or have different coating compositions and / or different manufacturing parameters, can be used or compared to these specific vials. Figures 8A, 8B, and 8C show nonlinear particle generation for uncoated Valor® vials at acceleration forces of 1 G, 2 G, and 3 G, respectively, above a baseline. The baseline was determined based on particles counted in an experiment conducted without a vial in the basket. The data demonstrate nonlinear particle generation over time, indicating nonlinear material durability. Figures 9A, 9B, and 9C show that coated Valor® vials produce essentially no particles above the room baseline for the different vibration forces tested (1 G, 2 G, and 3 G, respectively).

[0032] Glass articles The glass articles or containers described herein may have at least two performance attributes selected from resistance to delamination, improved strength, and increased damage resistance. For example, a glass container may have a combination of resistance to delamination and improved strength, a combination of improved strength and increased damage resistance, or a combination of resistance to delamination and increased damage resistance. In one particular embodiment, a glass container having delamination resistance and improved strength may include a body having an inner surface, an outer surface, and a thickened portion extending between the outer surface and the inner surface. The body may have a delamination coefficient of 10 or less. The body may also have a compressive stress layer extending from the outer surface of the body into the thickened portion. The compressive stress layer may have a surface compressive stress of 150 MPa or more. Glass containers having various combinations of resistance to delamination, improved strength, and increased damage resistance are described in more detail herein, particularly with reference to the accompanying drawings.

[0033] In the glass composition embodiments described herein, concentrations of components (e.g., SiO, AlO, BO, etc.) are specified in mole percent (mol%) on an oxide basis unless otherwise specified.

[0034] The term "substantially free," when used to describe the concentration and / or absence of a particular component in a glass composition, means that the component is not intentionally added to the glass composition. However, the glass composition may contain trace amounts of the component in amounts less than 0.1 mole percent as contaminants or tramps.

[0035] As used herein, the term "chemical durability" refers to the resistance of a glass composition to degradation when exposed to specified chemical conditions. Specifically, the chemical durability of the glass compositions described herein can be evaluated according to three established materials testing standards: DIN 12116, dated March 2001, entitled "Testing of glass—Resistance to attack by a boiling aqueous solution of hydrochloric acid—Method of test and classification," ISO 695:1991, entitled "Glass—Resistance to attack by a boiling aqueous solution of mixed alkali—Method of test and classification," ISO 720:1985, entitled "Glass—Hydrolytic resistance of glass grains at 121 degrees C—Method of test and classification," and ISO 719:1985, entitled "Glass—Hydrolytic resistance of glass grains at 98 degrees C—Method of test and classification." Each standard, and the classifications within each standard, are described in further detail herein. Alternatively, the chemical durability of glass compositions may be evaluated using a USP Surface Glass Test entitled "Surface Glass Test," which evaluates the durability of the glass surface. <660> and / or may be evaluated in accordance with European Pharmacopoeia 3.2.1 entitled "Glass Containers For Pharmaceutical Use."

[0036] As used herein, "strain point" and "T strain The term "glass viscosity" refers to a viscosity of 3x10 14 Refers to the temperature in poise.

[0037] As used herein, the term "softening point" refers to the point at which the viscosity of a glass composition reaches 1x107.6 Refers to the temperature in poise.

[0038] Conventional glass containers used to store pharmaceuticals and / or other consumables can be damaged during filling, packaging, and / or shipping. Such damage can be in the form of surface scratches, abrasions, and / or nicks that, if deep enough, can result in through-cracks or complete failure of the glass container, thereby compromising the contents of the glass package.

[0039] In addition, some conventional glass containers may be susceptible to delamination, especially if the glass container is made of alkali borosilicate glass. Delamination refers to the phenomenon in which glass particles are released from the glass surface after a series of leaching, corrosion, and / or weathering reactions. Typically, the glass particles are silica-rich glass flakes that form from the inner surface of the package as a result of leaching of modifier ions into the solution contained within the package. These flakes can generally be about 1 nm to about 2 microns (μm) thick and have a width greater than about 50 μm. Because these flakes are primarily composed of silica, the flakes generally do not further decompose after being released from the surface of the glass.

[0040] Previously, delamination has been hypothesized to result from phase separation that occurs in alkali borosilicate glasses when the glasses are exposed to the high temperatures used to reshape the glass into container shapes.

[0041] However, it is now believed that the delamination of silica-rich glass flakes from the interior surface of glass containers is due to the compositional characteristics of the glass containers as they are formed. Specifically, the high silica content of alkali borosilicate glasses causes the glasses to have relatively high melting and forming temperatures. However, the alkali and borate components in the glass composition melt and / or volatilize at much lower temperatures. In particular, the borate species in the glass are highly volatile and evaporate from the surface of the glass at the high temperatures required to form and reform the glass.

[0042] Specifically, glass stock is reformed into a glass container at high temperatures and over an open flame. The high temperatures required in more expensive equipment cause more volatile borate species to evaporate from portions of the glass surface. When this evaporation occurs within the interior volume of the glass container, the volatilized borate species are redeposited on other areas of the glass container's surface, causing compositional heterogeneity on the surface of the glass container, particularly with respect to the near-surface region of the interior of the glass container (i.e., the region at or directly adjacent to the interior surface of the glass container). For example, when one end of a glass tube is closed to form the bottom or floor of the container, borate species may evaporate from the bottom of the tube and redeposit elsewhere in the tube. Evaporation of material from the heel and floor of the container is particularly noticeable because these areas of the container undergo the most extensive reformation and are therefore exposed to the highest temperatures. As a result, areas of the container exposed to higher temperatures may have a silica-rich surface. Other areas of the container suitable for boron deposition may have a boron-rich layer on the surface. Areas suitable for boron deposition, at temperatures above the annealing point of the glass composition but below the maximum temperature the glass will experience during reshaping, can lead to the incorporation of boron into the surface of the glass. The solution contained in the container can leach boron from the boron-rich layer. Once the boron-rich layer is leached from the glass, a high-silica glass network (gel) remains, which swells and distorts during hydration and eventually fractures from the surface.

[0043] The glass containers described herein alleviate at least two of the aforementioned problems. Specifically, the glass containers have at least two performance attributes selected from resistance to delamination, improved strength, and increased damage resistance. For example, the glass containers may have a combination of resistance to delamination and improved strength, a combination of improved strength and increased damage resistance, or a combination of resistance to delamination and increased damage resistance. Each performance attribute, and methods for achieving that performance attribute, are described in further detail herein.

[0044] Although the glass articles described herein may be described with reference to a particular form (i.e., a vial), it is understood that the glass articles may have other geometric forms, including, but not limited to, Vacutainers®, cartridges, syringes, ampoules, bottles, flasks, vials, tubes, beakers, etc. Furthermore, it is understood that the glass containers described herein may be used in a variety of applications, including, but not limited to, pharmaceutical packaging, beverage containers, etc.

[0045] strength In some embodiments described herein, the glass article includes a compressive stress layer extending from at least the outer surface of the body to the wall thickness and from the outer surface of the body to a depth of layer (DOL). The compressive stress layer generally increases the strength of the glass container and also improves the damage tolerance of the glass container. Specifically, a glass container having a compressive stress layer can generally withstand a greater degree of surface damage, such as scratches or chips, without breaking compared to a non-tempered glass container because the compressive stress layer mitigates the propagation of cracks from surface damage in the compressive stress layer.

[0046] In embodiments described herein, the depth of layer of the compressive stress layer may be about 3 μm or greater. In some embodiments, the depth of layer may be about 25 μm or greater, or even about 30 μm or greater. For example, in some embodiments, the depth of layer may be about 25 μm or greater, up to about 150 μm. In some other embodiments, the depth of layer may be about 30 μm or greater and about 150 μm or greater. In still other embodiments, the depth of layer may be about 30 μm or greater and about 80 μm or less. In some other embodiments, the depth of layer may be about 35 μm or greater and about 50 μm or less.

[0047] The compressive stress layer generally has a surface compressive stress (i.e., compressive stress measured at the outer surface) of 150 MPa or greater. In some embodiments, the surface compressive stress can be 200 MPa or greater, or even 250 MPa or greater. In some embodiments, the surface compressive stress can be 300 MPa or greater, or even 350 MPa or greater. For example, in some embodiments, the surface compressive stress can be about 300 MPa or greater and about 750 MPa or less. In some other embodiments, the surface compressive stress can be about 400 MPa or greater and about 700 MPa or less. In yet other embodiments, the surface compressive stress can be about 500 MPa or greater and about 650 MPa or less. Stress within an ion-exchanged glass article can be measured with an FSM (Fundamental Stress Meter) instrument. This instrument couples light into and out of the birefringent glass surface. The measured birefringence is then related to stress through the material constant, the stress-optical coefficient or photoelastic coefficient (SOC or PEC). Two parameters are obtained: the maximum surface compressive stress (CS) and the depth of the exchanged layer (DOL). Alternatively, compressive stress and layer depth can be measured using refractive near-field stress measurement techniques.

