Antimicrobial glass compositions, glasses and polymeric articles containing same

Antimicrobial glass composition, glass and polymer articles containing said composition

The application is that the international application number is PCT/US2015/016104, and the international application date is February 17, 2015, and the application number entering China's national stage is 201580020546.6, and the title of invention is "antimicrobial glass composition, containing the A divisional application of the patent application for the invention of "glass and polymer articles of composition".

Related application cross-reference

The application requires the priority of following application according to 35U.SC § 119: the U.S. patent application No. 62/034,842 submitted on August 8th, 2014, the U.S. patent application No. 62/034,834 submitted on August 8th, 2014 , U.S. Patent Application No. 62/026,186, filed July 18, 2014, U.S. Provisional Patent Application No. 62/026177, filed July 18, 2014, U.S. Provisional Patent Application No. 61/992,987, filed May 14, 2014 , U.S. Provisional Patent Application No. 61/992,980 filed May 14, 2014 U.S. Provisional Patent Application No. 61/941,690 filed Feb. 19, 2014 U.S. Provisional Patent Application No. filed Feb. 19, 2014 61/941,677, this application is based on the content of these applications and is hereby incorporated by reference in their entirety.

[0004] Background

[0005] The present invention relates generally to antimicrobial glass compositions and articles comprising such compositions. In particular, various embodiments described herein relate to glasses having antimicrobial performance characteristics and articles comprising such glasses.

[0006] Consumer electronics articles of manufacture that include touch-activated or touch-interactive devices, such as screen surfaces (eg, surfaces of electronic devices with user interaction capabilities activated by touching specific portions of the surface), are becoming more common. As the level of touchscreen-based interaction between users and devices increases, the potential for surface-hosted microbes (eg, bacteria, fungi, viruses, etc.) to spread between users increases. Furthermore, housings comprising touch-activated or touch-interactive devices also contain surfaces on which such microorganisms are present and which can be transferred from one user to another. The problem of microbial transfer is also a concern for equipment, furniture and building articles used in medical settings or office environments and many other articles in which surfaces are touched by users.

[0007] In order to minimize the presence of microorganisms on various materials, various glasses have been endowed with so-called "antimicrobial" properties; however, there is a need in the art to provide monolithic articles (including housings and plate glass of any glass). Accordingly, antimicrobial articles for certain applications should be sufficiently durable for their intended use while also providing continuous antimicrobial properties that are passive and require no input from the user or external sources ( such as UV light) for additional activation. Additionally, antimicrobial glasses and articles should provide controlled antimicrobial activity.

Summary

[0009] A first aspect of the invention relates to an article comprising a carrier and glass. Examples of suitable supports include polymers, monomers, binders, solvents and other materials used to form molded articles, shaped articles, coatings on substrates or other such articles. Exemplary coatings may include anti-friction coatings, coatings exhibiting a low coefficient of friction, or coatings that form a surface exhibiting a low coefficient of friction.

[0010] The glass of one or more embodiments may further comprise a composition comprising, in mole percent: about 40 to about 70 SiO₂, about 0-about 20 Al₂o₃, about 10 to about 50 copper-containing oxides, about 0 to about 15 CaO, about 0 to about 15 MgO, about 0 to about 25 P₂o₅, about 0 - about 25 B₂o₃, about 0 - about 20 K₂O, about 0 to about 5 ZnO, about 0 to about 20 Na₂O, and about 0 to about 5 Fe₂o₃. In some embodiments, the amount of copper-containing oxide is greater than that of Al₂o₃amount (in some cases, its

may be about 5 mole percent or less). In some cases, the composition may be free of Al₂o₃. Examples of suitable copper-containing oxides may include CuO, Cu₂O or a combination thereof.

[0011] The article of one or more embodiments may comprise a plurality of Cu¹+ ions, Cu metal or combinations thereof. In some cases, the glass may be substantially free of cupolite.

[0012] The glass of one or more embodiments may comprise a cuprite phase and a glass phase. In some embodiments, the cuprite phase can comprise crystals having an average major dimension of about 5 microns (Um) or less, or even about 1 micron (Um) or less.

[0013] A second aspect of the invention relates to an article comprising a carrier and a glass having a plurality of Cu¹+ ions, containing B₂o₃,P₂o₅and R₂A degradable phase of at least one of O and containing SiO₂durable phase. Glass can be formed from the compositions described herein. In some cases, the durable phase is present in a greater amount than the degradable phase on a weight percent basis. The degradable phase of one or more embodiments leaches or is leachable in the presence of water.

[0014] The article may optionally comprise a cuprite phase, which may be dispersed in one or both of a degradable phase and a durable phase. The cuprite phase may have crystals having an average major dimension of about 5 micrometers (um) or less, about 1 micrometer (um) or less, or about 500 nanometers (nm) or less. The cuprite phase can comprise at least about 10% by weight or at least about 20% by weight of the glass.

[0015] In one or more embodiments, the glass comprises a surface portion (having a depth of less than about 5 nanometers (nm)) containing 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⁺。

[0016] A third aspect of the present invention relates to an article comprising a support and an inorganic material, wherein the inorganic material comprises a surface and a plurality of Cu disposed on the surface¹+ ions. Inorganic materials can include glass and can be formed from the compositions described herein. The inorganic material may be substantially free of cupolite.

In one or more embodiments, described multiple Cu¹+ ions can be dispersed in the glass network and/or glass matrix. In some cases, the glass network comprises atoms that interact with the plurality of Cu¹+Ions are linked by atoms. The multiple Cu¹The + ions may comprise cuprite crystals dispersed in a glass matrix.

[0018] The carrier may comprise a polymer, a monomer, a binder, a solvent, or a combination thereof. The carrier may comprise anti-friction materials such as fluorocarbons, fluorinated silanes, and alkylperfluorocarbosilanes. Polymers used in embodiments described herein may comprise organic polymers or inorganic polymers. Exemplary polymers can include thermoplastic polymers, polyolefins, cured polymers, ultraviolet or UV cured polymers, polymer emulsions, solvent-based polymers, and combinations thereof. Specific examples of monomers include catalyst-curable monomers, heat-curable monomers, radiation-curable monomers, and combinations thereof. The articles described herein may comprise a ratio of glass to carrier of about 10:90 to about 90:10 by weight percent.

[0019] The glasses and articles described herein exhibit a concentration of at least one of or log reduction equal to 2: Staphylococcus aureus, Enterobacter aerogenes, Pseudomomas aeruginosa bacteria, Methicillin-resistant Staphylococcus aureus and Escherichia coli (E.coli).

[0020] Under JIS Z 2801 (2000) test conditions, the glass and articles described herein according to one or more embodiments can exhibit a log reduction greater than or equal to 4 in the concentration of at least one of the following (e.g. , greater than or equal to a log reduction of 5): Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa, methicillin-resistant Staphylococcus aureus and Escherichia coli. Test conditions in modified JIS Z 2801 (2000) (hereinafter referred to as "modified JIS Z 2801 test for bacteria")

One or more embodiments of the glasses and articles described herein further exhibit a 4-log reduction (e.g., a 5-log reduction or greater) in the concentration of at least one of the following: golden yellow Staphylococcus, Enterobacter aerogenes, Pseudomonas aeruginosa, methicillin-resistant Staphylococcus aureus, and Escherichia coli. The modified JIS Z 2801 (2000) test for bacteria is described in more detail below.

In one or more embodiments, under the JIS Z 2801 (2000) test condition (hereinafter referred to as " the changed JIS Z 2801 for virus ") that is used to assess the change of virus, according to a The glasses and articles described herein of or various embodiments can exhibit a 2-log reduction or greater in the concentration of Murine Norovirus (e.g., a 4-log reduction or greater, or a greater than or equal to 5 log reduction). The modified JIS Z 2801 (2000) test for viruses is described in more detail below.

[0022] In some embodiments, glasses and articles may exhibit a log reduction as described herein (i.e., in EPA tests, JIS Z 2801 Test conditions under modified JIS Z 2801 test for bacteria and/or modified JIS Z 2801 test for viruses). The 1 month period or the 3 month period may begin at or after the glass is formed, or at or after the glass is bonded to the carrier.

[0023] In one or more embodiments, the article leaches copper ions when exposed to or contacts a leach solution. In one or more embodiments, the article leaches only copper ions when exposed to a leach solution comprising water.

[0024] The articles described herein may form housings for electronic devices.

[0025] A fourth aspect of the invention relates to a method of making an antimicrobial article. In one or more embodiments, the method comprises melting the glass composition to form a¹+ a glass of ionic and glassy phase, the glass being formed into at least one of particles and fibers, the at least one of particles and fibers being dispersed in a carrier, such as a polymer (as described herein), a single body or adhesive, thereby providing a filled carrier, and forming the filled carrier into an antimicrobial article. The glass composition may comprise the compositions described herein.

Propose other features and advantages of the present invention in the following detailed description, part feature and advantage wherein, for those skilled in the art, just find out easily according to done description, or comprise following detailed description, right by implementing Various embodiments described herein including claims and drawings are recognized.

[0027] It is to be understood that both the foregoing general description and the following detailed description are exemplary only, and are intended to provide a general overview or framework for understanding the nature and character of the claims. The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification. The drawings illustrate one or more implementations of the invention, and together with explain the principles and operations of the various implementations.

Accompanying drawing brief description

[0029] FIG. 1 is a side view of antimicrobial glass in sheet form, according to one or more embodiments;

[0030] FIG. 2 is a partially enlarged view of the antimicrobial glass shown in FIG. 1.

[0031] FIG. 3 is a perspective electron microscopy (TEM) image of an antimicrobial glass according to one or more embodiments;

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

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

[0034] FIG. 6 is an SEM image of antimicrobial glass according to one or more embodiments;

Figure 7A is the SEM energy-dispersive X-ray spectrum (EDX) hypermap (hypermap) of the cross-section of Example 30 after melting at 1650°C and annealing overnight at 650°C;

[0036] FIG. 7B is a SEM-EDX supergraph of a cross-section of Example 30 after quenching in water after melting at 1650°C; [0037] FIG. Fracture cross-section of 30;

[0038] FIG. 8B shows a polished cross-section of Example 30 after an additional heat treatment at 800° C. for 1 hour;

[0039] FIG. 9 shows the antimicrobial activity of glasses according to one or more embodiments;

[0040] FIG. 10 graphically shows the antimicrobial activity of antimicrobial glasses described herein after various time periods when formed into particles and combined with a polymeric carrier;

[0041] Figure 11 graphically shows the antimicrobial activity of various articles according to one or more embodiments; [0042] Figure 12 graphically shows the antimicrobial activity of various articles according to one or more embodiments; [0043] FIG. 13 graphically shows the antimicrobial activity of glasses with varying amounts of copper;

[0044] Figure 14 shows images of injection molded articles prepared from Example 12 and polymers; and

[0045] Figure 15 shows the antimicrobial activity of injection molded articles with and without different surface treatments according to one or more embodiments.

Detailed description

[0047] Reference will now be made in detail to various embodiments of the invention, examples of which are illustrated in the accompanying drawings.

[0048] A first aspect of the invention relates to antimicrobial glass compositions and glasses made from or comprising such compositions. The antimicrobial properties of the glass described herein include antiviral and/or bactericidal properties. As used herein, the term "antimicrobial" refers to a material or material surface that will kill or inhibit the growth of bacteria, viruses and/or fungi. The term as used herein does not imply that a material or material surface is capable of killing or inhibiting the growth of all microbial species in the group, but is capable of killing or inhibiting the growth of one or more microbial species from the group.

The term "logarithmic reduction" as used herein means Log(C_a/C₀), where C_a = number of colony forming units (CFU) on the antimicrobial surface, C₀ = number of colony forming units (CFU) of the control surface which is not an antimicrobial surface. For example, a 3 log reduction equals about 99.9% kill of bacteria, virus and/or fungi, 5 log reduction = kill of 99.999% of bacteria, virus and/or fungi.

[0050] In one or more embodiments, the antimicrobial glass comprises Cu species. In one or more alternative embodiments, the Cu species may comprise Cu¹⁺,Cu⁰, and/or Cu²⁺. The total amount of Cu species may be greater than or equal to about 10% by weight. However, as described in more detail below, making Cu²The amount of + is minimized or reduced so that the antimicrobial glass is substantially free of Cu²⁺. Cu¹The + ions may be present on or within the surface and/or bulk of the antimicrobial glass. In some embodiments, Cu¹+ ions are present in the glass network and/or glass matrix of the antimicrobial glass. When Cu¹+ ions are present in the glass network, Cu¹+ The ions are atomically connected to the atoms in the glass network. When Cu¹When + ions exist in the glass matrix, Cu¹+Ions can be dispersed in Cu in the glass matrix¹+ Exists in the form of crystals. In some embodiments Cu¹+Crystals contain cuprite (Cu₂O). In this embodiment, when there is Cu¹+ When crystalline, the material may be referred to as an antimicrobial glass-ceramic, which is used to refer to a special type of glass with crystals that may or may not be subjected to the traditional ceramization process by which the /or produce one or more crystalline phases. When Cu¹When the + ions are present in an amorphous form, the material can be referred to as an antimicrobial glass. In some embodiments, Cu¹+Crystal and Cu not associated with crystal¹+ ions are present in the antimicrobial glasses described herein.

[0051] In one or more embodiments, an antimicrobial glass can be formed from a composition that can include, in mole percent, from about 40 to about 70 SiO₂, about 0-about 20 Al₂o₃, about 10-about 30 copper-containing oxides, about 0-about 15 CaO, about 0-about 15 MgO, about 0-about 25 P₂o₅, about 0 to about 25 B₂o₃, about 0-about 20 K₂O, about 0-about 5 ZnO, about 0-about 20 Na₂O, and/or Fe from about 0 to about 5₂o₃. In this embodiment, the amount of copper-containing oxide is greater than that of Al₂o₃amount. In some embodiments, the composition may comprise R₂O content, where R can contain K, Na, Li, Rb, Cs and combinations thereof.

[0052] In an embodiment of the compositions described herein, SiO₂Used as the main glass-forming oxide. combination

SiO present in₂The amount should be sufficient to provide the glass exhibiting the desired chemical durability suitable for its use or application (eg, touch application, article housing, etc.). SiO can be selected₂to control the melting temperature of the compositions described herein. For example, excess SiO₂Melting temperatures at 200 poise can be driven to high temperatures at which defects such as clearing bubbles can appear, or be generated during processing and in the resulting glass. Furthermore, compared to most oxides, SiO₂Reduces compressive stresses formed by the ion exchange process of the resulting glass. In other words, with no excess SiO₂The compositions form glasses compared to those made with excess SiO₂The glass formed from the composition may not be ion-exchangeable to the same extent. Additionally or alternatively, the SiO present in the composition according to one or more embodiments₂Plastic deformation that can increase the existing shattering properties of the resulting glass. Increased SiO in glasses formed from compositions described herein₂The content can also increase the indentation fracture threshold of the glass.

[0053] In one or more embodiments, the composition comprises SiO in the following amounts in mole %₂: about 40-about 70, about 40-about 69, about 40-about 68, about 40-about 67, about 40-about 66, about 40-about 65, about 40-about 64, about 40-about 63, about 40-about 62, about 40-about 61, about 40-about 60, about 41-about 70, about 42-about 70, about 43-about 70, about 44-about 70, about 45-about 70, about 46 - About 70, about 47 - about 70, about 48 - about 70, about 49 - about 70, about 50 - about 70, about 41 - about 69, about 42 - about 68, about 43 - about 67 about 44 - about 66, About 45 to about 65, about 46 to about 64, about 47 to about 63, about 48 to about 62, about 49 to about 61, about 50 to about 60 and all ranges and subranges therebetween.

[0054] In one or more embodiments, the composition comprises Al in the following amounts in mole %₂o₃: about 0-about 20, about 0-about 19, about 0-about 18, about 0-about 17, about 0-about 16, about 0-about 15, about 0-about 14, about 0-about 13, about 0 - about 12, about 0 - about 11, about 0 - about 10, about 0 - about 9, about 0 - about 8, about 0 - about 7, about 0 - about 6, about 0 - about 5, about 0 - about 4, about 0 - about 3, about 0 - about 2, about 0 - about 1, about 0.1 - about 1, about 0.2 - about 1, about 0.3 - about 1, about 0.4 - about 1, about 0.5 - about 1, about 0 to about 0.5, about 0 to about 0.4, about 0 to about 0.3. From about 0 to about 0.2, from about 0 to about 0.1 and all ranges and subranges therebetween. In some embodiments, the composition is substantially free of Al₂o₃. As used herein, the term "substantially free" with respect to the components of the composition and/or resulting glass means that no active or deliberate This component is added to the composition, but this component may be present as an impurity. For example, a composition, glass, may be described as substantially free of a component when the component is present in an amount of less than about 0.01 mole percent.

[0055] Adjustable Al₂o₃to act as a glass-forming oxide and/or to control the viscosity of the molten composition. While not intending to be bound by theory, it is believed that when the alkali metal oxide (R₂O) with a concentration greater than or equal to Al₂o₃It was found that the aluminum ions form tetrahedral coordination with the alkali metal ions used as charge balancer. This tetrahedral coordination significantly enhances various post-processing (eg, ion exchange processes) of glasses formed from this composition. Divalent cationic oxides (RO) can also charge balance tetrahedral aluminum to various extents. While elements such as calcium, zinc, strontium, and collar behave equally as two basic ions, the high field strength of magnesium ions prevents them from fully charge-balancing aluminum when tetrahedrally coordinated, resulting in the formation of fivefold one and sixfold ones. Heavy-coordinated aluminum. Usually, Al₂o₃Can play an extremely important role in ion-exchangeable compositions and strengthened glasses because it achieves a strong network backbone (ie high strain point) while achieving a faster diffusion rate of alkali metal ions. However, when Al₂o₃When the concentration is too high, the composition can exhibit lower liquidus viscosity, therefore, the Al₂o₃The concentration is controlled within a reasonable range. Furthermore, as described in more detail below, it has been found that excess Al₂o₃Promote the formation of Cu²+ ions instead of the Cu required for formation¹+ ions.

[0056] In one or more embodiments, the composition comprises a copper-containing oxide in an amount of about 10 to about 50, about 10 to about 49, about 10 to about 48, in mole percent, About 10 - about 47, about 10 - about 46, about 10 - about 45, about 10 - about 44, about 10 - about 43, about 10 - about 42, about 10 - about 41, about 10 - about 40, about 10 -about 39,about 10-about 38,about 10-about 37,about 10-about 36,about 10-about 35,about 10-about 34,about 10-about 33,about 10-about 32,about 10-about 31, about 10-about 30, about 10-about 29, about 10-about

28, about 10 - about 27, about 10 - about 26, about 10 - about 25, about 10 - about 24, about 10 - about 23, about 10 - about 22, about 10 - about 21, about 10 - about 20, About 11-about 50, about 12-about 50, about 13-about 50, about 14-about 50, about 15-about 50, about 16-about 50, about 17-about 50, about 18-about 50, about 19 -about 50, about 20-about 50, about 10-about 30, about 11-about 29, about 12-about 28, about 13-about 27, about 14-about 26, about 15-about 25, about 16-about 24, about 17 to about 23, about 18 to about 22, about 19 to about 21 and all ranges and subranges therebetween. In one or more specific embodiments, the copper-containing oxide can be present in the composition in an amount of about 20 mole%, about 25 mole%, about 30 mole%, or about 35 mole%. Copper-containing oxides may contain CuO, Cu₂O and/or combinations thereof. [0057] The copper-containing oxide in the composition forms Cu present in the resulting glass¹+ ions. Copper can contain Cu⁰, Cu^{1 +} , and Cu²+Various forms are present in the composition and/or the glass comprising said composition. in Cu⁰or Cu¹The + form of copper provides antimicrobial activity. However, it is difficult to form and maintain antimicrobial copper in these states, and generally in known compositions, the formation of Cu²+ ions instead of the desired Cu0 or Cu¹+ ions.

