Antimicrobial glass compositions, glasses and polymeric articles incorporating the same

Abstract
Embodiments of the present invention pertain to antimicrobial glass compositions, glasses and articles. The articles include a glass, which may include a glass phase and a cuprite phase. In other embodiments, the glasses include as plurality of Cu1+ ions, a degradable phase including B2O3, P2O5 and K2O and a durable phase including SiO2. Other embodiments include glasses having a plurality of Cu1+ ions disposed on the surface of the glass and in the glass network and/or the glass matrix. The article may also include a polymer. The glasses and articles disclosed herein exhibit a 2 log reduction or greater in a concentration of at least one of Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa bacteria, Methicillin Resistant Staphylococcus aureus, and E. coli, under the EPA Test Method for Efficacy of Copper Alloy as a Sanitizer testing conditions and under Modified JIS Z 2801 for Bacteria testing conditions. In some embodiments, the glass and articles exhibit a 2 log reduction or greater in a concentration of Murine Norovirus under Modified JIS Z 2801 Test for Viruses testing conditions.
Description
BACKGROUND

The present disclosure relates generally to antimicrobial glass compositions and articles incorporating such compositions. More particularly, the various embodiments described herein relate to glasses having antimicrobial attributes and articles that incorporate such glasses.


Consumer electronics articles, including touch-activated or touch-interactive devices, such as screen surfaces (e.g., surfaces of electronic devices having user-interactive capabilities that are activated by touching specific portions of the surfaces), have become increasingly more prevalent. As the extent to which the touch screen-based interactions between a user and a device increases, so too does the likelihood of the surface harboring microorganisms (e.g., bacteria, fungi, viruses, and the like) that can be transferred from user to user. Moreover, the housings which incorporate the touch-activated or touch-interactive devices also include surfaces that harbor such microorganisms that can be transferred from user to user. The concern of microorganism transfer is also a concern with equipment, furniture and architectural articles used in medical or office settings and many other articles in which users come into contact with surfaces.


To minimize the presence of microbes on various materials, so-called “antimicrobial” properties have been imparted to a variety of glasses; however, there is a need to provide entire articles (including the housing and any glasses used as cover glass) that also exhibit antimicrobial properties. Accordingly, antimicrobial articles useful for certain applications should be durable enough for the purpose for which they are used, while also providing continuous antimicrobial properties that are passive or do not require additional activation by a user or outside source (e.g., UV light). In addition, antimicrobial glasses and articles should provide controlled antimicrobial activity.


SUMMARY

A first aspect of the present disclosure pertains to an article that includes a carrier and a glass. Examples of suitable carriers include polymers, monomers, binders, solvents, and other materials used to form molded articles, formed articles, coatings on substrates or other such articles. Exemplary coatings may include anti-frictive coatings, coatings exhibiting a low coefficient of friction, or coatings that form a surface exhibiting a low coefficient of friction.


The glass of one or more embodiments may also include a composition that includes, in mole percent: SiO2 in the range from about 40 to about 70, Al2O3 in the range from about 0 to about 20, a copper-containing oxide in the range from about 10 to about 50, CaO in the range from about 0 to about 15, MgO in the range from about 0 to about 15, P2O5 in the range from about 0 to about 25, B2O3 in the range from about 0 to about 25, K2O in the range from about 0 to about 20, ZnO in the range from about 0 to about 5, Na2O in the range from about 0 to about 20, and Fe2O3 in the range from about 0 to about 5. In some embodiments, the amount of copper-containing oxide is greater than the amount of Al2O3 (which may be about 5 mole percent or less, in some cases). In some instances, the composition may be free of Al2O3. Examples of suitable copper-containing oxides can include CuO, Cu2O, or a combination thereof.


The article of one or more embodiments may include a plurality of Cu1+ ions, Cu metal or a combination thereof. In some instances, the glass may be substantially free of tenorite.


The glass of one or more embodiments may include a cuprite phase and a glass phase. In some embodiments, the cuprite phase may include crystals that have an average major dimension of about 5 micrometers (μm) or less, or even about 1 micrometer (μm) or less.


A second aspect of the present disclosure pertains to an article that includes a carrier and a glass with a plurality of Cu1+ ions, a degradable phase comprising at least one of B2O3, P2O5 and R2O, and a durable phase comprising SiO2. The glass may be formed from the compositions described herein. In some instances, the durable phase is present in an amount by weight that is greater than the degradable phase. The degradable phase of one or more embodiments leaches or is leachable in the presence of water.


The article may optionally include a cuprite phase, which may be dispersed in one or both of the degradable phase and the durable phase. The cuprite phase may have crystals having an average major dimension of about 5 micrometers (μm) or less, about 1 micrometer (μm) or less, or about 500 nanometers (nm) or less. The cuprite phase may comprise at least about 10 weight percent or at least about 20 weight percent of the glass.


In one or more embodiments, the glass includes a surface portion (having a depth of less than about 5 nanometers (nm)) that includes a plurality of copper ions. In some embodiments, at least 75% of the plurality of copper ions is Cu1+. In other embodiments, less than about 25% of the plurality of copper ions is Cu2+.


A third aspect of the present disclosure pertains to an article including a carrier; and an inorganic material, wherein the inorganic material comprises a surface and a plurality of Cu1+ ions disposed on the surface. The inorganic material may include a glass and may be formed form the compositions described herein. The inorganic material may be substantially free of tenorite.


In one or more embodiments, the plurality of Cu1+ ions may be dispersed in a glass network and/or a glass matrix. In some instances, the glass network includes atoms to which the plurality of Cu1+ ions is atomically bonded. The plurality of ions may include cuprite crystals that are dispersed in the glass matrix.


The carrier may include a polymer, a monomer, a binder, a solvent, or combinations thereof. Carriers may include anti-frictive materials such as for example, fluorocarbons, fluorinated silanes, and alkyl perfluorocarbon silanes. The polymer used in the embodiments described herein can include organic or inorganic polymers. Exemplary polymers may include a thermoplastic polymer, a polyolefin, a cured polymer, an ultraviolet- or UV-cured polymer, a polymer emulsion, a solvent-based polymer, and combinations thereof. Specific examples of monomers include catalyst curable monomers, thermally-curable monomers, radiation-curable monomers and combinations thereof. The articles described herein may include a glass to carrier ratio in the range from about 10:90 to about 90:10, based on weight percent.


The glasses and articles described herein may exhibit a 2 log reduction or greater in a concentration of at least one of Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa bacteria, Methicillin Resistant Staphylococcus aureus, and E. coli, under the EPA Test Method for Efficacy of Copper Alloy as a Sanitizer testing conditions (herein, after the “EPA Test”).


The glasses and articles described herein according to one or more embodiments may exhibit a 4 log reduction or greater (e.g., 5 log reduction or greater) in a concentration of at least one of Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa bacteria, Methicillin Resistant Staphylococcus aureus, and E. coli, under JIS Z 2801 (2000) testing conditions. One or more embodiments of the glasses and articles described herein also exhibit a 4 log reduction or greater (e.g., 5 log reduction or greater) in a concentration of at least one of Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa Methicillin Resistant Staphylococcus aureus, and E. coli, under modified JIS Z 2801 (2000) testing conditions (hereinafter, “Modified JIS Z 2801 Test for Bacteria”. The Modified JIS Z 2801 (2000) Test for Bacteria is described in greater detail herein.


In one or more embodiments, the glasses and articles described herein according to one or more embodiments may exhibit a 2 log reduction or greater (e.g., 4 log reduction or greater, or a 5 log reduction or greater) in a concentration of Murine Norovirus, under modified JIS Z 2801 (2000) testing conditions for evaluating viruses (hereinafter, “Modified JIS Z 2801 for Viruses”). The Modified JIS Z 2801 (2000) Test for Viruses is described in greater detail herein.


In some embodiments, the glasses and articles may exhibit the log reductions described herein (i.e., under the EPA Test, the JIS Z 2801 testing conditions, the Modified JIS Z 2801 Test for Bacteria and/or the Modified JIS Z 2801 Test for Viruses), for a period of one month or greater or for a period of three months or greater. The one month period or three month period may commence at or after the formation of the glass, or at or after combination of the glass with a carrier.


In one or more embodiments, the articles leach the copper ions when exposed or in contact with a leachate. In one or more embodiments, the articles leach only copper ions when exposed to leachates including water.


The articles described herein may form the housing for an electronic device.


A fourth aspect of the present disclosure pertains to a method of making an antimicrobial article. In one or more embodiments, the method includes melting a glass composition to form a glass comprising a plurality of Cu1+ ions; and a glass phase, forming the glass into at least one of particulates and fibers, dispersing the at least one of particulates and fibers in a carrier, such as a polymer (as described herein), a monomer, or a binder, to provide a filled carrier and forming the filled carrier into the antimicrobial article. The glass composition may include the compositions described herein.


Additional features and advantages will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments as described herein, including the detailed description which follows, the claims, as well as the appended drawings.


It is to be understood that both the foregoing general description and the following detailed description are merely exemplary, and are intended to provide an overview or framework to understanding the nature and character of the claims. The accompanying drawings are included to provide a further understanding, and are incorporated in and constitute a part of this specification. The drawings illustrate one or more embodiment(s), and together with the description serve to explain principles and operation of the various embodiments.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1 is a side view of an antimicrobial glass in the form of a sheet according to one or more embodiments;



FIG. 2 is an enlarged partial view of the antimicrobial glass shown in FIG. 1.



FIG. 3 is a transmission electron microscopy (TEM) image of an antimicrobial glass, according to one or more embodiments;



FIG. 4 is a scanning electron microscopy (SEM) image of a cross-section of the antimicrobial glass shown in FIG. 3;



FIG. 5 is a SEM image of a fracture cross-section of the antimicrobial glass shown in FIG. 3;



FIG. 6 is an SEM image of the antimicrobial glass according to one or more embodiments;



FIG. 7A is a SEM-energy-dispersive X-ray spectroscopy (EDX) hypermap of a cross-section of Example 30, after being annealed overnight at 650° C. after melting at 1650° C.;



FIG. 7B is a SEM-EDX hypermap of a cross-section of Example 30 after being quenched in water after melting at 1650° C.;



FIG. 8A shows a fracture cross-section of Example 30, after an additional heat treatment at 800° C. for 1 hour;



FIG. 8B shows a polished cross-section of Example 30, after an additional heat treatment at 800° C. for 1 hour;



FIG. 9 illustrates the antimicrobial activity of glasses according to one or more embodiments;



FIG. 10 is a graph showing the antimicrobial activity of an antimicrobial glass described herein, when formed into particles and combined with a polymer carrier, after various time periods;



FIG. 11 is a graph illustrating the antimicrobial activity of various articles, according one or more embodiments;



FIG. 12 is a graph illustrating the antimicrobial activity of various articles, according to one or more embodiments;



FIG. 13 is a graph illustrating the antimicrobial activity of glasses having different amounts of copper;



FIG. 14 shows images of injection molded articles made from Example 12 and a polymer; and



FIG. 15 shows the antimicrobial activity of injection molded articles, according to one or more embodiments, with and without different surface treatments.





DETAILED DESCRIPTION

Reference will now be made in detail to various embodiment(s), examples of which are illustrated in the accompanying drawings.


A first aspect of the present disclosure pertains to antimicrobial glass compositions and glasses made from or including such compositions. The antimicrobial properties of the glasses disclosed herein include antiviral and/or antibacterial properties. As used herein the term “antimicrobial,” means a material, or a surface of a material that will kill or inhibit the growth of bacteria, viruses and/or fungi. The term as used herein does not mean the material or the surface of the material will kill or inhibit the growth of all species microbes within such families, but that it will kill or inhibit the growth or one or more species of microbes from such families.


As used herein the term “log reduction” means−log (Ca/C0), where Ca=the colony form unit (CFU) number of the antimicrobial surface and C0=the colony form unit (CFU) of the control surface that is not an antimicrobial surface. As an example, a 3 log reduction equals about 99.9% of the bacteria, viruses and/or fungi killed and a Log Reduction of 5=99.999% of bacteria, viruses and/or fungi killed.


In one or more embodiments, the antimicrobial glasses include a Cu species. In one or more alternative embodiments, the Cu species may include Cu1+, Cu0, and/or Cu2+. The combined total of the Cu species may be about 10 wt % or more. However, as will be discussed in more detail below, the amount of Cu2+ is minimized or is reduced such that the antimicrobial glass is substantially free of Cu2+. The Cu1+ ions may be present on or in the surface and/or the bulk of the antimicrobial glass. In some embodiments, the Cu1+ ions are present in the glass network and/or the glass matrix of the antimicrobial glass. Where the Cu1+ ions are present in the glass network, the Cu1+ ions are atomically bonded to the atoms in the glass network. Where the Cu1+ ions are present in the glass matrix, the Cu1+ ions may be present in the form of Cu1+ crystals that are dispersed in the glass matrix. In some embodiments the Cu1+ crystals include cuprite (Cu2O). In such embodiments, where Cu1+ crystals are present, the material may be referred to as an antimicrobial glass ceramic, which is intended to refer to a specific type of glass with crystals that may or may not be subjected to a traditional ceramming process by which one or more crystalline phases are introduced and/or generated in the glass. Where the Cu1+ ions are present in a non-crystalline form, the material may be referred to as an antimicrobial glass. In some embodiments, both Cu1+ crystals and Cu1+ ions not associated with a crystal are present in the antimicrobial glasses described herein.


In one or more embodiments, the antimicrobial glass may be formed from a composition that can include, in mole percent, SiO2 in the range from about 40 to about 70, Al2O3 in the range from about 0 to about 20, a copper-containing oxide in the range from about 10 to about 30, CaO in the range from about 0 to about 15, MgO in the range from about 0 to about 15, P2O5 in the range from about 0 to about 25, B2O3 in the range from about 0 to about 25, K2O in the range from about 0 to about 20, ZnO in the range from about 0 to about 5, Na2O in the range from about 0 to about 20, and/or Fe2O3 in the range from about 0 to about 5. In such embodiments, the amount of the copper-containing oxide is greater than the amount of Al2O3. In some embodiments, the composition may include a content of R2O, where R may include K, Na, Li, Rb, Cs and combinations thereof.


In the embodiments of the compositions described herein, SiO2 serves as the primary glass-forming oxide. The amount of SiO2 present in a composition should be enough to provide glasses that exhibit the requisite chemical durability suitable for its use or application (e.g., touch applications, article housing etc.). The upper limit of SiO2 may be selected to control the melting temperature of the compositions described herein. For example, excess SiO2 could drive the melting temperature at 200 poise to high temperatures at which defects such as fining bubbles may appear or be generated during processing and in the resulting glass. Furthermore, compared to most oxides, SiO2 decreases the compressive stress created by an ion exchange process of the resulting glass. In other words, glass formed from compositions with excess SiO2 may not be ion-exchangeable to the same degree as glass formed from compositions without excess SiO2. Additionally or alternatively, SiO2 present in the compositions according to one or more embodiments could increase the plastic deformation prior break properties of the resulting glass. An increased SiO2 content in the glass formed from the compositions described herein may also increase the indentation fracture threshold of the glass.


In one or more embodiments, the composition includes SiO2 in an amount, in mole percent, in the range from about 40 to about 70, from about 40 to about 69, from about 40 to about 68, from about 40 to about 67, from about 40 to about 66, from about 40 to about 65, from about 40 to about 64, from about 40 to about 63, from about 40 to about 62, from about 40 to about 61, from about 40 to about 60, from about 41 to about 70, from about 42 to about 70, from about 43 to about 70, from about 44 to about 70, from about 45 to about 70, from about 46 to about 70, from about 47 to about 70, from about 48 to about 70, from about 49 to about 70, from about 50 to about 70, from about 41 to about 69, from about 42 to about 68, from about 43 to about 67 from about 44 to about 66 from about 45 to about 65, from about 46 to about 64, from about 47 to about 63, from about 48 to about 62, from about 49 to about 61, from about 50 to about 60 and all ranges and sub-ranges therebetween.


In one or more embodiments, the composition includes Al2O3 an amount, in mole percent, in the range from about 0 to about 20, from about 0 to about 19, from about 0 to about 18, from about 0 to about 17, from about 0 to about 16, from about 0 to about 15, from about 0 to about 14, from about 0 to about 13, from about 0 to about 12, from about 0 to about 11 from about 0 to about 10, from about 0 to about 9, from about 0 to about 8, from about 0 to about 7, from about 0 to about 6, from about 0 to about 5, from about 0 to about 4, from about 0 to about 3, from about 0 to about 2, from about 0 to about 1, from about 0.1 to about 1, from about 0.2 to about 1, from about 0.3 to about 1 from about 0.4 to about 1 from about 0.5 to about 1, from about 0 to about 0.5, from about 0 to about 0.4, from about 0 to about 0.3 from about 0 to about 0.2, from about 0 to about 0.1 and all ranges and sub-ranges therebetween. In some embodiments, the composition is substantially free of Al2O3. As used herein, the phrase “substantially free” with respect to the components of the composition and/or resulting glass means that the component is not actively or intentionally added to the compositions during initial batching or subsequent post processing (e.g., ion exchange process), but may be present as an impurity. For example, a composition, a glass may be describe as being substantially free of a component, when the component is present in an amount of less than about 0.01 mol %.


The amount of Al2O3 may be adjusted to serve as a glass-forming oxide and/or to control the viscosity of molten compositions. Without being bound by theory, it is believed that when the concentration of alkali oxide (R2O) in a composition is equal to or greater than the concentration of Al2O3, the aluminum ions are found in tetrahedral coordination with the alkali ions acting as charge-balancers. This tetrahedral coordination greatly enhances various post-processing (e.g., ion exchange process) of glasses formed from such compositions. Divalent cation oxides (RO) can also charge balance tetrahedral aluminum to various extents. While elements such as calcium, zinc, strontium, and barium behave equivalently to two alkali ions, the high field strength of magnesium ions causes them to not fully charge balance aluminum in tetrahedral coordination, resulting in the formation of five- and six-fold coordinated aluminum. Generally, Al2O3 can play an important role in ion-exchangeable compositions and strengthened glasses since it enables a strong network backbone (i.e., high strain point) while allowing for the relatively fast diffusivity of alkali ions. However, when the concentration of Al2O3 is too high, the composition may exhibit lower liquidus viscosity and, thus, Al2O3 concentration may be controlled within a reasonable range. Moreover, as will be discussed in more detail below, excess Al2O3 has been found to promote the formation of Cu2+ ions, instead of the desired Cu1+ ions.