[0048] The compressive stress layer is herein defined as a layer extending from the outer surface of the body to a thickness T W Although shown and described as extending through the thickness T of the body, it should be understood that in some embodiments the body may further include a second compressive stress layer extending from the inner surface through the thickness of the body. In this embodiment, the depth of layer and surface compressive stress of the second compressive stress layer may be greater than the thickness T of the body. W This can reflect the depth of the compressive stress layer around the centerline and the surface compressive stress.

[0049] A compressive stress layer can be formed in the body of a glass container using several different techniques. For example, in embodiments in which the body is formed from an ion-exchangeable glass, the compressive stress layer can be formed in the body by ion exchange. In these embodiments, the compressive stress layer is formed by placing the glass container in a bath of molten salt to facilitate the exchange of relatively large ions in the molten salt with relatively small ions in the glass. Several different exchange reactions can be used to achieve the compressive stress layer. In one embodiment, the bath can contain molten KNO salt, while the glass from which the glass container is formed contains lithium and / or sodium ions. In this embodiment, potassium ions in the bath are exchanged for relatively small lithium and / or sodium ions in the glass, thereby forming the compressive stress layer. In another embodiment, the bath can contain NaNO salt, while the glass from which the glass container is formed contains lithium ions. In this embodiment, sodium ions in the bath are exchanged for relatively small lithium ions in the glass, thereby forming the compressive stress layer.

[0050] In one particular embodiment, the compressive stress layer can be formed by immersing the glass container in a molten salt bath of 100% KNO, or alternatively, a mixture of KNO and NaNO. For example, in one embodiment, the molten salt bath can include KNO with up to about 10% NaNO. In this embodiment, the glass from which the container is formed can include sodium and / or lithium ions. The temperature of the molten salt bath can be greater than or equal to 350°C and less than or equal to 500°C. In some embodiments, the temperature of the molten salt bath can be greater than or equal to 400°C and less than or equal to 500°C. In yet other embodiments, the temperature of the molten salt bath can be greater than or equal to 450°C and less than or equal to 475°C. The glass container can be maintained in the molten salt bath for a period sufficient to facilitate the exchange of relatively large ions in the salt bath with relatively small ions in the glass, thereby achieving the desired surface compressive stress and depth of layer. For example, the glass can be maintained in the molten salt bath for a period of greater than or equal to 0.05 hours and less than or equal to about 20 hours to achieve the desired depth of layer and surface compressive stress. In some embodiments, the glass container can be maintained in the molten salt bath for a period of at least 4 hours and not more than about 12 hours. In other embodiments, the glass container can be maintained in the molten salt bath for a period of at least about 5 hours and not more than about 8 hours. In one exemplary embodiment, the glass container can be ion-exchanged in a molten salt bath containing 100% KNO at a temperature of at least about 400° C. and not more than about 500° C. for a period of at least about 5 hours and not more than about 8 hours.

[0051] Typically, the ion exchange process is performed to lower the strain point (T strainion exchange strengthening is performed at temperatures above 150°C below the strain point of the glass. However, in some embodiments, a compressive stress layer is formed in a molten salt bath at a temperature above the strain point of the glass. This type of ion exchange strengthening is referred to herein as "high-temperature ion exchange strengthening." In high-temperature ion exchange strengthening, as described above, relatively small ions in the glass are exchanged for relatively large ions from a molten salt bath. As the relatively small ions are exchanged for relatively large ions at a temperature above the strain point, the resulting stress is released, or "relaxed." However, replacing the smaller ions in the glass with larger ions creates a surface layer in the glass that has a lower coefficient of thermal expansion (CTE) than the rest of the glass. As the glass cools, the CTE difference between the surface of the glass and the rest of the glass creates a compressive stress layer. This high-temperature ion exchange technique is particularly well-suited for strengthening glass articles, such as glass containers, that have complex shapes and typically shortens the strengthening process time relative to typical ion exchange processes and allows for greater layer depths.

[0052] In some embodiments, a compressive stress layer can be introduced into the body of a glass container by thermal tempering. The compressive stress layer is formed through thermal tempering by heating the glass container and differentially cooling the surface of the glass relative to the bulk of the glass. Specifically, rapidly cooled glass has a larger molar volume (or lower density) than glass that is cooled more slowly. Therefore, if the surface of the glass is intentionally rapidly cooled, the surface of the glass will have a larger volume, and the interior of the glass (i.e., the remainder of the glass below the outer surface) will necessarily cool at a slower rate, since heat must escape from the bulk through the surface. WThe resulting continuous gradient of molar volume (or thermal history / density) into the glass container creates a compressive stress layer with a parabolic stress profile (i.e., the compressive stress decreases parabolically with increasing distance from the outer surface of the body). Thermal tempering processes are generally faster and less expensive than ion exchange processes. However, the surface compressive stress resulting from a thermal tempering process is generally lower than the surface compressive stress resulting from an ion exchange process. In embodiments where the glass container is thermally strengthened, the resulting compressive stress layer extends from the outer surface 106 to the thickness T of the glass container. W For example, in some embodiments, the DOL extends to a thickness T W Approximately 5% to 22% of the thickness, or even thicker W It can be about 10% to about 22% of the total.

[0053] In a typical thermal tempering process, a glass container is first heated to its softening point, and then the outer surface of the body is quenched below the softening point using a fluid, such as a gas jet, to create a temperature differential between the outer surface and the remainder of the body, as described above. The temperature differential between the outer surface and the remainder of the body is created by a temperature differential between the outer surface and the thickness T of the body. W For example, the glass may be first heated to 50-150°C above its softening point and then quenched to room temperature by directing a fluid onto the glass. The fluid may include, but is not limited to, air, oil, or an oil-based fluid.

[0054] In some embodiments, a glass container can be formed from a laminated glass that facilitates the formation of a compressive stress layer on at least the outer surface of the body. Laminated glass generally includes a glass core layer and at least one glass cladding layer. The laminated glass can include a pair of glass cladding layers. In this embodiment, the glass core layer generally includes a first surface and a second surface opposite the first surface. The first glass cladding layer is fused to the first surface of the glass core layer, and the second glass cladding layer is fused to the second surface of the glass core layer. The glass cladding layer is fused to the glass core layer without any additional material, such as an adhesive or coating layer, disposed between the glass core layer and the glass cladding layer.

[0055] In embodiments, the glass core layer has an average core coefficient of thermal expansion, CTE core and the glass cladding layer is formed from a first glass composition having an average coefficient of thermal expansion CTE clad In the embodiments described herein, the glass is formed from a second, different glass composition having a CTE core is a CTE clad Since the CTE is not equal to , the compressive stress layer is present in at least one of the core layer or the cladding layer. core is a CTE clad In some other embodiments, such as when the laminated glass includes a single core layer and a single clad layer, the CTE is greater than 0.05, which allows the glass cladding layer to be compressively stressed without being ion-exchanged or thermally strengthened. clad is a CTE core , whereby the glass core layer is under compressive stress without being ion-exchanged or thermally strengthened. Laminated glass can be formed by a fusion lamination process, such as the process described in U.S. Pat. No. 4,214,886, which is incorporated herein by reference.

[0056] The laminated glass sheets can be formed into glass containers by press molding, blow molding, or vacuum forming. For example, in one embodiment, the laminated glass sheets can be vacuum formed as described in U.S. Patent No. 3,607,186, which is incorporated herein by reference in its entirety. Alternatively, the molten glass can be formed directly into a laminated glass tube as described in U.S. Patent No. 4,023,953, which is incorporated herein by reference.

[0057] In some embodiments in which the glass container is formed from laminated glass, at least one glass cladding layer forms the interior surface of the body of the glass container such that the at least one glass cladding layer is in direct contact with the product stored in the glass container. In these embodiments, the at least one cladding layer may be formed from a glass composition that is resistant to delamination, as described in more detail herein. Accordingly, it should be understood that the at least one cladding layer may have a delamination factor of 10 or less, as described in more detail herein.

[0058] Based on the above, it should be understood that in some embodiments, a glass container can include a compressive stress layer extending from at least the outer surface of the body to the thickness of the glass container. The compressive stress layer improves the mechanical strength of the glass container compared to a glass container that does not include a compressive stress layer. The compressive stress layer also improves the damage tolerance of the glass container, such that the glass container can withstand greater surface damage (i.e., scratches, chips, etc. that extend deeper into the thickness of the glass container) without breaking compared to a glass container that does not include a compressive stress layer. It should also be understood that in these embodiments, the compressive stress layer can be formed in the glass container by ion exchange, by heat tempering, or by forming the glass container from laminated glass. In some embodiments, the compressive stress layer can be formed by a combination of these techniques.