[0058] In one or more embodiments, in the composition, the amount of copper-containing oxide is greater than Al₂o₃amount. While not intending to be bound by theory, it is believed that about the same amount of copper-containing oxide and Al in the composition₂o₃results in the formation of cuprite (CuO) instead of cuprite (Cu₂O). The presence of cupolite reduces the Cu¹The amount of + is favorable for Cu²⁺, thus resulting in reduced antimicrobial activity. Furthermore, when the amount of copper-containing oxide is approximately equal to the amount of Al2O3, the aluminum is preferably in quadruple coordination and the copper in the composition and resulting glass is still in Cu²+ form, so the charges are still balanced. When the amount of copper-containing oxide exceeds Al2O₃, then it is believed that at least a portion of the copper remains freely in the Cu¹+ state instead of Cu²+ state, so Cu¹The presence of + ions increases.

[0059] In one or more embodiments, in mole %, the composition comprises P in the following amounts₂o₅: about 0-about 25, about 0-about 22, about 0-about 20, about 0-about 18, about 0-about 16, about 0-about 15, about 0-about 14, about 0-about 13, about 0-about 12, about 0-about 11, about 0-about 10, about 0-about 9, about 0-about 8, about 0-about 7, about 0-about 6, about 0-about 5, about 0-about 4, about 0 - about 3, about 0 - about 2, about 0 - about 1, about 0.1 - about 1, about 0.2 - about 1, about 0.3 - about 1, about 0.4 - about 1, about 0.5 - about 1, About 0 to about 0.5, about 0 to about 0.4, about 0 to about 0.3, about 0 to about 0.2, about 0 to about 0.1 and all ranges and subranges therebetween. In some embodiments, the composition comprises about 10 mole % or about 5 mole % P₂o₅, or, can be substantially free of P₂o₅。

In one or more embodiments, P₂o₅At least a portion of the less durable or degradable phase in the glass is formed. The relationship between the degradable phase of the glass and the antimicrobial activity is described in more detail below. In one or more embodiments, P can be adjusted₂o₅amount, thereby controlling the crystallization of the composition and/or glass during the forming process. For example, when P₂o₅Limiting the amount to about 5 mole percent or less or even 10 mole percent or less can minimize crystallization, or control it to be uniform. However, in some embodiments, the amount or uniformity of crystallization of the composition and/or glass may not be of concern, therefore, the P used in the composition₂o₅The amount can be greater than 10 mol%.

[0061] In one or more embodiments, P in the composition can be adjusted based on the desired damage resistance of the glass₂o₅amount, although P₂o₅Tends to form less durable or degradable phases in the glass. While not intending to be bound by theory, relative to SiO₂,P₂o₅Can reduce melt viscosity. In some cases, it is believed that P₂o₅Helps to suppress the viscosity of amalgam decomposition (i.e., amalgam decomposition to form ZrO₂viscosity), and in this respect compared to SiO₂More effective. When the glass is chemically strengthened by an ion exchange process, when combined with what is sometimes called a network former (e.g., SiO₂and/or B₂o₃) compared to other components, P₂o₅It can improve the diffusion coefficient and reduce the ion exchange time.

In one or more embodiments, in mole %, described composition comprises B with following amount₂o₃: about 0-about 25, about 0-about 22, about 0-about 20, about 0-about 18, about 0-about 16, about 0-about 15, about 0-about 14, about 0-about 13, about 0-about 12, about 0-about 11, about 0-about 10, about 0-about 9, about 0-about 8, about 0-about 7, about 0-about 6, about 0-about 5, about 0-about 4, about 0 - about 3, about 0 - about 2, about 0 - about 1, about 0.1 - about 1, about 0.2 - about 1, about 0.3 - about 1, about 0.4 - about 1, about 0.5 - about 1, about 0-about 0.5, about 0-about

0.4, about 0 to about 0.3, about 0 to about 0.2, about 0 to about 0.1 and all ranges and subranges therebetween. In some embodiments, the composition comprises a non-zero amount of B₂o₃, which may be, for example, about 10 mol % or about 5 mol %. Compositions of some embodiments may be substantially free of b₂o₃。

In one or more embodiments, B₂o₃A less durable or degradable phase forms in the glass formed from the composition. The relationship between the degradable phase of the glass and the antimicrobial activity is described in more detail below. While not intending to be bound by theory, it is believed that in the composition b₂o₃confers damage resistance in glasses containing this composition, although B₂o₃Tends to form less durable or degradable phases in the glass. The composition of one or more embodiments comprises one or more alkali metal oxides (R₂O) (for example, Li₂O,Na₂O,K₂O,Rb₂O and/or Cs₂o). In some embodiments, the alkali metal oxide alters the melting temperature and/or liquidus temperature of such compositions. In one or more embodiments, the amount of alkali metal oxide can be adjusted to provide a composition exhibiting a lower melting temperature and/or a lower liquidus temperature. While not intending to be bound by theory, the addition of alkali metal oxides can increase the coefficient of thermal expansion (CTE) and/or reduce the chemical durability of antimicrobial glasses comprising such compositions. In some cases, these performance characteristics can be altered significantly by the addition of alkali metal oxides.

[0064] In some embodiments, the antimicrobial glasses described herein can be chemically strengthened by an ion exchange process, where the presence of minor amounts of alkali metal oxides such as Li₂O and Na₂O) to facilitate interaction with larger alkali metal ions (e.g., K⁺), such as exchanging a smaller alkali metal ion from an antimicrobial glass with a larger alkali metal ion from a molten salt bath containing such larger alkali metal ions. Generally three types of ion exchange can be performed. One such ion exchange contains Na⁺-for-Li⁺In exchange, this yields a deeper layer depth but lower compressive stress. Another such ion exchange contains K⁺ -for-Li⁺In exchange, this results in smaller layer depths but larger compressive stresses. A third such ion exchange contains K⁺1 for -Na⁺exchanged, which yields intermediate layer depths and compressive stresses. In compositions, sufficiently high concentrations of smaller alkali metal oxides may be required to create larger compressive stresses in antimicrobial glasses comprising such compositions, since compressive stress is related to the exchange of alkali metal ions from the antimicrobial glass. The numbers are proportional.

In one or more embodiments, in mole %, described composition comprises K with following amount₂O: about 0-about 20, about 0-about 18, about 0-about 16, about 0-about 15, about 0-about 14, about 0-about 13, about 0-about 12, about 0-about 11, about 0 - about 10, about 0 about 9, about 0 - about 8, about 0 - about 7, about 0 - about 6, about 0 - about 5, about 0 - about 4, about 0 - about 3, about 0 - About 2, about 0 - about 1, about 0.1 - about 1, about 0.2 - about 1, about 0.3 - about 1, about 0.4 - about 1, about 0.5 - about 1, about 0 - about 0.5, about 0 - about 0.4 , about 0 to about 0.3, about 0 to about 0.2, about 0 to about 0.1 and all ranges and subranges therebetween. In some embodiments, the composition comprises a non-zero amount of K₂O, alternatively the composition may be substantially free of, as defined herein, K₂O. In addition to facilitating ion exchange, when applicable, in one or more embodiments, K₂O can also form less durable or degradable phases in the glass formed from the composition. The relationship between the degradable phase of the glass and the antimicrobial activity is described in more detail below.

In one or more embodiments, in mol%, described composition comprises Na with following amount₂O: about 0-about 20, about 0-about 18, about 0-about 16, about 0-about 15, about 0-about 14, about 0-about 13, about 0-about 12, about 0-about 11, About 0-about 10, about 0-about 9, about 0-about 8, about 0-about 7, about 0-about 6, about 0-about 5, about 0-about 4, about 0-about 3, about 0 - about 2, about 0 - about 1, about 0.1 about 1, about 0.2 - about 1, about 0.3 - about 1, about 0.4 - about 1, about 0.5 - about 1, about 0 - about 0.5, about 0 - about 0.4 , about 0 to about 0.3, about 0 to about 0.2, about 0 to about 0.1 and all ranges and subranges therebetween. In some embodiments, the composition comprises a non-zero amount of Na₂O, alternatively the composition may be substantially free of, as defined herein, Na₂O.

[0067] In one or more embodiments, the composition may comprise one or more divalent cationic oxides, such as alkaline earth oxides and/or ZnO. Such divalent cationic oxides may be included to improve the melt properties of the composition. As for ion exchange performance, the presence of divalent cation oxides can be used to reduce the basic mobility, so when using larger divalent cations

Oxides can have a negative impact on ion exchange performance. In addition, smaller divalent cation oxides generally contribute more to the development of compressive stress in ion-exchanged glasses than larger divalent cation oxides. Thus, divalent cationic oxides such as MgO and ZnO have many advantages for improving stress relaxation while minimizing negative effects on alkali metal diffusivity.

[0068] In one or more embodiments, in mole %, the composition comprises CaO in an amount of about 0 to about 15, about 0 to about 14, about 0 to about 13, about 0 to about 12, about 0 - about 11, about 0 - about 10, about 0 - about 9, about 0 - about 8, about 0 - about 7, about 0 - about 6, about 0 - about 5, about 0 - about 4, about 0 - about 3, about 0 - about 2, about 0 - about 1, about 0.1 - about 1, about 0.2 - about 1, about 0.3 - about 1, about 0.4 about 1, about 0.5 - about 1, about 0 - About 0.5, about 0 to about 0.4, about 0 to about 0.3, about 0 to about 0.2, about 0 to about 0.1 and all ranges and subranges therebetween. In some embodiments, the composition is substantially free of CaO.

[0069] In one or more embodiments, the composition comprises MgO in mole % in an amount of about 0 to about 15, about 0 to about 14, about 0 to about 13, about 0 to about 12, about 0 - about 11, about 0 - about 10, about 0 - about 9, about 0 - about 8, about 0 - about 7, about 0 - about 6, about 0 - about 5, about 0 - about 4, about 0 - about 3, about 0 - about 2, about 0 - about 1, about 0.1 - about 1, about 0.2 - about 1, about 0.3 - about 1, about 0.4 about 1, about 0.5 - about 1, about 0 - About 0.5, about 0 to about 0.4, about 0 to about 0.3, about 0 to about 0.2, about 0 to about 0.1 and all ranges and subranges therebetween. In some embodiments, the composition is substantially free of MgO.

In mole %, the composition of one or more embodiments can comprise ZnO with following amount: about 0-about 5, about 0-about 4, about 0-about 3, about 0-about 2, about 0-about 1, about 0.1-about 1, about 0.2-about 1, about 0.3-about 1, about 0.4-about 1, about 0.5-about 1, about 0-about 0.5, about 0-about 0.4, about 0- About 0.3, about 0 to about 0.2, about 0 to about 0.1 and all ranges and subranges therebetween. In some embodiments, the composition is substantially free of ZnO.

[0071] In mole percent, the composition of one or more embodiments may comprise Fe in the following amounts₂o₃: about 0-about 5, about 0-about 4, about 0-about 3, about 0-about 2, about 0-about 1, about 0.1-about 1, about 0.2-about 1, about 0.3-about 1, about 0.4 - about 1, about 0.5 to about 1, about 0 to about 0.5, about 0 to about 0.4, about 0 to about 0.3 about 0 to about 0.2, about 0 to about 0.1 and all ranges and subranges therebetween. In some embodiments, the composition is substantially free of Fe₂o₃。

[0072] In one or more embodiments, the composition may include one or more colorants. Examples of such colorants include NiO, TiO₂,Fe₂o₃,Cr₂o₃,Co₃o₄and other known colorants. In some embodiments, one or more colorants may be present in an amount up to about 10 mole percent. In some cases, one or more colorants can be present in the following amounts: about 0.01 mole % to about 10 mole %, about 1 mole % to about 10 mole %, about 2 mole % to about 10 mole %, about 5 mole % is about 10 mole %, about 0.01 mole % to about 8 mole %, or about 0.01 mole % to about 5 mole %.

[0073] In one or more embodiments, the composition may comprise one or more nucleating agents. Exemplary nucleating agents include TiO₂, ZrO₂and other nucleating agents known in the art. The composition may contain one or more different nucleating agents. The nucleating agent content of the composition may range from about 0.01 mole percent to about 1 mole percent. In some cases, the nucleating agent content can be from about 0.01 mole % to about 0.9 mole %, from about 0.01 mole % to about 0.8 mole %, from about 0.01 mole % to about 0.7 mole %, from about 0.01 mole % to about 0.6 mole % , about 0.01 mole % - about 0.5 mole %, about 0.05 mole % - about 1 mole %, about 0.1 mole % - about 1 mole %, about 0.2 mole % - about 1 mole %, about 0.3 mole % - about 1 mole % , or from about 0.4 mole percent to about 1 mole percent, and all ranges and subranges therebetween.

[0074] The glass formed from the composition may comprise a plurality of Cu¹+ ions. In some embodiments, this Cu¹+ ions form part of the glass network and can be characterized as glass modifiers. While not intending to be bound by theory, when Cu¹When + ions are part of the glass network, it is believed that in a typical glass-forming process, the cooling step of the molten glass proceeds too rapidly to achieve copper-containing oxides (e.g., CuO and/or Cu₂O) crystallization. Therefore, Cu¹+ remains in an amorphous state and becomes part of the glass network. In some cases, whether in the crystalline phase or in the glass matrix, Cu¹The total amount of + ions can be even

To higher, for example up to 40 mole %, up to 50 mole %, or up to 60 mole %.

[0075] In one or more embodiments, the glass formed from the compositions described herein comprises Cu¹+ ions, which act as Cu¹+ Crystals are dispersed in a glass matrix. In one or more embodiments, Cu¹+Crystals can exist in the form of cuprite. Cuprite present in glass can form a phase distinct from the glass matrix or glass phase. In other embodiments, cuprite may form part of, or may be associated with, one or more glassy phases (eg, the durable phases described herein). Cu¹+ Crystals may have the following average major dimensions: about 5 micrometers (um) or less, 4 micrometers (um) or less, 3 micrometers (um) or less, 2 micrometers (um) or less, about 1.9 micrometers (um) or less, about 1.8 microns (um) or less, about 1.7 microns (um) or less, about 1.6 microns (um) or less, about 1.5 microns (um) or less, about 1.4 microns (um) or less, about 1.3 microns (um) or less, about 1.2 microns (um) or less, about 1.1 microns or less, 1 micron or less, about 0.9 microns (um) or less Small, about 0.8 microns (um) or less, about 0.7 microns (um) or less, about 0.6 microns (um) or less, about 0.5 microns (um) or less, about 0.4 microns (um) or less Small, about 0.3 micrometer (um) or less, about 0.2 micrometer (um) or less, about 0.1 micrometer (um) or less, about 0.05 micrometer (um) or less, and all ranges in between and subranges. As used herein, and referring to the term "average major dimension", the word "average" refers to the average value and the word "principal dimension" is the largest dimension of a particle as measured with a SEM. In some embodiments, the cuprite phase can be present in the antimicrobial glass in an amount of at least about 10%, at least about 15%, at least about 20%, at least about 25%, and at least about 25% by weight of the antimicrobial glass. All ranges and subranges in between.

[0076] In some embodiments, the glass may comprise about 70% by weight or more Cu¹+ and about 30% by weight or less of

Cu²⁺°Cu²The + ions are present in the form of cupolite and/or even in the form of glass (ie not as a crystalline phase).

In some embodiments, the total amount of Cu in the glass can be about 10 to about 30, about 15 to about 25, about 11 to about 30, about 12 to about 30, about 13 to about 30 in weight percent. 30, about 14-about 30, about 15-about 30, about 16-about 30, about 17-about 30, about 18-about 30, about 19-about 30, about 20-about 30, about 10-about 29, About 10-about 28, about 10-about 27, about 10-about 26, about 10-about 25, about 10-about 24, about 10-about 23, about 10-about 22, about 10-about 21, about 10 - about 20, about 16 to about 24, about 17 to about 23, about 18 to about 22, about 19 to about 21 and all ranges and subranges therebetween. In one or more embodiments, Cu in the glass¹The ratio of + ions to the total amount of Cu 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 subranges in between. Cu amount and Cu¹The ratio of + ions to total Cu can be determined using inductively coupled plasma (ICP) techniques well known in the art.

[0078] In some embodiments, the glass can exhibit a specific Cu²+ Larger amount of Cu¹+ and/or Cu0. For example, taking Cu in glass¹⁺,Cu²The total amount of + and Cu0 is the benchmark, Cu¹+ and Cu⁰The sum of the percentages may be about 50% to about 99.9%, about 50% to about 99%, about 50% to about 95%, about 50% to about 90%, about 55% to about 99.9%, about 60% to About 99.9%, about 65% - about 99.9%, about 70% - about 99.9%, about 75% - about 99.9%, about 80% - about 99.9%, about 85% - about 99.9%, about 90% - about 99.9% %, about 95% to about 99.9%, and all ranges and subranges therebetween. Cu¹⁺,Cu²+ and Cu⁰The relative amount of can be determined using X-ray fluorescence spectroscopy (XPS) techniques well known in the art. The table below reports these quantities as measured by XPS. Specifically, the table reports that Cu²+ amount and Cu¹+ and Cu⁰The sum of the quantities. While not intending to be bound by theory, it is believed that most of the embodiments shown in Table 1 show that under the conditions under which the XPS was performed, copper was¹The form of + exists.

[0079] The antimicrobial glass comprises at least a first phase and a second phase. In one or more embodiments, the antimicrobial glass may comprise two or more phases, wherein the phases differ based on the ability of the linkages of atoms in a given phase to withstand interaction with the leach solution. Specifically, the glass of one or more embodiments may comprise a first phase that may be described as a degradable phase and a second phase that may be described as a durable phase. The terms "first phase" and "degradable phase" are used interchangeably. The term "second phase"

Used interchangeably with "durable phase". As used herein, the term "durable" refers to the tendency of the atomic linkages of a durable phase to remain intact during and after interaction with a leach solution. As used herein, the term "degradable" refers to the tendency of a degradable phase to break down the atomic linkages during and after interaction with one or more leach solutions. In one or more embodiments, the durable phase comprises SiO₂, the degradable phase contains B₂o₃,P₂o₅and R₂At least one of O (wherein R may contain any one or more of K, Na, Li, Rb and Cs). While not intending to be bound by theory, it is believed that components of the degradable phase (i.e., B₂0yp₂o₅and/or R₂O) It is easier to interact with the leach solution, and the connections between these components and the links of other components in the antimicrobial glass are more easily broken during or after the interaction with the leach solution. The leach solution may contain water, acid or other similar materials. In one or more embodiments, the degradable phase is resistant to degradation for 1 week or longer, 1 month or longer, 3 months or longer, or even 6 months or longer. In some embodiments, longevity can be characterized as maintaining antimicrobial efficacy over a specified period of time.

[0080] In one or more embodiments, the durable phase is present in an amount greater than the degradable phase by weight. In some cases, the degradable phase forms an island, and the durable phase forms a sea surrounding the island (ie, the durable phase). In one or more embodiments, one or both of the durable phase and the degradable phase may comprise cuprite. In such embodiments, the cuprite may be dispersed in each phase or in both phases.

[0081] In some embodiments, phase separation occurs without the use of 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 a temperature up to and including about 1600°C or 1650°C. While cooling the glass, keep the phases separated.

[0082] The antimicrobial glass may be provided as a sheet, or may have another shape such as particles, fibers, or the like. In one or more embodiments, as shown in FIGS. 1 and 2 , antimicrobial glass 100 includes surface 101 and surface portion 120 extending from surface 101 into the antimicrobial glass at a depth of less than or equal to about 5 nanometers (nm). The surface portion may comprise a plurality of copper ions, wherein at least 75% of the plurality of copper ions comprises Cu¹⁺-ion. For example, in some cases, 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 Contains 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 smaller) containing Cu²+ ions. For example, in some cases, 20% or less, 15% or less, 10% or less, 5% or less, 2% or less, 1% or less of the plurality of copper ions in the surface portion Small, 0.5% or less or 0.01% or less contains Cu²+ ions. In some embodiments, controlling Cu in antimicrobial glass¹+ Surface concentration of ions. In some cases, about 4 Ppm or greater Cu can be provided on the antimicrobial glass surface¹+ ion concentration.