In one or more embodiments, the composition includes a copper-containing oxide in an amount, in mole percent, in the range from about 10 to about 50, from about 10 to about 49, from about 10 to about 48, from about 10 to about 47, from about 10 to about 46, from about 10 to about 45, from about 10 to about 44, from about 10 to about 43, from about 10 to about 42, from about 10 to about 41, from about 10 to about 40, from about 10 to about 39, from about 10 to about 38, from about 10 to about 37, from about 10 to about 36, from about 10 to about 35, from about 10 to about 34, from about 10 to about 33, from about 10 to about 32, from about 10 to about 31, from about 10 to about 30, from about 10 to about 29, from about 10 to about 28, from about 10 to about 27, from about 10 to about 26, from about 10 to about 25, from about 10 to about 24, from about 10 to about 23, from about 10 to about 22, from about 10 to about 21, from about 10 to about 20, from about 11 to about 50, from about 12 to about 50, from about 13 to about 50, from about 14 to about 50, from about 15 to about 50, from about 16 to about 50, from about 17 to about 50, from about 18 to about 50, from about 19 to about 50, from about 20 to about 50, from about 10 to about 30, from about 11 to about 29, from about 12 to about 28, from about 13 to about 27, from about 14 to about 26, from about 15 to about 25, from about 16 to about 24, from about 17 to about 23, from about 18 to about 22, from about 19 to about 21 and all ranges and sub-ranges therebetween. In one or more specific embodiments, the copper-containing oxide may be present in the composition in an amount of about 20 mole percent, about 25 mole percent, about 30 mole percent or about 35 mole percent. The copper-containing oxide may include CuO, Cu2O and/or combinations thereof.


The copper-containing oxides in the composition form the Cu1+ ions present in the resulting glass. Copper may be present in the composition and/or the glasses including the composition in various forms including Cu0, Cu1+ and Cu2+. Copper in the Cu0 or Cu1+ forms provide antimicrobial activity. However forming and maintaining these states of antimicrobial copper are difficult and often, in known compositions, Cu2+ ions are formed instead of the desired Cu0 or Cu1+ ions.


In one or more embodiments, the amount of copper-containing oxide is greater than the amount of Al2O3 in the composition. Without being bound by theory it is believed that an about equal amount of copper-containing oxides and Al2O3 in the composition results in the formation of tenorite (CuO) instead of cuprite (Cu2O). The presence of tenorite decreases the amount of Cu1+ in favor of Cu2+ and thus leads to reduced antimicrobial activity. Moreover, when the amount of copper-containing oxides is about equal to the amount of Al2O3, aluminum prefers to be in a four-fold coordination and the copper in the composition and resulting glass remains in the Cu2+ form so that the charge remains balanced. Where the amount of copper-containing oxide exceeds the amount of Al2O3, then it is believed that at least a portion of the copper is free to remain in the Cu1+ state, instead of the Cu2+ state, and thus the presence of Cu1+ ions increases.


The composition of one or more embodiments includes P2O5 in an amount, in mole percent, in the range from about 0 to about 25, from about 0 to about 22, from about 0 to about 20, from about 0 to about 18, from about 0 to about 16, from about 0 to about 15, from about 0 to about 14, from about 0 to about 13, from about 0 to about 12, from about 0 to about 11, from about 0 to about 10, from about 0 to about 9, from about 0 to about 8, from about 0 to about 7, from about 0 to about 6, from about 0 to about 5, from about 0 to about 4, from about 0 to about 3, from about 0 to about 2, from about 0 to about 1, from about 0.1 to about 1, from about 0.2 to about 1, from about 0.3 to about 1 from about 0.4 to about 1 from about 0.5 to about 1, from about 0 to about 0.5, from about 0 to about 0.4, from about 0 to about 0.3 from about 0 to about 0.2, from about 0 to about 0.1 and all ranges and sub-ranges therebetween. In some embodiments, the composition includes about 10 mole percent or about 5 mole percent P2O5 or, alternatively, may be substantially free of P2O5.


In one or more embodiments, P2O5 forms at least part of a less durable phase or a degradable phase in the glass. The relationship between the degradable phase(s) of the glass and antimicrobial activity is discussed in greater detail herein. In one or more embodiments, the amount of P2O5 may be adjusted to control crystallization of the composition and/or glass during forming. For example, when the amount of P2O5 is limited to about 5 mol % or less or even 10 mol % or less, crystallization may be minimized or controlled to be uniform. However, in some embodiments, the amount or uniformity of crystallization of the composition and/or glass may not be of concern and thus, the amount of P2O5 utilized in the composition may be greater than 10 mol %.


In one or more embodiments, the amount of P2O5 in the composition may be adjusted based on the desired damage resistance of the glass, despite the tendency for P2O5 to form a less durable phase or a degradable phase in the glass. Without being bound by theory, P2O5 can decrease the melting viscosity relative to SiO2. In some instances, P2O5 is believed to help to suppress zircon breakdown viscosity (i.e., the viscosity at which zircon breaks down to form ZrO2) and may be more effective in this regard than SiO2. When glass is to be chemically strengthened via an ion exchange process, P2O5 can improve the diffusivity and decrease ion exchange times, when compared to other components that are sometimes characterized as network formers (e.g., SiO2 and/or B2O3).


The composition of one or more embodiments includes B2O3 in an amount, in mole percent, in the range from about 0 to about 25, from about 0 to about 22, from about 0 to about 20, from about 0 to about 18, from about 0 to about 16, from about 0 to about 15, from about 0 to about 14, from about 0 to about 13, from about 0 to about 12, from about 0 to about 11, from about 0 to about 10, from about 0 to about 9, from about 0 to about 8, from about 0 to about 7, from about 0 to about 6, from about 0 to about 5, from about 0 to about 4, from about 0 to about 3, from about 0 to about 2, from about 0 to about 1, from about 0.1 to about 1, from about 0.2 to about 1, from about 0.3 to about 1 from about 0.4 to about 1 from about 0.5 to about 1, from about 0 to about 0.5, from about 0 to about 0.4, from about 0 to about 0.3 from about 0 to about 0.2, from about 0 to about 0.1 and all ranges and sub-ranges therebetween. In some embodiments, the composition includes a non-zero amount of B2O3, which may be, for example, about 10 mole percent or about 5 mole percent. The composition of some embodiments may be substantially free of B2O3.


In one or more embodiments, B2O3 forms a less durable phase or a degradable phase in the glass formed form the composition. The relationship between the degradable phase(s) of the glass and antimicrobial activity is discussed in greater detail herein. Without being bound by theory, it is believed the inclusion of B2O3 in compositions imparts damage resistance in glasses incorporating such compositions, despite the tendency for B2O3 to form a less durable phase or a degradable phase in the glass. The composition of one or more embodiments includes one or more alkali oxides (R2O) (e.g., Li2O, Na2O, K2O, Rb2O and/or Cs2O). In some embodiments, the alkali oxides modify the melting temperature and/or liquidus temperatures of such compositions. In one or more embodiments, the amount of alkali oxides may be adjusted to provide a composition exhibiting a low melting temperature and/or a low liquidus temperature. Without being bound by theory, the addition of alkali oxide(s) may increase the coefficient of thermal expansion (CTE) and/or lower the chemical durability of the antimicrobial glasses that include such compositions. In some cases these attributes may be altered dramatically by the addition of alkali oxide(s).


In some embodiments, the antimicrobial glasses disclosed herein may be chemically strengthened via an ion exchange process in which the presence of a small amount of alkali oxide (such as Li2O and Na2O) is required to facilitate ion exchange with larger alkali ions (e.g., K+), for example exchanging smaller alkali ions from an antimicrobial glass with larger alkali ions from a molten salt bath containing such larger alkali ions. Three types of ion exchange can generally be carried out. One such ion exchange includes a Na+-for-Li+ exchange, which results in a deep depth of layer but low compressive stress. Another such ion exchange includes a K+-for-Li+ exchange, which results in a small depth of layer but a relatively large compressive stress. A third such ion exchange includes a K+-for-Na+ exchange, which results in intermediate depth of layer and compressive stress. A sufficiently high concentration of the small alkali oxide in compositions may be necessary to produce a large compressive stress in the antimicrobial glass including such compositions, since compressive stress is proportional to the number of alkali ions that are exchanged out of the antimicrobial glass.


In one or more embodiments, the composition includes K2O in an amount in the range from about 0 to about 20, from about 0 to about 18, from about 0 to about 16, from about 0 to about 15, from about 0 to about 14, from about 0 to about 13, from about 0 to about 12, from about 0 to about 11, from about 0 to about 10, from about 0 to about 9, from about 0 to about 8, from about 0 to about 7, from about 0 to about 6, from about 0 to about 5, from about 0 to about 4, from about 0 to about 3, from about 0 to about 2, from about 0 to about 1, from about 0.1 to about 1, from about 0.2 to about 1, from about 0.3 to about 1 from about 0.4 to about 1 from about 0.5 to about 1, from about 0 to about 0.5, from about 0 to about 0.4, from about 0 to about 0.3 from about 0 to about 0.2, from about 0 to about 0.1 and all ranges and sub-ranges therebetween. In some embodiments, the composition includes a non-zero amount of K2O or, alternatively, the composition may be substantially free, as defined herein, of K2O. In addition to facilitating ion exchange, where applicable, in one or more embodiments, K2O can also form a less durable phase or a degradable phase in the glass formed form the composition. The relationship between the degradable phase(s) of the glass and antimicrobial activity is discussed in greater detail herein.


In one or more embodiments, the composition includes Na2O in an amount in the range from about 0 to about 20, from about 0 to about 18, from about 0 to about 16, from about 0 to about 15, from about 0 to about 14, from about 0 to about 13, from about 0 to about 12, from about 0 to about 11, from about 0 to about 10, from about 0 to about 9, from about 0 to about 8, from about 0 to about 7, from about 0 to about 6, from about 0 to about 5, from about 0 to about 4, from about 0 to about 3, from about 0 to about 2, from about 0 to about 1, from about 0.1 to about 1, from about 0.2 to about 1, from about 0.3 to about 1 from about 0.4 to about 1 from about 0.5 to about 1, from about 0 to about 0.5, from about 0 to about 0.4, from about 0 to about 0.3 from about 0 to about 0.2, from about 0 to about 0.1 and all ranges and sub-ranges therebetween. In some embodiments, the composition includes a non-zero amount of Na2O or, alternatively, the composition may be substantially free, as defined herein, of Na2O.


In one or more embodiments, the composition may include one or more divalent cation oxides, such as alkaline earth oxides and/or ZnO. Such divalent cation oxides may be included to improve the melting behavior of the compositions. With respect to ion exchange performance, the presence of divalent cations can act to decrease alkali mobility and thus, when larger divalent cation oxides are utilized, there may be a negative effect on ion exchange performance. Furthermore, smaller divalent cation oxides generally help the compressive stress developed in an ion-exchanged glass more than the larger divalent cation oxides. Hence, divalent cation oxides such as MgO and ZnO can offer advantages with respect to improved stress relaxation, while minimizing the adverse effects on alkali diffusivity.


In one or more embodiments, the composition includes CaO in an amount, in mole percent, in the range from about 0 to about 15, from about 0 to about 14, from about 0 to about 13, from about 0 to about 12, from about 0 to about 11, from about 0 to about 10, from about 0 to about 9, from about 0 to about 8, from about 0 to about 7, from about 0 to about 6, from about 0 to about 5, from about 0 to about 4, from about 0 to about 3, from about 0 to about 2, from about 0 to about 1, from about 0.1 to about 1, from about 0.2 to about 1, from about 0.3 to about 1 from about 0.4 to about 1 from about 0.5 to about 1, from about 0 to about 0.5, from about 0 to about 0.4, from about 0 to about 0.3 from about 0 to about 0.2, from about 0 to about 0.1 and all ranges and sub-ranges therebetween. In some embodiments, the composition is substantially free of CaO.


In one or more embodiments, the composition includes MgO in an amount, in mole percent, in the range from about 0 to about 15, from about 0 to about 14, from about 0 to about 13, from about 0 to about 12, from about 0 to about 11, from about 0 to about 10, from about 0 to about 9, from about 0 to about 8, from about 0 to about 7, from about 0 to about 6, from about 0 to about 5, from about 0 to about 4, from about 0 to about 3, from about 0 to about 2, from about 0 to about 1, from about 0.1 to about 1, from about 0.2 to about 1, from about 0.3 to about 1 from about 0.4 to about 1 from about 0.5 to about 1, from about 0 to about 0.5, from about 0 to about 0.4, from about 0 to about 0.3 from about 0 to about 0.2, from about 0 to about 0.1 and all ranges and sub-ranges therebetween. In some embodiments, the composition is substantially free of MgO.


The composition of one or more embodiments may include ZnO in an amount, in mole percent, in the range from about 0 to about 5, from about 0 to about 4, from about 0 to about 3, from about 0 to about 2, from about 0 to about 1, from about 0.1 to about 1, from about 0.2 to about 1, from about 0.3 to about 1 from about 0.4 to about 1 from about 0.5 to about 1, from about 0 to about 0.5, from about 0 to about 0.4, from about 0 to about 0.3 from about 0 to about 0.2, from about 0 to about 0.1 and all ranges and sub-ranges therebetween. In some embodiments, the composition is substantially free of ZnO.


The composition of one or more embodiments may include Fe2O3, in mole percent, in the range from about 0 to about 5, from about 0 to about 4, from about 0 to about 3, from about 0 to about 2, from about 0 to about 1, from about 0.1 to about 1, from about 0.2 to about 1, from about 0.3 to about 1 from about 0.4 to about 1 from about 0.5 to about 1, from about 0 to about 0.5, from about 0 to about 0.4, from about 0 to about 0.3 from about 0 to about 0.2, from about 0 to about 0.1 and all ranges and sub-ranges therebetween. In some embodiments, the composition is substantially free of Fe2O3.


In one or more embodiments, the composition may include one or more colorants. Examples of such colorants include NiO, TiO2, Fe2O3, Cr2O3, Co3O4 and other known colorants. In some embodiments, the one or more colorants may be present in an amount in the range up to about 10 mol %. In some instances, the one or more colorants may be present in an amount in the range from about 0.01 mol % to about 10 mol %, from about 1 mol % to about 10 mol %, from about 2 mol % to about 10 mol %, from about 5 mol % to about 10 mol %, from about 0.01 mol % to about 8 mol %, or from about 0.01 mol % to about 5 mol %.


In one or more embodiments, the composition may include one or more nucleating agents. Exemplary nucleating agents include TiO2, ZrO2 and other known nucleating agents in the art. The composition can include one or more different nucleating agents. The nucleating agent content of the composition may be in the range from about 0.01 mol % to about 1 mol %. In some instances, the nucleating agent content may be in the range from about 0.01 mol % to about 0.9 mol %, from about 0.01 mol % to about 0.8 mol %, from about 0.01 mol % to about 0.7 mol %, from about 0.01 mol % to about 0.6 mol %, from about 0.01 mol % to about 0.5 mol %, from about 0.05 mol % to about 1 mol %, from about 0.1 mol % to about 1 mol %, from about 0.2 mol % to about 1 mol %, from about 0.3 mol % to about 1 mol %, or from about 0.4 mol % to about 1 mol %, and all ranges and sub-ranges therebetween.


The glasses formed from the compositions may include a plurality of Cu1+ ions. In some embodiments, such Cu1+ ions form part of the glass network and may be characterized as a glass modifier. Without being bound by theory, where Cu1+ ions are part of the glass network, it is believed that during typical glass formation processes, the cooling step of the molten glass occurs too rapidly to allow crystallization of the copper-containing oxide (e.g., CuO and/or Cu2O). Thus the Cu1+ remains in an amorphous state and becomes part of the glass network. In some cases, the total amount of Cu1+ ions, whether they are in a crystalline phase or in the glass matrix, may be even higher, such as up to 40 mol %, up to 50 mol %, or up to 60 mol %.


In one or more embodiments, the glasses formed form the compositions disclosed herein include Cu1+ ions that are dispersed in the glass matrix as Cu1+ crystals. In one or more embodiments, the Cu1+ crystals may be present in the form of cuprite. The cuprite present in the glass may form a phase that is distinct from the glass matrix or glass phase. In other embodiments, the cuprite may form part of or may be associated with one or more glasses phases (e.g., the durable phase described herein). The Cu1+ crystals may have an average major dimension of about 5 micrometers (μm) or less, 4 micrometers (μm) or less, 3 micrometers (μm) or less, 2 micrometers (μm) or less, about 1.9 micrometers (μm) or less, about 1.8 micrometers (μm) or less, about 1.7 micrometers (μm) or less, about 1.6 micrometers (μm) or less, about 1.5 micrometers (am) or less, about 1.4 micrometers (μm) or less, about 1.3 micrometers (μm) or less, about 1.2 micrometers (μm) or less, about 1.1 micrometers or less, 1 micrometers or less, about 0.9 micrometers (μm) or less, about 0.8 micrometers (μm) or less, about 0.7 micrometers (μm) or less, about 0.6 micrometers (μm) or less, about 0.5 micrometers (μm) or less, about 0.4 micrometers (μm) or less, about 0.3 micrometers (μm) or less, about 0.2 micrometers (μm) or less, about 0.1 micrometers (μm) or less, about 0.05 micrometers (μm) or less, and all ranges and sub-ranges therebetween. As used herein and with respect to the phrase “average major dimension”, the word “average” refers to a mean value and the word “major dimension” is the greatest dimension of the particle as measured by SEM. In some embodiments, the cuprite phase may be present in the antimicrobial glass in an amount of at least about 10 wt %, at least about 15 wt %, at least about 20 wt %, at least about 25 wt % and all ranges and subranges therebetween of the antimicrobial glass.


In some embodiments, the glasses may include about 70 wt % Cu1+ or more and about 30 wt % of Cu2+ or less. The Cu2+ ions may be present in tenorite form and/or even in the glass (i.e., not as a crystalline phase).