[0059] delamination resistance In some embodiments, the glass container may also resist delamination after prolonged exposure to certain chemical compositions stored in the container. As discussed above, delamination may result in the release of silica-rich glass flakes into a solution contained within the glass container after prolonged exposure to the solution. Thus, resistance to delamination may be characterized by the number of glass particles present in a solution contained within the glass container after exposure to the solution under specific conditions.

[0060] In some embodiments, a glass container having a delamination coefficient of 10 or less can be obtained by forming a glass container with a barrier coating on the inner surface of the body, such that the barrier coating is on the inner surface of the body. For example, the glass container can have a barrier coating deposited on at least a portion of the inner surface of the body. The barrier coating does not delaminate or otherwise decompose and prevents products (such as pharmaceutical compositions) stored in the interior volume of the glass container from contacting the inner surface of the body, thereby mitigating delamination of the glass container. Barrier coatings are generally impermeable to aqueous solutions, insoluble in water, and stable to hydrolysis.

[0061] In some embodiments described herein, the barrier coating is an adherent inorganic coating permanently attached to the inner surface of the glass container. For example, in some embodiments, the adherent inorganic coating can be formed from at least one metal oxide, such as Al2O3, TiO2, ZrO2, SnO, SiO2, Ta2O5, Nb2O5, Cr2O3, VO5, ZnO, or HfO2. In some other embodiments, the adherent inorganic coating can be formed from a combination of two or more of at least one metal oxide, such as Al2O3, TiO2, ZrO2, SnO, SiO2, Ta2O5, Nb2O5, Cr2O3, VO5, ZnO, or HfO2. In some other embodiments, the barrier coating can include a first layer of a first metal oxide deposited on the inner surface of the glass container and a second layer of a second metal oxide deposited on the first layer. In these embodiments, the barrier coating may be deposited using a variety of deposition techniques, including, but not limited to, atomic layer deposition, chemical vapor deposition, physical vapor deposition, etc. Alternatively, the barrier coating may be applied using one or more liquid application techniques, such as dip coating, spray coating, or plasma coating. Spray coating techniques may include high-volume, low-pressure (HVLP) and low-volume, low-pressure (LVLP) spray coating, electrostatic spray coating, airless spray coating, ultrasonic atomization with airless spray coating, aerosol jet coating, and inkjet coating. Plasma coating techniques may include standard primary and secondary plasma coating, microwave-assisted plasma coating, atmospheric pressure plasma coating, etc.

[0062] While embodiments of the barrier coating are described herein as including inorganic materials, it should be understood that in some embodiments, the barrier coating can be an organic coating. For example, in embodiments where the barrier coating is an organic coating, the organic coating can be selected from the group consisting of polybenzimidazoles, polybisoxazoles, polybisthiazoles, polyetherimides, polyquinolines, polythiophenes, phenylene sulfides, polysulfones, polycyanurates, parylenes, fluorinated polyolefins including polytetrafluoroethylene and other fluoro-substituted polyolefins, perfluoroalkoxy polymers, polyetheretherketones (PEEK), polyamides, epoxies, polyphenols, polyurethane acrylates, cyclic olefin copolymers and polymers, poly The barrier coating 131 may include polyolefins containing ethylene, polyethylene oxide, polypropylene, polyethylene / propylene copolymers, polyethylene / vinyl acetate copolymers, polyvinyl chloride, polyacrylates, polymethacrylates, polystyrene, polyterpenes, polyanhydrides, polymaleic anhydride, polyformaldehyde, polyacetals and copolymers of polyacetals, dimethyl, diphenyl, or mixed methyl / phenyl polysiloxanes, perfluorinated siloxanes and other substituted siloxanes, polyimides, polycarbonates, polyesters, paraffins and waxes, or various combinations thereof. In some embodiments, the organic coating used as the barrier coating 131 may include dimethyl, diphenyl, or mixed methyl / phenyl polysiloxanes. Alternatively, the organic coating may be polycarbonate or polyethylene terephthalate. In some embodiments, the barrier coating may be formed from a layered structure including one or more of the aforementioned polymers and / or copolymers.

[0063] The barrier coating may be utilized in conjunction with glass containers formed from any glass composition. However, the barrier coating is particularly well suited for use with glass containers formed from glass compositions that do not exhibit resistance to delamination when formed into glass containers. Such glass compositions may include, but are not limited to, those designated as Type I Class A, Type I Class B, and Type II glass compositions according to ASTM standard E438-92 (2011), entitled "Standard Specification for Glasses in Laboratory Apparatus." Such glass compositions may have the chemical durability required under the ASTM standard, but do not exhibit resistance to delamination.

[0064] In embodiments where the glass container is formed to have persistent layer homogeneity, the phrase "persistent layer homogeneity" means that the concentration of a component of the glass composition (e.g., SiO, AlO, NaO, etc.) in the interior region does not vary from the concentration of the same component at a midpoint through the thickness of the glass layer comprising the interior region by an amount that would result in delamination of the glass body upon prolonged exposure to a solution contained within the glass container. For example, in embodiments where the glass container is formed from a single glass composition, the glass body comprises a single layer of glass, and the concentration of the component in the interior region is compared to the concentration of the same component at a point along a mid-dotted line MP that evenly bisects the glass body between the inner and outer surfaces to determine whether persistent layer homogeneity exists. However, in embodiments where the glass container is formed from laminated glass where the glass cladding layer of the laminated glass forms the interior surface of the glass container, the concentration of the component in the interior region is compared to the concentration of the same component at a point along a mid-dotted line MP that evenly bisects the glass cladding layer that forms the interior surface of the glass container. In embodiments described herein, the persistent layer homogeneity in the interior region of the glass body is such that the extreme values ​​(i.e., minimum or maximum values) of the layer concentration of each of the components of the glass composition in the interior region are about 80% or more and about 120% or less of the same component at the midpoint of the glass layer comprising the interior region. As used herein, persistent layer homogeneity refers to the state of the glass container when it is in the as-formed condition or after one or more surface treatments, such as etching, applied to at least the interior surface of the glass container. In other embodiments, the persistent layer homogeneity in the interior region of the glass body is such that the extreme values ​​of the layer concentration of each of the components of the glass composition in the interior region are about 90% or more and about 110% or less of the same component at the midpoint of the thickness of the glass layer comprising the interior region. In yet another embodiment, the persistent layer homogeneity in the interior region of the glass body is such that the extreme layer concentrations of each of the components of the glass composition in the interior region are greater than or equal to about 92% and less than or equal to about 108% of the same component at the midpoint of the glass thickness of the glass layer that comprises the interior region.In some embodiments, persistent layer homogeneity excludes components of the glass composition present in amounts less than about 2 mol %.

[0065] As used herein, the term "as-formed condition" refers to the composition of a glass container after it has been formed from glass stock, but before the container has been exposed to any additional processing steps, such as ion exchange strengthening, coating, ammonium sulfate processing, etc. In some embodiments, the term "as-formed condition" includes the composition of a glass container after it has been formed and exposed to an etching process to selectively remove all or a portion of at least the interior surface of the glass container. In embodiments described herein, the layer concentrations of constituents in a glass composition are determined by collecting composition samples through the thickness of the glass body in an area of ​​interest using dynamic secondary ion mass spectroscopy (DSIMS). In embodiments described herein, the composition profile is sampled from an area of ​​the interior surface of the glass body. The maximum area sampled is 1 mm 2 This technique produces a composition profile of species in the glass as a function of depth from the inner surface of the glass body relative to the sampled area.

[0066] As explained above, forming a glass container with sustained layer homogeneity generally improves the glass container's resistance to delamination. Specifically, providing an interior region that is compositionally homogeneous (i.e., the extremes of component concentrations in the interior region are within + / - 20% of the same component at the midpoint of the glass thickness of the glass layer that includes the interior region) avoids localized concentrations of components of the glass composition that may be susceptible to leaching, thereby mitigating the loss of glass particles from the interior surface of the glass container if those components leach from the glass surface.

[0067] As described herein, a container having sustained layer homogeneity in the as-formed condition does not include a coating, including an inorganic and / or organic coating, applied to the inner surface of the glass body. It should be understood, therefore, that the body of the glass container is formed from a substantially single composition extending from the inner surface of the body to a depth of at least 250 nm, or even at least 300 nm. The term "single composition" refers to the fact that the glass portion of the body extending from the inner surface to a depth of at least 250 nm, or even at least 300 nm, through the thickness of the body is of a single material composition, compared to a coating material applied to another material, either of the same composition or a different composition. For example, in some embodiments, the body of the container can be constructed from a single glass composition. In other embodiments, the body of the container can be comprised of laminated glass, such that the inner surface of the body has a single composition extending from the inner surface to a depth of at least 250 nm, or even at least 300 nm. The glass container, as described above, can include an inner region extending from either the inner surface or 10 nm below the inner surface to a depth of at least 100 nm. This interior region may have a consistent layer homogeneity.

