EP2499269A1 - Antitarnish, antimicrobial copper alloys and surfaces made from such alloys - Google Patents
Antitarnish, antimicrobial copper alloys and surfaces made from such alloysInfo
- Publication number
- EP2499269A1 EP2499269A1 EP10830632A EP10830632A EP2499269A1 EP 2499269 A1 EP2499269 A1 EP 2499269A1 EP 10830632 A EP10830632 A EP 10830632A EP 10830632 A EP10830632 A EP 10830632A EP 2499269 A1 EP2499269 A1 EP 2499269A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alloys
- antimicrobial
- testing
- color
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/01—Alloys based on copper with aluminium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/04—Alloys based on copper with zinc as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/05—Alloys based on copper with manganese as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
Definitions
- This invention relates to antimicrobial copper alloys, and to surfaces made from such alloys, and in particular to tarnish resistant antimicrobial copper alloys and surfaces made from such alloys.
- Copper and copper alloys are known to have useful antimicrobial properties. These metals can kill human pathogens, including bacteria such as E. coli 0157, Listeria monocytogenes, Salmonella, and Methicillin-resistant Staphylococcus aureus (MRS A). The Environmental Protection Agency has declared that alloys containing 65% or more copper have inherent antimicrobial properties. See,
- Antimicrobial Copper Alloys Group I (EPA Reg. No. 82012-1), Antimicrobial Copper Alloys Group II (EPA Reg. No. 82012-2), Antimicrobial Copper Alloys Group III (EPA Reg. No. 82012-3), Antimicrobial Copper Alloys Group IV (EPA Reg. No. 82012-4), and Antimicrobial Copper Alloys Group V (EPA Reg. No. 82012-5), incorporated herein by reference.
- copper and copper alloys would at first blush appear to be good candidates for fabricating surfaces in health care and food service facilities, and even in home and industrial settings.
- silver-toned tarnish-resistant antimicrobial copper alloys are known (e.g., C710), for at least some applications it is desirable to avoid silver- toned colors because these may be confused with more familiar silver-toned surfaces such as stainless steel, which while they can be sterilized, are not regarded as
- C706 is another tarnish resistant antimicrobial copper alloy, but has a rose color, which may not be desirable for some applications.
- a preferred embodiment provides alloys with a combination of antimicrobial properties, attractive appearance, and tarnish resistance.
- the alloys of this preferred embodiment comprise at least 1% Ni, and up to 3 % Al.
- the alloys have a golden visual appearance, and contain Zn and/or Mn up to about 15%. Other elements that do not negatively impact tarnish resistance or
- antimicrobial activity of the alloy can be present.
- Embodiments of this invention provide alloys, and surfaces made with such, alloys, with a combination of antimicrobial properties, attractive appearance, and tarnish resistance.
- the alloy has an attractive golden visual appearance.
- the alloys of this preferred embodiment comprise between about 1 and about 4 % Ni, and up to 3 % Al. (Percentages are weight percentages unless otherwise indicated.) In a more preferred embodiment the alloys contain Zn and/or Mn up to about 15%. Other elements that do not negatively impact tarnish resistance or antimicrobial activity of the alloy can be present.
- alloys of Cu-Ni-Al provide a desirable combination of tarnish resistance and color
- alloys of Cu-Zn-Mn-Ni- Al such as those identified herein as K475, K476, K589, K592, and K593 provide a desirable combination of antimicrobial activity, tarnish resistance, and a desirable golden visual appearance.
- nickel is present in sufficient amounts to improve tarnish resistance. Generally, nickel in excess of about 1% improves tarnish resistance, and the nickel content is preferably at least 1.5%. In Cu-Ni-AI alloys the Ni content may be as high as 6.9% or higher. There is not necessarily an upper limit on nickel content, but nickel content is generally limited by its cost compared to the other alloying elements, and its effect, together with the other alloying elements, on the color of the alloy.