In some embodiments, the total amount of Cu by wt % in the glasses may be in the range from about 10 to about 30, from about 15 to about 25, from about 11 to about 30, from about 12 to about 30, from about 13 to about 30, from about 14 to about 30, from about 15 to about 30, from about 16 to about 30, from about 17 to about 30, from about 18 to about 30, from about 19 to about 30, from about 20 to about 30, from about 10 to about 29, from about 10 to about 28, from about 10 to about 27, from about 10 to about 26, from about 10 to about 25, from about 10 to about 24, from about 10 to about 23, from about 10 to about 22, from about 10 to about 21, from about 10 to about 20, from about 16 to about 24, from about 17 to about 23, from about 18 to about 22, from about 19 to about 21 and all ranges and sub-ranges therebetween. In one or more embodiments, the ratio of Cu1+ ions to the total amount Cu in the glass is about 0.5 or greater, 0.55 or greater, 0.6 or greater, 0.65 or greater, 0.7 or greater, 0.75 or greater, 0.8 or greater, 0.85 or greater, 0.9 or greater or even 1 or greater, and all ranges and sub-ranges therebetween. The amount of Cu and the ratio of Cu1+ ions to total Cu may be determined by inductively coupled plasma (ICP) techniques known in the art.


In some embodiments, the glass may exhibit a greater amount of Cu1+ and/or CuO than Cu2+. For example, based on the total amount of Cu1+, Cu2+ and CuO in the glasses, the percentage of Cu1+ and Cu0, combined, may be in the range from about 50% to about 99.9%, from about 50% to about 99%, from about 50% to about 95%, from about 50% to about 90%, from about 55% to about 99.9%, from about 60% to about 99.9%, from about 65% to about 99.9%, from about 70% to about 99.9%, from about 75% to about 99.9%, from about 80% to about 99.9%, from about 85% to about 99.9%, from about 90% to about 99.9%, from about 95% to about 99.9%, and all ranges and sub-ranges therebetween. The relative amounts of Cu1+, Cu2+ and Cu0 may be determined using x-ray photoluminescence spectroscopy (XPS) techniques known in the art. The tables below report these amounts as measured by XPS. Specifically, the tables report the amount of Cu2+ and the combination of Cu1+ and Cu0. Without being bound by theory, it is believed that most of the embodiments shown in Table 1 show copper as being present in the form of Cu1+, under the conditions the XPS was performed.


The antimicrobial glass comprises at least a first phase and second phase. In one or more embodiments, the antimicrobial glass may include two or more phases wherein the phases differ based on the ability of the atomic bonds in the given phase to withstand interaction with a leachate. Specifically, the glass of one or more embodiments may include a first phase that may be described as a degradable phase and a second phase that may be described as a durable phase. The phrases “first phase” and “degradable phase” may be used interchangeably. The phrases “second phase” and “durable phase” may be used interchangeably. As used herein, the term “durable” refers to the tendency of the atomic bonds of the durable phase to remain intact during and after interaction with a leachate. As used herein, the term “degradable” refers to the tendency of the atomic bonds of the degradable phase to break during and after interaction with one or more leachates. In one or more embodiments, the durable phase includes SiO2 and the degradable phase includes at least one of B2O3, P2O5 and R2O (where R can include any one or more of K, Na, Li, Rb, and Cs). Without being bound by theory, it is believed that the components of the degradable phase (i.e., B2O3, P2O5 and/or R2O) more readily interact with a leachate and the bonds between these components to one another and to other components in the antimicrobial glass more readily break during and after the interaction with the leachate. Leachates may include water, acids or other similar materials. In one or more embodiments, the degradable phase withstands degradation for 1 week or longer, 1 month or longer, 3 months or longer, or even 6 months or longer. In some embodiments, longevity may be characterized as maintaining antimicrobial efficacy over a specific period of time.


In one or more embodiments, the durable phase is present in an amount by weight that is greater than the amount of the degradable phase. In some instances, the degradable phase forms islands and the durable phase forms the sea surrounding the islands (i.e., the durable phase). In one or more embodiments, either one or both of the durable phase and the degradable phase may include cuprite. The cuprite in such embodiments may be dispersed in the respective phase or in both phases.


In some embodiments, phase separation occurs without any additional heat treatment of the antimicrobial glass. In some embodiments, phase separation may occur during melting and may be present when the glass composition is melted at temperatures up to and including about 1600° C. or 1650° C. When the glass is cooled, the phase separation is maintained.


The antimicrobial glass may be provided as a sheet or may have another shape such as particulate, fibrous, and the like. In one or more embodiments, as shown in FIGS. 1 and 2, the antimicrobial glass 100 includes a surface 101 and a surface portion 120 extending from the surface 101 into the antimicrobial glass at a depth of about 5 nanometers (nm) or less. The surface portion may include a plurality of copper ions wherein at least 75% of the plurality of copper ions includes Cu1+-ions. For example, in some instances, at least about 80%, at least about 85%, at least about 90%, at least about 95%, at least about 98%, at least about 99% or at least about 99.9% of the plurality of copper ions in the surface portion includes Cu1+ ions. In some embodiments, 25% or less (e.g., 20% or less, 15% or less, 12% or less, 10% or less or 8% or less) of the plurality of copper ions in the surface portion include Cu2+ ions. For example, in some instances, 20% or less, 15% or less, 10% or less, 5% or less, 2% or less, 1% or less, 0.5% or less or 0.01% or less of the plurality of copper ions in the surface portion include Cu2+ ions. In some embodiments, the surface concentration of Cu1+ ions in the antimicrobial glass is controlled. In some instances, a Cu1+ion concentration of about 4 ppm or greater can be provided on the surface of the antimicrobial glass.


The antimicrobial glass of one or more embodiments may a 2 log reduction or greater (e.g., 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5 and all ranges and sub-ranges therebetween) in a concentration of at least one of Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa, Methicillin Resistant Staphylococcus aureus, and E. coli, under the EPA Test. In some instances, the antimicrobial glass exhibits at least a 4 log reduction, a 5 log reduction or even a 6 log reduction in the concentration of at least one of Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa bacteria, Methicillin Resistant Staphylococcus aureus, and E. coli under the EPA Test.


The glasses described herein according to one or more embodiments may exhibit a 4 log reduction or greater (e.g., 5 log reduction or greater) in a concentration of at least one of Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa bacteria, Methicillin Resistant Staphylococcus aureus, and E. coli, under JIS Z 2801 (2000) testing conditions. One or more embodiments of the glasses described herein also exhibit a 4 log reduction or greater (e.g., 5 log reduction or greater) in a concentration of at least one of Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa Methicillin Resistant Staphylococcus aureus, and E. coli, under the Modified JIS Z 2801 Test for Bacterial. As used herein, Modified JIS Z 2801 Test for Bacteria includes evaluating the bacteria under the standard JIS Z 2801 (2000) test with modified conditions comprising heating the glass or article to a temperature of about 23 degrees Celsius to about 37 degrees Celsius at a humidity of about 38 percent to about 42 percent for about 6 hours.


In one or more embodiments described herein, the antimicrobial glasses exhibit a 2 log reduction or greater, a 3 log reduction or greater, a 4 log reduction or greater, or a 5 log reduction or greater in Murine Norovirus under a Modified JIS Z 2801 for Viruses test. The Modified JIS Z 2801 (2000) Test for Viruses includes the following procedure. For each material (e.g., the articles or glass of one or more embodiments, control materials, and any comparative glasses or articles) to be tested, three samples of the material (contained in individual sterile petri dishes) are each inoculated with a 20 μL aliquot of a test virus (where antimicrobial activity is measured) or a test medium including an organic soil load of 5% fetal bovine serum with or without the test virus (where cytotoxicity is measured). The inoculum is then covered with a film and the film is pressed down so the test virus and/or or test medium spreads over the film, but does not spread past the edge of the film. The exposure time begins when each sample was inoculated. The inoculated samples are transferred to a control chamber set to room temperature (about 20° C.) in a relative humidity of 42% for 2 hours. Exposure time with respect to control samples are discussed below. Following the 2-hour exposure time, the film is lifted off using sterile forceps and a 2.00 mL aliquot of the text virus and/or test medium is pipetted individually onto each sample of material and the underside of the film (or the side of the film exposed to the sample) used to cover each sample. The surface of each sample is individually scrapped with a sterile plastic cell scraper to collect the test virus or test medium. The test virus and/or test medium is collected (at 10−2 dilution), mixed using a vortex type mixer and serial 10-fold dilutions are prepared. The dilutions are then assayed for antimicrobial activity and/or cytotoxicity.


To prepare a control sample for testing antimicrobial activity (which are also referred to as “zero-time virus controls”) for the Modified JIS Z 2801 Test for Viruses, three control samples (contained in individual sterile petri dishes) are each inoculated with a 20 μL aliquot of the test virus. Immediately following inoculation, a 2.00 mL aliquot of test virus is pipetted onto each control sample. The surface of each sample was individually scrapped with a sterile plastic cell scraper to collect test virus. The test virus is collected (at 10−2 dilution), mixed using a vortex type mixer, and serial 10-fold dilutions were prepared. The dilutions are assayed for antimicrobial activity.


To prepare controls samples for cytotoxicity (which are also referred to as “2 hour control virus”) for the Modified JIS Z 2801 Test for Viruses, one control sample (contained in an individual sterile petri dish) is inoculated with a 20 μL aliquot of a test medium containing an organic soil load (5% fetal bovine serum), without the test virus. The inoculum is covered with a film and the film is pressed so the test medium spreads over the film but does not spread past the edge of the film. The exposure time begins when each control sample is inoculated. The control sample is transferred to a controlled chamber set to room temperature (20° C.) in a relative humidity of 42% for a duration of 2 hours exposure time. Following this exposure time, the film is lifted off using sterile forceps and a 2.00 mL aliquot of the test medium is pipetted individually onto each control sample and the underside of the film (the side exposed to the sample). The surface of each sample is individually scrapped with a sterile plastic cell scraper to collect the test medium. The test medium is collected (at 10−2 dilution), mixed using a vortex type mixer, and serial 10-fold dilutions were prepared. The dilutions were assayed for cytotoxicity.


The antimicrobial glass of one or more embodiments may exhibit the log reduction described herein for long periods of time. In other words, the antimicrobial glass may exhibit extended or prolonged antimicrobial efficacy. For example, in some embodiments, the antimicrobial glass may exhibit the log reductions described herein under the EPA Test, the JIS Z 2801 (2000) testing conditions, the Modified JIS Z 2801 Test for Bacteria and/or the Modified JIS Z 2801 Test for Viruses for up to 1 month, up to 3 months, up to 6 months or up to 12 months after the antimicrobial glass is formed or after the antimicrobial glass is combined with a carrier (e.g., polymers, monomers, binders, solvents and the like). These time periods may start at or after the antimicrobial glass is formed or combined with a carrier.


One or more embodiments, the antimicrobial glass may exhibit a preservative function, when combined with carriers described herein. In such embodiments, the antimicrobial glass may kill or eliminate, or reduce the growth of various foulants in the carrier. Foulants include fungi, bacteria, viruses and combinations thereof.


In one or more embodiments, the glasses and/or articles described herein leach the copper ions when exposed or in contact with a leachate. In one or more embodiments, the glass leaches only copper ions when exposed to leachates including water.


In one or more embodiments, the antimicrobial glass and/or articles described herein may have a tunable antimicrobial activity release. The antimicrobial activity of the glass and/or articles may be caused by contact between the antimicrobial glass and a leachate, such as water, where the leachate causes Cu1+ ions to be released from the antimicrobial glass. This action may be described as water solubility and the water solubility can be tuned to control the release of the Cu+1 ions.


In some embodiments, where the Cu1+ ions are disposed in the glass network and/or form atomic bonds with the atoms in the glass network, water or humidity breaks those bonds and the Cu1+ ions available for release and may be exposed on the glass or glass ceramic surface.


In one or more embodiments, the antimicrobial glass may be formed using formed in low cost melting tanks that are typically used for melting glass compositions such as soda lime silicate. The antimicrobial glass may be formed into a sheet using forming processes known in the art. For instance, example forming methods include float glass processes and down-draw processes such as fusion draw and slot draw.


The antimicrobial glass may be incorporated into a variety of articles, either alone or in combination with other materials, such as electronic devices (e.g., mobile phones, smart phones, tablets, video players, information terminal devices, laptop computer, etc.), architectural structures (e.g., countertops or walls), appliances (e.g., cooktops, refrigerator and dishwasher doors, etc.), information displays (e.g., whiteboards), and automotive components (e.g., dashboard panels, windshields, window components, etc.). When used in such articles, the antimicrobial glass can form at least part of the housing and/or display.


After formation, the antimicrobial glass may be formed into sheets and may be shaped, polished or otherwise processed for a desired end use. In some instances, the antimicrobial glass may be ground to a powder or particulate form. In other embodiments, the particulate antimicrobial glass may be combined with other materials or carriers into articles for various end uses. The combination of the antimicrobial glass and such other materials or carriers may be suitable for injection molding, extrusion or coatings or may be drawn into fibers. Such other materials or carriers may include polymers, monomers, binders, solvents, or a combination thereof as described herein. The polymer used in the embodiments described herein can include a thermoplastic polymer, a polyolefin, a cured polymer, an ultraviolet- or UV-cured polymer, a polymer emulsion, a solvent-based polymer, and combinations thereof. Examples of suitable polymers include, without limitation: thermoplastics including polystyrene (PS), high impact PS, polycarbonate (PC), nylon (sometimes referred to as polyamide (PA)), poly(acrylonitrile-butadiene-styrene) (ABS), PC-ABS blends, polybutyleneterephthlate (PBT) and PBT co-polymers, polyethyleneterephthalate (PET) and PET co-polymers, polyolefins (PO) including polyethylenes (PE), polypropylenes (PP), cyclicpolyolefins (cyclic-PO), modified polyphenylene oxide (mPPO), polyvinylchloride (PVC), acrylic polymers including polymethyl methacrylate (PMMA), thermoplastic elastomers (TPE), thermoplastic urethanes (TPU), polyetherimide (PEl) and blends of these polymers with each other. Suitable injection moldable thermosetting polymers include epoxy, acrylic, styrenic, phenolic, melamine, urethanes, polyesters and silicone resins. In other embodiments, the polymers may be dissolved in a solvent or dispersed as a separate phase in a solvent and form a polymer emulsion, such as a latex (which is a water emulsion of a synthetic or natural rubber, or plastic obtained by polymerization and used especially in coatings (as paint) and adhesives. Polymers may include fluorinated silanes or other low friction or anti-frictive materials. The polymers can contain impact modifiers, flame retardants, UV inhibitors, antistatic agents, mold release agents, fillers including glass, metal or carbon fibers or particles (including spheres), talc, clay or mica and colorants. Specific examples of monomers include catalyst curable monomers, thermally-curable monomers, radiation-curable monomers and combinations thereof.


In one example, acrylic latex paint may be combined with 20 wt % antimicrobial glass in particulate form and having a diameter of about 5 micrometers (μm). In some embodiments, the resulting combination of paint and antimicrobial glass included about 4 wt % CuO. In one or more embodiments, when combined with a carrier such as a polymer, monomer, binder or solvent, the amount of antimicrobial glass may be in the range from about 50 wt % to about 85 wt %. In some embodiments, the antimicrobial glass may be present in an amount in the range from about 55 wt % to about 85 wt %, from about 60 wt % to about 85 wt %, from about 65 wt % to about 85 wt %, from about 50 wt % to about 80 wt %, from about 50 wt % to about 75 wt %, from about 50 wt % to about 70 wt % and all ranges and sub-ranges therebetween, based on the total weight of the antimicrobial glass and carrier. In such embodiments, the total amount of CuO present in the may be about 20 wt %. In other embodiments, the amount of Cu2O present in the antimicrobial glass and carrier combination may be in the range from about 10 wt % to about 20 wt % or more specifically, about 15%. The ratio of antimicrobial glass to carrier, by vol %, may be in the range from about 90:10 to about 10:90, or more specifically about 50:50.


In one or more embodiments, the antimicrobial glass may be provided in particulate form and may have a diameter in the range from about 0.1 micrometers (μm) (μm) to about 10 micrometers (μm) (μm), from about 0.1 micrometers (μm) (μm) to about 9 micrometers (μm) (μm), from about 0.1 micrometers (μm) (μm) to about 8 micrometers (μm) (μm), from about 0.1 micrometers (μm) (μm) to about 7 micrometers (μm) (μm), from about 0.1 micrometers (μm) (μm) to about 6 micrometers (μm) (μm), from about 0.5 micrometers (μm) (μm) to about 10 micrometers (μm) (μm), from about 0.75 micrometers (μm) (μm) to about 10 micrometers (μm) (μm), from about 1 micrometers (μm) (μm) to about 10 micrometers (μm) (μm), from about 2 micrometers (μm) (μm) to about 10 micrometers (μm) (μm), from about 3 micrometers (μm) (μm) to about 10 micrometers (μm) (μm) from about 3 micrometers (μm) (μm) to about 6 micrometers (μm) (μm), from about 3.5 micrometers (μm) (μm) to about 5.5 micrometers (μm) (μm), from about 4 micrometers (μm) (μm), to about 5 micrometers (μm) (μm), and all ranges and sub-ranges therebetween. The particulate antimicrobial glass may be substantially spherical or may have an irregular shape. The particles may be provided in a solvent and thereafter dispersed in a carrier as otherwise described herein.


Without being bound by theory it is believed that the combination of the antimicrobial glass described herein and a carrier, such as latex paint, provides substantially greater antimicrobial efficacy as compared to the same latex paint that includes only Cu2O (cuprite), even when the same amount of copper is utilized. The presence of Cu1+ crystals in the antimicrobial glasses described herein, even when present as cuprite, tends to remain in the Cu1+ state. Without being bound by theory, it is believed that when Cu2O is provided alone, separate from the glasses described herein, the Cu ions are less stable and may change to Cu2+ from Cu1+.