[0068] In some embodiments described herein, the body of a glass container is etched to remove a layer of glass material from the inner surface of the glass body. The etching is sufficient to remove a thin skin layer of volatilized and redeposited species, thereby providing a persistent layer uniformity and / or persistent surface uniformity on at least the inner surface of the glass container body such that at least the inner surface of the glass body has a delamination coefficient of 10 or less. For example, in some embodiments, the body of a glass container is etched to remove glass material from the inner surface of the glass body to a depth of 1 μm or even 1.5 μm. In some other embodiments, the body of a glass container may be etched to remove glass material to a depth of more than 1.5 μm, including, but not limited to, 2 μm, 3 μm, or even 5 μm. In these embodiments, at least the interior surface of the glass container can be formed from a glass composition that meets the criteria for Type I, Class A (Type IA) or Type I, Class B (Type IB) glass under ASTM Standard E438-92 (2011), entitled "Standard Specification for Glasses in Laboratory Apparatus." Borosilicate glass meets the Type I (A or B) criteria and is routinely used for pharmaceutical packaging. Examples of borosilicate glass include, but are not limited to, Corning® Pyrex® 7740, 7800, Wheaton 180, 200, and 400, Schott Duran®, Schott Fiolax®, KIMAX® N-51A, Gerrescheimer GX-51 Flint, and the like.

[0069] Certain components of glass compositions may be sufficiently volatile at glass forming and reforming temperatures that they can cause compositional inhomogeneity and subsequent delamination. The forming and reforming temperatures of glass compositions generally correspond to temperatures at which the glass composition has a viscosity in the range of about 200 poise to about 100 kpoise. Thus, in some embodiments, the glass composition from which the glass container is formed is significantly volatile at temperatures corresponding to a viscosity in the range of about 200 poise to about 100 kpoise (i.e., the equilibrium partial pressure is about 10 -3 In some embodiments, the glass composition from which the glass container is formed does not contain any components that significantly volatilize at temperatures corresponding to a viscosity in the range of about 1 kpoise to about 50 kpoise. In some other embodiments, the glass composition from which the glass container is formed does not contain any components that significantly volatilize at temperatures corresponding to a viscosity in the range of about 1 kpoise to about 20 kpoise. In some other embodiments, the glass composition from which the glass container is formed does not contain any components that significantly volatilize at temperatures corresponding to a viscosity in the range of about 1 kpoise to about 10 kpoise. Without wishing to be bound by theory, compounds that significantly volatilize under these conditions include, but are not limited to, boron and boron compounds, phosphorus and phosphorus compounds, zinc and zinc compounds, fluorine and fluorine compounds, chlorine and chlorine compounds, tin and tin compounds, and sodium and sodium compounds.

[0070] In some embodiments described herein, glass containers are generally formed from aluminosilicate glass compositions, such as alkali aluminosilicate glass compositions or alkaline earth aluminosilicate glass compositions. As discussed above, boron-containing species in glass are highly volatile at the high temperatures used in forming and reforming glass, causing delamination of the resulting glass container. Furthermore, glass compositions containing boron are also susceptible to phase separation. Therefore, in the embodiments described herein, the boron concentration in the glass composition from which the glass container is formed is limited to mitigate both delamination and phase separation. In some embodiments, the glass composition from which the glass container is formed contains about 1.0 mol% or less of boron oxide and / or boron-containing compounds (including, but not limited to, BO). In some of these embodiments, the concentration of boron oxide and / or boron-containing compounds in the glass composition may be about 0.5 mol% or less, about 0.4 mol% or less, or even about 0.3 mol% or less. In some of these embodiments, the concentration of boron oxides and / or boron-containing compounds in the glass composition may be about 0.2 mol% or less, or even about 0.1 mol% or less, hi some other embodiments, the glass composition is substantially free of boron and boron-containing compounds.

[0071] Phosphorus, like boron, generally forms highly volatile species in glass compositions at the high temperatures used to form and reform glass. Therefore, phosphorus in a glass composition can cause compositional inhomogeneity in the finished glass container, which can lead to delamination. Therefore, in the embodiments described herein, the concentration of phosphorus and phosphorus-containing compounds (such as P2O5) in the glass composition from which the glass container is formed is limited to mitigate delamination. In some embodiments, the glass composition from which the glass container is made contains about 0.3 mol % or less of phosphorus oxides and / or phosphorus-containing compounds. In some of these embodiments, the concentration of phosphorus oxides and / or phosphorus-containing compounds in the glass composition can be about 0.2 mol % or less, or even about 0.1 mol % or less. In some other embodiments, the glass composition is substantially free of phosphorus and phosphorus-containing compounds.

[0072] Zinc, like boron and phosphorus, generally forms highly volatile species in glass compositions at the high temperatures used to form and reform glass. Therefore, zinc in a glass composition can cause compositional inhomogeneity in the finished glass container, which can lead to delamination. Therefore, in the embodiments described herein, the concentration of zinc and zinc-containing compounds (such as ZnO) in the glass composition from which the glass container is formed is limited to mitigate delamination. In some embodiments, the glass composition from which the glass container is made contains about 0.5 mol % or less of zinc oxide and / or zinc-containing compounds. In some embodiments, the glass composition from which the glass container is made contains about 0.3 mol % or less of zinc oxide and / or zinc-containing compounds. In some of these embodiments, the concentration of zinc oxide or zinc-containing compounds in the glass composition can be about 0.2 mol % or less, or even about 0.1 mol % or less. In some other embodiments, the glass composition is substantially free of zinc and zinc-containing compounds.

[0073] Lead and bismuth also form highly volatile species in the glass composition at the high temperatures used to form and reform the glass. Therefore, in the embodiments described herein, the concentrations of lead, bismuth, lead-containing compounds, and bismuth-containing compounds in the glass composition from which the glass container is formed are limited to mitigate delamination. In some embodiments, lead oxide, bismuth oxide, lead-containing compounds, and / or bismuth-containing compounds are each present in the glass composition at a concentration of about 0.3 mol % or less. In some of these embodiments, lead oxide, bismuth oxide, lead-containing compounds, and / or bismuth-containing compounds are each present in the glass composition at a concentration of about 0.2 mol % or less, or even less than about 0.1 mol %. In some other embodiments, the glass composition is substantially free of lead and / or bismuth, and zinc and / or bismuth-containing compounds.

[0074] Species containing chlorine, fluorine, and tin oxides are also highly volatile at the high temperatures used in forming and reforming glass. Thus, in the embodiments described herein, chlorine, fluorine, and tin oxides, as well as compounds containing tin, chlorine, or fluorine, are present in the glass composition at concentrations that do not affect the resulting glass's resistance to delamination. Specifically, chlorine, fluorine, and tin oxides, as well as compounds containing tin, chlorine, or fluorine, are present in the glass composition from which the glass container is formed at concentrations of about 0.5 mol% or less, or even about 0.3 mol% or less. In some other embodiments, the glass composition is substantially free of tin, chlorine, and fluorine, as well as compounds containing tin, chlorine, or fluorine.

[0075] While some embodiments of glass containers may not contain readily volatile components, as described above, in certain other embodiments, for example, when the glass container includes a barrier layer, the glass container may be formed from a glass composition that includes these volatile components.

[0076] The glass composition from which the container is formed is not phase separated. As used herein, the term "phase separated" refers to the separation of a glass composition into distinct phases, each phase having different compositional properties. For example, alkali borosilicate glasses are known to generally phase separate into a boron-rich phase and a silica-rich phase at elevated temperatures (e.g., forming and reforming temperatures). In some embodiments described herein, the concentration of boron oxide in the glass composition is sufficiently low (i.e., about 1.0 mol% or less) so that the glass composition does not undergo phase separation.

[0077] The glass compositions described herein can be formed into various forms, such as sheets, tubes, etc. Chemically durable glass compositions are particularly well suited for use in forming pharmaceutical packaging for containing liquid, powder, and other pharmaceutical formulations. For example, the glass compositions described herein can be used to form glass containers, such as vials, ampoules, cartridges, syringe bodies, and / or any other glass container for storing pharmaceutical formulations. Furthermore, the ability to chemically strengthen the glass composition through ion exchange can be utilized to improve the mechanical durability of such pharmaceutical packaging. Thus, it should be understood that in at least one embodiment, the glass composition is incorporated into pharmaceutical packaging to improve the chemical and / or mechanical durability of the pharmaceutical packaging.

[0078] Additionally, in some embodiments, the glass container meets the standards of DIN 12116, ISO 695, ISO 719, ISO 720, USP <660> The glass may be formed from a glass composition that is chemically durable and resistant to degradation as determined by testing and / or European Pharmacopoeia 3.2.1 testing.