- Aluminum is preferably present in amounts up to about 3%. It is generally preferred that aluminum be present at a level of at least 0.6%. Additional aluminum above 3% does not appear to be necessary, and in amounts above about 8% to 11%, can negatively affect antimicrobial activity of the alloy. See, Use of Copper Cast Alloys to Control
- Zinc alone or in combination with manganese, improves the tarnish resistance of Ni-Cu and Ni-Al-Cu alloys, and affects their color. If zinc is present without manganese, then the zinc content is preferably at least about 6.8%, and preferably less than about 15%. If zinc and manganese are both present, zinc can be present in any amount, but it is preferable that the total content of zinc and manganese does not exceed a level which increases susceptibility to stress corrosion cracking, generally believed to be about 15%. Where both zinc and manganese are present, the zinc content is preferably between about 6.8% and about 10.8%. Considerations in setting the upper limit of the zinc content include resisting stress corrosion cracking, and maintaining desired color. Manganese
- Manganese alone or in combination with zinc, improves the tarnish resistance of Ni-Cu and Ni-Al-Cu alloys, and affects their color. If manganese is present without zinc, then the manganese content is preferably at least about 4.8%, and preferably less than about 15%. If manganese and zinc are both present, manganese can be present in any amount, but it is preferable that the total content of zinc and manganese does not exceed a level which increases susceptibility to stress corrosion cracking, generally believed to be about 15%. Where both zinc and manganese are present, the manganese content is preferably between about 4.8% and about 6.9%. Considerations in setting the upper limit of the manganese content include resisting stress corrosion cracking, and maintaining desired color.
- Experimental alloys (identified with prefix IC) for Examples 1-5 were prepared by casting into 10 pound laboratory ingots. Alloys for Example 6 were prepared by direct chill casting into 7 inch x 30 inch x 25 foot bars. The production bars and laboratory ingots were both processed to mill plate by soaking at about 850° C and hot rolling to between 0.5-0.6 inch thick. In each case, the hot rolled plate or coil was milled to remove surface oxides developed during hot rolling. The alloys were then processed to the condition in which they were tested by sequential cold rolling and annealing steps to produce the desired metallurgical condition.
- the tested alloys were either as-rolled (AR) or roughened with Scotch-Brite® (SB).
- Touch testing consisted of having a plurality of different people touch the samples of each of the alloys (except 304LSS) for 5 minutes twice daily for 21 days. Alloys were rotated among people each week for 3 weeks. All tested alloys were judged by at least three independent judges according to the following criteria:
- Touch testing consisted of having a variety of people touch the samples of each of the alloys for 5 minutes twice daily for 21 days. Alloys were rotated among people each week for 3 weeks. All tested alloys were judged by at least three independent judges according to the following criteria:
- K475 performed equal to stainless steel in both the touching and humidity tests.
- the other two developmental alloys, K476 and K477 both are very close in performance to the stainless. These alloys appear to be relatively unaffected by humidity or human touch in this testing.
- the combination of Ni + Al appears to be beneficial to resistance from tarnishing from touching and humidity, at least under these testing conditions.
- Table 12 collects the results of the testing from Examples 1 through 3.
- data for alloys K538 - K543 and alloys K589 - K602 comes from testing, in accordance with the procedures set forth in Example 2.
- alloys with clean test scores of less than 4.5 and touch test scores of 2 or less are indicated as having "good" tarnish resistance.
- Color information for selected alloys is also indicated in Table 12, based upon the following comparative scale:
- color determination may be by spectroscopy or other objective means.
- Hue is color perception, the recognition of an object as green, blue, red, yellow, etc.
- Chroma is color concentration and ranges from grey to pure hue. Value is the lightness of the color and ranges from white to black.
- CIELAB scale CIE stands for Commission Internationale de 1' Eclairage (International Commission on Illumination) and LAB stands for the Hunter L,a,b scale.
- the CIELAB color chart expresses hue as a combination of an a* value and a b* value extending arcuately about the color chart, with +a* being red, -a* being green, +b* being yellow and -b* being blue.