The antimicrobial performance of the articles described herein may be impacted by the presence of a thin layer of polymer on the surface of the article. This thin layer may exhibit hydrophobic properties and may block the active copper species (Cu1+) from exposure to air or from leaching to the surface. In one or more embodiments, the articles may use polymers that have balanced hydrophobic-hydrophilic properties that facilitate leaching of the active copper species. Examples of such polymers include hygroscopic/water soluble polymers and surfactants, amphiphilic polymers and/or a combination of amphiphilic polymers and hygroscopic materials. In one or more embodiments, the exposure to air and/or leaching of the active copper species to the surface may be facilitated by providing articles with an exposed treated surface. In one or more embodiments, the exposed treated surface is a surface that has been mechanically or chemically treated to expose at least some of the glass contained in the article to the air or to provide some of the glass at the surface of the article. Specific methods for providing an exposed treated surface include sanding, polishing, plasma treating (e.g., air, N2, O2, H2, N2 and/or Argon based plasma) and other methods that will remove a thin layer of the polymer material. In one or more alternative embodiments, the exposed treated surface includes functional groups, particularly hydroxyl and carbonyl groups, which are introduced into or to the exposed treated surface, to make such surface more hydrophilic. By providing an exposed treated surface, the active copper species is exposed to air or more readily leaches the surface of the article.


To improve processability, mechanical properties and interactions between the polymer and the glass described herein (including any fillers and/or additives that may be used), processing agents/aids may be included in the articles described herein. Exemplary processing agents/aids can include solid or liquid materials. The processing agents/aids may provide various extrusion benefits, and may include silicone based oil, wax and free flowing fluoropolymer. In other embodiments, the processing agents/aids may include compatibilizers/coupling agents, e.g., organosilicon compounds such as organo-silanes/siloxanes that are typically used in processing of polymer composites for improving mechanical and thermal properties. Such compatibilizers/coupling agents can be used to surface modify the glass and can include (3-acryloxy-propyl)trimethoxysilane; N-(2-aminoethyl)-3-aminopropyltrimethoxysilane; 3-aminopropyltri-ethoxysilane; 3-aminopropyltrimethoxysilane; (3-glycidoxypropyl)trimethoxysilane; 3-mercapto-propyltrimethoxysilane; 3-methacryloxypropyltrimethoxysilane; and vinyltrimethoxysilane.


In some embodiments, the articles described herein may include fillers including pigments, that are typically metal based inorganics can also be added for color and other purposes, e.g., aluminum pigments, copper pigments, cobalt pigments, manganese pigments, iron pigments, titanium pigments, tin pigments, clay earth pigments (naturally formed iron oxides), carbon pigments, antimony pigments, barium pigments, and zinc pigments.


After combining the antimicrobial glass described herein with a carrier, as described herein, the combination may be formed into a desired article. Examples of such articles include housings for electronic devices (e.g., mobile phones, smart phones, tablets, video players, information terminal devices, laptop computer, etc.), architectural structures (e.g., countertops or walls), appliances (e.g., cooktops, refrigerator and dishwasher doors, etc.), information displays (e.g., whiteboards), and automotive components (e.g., dashboard panels, windshields, window components, etc.).


In one or more embodiments, the articles may exhibit desired porosity and may be made into different shapes, including complex shapes and in different forms including plastics, rubbers and fiber/fabrics, which can have the same or different applications. Porous articles can also be used as antimicrobial filters. For example, the articles may be extruded into a honeycomb structure, which not only includes channels but also porous channel walls.


In other embodiments, the articles may include a high glass loading. Such articles may be formed from a melting process or the wet process. In such embodiments, in addition to using the articles themselves as an antimicrobial material, the polymer can be burnt out or removed to provide a pure copper glass antimicrobial article that is porous, with a simple or complex shape.


Cu(I) is an excellent catalyst for organic reactions, particularly for mild organic reactions, such as polymerization of acrylic monomers and oleochemical applications (e.g., hydrogenolysis of fatty esters to fatty alcohols including both methyl ester and wax ester processes, alkylation of alcohols with amines and amination of fatty alcohols), just to name a few. The articles described herein may be used for such applications.


Examples of the various uses and application of the articles described herein are shown in FIG. 13.


The articles described herein, including the antimicrobial glass and a polymer, may exhibit a 2 log reduction or greater in a concentration of at least one of Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa bacteria, Methicillin Resistant Staphylococcus aureus, and E. coli, under the EPA Test. In some instances, the article exhibits at least a 4 log reduction, a 5 log reduction or even a 6 log reduction in the concentration of at least one of Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa bacteria, Methicillin Resistant Staphylococcus aureus, and E. coli under the EPA Test.


The articles described herein according to one or more embodiments may exhibit a 2 log reduction or greater (e.g., 3 log reduction or greater, 4 log reduction or greater, or 5 log reduction or greater) in a concentration of at least one of Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa bacteria, Methicillin Resistant Staphylococcus aureus, and E. coli, under the JIS Z 2801 (2000) testing conditions and/or the Modified JIS Z 2801 Test for Bacteria. One or more embodiments of the articles described herein also exhibit a 4 log reduction or greater (e.g., 5 log reduction or greater) in a concentration of Murine Norovirus (strain MNV-1), under the Modified JIS Z 2801 Test for Viruses.


The articles of one or more embodiments may exhibit the log reduction described herein for long periods of time. In other words, the article may exhibit extended or prolonged antimicrobial efficacy. For example, in some embodiments, the article may exhibit the log reductions in bacteria and/or viruses described herein for up to 1 month, up to 3 months, up to 6 months or up to 12 months after the antimicrobial glass is formed or after the antimicrobial glass is combined with a carrier. These time periods may start at or after the antimicrobial glass is formed or combined with a carrier.


In one or more embodiments, the article may include a coating that may be applied on a surface, forming a coated surface. The coated surface may exhibit a stable color that does not undergo substantial changes after exposure to specific environments. For example, the coated surface may exhibit a delta (Δ) E of less than about 2 or even less than about 1, as measured by ASTM D2247, after being exposed to a temperature of 38° C. at 100% relative humidity for 7 days. As used herein, the phrase “delta (A) E” refers to the total color distance as measured by the distance between two color coordinates, provided under the CIELAB color space (ΔE*ab=√{square root over ((L2*−L1*)2+a2*−a1*)2+b2*−b1*)2)}).


The coated surface may also exhibit chemical resistance to various chemicals, as measured by ASTM D1308, after exposure to chemicals in the center of a test piece for 1 hour.


The articles described herein may include pigments to impart color. Accordingly, the coatings made from such articles may exhibit a wide variety of colors, depending on the carrier color, mixture of carriers and amount of particle loading. Moreover, the articles and/or coatings described herein showed no adverse effect to paint adhesion as measured by ASTM D4541. In some instances, the adhesion of the article or coating to an underlying substrate was greater than the cohesive strength of the substrate. In other words, in testing, the adhesion between the coating and the substrate was so strong that the underlying substrate failed before the coating was separated from the surface of the substrate. For example, where the substrate includes wood, the adhesion between the coating and the substrate may be about 300 psi or greater, 400 psi or greater, 500 psi or greater, 600 psi or greater and all ranges-sub-ranges therebetween, as measured by ASTM D4541. In some instances, the article, when applied to a substrate as a coating, exhibits an anti-sag index value of about 3 or greater, about 5 or greater, 7 or greater, 8 or greater, 9 or greater, 10 or greater, 11 or greater, 12 or greater, 13 or greater, 14 or greater or even 15 or greater, as measured by ASTM D4400.


The article and/or coating may exhibit sufficient durability for use in household and commercial applications. Specifically, the article, when applied to a substrate as a coating, exhibits a scrub resistance as measured by ASTM D4213 of about 4 or greater, 5 or greater, 6 or greater, 7 or greater and all ranges and sub-ranges therebetween.


In one or more embodiments, the article and/or coating may be resistant to moisture. For example, after exposure of the article and/or coating to an environment of up to about 95% relative humidity for 24 hours, the article and/or coating exhibited no change in antimicrobial activity.


One or more embodiments of the article may include an antimicrobial glass and a carrier with a loading level of the antimicrobial glass such that the article exhibits resistance or preservation against the presence or growth of foulants. Foulants include fungi, bacteria, viruses and combinations thereof. In some instances, the presence or growth of foulants in articles, such as paints, varnishes and the like, can cause color changes to the article, can degrade the integrity of the article and negatively affect various properties of the article. By including a minimum loading of antimicrobial glass, (e.g., about 5 wt % or less, about 4 wt % or less, about 3 wt % or less, about 2 wt % or less, or about 1 wt % or less) to the carrier, the foulants can be eliminated or reduced. In some instances, the carrier formulation need not include certain components, when fouling is eliminated or reduced. Thus, the carrier formulations used in one or more embodiments of the articles described herein may have more flexibility and variations than previously possible, when in known articles that do not include the antimicrobial glass.


Another aspect of this disclosure pertains to a method of making an antimicrobial article. In one or more embodiments, the method includes melting a glass composition (such as the compositions disclosed herein) to form a glass, forming the glass into particles, fibers or a combination thereof, dispersing the particles and/or fibers into a carrier (e.g., polymer) to provide a filled polymer and forming the filled polymer into an antimicrobial article.


In one or more embodiments, method includes loading a selected amount of glass into the polymer, depending on the application of the article. Various methods and processes can be used to such as, for example, an in situ process through mixing monomers with the glass (which may be ground into particles or other form) and then polymerized (into a thermosetting or a thermoplastic polymer matrix) or by mixing polymer with the glass through a process of solution or melt compounding (e.g. using a Brabender compounder or an extruder, single screw or twin screw, reactive or non-reactive), etc.


In one or more embodiments, forming the filled polymer into the antimicrobial article may include extruding or molding the filled polymer. In one or more embodiments, the antimicrobial article may be further processed to expose at least a portion of the glass to an exterior surface. The exterior surface may be a surface with which the user of the antimicrobial article interacts (e.g., the exterior surface of a mobile phone, the display of the mobile phone etc.). In one or more embodiments, the method may include removing a surface portion of the antimicrobial article to expose the glass dispersed in the filled polymer. Exemplary methods of removing a surface portion of the antimicrobial article may include etching (by plasma, acid or mechanical means such as sanding or polishing).


EXAMPLES

Various embodiments will be further clarified by the following examples.


Examples 1-62

Non-limiting examples of compositions described herein are listed in Table 1. The compositions in Table 1 were batched, melted and formed into glasses. Table 2 lists selected properties of the compositions of Table 1 and/or glasses formed therefrom, including the conditions for melting, annealing, appearance of the melt, density, anneal point (as measured by Beam Bending Viscometer (BBV)), strain point (as measured by BBV), softening point (as measured by parallel plate viscometer (PPV)), Vickers hardness, Vickers crack initiation, fracture toughness by chevron notch, coefficient of thermal expansion and the and other properties. Table 2 also includes the weight percent of Cu oxides, as determined by ICP techniques, and the ratio of Cu1+:Cu2+ for selected glasses.


Table 3 includes information related to the crystalline phases of crystal phase assemblages and/or crystal sizes of selected glasses as determined using X-ray diffraction (XRD) techniques known to those in the art, using such commercially available equipment as the model as a PW1830 (Cu Kα radiation) diffractometer manufactured by Philips, Netherlands. Spectra were typically acquired for 20 from 5 to 80 degrees. Table 3 also includes elemental profile information of selected glasses determined XPS techniques.


The glasses where then tested under the EPA test using Staphylococcus aureus under two conditions, as shown in Table 4. Table 4 also includes the total amount of Cu and Cu1+ found in selected examples, as determined by ICP techniques.









TABLE 1





Table 1




















Example
Ex. 1
Ex. 2
Ex. 3
Ex. 4
Ex. 5





Batched Composition


(mol %)


SiO2
65
65
60
60
60


Al2O3
17.5
17.5
20
15
15


CuO
17.5
17.5
20
20
20


Na2O



5


K2O




5


B2O3


P2O5


ZnO


Batched Composition


(wt %)


SiO2
55.2
55.2
49.8
51.2
50.1


Al2O3
25.2
25.2
28.2
21.7
21.3


CuO
19.7
19.7
22.0
22.6
22.1


Na2O



4.4


K2O




6.5


B2O3


P2O5


ZnO





Example
Ex. 6
Ex. 7
Ex. 8
Ex. 9
Ex. 10





Batched Composition


(mol %)


SiO2
60
60
60
60
60


Al2O3
10
10
5
5


CuO
20
20
20
20
20


Na2O
10

10
5


K2O

10
5
10
10


B2O3




10


P2O5


ZnO


Batched Composition


(wt %)


SiO2
52.7
50.4
53.0
51.8
52.8


Al2O3
14.9
14.2
7.5
7.3
0.0


CuO
23.3
22.2
23.4
22.9
23.3


Na2O
9.1

9.1
4.5


K2O

13.2
6.9
13.5
13.8


B2O3




10.2


P2O5


ZnO





Example
Ex. 11
Ex. 12
Ex. 13
Ex. 14
Ex. 15





Batched Composition


(mol %)


SiO2
60
60
60
50
50


Al2O3

5


CuO
20
20
20
20
20


Na2O


K2O
10
10
10
10
10


B2O3


5
10


P2O5
10
5
5
10
20


ZnO


Batched Composition


(wt %)


SiO2
47.7
49.0
50.1
39.3
35.9


Al2O3

6.9


CuO
21.0
21.6
22.1
20.8
19.0


Na2O


K2O
12.5
12.8
13.1
12.3
11.2


B2O3


4.8
9.1


P2O5
18.8
9.6
9.9
18.5
33.9


ZnO

0.05


MgO

0.05


Fe2O3

0.11


CaO

0.01





Example
Ex. 16
Ex. 17
Ex. 18
Ex. 19
Ex. 20





Batched Composition


(mol %)


SiO2
50
50
50
50
50


Al2O3
25
20
25
25
20


CuO
25
30
25
25
20


Na2O


5

10


K2O



5


B2O3


P2O5


ZnO


Batched Composition


(wt %)


SiO2
39.8
40.4
38.3
37.5
41.4


Al2O3
33.8
27.4
32.5
31.8
28.1


CuO
26.4
32.1
25.3
24.8
21.9


Na2O


3.9

8.5


K2O



5.9


B2O3


P2O5


ZnO





Example
Ex. 21
Ex. 22
Ex. 23
Ex. 24
Ex. 25





Batched Composition


(mol %)


SiO2
50
60
60
50
60


Al2O3
20
5


5


CuO
20
20
20
20
20


Na2O




10


K2O
10
10
10
10


B2O3


5
10


P2O5

5
5
10
5


ZnO


Batched Composition


(wt %)


SiO2
39.7
49.0
50.1
39.3
51.2


Al2O3
26.9
6.9


7.2


CuO
21.0
21.6
22.1
20.8
22.6


Na2O




8.8


K2O
12.4
12.8
13.1
12.3


B2O3


4.8
9.1


P2O5

9.6
9.9
18.5
10.1


ZnO





Example
Ex. 26
Ex. 27
Ex. 28
Ex. 29
Ex. 30





Batched Composition


(mol %)


SiO2
60
50
50
50
55


Al2O3


5
5


CuO
20
20
20
20
20


Na2O
10
10
10


K2O



10
10


B2O3
5
10
10
10
10


P2O5
5
10
5
5
5


ZnO


Batched Composition


(wt %)


SiO2
52.5
41.0
42.1
40.3
45.6


Al2O3


7.1
6.8


CuO
23.1
21.7
22.3
21.3
22.0


Na2O
9.0
8.5
8.7


K2O



12.6
13.0


B2O3
5.1
9.5
9.8
9.3
9.6


P2O5
10.3
19.4
10.0
9.5
9.8


ZnO





Example
Ex. 31
Ex. 32
Ex. 33
Ex. 34
Ex. 35





Batched Composition


(mol %)


SiO2
55
60
55
60
55


Al2O3


5
5


CuO
20
20
20
20
20


Na2O
10
15
15


K2O



10
10


B2O3
10



10


P2O5
5
5
5
5
5


ZnO


Batched Composition


(wt %)


SiO2
47.7
52.7
46.9
49.0
45.6


Al2O3


7.2
6.9


CuO
23.0
23.3
22.6
21.6
22.0


Na2O
9.0
13.6
13.2


K2O



12.8
13.0


B2O3
10.1



9.6


P2O5
10.3
10.4
10.1
9.6
9.8


ZnO





Example
Ex. 36
Ex. 37
Ex. 38
Ex. 39
Ex. 40





Batched Composition


(mol %)


SiO2
50
45
40
55
55


Al2O3


CuO
20
20
20
20
20


Na2O


K2O
10
10
12.5
10
10


B2O3
10
10
10
10
10


P2O5
5
5
5
5
5


ZnO
5
10
12.5


Batched Composition


(wt %)


SiO2
40.9
36.3
31.6
45.6
45.6


A12O3


CuO
21.6
21.3
20.9
22.0
22.0


Na2O


K2O
12.8
12.6
15.5
13.0
13.0


B2O3
9.5
9.3
9.2
9.6
9.6


P2O5
9.7
9.5
9.3
9.8
9.8


ZnO
5.5
10.9
13.4





Example
Ex. 41
Ex. 42
Ex. 43
Ex. 44
Ex. 45





Batched Composition


(mol %)


SiO2
51.5
51.5
48
48
55


Al2O3
0
0
0
0


CuO
25
25
30
30
20


Na2O
0
0
0
0


K2O
9.4
9.4
8.8
8.8
10


B2O3
9.4
9.4
8.8
8.8
10


P2O5
4.7
4.7
4.4
4.4
5


ZnO
0
0
0
0
55


Batched Composition


(wt %)


SiO2
42.4
42.4
39.3
39.3


Al2O3
0.0
0.0
0.0
0.0


CuO
27.3
27.3
32.5
32.5


Na2O
0.0
0.0
0.0
0.0


K2O
12.1
12.1
11.3
11.3


B2O3
9.0
9.0
8.4
8.4


P2O5
9.2
9.2
8.5
8.5


ZnO
0.0
0.0
0.0
0.0





Example
Ex. 46
Ex. 47
Ex. 48
Ex. 49
Ex. 50





Batched Composition


(mol %)


SiO2
50
50
50
50
55


Al2O3
0
0
0
0
0


CuO
20
20
20
20
20


Na2O
0
0
0
0
0


K2O
10
10
10
10
10


B2O3
10
10
10
10
10


P2O5
5
5
5
5
5


ZnO
0
0
0
0
0


TiO2
5
0
0
0
0


Fe2O3
0
5
0
0
0


Cr2O3
0
0
5
0
0


Co3O4
0
0
0
5
0


NiO
0
0
0
0
0





Example
Ex. 51
Ex. 52
Ex. 53
Ex. 54
Ex. 55





Batched Composition


(mol %)


SiO2
40
45
50
55
50


Al2O3
15
15
15
15
15


CuO
20
20
20
20
20


Na2O


K2O
10
10
10
5
5


B2O3
10
5
0
0
5


P2O5
5
5
5
5
5


ZnO
0
0
0
0
0


TiO2
0
0
0
0
0


Fe2O3
0
0
0
0
0


Cr2O3
0
0
0
0
0


Co3O4
0
0
0
0
0


NiO
0
0
0
0
0





Example
Ex. 56
Ex. 57
Ex. 58
Ex. 59
Ex. 60





Batched Composition


(mol %)


SiO2
45
55
50
45
45


Al2O3


CuO
35
30
35
40
25


Na2O


K2O
7.5
10
10
10
10


B2O3
7.5


P2O5
5
5
5
5
5


ZnO


TiO2


Fe2O3


Cr2O3


Co3O4




15


NiO














Example
Ex. 61
Ex. 62







Batched Composition



(mol %)



SiO2
45
45



Al2O3
0
0



CuO
25
30



Na2O
0
0



K2O
10
10



B2O3
0
0



P2O5
5
5



ZnO
0
0



TiO2
0
10



Fe2O3
0
0



Cr2O3
0
0



Co3O4
0
0



NiO
15
0

















TABLE 2





Table 2




















Example
Ex. 1
Ex. 2
Ex. 3
Ex. 4
Ex. 5





Melt Temp (° C.)
1500
1650
1650
1650
1650


Melt Time (hrs)
6
overnight
overnight
overnight
overnight


Crucible Type
Alumina
Quartz
Quartz
Quartz
Quartz


Anneal Temp (° C.)
700
700
700
700
700


Melt Appearance
Very Poor,
High Quality,
High Quality,
Grey Surface,
Grey Surface,



full of large
Surface Oxidation,
Surface Oxidation,
black interior
black interior



bubbles
Gray surface,
Gray surface,




black interior
black interior


Density by buoyancy (g/cm3)

2.705
2.781
2.758
2.741


Effective molecular wt (g/mol)
70.821
70.821
72.354


Molar Volume (cm3/mol)

26.2
26.0


Anneal Point by BBV (° C.)

