Antimicrobial Products Containing Silver and Copper Particles

Abstract

This invention relates to an antimicrobial product containing silver-copper particles and its preparation method. The product includes a substrate and positively charged silver particles with a particle size of 15 μm to 50 μm, and a positively charged copper particle with a particle size of 10 μm to 50 μm, wherein the copper particle size ratio to the silver particle is 0.8 to 1.2. The silver particle, the copper particle and the substrate are combined by means of semi-fused sintering, wherein the ratio of the silver particle to the copper particle is 40:60 to 95:5. The sum of the substrate, the silver particles and the total particles of the copper particles is less than or equal to 10%.

Claims

1. An antimicrobial product containing silver-copper particles, characterized in that the product comprises a substrate and positively charged silver particles with a particle size of 15 μm to 50 μm and positively charged copper particles with a particle size of 10 μm to 50 μm, Wherein the particle size ratio of the silver particles to the copper particles is 0.8 to 1.2, and the silver particles, the copper particles and the substrate are combined by means of semi-fused sintering; Wherein the ratio of the number of silver particles to the copper particles is 40:60 to 95:5, and based on the total number of particles of the substrate, the silver particles and the copper particles, the silver particles and the sum of the copper particles is less than or equal to 10%, preferably less than or equal to 8%, more preferably less than or equal to 5%.

2. The antimicrobial particle according to claim 1, wherein the silver particles have a particle size of 20 μm to 45 μm, preferably 25 μm to 40 μm, more preferably 28 μm to 38 μm.

3. The antimicrobial article according to claim 1, wherein the copper particles have a particle size of 10 μm to 45 μm, preferably 15 μm to 40 μm, more preferably 22 μm to 38 μm.

4. The antimicrobial article according to claim 1, wherein the particle number ratio of the silver particles to the copper particles is 50:50 to 95:5, preferably 55:45 to 90:10, more preferably 60:40 to 80:20.

5. The antimicrobial article according to any one of claims 1 to 4, wherein the elemental silver particles and elemental copper particles undergo high velocity thermal spray, high velocity plasma spray or low velocity flame spray to become positively charged silver particles and positively charged copper particles, and wherein in the high velocity thermal spray, high velocity plasma spray, the particle velocity is greater than 340 m/s, wherein in the low velocity flame spray, the particle velocity is less than or equal to 50 m/s.

6. The antimicrobial article according to claim 5, wherein the silver particles, copper particles and the base material are mixed together, and then form semi-fused bond by high velocity thermal spray, high velocity plasma spray or low velocity flame spray.

7. The antimicrobial article according to claim 5, wherein the substrate is selected from the group consisting of nickel-based tungsten carbide, cobalt-based tungsten carbide, nickel-chromium chromium carbide, nickel-based alloys, cobalt-based alloys, and combinations thereof, and wherein silver particles, copper particles and the base material are mixed together, and then form semi-fused bond by high velocity flame spray or high velocity plasma spray.

8. The antimicrobial article according to claim 5, wherein the substrate is selected from the group consisting of glass beads, calcium carbonate, ceramics, and combinations thereof, and wherein silver particles, copper particles and the substrate are mixed together, and then processed by low velocity flame spray to form semi-fused bonding.

9. The antimicrobial article according to claim 1, further comprising a polymer film disposed on the outer surface, wherein the thickness of the polymer film is 0.5 μm to 60 μm.

10. The method for preparing a product comprising the antimicrobial product according to any one of claims 1 to 9, characterized in that the method comprises: Mix the silver particles, copper particles and substrate particles uniformly to obtain a particle mixture, When the substrate is selected from nickel-based tungsten carbide, cobalt-based tungsten carbide, nickel-chromium chromium carbide, nickel-based alloys, cobalt-based alloys, and combinations thereof, the particulate mixture is sprayed by high velocity thermal spray, high velocity plasma spray, directly spraying on the metal substrate to form an antimicrobial coating, thereby obtaining the product; When the substrate is selected from glass beads, calcium carbonate, ceramics, and combinations thereof, the particulate mixture is sprayed into a collection tank by low velocity flame spray to obtain antimicrobial powder, and then the antimicrobial powder and the carrier undergoes spinning, bonding, coating, embedding, extrusion or extrusion process to form the product.

Description

EXAMPLES

[0047] The below specific implementations of this application as disclosed will be explained in detail through the following examples, so as to better understand the various aspects and advantages of this application. However, it should be understood that the following examples are non-limiting and are only used to illustrate certain implementations of this application.