[0083] The antimicrobial glass of one or more embodiments can provide a log reduction greater than or equal to 2 logarithmic in the concentration of at least one of the following (e.g., 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5 and all ranges and subranges in between): Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa, MRSA and Escherichia coli. In some cases, 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 the following under EPA testing: Staphylococcus aureus, Enterobacter aerogenes, Green Pseudomonas pyogenes, methicillin-resistant Staphylococcus aureus, and Escherichia coli.

[0084] Under the test conditions of JIS Z 2801 (2000), the glass described herein according to one or more embodiments can exhibit a logarithmic reduction of at least one of the following concentrations greater than or equal to 4 (for example, greater than or equal to a log reduction of 5): Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa, methicillin-resistant Staphylococcus aureus and Escherichia coli. One or more embodiments of the glasses described herein also exhibit a 4-log reduction or greater in the concentration of at least one of the following (e.g., greater than or equal to logarithmic reduction of 5): golden yellow grapes

cocci, Enterobacter aerogenes, Pseudomonas aeruginosa, methicillin-resistant Staphylococcus aureus and Escherichia coli. As used herein, the modified JIS Z 2801 test for bacteria involves evaluating bacteria under the standard JIS Z 2801 (2000) test with modified conditions, including at a humidity of about 38% to about 42%, the glass Or the article is heated to a temperature of about 23°C to about 37°C and held for about 6 hours.

[0085] In one or more embodiments described herein, the antimicrobial glass exhibits a log reduction of greater than or equal to 2 logs for murine norovirus under a modified JIS Z 2801 test for viruses, greater than or equal to 3 log reduction, greater than or equal to 4 log reduction, or greater than or equal to 5 log reduction. The modified JIS Z 2801 (2000) test for viruses includes the following steps. For each material to be tested (e.g., an article or glass of one or more embodiments, a control material, and any comparative glass or article), inoculate 3 separate material samples (contained in a single sterile petri dish) 20 microliter aliquots of test virus (where antimicrobial activity was measured), or organic soil-loaded test medium (where cytotoxicity was measured) included 5% fetal calf serum with or without test virus. The inoculum is then covered with a membrane and the membrane is pressed down so that the test virus and/or test medium spreads over the membrane but does not spread beyond the edge of the membrane. The exposure time begins when each sample is inoculated. The inoculated samples were then transferred to a control chamber set to room temperature (approximately 20°C) at 42% relative humidity for 2 hours. The exposure times for the control samples are as follows. After 2 hours of exposure time, Lift the membrane using sterile forceps and pipette 2.00 mL aliquots of the test virus and/or test medium individually onto each material sample with the underside of the membrane (or the side of the membrane exposed to the sample) sides) are used to cover each sample. The surface of each sample was scraped individually using a sterile plastic cell scraper to collect test virus or test medium. Collect (in 10^-2Dilution) test virus and/or test medium, use a vortex mixer to mix, and prepare a series of 10-fold dilutions. The dilutions are then assessed for antimicrobial activity and/or cytotoxicity.

In order to prepare the control sample for testing antimicrobial activity (it is also referred to as " zero time virus control ") for the JIS Z 2801 test that is used for changing for virus, give 3 control samples respectively (contained in separate Inoculate a 20 μl aliquot of the test virus. Immediately after inoculation, a 2.00 mL aliquot of test virus was pipetted onto each control sample. The surface of each sample was scraped individually using a sterile plastic cell scraper to collect the test virus. Collect (in 10^-2Dilution) to test the virus, use a vortex mixer to mix, and prepare a series of 10-fold dilutions. Evaluate the antimicrobial activity of the dilution.

In order to prepare the control sample for cytotoxicity (it is also referred to as " 2 hours control virus ") for the JIS Z 2801 test of change for virus, be 1 control sample (contained in separate sterile Petri dish) was inoculated with a 20 μl aliquot of test medium containing an organic soil load (5% fetal bovine serum) but no test virus. The inoculum was covered with a membrane and the membrane was squeezed so that the test medium spread across the membrane, but not beyond the edge of the membrane. The exposure time began when each control sample was inoculated. The control samples were transferred to a control room set to room temperature (20°C) at a relative humidity of 42% and kept for a duration of exposure time of 2 hours. After this exposure time, the membrane was lifted using sterile forceps, and a 2.00 ml aliquot of test medium was individually pipetted onto each control sample and the underside of the membrane (the side exposed to the sample) ). The surface of each sample was scraped individually using a sterile plastic cell scraper to collect the test medium. Collect (in 10^-2dilution) test medium, mixed using a vortex mixer, and prepared a series of 10-fold dilutions. Assess the cytotoxicity of the dilutions.

[0088] The antimicrobial glass of one or more embodiments can exhibit a log reduction as described herein over an extended period of time. In other words, the antimicrobial glass can exhibit extended or prolonged antimicrobial efficacy. For example, in some embodiments, up to 1 month, up to 3 months after forming the antimicrobial glass or after combining the antimicrobial glass with a carrier (e.g., polymer, monomer, binder, solvent, etc.) months, up to 6 months, or up to 12 months, anti-

The microbial glass may exhibit a log reduction under the EPA test, the JIS Z 2801 (2000) test conditions, the modified JIS Z 2801 test for bacteria, and/or the modified JIS Z 2801 test for viruses described herein. These time periods may begin at or after forming the antimicrobial glass or combining the antimicrobial glass with the carrier.

[0089] In one or more embodiments, the antimicrobial glass can exhibit anti-corrosion functionality when combined with the carriers described herein. In such embodiments, the antimicrobial glass kills or eliminates or reduces the growth of various contaminants in the carrier. Contamination includes fungi, bacteria, viruses and combinations thereof.

[0090] In one or more embodiments, the glasses and/or articles described herein leach copper ions when exposed to or contacted with a leach solution. In one or more embodiments, the glass leaches only copper ions when exposed to a leach solution comprising water.

[0091] In one or more embodiments, the antimicrobial glasses and/or articles described herein can have a tunable release of antimicrobial activity. The antimicrobial activity of the glass and/or article is produced by contact between the antimicrobial glass and a leach solution (e.g. water) which results in Cu¹+ Ions are released from the antimicrobial glass. This effect can be described as water solubility, and water solubility can be adjusted to control Cu⁺¹release of ions.

[0092] In some embodiments, when Cu¹+ As the ions settle in and/or form atomic connections with atoms in the glass network, water or humidity breaks those connections, and the Cu¹+Ions are available for release and can be exposed on glass or glass-ceramic surfaces.

[0093] In one or more embodiments, the antimicrobial glass can be formed in low cost melting tanks, which are commonly used to melt glass compositions such as soda lime silicates. The antimicrobial glass can be formed into a sheet using processes known in the art. For example, example forming methods include floating glass processes, and down-draw methods such as fusion draw and slot draw.

[0094] Antimicrobial glass can be incorporated into various articles alone or in combination with other materials, such as electronic devices (such as mobile phones, smart phones, tablet computers, video players, information terminal equipment, notebook computers, etc.), architectural structures ( such as countertops or walls), appliances (such as cooktops, refrigerator doors, and dishwasher doors, etc.), information displays (such as whiteboards), and automotive components (such as fenders, windshields, window assemblies, etc.). When used in such articles, the antimicrobial glass may form at least a portion of the housing and/or display.

[0095] After forming, the antimicrobial glass can be formed into a sheet and can be shaped, polished, or otherwise treated for the desired end use. In some cases, the antimicrobial glass can be ground into powder or granular form. In other embodiments, particulate antimicrobial glass can be combined with other materials or carriers into articles for various end-use applications. Combinations of antimicrobial glass and such other materials or carriers may be suitable for injection molding, extrusion or coating or may be drawn into fibers. Such other materials or carriers may comprise polymers, monomers, binders, solvents, or combinations thereof as described herein. Polymers used in embodiments described herein may include thermoplastic polymers, polyolefins, cured polymers, ultraviolet or UV-cured polymers, polymer emulsions, solvent-based polymers, and combinations thereof. Examples of suitable polymers include, but are not limited to: thermoplastic resins, including polystyrene (PS), high impact PS, polycarbonate (PC), nylon (sometimes referred to as polyamide (PA)), poly(propylene Nitrile-butadiene-styrene) (ABS) , PC-ABS blends, polybutylene terephthalate (PBT) and PBT copolymers, polyethylene terephthalate (PET) and PET copolymers, polyolefins (PO), which include Polyethylene (PE), polypropylene (PP), cyclic polyolefins (cyclic-PO), modified polypropylene oxide (mPPO), polyvinyl chloride (PVC), acrylic polymers, including polymethyl Methyl acrylate (PMMA), thermoplastic elastomer (TPE), thermoplastic polyurethane (TPU), polyetherimide (PEI) and blends of these polymers. Suitable injection moldable thermoset polymers include epoxy, acrylic, styrenic, phenolic, melamine, urethane, polyester, and silicone resins. in other implementations

In , the polymer can be dissolved in a solvent, or dispersed in a solvent as a separate phase and form a polymer emulsion, such as latex (which is an aqueous emulsion of synthetic rubber or natural rubber, or a plastic obtained by polymerization, and is used in particular For coatings (as paints) and adhesives). The polymer may contain fluorinated silanes or other low or anti-friction materials. The polymer may 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 Colorant. Specific examples of monomers include catalyst-curable monomers, heat-curable monomers, radiation-curable monomers, and combinations thereof.

[0096] In one example, an acrylic latex paint can be combined with 20% by weight antimicrobial glass in particle form and having a diameter of about 5 micrometers (pm). In some embodiments, the resulting combination of paint and antimicrobial glass comprises about 4% by weight CuO. In one or more embodiments, the antimicrobial glass may range from about 50% to about 85% by weight when combined with a carrier such as a polymer, monomer, binder, or solvent. In some embodiments, the antimicrobial glass may be present in an amount of about 55% to about 85% by weight, about 60% to about 85% by weight, about 65% by weight, based on the total weight of the antimicrobial glass and carrier. % to about 85% by weight, about 50% to about 80% by weight, about 50% to about 75% by weight, about 50% to about 70% by weight and all ranges and subranges therebetween. In such an embodiment, the total amount of CuO present may be about 20% by weight. In other embodiments, the Cu present in the antimicrobial glass and carrier combination₂The amount of O may range from about 10% to about 20% by weight or specifically, about 15%. The ratio of antimicrobial glass to carrier may be from about 90:10 to about 10:90, or specifically about 50:50, in volume percent.

[0097] In one or more embodiments, the antimicrobial glass may be provided in granular form and may have the following diameters: About 0.1 micron (pm) (pm) - about 10 micron (pm) (pm), about 0.1 micron (pm) (pm) - about 9 micron (pm) (pm), about 0.1 micron (pm) (pm) - about 8 Micron (pm) (pm), about 0.1 micron (pm) (pm) - about 7 micron (pm) (pm), about 0.1 micron (pm) (pm) - about 6 micron (pm) (pm), about 0.5 Micron (pm) (pm) - about 10 micron (pm) (pm), about 0.75 micron (pm) (pm) - about 10 micron (pm) (pm), about 1 micron (pm) (pm) - about 10 Micron (pm) (pm), about 2 microns (pm) (pm) - about 10 microns (pm) (pm), about 3 microns (pm) (pm) - about 10 microns (pm) (pm) about 3 microns (pm) (pm) - about 6 microns (pm) (pm), about 3.5 microns (pm) (pm) - about 5.5 microns (pm) (pm), about 4 microns (pm) (pm), - about 5 Micrometer (pm) (pm), and all ranges and subranges in between. The particulate antimicrobial glass can be substantially spherical or can have an irregular shape. Particles may be provided in a solvent and then dispersed in a vehicle as described elsewhere herein.

[0098] While not intending to be bound by theory, it is believed that₂The combination of antimicrobial glass and carrier described herein (eg, latex paint) provides significantly greater antimicrobial efficiency than the same latex paint of O (Cuprite), even when the same amount of copper is used. Cu in the antimicrobial glass described herein¹+Crystalline present, even when present as cuprite, tends to remain in Cu¹+status. While not intending to be bound by theory, it is believed that when Cu alone provides₂When O, separated from the glass described in this paper, Cu ions are more unstable and can be separated from Cu¹+ becomes Cu²⁺。

[0099] The antimicrobial properties of the articles described herein can be affected by the presence of a thin layer of polymer on the surface of the article. This thin layer can be rendered hydrophobic and can block reactive copper species (Cu¹⁺) exposed to air, or leached to the surface. In one or more embodiments, the article may utilize a polymer with balanced hydrophobic-hydrophilic properties that facilitates leaching of active copper species. Examples of such polymers include hygroscopic/water soluble polymers and surfactants, amphoteric polymers and/or combinations of amphoteric polymers and hygroscopic materials. In one or more embodiments, exposure to air and/or leaching of reactive copper species to the surface can be facilitated by providing the article 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 treatment (e.g., air, n₂,o₂,h₂,n₂and/or argon-based plasma) and will remove polymer

Other methods for thin layers of material. In one or more alternative embodiments, the exposed treated surface comprises functional groups, particularly hydroxyl and carbonyl groups, introduced into or accessible to the exposed treated surface, thereby rendering such surface more hydrophilic. By providing an exposed treated surface, the active copper species is exposed to the air, or more easily leached from the surface of the article.

[0100] 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/processing agents may be included in the articles described herein. Auxiliary. Exemplary processing reagents/processing aids may comprise solid or liquid materials. Processing agents/aids can provide various extrusion benefits and can include silicone-based oils, waxes, and free-flowing fluoropolymers. In other embodiments, processing reagents/processing aids may include compatibilizers/coupling agents, such as organosilicon compounds, such as organosilanes/siloxanes commonly used in processing polymer composites, to improve mechanical properties and thermal nature. Such compatibilizers/coupling agents are useful for surface modification of glass and may include (3-3-acryloyloxy-propyl)trimethoxysilane; N-(2-aminoethyl)-3-amino Propyltrimethoxysilane; 3-aminopropyltri-ethoxysilane; 3-aminopropyltrimethoxysilane; (3-glycidylpropyl)trimethoxysilane; 3-mercapto-propyltrimethoxysilane 3-methacryloxypropyltrimethoxysilane; and vinyltrimethoxysilane.

[0101] In some embodiments, the articles described herein may comprise pigment-containing fillers, which are typically metal-based inorganics to which additional color and other purposes may be added, such as aluminum pigments, copper pigments, cobalt pigments, manganese Pigments, iron pigments, titanium pigments, tin pigments, clay pigments (naturally occurring iron oxides), carbon pigments, antimony pigments, collar pigments, and zinc pigments.

[0102] After combining the antimicrobial glass described herein with the carrier as described herein, the combination can be formed into a desired article. Examples of such articles include electronic devices (such as mobile phones, smartphones, tablet computers, video players, information terminal equipment, laptops, etc.), building structures (such as countertops or walls), electrical appliances (such as cooktops, refrigerators) doors and dishwasher doors, etc.), information displays (e.g. whiteboards), and housings for automotive components (e.g. fenders, windshields, window assemblies, etc.).

[0103] In one or more embodiments, the article can exhibit a desired porosity and can be made in different shapes, including complex shapes and in different forms, including plastics, rubbers, and fibers/fabrics, which Can have the same or different applications. Porous articles can also be used as antimicrobial filters. For example, the article can be extruded into a honeycomb structure that contains not only channels but also porous channel walls.

[0104] In other embodiments, the article may comprise a high glass loading. Such articles can be formed by melt or wet processes. In such an embodiment, in addition to using the article itself as an antimicrobial material, the polymer can be burned off or removed to provide a pure copper glass antimicrobial article that is porous and has simple or complex shapes.

Cu(I) is an excellent catalyst for organic reactions, especially mild organic reactions such as the polymerization of acrylic acid monomers and oleochemical applications (e.g. hydrogenolysis of fatty esters to fatty alcohols, including methyl esters and wax ester processes, alkylation of alcohols with amines and amination of fatty alcohols) and more. The articles described herein are useful in such applications.

[0106] See Figure 13 for examples of various uses and applications of the articles described herein.

The articles described herein comprising antimicrobial glass and polymers exhibit a greater than or equal to 2 log reduction in the concentration of at least one of the following under EPA testing: Staphylococcus aureus, Enterobacter aerogenes , Pseudomonas aeruginosa, methicillin-resistant Staphylococcus aureus and Escherichia coli. In some cases, the preparation 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 the following under the EPA test: Staphylococcus aureus, Enterobacter aerogenes, Green Pseudomonas pyogenes, methicillin-resistant Staphylococcus aureus, and Escherichia coli.

Under the JIS Z 2801 (2000) test conditions and/or the JIS Z 2801 test that is used for bacteria of change, the article described herein according to one or more embodiments can make the concentration of following at least one Presenting a log reduction greater than or equal to 2 (eg, log reduction greater than or equal to 3, log reduction greater than or equal to 4, log reduction greater than or equal to 5):

Staphylococcus aureus, Enterobacter aerogenes, Pseudomonas aeruginosa, methicillin-resistant Staphylococcus aureus, and Escherichia coli. One or more embodiments of the articles of manufacture described herein also exhibit a greater than or equal to 4 log reduction in murine norovirus (strain MNV-1 ) under the modified JIS Z 2801 test for viruses (e.g., logarithmic reduction greater than or equal to 5).

[0109] The article of one or more embodiments can exhibit a log reduction as described herein over an extended period of time. In other words, the article may exhibit extended or prolonged antimicrobial efficacy. For example, in some embodiments, the article is up to 1 month, up to 3 months, up to 6 months, or up to 12 months after forming the antimicrobial glass or after combining the antimicrobial glass with the carrier. A log reduction in bacteria and/or viruses described herein may be exhibited. These time periods may begin at or after forming the antimicrobial glass or combining the antimicrobial glass with the carrier.

[0110] In one or more embodiments, an article can include a coating that can be applied on a surface to form a coated surface. The coated surface can exhibit a stable color that does not undergo significant change after exposure to a particular environment. For example, the coated surface may exhibit a delta (A)E of less than about 2, or even less than about 1 after exposure for 7 days at 100% relative humidity and 38° C., as measured according to ASTM D2247. As used herein, the term "delta(A)E" refers to the total color distance provided in the CIELAB color space as measured by the distance between two color coordinates (limit = same center)2 + (period Household Eleven corpses).

[0111] The coated surfaces also exhibited chemical durability to various chemicals as measured according to ASTM D1308 after exposing the chemicals to the center of the test piece for 1 hour.

[0112] The articles described herein may include pigments to impart color. Thus, coatings prepared from such articles can exhibit various colors depending on the color of the carrier, the mixture of carriers, and the amount of particle loading. Furthermore, the articles and/or coatings described herein exhibit no adverse effect on paint adhesion as measured by ASTM D4541. In some cases, the adhesion of the article or coating to the underlying substrate is greater than the cohesive strength of the substrate. In other words, during the test, the bond between the coating and the substrate was so strong that the underlying substrate failed before the coating separated from the substrate surface. For example, when the substrate comprises wood, the adhesion between the coating and the substrate can be about 300 psi or greater, 400 psi or greater, 500 psi or greater, 600 psi or greater as measured by ASTM D4541 and All ranges and subranges in between. In some cases, the article exhibits an anti-sag index value when applied as a coating to a substrate as measured by ASTM D4400: about 3 or greater, about 5 or greater, 7 or more, 8 or more, 9 or more, 10 or more, 11 or more, 12 or more, 13 or more, 14 or more or even 15 or more.

[0113] The article and/or coating can exhibit sufficient durability to be used in everyday and commercial applications. Specifically, the article, when applied to a substrate as a coating, exhibits an OD of about 4 or greater, 5 or greater, 6 or greater, 7 or greater, and in between, as measured by ASTM D4213. Scrub resistance for all ranges and sub-ranges.