694.1
684.9
598.6


Strain Point by BBV (° C.)

652.5
642.3
558.9


Softening Point by PPV (° C.)

xstallized
xstallized


Vickers Hardness (kgf/mm2)

595
586


Vickers Crack Initiation (kgf)

1-2
1-2


Fracture Toughness by

0.875
0.887


Chevron Notch (MPa m0.5)


CTE (ppm/° C.)

1.06
1.15


ICP wt % oxides (Cu)
19.6
19
21.6


ratio Cu+1/Cu2+















Example
Ex. 6
Ex. 7
Ex. 8
Ex. 9
Ex. 10





Melt Temp (° C.)
1650
1650
1650
1650
1650


Melt Time (hrs)
overnight
overnight
overnight
overnight
overnight


Crucible Type
Quartz
Quartz
Quartz
Quartz
Quartz


Anneal Temp (° C.)
700
700
700
700
600


Melt Appearance
Black and
Black and

Black and grey surface,
Grey lustrous



gray lustrous
gray lustrous

primarily black interior
surface, dark



surface, brown and
surface, brown and

with some green and
yellow interior



yellow interior
yellow interior

brown streaks


Density by buoyancy (g/cm3)
2.706
2.666

2.596
2.716


Effective molecular wt (g/mol)


Molar Volume (cm3/mol)


Anneal Point by BBV (° C.)
737.2



575.7


Strain Point by BBV (° C.)
684.4



535.2


Softening Point by PPV (° C.)


Vickers Hardness (kgf/mm2)


Vickers Crack Initiation (kgf)


Fracture Toughness by


Chevron Notch (MPa m0.5)


CTE (ppm/° C.)


ICP wt % oxides (Cu)


ratio Cu+1/Cu2+















Example
Ex. 11
Ex. 12
Ex. 13
Ex. 14
Ex. 15





Melt Temp (° C.)
1650
1650
1650
1650
1650


Melt Time (hrs)
overnight
overnight
overnight
overnight
overnight


Crucible Type
Quartz
Quartz
Quartz
Quartz
Quartz


Anneal Temp (° C.)
600
700
600
600
600


Melt Appearance
Ceramic, brittle,
Shiny metallic
Shiny metallic
Dark yellow
Ceramic, grey



gray, brown, and
surface, dark
surface, dark
surface w/some
surface, light



green
yellow interior
yellow interior
ceramic, dark
brown interior






yellow interior






w/ some ceramic


Density by buoyancy (g/cm3)

2.669
2.673
2.608


Effective molecular wt (g/mol)


Molar Volume (cm3/mol)


Anneal Point by BBV (° C.)


Strain Point by BBV (° C.)

701
569
572.5


Softening Point by PPV (° C.)

759.8
602.8
510.7


Vickers Hardness (kgf/mm2)


Vickers Crack Initiation (kgf)


Fracture Toughness by


Chevron Notch (MPa m0.5)


CTE (ppm/° C.)


ICP wt % oxides (Cu)


ratio Cu+1/Cu2+















Example
Ex. 16
Ex. 17
Ex. 18
Ex. 19
Ex. 20





Melt Temp (° C.)
1650
1650
1650
1650
1650


Melt Time (hrs)
overnight
overnight
overnight
overnight
overnight


Crucible Type
Quartz
Quartz
Quartz
Quartz
Quartz


Anneal Temp (° C.)
700
700
700
700
700


Melt Appearance
Grey Surface,
Grey Surface,
Grey Surface,
Grey Surface,
Grey Surface,



black interior,
black interior
black interior
black interior
black interior



copper precipitated


Density by buoyancy (g/cm3)
2.91
2.901
2.887
2.876
2.797


Effective molecular wt (g/mol)


Molar Volume (cm3/mol)


Anneal Point by BBV (° C.)


Strain Point by BBV (° C.)


Softening Point by PPV (° C.)


Vickers Hardness (kgf/mm2)


Vickers Crack Initiation (kgf)


Fracture Toughness by


Chevron Notch (MPa m0.5)


CTE (ppm/° C.)


ICP wt % oxides (Cu)


ratio Cu+1/Cu2+





Example
Ex. 16
Ex. 17
Ex. 18
Ex. 19
Ex. 20





Melt Temp (° C.)
1650
1650
1650
1650
1650


Melt Time (hrs)
overnight
overnight
overnight
overnight
overnight


Crucible Type
Quartz
Quartz
Quartz
Quartz
Quartz


Anneal Temp (° C.)
700
700
700
700
700


Melt Appearance
Grey Surface,
Grey Surface,
Grey Surface,
Grey Surface,
Grey Surface,



black interior,
black interior
black interior
black interior
black interior



copper precipitated


Density by buoyancy (g/cm3)
2.91
2.901
2.887
2.876
2.797


Effective molecular wt (g/mol)


Molar Volume (cm3/mol)


Anneal Point by BBV (° C.)


Strain Point by BBV (° C.)


Softening Point by PPV (° C.)


Vickers Hardness (kgf/mm2)


Vickers Crack Initiation (kgf)


Fracture Toughness by


Chevron Notch (MPa m0.5)


CTE (ppm/° C.)


ICP wt % oxides (Cu)


ratio Cu+1/Cu2+















Example
Ex. 21
Ex. 22
Ex. 23
Ex. 24
Ex. 25





Melt Temp (° C.)
1650
1650
1650
1650
1650


Melt Time (hrs)
Overnight
overnight
overnight
Overnight
overnight


Crucible Type
Quartz
Quartz
Quartz
Quartz
Quartz


Anneal Temp (° C.)
700
650
650
650
650


Melt Appearance
Grey Surface,
Grey Surface,
Grey Surface,
Crystallized
Grey Surface,



yellow interior
Yellow/orange
Yellow/orange

Yellow/orange




interior
interior

interior (looks







more crystalline







than Ex. 22)


Density by buoyancy (g/cm3)
2.774


Effective molecular wt (g/mol)


Molar Volume (cm3/mol)


Anneal Point by BBV (° C.)


Strain Point by BBV (° C.)


Softening Point by PPV (° C.)


Vickers Hardness (kgf/mm2)


Vickers Crack Initiation (kgf)


Fracture Toughness by


Chevron Notch (MPa m0.5)


CTE (ppm/° C.)


ICP wt % oxides (Cu)


ratio Cu+1/Cu2+















Example
Ex. 26
Ex. 27
Ex. 28
Ex. 29
Ex. 30





Melt Temp (° C.)
1650
1650
1650
1650
1650


Melt Time (hrs)
overnight
overnight
overnight
overnight
overnight


Crucible Type
Quartz
Quartz
Quartz
Quartz
Quartz


Anneal Temp (° C.)
650
650
650
650
650


Melt Appearance
Grey Surface,
crystallized
Shiny exterior,
Shiny exterior,
Shiny exterior,



Yellow/orange

yellow/orange
yellow/orange
yellow/orange



interior (looks

interior
interior
interior



more crystalline



than Ex. 23)


Density by buoyancy (g/cm3)




2.626


Effective molecular wt (g/mol)


Molar Volume (cm3/mol)


Anneal Point by BBV (° C.)


Strain Point by BBV (° C.)




602.4


Softening Point by PPV (° C.)




544.4


Vickers Hardness (kgf/mm2)


Vickers Crack Initiation (kgf)


Fracture Toughness by


Chevron Notch (MPa m0.5)


CTE (ppm/° C.)


ICP wt % oxides (Cu)


ratio Cu+1/Cu2+















Example
Ex. 31
Ex. 32
Ex. 33
Ex. 34
Ex. 35





Melt Temp (° C.)
1650
1650
1650
1650
1650


Melt Time (hrs)
overnight
overnight
overnight
overnight
overnight


Crucible Type
Quartz
Quartz
Quartz
Quartz
Quartz


Anneal Temp (° C.)
650
650
650
650
650


Melt Appearance
Shiny exterior,
Lighter yellow,
Lighter yellow,
Orange Interior,
Orange Interior,



yellow/orange
more crystalline
crystallized
shiny metallic
shiny metallic



interior


surface
surface


Density by buoyancy (g/cm3)


Effective molecular wt (g/mol)


Molar Volume (cm3/mol)


Anneal Point by BBV (° C.)


Strain Point by BBV (° C.)


Softening Point by PPV (° C.)


Vickers Hardness (kgf/mm2)


Vickers Crack Initiation (kgf)


Fracture Toughness by


Chevron Notch (MPa m0.5)


CTE (ppm/° C.)


ICP wt % oxides (Cu)


ratio Cu+1/Cu2+















Example
Ex. 36
Ex. 37
Ex. 38
Ex. 39
Ex. 40





Melt Temp (° C.)
1650
1650
1650
1650
1650


Melt Time (hrs)
overnight
overnight
overnight
overnight
overnight


Crucible Type
Quartz
Quartz
Quartz
Quartz
Quartz


Anneal Temp (° C.)
650
650
650
none
650


Melt Appearance
Orange Interior,
Orange Interior,
Orange Interior,
Yellow,
Orange Interior,



shiny metallic
shiny metallic
shiny metallic
Orange
shiny metallic



surface
surface
surface

surface


Density by buoyancy (g/cm3)


Effective molecular wt (g/mol)


Molar Volume (cm3/mol)


Anneal Point by BBV (° C.)


Strain Point by BBV (° C.)


Softening Point by PPV (° C.)


Vickers Hardness (kgf/mm2)


Vickers Crack Initiation (kgf)


Fracture Toughness by


Chevron Notch (MPa m0.5)


CTE (ppm/° C.)


ICP wt % oxides (Cu)


ratio Cu+1/Cu2+





Example
Ex. 36
Ex. 37
Ex. 38
Ex. 39
Ex. 40





Melt Temp (° C.)
1650
1650
1650
1650
1650


Melt Time (hrs)
overnight
overnight
overnight
overnight
overnight


Crucible Type
Quartz
Quartz
Quartz
Quartz
Quartz


Anneal Temp (° C.)
650
650
650
none
650


Melt Appearance
Orange Interior,
Orange Interior,
Orange Interior,
Yellow,
Orange Interior,



shiny metallic
shiny metallic
shiny metallic
Orange
shiny metallic



surface
surface
surface

surface


Density by buoyancy (g/cm3)


Effective molecular wt (g/mol)


Molar Volume (cm3/mol)


Anneal Point by BBV (° C.)


Strain Point by BBV (° C.)


Softening Point by PPV (° C.)


Vickers Hardness (kgf/mm2)


Vickers Crack Initiation (kgf)


Fracture Toughness by


Chevron Notch (MPa m0.5)


CTE (ppm/° C.)


ICP wt % oxides (Cu)


ratio Cu+1/Cu2+














Example
Ex. 41
Ex. 42
Ex. 43
Ex. 44





Melt Temp (° C.)
1650
1650
1650
1650


Melt Time (hrs)
overnight
overnight
overnight
overnight


Crucible Type
Quartz
Quartz
Quartz
Quartz


Anneal Temp (° C.)
none
650
none
650


Melt Appearance
Yellow,
Orange Interior,
Yellow,
Orange Interior,



Orange
shiny metallic
Orange
shiny metallic




surface

surface


Density by buoyancy (g/cm3)


2.816


Effective molecular wt (g/mol)


Molar Volume (cm3/mol)


Anneal Point by BBV (° C.)


Strain Point by BBV (° C.)


Softening Point by PPV (° C.)


Vickers Hardness (kgf/mm2)


Vickers Crack Initiation (kgf)


Fracture Toughness by


Chevron Notch (MPa m0.5)


CTE (ppm/° C.)


ICP wt % oxides (Cu)


ratio Cu+1/Cu2+















Example
Ex. 46
Ex. 47
Ex. 48
Ex. 49
Ex. 50





Melt Temp (° C.)


Melt Time (hrs)


Crucible Type


Anneal Temp (° C.)


Melt Appearance
reddish orange
orange
greenish
light green,





crystallized
greener than






Ex. 48


Density by buoyancy (g/cm3)


Effective molecular wt (g/mol)


Molar Volume (cm3/mol)


Anneal Point by BBV (° C.)


Strain Point by BBV (° C.)


Softening Point by PPV (° C.)


Vickers Hardness (kgf/mm2)


Vickers Crack Initiation (kgf)


Fracture Toughness by


Chevron Notch (MPa m0.5)


CTE (ppm/° C.)


ICP wt % oxides (Cu)


ratio Cu+1/Cu2+















Example
Ex. 51
Ex. 52
Ex. 53
Ex. 54
Ex. 55





Melt Temp (° C.)


Melt Time (hrs)


Crucible Type


Anneal Temp (° C.)


Melt Appearance
Yellow and
Yellow and
Yellow
Black with
Black with



Black
Brown

some orange
some orange






on bottom
on edges


Density by buoyancy (g/cm3)


Effective molecular wt (g/mol)


Molar Volume (cm3/mol)


Anneal Point byBBV (° C.)


Strain Point by BBV (° C.)


Softening Point by PPV (° C.)


Vickers Hardness (kgf/mm2)


Vickers Crack Initiation (kgf)


Fracture Toughness by


Chevron Notch (MPa m0.5)


CTE (ppm/° C.)


ICP wt % oxides (Cu)


ratio Cu+1/Cu2+













Example
Ex. 56







Melt Temp (° C.)



Melt Time (hrs)



Crucible Type



Anneal Temp (° C.)



Melt Appearance
Pumpkin-




colored



Density by buoyancy (g/cm3)



Effective molecular wt (g/mol)



Molar Volume (cm3/mol)



Anneal Point by BBV (° C.)



Strain Point by BBV (° C.)



Softening Point by PPV (° C.)



Vickers Hardness (kgf/mm2)



Vickers Crack Initiation (kgf)



Fracture Toughness by



Chevron Notch (MPa m0.5)



CTE (ppm/° C.)



ICP wt % oxides (Cu)



ratio Cu+1/Cu2+







*The term “crystallized” as used here refers to a non-glassy appearance.