[0048] In the examples herein, all materials are commercially available products. Specifically, 450-800 mesh silver powder and copper powder were purchased from Shanghai Didan Metal Materials Co., Ltd., glass beads were purchased from Singarpore Pan Abrasives grade AQ, and tungsten carbide was purchased from Praxair, USA. Powder 1350vm (cobalt-based), 1310vm (nickel-based).

Example 1

[0049] Weigh silver powder (38 μm), copper powder (38 μm) and tungsten carbide powder (45 μm), mix them evenly at a particle ratio of 5%:3%:92%, and add them into the powder feeder, and delivery to high velocity flame spray gun. Then, the stainless-steel sheet target is placed and clamped tightly. The uniformly mixed powder mixture is sprayed directly onto the stainless-steel sheet in the target, the particle at a sound speed (greater than 340 m/s) through a spray gun, to form a coating with a thickness of 200 μm.

Example 2

[0050] Weigh silver powder (28 μm), copper powder (27 μm) and tungsten carbide powder (41 μm), mix them evenly at a particle ratio of 7%:2%:91%, and add them into the powder feeder, and delivery to high velocity flame spray gun. Then, the stainless-steel sheet target is placed and clamped tightly. The uniformly mixed powder mixture is sprayed directly onto the stainless-steel sheet in the target, the particle at a sound speed (greater than 340 m/s) through a spray gun, to form a coating with a thickness of 200 μm.

Example 3

[0051] Weigh silver powder (25 μm), copper powder (25 μm) and tungsten carbide powder (38 μm), mix them evenly at a particle ratio of 4%:3%:93%, and add them to the powder feeder, and delivery to high velocity flame spray gun. Then, the stainless-steel sheet target is placed and clamped tightly. The uniformly mixed powder mixture is sprayed directly onto the stainless-steel sheet in the target, the particle at a sound speed (greater than 340 m/s) through a spray gun, to form a coating with a thickness of 200 μm.

Example 4

[0052] Weigh silver powder (25 μm), copper powder (25 μm) and glass beads (38 μm), mix them evenly at a particle ratio of 4%:4%:92%, and add them to the powder feeder, and delivery to the oxygen-acetylene spray gun. Then, the evenly mixed powder mixture is sprayed into the collection tank through the spray gun to obtain the antibacterial powder.

Example 5

[0053] Weigh silver powder (38 μm), copper powder (38 μm) and ceramic powder (52 μm), mix them evenly at a particle ratio of 7%:2%:91%, and add them to the powder feeder, and delivery to the oxygen-acetylene spray gun. Then, the evenly mixed powder mixture is sprayed into the collection tank through the spray gun to obtain the antibacterial powder.

Comparative Example 1

[0054] Weigh silver powder (38 μm) and tungsten carbide powder (45 μm), mix them evenly at a particle ratio of 5%:95%, and add them to the powder feeder, and delivery to high velocity flame spray gun. Then, the stainless-steel sheet target is placed and clamped tightly. The uniformly mixed powder mixture is sprayed directly onto the stainless-steel sheet in the target, the particle at a sound speed (greater than 340 m/s) through a spray gun, to form a coating with a thickness of 200 μm.

Comparative Example 2

[0055] Weigh silver powder (38 μm) and ceramic powder (52 μm), mix them evenly at a particle ratio of 9%:91%, and add them to the powder feeder, and delivery to the oxygen-acetylene spray gun. Then, the evenly mixed powder mixture is sprayed into the collection tank through the spray gun to obtain the antibacterial powder.

[0056] Test Case 1

[0057] The silver copper tungsten carbide coating prepared in Example 1 was used, the test bacteria was influenza A virus H1N1, and the host cells were MDCK cells. The test time is 12 hours and the test method is ISO21702:2019. The test results are shown in Table 1 below. In addition, the coating in Comparative Example 1 was used as a control group, and the test results are shown in Table 2 below:

TABLE-US-00001 TABLE 1 Silver Copper-Carrier Coating 12 Hours 0 Hour Experimental Virus Group Virus Virus Group Titer Titer Influenza A Virus 1 7.33 5.67 H1N1 2 7.00 6.00 Host MDCK Cells 3 7.00 5.67 Average Ig 7.11 5.78 (TCID.sub.50/mL). Average Ig 6.91 5.58 (TCID.sub.50/cm.sup.2). Kill Rate (%) 78.12