[0114] In one or more embodiments, the article and/or coating may be moisture resistant. For example, the antimicrobial activity of the article and/or coating does not exhibit a change after exposing the article and/or coating to an environment of up to about 95% relative humidity for 24 hours.

[01151 One or more embodiments of the article may comprise an antimicrobial glass and a carrier, and the level of loading of the antimicrobial glass is such that the article exhibits resistance or retention to the presence or growth of soils. Contamination includes fungi, bacteria, viruses and combinations thereof. In some cases, the presence or growth of contaminants in articles such as paints, varnishes, etc., can cause discoloration of the article, can damage the integrity of the article and negatively affect various properties of the article. By including a minimum loading of antimicrobial glass to the carrier, (e.g., about 5% by weight or less, about 4% by weight or less, about 3% by weight or less, about 2% by weight or less, or about 1% by weight % or less), can eliminate or reduce contamination. In some cases, when fouling is eliminated or reduced,

A carrier formulation need not contain certain components. Thus, the carrier formulations used in one or more embodiments of the articles described herein may have more flexibility and Variety.

[0116] Another aspect of the invention relates to methods of making antimicrobial articles. In one or more embodiments, the method comprises melting a glass composition, such as a composition described herein, to form glass, forming the glass into particles, fibers, or a combination thereof, combining the particles and/or Or the fibers are dispersed into a carrier (eg, polymer) to provide a filled polymer, and the filled polymer is formed into an antimicrobial article.

[0117] In one or more embodiments, depending on the application of the article, the method comprises loading a selected amount of glass into the polymer. Various methods and processes can be used, such as by in situ process of mixing monomers with glass (which can be ground into pellets or other forms) and subsequent polymerization (into a thermoset or thermoplastic polymer matrix), or by solution or melt mixing ( For example, using a Brabender mixer or extruder, single screw or twin screw, reactive or non-reactive) to mix polymers with glass and the like.

[0118] In one or more embodiments, forming the filled polymer into an antimicrobial article may comprise extruding or molding the filled polymer. In one or more embodiments, the antimicrobial article can be further treated to expose at least a portion of the glass to the exterior surface. The exterior surface can be a surface that interacts with a user of the antimicrobial article (eg, exterior surface of a cell phone, cell phone display, etc.). In one or more embodiments, the method can comprise removing a surface portion of the antimicrobial article to expose the glass dispersed in the filled polymer. Exemplary methods of removing portions of the surface of the antimicrobial article may include etching (by plasma, acid, or mechanical means such as sanding or polishing).

Example

[0119] Further illustrate different embodiments of the invention by the following examples.

Embodiment 1-62

[0121] See Table 1 for non-limiting examples of compositions described herein. Ingredients The composition shown in Table 1 was melted and formed into a glass. Table 2 lists selected properties of the compositions of Table 1 or glasses formed from the compositions of Table 1, including conditions for melting, conditions for annealing, melt appearance, density, annealing point (such as 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, Humanoid Cut (chevron notch) fracture toughness, thermal expansion coefficient and other properties. Table 2 also includes the weight percent of Cu oxide as determined by ICP technique for selected glasses, and the Cu¹⁺:Cu²+ Scale.

Table 3 includes information relating to the crystal phase and crystal size of crystal phase aggregates of selected glasses as determined using X-ray diffraction (XRD) techniques well known in the art, using commercially available equipment such as Philips, Netherlands ( Model PW1830 (Cum radiation) diffractometer manufactured by Phil ips). Spectra are typically collected from 20 at 5-80 degrees. Table 3 also includes elemental distribution information for selected glasses as determined by XPS techniques.

[0123] The glass was then tested according to the EPA test under two conditions using Staphylococcus aureus, as shown in Table 4. Table 4 also includes Cu and Cu found in selected examples as determined by ICP techniques¹+ the total amount.

Table 1

[0125]

<td colspan="6">I 1</td>

<td>Example</td><td>Example 1</td><td>Example 2</td><td>Example 3</td><td>Example 4</td><td>Example 5</td>

<td>Batch composition (mol%)</td><td></td><td></td><td></td><td></td><td></td>

<td>SiO₂</td><td>65</td><td>65</td><td>60</td><td>60</td><td>60</td>

<td>A IfOg</td><td>17. 5</td><td>17. 5</td><td>20</td><td>15</td><td>15</td>

<td>CuO</td><td>17. 5</td><td>17. 5</td><td>20</td><td>20</td><td>20</td>

<td>Na₂0</td><td></td><td></td><td></td><td>5</td><td></td>

<td>K₂0</td><td></td><td></td><td></td><td></td><td>5</td>

<td>B*3</td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>ZnO</td><td></td><td></td><td></td><td></td><td></td>

<td>Batch Composition (wt%)</td><td></td><td></td><td></td><td></td><td></td>

<td>SiO₂</td><td>55. 2</td><td>55. 2</td><td>49. 8</td><td>51. 2</td><td>50. 1</td>

<td>AI2O3</td><td>25. 2</td><td>25. 2</td><td>28. 2</td><td>21. 7</td><td>21. 3</td>

<td>CuO</td><td>19. 7</td><td>19. 7</td><td>22. 0</td><td>22. 6</td><td>22. 1</td>

<td>Na₂0</td><td></td><td></td><td></td><td>4. 4</td><td></td>

<td>K2O</td><td></td><td></td><td></td><td></td><td>6. 5</td>

<td>B2O3</td><td></td><td></td><td></td><td></td><td></td>

<td>P2O5</td><td></td><td></td><td></td><td></td><td></td>

<td>ΖηΟ</td><td></td><td></td><td></td><td></td><td></td>

[0126]

<td colspan="6">Table 1 (continued)</td>

<td>Example</td><td>Shi 6 Examples</td><td>Shi 7 Examples</td><td>Example 8</td><td>Example 9</td><td>Example 10</td>

<td>Batch composition (mol%)</td><td></td><td></td><td></td><td></td><td></td>

<td>SiO₂</td><td>60</td><td>60</td><td>60</td><td>60</td><td>60</td>

<td>AIK%</td><td>10</td><td>10</td><td>5</td><td>5</td><td></td>

<td>CuO</td><td>20</td><td>20</td><td>20</td><td>20</td><td>20</td>

<td>N M</td><td>10</td><td></td><td>10</td><td>5</td><td></td>

<td>κ, ο</td><td></td><td>10</td><td>5</td><td>10</td><td>10</td>

<td>B₂03</td><td></td><td></td><td></td><td></td><td>10</td>

<td>“5</td><td></td><td></td><td></td><td></td><td></td>

<td>ZnO</td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>Batch Composition (wt%)</td><td></td><td></td><td></td><td></td><td></td>

<td>SiO₂</td><td>52. 7</td><td>50. 4</td><td>53. 0</td><td>51.8</td><td>52. 8</td>

<td>AlQa</td><td>14. 9</td><td>14. 2</td><td>7. 5</td><td>7. 3</td><td>0. 0</td>

<td>CuO</td><td>23. 3</td><td>22. 2</td><td>23.4</td><td>22. 9</td><td>23. 3</td>

<td>Na₂0</td><td>9. 1</td><td></td><td>9. 1</td><td>4. 5</td><td></td>

<td>K₂0</td><td></td><td>13. 2</td><td>6. 9</td><td>13. 5</td><td>13. 8</td>

<td>B?. ?</td><td></td><td></td><td></td><td></td><td>10. 2</td>

<td>P=o₅</td><td></td><td></td><td></td><td></td><td></td>

<td>ZnO</td><td></td><td></td><td></td><td></td><td></td>

<td colspan="6">Table] (continued)</td>

<td>Example</td><td>Example 11</td><td>Example 12</td><td>Example 13</td><td></td><td>Example 15</td>

<td>Batch composition (mol%)</td><td></td><td></td><td></td><td></td><td></td>

<td>SiO₂</td><td>60</td><td>60</td><td>60</td><td>50</td><td>50</td>

<td>AΙΑ</td><td></td><td>5</td><td></td><td></td><td></td>

<td>CuO</td><td>20</td><td>20</td><td>20</td><td>20</td><td>20</td>

<td>Na₂0</td><td></td><td></td><td></td><td></td><td></td>

<td>kappa_:ο</td><td>10</td><td>10</td><td>10</td><td>10</td><td>10</td>

<td>B,03</td><td></td><td></td><td>5</td><td>10</td><td></td>

<td>PQ</td><td>10</td><td>5</td><td>5</td><td>10</td><td>20</td>

<td>ZnO</td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>Batch Composition (wt%)</td><td></td><td></td><td></td><td></td><td></td>

<td>SiO₂</td><td>47. 7</td><td>49. 0</td><td>50. 1</td><td>39. 3</td><td>35.9</td>

<td>Αία</td><td></td><td>6.9</td><td></td><td></td>

<td>CuO</td><td>21.0</td><td>21. 6 22. 1</td><td>20. 8</td><td>19. 0</td>

<td>NaQ</td><td></td><td></td><td></td><td></td>

<td>K,O</td><td>12.5</td><td>12.8 13. 1</td><td>12. 3</td><td>11. 2</td>

<td>B#3</td><td></td><td>‘4.8</td><td>9. 1</td><td></td>

<td>p₂o₅</td><td>18. 8</td><td>9.6 9.9</td><td>18. 5</td><td>33. 9</td>

<td>ZnO</td><td></td><td>0. 05 .</td><td></td><td></td>

<td>MgO</td><td></td><td>0. 05 .</td><td></td><td></td>

<td>Fe₂0₃</td><td></td><td>0. 11</td><td></td><td></td>

<td>CaO</td><td></td><td>0. 01</td><td></td><td></td>

[0127]

<td colspan="6">Table 1 (continued)</td>

<td>Example</td><td>Example 16</td><td>Example 17</td><td>Example 18</td><td>Example 19</td><td>Example 20</td>

<td>Batch composition (mol%)</td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>50</td><td>50</td><td>50</td><td>50</td><td>50</td>

<td>A 1 2 () 3</td><td>25</td><td>20</td><td>25</td><td>25</td><td>20</td>

<td>CuO</td><td>25</td><td>30</td><td>25</td><td>25</td><td>20</td>

<td>Na?0</td><td></td><td></td><td>5</td><td></td><td>10</td>

<td>MO</td><td></td><td></td><td></td><td>5</td><td></td>

<td>Β₂03</td><td></td><td></td><td></td><td></td><td></td>

<td>Ρ&amp;</td><td></td><td></td><td></td><td></td><td></td>

<td>ΖηΟ</td><td></td><td></td><td></td><td></td><td></td>

<td>Batch Composition (wt%)</td><td></td><td></td><td></td><td></td><td></td>

<td>SiO₂</td><td>39. 8</td><td>40. 4</td><td>38. 3</td><td>37. 5</td><td>41. 4</td>

<td>A12O3</td><td>33. 8</td><td>27. 4</td><td>32. 5</td><td>31. 8</td><td>28. 1</td>

<td>CuO</td><td>26. 4</td><td>32. 1</td><td>25. 3</td><td>24. 8</td><td>21. 9</td>

<td>Na₂0</td><td></td><td></td><td>3. 9</td><td></td><td>8.5</td>

<td>K2O</td><td></td><td></td><td></td><td>5. 9</td><td></td>

<td>B2W</td><td></td><td></td><td></td><td></td><td></td>

<td>P2O5</td><td></td><td></td><td></td><td></td><td></td>

<td>ZnO</td><td></td><td></td><td></td><td></td><td></td>

<td colspan="6">Table 1 (continued)</td>

<td>Example</td><td>Shi 21 Examples</td><td>Example 22</td><td>Shi 23 Examples</td><td>Example 24</td><td>Example 25</td>

<td>Batch composition (mol%)</td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>50</td><td>60</td><td>60</td><td>50</td><td>60</td>

<td>Aka</td><td>20</td><td>5</td><td></td><td></td><td>5</td>

<td>CuO</td><td>20</td><td>20</td><td>20</td><td>20</td><td>20</td>

<td>N&amp;0</td><td></td><td></td><td></td><td></td><td>10</td>

<td>KQ</td><td>10</td><td>10</td><td>10</td><td>10</td><td></td>

<td>B2O3</td><td></td><td></td><td>5</td><td>10</td><td></td>

<td>P2O5</td><td></td><td>5</td><td>5</td><td>10</td><td>5</td>

<td>ZnO</td><td></td><td></td><td></td><td></td><td></td>

[0128]

<td>Batch Composition (wt%)</td><td></td><td></td><td></td><td></td><td></td>

<td>SiO₃</td><td>39. 7</td><td>49. 0</td><td>50. 1</td><td>39. 3</td><td>51. 2</td>

<td>A12O3</td><td>26. 9</td><td>6.9</td><td></td><td></td><td>7. 2</td>

<td>CuO</td><td>21.0</td><td>21. 6</td><td>22. 1</td><td>20. 8</td><td>22. 6</td>

<td>Na₂()</td><td></td><td></td><td></td><td></td><td>8. 8</td>

<td>QZ</td><td>12. 4</td><td>12.8</td><td>13. 1</td><td>12. 3</td><td></td>

<td>BfO</td><td></td><td></td><td>-1. 8</td><td>9. 1</td><td></td>

<td>P2O5</td><td></td><td>9. 6</td><td>9. 9</td><td>18. 5</td><td>10. 1</td>

<td>ZnO</td><td></td><td></td><td></td><td></td><td></td>

<td colspan="6">Table 1 (continued)</td>

<td>Example</td><td>Example 26</td><td>Example 27</td><td>Example 28</td><td>Example 29</td><td>Example 30</td>

<td>Batch composition (mol%)</td><td></td><td></td><td></td><td></td><td></td>

<td>Si()2</td><td>6()</td><td>50</td><td>50</td><td>50</td><td>55</td>

<td>Al %</td><td></td><td></td><td>5</td><td>5</td><td></td>

<td>CuO</td><td>20</td><td>20</td><td>20</td><td>20</td><td>20</td>

<td>Na₂o</td><td>10</td><td>10</td><td>10</td><td></td><td></td>

<td>K₂0</td><td></td><td></td><td></td><td>10</td><td>10</td>

<td>BQ?</td><td>5</td><td>10</td><td>10</td><td>10</td><td>10</td>

<td>P2O5</td><td>5</td><td>10</td><td>5</td><td>5</td><td>5</td>

<td>ZnO</td><td></td><td></td><td></td><td></td><td></td>

<td>Batch Composition (wt%)</td><td></td><td></td><td></td><td></td><td></td>

<td>5 electricity</td><td>52. 5</td><td>41. 0</td><td>42. 1</td><td>40. 3</td><td>45. 6</td>

<td>Al?. ?</td><td></td><td></td><td>7. 1</td><td>6. 8</td><td></td>

<td>CuO</td><td>23. 1</td><td>21. 7</td><td>22. 3</td><td>21. 3</td><td>22.0</td>

<td>Na₂()</td><td>9. 0</td><td>8. 5</td><td>8. 7</td><td></td><td></td>

<td>K type}</td><td></td><td></td><td></td><td>12. 6</td><td>13.()</td>

<td></td><td>5. 1</td><td>9. 5</td><td>9. 8</td><td>9. 3</td><td>9. 6</td>

<td></td><td>10. 3</td><td>19.4</td><td>10. 0</td><td>9. 5</td><td>9. 8</td>

I ZnO

<td colspan="6">Table 1 (continued)</td>

<td>Example</td><td>Example 31</td><td>Shi 32 Examples</td><td>Example 33</td><td>Example 34</td><td>Example 35</td>

<td>Batch composition (mol%)</td><td></td><td></td><td></td><td></td><td></td>

<td>SiO₂</td><td>55</td><td>60</td><td>55</td><td>60</td><td>55</td>

<td>A12O3</td><td></td><td></td><td>5</td><td>5</td><td></td>

<td>CuO</td><td>20</td><td>20</td><td>20</td><td>20</td><td>20</td>

<td>Na₂()</td><td>10</td><td>15</td><td>15</td><td></td><td></td>

<td>QZ</td><td></td><td></td><td></td><td>10</td><td>10</td>

<td></td><td>10</td><td></td><td></td><td></td><td>10</td>

<td>P2O5</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td>

<td>ZnO</td><td></td><td></td><td></td><td></td><td></td>

[0129]

<td>Batch Composition (wt%)</td><td></td><td></td><td></td><td></td><td></td>

<td>SiO₂</td><td>47. 7</td><td>52. 7</td><td>-16.9</td><td>49. 0</td><td>45. 6</td>

<td>A12O3</td><td></td><td></td><td>7. 2</td><td>6. 9</td><td></td>

<td>CuO</td><td>23. 0</td><td>23.3</td><td>22. 6</td><td>21. 6</td><td>22. 0</td>

<td>Na₂o</td><td>9. 0</td><td>13. 6</td><td>13. 2</td><td></td><td></td>

<td>K2O</td><td></td><td></td><td></td><td>12. 8</td><td>13. 0</td>

<td>wind</td><td>10. 1</td><td></td><td></td><td></td><td>9. 6</td>

<td>p₂o₅</td><td>10. 3</td><td>10.4</td><td>10. 1</td><td>9. 6</td><td>9. 8</td>

<td>ZnO</td><td></td><td></td><td></td><td></td><td></td>

<td colspan="6">Table 1 (continued)</td>

<td>Example</td><td>Example 36</td><td>Shi 37 Examples</td><td>Example 38</td><td>Example 39</td><td>Example 40</td>

<td>Batch composition (mol%)</td><td></td><td></td><td></td><td></td><td></td>

<td>SiO₂</td><td>50</td><td>45</td><td>40</td><td>55</td><td>55</td>

<td>A 1 formula) 3</td><td></td><td></td><td></td><td></td><td></td>

<td>CuO</td><td>20</td><td>20</td><td>20</td><td>20</td><td>20</td>

<td>Na₂o</td><td></td><td></td><td></td><td></td><td></td>

<td>QZ</td><td>10</td><td>10</td><td>12. 5</td><td>10</td><td>10</td>

<td>B2O3</td><td>10</td><td>10</td><td>10</td><td>10</td><td>10</td>

<td>P2O5</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td>

<td>ZnO</td><td>5</td><td>10</td><td>12. 5</td><td></td><td></td>

<td>Batch Composition (wt%)</td><td></td><td></td><td></td><td></td><td></td>

<td>SiO₂</td><td>40. 9</td><td>36. 3</td><td>31. 6</td><td>45.6</td><td>45. 6</td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>CuO</td><td>21. 6</td><td>21. 3</td><td>20. 9</td><td>22.0</td><td>22. 0</td>

<td>Na₂0</td><td></td><td></td><td></td><td></td><td></td>

<td>K₂0</td><td>12. 8</td><td>12. 6</td><td>15. 5</td><td>13.0</td><td>13. 0</td>

<td>QQ</td><td>9. 5</td><td>9. 3</td><td>9. 2</td><td>9. 6</td><td>9. 6</td>

<td>P2&amp;</td><td>9. 7</td><td>9. 5</td><td>9. 3</td><td>9. 8</td><td>9. 8</td>

<td>ZnO</td><td>5. 5</td><td>10. 9</td><td>13. 4</td><td></td><td></td>

[0130]

<td colspan="6">Table 1 (continued)</td>

<td>Example</td><td>Example 41</td><td>Example 42</td><td>Example 43</td><td>Example 44</td><td>Example 45</td>