TABLE 3









Example















Ex. 1
Ex. 2
Ex. 3
Ex. 4
Ex. 5







XRD powder


none
Tenorite
Tenorite







(CuO)
(CuO)



XRD surface



Tenorite
Tenorite







(CuO)
(CuO)



XPS vacuum fracture +



2 min air



% Cu1+ and Cu0




85.2



% Cu2+




14.8



StDev




1



XPS vacuum fracture



% Cu1+ and Cu0



% Cu2+



StDev













Example















Ex. 6
Ex. 7
Ex. 8
Ex. 9
Ex. 10







XRD powder
Tenorite
Tenorite

Cuprite
Cuprite




(CuO) and
(CuO)

(Cu2O)
(Cu2O)




Cuprite
and




(Cu2O)
Cuprite





(Cu2O)



XRD surface
Tenorite
Tenorite

no peaks
Tenorite




(CuO) and
(CuO)


(CuO) and




Cuprite
and


Cuprite




(Cu2O)
Cuprite


(Cu2O)





(Cu2O)



XPS vacuum fracture +



2 min air



% Cu1+ and Cu0
84.2



74.6



% Cu2+
15.8



25.4



StDev
0.1



1.5



XPS vacuum fracture



% Cu1+ and Cu0



% Cu2+



StDev













Example













Ex. 11
Ex. 12
Ex. 13
Ex. 14
Ex. 15





XRD powder

Cuprite (Cu2O), K1—xAl1+xSi1—xO4,
Cuprite
Cuprite




Al2O3*0.95P2O5,
(Cu2O)
(Cu2O)




Cu1.82K0.2(Al3.9Si8.1O24),




K2SiO3


XRD surface

Tenorite (CuO), Cuprite
Cuprite
Cuprite




(Cu2O), K1—xAl1+xSi1—xO4,
(Cu2O)
(Cu2O)




Al2O3*0.95P2O5


XPS vacuum


fracture + 2 min


air


% Cu1+ and Cu0

92.4
80.3
91.3


% Cu2+

7.6
19.7
8.7


StDev

1.2
2.5
0.4


XPS vacuum


fracture


% Cu1+ and Cu0

87.1

93.1


% Cu2+

12.9

6.9


StDev

2.6

0.6












Example















Ex. 16
Ex. 17
Ex. 18
Ex. 19
Ex. 20







XRD powder
Tenorite
Tenorite (CuO)
Tenorite
none
Tenorite




(CuO)

(CuO)

(CuO)



XRD surface
Tenorite
Tenorite (CuO)
Tenorite
Tenorite
Tenorite




(CuO)

(CuO)
(CuO)
(CuO)



XPS vacuum



fracture + 2 min



air



% Cu1+ and Cu0



% Cu2+



StDev



XPS vacuum



fracture



% Cu1+ Cu0



% Cu2+



StDev













Example















Ex. 21
Ex. 22
Ex. 23
Ex. 24
Ex. 25







XRD powder
Cuprite
Cuprite, Tenorite,
Cuprite
Cristobalite,
Cuprite,




(Cu2O)
Sodium Borate

Copper
Sodium





(Na2B18O28),


Silicate





Potassium Aluminum


(Na2Si2O5),





Silicate (KAlSiO4)


Aluminum








Phosphate








(AlPO4)



XRD surface
Tenorite
Cuprite, Tenorite,
Cuprite,
Cuprite
Cuprite,




(CuO)
Sodium Borate
Tenorite,

Tenorite,






Sodium

Sodium






Borate

Silicate








(Na2Si2O5),








Aluminum








Phosphate








(AlPO4)



XPS vacuum



fracture + 2 min



air



% Cu1+ and
81.7



Cu0



% Cu2+
18.3



StDev
0.2



XPS vacuum



fracture



% Cu1+ and



Cu0



% Cu2+



StDev













Example















Ex. 26
Ex. 27
Ex. 28
Ex. 29
Ex. 30







XRD powder
Cristobalite,
Copper, Cuprite,
Cuprite
Cuprite
Cuprite




Cuprite,
Sodium Copper




Copper
Phosphate




Phosphate
(Na6Cu9(PO4)6)




(Cu3(PO4)2



XRD surface
Cristobalite,
Copper, Cuprite,
Cuprite,
Cuprite
Cuprite,




Cuprite,
Tenorite, Sodium
Sodium

Tenorite




Tenorite,
Copper Phosphate
Borate




Copper

Hydrate




Phosphate



XPS vacuum



fracture + 2 min



air



% Cu1+ and



87.1
75



Cu0



% Cu2+



12.9
25



StDev



1.2
0.2



XPS vacuum



fracture



% Cu1+ and



Cu0



% Cu2+



StDev













Example













Ex. 31
Ex. 32
Ex. 33
Ex. 34
Ex. 35





XRD
Cuprite
Cristobalite,
Cuprite, Sodium Phosphate,


powder

Cuprite,
Na0.24H4.9((Al5.14Si48.86)O106)(H2O)26.5




Sodium




Phosphate




(Na3PO4),




Aluminum




Phosphate




Hydrate




(AlPO4*xH2O),




Copper




Phosphate




(Cu5P2O10)


XRD
Cuprite, Tenorite,
Cristobalite,
Tenorite, Sodium Phosphate,


surface
Tincalconite
Tenorite,
Cuprite



(Na2B4O7*5H2O),
Sodium



Copper Phosphate
Phosphate



Hydrate
(Na3PO4),



Cu3(PO3)6*14H2O
Aluminum




Phosphate




Hydrate




(AlPO4*xH2O),




Copper




Phosphate




(Cu5P2O10)


XPS


vacuum


fracture +


2 min air


% Cu1+
68.7


and Cu0


% Cu2+
31.3


StDev
0.6


XPS


vacuum


fracture


% Cu1+


and Cu0


% Cu2+


StDev












Example













Ex. 36
Ex. 37
Ex. 38
Ex. 39
Ex. 40





XRD
Cuprite,
Cuprite, Potassium
Cuprite, Potassium
Cuprite
Cuprite


powder
Potassium
Zinc Phosphate,
Zinc Phosphate



Zinc
Potassium Zinc
(KZnPO4), Potassium



Phosphate
Silicate
Zinc Silicate,



(KZnPO4)
(K1.10Zn0.55Si1.45O4),
Potassium Zinc




Potassium Zinc
Phosphate




Phosphate




(K6Zn(P2O7)2


XRD
Cuprite,
Tenorite, Copper
Tenorite, Potassium


surface
Potassium
Zinc Phosphate
Zinc Phosphate,



Zinc
(CuZn(P2O7),
Potassium Zinc



Phosphate
Potassium
Silicate, Potassium



(KZnPO4),
Phosphate
Copper Oxide



Copper Silicon
(K4(P2O8),
(K3CuO4), Cuprite,



Phosphide
Aluminum
Copper Oxide



(Cu0.56Si1.44)P2,
Phosphate (AlPO4)
Phosphate



Tenorite

(Cu4O(PO4)2


XPS


vacuum


fracture +


2 min air


% Cu1+


and Cu0


% Cu2+


StDev


XPS


vacuum


fracture


% Cu1+


and Cu0


% Cu2+


StDev












Example















Ex. 41
Ex. 42
Ex. 43
Ex. 44
Ex. 45







XRD
Cuprite
Cuprite
Cuprite
Cuprite



powder



XRD



surface



XPS



vacuum



fracture +



2 min air



% Cu1+



Cu0



% Cu2+



StDev



XPS



vacuum



fracture



% Cu1+



Cu0



% Cu2+



StDev













Example















Ex. 46
Ex. 47
Ex. 48
Ex. 49
Ex. 50







XRD
Cuprite, Copper


Cuprite



powder
Titanium Oxide,




Anatase



XRD
Cuprite, Copper



surface
Titanium Oxide,




Anatase



XPS



vacuum



fracture +



2 min air



% Cu1+



Cu0



% Cu2+



StDev



XPS



vacuum



fracture



% Cu1+



Cu0



% Cu2+



StDev













Example















Ex. 51
Ex. 52
Ex. 53
Ex. 54
Ex. 55







XRD
Cuprite
Tenorite and
cuprite
tenorite and
tenorite and



powder

cuprite

cuprite
cuprite



XRD
Tenorite and
Tenorite and
Tenorite and
tenorite
tenorite



surface
cuprite
cuprite
cuprite



XPS



vacuum



fracture +



2 min air



% Cu1+



Cu0



% Cu2+



StDev



XPS



vacuum



fracture



% Cu1+



Cu0



% Cu2+



StDev















Example




Ex. 56







XRD powder
Cuprite and copper




potassium oxide



XRD surface
cuprite and tenorite




and potassium




borate



XPS vacuum



fracture + 2 min



air



% Cu1+ Cu0



% Cu2+



StDev



XPS vacuum



fracture



% Cu1+ Cu0



% Cu2+



StDev



















TABLE 4









Example













Ex. 1
Ex. 2
Ex. 3
Ex. 4
Ex. 5





Coupon Testing As-

<log 1
<log 1
<log 1
<log 1


Received EPA Test


(S. Aureus)


Coupon Testing As-



<log 1


Received EPA Re-


Test


Coupon Testing 1


Day 85° C./85% RH


EPA Test


ICP Total Cu in wt %



21.6
21.7


ICP Cu+1/total Cu


0.86
0.87
0.88












Example













Ex. 6
Ex. 7
Ex. 8
Ex. 9
Ex. 10





Coupon Testing As-
>log 3
log 2.84

<log 1
<log 1


Received EPA Test


(S. Aureus)


Coupon Testing As-
>log 1


<log 1
<log 1


Received EPA Re-


Test


Coupon Testing 1


Day 85° C./85% RH


EPA Test


ICP Total Cu in wt %
19.6


15.8
22


ICP Cu+1/total Cu
0.88
0.86

0.78
0.8












Example













Ex. 11
Ex. 12
Ex. 13
Ex. 14
Ex. 15





Coupon Testing As-

>log 4
>log 3
>log 6


Received EPA Test


(S. Aureus)


Coupon Testing As-

>log 3
>log 4


Received EPA Re-


Test


Coupon Testing 1


Day 85° C./85% RH


EPA Test


ICP Total Cu in wt %

20.8
20.8
20.5


ICP Cu+1/total Cu

0.85
0.77
0.85












Example













Ex. 21
Ex. 22
Ex. 23
Ex. 24
Ex. 25





Coupon Testing As-

<log 1
<log 1

>log 4


Received EPA Test


(S. Aureus)


Coupon Testing As-


Received EPA Re-


Test


Coupon Testing 1

<log 1
<log 1

<log 1


Day 85° C./85% RH


EPA Test


ICP Total Cu in wt %
18.1
21.5
21.9

21.5


ICP Cu+1/total Cu
0.92
0.8
0.8

0.85












Example













Ex. 26
Ex. 27
Ex. 28
Ex. 29
Ex. 30





Coupon Testing As-


>log 3
>log 3
>log 4


Received EPA Test


(S. Aureus)


Coupon Testing As-


Received EPA Re-


Test


Coupon Testing 1


>log 2
>log 2
>log 4


Day 85° C./85% RH


EPA Test


ICP Total Cu in wt %
21.3

21.4
22.2
21.6


ICP Cu+1/total Cu
0.75

0.82
0.89
0.86












Example













Ex. 31
Ex. 32
Ex. 33
Ex. 34
Ex. 35





Coupon Testing As-
>log 3


Received EPA Test


(S. Aureus)


Coupon Testing As-


Received EPA Re-


Test


Coupon Testing 1
>log 2


Day 85° C./85% RH


EPA Test


ICP Total Cu in wt %
22.4
19.8
19.1


ICP Cu+1/total Cu
0.86
0.77
0.85












Example












Ex. 41
Ex. 42
Ex. 43
Ex. 44





Coupon Testing As-


>log 6
log 5.93


Received EPA Test


(S. Aureus)


Coupon Testing As-


Received EPA Re-


Test


Coupon Testing 1


Day 85° C./85% RH


EPA Test


ICP Total Cu in wt %


ICP Cu+1/total Cu


0.88












Example












Ex. 46
Ex. 49
Ex. 56
Ex. 58





Coupon Testing As-
0.53
1.42
6.151
6.151


Received EPA Test


(S. Aureus)


Coupon Testing As-


Received EPA Re-


Test


Coupon Testing 1


Day 85° C./85% RH


EPA Test


ICP Total Cu in wt %


ICP Cu+1/total Cu









Regarding Example 13, SEM images indicate that phase separation occurred and included a glassy matrix phase and a dispersed glassy second phase. The dispersed phase is considered a degradable phase and included cuprite crystals. The degradation of the dispersed phase was evident when that phase partially dissolved when the formed glass was polished in water. EDS analysis showed a glassy phase enriched in silicon (i.e., a durable phase) relative to both the glassy second phase and crystalline phase. The crystalline phase was the most copper-rich. Without being bound by theory, it is believed that the glassy second phase is enriched in boron. The phase separation of the degradable phase (including the precipitation of cuprite crystals) occurred readily without additional heat treatment beyond simple post-melt annealing.



FIGS. 3-5 are TEM and SEM images of a glasses made from the composition of Example 30. FIG. 3 shows a TEM image in which the darkest areas indicate a silica-rich glassy phase and the lighter areas are phase-separated glassy regions enriched with phosphorus, boron and potassium. As discussed above, these phase-separated glassy regions are degradable regions, and the silica-rich glassy phase is a durable phase. Both the degradable phase and durable phase form the glass phase of the glass. The lightest areas shown in the TEM image of FIG. 3 indicate cuprite crystals. The areas that are appear darker than the lightest areas indicate phase-separated glassy regions enriched with phosphorus, boron and potassium (i.e., the degradable phase). The silica-rich glassy phase is indicated by the darkest regions in FIG. 3. Facets of the cuprite crystals can be seen in the TEM image of FIG. 3. FIG. 4 shows a SEM image of a cross-section of the glass, after polishing with water. From FIG. 4, a preferential dissolution of a degradable phase (i.e., the phase-separated glassy regions enriched with phosphorus, boron and potassium shown in FIG. 3) in water can be seen. The Cu1+ ions contained in the cuprite crystals that form the degradable phase are released by the dissolution of the degradable phase.



FIG. 6 shows an STEM image of the glasses made from the compositions described herein. FIG. 6 shows a three-phase morphology in which copper is present in a particulate form and wrapped by phosphate and distributed in a glass matrix. Because the phosphate is lightly soluble in water and hence it will be dissolved by water, exposing the Cu particles that will release active Cu species to function (killing viruses and bacteria).


Phase separation of the glass upon melting is shown in FIGS. 7A-7B and 8A-8C, which are EDX hypermaps of cross-section TEM images of samples lifted from bulk and surface areas. The same magnification was used to in both TEM images. FIGS. 7A-7B show the bulk and surface areas, respectively, of Example 30 immediately after melting at 1650° C. and annealing at 650° C. versus quenching in water from the 1650° C. melt temperature. FIG. 7A, which shows the quenched sample, is phase separated and includes cuprite crystals within a degradable phase. Accordingly, the phase separation and formation of crystals was not suppressed by quenching. Accordingly, FIG. 7A shows phase separation occurs at 1600° C. or in the melt. Specifically, FIG. 7A shows a durable phase as the darkest color, the lightest parts indicate the presence of copper and parts surrounding the lightest parts and having a slightly darker color represents phosphorus. FIGS. 8A-8B show SEM images of a fracture cross-section and a polished cross-section, respectively, of Example 30 following an additional heat treatment at 800° C. for 1 hour. The additional heat treatment appears to have ripened the microstructure. The size of largest cuprite crystals increased and the number of nanoscale bright contrast phases is significantly reduced when compared to samples prepared by a standard method, as shown in FIGS. 4 and 5. In some embodiments, the concentration of copper exceeds the solubility limit in the degradable phase and the copper precipitates out of the degradable phase. Accordingly, the antimicrobial glass has antimicrobial activity in the molten state and when cooled into the finished state, without any additional heat treatment (e.g., heat treatment in hydrogen at temperatures up to about 600° C.). The antimicrobial glass includes Cu1+ and/or Cu0 in sufficient amounts and present in the degradable phase, that copper ions are leached out and provide antimicrobial efficacy.


The release of the Cu1+ ions provides the antimicrobial activity, as demonstrated in the log reduction of Staphylococcus aureus under the EPA Test when the glass was tested as-received and after 1 day under the conditions listed in Table 4.


The antimicrobial performance of the glasses described herein was tested by forming a coupon or substrate article having dimensions of 2.5 cm×2.5 cm.


To test the antimicrobial activity of the examples, the EPA Test was utilized. In the examples described herein, Staphylococcus aureus (ATCC 6538) was cultured for 5 consecutive days before the testing was performed. Bacterial culture was mixed with serum (5% final concentration) and Triton X-100 (final concentration 0.01%). Each sample/carrier was inoculated with 20 ul of the bacterial suspension and allowed to dry (typically, for about 20 minutes to 40 minutes) at room temperature and 42% relative humidity prior to being exposed to bacterial for a 2 hour exposure period. After 2 hours of exposure, bacteria are washed from the carrier using neutralizer buffer and plated onto Tryptic soy agar plates. Twenty-four hours after incubation at 37° C., bacteria colony formation was examined and counted. Geometric mean and percent reduction were calculated based on the colony number from samples relative to glass carrier or appropriate paint control.


The articles according to one or more embodiments were formed as follows. The glass was ground into a powder and mixed with a commercially available carrier described as a clear gloss protective finish, available under the trademark Polycrylic® from Minwax Company. The copper loading (wt %/wt %) was either about 5%, 10% or 15% (calculated on the basis that the glass includes about 20 wt % Cu). The mixed carrier and glass powder was then brush coated onto Pyvek® paper that was backed with a polymer film, before being coated. The coated Pyvek® paper was cut into 2.5×2.5 cm coupons for the antimicrobial performance testing.


Where a thermoplastic polymer was utilized, the glass powder was compounded with a commercially available polymer, having the trademark Peralthane®, at a temperature in the range from between 195° C.-220° C. and a rate of 50 rpm. The loading of the glass was at about 60-80%. The resulting polymer and glass composite was made into 2.5×2.5 cm coupons by a hot press process.


In some examples, an epoxy resin was utilized. In such examples, about 3.0 g of a commercially available epoxy resin, Erisys GE22, was combined with about 1 g of a curing agent, Amicure PACM and 2 g of ethanol in a 20 mL vial, and mixed well. About 10 g of the powdered glass was added and mixed well. The resulting mixture was cured at room temperature for a few days and then the vial was broken to gel the combination, which was further dried at room temperature for one day and at 65° C. for several hours. This results in dried epoxy resin/glass composite.


The examples that were combined with an epoxy resin were also tested to determine the density or porosity of the composite. This included placing the example in water for 2 minutes and then removing the example. The mass difference before and after placement in the water was measured to demonstrate the porosity of the example.


Coupons made entirely of the glasses of Examples 4, 5, 6, 9, 10, 12, 13, 14 and 21 were tested under the EPA Test. In addition, a Comparative Substrate of pure copper metal was also tested under the EPA Test. FIG. 9 illustrates the antimicrobial performance of those glasses. Example 14 exhibited at least the same antimicrobial performance as the Comparative Substrate, with Examples 6, 12 and 13 exhibiting greater than 3 log reduction in Staphylococcus aureus.


Glass 56 was formed into particles having an average major dimension of about 1 μm or less. The particles were combined with a polymer carrier. The loading of the particles in the carrier was about 5%. The antimicrobial efficacy, as measured by the EPA test for S. aureus was evaluated immediately after the combination of the particles and the polymer carrier, one week after combination of the particles and the polymer carrier, one month after combination of the particles and the polymer carrier and three months after combination of the particles and the polymer carrier. FIG. 10 is a graph showing the antimicrobial efficacy after each period of time. As shown in FIG. 10, the glass exhibits at least a 2 log reduction in S. aureus even at three months after being formed into particles and combined with a polymer carrier. In addition, the combination of the glass particles and the polymer carrier exhibited greater than 5 log reduction at one month after combination.