TABLE-US-00002 TABLE 2 Silver- Carrier Coating Inoculation Average Virus Titer After concentration 12 Hours of Exposure Kill Virus (cfu/mL) Test Group 1 2 Rate Influenza A 1 × 10.sup.7 Sample 6.50 6.67 44.78% Virus H1N1 Control Sample 6.83 7.00

[0058] Test Case 2

[0059] The antibacterial powder prepared in Example 5 was adhered to a plastic film to form a 200 nm coating, which was used as a sample. The test bacteria are Staphylococcus aureus, and the test method is JIS Z 2801:2010. The test results are shown in Tables 3 to 5 below. In addition, the antibacterial powder of Comparative Example 2 was used as a control, and the test results are shown in Table 6 below.

TABLE-US-00003 TABLE 3 SilverCopper + Carrier 0.5 HourTest The average number of logarithmic values of the number of bacteria Concentration (cfu/cm2) obtained after different of Inoculum amount exposure times Experimental Solution Inoculum 0.5 Kill Strain (cfu/mL) (mL) / 0 hours hours Rate Staphylococcus 1.4 × 10.sup.5 0.2 Sample / 4.1 × 10.sup.4 70.71% aureus ControlSample 1.4 × 10.sup.5 1.4 × 10.sup.5

TABLE-US-00004 TABLE 4 SilverCopper + Carrier 1 Hour Test The average number of logarithmic Concentration values of the number of bacteria of Inoculum Inoculum (cfu/cm2) obtained after different Experimental Solution amount exposure times Kill Strain (cfu/mL) (mL) / 0 hours 1 hour Rate Staphylococcus 1.4 × 10.sup.5 0.2 Sample / 1.3 × 10.sup.4 90.71% aureus ControlSample 1.4 × 10.sup.5 1.4 × 10.sup.5

TABLE-US-00005 TABLE 5 SilverCopper + Carrier 1 Hour Test The average number of logarithmic Concentration values of the number of bacteria of Inoculum Inoculum (cfu/cm2) obtained after different Experimental Solution amount exposure times Kill Strain (cfu/mL) (mL) / 0 hours 1 hour Rate Staphylococcus 6.2 × 10.sup.4 0.2 Sample / 6.0 × 10.sup.2 99.54% aureus ControlSample 6.2 × 10.sup.4 1.3 × 10.sup.5

TABLE-US-00006 TABLE 6 SilverCopper + Carrier 1 Hour Test The average number of logarithmic Concentration values of the number of bacteria of Inoculum (cfu/cm2) obtained after different Experimental Solution exposure times Kill Strain (cfu/mL) / 0 hours 1 hour Rate Staphylococcus 2.4 × 10.sup.5 2.4 × 10.sup.5 <50 99.98% aureus

[0060] Test results shows, the silver-copper antibacterial powder of the present application can achieve a microbial killing rate roughly equivalent to that of pure silver antibacterial powder, but because 22% of the silver is replaced by copper, the price is greatly reduced, which makes the final antibacterial powder Microbial products are more competitive.

[0061] Test Case 3

[0062] The silver-copper tungsten carbide coating prepared in Example 1 with a thickness of 200 μm was used, and a polytetrafluoroethylene coating with a thickness of 30 μm was covered on it, and a square of 5×5 cm was cut out to obtain a sample. The test bacteria is Staphylococcus aureus, and the test method is JIS Z 2801:2010. The test results are shown in Table 7 below.

TABLE-US-00007 TABLE 7 Concentration of Concentration of Concentration of viable bacteria at viable bacteria 24 viable bacteria 24 0 hours after hours after hours after inoculation of inoculation of the inoculation of Test the blank sample blank sample antibacterial Antibacterial Microorganisms (cfu/mL) (cfu/mL) sample (cfu/mL) Rate (%) Staphylococcus 2.7 × 10.sup.5 3.8 × 10.sup.5 <20 >99.99 aureus

[0063] Test results shows, the silver-copper tungsten carbide of the present application is sterilized in a non-contact manner, and due to the presence of a polymer film covering the coating, it can prevent the silver/copper particles from spreading to the outside and causing unnecessary contamination.

[0064] It can be understood from the foregoing that although the specific examples of the present application are described for illustrative purposes, those skilled in the art can make various modifications or improvements without departing from the spirit and scope of the present application. These deformations or modifications should fall within the scope of the appended claims of this application.