<td>Batch composition (mol%)</td><td></td><td></td><td></td><td></td><td></td>

<td>SiO₂</td><td>51. 5</td><td>51. 5</td><td>48</td><td>48</td><td>55</td>

<td>A12O3</td><td>0</td><td>0</td><td>0</td><td>0</td><td></td>

<td>CuO</td><td>25</td><td>25</td><td>30</td><td>30</td><td>20</td>

<td>Na₂0</td><td>0</td><td>0</td><td>0</td><td>0</td><td></td>

<td>K#</td><td>9.4</td><td>9. 4</td><td>&amp; 8</td><td>8. 8</td><td>1()</td>

<td>Min 03</td><td>9.4</td><td>9. 4</td><td>8. 8</td><td>8. 8</td><td>10</td>

<td></td><td>4. 7</td><td>4. 7</td><td>4. 4</td><td>4. 4</td><td>5</td>

<td>ZnO</td><td>0</td><td>0</td><td>0</td><td>0</td><td>55</td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>Batch Composition (wt%)</td><td></td><td></td><td></td><td></td><td></td>

<td>SiO_;</td><td>42. 4</td><td>42. 4</td><td>39. 3</td><td>39. 3</td><td></td>

<td>A12O3</td><td>0. 0</td><td>0. 0</td><td>0. 0</td><td>0. 0</td><td></td>

<td>CuO</td><td>27. 3</td><td>27. 3</td><td>32. 5</td><td>32. 5</td><td></td>

<td>Na₂()</td><td>0. 0</td><td>0. 0</td><td>0. ϋ</td><td>0. 0</td><td></td>

<td>K₂0</td><td>12. 1</td><td>12. 1</td><td>11. 3</td><td>11. 3</td><td></td>

<td>B2O3</td><td>9. 0</td><td>9. 0</td><td>8. 4</td><td>8. 4</td><td></td>

<td>P2O5</td><td>9. 2</td><td>9. 2</td><td>8. 5</td><td>8. 5</td><td></td>

<td>ZnO</td><td>0. 0</td><td>0. 0</td><td>0. 0</td><td>0. 0</td><td></td>

<td colspan="6">Table 1 (continued)</td>

<td>Example</td><td>Example 46</td><td>Example 47</td><td>Example 48</td><td>Example 49</td><td>Example 50</td>

<td>Batch composition (mol%)</td><td></td><td></td><td></td><td></td><td></td>

<td>SiO₂</td><td>50</td><td>50</td><td>50</td><td>50</td><td>55</td>

<td>AI2O3</td><td>0</td><td>0</td><td>0</td><td>0</td><td>0</td>

<td>CuO</td><td>20</td><td>20</td><td>20</td><td>20</td><td>20</td>

<td>Na₂o</td><td>0</td><td>0</td><td>0</td><td>0</td><td>0</td>

<td>κ.ο</td><td>10</td><td>10</td><td>10</td><td>10</td><td>10</td>

<td>B^Oa</td><td>10</td><td>10</td><td>10</td><td>10</td><td>10</td>

<td>ρ₂0₅</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td>

<td>ΖηΟ</td><td>0</td><td>0</td><td>0</td><td>0</td><td>0</td>

<td>TiO₂</td><td>5</td><td>0</td><td>0</td><td>0</td><td>0</td>

<td>Fe^Os</td><td>0</td><td>5</td><td>0</td><td>0</td><td>0</td>

<td>Cr₂o₃</td><td>0</td><td>0</td><td>5</td><td>0</td><td>0</td>

<td>C03O4</td><td>0</td><td>0</td><td>0</td><td>5</td><td>0</td>

<td>NiO</td><td>0</td><td>0</td><td>0</td><td>0</td><td>0</td>

[0131]

<td colspan="6">Table 1 (continued)</td>

<td>Example</td><td>Example 51</td><td>Shi 52 Examples</td><td>Example 53</td><td>Example 54</td><td>Example 55</td>

<td>Batch composition (mol%)</td><td></td><td></td><td></td><td></td><td></td>

<td>Si0₂</td><td>40</td><td>45</td><td>50</td><td>55</td><td>50</td>

<td>AI2O3</td><td>15</td><td>15</td><td>15</td><td>15</td><td>15</td>

<td>CuO</td><td>20</td><td>20</td><td>20</td><td>20</td><td>20</td>

<td>Na^O</td><td></td><td></td><td></td><td></td><td></td>

<td>&amp;O</td><td>10</td><td>10</td><td>10</td><td>5</td><td>5</td>

<td>B2O3</td><td>10</td><td>5</td><td>0</td><td>0</td><td>5</td>

<td>Ρ&amp;</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td>

<td>ΖηΟ</td><td>0</td><td>0</td><td>0</td><td>0</td><td>0</td>

<td>Ti0₂</td><td>0</td><td>0</td><td>0</td><td>0</td><td>0</td>

<td>Fe₂o₃</td><td>0</td><td>0</td><td>0</td><td>0</td><td>0</td>

<td>Cr_£o₃</td><td>0</td><td>0</td><td>0</td><td>0</td><td>0</td>

<td>C03O4</td><td>0</td><td>0</td><td>0</td><td>0</td><td>0</td>

<td>NiO</td><td>0</td><td>0</td><td>0</td><td>0</td><td>0</td>

<td colspan="6">Table 1 (continued)</td>

<td>Example</td><td>Shi 56 Example</td><td>Shi 57 Example</td><td>Shi 58 Example</td><td>Example 59</td><td>Example 60</td>

<td>Batch composition (mol%)</td><td></td><td></td><td></td><td></td><td></td>

<td>SiO₂</td><td>45</td><td>55</td><td>50</td><td>45</td><td>45</td>

<td>A</td><td></td><td></td><td></td><td></td><td></td>

<td>CuO</td><td>35</td><td>30</td><td>35</td><td>40</td><td>25</td>

<td>Na₂o</td><td></td><td></td><td></td><td></td><td></td>

<td>MO</td><td>7. 5</td><td>10</td><td>10</td><td>10</td><td>10</td>

<td>B2O3</td><td>7. 5</td><td></td><td></td><td></td><td></td>

<td>PM</td><td>5</td><td>5</td><td>5</td><td>5</td><td>5</td>

<td>ZnO</td><td></td><td></td><td></td><td></td><td></td>

<td>TiO₂</td><td></td><td></td><td></td><td></td><td></td>

<td>Fe M</td><td></td><td></td><td></td><td></td><td></td>

<td>Cr₂o₃</td><td></td><td></td><td></td><td></td><td></td>

<td>co₃0₄</td><td></td><td></td><td></td><td></td><td>15</td>

<td>NiO</td><td></td><td></td><td></td><td></td><td></td>

[0132]

<td colspan="3">Table 1 (continued)</td>

<td>Example</td><td>Example 61</td><td>Example 62</td>

<td>Batch composition (mol%)</td><td></td><td></td>

<td>Si0₂</td><td>45</td><td>45</td>

<td>AI2O3</td><td>0</td><td>0</td>

<td>CuO</td><td>25</td><td>30</td>

<td>Na₂o</td><td>0</td><td>0</td>

<td>MO</td><td>10</td><td>10</td>

<td>B2O3</td><td>0</td><td>0</td>

<td>P2O5</td><td>5</td><td>5</td>

<td>ZnO</td><td>0</td><td>0</td>

<td>Ti0₂</td><td>0</td><td>10</td>

<td>Fe M</td><td>0</td><td>0</td>

<td>Cr₂o₃</td><td>0</td><td>0</td>

<td>C03O4</td><td>0</td><td>0</td>

<td>NiO</td><td>15</td><td>0</td>

Table 2

[0134]

<td colspan="6">Table 2</td>

<td>Example</td><td>Example 1</td><td>Example 2</td><td>Example 3</td><td>Example 4</td><td>Example 5</td>

<td>Melting temperature (°C)</td><td>1500</td><td>1650</td><td>1650</td><td>1650</td><td>1650</td>

<td>Melting time (hours)</td><td>6</td><td>overnight</td><td>over</td><td>overnight</td><td>overnight</td>

<td>Types of J Amazawa</td><td>Aluminum oxide</td><td>quartz</td><td>quartz</td><td>quartz</td><td>quartz</td>

<td>Annealing temperature (°C)</td><td>700</td><td>700</td><td>700</td><td>700</td><td>700</td>

<td>Melt Appearance</td><td>Very poor, all big bubbles</td><td>High quality, surface oxidation, gray surface, black interior</td><td>High quality, surface oxidation, gray surface, black interior</td><td>Table black part gray face color</td><td>gray exterior, black interior</td>

<td>Density by buoyancy (g/cm³)</td><td></td><td>2. 705</td><td>2. 781</td><td>2. 758</td><td>2. 741</td>

<td>Effective points-weight (g/mol)</td><td>70. 821</td><td>70. 821</td><td>72. 354</td><td></td><td></td>

<td>Molar volume (CH?/mole)</td><td></td><td>26. 2</td><td>26. 0</td><td></td><td></td>

<td>Annealing point through BBV ("C)</td><td></td><td>694. 1</td><td>684. 9</td><td>598. 6</td><td></td>

<td>Strain point through BBV (°C)</td><td></td><td>652.5</td><td>642. 3</td><td>558.9</td><td></td>

<td>Softening point through PPV (°C }</td><td></td><td>Crystallized (xstailized)</td><td>crystallization</td><td></td><td></td>

<td>Vickers hardness (kgf/nim^£)</td><td></td><td>595</td><td>586</td><td></td><td></td>

<td>Vickers crack initiation (kgf)</td><td></td><td>1-2</td><td>1-2</td><td></td><td></td>

<td>Fracture toughness through humanoid incision (MPa in*</td><td></td><td>0.875</td><td>0. 887</td><td></td><td></td>

<td>CTE (ppm/©</td><td></td><td>1. 06</td><td>1. 15</td><td></td><td></td>

<td>TCP weight % oxide (Cu)</td><td>19. 6</td><td>19</td><td>21. 6</td><td></td><td></td>

<td>Ratio Cu⁺7Cu^£'</td><td></td><td></td><td></td><td></td><td></td>

[0135]

<td colspan="6">Table 2 (continued)</td>

<td>Example</td><td>Example 6</td><td>Example 7</td><td>Example 8</td><td>Example 9</td><td>Example 10</td>

<td>Melting temperature (°C)</td><td>1650</td><td>1650</td><td>1650</td><td>1650</td><td>1650</td>

<td>Melting time (hours)</td><td>overnight</td><td>overnight</td><td>overnight</td><td>overnight</td><td>overnight</td>

<td>Ground pot type</td><td>quartz</td><td>quartz</td><td>quartz</td><td>quartz</td><td>quartz</td>

<td>Annealing temperature (°C)</td><td>700</td><td>700</td><td>700</td><td>700</td><td>600</td>

<td>Melt Appearance</td><td>black and gray glossy finish, brown and yellow interior</td><td>And has appearance and color luster, yellow part black gray light corridor and year</td><td></td><td>It is the same color as the main black with green-brown stripes inside, and it is the same color as the short black and gray surface</td><td>Deep surface and inner color, grayish yellow surface</td>

<td>Density by buoyancy (g/cm³)</td><td>2. 706</td><td>2. 666</td><td></td><td>2. 596</td><td>2. 716</td>

<td>Effective molecular weight (g/mol)</td><td></td><td></td><td></td><td></td><td></td>

<td>Molar volume (cnp/mole)</td><td></td><td></td><td></td><td></td><td></td>

<td>Annealing point through BBV (°C)</td><td>737. 2</td><td></td><td></td><td></td><td>575. 7</td>

<td>Strain point through BBV (°C)</td><td>684. 4</td><td></td><td></td><td></td><td>535. 2</td>

<td>Softening point through PPV (°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Vickers hardness (kgf/nun³)</td><td></td><td></td><td></td><td></td><td></td>

<td>Vickers crack initiation (kgf)</td><td></td><td></td><td></td><td></td><td></td>

<td>Fracture toughness through humanoid incision (MPa Π!*)</td><td></td><td></td><td></td><td></td><td></td>

<td>CTE (ρρπι/°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>ICP weight % oxide (Cu)</td><td></td><td></td><td></td><td></td><td></td>

<td>Ratio Cu'7Cu^£+</td><td></td><td></td><td></td><td></td><td></td>

[0136]

<td colspan="6">Table 2 (continued)</td>

<td>Example</td><td>Example 11</td><td>Example 12</td><td>Example 13</td><td>Example 14</td><td>Example 15</td>

<td>Melting temperature (°C)</td><td>1650</td><td>1650</td><td>1650</td><td>1650</td><td>1650</td>

<td>Melting time (hours)</td><td>overnight</td><td>overnight</td><td>overnight</td><td>overnight</td><td>overnight</td>

<td>Types of raw pot</td><td>quartz</td><td>quartz</td><td>quartz</td><td>quartz</td><td>quartz</td>

<td>Annealing temperature (°C)</td><td>600</td><td>700</td><td>600</td><td>600</td><td>600</td>

<td>Melt Appearance</td><td>ceramic, brittle, grey, brown and green</td><td>Shiny metallic surface, dark yellow interior</td><td>Shiny metallic surface, dark yellow interior</td><td>Dark yellow surface w/some ceramic, dark yellow interior period/some ceramic</td><td>, the surface is light and the inner porcelain color, the brown part of the color pottery gray surface</td>

<td>Density by buoyancy (g/cm³)</td><td></td><td>2. 669</td><td>2. 673</td><td>2.608</td><td></td>

<td>Effective molecular weight (g/mol)</td><td></td><td></td><td></td><td></td><td></td>

<td>Molar volume (cnp/mole)</td><td></td><td></td><td></td><td></td><td></td>

<td>Annealing point through BBV (°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Strain point through BBV (°C)</td><td></td><td>701</td><td>569</td><td>572. 5</td><td></td>

<td>Softening point through PPV (°C)</td><td></td><td>759. 8</td><td>602. 8</td><td>510. 7</td><td></td>

<td>Vickers hardness (kgf/mni²)</td><td></td><td></td><td></td><td></td><td></td>

<td>Vickers crack initiation (kgf)</td><td></td><td></td><td></td><td></td><td></td>

<td>Fracture toughness through humanoid incision (MPa ms)</td><td></td><td></td><td></td><td></td><td></td>

<td>CTE (ρρπι/°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>I CP weight % oxide (Cu)</td><td></td><td></td><td></td><td></td><td></td>

<td>Ratio Cu'7Cu^£H</td><td></td><td></td><td></td><td></td><td></td>

[0137]

<td colspan="6">Table 2 (continued)</td>

<td>Example</td><td>Example 16</td><td>Example 17</td><td>Example 18</td><td>Example 19</td><td>Example 20</td>

<td>Melting temperature (°C)</td><td>1650</td><td>1650</td><td>1650</td><td>1650</td><td>1650</td>

<td>Melting time (hours)</td><td>overnight</td><td>overnight</td><td>overnight</td><td>overnight</td><td>overnight</td>

<td>Types of Shikan Pot</td><td>quartz</td><td>quartz</td><td>quartz</td><td>quartz</td><td>quartz</td>

<td>Annealing temperature (°C)</td><td>700</td><td>700</td><td>700</td><td>700</td><td>700</td>

<td>Melt Appearance</td><td>gray surface, black interior, precipitated copper</td><td>gray exterior, black interior</td><td>gray exterior, black interior</td><td>gray exterior, black interior</td><td>¥ gray face</td>

<td>Density by buoyancy (g/cm³)</td><td>2.91</td><td>2. 901</td><td>2. 887</td><td>2.876</td><td>2. 797</td>

<td>Effective Molecular Weight (g/mol)</td><td></td><td></td><td></td><td></td><td></td>

<td>Molar volume (cn?/mole)</td><td></td><td></td><td></td><td></td><td></td>

<td>Annealing point through BBV (C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Strain point through BBV (C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Softening point through PPV (°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Vickers hardness (kgf/mm²)</td><td></td><td></td><td></td><td></td><td></td>

<td>Vickers crack initiation (kgf)</td><td></td><td></td><td></td><td></td><td></td>

<td>Fracture toughness through humanoid incision (MPa m^{0 6})</td><td></td><td></td><td></td><td></td><td></td>

<td>CTE (ppm/°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>ICP weight % oxide (Cu)</td><td></td><td></td><td></td><td></td><td></td>

<td>Ratio Cu⁺¹/Cu²⁺</td><td></td><td></td><td></td><td></td><td></td>

[0138]

<td colspan="6">Table 2 (continued)</td>

<td>Example</td><td>Example 16</td><td>Example 17</td><td>Example 18</td><td>Example 19</td><td>Example 20</td>

<td>Melting temperature (°C)</td><td>1650</td><td>1650</td><td>1650</td><td>1650</td><td>1650</td>

<td>Melting time (hours)</td><td>overnight</td><td>overnight</td><td>overnight</td><td>overnight</td><td>overnight</td>

<td>Ground pot type</td><td>quartz</td><td>quartz</td><td>quartz</td><td>quartz</td><td>quartz</td>

<td>Annealing temperature (°C)</td><td>700</td><td>700</td><td>700</td><td>700</td><td>700</td>

<td>Melt Appearance</td><td>gray surface, black interior, precipitated copper</td><td>gray exterior, black interior</td><td>gray exterior, black interior</td><td>gray exterior, black interior</td><td>gray exterior, black interior</td>

<td>Density by buoyancy (g/cm³)</td><td>2. 91</td><td>2. 901</td><td>2. 887</td><td>2. 876</td><td>2. 797</td>

<td>Effective Molecular Weight (g/mol)</td><td></td><td></td><td></td><td></td><td></td>

<td>Molar volume (cm²7 moles)</td><td></td><td></td><td></td><td></td><td></td>

<td>Annealing point through BBV ("C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Strain point through BBV (°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Softening point through PPV (°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Vickers hardness (kgf/mm²)</td><td></td><td></td><td></td><td></td><td></td>

<td>Vickers crack initiation (kgf)</td><td></td><td></td><td></td><td></td><td></td>

<td>Fracture toughness through humanoid incision (MPa m*</td><td></td><td></td><td></td><td></td><td></td>

<td>CTE (ppm/°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>ICP weight % oxide (Cu)</td><td></td><td></td><td></td><td></td><td></td>

<td>Ratio Cu⁺¹/Cu²⁺</td><td></td><td></td><td></td><td></td><td></td>

[0139]

<td colspan="6">Table 2 (continued)</td>

<td>Example</td><td>Example 21</td><td>Example 22</td><td>Example 23</td><td>Example 24</td><td>Example 25</td>

<td>Melting temperature (°C)</td><td>1650</td><td>1650</td><td>1650</td><td>1650</td><td>1650</td>

<td>Melting time (hours)</td><td>overnight</td><td>overnight</td><td>overnight</td><td>overnight</td><td>overnight</td>

<td>Type of pot</td><td>quartz</td><td>quartz</td><td>quartz</td><td>quartz</td><td>quartz</td>

<td>Annealing temperature (°C)</td><td>700</td><td>650</td><td>650</td><td>650</td><td>650</td>

<td>Melt Appearance</td><td>gray surface, yellow interior</td><td>gray exterior, yellow/orange interior</td><td>gray exterior, yellow/orange interior</td><td>crystallization</td><td>Gray surface, yellow/orange interior (looks more crystalline than Example 22)</td>

<td>Density by buoyancy (g/cm³)</td><td>2. 774</td><td></td><td></td><td></td><td></td>

<td>Effective Molecular Weight (g/mol)</td><td></td><td></td><td></td><td></td><td></td>

<td>Molar volume (cn?/mole)</td><td></td><td></td><td></td><td></td><td></td>

<td>Annealing point through BBV (°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Strain point through BBV (°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Softening point through PPV (°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Vickers hardness (kgf/mm²)</td><td></td><td></td><td></td><td></td><td></td>

<td>Vickers crack initiation (kgf)</td><td></td><td></td><td></td><td></td><td></td>

<td>Fracture toughness through humanoid incision (MPa m*</td><td></td><td></td><td></td><td></td><td></td>

<td>CTE (ppm/°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>ICP weight % oxide (Cu)</td><td></td><td></td><td></td><td></td><td></td>

<td>Ratio Cu/Cu</td><td></td><td></td><td></td><td></td><td></td>

*The term "crystalline" is used here to refer to a non-glassy appearance.