[0079] Specifically, the DIN 12116 standard is a measure of the resistance of glass to degradation when placed in an acidic solution. The DIN 12116 standard is divided into individual classes: Class S1 is a maximum of 0.7 mg / dm 2 Class S2 shows a weight loss of 0.7 mg / dm2 ~Max 1.5mg / dm 2 Class S3 shows a weight loss of 1.5 mg / dm 2 ~Up to 15mg / dm 2 Class S4 indicates a weight loss of 15 mg / dm 2 The glass compositions described herein have an acid resistance of class S3 or better, according to DIN 12116, with some embodiments having an acid resistance of at least class S2 or better, or even class S1. It should be understood that lower classes improve acid resistance performance. Thus, compositions rated S1 have better acid resistance than compositions rated class S2.

[0080] The ISO 695 standard is a measure of the resistance of glass to degradation when placed in a basic solution. The ISO 695 standard is divided into individual classes: Class A1 is for glass with a maximum of 75 mg / dm 2 Class A2 shows a weight loss of 75 mg / dm 2 ~Up to 175mg / dm 2 Class A3 shows a weight loss of 175 mg / dm 2 The glass compositions described herein have a base resistance of Class A2 or better, according to ISO 695, with some embodiments having a base resistance of Class A1. It should be understood that lower classes improve base resistance performance. Thus, compositions rated A1 have better base resistance than compositions rated Class A2.

[0081] The glass composition from which the glass container is formed is chemically durable and resistant to degradation as determined by the ISO 720 standard. The ISO 720 standard is a measure of the resistance of glass to degradation in distilled water (i.e., the hydrolytic resistance of the glass). Non-ion-exchanged samples of glass are evaluated according to the ISO 720 protocol. Ion-exchanged samples of glass are evaluated using a modified ISO 720 protocol, in which the glass is crushed to the particle size required by the ISO 720 standard, ion-exchanged in a molten salt bath of 100% KNO3 at a temperature of 450°C for at least 5 hours to induce a compressive stress layer in the individual particles of the glass, and then tested according to the ISO 720 standard. The ISO 720 standard is divided into individual types. Type HGA1 exhibits an extractable equivalent of Na2O up to 62 μg, Type HGA2 exhibits an extractable equivalent of Na2O greater than 62 μg and up to 527 μg, and Type HGA3 exhibits an extractable equivalent of Na2O greater than 527 μg and up to 930 μg. The glass compositions described herein have ISO 720 hydrolysis resistance of Type HGA2 or better, with some embodiments having hydrolysis resistance of Type HGA1 or better. It should be understood that lower classes improve hydrolysis resistance performance. Thus, compositions rated HGA1 have better hydrolysis resistance than compositions rated in Class HGA2.

[0082] The glass compositions from which the glass containers are formed are also chemically durable and resistant to degradation, as determined by the ISO 719 standard. The ISO 719 standard is a measure of the resistance of glass to degradation in distilled water (i.e., the hydrolytic resistance of the glass). Non-ion-exchanged samples of glass are evaluated according to the ISO 719 protocol. Ion-exchanged samples of glass are evaluated using a modified ISO 719 protocol, in which the glass is crushed to the particle size required by the ISO 719 standard, ion-exchanged in a molten salt bath of 100% KNO3 at a temperature of 450°C for at least 5 hours to induce a compressive stress layer in the individual particles of the glass, and then tested according to the ISO 719 standard. The ISO 719 standard is divided into individual types. Type HGB1 exhibits an extractable equivalent of NaO up to 31 μg, Type HGB2 exhibits an extractable equivalent of NaO greater than 31 μg and up to 62 μg, Type HGB3 exhibits an extractable equivalent of NaO greater than 62 μg and up to 264 μg, Type HGB4 exhibits an extractable equivalent of NaO greater than 264 μg and up to 620 μg, and Type HGB5 exhibits an extractable equivalent of NaO greater than 620 μg and up to 1085 μg. The glass compositions described herein have ISO 719 hydrolysis resistance of Type HGB2 or better, with some embodiments having the hydrolysis resistance of Type HGB1. It should be understood that lower classes improve hydrolysis resistance performance. Thus, compositions rated HGB1 have better hydrolysis resistance than compositions rated in Class HGB2.

[0083] USP <660> With respect to the USP 3.2.1 test and / or the European Pharmacopoeia 3.2.1 test, the glass containers described herein have a chemical durability of Type 1. <660> and European Pharmacopoeia 3.2.1 tests are performed on intact glass containers, not on crushed glass particles, and therefore, USP <660> and the European Pharmacopoeia 3.2.1 test can be used to directly assess the chemical durability of the inner surface of glass containers.

[0084] When referring to the above-referenced classifications according to ISO 719, ISO 720, ISO 695, and DIN 12116, it should be understood that a glass composition or glass article having a specified classification "or better" means that the performance of the glass composition is equal to or better than the specified classification. For example, a glass article having an ISO 719 hydrolytic resistance of "HGB2" or better may have an ISO 719 classification of either HGB2 or HGB1.

[0085] Damage resistance As described hereinabove, glass containers can be subject to damage, such as impact damage, scratches, and / or abrasion, as the containers are processed and filled. Such damage is often caused by contact between individual glass containers or between the glass container and manufacturing equipment. This damage generally reduces the mechanical strength of the container and can cause through cracks that can compromise the integrity of the container's contents. Accordingly, in some embodiments described herein, the glass container further includes a lubricious coating positioned on at least a portion of the exterior surface of the body. The lubricious coating reduces the coefficient of friction of the portion of the body with the coating, thereby reducing the occurrence of abrasion and surface damage on the exterior surface of the glass body. Essentially, the coating allows the container to "slide" against another object (or container), thereby reducing the likelihood of surface damage on the glass. Furthermore, the lubricious coating also cushions the body of the glass container, thereby mitigating the effects of blunt impact damage to the glass container.

[0086] As used herein, the term lubricious means that the coating applied to the exterior surface of a glass container has a lower coefficient of friction than an uncoated glass container, thereby providing the glass container with improved resistance to scratches, abrasions, and other damage.

[0087] Various properties of the coated glass containers (i.e., coefficient of friction, horizontal compressive strength, four-point flexural strength, transparency, colorlessness, etc.) can be measured when the coated glass containers are in the as-coated condition (i.e., after application of the coating without any additional processing) or after one or more processing steps, such as those similar to or identical to those performed on pharmaceutical filling lines, including, but not limited to, washing, lyophilization, depyrogenation, autoclaving, etc.

[0088] Depyrogenation is a process by which pyrogens are removed from a material. Depyrogenation of glass articles, such as pharmaceutical packages, can be performed by a heat treatment applied to a sample, in which the sample is heated to an elevated temperature for a certain period of time. For example, depyrogenation can involve heating a glass container to a temperature of about 250°C to about 380°C for a period of about 30 seconds to about 72 hours (including, but not limited to, 20 minutes, 30 minutes, 40 minutes, 1 hour, 2 hours, 4 hours, 8 hours, 12 hours, 24 hours, 48 ​​hours, and 72 hours). After the heat treatment, the glass container is cooled to room temperature. One conventional depyrogenation condition commonly employed in the pharmaceutical industry is heat treatment at a temperature of about 250°C for about 30 minutes. However, it is contemplated that the heat treatment time can be shortened if a higher temperature is utilized. The coated glass container can be exposed to an elevated temperature for a certain period of time, as described herein. The elevated temperatures and durations of heating described herein may or may not be sufficient to depyrogenate the glass container. However, it should be understood that some of the heating temperatures and durations described herein are sufficient to depyrogenate coated glass containers, such as the coated glass containers described herein. For example, as described herein, coated glass containers may be exposed to temperatures of about 260°C, about 270°C, about 280°C, about 290°C, about 300°C, about 310°C, about 320°C, about 330°C, about 340°C, about 350°C, about 360°C, about 370°C, about 380°C, about 390°C, or about 400°C for a period of 30 minutes.

[0089] As used herein, lyophilization conditions (i.e., freeze-drying) refers to the process of filling a sample with a liquid containing the protein and then freezing at -100°C, followed by sublimation of water at -15°C under vacuum for 20 hours.

[0090] As used herein, autoclaving conditions refer to steam purging the sample at 100°C for 10 minutes, followed by a dwell time of 20 minutes, during which the sample is exposed to a 121°C environment, followed by thermal processing at 121°C for 30 minutes.

[0091] The coefficient of friction (μ) of a portion of a coated glass container bearing a lubricious coating may be lower than the surface of an uncoated glass container formed from the same glass composition. The coefficient of friction (μ) is a quantitative measure of friction between two surfaces and is a function of the mechanical and chemical properties of the first and second surfaces, including surface roughness and environmental conditions such as, but not limited to, temperature and humidity. As used herein, coefficient of friction measurements for coated glass containers 100 are reported as the coefficient of friction between the outer surface of a first glass container (having an outer diameter of about 16.00 mm to about 17.00 mm) and the outer surface of a second glass container that is identical to the first glass container, where the first and second glass containers have the same body and coating composition (if applied), and are exposed to the same environment before, during, and after fabrication. Unless otherwise indicated herein, the coefficient of friction refers to the maximum coefficient of friction measured at a rated load of 30 N measured in a vial-on-vial test fixture, as described herein. However, it should be understood that a coated glass container that exhibits a maximum coefficient of friction at a particular applied load will also exhibit the same or better (i.e., lower) maximum coefficient of friction at a lesser load. For example, if a coated glass container exhibits a maximum coefficient of friction of 0.5 or less under an applied load of 50 N, the coated glass container will also exhibit a maximum coefficient of friction of 0.5 or less under an applied load of 25 N.