Glass 56 and a Comparative Glass (A) (including 10% by weight silver ion content diffused therein) were evaluated for antimicrobial activity with respect to Murine Norovirus and cytotoxicity, under the Modified JIS Z 2801 Test for Viruses. Antimicrobial activity control samples and cytotoxicity control samples of Glass 56 and Comparative Glass A were also prepared, as described per the Modified JIS Z 2801 Test for Viruses. Table 5 shows the input virus control and the antimicrobial activity control results, Table 6 shows the cytotoxicity control results, Table 7 shows the results of Comparative Glass A after a 2-hour exposure time to Murine Norovirus, Table 8 shows the results of Glass 56 after a 2-hour exposure time to Murine Norovirus, Table 9 shows the cytotoxicity of Comparative Glass A and Glass 56 on RAW 264.7 cell cultures, and Table 10 shows the non-virucidal level of the test virus as measured on the cytotoxicity control samples for Comparative Glass A and Glass 56.









TABLE 5







Input Virus Control and Antimicrobial Activity Control Results.










Input Virus
Antimicrobial Activity Control











Dilution
Control
Replicate #1
Replicate #2
Replicate #3





Cell control
0 0
0 0 0 0
0 0 0 0
0 0 0 0


10−1
+ +
NT
NT
NT


10−2
+ +
+ + + +
+ + + +
+ + + +


10−3
+ +
+ + + +
+ + + +
+ + + +


10−4
+ +
+ + + +
+ + + +
+ + + +


10−5
+ +
+ + + +
+ + + +
+ + + +


10−6
+ +
0 + + +
+ + 0 +
+ + + +


10−7
0 0
0 0 0 0
0 0 0 0
0 0 0 0


10−8
0 0
0 0 0 0
0 0 0 0
0 0 0 0


PFU50/250 μL
106.50
106.25
106.25
106.50









Mean PFU-50/
NA
106.33


250 μL





(+) = positive for presence of test virus


(0) = No test virus recovered and/or no cytotoxicity present


(NA) = Not applicable


(NT) = Not tested













TABLE 6







Cytotoxicity Control Results.









Cytotoxicity Control



(after 2 hour exposure time)












Dilution
Replicate #1
Replicate #2
Replicate #3







Cell control
0 0 0 0
0 0 0 0
0 0 0 0



10−2
+ + + +
+ + + +
+ + + +



10−3
+ + + +
+ + + +
+ + + +



10−4
+ + + +
+ + + +
+ + + +



10−5
+ + + +
+ + + +
+ + + +



10−6
0 0 0 0
0 0 + 0
0 + 0 0



10−7
0 0 0 0
0 0 0 0
0 0 0 0



10−8
0 0 0 0
0 0 0 0
0 0 0 0



PFU50/250 μL
105.50
105.75
105.75










Mean PFU-50/
105.67



250 μL







(+) = positive for presence of test virus



(0) = No test virus recovered and/or no cytotoxicity present













TABLE 7







Results of Comparative Glass A after 2 hour exposure time to


Murine Norovirus.









Comparative Glass A -



exposure to Murine Norovirus










Dilution
Replicate #1
Replicate #2
Replicate #3





Cell control
0 0 0 0
0 0 0 0
0 0 0 0


10−2
+ + + +
+ + + +
+ + + +


10−3
+ + + +
+ + + +
+ + + +


10−4
+ + + +
+ + + +
+ + + +


10−5
+ + + +
+ + + +
+ + + +


10−6
0 + + 0
+ 0 0 +
+ + 0 0


10−7
0 0 0 0
0 0 0 0
0 0 0 0


10−8
0 0 0 0
0 0 0 0
0 0 0 0


PFU50/250 μL
106.00
106.00
106.00








Mean PFU50/250 μL
106.00


Mean % reduction (based on
No reduction


cytotoxicity control)


Mean Log10 Reduction (based
No reduction


on cytotoxicity control)


Mean % reduction (based on
53.2%


antimicrobial activity control)


Mean Log10 Reduction (based
0.33 Log10


on antimicrobial activity


control)





(+) = positive for presence of test virus


(0) = No test virus recovered and/or no cytotoxicity present













TABLE 8







Results of Glass 56 after 2 hour exposure time to


Murine Norovirus.









Glass 56 - exposure to Murine Norovirus










Dilution
Replicate #1
Replicate #2
Replicate #3





Cell control
0 0 0 0
0 0 0 0
0 0 0 0


10−2
+ + + +
0 0 0 0
0 0 0 0


10−3
+ 0 + 0
0 0 0 0
0 0 0 0


10−4
0 0 0 0
0 0 0 0
0 0 0 0


10−5
0 0 0 0
0 0 0 0
0 0 0 0


10−6
0 0 0 0
0 0 0 0
0 0 0 0


10−7
0 0 0 0
0 0 0 0
0 0 0 0


10−8
0 0 0 0
0 0 0 0
0 0 0 0


PFU50/250 μL
≦103.00
≦101.50
≦101.50








Mean PFU50/250 μL
≦102.00


Mean % reduction (based on
 ≧99.98%


cytotoxicity control)


Mean Log10 Reduction (based
≧3.67 Log10


on cytotoxicity control)


Mean % reduction (based on
≧99.995%


antimicrobial activity control)


Mean Log10 Reduction (based
≧4.33 Log10


on antimicrobial activity


control)





(+) = positive for presence of test virus


(0) = No test virus recovered and/or no cytotoxicity present













TABLE 9







Cytotoxicity of Control Comparative Glass A and Control


Glass 56 on RAW 264.7 Cell Cultures.










Cytotoxicity Control













Comparative




Dilution
Glass A
Glass 56







Cell control
0 0
0 0



10−2
0 0
0 0



10−3
0 0
0 0



10−4
0 0
0 0



10−5
0 0
0 0



10−6
0 0
0 0



10−7
0 0
0 0



10−8
0 0
0 0



TCD50/250 μL
≦101.50
≦101.50







(0) = No test virus recovered and/or no cytotoxicity present













TABLE 10







Non-virucidal Level of Test Substance (Neutralization Control).










Antimicrobial Activity +




Cytotoxicity Control












Comparative




Dilution
Glass A
Glass 56







Cell control
0 0
0 0



10−2
+ +
+ +



10−3
+ +
+ +



10−4
+ +
+ +



10−5
+ +
+ +



10−6
+ +
+ +



10−7
+ +
+ +



10−8
+ +
+ +







(+) = Positive for the presence of test virus after low titer stock virus added (neutralization control)



(0) = No test virus recovered and/or no cytotoxicity present






Comparative Glass A exhibited a 0.33 log reduction in Murine Norovirus (or a 53.2% mean reduction), following a 2 hour exposure time at room temperature (20° C.) in a relative humidity of 42%, as compared to the antimicrobial activity control sample. Glass 56, however, exhibited a greater than 4.33 log reduction in Murine Norovirus (or 99.995% mean reduction or greater), following a 2 hour exposure time at room temperature (20° C.) in a relative humidity of 42%, as compared to the antimicrobial activity control sample.


Comparative Glass A did not demonstrate a mean reduction in viral titer of Murine Norovirus, following a 2 hour exposure time at room temperature (20° C.) in a relative humidity of 42%, in the presence of a 5% fetal bovine serum organic soil load, as compared to the cytotoxicity control sample. Glass 56, however, exhibited a greater than 3.67 mean log reduction in Murine Norovirus (or at least 99.98% or greater mean reduction), following a 2 hour exposure time at room temperature (20° C.) in a relative humidity of 42%, in the presence of a 5% fetal bovine serum organic soil load, as compared to the cytotoxicity control sample.


The results shown in Table 10 indicate that each test sample was neutralized at a PFU50/250 μL of ≦1.5 log10.


Examples 12, 13 and 14 were formed into a powder and mixed with Polycrylic® at different loadings, based on Cu2O content. The mixtures were then coated onto Pyvek® paper (that was backed with a plastic film before coated) through a brushing process and cured for 1 week. The coated paper was cut into coupons for testing under the EPA Test. FIGS. 11 and 12 illustrate the results. FIG. 11 shows the antimicrobial performance of the coupons, having different copper loadings. FIG. 12 illustrates the antimicrobial performance of the composites with 15% Cu2O.


Example 12 was ground into a powder and mixed with Pearlthane® polyurethane to provide a composite having different amounts of glass (by weight percent). The powdered glass and polyurethane were mixed at 195-220° C. for several minutes. The resulting combination was made into a 2.5 cm×2.5 cm coupon using melt processing, and evaluated for antimicrobial performance using the EPA Test. The results are provided in FIG. 13.


Injection molded articles were formed to evaluate antimicrobial activity when the surface is typically covered by a thin layer of matrix polymer. In such articles, the matrix polymer is typically hydrophobic and may affect antimicrobial performance. As shown in FIG. 14, surface treatment can improve antimicrobial performance. To prepare the injection molded samples, Example 12 was ground into a powder and mixed with Pearlthane® polyurethane to provide an injection moldable composite having 60 wt % glass. The composite was injection molded in a petri dish as shown in FIG. 14 to provide four injection molded samples (Samples A-D) that were evaluated for antimicrobial performance using the EPA Test. Sample A was not subjected to surface treatment. Sample B was sanded to remove about 10 mg of top surface of the sample. Samples C and D were subjected to plasma treatment using 100 W of power and pressure of 2 torr for 5 minutes using two different gases, as shown in Table 11. FIG. 15 shows the log reduction of Samples A-D.









TABLE 11







Plasma Treatment condition for Samples C and D.


Table 115












Time,

Pressure,



Material
min
Power, W
torr
Gas





Sample C
5
100
2
air


Sample D
5
100
2
N2/H2 (94/6% by






volume)









As discussed herein, thermoplastic polymers may be utilized to form the articles described herein through melt compounding processes. Articles using a thermoplastic polymer may also be formed by in situ polymerization and then into an article by a casting process. An epoxy resin (which is a thermosetting polymer) was used to demonstrate the concept. The epoxy resin was made from Erisys GE22 and Amicure PACM, which were mixed well in presence of alcohol. Example 12 was ground into a powder and added to the mixture according to Table 12, resulting in a paste-like material that was cast into a mold. In this example, a glass vial was used as a mold. The combination of the epoxy resin and ground glass was then cured at room temperature for a few days. The mold was then removed and the resulting article was dried at room temperature for one day and at 65° C. for a few hours.









TABLE 12







Composition for making an article with epoxy resin and


ground glass from Example 12.


Table 12










Materials
Weight, parts
Weight, parts
Weight, parts













Erisys GE22
1
1
3


Amicure PACM
0.3
0.3
1


Ethanol
6
5
2


Example 12
15
10
10









Depending on the loading of the glass in the article, the resulting article may be porous or dense. The porosity increases with the increase of glass loading as seen in Table 13, in which the water uptake by the articles was measured after soaking the article in water for 2 minutes. Different articles were made from the same epoxy as used in Table 12 was combined with different amounts of ground glass from Example 12. The article was made using gel casting.









TABLE 13







water uptake of articles using epoxy resin and different loadings


of ground glass from Example 12.


Table 13










Example 12 glass loading




(wt %/wt %)
Water uptake in 2 minutes, %














71
0.5



88
5.9



92
20.7










It will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit or scope of the invention.

Claims
  • 1. An article comprising a glass, wherein the glass comprises a cuprite phase comprising a plurality of Cu1+ ions; a first phase comprising at least one of B2O3, P2O5 and R2O, wherein R is selected from the group consisting of K, Na, Li, Rb, Cs and combinations thereof; anda second phase,wherein the glass comprises a surface portion having a depth of less than about 5 nanometers (nm), the surface portion comprising a plurality of copper ions wherein at least 75% of the plurality of copper ions are Cu1+.
  • 2. The article of claim 1, further comprising a polymer, wherein the polymer comprises a thermoplastic polymer, a polyolefin, an injection moldable thermosetting polymer or combinations thereof.
  • 3. The article of claim 2, further comprising a glass to polymer ratio in the range from about 10:90 to about 90:10, based on weight percent.
  • 4. The article of claim 1, further exhibiting any one or more of a 2 log reduction or greater in a concentration of any one or more of Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa bacteria, Methicillin Resistant Staphylococcus aureus, and E. coli, under the EPA Test Method for Efficacy of Copper Alloy as a Sanitizer testing conditions,a 4 log reduction or greater in a concentration of any one or more of Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa bacteria, Methicillin Resistant Staphylococcus aureus, and E. coli, under the JIS Z 2801 (2000) testing conditions or a Modified JIS Z 2801 Test for Bacteria, anda 4 log reduction or greater in a concentration of Murine Norovirus, under a Modified JIS Z 2801 Test for Viruses.
  • 5. The article of claim 1, wherein the cuprite phase is dispersed in at least one of the first phase and the second phase.
  • 6. The article of claim 1, wherein the second phase comprises SiO2.
  • 7. The article of claim 1, wherein the first phase comprises Cu′.
  • 8. The article of claim 1, wherein the cuprite phase comprises at least about 10 weight percent of the glass.
  • 9. The article of claim 1, wherein the glass comprises a surface, a glass network and a glass matrix, and wherein the plurality of Cu1+ ions is disposed on the surface and in at least one of the glass network and the glass matrix.
CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority under 35 U.S.C. §119 of U.S. Provisional Application Ser. No. 62/034,842 filed on Aug. 8, 2014, U.S. Provisional Application Ser. No. 62/034,834, filed Aug. 8, 2014, U.S. Provisional Application Ser. No. 62/026,186 filed on Jul. 18, 2014, U.S. Provisional Application Ser. No. 62/026,177, filed Jul. 18, 2014, U.S. Provisional Application Ser. No. 61/992,987 filed on May 14, 2014, U.S. Provisional Application Ser. No. 61/992,980, filed May 14, 2014, U.S. Provisional Application Ser. No. 61/941,690 filed on Feb. 19, 2014, and U.S. Provisional Application Ser. No. 61/941,677, filed Feb. 19, 2014, the content of which are relied upon and incorporated herein by reference in their entirety.