[0140]

[0141]

<td colspan="6">Table 2 (continued)</td>

<td>Example</td><td>Example 26</td><td>Example 27</td><td>Example 28</td><td>Shi 29 Examples</td><td>Example 30</td>

<td>Melting temperature (°C)</td><td>1650</td><td>1650</td><td>1650</td><td>1650</td><td>1650</td>

<td>Melting time (hours)</td><td>overnight</td><td>overnight</td><td>overnight</td><td>overnight</td><td>overnight</td>

<td>Ground pot type</td><td>quartz</td><td>quartz</td><td>quartz</td><td>quartz</td><td>quartz</td>

<td>Annealing temperature (°C)</td><td>650</td><td>650</td><td>650</td><td>650</td><td>650</td>

<td>Melt Appearance</td><td>Gray exterior, more b/orange interior (looks more crystal than Example 23)</td><td>crystallization</td><td>Shiny exterior, yellow/orange interior</td><td>Yao LM yellow inner color flashes outer yellow orange part</td><td>Shiny exterior, yellow/orange interior</td>

<td>Density through buoyancy (g in</td><td></td><td></td><td></td><td></td><td>2. 626</td>

<td>Effective Molecular Weight (g/mol)</td><td></td><td></td><td></td><td></td><td></td>

<td>Molar volume (cn?/mole)</td><td></td><td></td><td></td><td></td><td></td>

<td>Annealing point through BBV (°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Strain point through BBV (°C)</td><td></td><td></td><td></td><td></td><td>602. 4</td>

<td>Softening point through PPV (°C)</td><td></td><td></td><td></td><td></td><td>544. 4</td>

<td>Vickers hardness (kgf/mni²)</td><td></td><td></td><td></td><td></td><td></td>

<td>Vickers crack initiation (kgf)</td><td></td><td></td><td></td><td></td><td></td>

<td>Fracture toughness through humanoid cut II (MPa m*</td><td></td><td></td><td></td><td></td><td></td>

<td>CTE (ppm/°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>ICP weight % oxide (Cu)</td><td></td><td></td><td></td><td></td><td></td>

<td>Ratio Cu/Cu"</td><td></td><td></td><td></td><td></td><td></td>

[0142]

<td colspan="5">Table 2 (continued)</td>

<td>Example</td><td>Example 31</td><td>Example 32</td><td>Example 33</td><td>Example Example 34 35</td>

<td>Melting temperature (°C)</td><td>1650</td><td>1650</td><td>1650</td><td>1650 1650</td>

<td>Melting time (hours)</td><td>overnight</td><td>overnight</td><td>overnight</td><td>overnight overnight</td>

<td>Types of Soil Pot</td><td>quartz</td><td>quartz</td><td>quartz</td><td>Quartz Quartz</td>

<td>Annealing temperature (°C)</td><td>650</td><td>650</td><td>650</td><td>650 650</td>

<td>Melt Appearance</td><td>Sparkle exterior, yellow/orange interior</td><td>lighter yellow, more crystal-like</td><td>pale yellow, crystalline</td><td>Orange inside Orange inside, shine part, shine metal surface metal surface</td>

<td>Density by buoyancy (g/cn?)</td><td></td><td></td><td></td><td></td>

<td>Effective fraction weight (g/mol)</td><td></td><td></td><td></td><td></td>

<td>Molar body trifoliate (cn?/mole)</td><td></td><td></td><td></td><td></td>

<td>Annealing point through BBV (°C)</td><td></td><td></td><td></td><td></td>

<td>Strain point through BBV (°C)</td><td></td><td></td><td></td><td></td>

<td>Softening point through PPV (°C)</td><td></td><td></td><td></td><td></td>

<td>Vickers hardness (kgf/mni²)</td><td></td><td></td><td></td><td></td>

<td>Vickers crack initiation (kgf)</td><td></td><td></td><td></td><td></td>

<td>Fracture toughness (MPa πm) through humanoid cut⁰·⁵)</td><td></td><td></td><td></td><td></td>

<td>CTE (ppm/°C)</td><td></td><td></td><td></td><td></td>

<td>ICP weight % oxide (Cu)</td><td></td><td></td><td></td><td></td>

<td>Ratio Cu⁺¹/Cu²⁺</td><td></td><td></td><td></td><td></td>

[0143]

<td colspan="6">Table 2 (continued)</td>

<td>Example</td><td>Example 36</td><td>Example 37</td><td>Example 38</td><td>Example 39</td><td>Example 40</td>

<td>Melting temperature (°C)</td><td>1650</td><td>1650</td><td>1650</td><td>1650</td><td>1650</td>

<td>Melting time (hours)</td><td>overnight</td><td>overnight</td><td>overnight</td><td>overnight</td><td>overnight</td>

<td>Ground pot type</td><td>quartz</td><td>quartz</td><td>quartz</td><td>quartz</td><td>quartz</td>

<td>Annealing temperature (°C)</td><td>650</td><td>650</td><td>650</td><td>none</td><td>650</td>

<td>Melt Appearance</td><td>Orange interior, shiny gold surface</td><td>Orange interior with shiny metallic surfaces</td><td>Orange interior with shiny metallic surfaces</td><td>Whole body color yellow-yellow</td><td>Orange interior, shiny golden surface</td>

<td>Density by buoyancy (g/cn?)</td><td></td><td></td><td></td><td></td><td></td>

<td>Effective Molecular Weight (g/mol)</td><td></td><td></td><td></td><td></td><td></td>

<td>Molar volume 9ηΛ mole)</td><td></td><td></td><td></td><td></td><td></td>

<td>Annealing point through BBV (°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Strain point through BBV (C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Softening point through PPV (°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Vickers hardness (kgf/mni²)</td><td></td><td></td><td></td><td></td><td></td>

<td>Vickers crack initiation (kgf)</td><td></td><td></td><td></td><td></td><td></td>

<td>Fracture toughness through humanoid incision (MPa m⁰⁵)</td><td></td><td></td><td></td><td></td><td></td>

<td>CTE (ρρπι/°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>ICP weight % oxide (Cu)</td><td></td><td></td><td></td><td></td><td></td>

<td>Ratio Cu'7c</td><td></td><td></td><td></td><td></td><td></td>

[0144]

<td colspan="6">Table 2 (continued)</td>

<td>Example</td><td>Example 36</td><td>Example 37</td><td>Example 38</td><td>Example 39</td><td>Example 40</td>

<td>Melting temperature (°C)</td><td>1650</td><td>1650</td><td>1650</td><td>1650</td><td>1650</td>

<td>Melting time (hours)</td><td>overnight</td><td>overnight</td><td>overnight</td><td>overnight</td><td>overnight</td>

<td>Ground pot type</td><td>quartz</td><td>quartz</td><td>quartz</td><td>quartz</td><td>quartz</td>

<td>Annealing temperature (°C)</td><td>650</td><td>650</td><td>650</td><td>none</td><td>650</td>

<td>Melt Appearance</td><td>Orange interior, shiny gold surface</td><td>Orange interior with shiny metallic surfaces</td><td>Orange interior with shiny metallic surfaces</td><td>Whole body color yellow-yellow</td><td>Orange interior, shiny golden surface</td>

<td>Density by buoyancy (g/cn?)</td><td></td><td></td><td></td><td></td><td></td>

<td>Effective Molecular Weight (g/mol)</td><td></td><td></td><td></td><td></td><td></td>

<td>Molar volume 9ηΛ mole)</td><td></td><td></td><td></td><td></td><td></td>

<td>Annealing point through BBV (°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Strain point through BBV (C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Softening point through PPV (°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Vickers hardness (kgf/mni²)</td><td></td><td></td><td></td><td></td><td></td>

<td>Vickers crack initiation (kgf)</td><td></td><td></td><td></td><td></td><td></td>

<td>Fracture toughness through humanoid incision (MPa m⁰⁵)</td><td></td><td></td><td></td><td></td><td></td>

<td>CTE (ρρπι/°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>ICP weight % oxide (Cu)</td><td></td><td></td><td></td><td></td><td></td>

<td>Ratio Cu'7c</td><td></td><td></td><td></td><td></td><td></td>

[0145]

<td colspan="5">Table 2 (continued)</td>

<td>Example</td><td>Example 41</td><td>Example 42</td><td>Example 43</td><td>Example 44</td>

<td>Melting temperature (°C)</td><td>1650</td><td>1650</td><td>1650</td><td>1650</td>

<td>Melting time (hours)</td><td>overnight</td><td>overnight</td><td>overnight</td><td>overnight</td>

<td>Pot type</td><td>quartz</td><td>quartz</td><td>quartz</td><td>quartz</td>

<td>Annealing temperature (°C)</td><td>none</td><td>650</td><td>none</td><td>650</td>

<td>Melt Appearance</td><td>yellow, orange</td><td>Orange interior with shiny metallic surfaces</td><td>yellow, orange</td><td>Orange interior with shiny metallic surfaces</td>

<td>Density by buoyancy (g/cm³)</td><td></td><td></td><td>2.816</td><td></td>

<td>Effective Molecular Weight (g/mol)</td><td></td><td></td><td></td><td></td>

<td>Molar volume (cn?/mole)</td><td></td><td></td><td></td><td></td>

<td>Annealing point through BBV ("C)</td><td></td><td></td><td></td><td></td>

<td>Strain point through BBV (°C)</td><td></td><td></td><td></td><td></td>

<td>Softening point through PPV (°C)</td><td></td><td></td><td></td><td></td>

<td>Vickers hardness (kgf/mni²)</td><td></td><td></td><td></td><td></td>

<td>Vickers crack initiation (kgf)</td><td></td><td></td><td></td><td></td>

<td>Fracture toughness through humanoid incision (MPa πΤ)</td><td></td><td></td><td></td><td></td>

<td>CTE (ppm/°C)</td><td></td><td></td><td></td><td></td>

<td>ICP weight % oxide (Cu)</td><td></td><td></td><td></td><td></td>

<td>Ratio Cu/Cu</td><td></td><td></td><td></td><td></td>

[0146]

<td colspan="6">Table 2 (continued)</td>

<td>Example</td><td>Example 46</td><td>Example 47</td><td>Example 48</td><td>Example 49</td><td>Example 50</td>

<td>Melting temperature (°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Melting time (hours)</td><td></td><td></td><td></td><td></td><td></td>

<td>Ground pot type</td><td></td><td></td><td></td><td></td><td></td>

<td>Annealing temperature (°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Melt Appearance</td><td>reddish orange</td><td>Orange</td><td>microgreen crystal</td><td>Light green, greener than Example 48</td><td></td>

<td>Density by buoyancy (g/cm³)</td><td></td><td></td><td></td><td></td><td></td>

<td>Shou Molecular Weight (g/mol)</td><td></td><td></td><td></td><td></td><td></td>

<td>Molar volume (cn?/mole)</td><td></td><td></td><td></td><td></td><td></td>

<td>Annealing point through BBV (K)</td><td></td><td></td><td></td><td></td><td></td>

<td>Strain point through BBV {°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Softening point by FPV (°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Vickers hardness (kgf/mni²)</td><td></td><td></td><td></td><td></td><td></td>

<td>Vickers crack initiation (kgf)</td><td></td><td></td><td></td><td></td><td></td>

<td>Fracture toughness through humanoid incision (MPa Ui-</td><td></td><td></td><td></td><td></td><td></td>

<td>CTE (ρρπι/°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>I CP weight % oxide (Cu)</td><td></td><td></td><td></td><td></td><td></td>

<td>Ratio Cu+'/Cu*</td><td></td><td></td><td></td><td></td><td></td>

[0147]

<td colspan="6">Table 2 (continued)</td>

<td>Example</td><td>Example 51</td><td>Example 52</td><td>Example 53</td><td>Example 54</td><td>Example 55</td>

<td>Melting temperature (°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Melting time (hours)</td><td></td><td></td><td></td><td></td><td></td>

<td>Ground pot type</td><td></td><td></td><td></td><td></td><td></td>

<td>Annealing temperature (°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Melt Appearance</td><td>yellow and black</td><td>yellow and brown</td><td>yellow</td><td>black with some orange on the underside</td><td>black with some orange on the edges</td>

<td>Density by buoyancy (g/cn?)</td><td></td><td></td><td></td><td></td><td></td>

<td>Effective Molecular Weight (g/mol)</td><td></td><td></td><td></td><td></td><td></td>

<td>Molar volume 9ηΛ mole)</td><td></td><td></td><td></td><td></td><td></td>

<td>Annealing point through BBV (°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Strain point through BBV (C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Softening point through PPV (°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>Vickers hardness (kgf/mm²)</td><td></td><td></td><td></td><td></td><td></td>

<td>Vickers crack initiation (kgf)</td><td></td><td></td><td></td><td></td><td></td>

<td>Fracture toughness through humanoid incision (MPa m⁰⁵)</td><td></td><td></td><td></td><td></td><td></td>

<td>CTE (ρρπι/°C)</td><td></td><td></td><td></td><td></td><td></td>

<td>ICP weight % oxide (Cu)</td><td></td><td></td><td></td><td></td><td></td>

<td>Ratio Cu'7c</td><td></td><td></td><td></td><td></td><td></td>

[0148]

<td colspan="2">Table 2 (continued)</td>

<td>Example</td><td>Example 56</td>

<td>Melting temperature (°C)</td><td></td>

<td>Melting time (hours)</td><td></td>

<td>Type of pot</td><td></td>

<td>Annealing temperature (°C)</td><td></td>

<td>Melt Appearance</td><td>pumpkin colored</td>

<td>Density by buoyancy (g/cm³)</td><td></td>

<td>Effective Molecular Weight (g/mol)</td><td></td>

<td>Molar volume (cn?/mole)</td><td></td>

<td>Annealing point through BBV (°C)</td><td></td>

<td>Strain point through BBV (°C)</td><td></td>

<td>Softening point through PPV (°C)</td><td></td>

<td>Vickers hardness (kgf/mm²)</td><td></td>

<td>Vickers crack initiation (kgf)</td><td></td>

<td>Fracture toughness through humanoid incision (MPa core)</td><td></td>

<td>CTE (ppm/C)</td><td></td>

<td>ICP weight % oxide (Cu)</td><td></td>

<td>Ratio Cu⁺¹/Cu²⁺</td><td></td>

[0149]

<td colspan="6">table 3</td>

<td>Example</td><td>Example 1</td><td>Example 2</td><td>Example 3</td><td>Example 1</td><td>Example 5</td>

<td>XRD powder</td><td></td><td></td><td>none</td><td>Copperite (CuO)</td><td>Copperite (CuO)</td>

<td>XRD surface</td><td></td><td></td><td></td><td>Copperite (CuO)</td><td>Copperite (CuO)</td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>XPS Vacuum Break + 2 Min Air</td><td></td><td></td><td></td><td></td><td></td>

<td>Rock u and Cu°</td><td></td><td></td><td></td><td></td><td>85. 2</td>

<td>%Cu²⁺</td><td></td><td></td><td></td><td></td><td>14. 8</td>

<td>standard deviation</td><td></td><td></td><td></td><td></td><td>1</td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>XPS Vacuum Break</td><td></td><td></td><td></td><td></td><td></td>

<td>Rock u and Cu°</td><td></td><td></td><td></td><td></td><td></td>

<td>%Cu²⁺</td><td></td><td></td><td></td><td></td><td></td>

<td>standard deviation</td><td></td><td></td><td></td><td></td><td></td>

[0150]

<td colspan="6">Table 3 (continued)</td>

<td>Example</td><td>Example 6</td><td>Example 7</td><td>Example 8</td><td>Example 9</td><td>Example 10</td>

<td>XRD powder</td><td>Cuprite (CuO) and Cuprite (CuQ)</td><td>Copperite (CuO) and cuprite (Cu₂0)</td><td></td><td>Cuprite (Cu₂0)</td><td>Cuprite (Cu.O)</td>

<td>XRD surface</td><td>Copperite (CuO) and cuprite (Cu₂O)</td><td>Black copper rough (CuO) and cuprite (Cu₂0)</td><td></td><td>no peak</td><td>Mine and mine copper 8 copper eight black ίουίι^</td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>XPS Vacuum Break + 2 Min Air</td><td></td><td></td><td></td><td></td><td></td>

<td>Cu and Cu°</td><td>84. 2</td><td></td><td></td><td></td><td>74. 6</td>

<td>%Cu²⁺</td><td>15. 8</td><td></td><td></td><td></td><td>25. 4</td>

<td>standard deviation</td><td>0. 1</td><td></td><td></td><td></td><td>L 5</td>

<td></td><td></td><td></td><td></td><td></td><td></td>

[0151]

<td>XPS Vacuum Break</td><td></td><td></td><td></td><td></td><td></td>

<td>Rock u and Cu°</td><td></td><td></td><td></td><td></td><td></td>

<td>%Cu²⁺</td><td></td><td></td><td></td><td></td><td></td>

<td>standard deviation</td><td></td><td></td><td></td><td></td><td></td>

[0152]

<td colspan="6">Table 3 (continued)</td>

<td>Example</td><td>Example 11</td><td>Example 12</td><td>Example 13</td><td>Example 14</td><td>Example 15</td>

<td>XRD powder</td><td></td><td>Cuprite (Cu_;0), GAdOd,A1₂0₃*0. 95P2Ο5,Cui.32K().2 (Al^.eSis. 1Ο24), K₂SiO_{: i}</td><td>Cuprite (Cu₂O)</td><td>Copperite (Cu?Q)</td><td></td>

<td>XRD surface</td><td></td><td>Copperite (CuO), Cuprite (Cu₂0),GAdO4,AhO,*0. 95P&amp;</td><td>Cuprite (Cu₂O)</td><td>Cuprite (Cu₂O)</td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>XPS Vacuum Break + 2 Min Air</td><td></td><td></td><td></td><td></td><td></td>

<td>U and Cu°</td><td></td><td>92. 4</td><td>80. 3</td><td>91. 3</td><td></td>

<td>%Cu²⁺</td><td></td><td>7. 6</td><td>19. 7</td><td>8. 7</td><td></td>

<td>standard deviation</td><td></td><td>1. 2</td><td>2. 5</td><td>0. 4</td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>XPS Vacuum Break</td><td></td><td></td><td></td><td></td><td></td>

<td>Rock u and Cu°</td><td></td><td>87. 1</td><td></td><td>93. 1</td><td></td>

<td>%Cu²⁺</td><td></td><td>12. 9</td><td></td><td>6. 9</td><td></td>

<td>standard deviation</td><td></td><td>2. 6</td><td></td><td>0. 6</td><td></td>

<td colspan="6">Table 3 (continued)</td>

<td>Example</td><td>Example 16</td><td>Example 17</td><td>Example 18</td><td>Example 19</td><td>Example 20</td>

<td>XRD powder</td><td>Copperite (CuO)</td><td>Copperite (CuO)</td><td>Copperite (CuO)</td><td>none</td><td>Copperite (CuO)</td>

<td>XRD surface</td><td>Copperite (CuO)</td><td>Copperite (CuO)</td><td>Copperite (CuU)</td><td>Copperite (CuO)</td><td>Copperite (CuO)</td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>XPS Vacuum Break + 2 Min Air</td><td></td><td></td><td></td><td></td><td></td>

<td>Rock u and Cu°</td><td></td><td></td><td></td><td></td><td></td>

<td>%Cu²⁺</td><td></td><td></td><td></td><td></td>

<td>standard deviation</td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td>

<td>XPS Vacuum Break</td><td></td><td></td><td></td><td></td>

<td>%CuCu°</td><td></td><td></td><td></td><td></td>

<td>%Cu²⁺</td><td></td><td></td><td></td><td></td>

<td>standard deviation</td><td></td><td></td><td></td><td></td>

<td colspan="6">Table 3 (continued)</td>

<td>Example</td><td>Example 21</td><td>Example 22</td><td>Example 23</td><td>Example 24</td><td>Example 25</td>