[0092] In the embodiments described herein, the portion of the coated glass container having the lubricious coating has a coefficient of friction of about 0.7 or less against a similarly coated glass container, as determined by a vial-on-vial fixture. In other embodiments, the coefficient of friction may be about 0.6 or less, or even about 0.5 or less. In some embodiments, the portion of the coated glass container having the lubricious coating has a coefficient of friction of about 0.4 or less, or even about 0.3 or less. Coated glass containers with a coefficient of friction of about 0.7 or less generally exhibit improved resistance to abrasive damage, resulting in improved mechanical properties. For example, conventional glass containers (without a lubricious coating) may have a coefficient of friction greater than 0.7.

[0093] In some embodiments described herein, the coefficient of friction of the portion of the coated glass container having the lubricious coating is at least 20% less than the coefficient of friction of the surface of an uncoated glass container formed from the same glass composition. For example, the coefficient of friction of the portion of the coated glass container having the lubricious coating may be at least 20% less, at least 25% less, at least 30% less, at least 40% less, or even at least 50% less than the coefficient of friction of the surface of an uncoated glass container formed from the same glass composition.

[0094] In some embodiments, the portion of the coated glass container having the lubricious coating may have a coefficient of friction of about 0.7 or less after exposure to temperatures of about 260°C, about 270°C, about 280°C, about 290°C, about 300°C, about 310°C, about 320°C, about 330°C, about 340°C, about 350°C, about 360°C, about 370°C, about 380°C, about 390°C, or about 400°C for a period of 30 minutes (i.e., depyrogenation conditions). In other embodiments, the portion of the coated glass container having the lubricious coating may have a coefficient of friction of about 0.7 or less (i.e., about 0.6 or less, about 0.5 or less, about 0.4 or less, or even about 0.3 or less) after exposure to a temperature of about 260° C., about 270° C., about 280° C., about 290° C., about 300° C., about 310° C., about 320° C., about 330° C., about 340° C., about 350° C., about 360° C., about 370° C., about 380° C., about 390° C., or about 400° C. for a period of 30 minutes. In some embodiments, the coefficient of friction of the portion of the coated glass container having the lubricious coating may not increase by more than about 30% after exposure to a temperature of about 260° C. for 30 minutes. In other embodiments, the coefficient of friction of the portion of the coated glass container having the lubricious coating may not increase by more than about 30% (i.e., about 25%, about 20%, about 15%, or even about 10%) after exposure to temperatures of about 260°C, about 270°C, about 280°C, about 290°C, about 300°C, about 310°C, about 320°C, about 330°C, about 340°C, about 350°C, about 360°C, about 370°C, about 380°C, about 390°C, or about 400°C for a period of 30 minutes. In other embodiments, the coefficient of friction of the portion of the coated glass container having the lubricious coating may not increase by more than about 0.5 (i.e., about 0.45, about 0.04, about 0.35, about 0.3, about 0.25, about 0.2, about 0.15, about 0.1, or even about 0.5) after exposure to temperatures of about 260°C, about 270°C, about 280°C, about 290°C, about 300°C, about 310°C, about 320°C, about 330°C, about 340°C, about 350°C, about 360°C, about 370°C, about 380°C, about 390°C, or about 400°C for a period of 30 minutes.In some embodiments, the coefficient of friction of the portion of the coated glass container having the lubricious coating may not increase at all after exposure to temperatures of about 260°C, about 270°C, about 280°C, about 290°C, about 300°C, about 310°C, about 320°C, about 330°C, about 340°C, about 350°C, about 360°C, about 370°C, about 380°C, about 390°C, or about 400°C for a period of 30 minutes.

[0095] In some embodiments, the portion of the coated glass container having the lubricious coating may have a coefficient of friction of about 0.7 or less after being immersed in a water bath for 10 minutes at a temperature of about 70° C. In other embodiments, the portion of the coated glass container having the lubricious coating may have a coefficient of friction of about 0.7 or less (i.e., about 0.6 or less, about 0.5 or less, about 0.4 or less, or even about 0.3 or less) after being immersed in a water bath for 5, 10, 20, 30, 40, 50 minutes, or even 1 hour at a temperature of about 70° C. In some embodiments, the coefficient of friction of the portion of the coated glass container having the lubricious coating may not increase by more than about 30% after being immersed in a water bath for 10 minutes at a temperature of about 70° C. In other embodiments, the coefficient of friction of the portion of the coated glass container having the lubricious coating may not increase by more than about 30% (i.e., about 25%, about 20%, about 15%, or even about 10%) after being immersed in a water bath for 5, 10, 20, 30, 40, 50 minutes, or even 1 hour at a temperature of about 70° C. In some embodiments, the coefficient of friction of the portion of the coated glass container having the lubricious coating may not increase at all after being immersed in a water bath for 5, 10, 20, 30, 40, 50 minutes, or even 1 hour at a temperature of about 70° C.

[0096] In some embodiments, the lubricious coating portion of the coated glass container may have a coefficient of friction of about 0.7 or less after exposure to freeze-drying conditions. In other embodiments, the lubricious coating portion of the coated glass container may have a coefficient of friction of about 0.7 or less (i.e., about 0.6 or less, about 0.5 or less, about 0.4 or less, or even about 0.3 or less) after exposure to freeze-drying conditions. In some embodiments, the coefficient of friction of the lubricious coating portion of the coated glass container may not increase by more than about 30% after exposure to freeze-drying conditions. In other embodiments, the coefficient of friction of the lubricious coating portion of the coated glass container may not increase by more than about 30% after exposure to freeze-drying conditions (i.e., about 25%, about 20%, about 15%, or even about 10%). In some embodiments, the coefficient of friction of the lubricious coating portion of the coated glass container may not increase at all after exposure to freeze-drying conditions.

[0097] In some embodiments, the portion of the coated glass container having the lubricious coating may have a coefficient of friction of about 0.7 or less after exposure to autoclaving conditions. In other embodiments, the portion of the coated glass container having the lubricious coating may have a coefficient of friction of about 0.7 or less (i.e., about 0.6 or less, about 0.5 or less, about 0.4 or less, or even about 0.3 or less) after exposure to autoclaving conditions. In some embodiments, the coefficient of friction of the portion of the coated glass container having the lubricious coating may not increase by more than about 30% after exposure to autoclaving conditions. In other embodiments, the coefficient of friction of the portion of the coated glass container having the lubricious coating may not increase by more than about 30% after exposure to autoclaving conditions (i.e., about 25%, about 20%, about 15%, or even about 10%). In some embodiments, the coefficient of friction of the portion of the coated glass container having the lubricious coating may not increase at all after exposure to autoclaving conditions.

[0098] In the embodiments described herein, the glass container may be coated with an inorganic coating, a fugitive organic coating, and / or an adherent organic coating to achieve the desired low coefficient of friction and resistance to marring.

[0099] Inorganic Coating In some embodiments described herein, the lubricious coating is an inorganic coating. The inorganic coating can be an adhesive inorganic coating permanently adhered to the outer surface of the body of the glass container. The properties of the adhesive inorganic coating are not degraded by exposure to high temperatures, and therefore the coefficient of friction and horizontal compressive strength of the glass container having the adhesive inorganic coating are substantially the same before and after exposure to high temperatures, including, but not limited to, temperatures in the range of about 260°C to about 400°C. The adhesive inorganic coating is a continuous coating applied to the outer surface of the body and is generally insoluble in water and / or organic solvents. For example, in some embodiments, the adhesive inorganic coating can include a metal nitride coating, a metal sulfide coating, a metal oxide coating, SiO2, diamond-like carbon, or a carbide coating. For example, the adherent inorganic coating can include at least one of TiN, BN, hBN, TiO2, Ta2O5, HfO2, Nb2O5V2O5, SnO, SnO2, ZrO2, Al2O3, SiO2, ZnO, MoS2, BC, SiC, or similar metal oxide, metal nitride, and carbide coatings, which exhibit a relatively low coefficient of friction and relatively high thermal stability relative to similarly coated glass containers. In these embodiments, the coating can be applied to the exterior surface of the glass container by a physical vapor deposition method, such as evaporation, electron beam evaporation, DC magnetron sputtering, unbalanced DC magnetron sputtering, AC magnetron sputtering, and unbalanced AC magnetron sputtering. Alternatively, the coating can be applied by powder coating. Coatings can also be applied using chemical vapor deposition (CVD) techniques, including ultra-high vacuum CVD, low pressure CVD, atmospheric pressure CVD, metal organic CVD, laser CVD, photochemical CVD, aerosol-assisted CVD, microwave plasma-assisted CVD, plasma CVD, direct liquid injection CVD, atomic layer CVD, combustion CVD, hot wire CVD, rapid thermal CVD, chemical vapor infiltration, and chemical beam epitaxy.

[0100] In one particular embodiment, the adherent inorganic coating is diamond-like carbon. Films or coatings formed from diamond-like carbon generally exhibit a low coefficient of friction and high hardness. Specifically, a significant amount of carbon in DLC coatings is SP3 hybridized carbon. This material imparts some of the properties of diamond to these coatings, such as high hardness and excellent wear resistance. The hardness of DLC coatings is directly proportional to the SP3 hybridization content. DLC coatings can be deposited on the exterior surface of glass containers by ion beam deposition, cathodic arc spraying, pulsed laser ablation, argon ion sputtering, and plasma chemical vapor deposition. Depending on the thickness of the deposited DLC coating, the specific deposition method, and the coating composition, the color of the deposited layer can vary from optically transparent yellow (i.e., a 0.1 μm thick DLC film can be optically transparent with a slight yellow tint) to amber and black.

[0101] Alternatively, the lubricious coating can be an inorganic coating, such as a fugitive coating, that is temporarily applied to the exterior surface of the glass container. In these embodiments, the fugitive coating can include inorganic salts, such as MgSO, CaSO, Ca(PO), Mg(PO), KNO, KPO, etc.

[0102] organic coating In some alternative embodiments, the lubricious coating may be a fugitive coating that is temporarily affixed to the exterior surface of the glass container, or an organic coating, such as an adhesive organic coating that is permanently affixed to the exterior surface of the glass container.

[0103] For organic fugitive coatings, it is desirable to protect the surface of glass articles (such as glass containers) from damage during manufacturing to mitigate the reduction in mechanical strength of the glass due to surface scratches caused by contact with the glass. This is generally achieved by applying a coating with a low coefficient of friction, as described above. However, because the glass container may undergo further processing, the coating does not need to be permanently attached to the outer surface of the glass container; instead, the coating can be removed in a downstream processing step after serving its purpose of protecting the glass article. For example, the fugitive coating can be removed by pyrolysis. In the embodiments described herein, the fugitive coating can be pyrolyzed at a temperature of 300°C or less within a period of 1 hour or less. Alternatively, the fugitive coating can be pyrolyzed at a temperature of 265°C for 2.5 hours, or even at 360°C for 10 minutes or less.

[0104] A variety of organic materials can be utilized to form the fugitive coating. For example, in some embodiments, the fugitive coating can include a mixture of polyoxyethylene glycol, methacrylic acid resin, melamine formaldehyde resin, and polyvinyl alcohol, as disclosed in U.S. Patent No. 3,577,256. Once formed, such a coating can be applied to the exterior surface of a glass container and thermally decomposed from the glass surface by annealing.

[0105] In another embodiment, the fugitive organic coating may comprise one or more polysaccharides, as disclosed in U.S. Patent No. 6,715,316 B2, which describes a removable protective coating. Such coatings may be removed from glass surfaces using a mild aqueous detergent, such as, for example, 2% Semiclean KG in water.

[0106] In another embodiment, the fugitive organic coating can be a "cold end" coating as described in U.S. Patent No. 4,055,441, or a similar coating. Such coatings include poly(ethylene oxide), poly(propylene oxide), ethylene oxide-propylene oxide copolymers, polyvinyl-pyrrolidinone, polyethyleneimine, poly(methyl vinyl ether), polyacrylamide, polymethacrylamide, polyurethanes, poly(vinyl acetate), polyvinyl formal, polyformaldehyde including polyacetal and acetal copolymers, poly(alkyl methacrylate), methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, sodium carboxymethyl cellulose, methylhydroxypropyl cellulose, poly(acrylic acid) and its salts, poly(methacrylic acid) and its salts, ethylene The polymeric polyurethane may be formed from at least one of polyethylene-maleic anhydride copolymers, ethylene vinyl alcohol polymers, ethylene-acrylic acid copolymers, vinyl acetate-vinyl alcohol copolymers, methyl vinyl ether-maleic anhydride copolymers, emulsion polyurethanes, polyoxyethylene stearates, and polyolefins including polyethylene, polypropylene, and copolymers thereof, starch and modified starches, polyacrylamides, vegetable and animal fats, waxes, tallow, soaps, stearin-paraffin emulsions, dimethyl or diphenyl or mixed methyl / phenyl polysiloxanes, perfluorinated siloxanes and other substituted siloxanes, alkyl silanes, aromatic silanes, and polyethylene oxide.

[0107] The fugitive organic coating can be applied by directly contacting the coating with the glass container. For example, the coating can be applied by a dipping process, or alternatively, by spraying or other suitable means. The coating can then be dried and, optionally, cured at elevated temperatures.

[0108] Adhesive Organic Coating In some embodiments, the lubricious coating is an adhesive organic coating adhered to at least a portion of the outer surface of the glass body. The adhesive organic coating has a low coefficient of friction and is thermally stable at high temperatures, as described above. The lubricious coating has an outer surface and a glass-contacting surface. In embodiments where the lubricious coating is an adhesive organic coating, the lubricious coating may include a coupling agent layer in direct contact with the outer surface of the glass body and a polymer layer in direct contact with the coupling agent layer. However, it should be understood that in some embodiments, the lubricious coating may not include a coupling agent layer, and the polymer layer may be in direct contact with the outer surface of the glass body.

[0109] The lubricious coating applied to the outer surface of the glass body can have a thickness of less than about 100 μm, or even less than about 1 μm. In some embodiments, the lubricious coating can have a thickness of less than about 100 nm. In other embodiments, the lubricious coating can be less than about 90 nm, less than about 80 nm, less than about 70 nm, less than about 60 nm, less than about 50 nm, or even less than about 25 nm. In some embodiments, the lubricious coating may not be of uniform thickness throughout the glass body. For example, a coated glass container may have a thicker lubricious coating in some areas due to the process of contacting the outer surface of the glass body with one or more coating solutions that form the lubricious coating. In some embodiments, the lubricious coating may have a non-uniform thickness. For example, the coating thickness may vary across different regions of the coated glass container, which may promote protection in selected areas. In another embodiment, only selected portions of the outer surface of the glass body are coated with the lubricious coating.

[0110] It should be understood that the glass containers described herein may have at least two performance attributes selected from resistance to delamination, improved strength, and increased damage resistance. For example, the glass container may have a combination of resistance to delamination and improved strength, a combination of improved strength and increased damage resistance, or a combination of resistance to delamination and increased damage resistance.

[0111] For example, in one embodiment, a glass container may include a body having an inner surface, an outer surface, and a thickened portion extending between the outer surface and the inner surface. The body may have a delamination coefficient of 10 or less. The body may also have a compressive stress layer extending from the outer surface of the body into the thickened portion. The compressive stress layer may have a surface compressive stress of 150 MPa or more.

[0112] In another embodiment, a glass container may include a body having an inner surface, an outer surface, and a thickened portion extending between the outer and inner surfaces. In this embodiment, the body may be formed from a Type IB glass composition. The body may also have a compressive stress layer extending from the outer surface of the body into the thickened portion. The compressive stress layer may have a surface compressive stress of 150 MPa or greater. A barrier coating may be positioned on the inner surface of the body such that a composition contained in the glass container contacts the barrier coating rather than the inner surface of the body, thereby preventing delamination.

[0113] Alternatively, the glass container may include a body having an inner surface, an outer surface, and a thickened portion extending from the outer surface to the inner surface. The body may be formed from a glass composition substantially free of boron and boron-containing compounds. The body may also have a compressive stress layer extending from the outer surface of the body into the thickened portion. The compressive stress layer may have a surface compressive stress of 150 MPa or more.

[0114] In yet another embodiment, a glass container can include a body having an inner surface, an outer surface, and a thickened portion extending between the outer surface and the inner surface. The body can be formed from a Type IB glass composition under processing conditions that mitigate evaporation of volatile species in the glass composition. The body can also include a compressive stress layer extending from the outer surface of the body into the thickened portion. The compressive stress layer has a surface compressive stress of 150 MPa or greater.

[0115] In yet another embodiment, a glass container can include a body having an inner surface, an outer surface, and a thickened portion extending between the outer surface and the inner surface. The body can be a mold former comprising a Type IB glass composition. The body can also include a compressive stress layer extending from the outer surface of the body into the thickened portion. The compressive stress layer has a surface compressive stress of 150 MPa or greater.

[0116] In yet another embodiment, a glass container may include a body having an inner surface, an outer surface, and a thickened portion extending between the outer surface and the inner surface. The body may have a compressive stress layer extending from the outer surface of the body into the thickened portion. The compressive stress layer may have a surface compressive stress of 150 MPa or more. A lubricious coating may be positioned on at least a portion of the outer surface of the body. The outer surface of the body having the lubricious coating may have a coefficient of friction of 0.7 or less.

[0117] In yet another embodiment, a glass container can include a body having an inner surface, an outer surface, and a thickened portion extending between the outer surface and the inner surface. The body can be formed from a Type IB glass composition. A compressive stress layer can extend from the outer surface of the body into the thickened portion, the compressive stress layer having a surface compressive stress of 150 MPa or greater. A lubricious coating can be positioned on at least a portion of the outer surface of the body, the outer surface of the body having the lubricious coating having a coefficient of friction of 0.7 or less.

[0118] In some other embodiments, the glass container may include a body having an inner surface, an outer surface, and a thickened portion extending from the outer surface to the inner surface, the body being formed from a glass composition substantially free of boron and boron-containing compounds. A compressive stress layer may extend from the outer surface of the body into the thickened portion, the compressive stress layer having a surface compressive stress of 150 MPa or more. A lubricious coating may be positioned on at least a portion of the outer surface of the body. The outer surface of the body having the lubricious coating may have a coefficient of friction of 0.7 or less.

[0119] In yet another embodiment, a glass container can include a body having an inner surface, an outer surface, and a thickened portion extending between the outer and inner surfaces. At least the inner surface of the body can have a delamination coefficient of 10 or less. An adhesive inorganic coating can be positioned on at least a portion of the outer surface of the body. The outer surface of the body having the adhesive inorganic coating has a coefficient of friction of 0.7 or less.

[0120] Alternatively, the glass container may include a body having an inner surface, an outer surface, and a thickened portion extending between the outer and inner surfaces. At least the inner surface of the body may have a delamination coefficient of 10 or less. A fugitive coating may be positioned on at least a portion of the outer surface of the body. The fugitive coating may be thermally decomposed at a temperature of 300°C or less in 1 hour or less. The outer surface of the body having the fugitive coating may have a coefficient of friction of 0.7 or less.

[0121] In yet another embodiment, a glass container may include a body having an inner surface, an outer surface, and a thickened portion extending between the outer and inner surfaces. At least the inner surface of the body may have a delamination coefficient of 10 or less. An adhesive organic coating may be positioned on at least a portion of the outer surface of the body. The outer surface of the body having the adhesive organic coating may have a coefficient of friction of 0.7 or less.

[0122] In some other embodiments, a glass container includes a body having an inner surface, an outer surface, and a thickened portion extending between the outer and inner surfaces. The glass body may be formed from a Type IB glass composition. A barrier coating may be positioned on the inner surface of the body so that a composition contained in the glass container does not contact the inner surface of the body. A lubricious coating may be positioned on at least a portion of the outer surface of the body. The outer surface of the body having the lubricious coating may have a coefficient of friction of 0.7 or less.

[0123] Alternatively, the glass container may include a body having an inner surface, an outer surface, and a thickened portion extending from the outer surface to the inner surface. The body may be formed from a glass composition that is substantially free of boron and boron-containing compounds. A lubricious coating may be positioned on at least a portion of the outer surface of the body, and the outer surface of the body having the lubricious coating has a coefficient of friction of 0.7 or less.

[0124] In some other embodiments, a glass container can include a body having an inner surface, an outer surface, and a thickened portion extending between the outer surface and the inner surface. The body can be formed from a Type IB glass composition under processing conditions that reduce evaporation of volatile species in the glass composition. A lubricious coating can be positioned on at least a portion of the outer surface of the body, and the outer surface of the body bearing the lubricious coating has a coefficient of friction of 0.7 or less.

[0125] In some other embodiments, the glass container may include a body having an inner surface, an outer surface, and a thickened portion extending between the outer surface and the inner surface. The body may include a Type IB glass composition. A lubricious coating may be positioned on at least a portion of the outer surface of the body, and the outer surface of the body having the lubricious coating has a coefficient of friction of 0.7 or less.

[0126] Ranges can be expressed herein as from "about" one particular value, and / or to "about" another particular value. When such a range is expressed, another embodiment includes from the one particular value and / or to the other particular value. Similarly, when values ​​are expressed as approximations, by use of "about," it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each range are significant both in relation to the other endpoint, and independently of the other endpoint.

[0127] Unless otherwise expressly stated, any method set forth herein is in no way intended to be construed as requiring its steps to be performed in a particular order, nor is it intended that a particular orientation be required by any apparatus. Thus, where a method claim does not actually recite the order in which its steps are to be followed, or where any apparatus claim does not actually recite an order or orientation for individual components, or where the claim or specification does not specifically state that the steps are to be limited to a particular order, or that no particular order or orientation for the apparatus components is recited, no order or orientation is intended to be inferred in any respect. This holds for any possible implicit basis for interpretation, including logical matters regarding the arrangement of steps, workflow, component order, or component orientation, the apparent meaning derived from grammatical construction or punctuation, and the number or type of embodiments set forth in the specification.

[0128] As used herein, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a component" includes aspects having two or more such components unless the context clearly dictates otherwise.

[0129] It will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments described herein without departing from the spirit and scope of the claimed subject matter. Thus, it is intended that the present specification cover the modifications and variations of the various embodiments described herein, provided that such modifications and variations come within the scope of the appended claims and their equivalents.

Claims

1. 1. A particle detection system for a glass article, comprising: a light source configured to emit a light beam, the light beam being formed into a light sheet and directed toward an area below the glass article; a camera configured to capture an image of an inspection area within the light sheet, the inspection area being below the glass article.

2. 10. The particle detection system of claim 1, further comprising an optical system configured to shape the light beam into the light sheet, the optical system disposed in an optical path of the light beam between the light source and the inspection area.

3. 3. The particle detection system of claim 1, further comprising a mirror for reflecting an image of the inspection area towards the camera.

4. The particle detection system according to any one of claims 1 to 3, wherein the light source is a laser light source.

5. The particle detection system of any one of claims 1 to 4, further comprising a holder for holding the glass article.

6. 6. The particle detection system of claim 5, wherein the holder comprises a support surface configured to support the glass article thereon.

7. 7. The particle detection system of claim 6, wherein the support surface has an open or porous structure configured to allow particles generated by the glass article to fall through the support surface and into the inspection area.

8. 8. The particle detection system of claim 6 or 7, wherein the inspection area is disposed below the support surface and is disposed in a position where particles generated by the glass article can fall.

9. 9. The particle detection system of claim 1, further comprising an actuator configured to move the glass article.

10. The particle detection system of claim 9 , wherein the actuator is coupled to the holder.

11. 11. The particle detection system of claim 9 or 10, wherein the actuator is an acceleration table configured to move the glass articles in a manner that causes the glass articles to collide with each other.

12. 12. The particle detection system of claim 1, further comprising a computing device communicatively coupled to the camera, the computing device comprising at least one processor and at least one memory that stores computer readable and executable instructions, the computer readable and executable instructions, when executed by the at least one processor, causing the computing device to determine whether a particle is present within the inspection area.

13. The particle detection system of claim 12 , wherein the computer readable and executable instructions, when executed by the processor, cause the computing device to record the time when the particle is detected within the examination area.

14. 14. The particle detection system of claim 12 or 13, wherein the computer readable and executable instructions, when executed by the processor, cause the computing device to process the image from the camera and convert the image into a binary mask.

15. 15. The particle detection system of claim 12, wherein the computer readable and executable instructions, when executed by the processor, cause the computing device to perform image processing tasks on the images received from the camera, the image processing tasks being selected from the group consisting of edge enhancement, contrast enhancement, particle magnification, brightness adjustment, threshold filtering, particle filtering, or noise reduction.

16. 16. The particle detection system of any one of claims 12 to 15, wherein the computer readable and executable instructions, when executed by the processor, cause the computing device to record the detection of a particle and its association with one or more glass articles above the inspection area at or near the time of detection.

17. The particle detection system of any one of claims 12 to 16, wherein the computer readable and executable instructions, when executed by the processor, cause the computing device to determine a particle generation rate.

18. A particle detection system according to any preceding claim, wherein the camera is configured to image the inspection area at a frame rate of about 100 Hz.

19. A particle detection system according to any preceding claim, wherein the camera is configured to image the inspection area with an exposure time of about 10 ms or less.

20. 1. A method for detecting particles generated from the impact of a glass article, the method comprising: directing a light beam to an area beneath one or more glass articles; capturing, with a camera, an image of an inspection area within the light beam beneath the one or more glass articles; and determining whether a particle is present in the image.

21. 21. The method of claim 20, further comprising forming the light beam into the light sheet such that the inspection area is within the light sheet.

22. 22. The method of claim 21, wherein the light sheet is parallel to a horizontal surface supporting the glass article.

23. further comprising accelerating the one or more glass articles to cause an impact of the glass articles; 23. The method of any one of claims 20 to 22, wherein the inspection area is imaged by the camera while accelerating the one or more glass articles.

Images