US Referenced Citations (304)
Number Name Date Kind
3414465 Baak et al. Dec 1968 A
3564587 Ellis Feb 1971 A
4098610 Wexell Jul 1978 A
4328022 Bonk et al. May 1982 A
5290544 Shimono et al. Mar 1994 A
5766611 Shimono et al. Jun 1998 A
6143318 Gilchrist et al. Nov 2000 A
6238686 Burrell et al. May 2001 B1
6303183 Wilczynski et al. Oct 2001 B1
6342460 Akimoto et al. Jan 2002 B1
6417423 Koper et al. Jul 2002 B1
6485735 Steen et al. Nov 2002 B1
6485950 Kumar et al. Nov 2002 B1
6582715 Barry et al. Jun 2003 B1
6652875 Bannister Nov 2003 B1
6749759 Denes et al. Jun 2004 B2
6939820 Numaguchi et al. Sep 2005 B2
7098256 Ong et al. Aug 2006 B2
7192602 Fechner et al. Mar 2007 B2
7282194 Sung et al. Oct 2007 B2
7311944 Sambasivan et al. Dec 2007 B2
7329301 Chang et al. Feb 2008 B2
7357949 Trogolo et al. Apr 2008 B2
7374693 Routberg et al. May 2008 B1
7381751 Sarangapani Jun 2008 B2
7390343 Tepper et al. Jun 2008 B2
7491554 Fujimura et al. Feb 2009 B2
7521056 Chang et al. Apr 2009 B2
7521394 Xie et al. Apr 2009 B2
7556789 Fahlman Jul 2009 B2
7595355 Trogolo Sep 2009 B2
7597900 Zimmer et al. Oct 2009 B2
7704903 Seneschal et al. Apr 2010 B2
7709027 Fechner et al. May 2010 B2
7781498 Krishnan Aug 2010 B2
7816292 Zimmer et al. Oct 2010 B2
7833340 Wakizaka Nov 2010 B2
7963646 Magdassi et al. Jun 2011 B2
8034732 Kobayashi et al. Oct 2011 B2
8056733 Koslow Nov 2011 B2
8080490 Fechner et al. Dec 2011 B2
8083851 Crudden et al. Dec 2011 B2
8092912 Veerasamy et al. Jan 2012 B2
8187473 Prasad May 2012 B2
8221833 Veerasamy et al. Jul 2012 B2
8256233 Boyden et al. Sep 2012 B2
8257714 Aylsworth et al. Sep 2012 B2
8257732 Huey et al. Sep 2012 B2
8258202 Chasser et al. Sep 2012 B2
8258296 Paredes et al. Sep 2012 B2
8262568 Albrecht et al. Sep 2012 B2
8262868 Brooks et al. Sep 2012 B2
8263114 Berlat Sep 2012 B2
8263153 Forchhammer et al. Sep 2012 B2
8263503 Cawse et al. Sep 2012 B2
8263656 Firooznia et al. Sep 2012 B2
8268343 Saxena et al. Sep 2012 B2
8273303 Ferlic et al. Sep 2012 B2
8273404 Dave et al. Sep 2012 B2
8273452 Guo et al. Sep 2012 B2
8277807 Gallagher et al. Oct 2012 B2
8277827 Toreki et al. Oct 2012 B2
8277899 Krogman et al. Oct 2012 B2
8282776 Smith et al. Oct 2012 B2
8317516 Rusin et al. Nov 2012 B2
8568849 Shi et al. Oct 2013 B2
8809820 Dahm Aug 2014 B2
8900624 Karandikar et al. Dec 2014 B2
9028962 Borrelli et al. May 2015 B2
9115470 Musick et al. Aug 2015 B2
9144242 Averett et al. Sep 2015 B2
9193820 Karandikar et al. Nov 2015 B2
9228090 Musick Jan 2016 B2
9307759 Musick Apr 2016 B2
20020045010 Rohrbaugh et al. Apr 2002 A1
20020128249 Cook Sep 2002 A1
20030167878 Al-Salim et al. Sep 2003 A1
20030213503 Price et al. Nov 2003 A1
20040206267 Sambasivan et al. Oct 2004 A1
20040234604 Mecking et al. Nov 2004 A1
20040253435 Nomura Dec 2004 A1
20050031703 Beier et al. Feb 2005 A1
20050095303 Krenitski et al. May 2005 A1
20050152955 Akhave et al. Jul 2005 A1
20050175552 Hoic et al. Aug 2005 A1
20050175649 Disalvo et al. Aug 2005 A1
20050182152 Nonninger et al. Aug 2005 A1
20050207993 Bazemore et al. Sep 2005 A1
20050224417 Wien et al. Oct 2005 A1
20050224419 Wien et al. Oct 2005 A1
20050258288 Dalziel et al. Nov 2005 A1
20060115536 Yacaman et al. Jun 2006 A1
20060127310 Russell-Jones et al. Jun 2006 A1
20060142413 Zimmer et al. Jun 2006 A1
20060166806 Fechner et al. Jul 2006 A1
20060172013 Hirai Aug 2006 A1
20060188580 Sacks Aug 2006 A1
20060193902 Tardi et al. Aug 2006 A1
20060198903 Storey et al. Sep 2006 A1
20060272542 Horner et al. Dec 2006 A1
20060280785 Easterly et al. Dec 2006 A1
20060281961 Prasad Dec 2006 A1
20060286051 Tanaka et al. Dec 2006 A1
20070062870 Chen et al. Mar 2007 A1
20070081958 Bechert et al. Apr 2007 A1
20070116734 Akash May 2007 A1
20070122356 Kessler et al. May 2007 A1
20070122359 Wang et al. May 2007 A1
20070158611 Oldenburg Jul 2007 A1
20070195259 Olsson Aug 2007 A1
20070196605 Ong Aug 2007 A1
20070199890 Trogolo Aug 2007 A1
20070208102 Reynaud et al. Sep 2007 A1
20070225409 Matsumoto Sep 2007 A1
20070243237 Khaled et al. Oct 2007 A1
20070243263 Trogolo Oct 2007 A1
20070254163 Veerasamy et al. Nov 2007 A1
20070292355 Tamarkin et al. Dec 2007 A1
20080031938 Easterly et al. Feb 2008 A1
20080032060 Nesbitt Feb 2008 A1
20080047894 Trogolo et al. Feb 2008 A1
20080051493 Trogolo et al. Feb 2008 A1
20080053922 Honsinger et al. Mar 2008 A1
20080066741 LeMahieu et al. Mar 2008 A1
20080085326 Ruan Apr 2008 A1
20080156232 Crudden et al. Jul 2008 A1
20080171068 Wyner et al. Jul 2008 A1
20080220037 Denizot et al. Sep 2008 A1
20080269186 Bignozzi et al. Oct 2008 A1
20080292671 Ho et al. Nov 2008 A1
20080292675 Edermatt et al. Nov 2008 A1
20080299160 Agboh et al. Dec 2008 A1
20090001012 Kepner Jan 2009 A1
20090023867 Nishijima et al. Jan 2009 A1
20090048368 Bash et al. Feb 2009 A1
20090068241 Britz et al. Mar 2009 A1
20090098366 Smoukov et al. Apr 2009 A1
20090104369 Rajala et al. Apr 2009 A1
20090130161 Sarangapani May 2009 A1
20090131517 Height et al. May 2009 A1
20090133583 Lee et al. May 2009 A1
20090133810 Penalva May 2009 A1
20090142584 Bedel et al. Jun 2009 A1
20090147370 Parkin et al. Jun 2009 A1
20090151571 Lee et al. Jun 2009 A1
20090162695 Hevesi et al. Jun 2009 A1
20090186013 Stucky et al. Jul 2009 A1
20090186756 Cheng et al. Jul 2009 A1
20090209629 Mirkin et al. Aug 2009 A1
20090263496 Kijlstra et al. Oct 2009 A1
20090314628 Lee et al. Dec 2009 A1
20090317435 Vandesteeg et al. Dec 2009 A1
20090324990 Pilloy et al. Dec 2009 A1
20100003203 Karpov et al. Jan 2010 A1
20100004350 Zalich et al. Jan 2010 A1
20100021559 Kuznicki Jan 2010 A1
20100034873 Delprete Feb 2010 A1
20100035047 Ajayan et al. Feb 2010 A1
20100040655 Ren et al. Feb 2010 A1
20100086605 Bignozzi et al. Apr 2010 A1
20100111844 Boyden et al. May 2010 A1
20100111845 Boyden et al. May 2010 A1
20100119829 Karpov et al. May 2010 A1
20100120942 Ajayan et al. May 2010 A1
20100158851 Yeung et al. Jun 2010 A1
20100178270 Helling Jul 2010 A1
20100189901 Chung et al. Jul 2010 A1
20100190004 Gibbins et al. Jul 2010 A1
20100193744 Avakian Aug 2010 A1
20100205709 Grune et al. Aug 2010 A1
20100227052 Carter et al. Sep 2010 A1
20100230344 Srinivas et al. Sep 2010 A1
20100233146 McDaniel Sep 2010 A1
20100234209 Furukawa et al. Sep 2010 A1
20100247590 Anton et al. Sep 2010 A1
20100255080 Sanmiguel et al. Oct 2010 A1
20100264401 Adivarahan et al. Oct 2010 A1
20100266646 Dvorak et al. Oct 2010 A1
20100278771 Lobe et al. Nov 2010 A1
20100297376 Shi et al. Nov 2010 A1
20100304182 Facchini et al. Dec 2010 A1
20100330380 Colreavy et al. Dec 2010 A1
20110005997 Kurth et al. Jan 2011 A1
20110014258 Gan et al. Jan 2011 A1
20110014300 Muthusamy et al. Jan 2011 A1
20110027385 Cairns et al. Feb 2011 A1
20110027599 Hoek et al. Feb 2011 A1
20110028311 Etacheri et al. Feb 2011 A1
20110111204 Veerasamy et al. May 2011 A1
20110127464 Zinn et al. Jun 2011 A1
20110132144 Mezger et al. Jun 2011 A1
20110143417 Chang et al. Jun 2011 A1
20110144765 Jones et al. Jun 2011 A1
20110155968 Iha et al. Jun 2011 A1
20110182951 Burger et al. Jul 2011 A1
20110189250 John et al. Aug 2011 A1
20110193007 Avakian Aug 2011 A1
20110193034 Nakamoto et al. Aug 2011 A1
20110200656 Olsson Aug 2011 A1
20110212832 Nakano et al. Sep 2011 A1
20110217544 Young et al. Sep 2011 A1
20110223057 Della Valle et al. Sep 2011 A1
20110223258 Nikolaev Sep 2011 A1
20110226786 Remington et al. Sep 2011 A1
20110236343 Chisholm et al. Sep 2011 A1
20110236430 Lin et al. Sep 2011 A1
20110236441 Ohrlander et al. Sep 2011 A1
20110252580 Miller et al. Oct 2011 A1
20110268802 Dihora et al. Nov 2011 A1
20110281070 Mittal et al. Nov 2011 A1
20110295190 David et al. Dec 2011 A1
20110311604 Xu et al. Dec 2011 A1
20120066956 Lyngstadaas et al. Mar 2012 A1
20120115981 Verne' et al. May 2012 A1
20120145651 Chen et al. Jun 2012 A1
20120223022 Hassler et al. Sep 2012 A1
20120225027 Exner et al. Sep 2012 A1
20120225905 Padilla et al. Sep 2012 A1
20120230870 Franciskovich et al. Sep 2012 A1
20120231704 Mase et al. Sep 2012 A1
20120232225 Baker et al. Sep 2012 A1
20120232298 Fang et al. Sep 2012 A1
20120234176 Lee Sep 2012 A1
20120237406 Lee Sep 2012 A1
20120237789 Wang et al. Sep 2012 A1
20120240452 Erdoes, Jr. et al. Sep 2012 A1
20120241498 Gonzalez et al. Sep 2012 A1
20120241502 Aldridge et al. Sep 2012 A1
20120244139 Madison et al. Sep 2012 A1
20120244369 Ober et al. Sep 2012 A1
20120251381 Bedworth et al. Oct 2012 A1
20120251517 Frost et al. Oct 2012 A1
20120251756 Buckley et al. Oct 2012 A1
20120252774 White et al. Oct 2012 A1
20120255623 Bell et al. Oct 2012 A1
20120258176 Sung et al. Oct 2012 A1
20120258244 Veerasamy et al. Oct 2012 A1
20120258313 Wen et al. Oct 2012 A1
20120259052 Nelson et al. Oct 2012 A1
20120259073 Ait-Haddou et al. Oct 2012 A1
20120259376 Godden Oct 2012 A1
20120259391 Godden Oct 2012 A1
20120261344 Kurth et al. Oct 2012 A1
20120263807 Horinek et al. Oct 2012 A1
20120263863 Nesbitt Oct 2012 A1
20120264078 Patel et al. Oct 2012 A1
20120264884 Liu et al. Oct 2012 A1
20120269870 Jiang et al. Oct 2012 A1
20120271248 Nesbitt et al. Oct 2012 A1
20120271396 Zheng et al. Oct 2012 A1
20120275960 Seck Nov 2012 A1
20120276219 Taylor et al. Nov 2012 A1
20120279953 Augustine et al. Nov 2012 A1
20120282434 Cawse et al. Nov 2012 A1
20120283171 Putman Nov 2012 A1
20120283172 Wallen, III Nov 2012 A1
20120283410 Mirosevich et al. Nov 2012 A1
20120283538 Rose et al. Nov 2012 A1
20120284946 Green Nov 2012 A1
20120285574 Mason Nov 2012 A1
20120288678 Grube et al. Nov 2012 A1
20120288697 Wu et al. Nov 2012 A1
20120288813 Reid et al. Nov 2012 A1
20120289107 Beissinger et al. Nov 2012 A1
20120289686 Baker et al. Nov 2012 A1
20120289887 Visco et al. Nov 2012 A1
20120296029 Liu et al. Nov 2012 A1
20120296284 Anderson et al. Nov 2012 A1
20120301533 Uhlmann et al. Nov 2012 A1
20120304402 Miracle et al. Dec 2012 A1
20120305132 Maness Dec 2012 A1
20120305804 Goldman Dec 2012 A1
20120308623 Taxt-Lamolle et al. Dec 2012 A1
20120308630 Averett et al. Dec 2012 A1
20120312797 Augustine et al. Dec 2012 A1
20120315201 Ferlic et al. Dec 2012 A1
20120315240 Alper Dec 2012 A1
20120315336 Ruddy et al. Dec 2012 A1
20120321553 Zeng et al. Dec 2012 A1
20120321691 Huey et al. Dec 2012 A1
20120321698 Narain et al. Dec 2012 A1
20120321870 Allen et al. Dec 2012 A1
20120322903 Karandikar et al. Dec 2012 A1
20120328564 Govindan et al. Dec 2012 A1
20120328615 Romagne et al. Dec 2012 A1
20120328683 Song et al. Dec 2012 A1
20120328713 Olson et al. Dec 2012 A1
20120328804 Allen et al. Dec 2012 A1
20120329675 Olson et al. Dec 2012 A1
20130001066 Brooks et al. Jan 2013 A1
20130001204 Mistry et al. Jan 2013 A1
20130002776 Nagashima et al. Jan 2013 A1
20130004778 Tucker, III Jan 2013 A1
20130005811 Walcott Jan 2013 A1
20130006184 Albrecht et al. Jan 2013 A1
20130006194 Anderson et al. Jan 2013 A1
20140017462 Borrelli et al. Jan 2014 A1
20140120322 Fu et al. May 2014 A1
20140170204 Desai et al. Jun 2014 A1
20140194733 Goforth et al. Jul 2014 A1
20140202943 Pradeep et al. Jul 2014 A1
20140205546 Macoviak Jul 2014 A1
20140220091 Tofail et al. Aug 2014 A1
20140308867 Van Emmerick et al. Oct 2014 A1
Foreign Referenced Citations (116)
Number Date Country
2503446 May 2004 CA
2515956 Oct 2002 CN
1420146 May 2003 CN
101189971 Jun 2008 CN
101638537 Feb 2010 CN
101805546 Aug 2010 CN
101884807 Nov 2010 CN
101889582 Nov 2010 CN
102348844 Feb 2012 CN
102380127 Mar 2012 CN
0665004 Aug 1995 EP
0677989 Oct 1995 EP
1603600 Dec 2005 EP
1715915 Nov 2006 EP
1748353 Jan 2007 EP
1780318 May 2007 EP
1809306 Jul 2007 EP
1886981 Feb 2008 EP
2004246 Dec 2008 EP
2016115 Jan 2009 EP
2016200 Jan 2009 EP
2113282 Apr 2009 EP
2123400 Nov 2009 EP
2506792 Dec 2009 EP
2509622 Dec 2009 EP
2509710 Dec 2009 EP
2157211 Feb 2010 EP
2303352 Apr 2011 EP
2502941 Sep 2012 EP
2507248 Oct 2012 EP
2508341 Oct 2012 EP
2513238 Oct 2012 EP
2514359 Oct 2012 EP
2515855 Oct 2012 EP
2516002 Oct 2012 EP
2517720 Oct 2012 EP
2522377 Nov 2012 EP
2537529 Dec 2012 EP
2540309 Jan 2013 EP
2540491 Jan 2013 EP
2540755 Jan 2013 EP
2562624 Feb 2013 EP
2953213 Jun 2011 FR
2473813 Mar 2011 GB
2490644 Jul 2012 GB
2490239 Oct 2012 GB
2490241 Oct 2012 GB
2490242 Oct 2012 GB
2490243 Oct 2012 GB
60036349 Feb 1985 JP
1993041636 Jun 1993 JP
1993042574 Jun 1993 JP
1993042624 Jun 1993 JP
1993045015 82 Jul 1993 JP
1993046389 Jul 1993 JP
05060670 Sep 1993 JP
1993064311 82 Sep 1993 JP
1993068530 Sep 1993 JP
1993074652 Oct 1993 JP
1996027404 Jan 1996 JP
11209143 Aug 1999 JP
2000191339 Jul 2000 JP
04163778 Oct 2008 JP
5089165 Dec 2012 JP
5099520 Dec 2012 JP
2013233492 Nov 2013 JP
2011127748 Nov 2011 KR
2414902 Mar 2011 RU
WO0027768 May 2000 WO
03018494 Apr 2003 WO
03050052 Jun 2003 WO
2005079738 Sep 2005 WO
2007071991 Jun 2007 WO
WO2007076413 Jul 2007 WO
WO2007101062 Sep 2007 WO
WO2007134176 Nov 2007 WO
WO2009100164 Aug 2009 WO
2010041760 Apr 2010 WO
2010068985 Jun 2010 WO
2011047312 Apr 2011 WO
2011053562 May 2011 WO
2011053719 May 2011 WO
2011056934 May 2011 WO
2011057111 May 2011 WO
2011062938 May 2011 WO
2011063259 May 2011 WO
2011063990 Jun 2011 WO
2011065997 Jun 2011 WO
2011068545 Jun 2011 WO
2011068892 Jun 2011 WO
2011070364 Jun 2011 WO
2011071130 Jun 2011 WO
2011072392 Jun 2011 WO
2011073969 Jun 2011 WO
2011075798 Jun 2011 WO
2011078804 Jun 2011 WO
2011084811 Jul 2011 WO
2011090760 Jul 2011 WO
2011092522 Aug 2011 WO
2011094293 Aug 2011 WO
2011097347 Aug 2011 WO
2011100425 Aug 2011 WO
2011101642 Aug 2011 WO
2011103183 Aug 2011 WO
2011103578 Aug 2011 WO
2011107592 Sep 2011 WO
2011109136 Sep 2011 WO
2011109400 Sep 2011 WO
2011145592 Nov 2011 WO
2012015362 Feb 2012 WO
2012129305 Sep 2012 WO
2012135194 Oct 2012 WO
WO2012135193 Oct 2012 WO
2012159632 Nov 2012 WO
WO2014025949 Feb 2014 WO
2014085379 Jun 2014 WO
Non-Patent Literature Citations (9)
Entry
Matusita K.' ‘Sakka S.’ ‘Shouji T.’, Thermal Expansion of Substituted Copper Aluminosilicate Glasses, J.Am.Ceram.Soc., 1983, vol. 66, No. 1, p. 33.
Patent Cooperation Treaty International Notification of Transmittal of the International Search Report and The Written Opinion of the International Searching Authority, international application No. PCT/US2015/016104: mailing date Jun. 25, 2015, 15 pages.
Hamzawy et al. “Crystallisation of Cu-containing K-fluor-richterite (KNaCa(Mg, Cu)5 Si8O22F2) glasses.” Glass Technology, 2005, 46 (3), 281-286.
Ahmed et al., “Effect of Heat Treatment on the Crystallisation of Cuprous Oxide in Glass,” Glass Research Laboratory, National Research Center, Dokki, Cairo, Egypt, Glass Technology, vol. 22, No. 1, Feb. 1981.
Esteban-Tejeda et al. “Antibacterial and Antifungal Activity of a Soda-Lime Glass Containing Copper Nanoparticles,” Nanotechnology 20 (2009) 505701 (6pp).
Esteban-Tejeda et al., “Glass-(nAg, nCu) Biocide Coatings on Ceramic Oxide Substrates.” Plos One, Mar. 2012, vol. 7, Issue 3, p. 1-6.
Sherwin Williams Copper Bottom Anti-Fouling Paint #45—Protective and marine.
Bolshii Ya.Ya.' ‘Mezhinskii G.Kh.’ ‘Sedmalis U.Ya.’ ‘Igaune S.A.’ , Izv.Akad.Nauk Latv.SSR,Ser.Khim., 1983, No. 2, p. 194.
Tretjakova N.I.' ‘Mazurin 0.V.’ , Vliyanie Okislov Dvukhvalentnykh Metallov na Vyazkost Prostykh Silikatnykh Stekol. Deposited in VINITI, Moscow, No. 995-69 Dep., 1969.
Related Publications (1)
Number Date Country
20150230476 A1 Aug 2015 US
Provisional Applications (8)
Number Date Country
62034842 Aug 2014 US
62034834 Aug 2014 US
62026186 Jul 2014 US
62026177 Jul 2014 US
61992987 May 2014 US
61992980 May 2014 US
61941690 Feb 2014 US
61941677 Feb 2014 US