<td>XRD powder</td><td>Red Tongren (Cu₂O)</td><td>Cuprite, Cuprite, Sodium Borate (Na₂B_ls0 J, potassium aluminum silicate (KAlSiOi)</td><td>Cuprose</td><td>cristobalite, copper</td><td>Cuprite, sodium silicate 'azSiQs), aluminum phosphate (A1P0J</td>

<td>XRD surface</td><td>Copperite (CuO)</td><td>Cuprite, Cuprite, Sodium Borate</td><td>--η^ΒΗ ' τη lead dancer silver, mineral acid red r, copper boron</td><td>Cuprose</td><td>Cuprite, Cuprite, Sodium Silicate (Xa₂SiA ), aluminum phosphate (AlPUj</td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>XPS Vacuum Break + 2 Min Air</td><td></td><td></td><td></td><td></td><td></td>

<td>U and Cu°</td><td>81. 7</td><td></td><td></td><td></td><td></td>

<td>%Cu²⁺</td><td>18. 3</td><td></td><td></td><td></td><td></td>

<td>standard deviation</td><td>0. 2</td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>XPS Vacuum Break</td><td></td><td></td><td></td><td></td><td></td>

<td>%Cu and Cu°</td><td></td><td></td><td></td><td></td><td></td>

<td>%Cu^2t</td><td></td><td></td><td></td><td></td><td></td>

<td>standard deviation</td><td></td><td></td><td></td><td></td><td></td>

[0154]

<td colspan="6">Table 3 (continued)</td>

<td>Example</td><td>Example 26</td><td>Example 27</td><td>Example 28</td><td>Example 29</td><td>Example 30</td>

<td>XRD powder</td><td>,, copper storage side red phosphorus UC</td><td>Copper, Cuprite, Sodium Copper Phosphate (Na₆Cu,(PO₄)_e)</td><td>Cuprose</td><td>Cuprose</td><td>Cuprose</td>

<td>XRD surface</td><td>Cristobalite, Cuprite, Cuprite, Copper Phosphate</td><td>Copper, Cuprite, Cuprosite, Sodium Copper Phosphate</td><td>Red copper r, sodium borate hydrate</td><td>Cuprose</td><td>copper ore, black copper ore</td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>XPS Vacuum Break + 2 Min Air</td><td></td><td></td><td></td><td></td><td></td>

<td>Heart and Cu°</td><td></td><td></td><td></td><td>87. 1</td><td>75</td>

<td>hang heart</td><td></td><td></td><td></td><td>12. 9</td><td>25</td>

<td>standard deviation</td><td></td><td></td><td></td><td>1. 2</td><td>0. 2</td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>XPS Vacuum Break</td><td></td><td></td><td></td><td></td><td></td>

<td>Set Guang and Cu°</td><td></td><td></td><td></td><td></td><td></td>

<td>%Cu^£+</td><td></td><td></td><td></td><td></td><td></td>

<td>standard deviation</td><td></td><td></td><td></td><td></td><td></td>

[0155]

<td colspan="6">Table 3 (continued)</td>

<td>Example</td><td>Example 31</td><td>Example 32</td><td>Example 33</td><td>Example 34</td><td>Example 35</td>

<td>XRD powder</td><td>Cuprose</td><td>Cristobalite, cuprite, sodium phosphate (NaFOj, aluminum phosphate hydrate (Α1PO^χΗ₂0 ), copper phosphate (CujP 2Ο1Ο)</td><td>Cuprite, sodium phosphate, Naq. Baji, 9 ( (A 1^_P 14S i 48.86)0106 )(H2O)26.S</td><td></td><td></td>

<td>XRD surface</td><td>Cuprite, black copper ore, octahedral borax (N3₂beta_Ί0γ*5Η_;0) ,copper phosphate hydrate C*(P03,*14H2 0</td><td>Cristobalite, Culloxite, Sodium Phosphate (NasPOj Aluminum Phosphate Hydrate (AHWxHsO ), Copper Phosphate (Cll5P 2010)</td><td>Cumulite, Sodium Phosphate, Cuprite</td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>XPS Vacuum Break + 2 Min Air</td><td></td><td></td><td></td><td></td><td></td>

<td>%Cu¹⁺ and Cu.</td><td>68. 7</td><td></td><td></td><td></td><td></td>

<td>%Cu²⁺</td><td>31. 3</td><td></td><td></td><td></td><td></td>

<td>standard deviation</td><td>0.6</td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>XPS Vacuum Break</td><td></td><td></td><td></td><td></td><td></td>

<td>%Cu¹⁺ Not Cu°</td><td></td><td></td><td></td><td></td><td></td>

<td>%Cu²⁺</td><td></td><td></td><td></td><td></td><td></td>

<td>standard deviation</td><td></td><td></td><td></td><td></td><td></td>

[0156]

<td colspan="6">Table 3 (continued)</td>

<td>Example</td><td>Example 36</td><td>Example 37</td><td>Example 38</td><td>Example 39</td><td>Example 40</td>

<td>XRD powder</td><td>Red copper, zinc potassium phosphate (KZnPOj</td><td>Cuprite, zinc potassium phosphate, zinc potassium silicate (Kl loZllo. 5$Si 1. 4₅o₄), zinc potassium phosphate CK₆Zn(P₂0,)₂</td><td>Red copper, zinc potassium phosphate (KZnPOj, zinc potassium silicate, zinc potassium phosphate</td><td>Cuprose</td><td>Cuprose</td>

<td>XRD surface</td><td>Cuprite, zinc potassium phosphate (KZnPOj, copper phosphide silicon (Cuo, i,eSi ί, ^4) % cuprosite</td><td>Cuprite, copper zinc phosphate (CuZn (Ρα), potassium phosphate (KJPQJ, aluminum phosphate (A1P0J</td><td>Copperite, Zinc Potassium Phosphate, Zinc Potassium Silicate, Potassium Copper Oxide (K₃CuO₄), cuprite, copper oxide phosphate (Cu₄0(P03</td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>XPS Vacuum Break + 2 Min Air</td><td></td><td></td><td></td><td></td><td></td>

<td>%Cu^1T and Cu°</td><td></td><td></td><td></td><td></td><td></td>

<td>%Cu²⁺</td><td></td><td></td><td></td><td></td><td></td>

<td>standard deviation</td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>XPS Vacuum Break</td><td></td><td></td><td></td><td></td><td></td>

<td>stagger U and Cu°</td><td></td><td></td><td></td><td></td><td></td>

<td>%Cu²⁺</td><td></td><td></td><td></td><td></td><td></td>

<td>standard deviation</td><td></td><td></td><td></td><td></td><td></td>

[0157]

<td colspan="6">Table 3 (continued)</td>

<td>Example</td><td>Example 41</td><td>Example 42</td><td>Example 43</td><td>Example 44</td><td>Example 45</td>

<td>XRD powder</td><td>Cuprose</td><td>Cuprose</td><td>Cuprose</td><td>Cuprose</td><td></td>

<td>XRD surface</td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>XPS Vacuum Break Ten 2 Minutes Air</td><td></td><td></td><td></td><td></td><td></td>

<td>%Cu^1-Cu°</td><td></td><td></td><td></td><td></td><td></td>

<td>Version u</td><td></td><td></td><td></td><td></td><td></td>

<td>standard deviation</td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>XPS Vacuum Break</td><td></td><td></td><td></td><td></td><td></td>

<td>%Cu~Cu</td><td></td><td></td><td></td><td></td><td></td>

<td>Dirty property</td><td></td><td></td><td></td><td></td><td></td>

<td>standard deviation</td><td></td><td></td><td></td><td></td><td></td>

[0158]

<td colspan="6">Table 3 (continued)</td>

<td>Example</td><td>Example 46</td><td>Example 47</td><td>Example 48</td><td>Example 49</td><td>Example 50</td>

<td>XRD powder</td><td>cuprite, copper titanium oxide, anatase</td><td></td><td></td><td>Cuprose</td><td></td>

<td>XRD surface</td><td>cuprite, copper titanium oxide, anatase</td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>XPS Vacuum Break + 2 Min Air</td><td></td><td></td><td></td><td></td><td></td>

<td>%Cu¹⁺Cu°</td><td></td><td></td><td></td><td></td><td></td>

<td>%Cu²⁺</td><td></td><td></td><td></td><td></td><td></td>

<td>standard deviation</td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>XPS Vacuum Break</td><td></td><td></td><td></td><td></td><td></td>

<td>%Cu¹⁺Cu°</td><td></td><td></td><td></td><td></td><td></td>

<td>%Cu²⁺</td><td></td><td></td><td></td><td></td><td></td>

<td>standard deviation</td><td></td><td></td><td></td><td></td><td></td>

[0159]

<td colspan="6">Table 3 (continued)</td>

<td>Example</td><td>Example 51</td><td>Example 52</td><td>Example 53</td><td>Example 54</td><td>Example 55</td>

<td>XRD powder</td><td>Cuprose</td><td>Copperite and Copperite</td><td>Cuprose</td><td>Copperite and Copperite</td><td>Copperite and Copperite</td>

<td>XRD surface</td><td>Copperite and Copperite</td><td>Copperite and Copperite</td><td>Copperite and Copperite</td><td>Copper Ore</td><td>Copper Ore</td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>XPS Vacuum Break Ten 2 Minutes Air</td><td></td><td></td><td></td><td></td><td></td>

<td>%CuCu°</td><td></td><td></td><td></td><td></td><td></td>

<td>%Cu²⁺</td><td></td><td></td><td></td><td></td><td></td>

<td>standard deviation</td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td>XPS Vacuum Break</td><td></td><td></td><td></td><td></td><td></td>

<td>%Cu^ltCu°</td><td></td><td></td><td></td><td></td><td></td>

<td>%Cu²⁺</td><td></td><td></td><td></td><td></td><td></td>

<td>standard deviation</td><td></td><td></td><td></td><td></td><td></td>

<td colspan="2">Table 3 (continued)</td>

<td>Example</td><td>Example 56</td>

<td>XRD powder</td><td>Cuprite and Copper Potassium Oxide</td>

<td>XRD surface</td><td>Cuprite and Cullite and Potassium Borate</td>

<td></td><td></td>

<td>XPS Vacuum Break + 2 Min Air</td><td></td>

<td>%Cu¹⁺Cu°</td><td></td>

<td>%Cu²⁺</td><td></td>

<td>standard deviation</td><td></td>

<td></td><td></td>

XPS Vacuum Break

[0160]

<td>%CuCu°</td><td></td>

<td>%Cu²⁺</td><td></td>

<td>standard deviation</td><td></td>

[0161]

<td colspan="6">Table 4</td>

<td>Example</td><td>Example 1</td><td>Example 2</td><td>Example 3</td><td>Example 1</td><td>Example 5</td>

<td>Hanging plate test, untreated EPA test (Staphylococcus aureus)</td><td></td><td>&lt; log1</td><td>&lt; log 1</td><td>&lt; log 1</td><td>&lt; log 1</td>

<td>Coupon test, untreated EPA test again</td><td></td><td></td><td></td><td>&lt; log 1</td><td></td>

<td>Coupon test, 1 day 85°C/85%RH EPA test</td><td></td><td></td><td></td><td></td><td></td>

<td>ICP, total amount of Cu, % by weight</td><td></td><td></td><td></td><td>21. 6</td><td>21. 7</td>

<td>ICP, total CG/Cu</td><td></td><td></td><td>0. 86</td><td>0. 87</td><td>0. 88</td>

[0162]

<td colspan="6">Table 4 (continued)</td>

<td>Example</td><td>Example 6</td><td>Example 7</td><td>Example 8</td><td>Example 9</td><td>Example 10</td>

<td>Hanging plate test, untreated direct use EPA test (Staphylococcus aureus)</td><td>&gt; log 3</td><td>log2.84</td><td></td><td>&lt; log 1</td><td>&lt; log 1</td>

<td>Coupon test, untreated EPA test again</td><td>&gt; log 1</td><td></td><td></td><td>&lt; log 1</td><td>&lt; log 1</td>

<td>Coupon test, 1 day 85°C/85%RH EPA test</td><td></td><td></td><td></td><td></td><td></td>

<td>ICP, total amount of Cu, % by weight</td><td>19. 6</td><td></td><td></td><td>15. 8</td><td>22</td>

<td>ICP, Cu/Total Cu</td><td>0. 88</td><td>0. 86</td><td></td><td>ϋ. 78</td><td>0. 8</td>

<td colspan="6">Table 4 (continued)</td>

<td>Example</td><td>Example 11</td><td>Example 12</td><td>Example 13</td><td>Example 14</td><td>Example 15</td>

<td>Hanging plate test, use EPA directly without treatment</td><td></td><td>&gt; log4</td><td>&gt; log 3</td><td>&gt; log 6</td><td></td>

[0163]

<td>Test (Staphylococcus aureus)</td><td></td><td></td><td></td><td></td><td></td>

<td>Coupon test, untreated EPA test again</td><td></td><td>&gt; log3</td><td>&gt; 1 og 4</td><td></td><td></td>

<td>Coupon test, 1 day 85°C/85%RH EPA test</td><td></td><td></td><td></td><td></td><td></td>

<td>ICP, total amount of Cu, % by weight</td><td></td><td>20. 8</td><td>20. 8</td><td>20. 5</td><td></td>

<td>ICP, total Cu/Cu</td><td></td><td>0. 85</td><td>0. 77</td><td>0. 85</td><td></td>

<td colspan="6">Table 4 (continued)</td>

<td>Example</td><td>Example 21</td><td>Example 22</td><td>Example 23</td><td>Example 24</td><td>Example 25</td>

<td>Hanging plate test, untreated direct use EPA test (Staphylococcus aureus)</td><td></td><td>&lt; log1</td><td>&lt; log 1</td><td></td><td>&gt; log 4</td>

<td>Coupon test, untreated EPA test again</td><td></td><td></td><td></td><td></td><td></td>

<td>Coupon test, 1 day 85°C/85%RH EPA test</td><td></td><td>&lt; log1</td><td>&lt; 1 og 1</td><td></td><td>&lt; log 1</td>

<td>TCP, total amount of Cu, % by weight</td><td>18. 1</td><td>21. 5</td><td>21. 9</td><td></td><td>21. 5</td>

<td>ICP, Cu/Total Cu</td><td>0. 92</td><td>0. 8</td><td>0. 8</td><td></td><td>0. 85</td>

[0164]

<td colspan="6">Table 4 (continued)</td>

<td>Example</td><td>Example 26</td><td>Example 27</td><td>Example 28</td><td>Example 29</td><td>Example 30</td>

<td>Mounting plate test, untreated should use EPA test directly (Staphylococcus aureus)</td><td></td><td></td><td>&gt; log 3</td><td>&gt; log 3</td><td>&gt; log 4</td>

<td>Coupon test, untreated EPA test again</td><td></td><td></td><td></td><td></td><td></td>

<td>Coupon test, 1 day 85°C/85%RH EPA test</td><td></td><td></td><td>&gt; log2</td><td>&gt; log2</td><td>&gt; log 4</td>

<td>TCP, total amount of Cu, % by weight</td><td>21. 3</td><td></td><td>21.4</td><td>22. 2</td><td>21. 6</td>

<td>ICP, Cu/Total Cu</td><td>0. 75</td><td></td><td>0. 82</td><td>0. 89</td><td>0. 86</td>

<td colspan="6">Table 4 (continued)</td>

<td>Example</td><td>Example 31</td><td>Example 32</td><td>Example 33</td><td>Example 34</td><td>Example 35</td>

<td>Coupon test, untreated</td><td>&gt; log 3</td><td></td><td></td><td></td><td></td>

[0165]

<td>Rationale directly using the EPA test (Staphylococcus aureus)</td><td></td><td></td><td></td><td></td><td></td>

<td>Coupon test, untreated EPA test again</td><td></td><td></td><td></td><td></td><td></td>

<td>Coupon test, 1 day 85°C/85%RH EPA test</td><td>&gt; log2</td><td></td><td></td><td></td><td></td>

<td>ICP, total amount of Cu, % by weight</td><td>22. 4</td><td>19. 8</td><td>19. 1</td><td></td><td></td>

<td>TCP, Cu+*/total Cu</td><td>0. 86</td><td>0. 77</td><td>0. 85</td><td></td><td></td>

<td colspan="5">Table 4</td>

<td>Example</td><td>Example 41</td><td>Example 42</td><td>Example 43</td><td>Example 44</td>

<td>Hanging plate test, untreated direct use EPA test (Staphylococcus aureus)</td><td></td><td></td><td>&gt; log 6</td><td>log 5. 93</td>

<td>Coupon test, untreated EPA test again</td><td></td><td></td><td></td><td></td>

<td>Coupon test, 1 day 85°C/85%RH EPA test</td><td></td><td></td><td></td><td></td>

<td>ICP, total amount of Cu, % by weight</td><td></td><td></td><td></td><td></td>

<td>ICP, total Cu'1/Cu</td><td></td><td></td><td>0. 88</td><td></td>

[0166]

<td colspan="5">Table 4</td>

<td>Example</td><td>Example 46</td><td>Example 49</td><td>Example 56</td><td>Example 58</td>

<td>Hanging plate test, untreated direct use EPA test (Staphylococcus aureus)</td><td>0. 53</td><td>1. 42</td><td>6. 151</td><td>6. 151</td>

<td>Coupon test, untreated EPA test again</td><td></td><td></td><td></td><td></td>

<td>Coupon test, 1 day 85°C/85%RH EPA test</td><td></td><td></td><td></td><td></td>

<td>ICP, total amount of Cu, % by weight</td><td></td><td></td><td></td><td></td>

<td>ICP, total Cu'i/Cu</td><td></td><td></td><td></td><td></td>

[0167] With respect to Example 13, the SEM images indicated that phase separation occurred and consisted of a glassy matrix phase and a dispersed glassy second phase. The dispersed phase is considered the degradable phase and includes cuprite crystals. When the formed glass was polished in water, the dispersed phase was partially dissolved and the degradation of the dispersed phase was evident. EDS analysis indicated that the glassy phase was enriched in silicon (ie, the durable phase) relative to the glassy second phase and the crystalline phase. The crystalline phase is the most copper-rich. While not intending to be bound by theory, it is believed that the glassy second phase is enriched in boron. Phase separation of degradable phases, including precipitation of cuprite crystals, proceeds readily without additional heat treatment beyond simple post-melt annealing.

[0168] Figures 3-5 are TEM and SEM images of glass made from the composition of Example 30. Figure 3 shows the TEM image

image, where the darkest regions represent silica-rich glassy phases, and the lighter regions are phase-separated glassy regions enriched in phosphorus, boron, and potassium. As noted above, these phase-separated glassy regions are the degradable regions, and the silica-rich glassy phase is the durable phase. The degradable phase and the durable phase form the glassy phase of the glass. The lightest colored areas shown in the TEM image of Figure 3 represent cuprite crystals. Regions that appear darker than the lightest region represent phase-separated glassy regions that are enriched in phosphorus, boron, and potassium (ie, degradable phases). In Figure 3, the silica-rich glassy phase is represented by the darkest region. In the TEM image of Figure 3 the crystal faces of the cuprite crystals can be seen. Figure 4 shows a SEM image of a cross-section of the glass after polishing with water. It can be seen from Fig. 4 that in water, the degradable phase (ie, the phase-separated glassy region enriched in P, B, and K shown in Fig. 3) is preferentially dissolved. Cu contained in cuprite crystals forming the degradable phase is released by dissolution of the degradable phase¹+ ions.

[0169] Figure 6 shows a STEM image of glass made from the compositions described herein. Figure 6 shows a three-phase morphology in which copper exists as particles and is entangled with phosphate and distributed in a glass matrix. Since phosphate is easily soluble in water, it will be dissolved by water, exposing the Cu particles, which release the active Cu species to function (kill viruses and bacteria).