- Chroma is expressed as a value from the center of the circle with the center (0) being grey and +/- 60 being full richness of the specified color.
- Value is expressed as an L* number ranging from white to black, such that the combination of hue, chroma and lightness represents a specific point on. a three-dimensional sphere and a specific color.
- alloys K475, K475A and K476 provide antimicrobial materials with good tarnish resistance and a whitish golden color
- alloy K477 provides an antimicrobial material with good tarnish resistance and a yellowish golden color.
- Tables 13-15 show mechanical properties for some of the alloys in
- Table 16 is a table of other possible antimicrobial, tarnish-resistant alloys, with desirable appearance and color traits.
- Ni-1.5 Al would give good cleaning and touch results based upon the results of Example 4.
- a new series of alloys were cast, hot rolled HR75% (reduction in thickness), milled and cold rolled CR 92%, annealed under different conditions and given a small 1044% final reduction.
- the compositions and mechanical test results are reported in Table 18. Alloys in Table 18 were cleaned and evaluated as in Example 4. All alloys scored 1 when cleaned with Proxi®, Dawn® diluted with water(l :10), and antimicrobial Fantastik. As before, the alloys did poorly when cleaned with CleanCide wipes, rating 3-4.
- Mattsson's solution is composed of copper sulfate pentahydrate, ammonium sulfate, and ammonium hydroxide in water. The pH is controlled from 7.1 to 7.5, the region of highest SCC susceptibility. Test specimens are examined periodically for cracks under a stereo microscope at 30x. A visible penetrating crack is judged a failure. In addition, the samples are evaluated for stress relaxation. If the remaining stress on the sample falls below 80% of the original stress level, the sample has failed. The recommended test duration in ASTM G37-98 is 1000 hours.
- Nickel can cause some people to have an adverse reaction. It is a desirable, but not necessary property that the alloy has low Ni release.
- Various methods of determining whether an alloy would release enough nickel to cause reactions in individuals with sensitivity to nickel are known. One such test consists of mixing solutions of dimethylglyoxime and ammonium hydroxide on the surface of the test article. If nickel is released, a light pink to red color results on the test article. Additional information about such testing is disclosed in http://corrosion- doctors.org/Allergies/nickelallergy.htm, incorporated herein by reference; and. in
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Detergent Compositions (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US25983709P | 2009-11-10 | 2009-11-10 | |
US12/943,196 US20110165013A1 (en) | 2009-11-10 | 2010-11-10 | Antitarnish, antimicrobial copper alloys and surfaces made from such alloys |
PCT/US2010/056179 WO2011060034A1 (en) | 2009-11-10 | 2010-11-10 | Antitarnish, antimicrobial copper alloys and surfaces made from such alloys |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2499269A1 true EP2499269A1 (en) | 2012-09-19 |
Family
ID=43991996
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP10830632A Withdrawn EP2499269A1 (en) | 2009-11-10 | 2010-11-10 | Antitarnish, antimicrobial copper alloys and surfaces made from such alloys |
Country Status (5)
Country | Link |
---|---|
US (1) | US20110165013A1 (en) |
EP (1) | EP2499269A1 (en) |
KR (1) | KR20120099254A (en) |
CN (1) | CN102725430A (en) |
WO (1) | WO2011060034A1 (en) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012083996A1 (en) * | 2010-12-23 | 2012-06-28 | Dot Gmbh | Fitting having an antibacterial coating and method for producing said fitting |
US20130035900A1 (en) * | 2011-08-01 | 2013-02-07 | Ricky Wayne Purcell | Method for Promoting Hygiene and Cleanliness |
DE102012014851A1 (en) * | 2011-09-22 | 2013-03-28 | Kme Germany Gmbh & Co. Kg | Copper material for the production of a silver-colored product with an antimicrobial surface |
MX370072B (en) | 2012-10-26 | 2019-11-29 | Sloan Valve Co | White antimicrobial copper alloy. |
US9381588B2 (en) | 2013-03-08 | 2016-07-05 | Lotus BioEFx, LLC | Multi-metal particle generator and method |
WO2014102089A1 (en) * | 2013-04-05 | 2014-07-03 | Herm. Sprenger Gmbh & Co. Kg | Copper alloy for producing horse bits or horse bit parts |
US9204749B1 (en) * | 2013-08-28 | 2015-12-08 | Vincent Trapani | Quick release antimicrobial hospital curtain |
CA2980020C (en) | 2015-03-30 | 2023-08-01 | Giridhar Thiagarajan | Application of antimicrobial agents to medical devices |
GB2579601A (en) * | 2018-12-05 | 2020-07-01 | Copper Clothing Ltd | Antimicrobial material |
US20220372596A1 (en) * | 2019-10-03 | 2022-11-24 | Advanced Alloy Holdings Pty Ltd | Copper alloys |
FR3111145A1 (en) * | 2020-06-05 | 2021-12-10 | Le Bronze Alloys | Antimicrobial alloy rich in copper, part made from this alloy, and method of manufacturing such a part, with stabilization of an active contact layer on the surface of said alloy |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2101087A (en) * | 1937-02-18 | 1937-12-07 | American Brass Co | Copper base alloy |
US4038068A (en) * | 1976-02-19 | 1977-07-26 | Olin Corporation | Method of melting copper alloys with a flux |
JPS5952223B2 (en) * | 1979-04-23 | 1984-12-18 | 三菱マテリアル株式会社 | Copper alloy for aquaculture cages |
JPS5976453A (en) * | 1982-10-19 | 1984-05-01 | Mitsubishi Metal Corp | Cu alloy clad material for lead material of semiconductor device |
US4589938A (en) * | 1984-07-16 | 1986-05-20 | Revere Copper And Brass Incorporated | Single phase copper-nickel-aluminum-alloys |
CN1006304B (en) * | 1987-06-27 | 1990-01-03 | 上海联谊有色金属型材厂 | Copper alloy used for gold-like decorative purpose |
KR100390591B1 (en) * | 1999-05-05 | 2003-07-07 | 올린 코포레이션 | Copper alloy with a golden visual appearance |
CN1256451C (en) * | 2001-12-19 | 2006-05-17 | 浙江大学 | Anticorrosion cast multi-element Cu-alloy simulating golden colour and its preparing process |
WO2005087957A1 (en) * | 2004-03-12 | 2005-09-22 | Sumitomo Metal Industries, Ltd. | Copper alloy and method for production thereof |
US20060124487A1 (en) * | 2004-12-15 | 2006-06-15 | Brown James S | Antimicrobial holder for writing implements and the like |
-
2010
- 2010-11-10 US US12/943,196 patent/US20110165013A1/en not_active Abandoned
- 2010-11-10 EP EP10830632A patent/EP2499269A1/en not_active Withdrawn
- 2010-11-10 KR KR1020127014925A patent/KR20120099254A/en not_active Application Discontinuation
- 2010-11-10 WO PCT/US2010/056179 patent/WO2011060034A1/en active Application Filing
- 2010-11-10 CN CN2010800603973A patent/CN102725430A/en active Pending
Non-Patent Citations (1)
Title |
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See references of WO2011060034A1 * |
Also Published As
Publication number | Publication date |
---|---|
KR20120099254A (en) | 2012-09-07 |
CN102725430A (en) | 2012-10-10 |
WO2011060034A1 (en) | 2011-05-19 |
US20110165013A1 (en) | 2011-07-07 |
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RIC1 | Information provided on ipc code assigned before grant |
Ipc: C22C 9/05 20060101ALI20150911BHEP Ipc: C22C 9/04 20060101ALI20150911BHEP Ipc: C22C 9/06 20060101ALI20150911BHEP Ipc: C22C 9/01 20060101AFI20150911BHEP |
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Effective date: 20151113 |