[0170] Phase separation of glasses upon melting See Figures 7A-7B and 8A-8B, which are EDX supermaps of cross-sectional TEM images of samples obtained from bulk and surface regions. Both TEM images use the same magnification. Figures 7A-7B show the bulk and surface area of Example 30 immediately after melting at 1650°C and annealing at 650°C relative to quenching in water from the melting temperature of 1650°C, respectively. Figure 7A shows a quenched sample that is phase separated and includes cuprite crystals within the degradable phase. Therefore, phase separation and crystal formation are not inhibited by quenching. Thus, Figure 7A shows that phase separation occurs at 1600°C or in the melt. In particular, Figure 7A shows the durable phase as the darkest color, the lightest portion indicating the presence of copper, and the slightly darker color surrounding the lightest portion representing phosphorous. 8A-8B are shown at 800 SEM images of the fractured and polished cross-sections of Example 30 after an additional heat treatment of 1 hour at °C. Additional heat treatment seems to mature the microstructure. As shown in Figures 4 and 5, the size of the largest cuprite crystals was increased and the number of nanoscale bright contrast phases was significantly reduced compared to samples prepared by the standard method. In some embodiments, the copper concentration in the degradable phase exceeds the solubility limit and copper precipitates out of the degradable phase. Thus, the antimicrobial glass has antimicrobial activity in the molten state and when cooled to the final state without any additional heat treatment (eg, heat treatment in hydrogen at temperatures up to about 600° C.). Antimicrobial glass includes Cu present in sufficient amount in degradable phase¹+ and/or Cu0, the copper ions are leached out and provide antimicrobial efficiency.

[0171] When testing untreated glass and glass after 1 day under the conditions listed in Table 4, Cu¹The release of + ions provides antimicrobial activity.

[0172] The antimicrobial properties of the glasses described herein were tested by forming sheets or substrate articles having dimensions of 2.5 cm x 2.5 cm.

[0173] In order to test the antimicrobial activity of the examples, the EPA test was utilized. In the examples described herein, Staphylococcus aureus (ATCC 6538) was continuously cultured for 5 days prior to testing. Mix the bacterial culture medium with serum (5% final concentration) and Triton XT00 (0.01% final concentration). Inoculate 20 microliters of bacterial suspension for each sample/vehicle and allow it to dry at room temperature and 42% relative humidity (typically, dry for about 20 min-40 min) before exposing it to bacteria for 2 hours exposure time period. After 2 hours of exposure, bacteria were washed from the carrier using neutralizer buffer and placed on tryptic soy agar plates. After 24 hours of incubation at 37°C, bacterial colony formation was detected and counted. Count geometric means and percent reductions are based on the number of colonies from the samples relative to the glass carrier or appropriate paint controls.

[0174] An article according to one or more embodiments is formed as follows. Grind the glass into a powder, and with the description

Mixed with a commercially available carrier of a clear gloss protective finish available from the Minwax Company under the Polycryl ic® trade mark. The copper loading (wt%/wt%) is about 5%, 10% or 15% (based on a glass containing about 20wt% Cu). The mixed carrier and glass powder were then brush coated onto Pyvek® paper, which was backed with a polymer film, and then coated. The coated Pyvek® paper was cut into 2.5x2.5 cm pieces for antimicrobial performance testing .

[0175] When using a thermoplastic polymer, the glass powder was mixed with a commercially available polymer (under the trademark Peralthane®) at a temperature range of 195°C - 220°C and a speed of 50 rpm (revolutions per minute). The glass loading is about 60-80%. The resulting polymer and glass composites were fabricated into 2.5x2.5 cm sheets by a hot pressing process.

[0176] In some embodiments, epoxy resins are utilized. In this example, about 3.0 grams of a commercially available epoxy resin (Erisys GE22) was combined with about 1 g of curing agent (Amicure PACM) and 2 grams of ethanol in a 20 ml vial and mixed well. Add about 10 grams of powdered glass and mix well. The resulting mixture was solidified at room temperature for a few days and then the vial was broken to form a gel from the combination, which was further dried at room temperature for 1 day and at 65°C for several hours. This yields a dry epoxy/glass composite.

[0177] The examples were also tested in combination with epoxy resin to determine the density or porosity of the composite. This involves placing the example in water for 2 minutes, then removing the example. The difference in mass before and after being placed in water was measured to detect the porosity of the examples.

[0178] Under the EPA test, sheets made entirely of the glass of Examples 4, 5, 6, 9, 10, 12, 13, 14 and 21 were tested. In addition, a comparative substrate of pure copper metal was tested under EPA testing. Figure 9 shows the antimicrobial properties of those glasses. Example 14 exhibited at least the same antimicrobial performance as the comparative substrate, and Examples 6, 12, and 13 exhibited a greater than 3 log reduction in Staphylococcus aureus.

[0179] The glass 56 is formed as particles having an average major dimension of less than or equal to about 1 micron. The particles are combined with a polymeric carrier. The loading of particles in the carrier is about 5%. As measured by the EPA test for Staphylococcus aureus, the antimicrobial efficacy was assessed at the following time points: immediately after the combination of particles and polymeric carrier, 1 week after combination of particles and polymeric carrier, and after combination of particles and polymeric carrier 1 month, and 3 months after combination of particles and polymeric carrier. Figure 10 is a graph showing the antimicrobial efficiency after each time period. As shown in Figure 10, the glass exhibited at least a 2 log reduction in S. aureus even 3 months after being formed into particles and combined with the polymeric carrier. Furthermore, the combination of glass particles and polymeric carrier exhibited a greater than 5 log reduction 1 month after combination.

Antimicrobial activity of glass 56 and comparative glass (A) (comprising 10% by weight of silver ion content diffused therein) relative to murine norovirus and cellular toxicity. In addition, antimicrobial activity control samples and cytotoxicity control samples of Glass 56 and Comparative Glass A were prepared as described for the modified JIS Z 2801 test for viruses. Table 5 shows the results of the input virus control and the antimicrobial activity control, Table 6 shows the results of the cytotoxicity control, Table 7 shows the results of comparative glass A after being exposed to murine norovirus for an exposure time of 2 hours, and Table 8 shows the results of the comparative glass A after exposure to murine norovirus. Glass 56 after an exposure time of 2 hours to murine norovirus, Table 9 shows the cytotoxicity of comparative Glass A and Glass 56 to RAW 264.7 cell cultures, and Table 10 shows the non-virucidal levels of the tested virus, as measured in Measured on comparative Glass A and Glass 56 cytotoxicity control samples.

Table 5: input virus control and antimicrobial activity control result

[0182]

[0183]

<td rowspan="2">dilution</td><td rowspan="2">input virus control</td><td colspan="3">Antimicrobial activity control</td>

<td>Replica #1</td><td>Rework #2</td><td>Replica #3</td>

<td>cell control</td><td>0 0</td><td>0 0 0 0</td><td>0 0 0 0</td><td>0 0 0 0</td>

<td>10^-1</td><td>+ +</td><td>NT</td><td>NT</td><td>NT</td>

<td>10 ²</td><td>+ +</td><td>+ + + +</td><td>ten + +</td><td>+ + + +</td>

<td>O</td><td>+ +</td><td>+ + 44</td><td>+ + 44</td><td>+ + + +</td>

<td>10 ⁴</td><td>+ +</td><td>+ten+ +</td><td>+ + + +</td><td>+ + + +</td>

<td>10 3</td><td>+ +</td><td>+ + + +</td><td>+ + + +</td><td>+ + + +</td>

<td>10^-6</td><td>+ +</td><td>0 + + +</td><td>+ + 0 +</td><td>+ + + +</td>

<td>10^-7</td><td>0 0</td><td>0 0 0 0</td><td>0 0 0 0</td><td>0 0 0 0</td>

<td>©</td><td>ϋ 0</td><td>0 0 0 0</td><td>0 0 0 0</td><td>ϋ ϋ 0 ϋ</td>

<td>PFUso/250μΐ</td><td>10⁶·⁵⁰</td><td>1 production</td><td>[slide 5</td><td>]Produce</td>

<td>Average PFU_m/250μ.</td><td>NA</td><td colspan="3">]0% 3M</td>

(+) = positive for the presence of test virus (0) = no test virus recovered and/or absence of cytotoxicity (ha) = not applicable (NT) = not tested Table 6: Cytotoxicity control results.

[0184]

<td>dilution</td><td colspan="2">Cytotoxicity control (after 2 hours exposure time)</td>

<td></td><td>Replica #1 Replica #2</td><td>Replica #3</td>

<td>cell control</td><td>0 0 0 0 0 0 0 0</td><td>0 0 0 0</td>

<td>10^-2</td><td>+ + + + + + + +</td><td>+ + + +</td>

<td>10^-3</td><td>+ + + + + + + +</td><td>+ + + +</td>

<td>10^-4</td><td>+ + + + + + + +</td><td>+ + + +</td>

<td>10^-5</td><td>+ + + + + + + +</td><td>+ + + +</td>

<td>10^-s</td><td>0 0 0 0 0 0 + 0</td><td>0 + 00</td>

<td>10-</td><td>0 0 0 0 0 0 0 0</td><td>0 0 0 0</td>

<td>10^-8</td><td>0 0 0 0 0 0 0 0</td><td>0 0 0 0</td>

<td>PFU₅o/25O μL</td><td>1 q 5. 50 ] q 5. 7 5</td><td>105.75</td>

<td>average</td><td>] limit 67</td><td></td>

<td>PFU5q/250 μE</td><td></td><td></td>

Even) ii positive for the presence of test virus (0) ii no test virus recovered and/or absence of cytotoxicity

[0185]

Table 7: Results for Comparative Glass A after exposure to murine norovirus for an exposure time of 2 hours.

<td rowspan="2">dilution</td><td colspan="3">Comparative glass a-exposure to murine norovirus</td>

<td>Replica #1</td><td>Replica #2</td><td>Replica #3</td>

<td>cell control</td><td>0 0()0</td><td>0 0 0 ()</td><td>0 0 0 0</td>

<td></td><td>+ + ++</td><td>+ + + +</td><td>+ + + +</td>

<td>10^-3</td><td>+ + ++</td><td>+ + + +</td><td>+ + + +</td>

<td>10^-4</td><td>+ + ++</td><td>+ + + +</td><td>+ + 4 +</td>

[0187]

<td></td><td>+ + - ten</td><td>+ 4 + 4 + 4 + -Η</td>

<td></td><td>0 + +0</td><td>+ 00+ + + 00</td>

<td>I0^-7</td><td>0 0 00</td><td>0 0 0 0 0 0 0 0</td>

<td>10^-8</td><td>ο ο ϋ0</td><td>o ϋ ϋ ο ο ο ο ο</td>

<td>PFU_5O/250 Spit</td><td>10"°ΰ</td><td>10 to 00 1 0 to 00</td>

<td>Average PHΛ°/250°</td><td colspan="2">]q6. Lice</td>

<td>Mean % reduction (based on cytotoxic control)</td><td colspan="2">no reduction</td>

<td>Mean Logi. Reduction (Based on Cytotoxicity Control)</td><td colspan="2">no reduction</td>

<td>Mean % reduction (based on antimicrobial activity control)</td><td colspan="2">53. 2%</td>

<td>Mean Logi. Reduction (based on antimicrobial activity control)</td><td colspan="2">0. 33Logo</td>

<td colspan="3">(+) = Positive for presence of test virus (0) = No test virus recovered and/or absence of cytotoxicity</td>

Table 8: Results for Glass 56 after exposure to murine norovirus for an exposure time of 2 hours.

[0188]

[0189]

<td rowspan="2">dilution</td><td colspan="3">Glass 56 - Exposure to Murine Norovirus</td>

<td>Replica #1</td><td>Replica #2</td><td>Replica #3</td>

<td>cell control</td><td>0 0 00</td><td>0 0 0 0</td><td>0 0 0 0</td>

<td>10^-2</td><td>+ + ++</td><td>0 0 0 0</td><td>0 0 0 0</td>

<td>10^-3</td><td>+ 0 +0</td><td>0 0 0 0</td><td>0 0 0 0</td>

<td>10-⁴</td><td>0 0 00</td><td>0 0 0 0</td><td>0 0 0 0</td>

<td>10^-1</td><td>0 0 00</td><td>0 0 0 0</td><td>0 0 0 0</td>

<td>10^-6</td><td>0 0 00</td><td>0 0 0 0</td><td>0 0 0 0</td>

<td>10^-7</td><td>0 0 00</td><td>0 0 0 0</td><td>0 0 0 0</td>

<td>10^-3</td><td>0 0 00</td><td>0 0 0 0</td><td>0 0 0 0</td>

<td>PFUo/250μΐ</td><td>&lt;10³0°</td><td>&lt;10* ⁵⁰</td><td>Three 101.50</td>

<td>Average FFU5o/25O μΐ.</td><td colspan="3">&lt;io^2w</td>

<td>Mean % reduction (based on cytotoxic control)</td><td colspan="3">&gt;99.98%</td>

<td>Mean Logi. Reduction (Based on Cytotoxicity Control)</td><td colspan="3">&gt;3.67Logo</td>

<td>Average % reduction (based on antimicrobial activity control)</td><td colspan="3">&gt;99.995%</td>

<td>Mean Logi. reduce (with antimicrobial activity</td><td colspan="3">&gt;4. 33 Log₁₀</td>

<td>sex control as the benchmark)</td><td></td>

<td colspan="2">(+) = positive for presence of test virus (0) = no test virus recovered and/or absence of cytotoxicity</td>

Table 9: Cytotoxicity of Control Comparative Glass A and Control Glass 56 to RAW 264.7 Cell Cultures

<td rowspan="2">dilution</td><td>Cytotoxicity Control</td>

<td>Comparative Glass a Glass 56</td>

<td>cell control</td><td>0 0 0 0</td>

<td>10^-2</td><td>0 0 0 0</td>

<td>10^-3</td><td>0 0 0 0</td>

<td>10^-4</td><td>0 0 0 0</td>

<td></td><td>0 0 0 0</td>

<td>10*</td><td>0 0 0 0</td>

<td>10-</td><td>0 0 0 0</td>

<td></td><td>0 0 0 0</td>

<td>TCDso/250 μΕ</td><td>&lt;101·⁵⁰</td>

(0) = No test virus recovered and/or absence of cytotoxicity

Table 10: Non-Virucidal Levels of Test Substances (Neutralization Control)

[0194]

<td rowspan="2">dilution</td><td>Antimicrobial Activity + Cytotoxicity Control</td>

<td>Comparative Glass A Glass 56</td>

<td>cell control</td><td>0 0 0 0</td>

<td>10^-2</td><td>+ + + +</td>

<td>10^-3</td><td>+ + + +</td>

<td>10^-4</td><td>+ + + +</td>

<td>10^-5</td><td>+ + + +</td>

<td>10^-s</td><td>+ + + +</td>

<td>10^-7</td><td>+ + + +</td>

<td></td><td>+ + + +</td>

<td colspan="2">(+) 2 Positive for the presence of test virus after addition of low titer stock virus (neutralization control) (0) 2 No test virus recovered and/or absence of cytotoxicity</td>

Compared with the antimicrobial activity control sample, after an exposure time of 2 hours at room temperature (20° C.) and 42% relative humidity, comparative glass A presents a 0.33 log reduction (or 53.2 % average reduction). However, Glass 56 exhibited a greater than 4.33 log reduction in murine norovirus (or 99.995% average reduction or greater).

Compared with the cytotoxicity control sample, after an exposure time of 2 hours at room temperature (20° C.) and a relative humidity of 42% in the presence of 5% fetal calf serum organic soil loading, comparative glass A did not cause There was an average reduction in viral titers for murine norovirus. However, in the presence of 5% fetal bovine serum organic soil loading, after an exposure time of 2 hours at room temperature (20°C) and 42% relative humidity, glass 56 smothered murine norovirus compared to the cytotoxic control sample. The viral titers exhibited a mean log reduction of greater than 3.67 (or a mean reduction of at least 99.98% or greater).

The results shown in Table 10 show that each test sample was neutralized at a PFU50/250uL of 1.5 logio.

[0198] Examples 12, 13 and 14 were formed into powders and mixed with Polycrlic® at various loadings based on Czo content. Then, by a brushing process, the mixture was applied to Pyvek® paper (which was backed with a plastic film before coating) and allowed to cure for 1 week. The coated paper was cut into pieces for testing under the EPA test. Figures 11 and 12 show the results. Figure 11 shows the antimicrobial performance of tablets with different copper loadings. Figure 12 shows the antimicrobial performance of the composite with 15% CU20.

[0199] Example 12 was ground into a powder and mixed with Pear 1 Thane® polyurethane to provide composites with varying amounts of glass (in weight percent). The powdered glass and polyurethane were mixed for a few minutes at 195-220°C. The resulting combination was fabricated into 2.5 cm x 2.5 cm sheets using melt processing techniques and evaluated for antimicrobial performance using the EPA test. result

See Figure 13.

[0200] Injection molded articles were formed to evaluate antimicrobial activity when the surface was generally covered by a thin layer of matrix polymer. In such articles, the matrix polymer is typically hydrophobic and can affect antimicrobial performance. As shown in Figure 14, surface treatment can improve antimicrobial performance. To prepare injection molded samples, Example 12 was ground into a powder and mixed with Pearlthane® polyurethane to provide an injection moldable composite with 60% glass by weight. The composites were injection molded in petri dishes as shown in Figure 14 to provide 4 injection molded samples (sample aD) for evaluation of their antimicrobial properties using the EPA test. Sample A had no surface treatment. Sand sample B to remove approximately 10 mg of the top surface of the sample. As shown in Table 11, samples C and D were plasma treated for 5 minutes using two different gases, using a power of 100 W and a pressure of 2 Torr. Figure 15 shows the log reduction for samples aD.

Table 11: Plasma Treatment Conditions for Samples C and D.

<td colspan="5">Form 115</td>

<td>Material</td><td>time, minutes</td><td>Power, W</td><td>pressure</td><td>gas</td>

<td>Sample C</td><td>5</td><td>100</td><td>2</td><td>Air</td>

<td>Sample D</td><td>5</td><td>100</td><td>2</td><td>(94/6 volume %)</td>

[0203] As described herein, thermoplastic polymers can be used to form the articles described herein by a melt mixing process. Additionally, thermoplastic polymers can be formed by in situ polymerization and subsequently formed into articles by a casting process. products of things. Epoxy resin, which is a thermoplastic polymer, was used to prove the concept. Epoxy resins were prepared from Erisys GE22 and Amicure PACM, which mixed well in the presence of alcohol. Example 12 was ground into a powder and added to the mixture according to Table 12, resulting in a slurry-like material that was cast into a mould. In this example, glass vials were used as molds. Then, the combination of epoxy resin and ground glass was cured for several days at room temperature. The mold was then removed and the resulting article was dried at room temperature for 1 day and at 65°C for several hours.

Table 12: Composition for the preparation of articles with epoxy resin and ground glass from Example 12

<td colspan="4">Table 12</td>

<td>Material</td><td>weight, parts</td><td>Quantity, number of copies</td><td>weight, parts</td>

<td>Erisys GE22</td><td></td><td>1</td><td>3</td>

<td>Amicure PACM</td><td>0. 3</td><td>0. 3</td><td>1</td>

<td>ethanol</td><td>6</td><td>5</td><td>2</td>

<td>Example 12</td><td>15</td><td>10</td><td>10</td>

[0206] Depending on the loading of glass in the article, the resulting article can be porous or dense. As can be seen from Table 13, the porosity increases with increasing glass loading, where the water absorption of the articles was measured after soaking the articles in water for 2 minutes. Different articles were prepared from the same epoxy resin used in Table 12 combined with different amounts of ground glass from Example 12. The articles were prepared using gel casting.

Table 13: Water absorption using epoxy resin and different ground glass supported articles from Example 12.

<td colspan="2">Table 13</td>

<td>Example 12 Glass Loading (wt%/wt%)</td><td>Water absorption within 2 minutes, %</td>

<td>71</td><td>0. 5</td>

<td>88</td><td>5. 9</td>

<td>92</td><td>20. 7</td>

[0209] It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention.