CN102149834B - White-colored copper alloy with reduced nickel content - Google Patents

White-colored copper alloy with reduced nickel content Download PDF

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CN102149834B
CN102149834B CN200980134815.6A CN200980134815A CN102149834B CN 102149834 B CN102149834 B CN 102149834B CN 200980134815 A CN200980134815 A CN 200980134815A CN 102149834 B CN102149834 B CN 102149834B
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alloy
copper alloy
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copper
color
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CN102149834A (en
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C·克拉克
R·普拉特
T·D·约翰逊
T·徐
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PMX Ind Inc
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    • 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
    • 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

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Abstract

Disclosed is a white-colored copper alloy comprising by weight up to 30% zinc, up to 20% manganese, up to 5% nickel with the balance copper. This alloy may have from 6% to 25% zinc, from 4% to 17% manganese, from 0.1% to 3.5% nickel and the balance copper. The balance copper in the alloy may further contain at least one of: up to 0.5% of at least one of the group which consists of Sn, Si, Co, Ti, Cr, Fe, Mg, Zr, and Ag; and up to 0.1% of at least one of the group which consists of P, B, Ca, Ge, Se, Te. It may also contain up to 0.3% Zr by weight. The alloy may have an electrical conductivity greater than 2.5% IACS at eddy current gauge exciting frequencies between 60 kHz and 480 kHz.

Description

Have reduce nickel content white copper alloy
The present invention requires the U.S. Provisional Patent Application No.61/095 of submission on September 10th, 2008, the U.S. Provisional Patent Application No.61/095 that 719 " WHITE-COLORED COPPER ALLOY WITH REDUCED NICKEL CONTENT " and on September 10th, 2008 submit to, the right of priority of 733 " IMPROVED WHITE-COLORED COPPER ALLOY WITH REDUCED NICKEL CONTENT ".
Technical field
The present invention relates to the copper base alloy of white or silver color, comparing with the standard alloy of Similar color, this alloy has the nickel content of reduction.
Background technology
Copper base alloy is widely used, and is easy to preparation, erosion resistance, electricity and heat conductivity and can obtains the attractive color of wide region because they have been gathered.They are preferred materials of currency in the world, in many cases as the part of multilayer materials system.In addition, nearest studies show that can be made for the copper and copper alloy surface antimicrobial, makes various bacteria inactivation rates within two hours or shorter time.
Although copper itself is red color, the interpolation of most of alloy element causes little red or little yellow more or less.These colors are typically well-known with descriptive title (brassiness, gold, bronze colour etc.).Also can obtain to have the more alloy of white colour (reflecting more uniformly all light wavelengths), although usually be difficult to obtain not to be with strong little red or little yellow color good white colour, particularly after material variable color or partial oxidation.These whiter alloys add acquisition (copper-nickel alloy and nickeline) with a large amount of nickel usually.Regrettably, nickel is more expensive than other alloy element of great majority.And show, when being used for contacting with other tissue with human body skin, nickel is the major cause that causes the contact dermatitis case to increase.The purpose of this invention is to provide the copper alloy with good white colour, but use the nickel content that reduces.
The alloy that mainly is made of copper and mickel (having other a small amount of element adds) is called copper-nickel alloy or cupronickel.Along with nickel content increases, color from the copper red look to 10%Ni (C706) light little red/purple is again to the suitable pure white of 25%Ni (C713).The cupronickel of this white is widely used in U.S.'s currency, as the material of 5 coin-dividings, also as the skin of the 3-layer composite material of 10 minutes, 25 minutes and 50 coin-dividings.Although be attractive and durable, this alloy is expensive due to high nickel content, because Ni is typically greater than the twice of the price of copper.The expensive of C713 is to cause the U.S. to use the partly cause of matrix material currency; By substituting core with more not expensive copper, using the C713 of silver color on every side, can obtain with lower cost the outward appearance of expectation.Another expensive replacement scheme of white cupronickel is to use zinc Substitute For Partial copper in alloy, and the alloy of formation is called as " nickeline " because of its silver color.Although zinc is effective not as nickel as the whitening agent of copper alloy, zinc has reduced the demand of nickel, and compares with copper or nickel, has not only reduced weight but also more not expensive.The copper alloy of high Mn content (20% or more) is also white reliably, but has the shortcoming that is difficult to hot-work and low-down electricity and heat conductivity, therefore they are mainly used in foundry goods, compare with " nickeline " herein, and the fusing point that they are lower and the mobility of increase are advantages.
By use the most nickel of combination replacement of Zn and Mn in the copper alloy of white, the alloy more cheaply with similar outward appearance and other new capability is possible.Although the copper base alloy that other white colour was disclosed in the past, on these alloy surfaces with the alloy phase that proposes seemingly, the compositing range of the present invention that neither one will provide below meeting.
A lot of copper alloy producers provides several to have more or less cupronickel and the nickeline of white colour.In 41 kinds of Deformed Copper nickelalloys listing in copper development association (CDA) database, only have two kinds (C71640 and C72420) to have manganese content greater than 1%; There is no a kind of Zn that contains greater than 1% in these alloys.In listed 25 kinds of deformation nickelines (Cu-Zn-Ni alloy), only there are four kinds to have minimum Mn content; All these alloys have all added Pb to improve machinability.X alloy (xantal) contains Zn or Mn, but is not both to have.The Cu-Zn-Mn alloy that two kinds of deformation are only arranged of listing in the CDA database does not contain nickel-C66900 and C66950.The first contains the Fe (as impurity) of maximum 0.25% and other impurity of maximum 0.20%, there is no other additive.The second (Wieland alloy FX9) contains 14-15%Zn, 14-15%Mn, the Cu of 1.0-1.5%Al and surplus.
The casting alloy of listing in the CDA database has shown similar trend; Contain more than 1% Mn and the alloy of Zn and also contain at least 0.5% Al.An exception of this trend is to be called " Bronwite " alloy (C99750), and it contains 17-23%Mn, 17-23%Zn and 0.5%Pb at least, and the highest 5%Ni.Very white of Bronwite, mobility is very good and have a relatively low melt temperature, this makes it for little, thin very excellent with meticulous foundry goods such as costume jewellery, but its Pb that contains is enough to cause at present the problem to Hazardous substances limits (Restrictions on Hazardous Substances (RoHS)) and consumer products safety rules (Consumer Product Safety regulations).
Several white metals without nickel were disclosed in the past.Wieland alloy FX9 already mentioned above (C66950).The YKK Corporation of Tokyo holds several patents without nickelalloy.United States Patent (USP) 5997663 comprises two scopes: 1) 70-85%Cu, 5-22%Zn, 7-15%Mn, and the combination (having white colour) of 0-4%Al or Sn or Al and Sn; And 2) 70-85%Cu, 10-25%Zn, 0-7%Mn, and the combination (having unique glutinous rehmannia color) of 0-3%Al or Sn or Al and Sn.Second YKK patent (US 6340446) discloses and contained 0.5-5%Zn, 7-17%Mn, 0.5-4%Al and surplus copper without nickelalloy, it also can contain the highest 0.3% Cr, Si and/or Ti one or more.The 3rd such patent (EP1306453) instructed without the nickel white metal, and it has 0.5-30%Zn and 1-7%Ti, randomly comprises one or more the combination of the highest 4% Al, Sn, Mg and/or Mn.
Another European patent (EP0685564) discloses a kind of without the Ni alloy, and it has the copper lower than YKK patent (50-70%Cu) and higher Mn (8-25%Mn) usually, and surplus is zinc.These are disclosed before this is intended to satisfy the EU regulations by eliminating Ni fully without the great majority in the Ni white metal, these regulations are (due to allergy and the allergy of tissue) restriction Ni in the like product of jewellery, glasses and " directly also contacting with human skin for a long time ", and usually is intended to as cast product or as wire product.
The disclosed alloy of United States Patent (USP) 6432556 (Brauer etc.) contains 5-10%Mn, 10-14%Zn, and 3.5-4.5%Ni and less than 0.07% Al, surplus is Cu.The alloy content of patent 6432556 is specifically balanced, in order to " golden visual appearance " and specific conductivity are provided, this specific conductivity is suitable for use as alternate standard alloy C713 (75Cu-25Ni), use as independent and coating layer form in the American currency of circulation, in particular as the yellow metal that substitutes SusanBAnthony (SBA) dollar of coin, and at present just as the Sacajawea dollar of currency and the coating of U.S. Presidental dollar series.Relevant more early stage patent (United States Patent (USP) 2445868, authorize Berwick and transfer Olin Inc.), it is incorporated in patent application 6432556 as a reference, instructed about Cu-Zn-Ni-Mn type quaternary (4 component) alloy, this alloy has minimum 5%Ni, and there is no other additive.
United States Patent (USP) 3778237 (Shapiro etc.) discloses the alloy of another kind of essentially no Ni, particularly as the dish of silver-plated goods such as food and beverage sevice or the base material of holloware.This alloy is by 8-16%Mn, and the Cu of 20-31%Zn and surplus forms, and allows but do not require to add a small amount of other element (Al, Fe, Sn, Si, Co, Mg, Mo, Ni, P, As, Sb).Allow the highest 0.3% nickel, but preferably do not add nickel.United States Patent (USP) 3778236 (Goldman etc.) is the alloy patent that contains 0.5-5%Ni, also limits the base material as silver-plated goods.Other Cu-Mn-Zn alloy without Ni is disclosed at United States Patent (USP) 2772962 (Reichenecker is used for the casting resistance alloy) and United States Patent (USP) 2479596 (Anderson and Jillson etc.).
U.S. Patent No. 5997663,6340446,6432556,2445868,3778236,3778237,2772962 and European patent No.EP1306453 and EP0685564 is incorporated it into this paper by reference in full.
Summary of the invention
The purpose of at least one embodiment of the present invention is to provide the copper base alloy with white or silvery appearance, and this alloy to the traditional copper alloy phase with similar outward appearance than the nickel content with reduction.Another purpose of at least one embodiment of the present invention is other copper alloy that discoloration-resistant that alloy of the present invention represents is equal to Similar color at least.Another purpose of at least one embodiment of the present invention be the resistance to crocking that represents of alloy of the present invention (when stand human body skin repeat to contact the time) be equal at least other copper alloy of Similar color.Another purpose of at least one embodiment of the present invention is that the electric conductivity that alloy of the present invention represents is used for the electric conductivity of the alloy of currency at present similar in appearance to stainless electric conductivity or similar in appearance to those basically.Another purpose of at least one embodiment of the present invention is that these alloys represent antimicrobial properties, makes inactivation ratio that the bacterium on the uncoated surface that is exposed to this alloy represents equal or exceed the public data of Similar color copper base alloy and significantly surpasses the stainless steel of Similar color.
Target recited above, Characteristics and advantages will become clearer by following specification sheets and accompanying drawing.
(1) feature of at least one embodiment of the present invention is the outward appearance that copper base alloy required for protection has white or silver color, makes it be suitable for making dissimilar decorated articles, the particularly metalwork of (but being not limited to) buildings and building.Can also use with whole (monolithic) form, or as with the part of the matrix material system of other material, the color of alloy of the present invention, discoloration-resistant and microbial resistance and other performance allow to produce new material system in this case, and this system has the feature that customizes separately according to application-specific.
(2) another feature of at least one embodiment of the present invention is that alloy contains zinc and manganese, and has with respect to the copper base alloy of traditional white and fall low-level nickel.
(3) another feature of at least one embodiment of the present invention be can with iron as nickel substitute or replenish with improve color and
(4) discoloration-resistant and
(5) resistance to crocking is with the alloy phase ratio that there is no nickel or iron.
(6) another feature of at least one embodiment of the present invention is that this alloy has white visual appearance, and its electric conductivity is similar in appearance to the electric conductivity of circulation American currency CDA alloy C713 used.
(7) another feature of at least one embodiment of the present invention is that alloy has similar in appearance to stainless outward appearance, and also shows the electric conductivity with the stainless steel same range as.
One of these advantages of at least one embodiment of the present invention are that the copper base alloy of white of the present invention has antimicrobial properties.Be placed on the bacteria inactivation rate that lip-deep bacteria inactivation rate that the alloy by at least one embodiment of the present invention consists of has surpassed other copper base alloy of Similar color, and also as surpassed the inactivation ratio of being found by the business binary alloy of the component of copper and the alloy of carrying with expecting.
According to the present invention, the copper alloy of white is being provided, this alloy comprises the highest 30% zinc by weight, the highest 20% manganese, the highest 5% nickel and the copper of surplus.This alloy more preferably contains the zinc of 6%-25%, the manganese of 4%-17%, the nickel of 0.1%-3.5% and the copper of surplus.Surplus copper in alloy can also contain with lower at least a: the highest 0.5% be selected from least a of Sn, Si, Co, Ti, Cr, Fe, Mg, Zr and Ag; And the highest 0.1% be selected from least a of P, B, Ca, Ge, Se, Te.This alloy preferably contains 12%-20%Zn, 10%-17%Mn and 0.5%-3.5%Ni.More preferably contain 13%-16%Zn, 14%-17%Mn, and 1.5%-2.5%Ni.Can also contain the highest 0.3% Zr by weight.
According to the present invention, the copper alloy of white also is being provided, this alloy comprises the highest 30% zinc by weight, the highest 20% manganese, the highest 4% iron and the copper of surplus.This alloy more preferably contains the zinc of 6%-25%, the manganese of 4%-17%, the iron of 0.1%-2.5% and the copper of surplus.In alloy, the copper of surplus can also contain with lower at least a: the highest 0.5% be selected from least a of Sn, Si, Co, Ti, Cr, Ni, Mg, Zr and Ag; And the highest 0.1% be selected from least a of P, B, Ca, Ge, Se, Te.This alloy preferably only contains nickel (namely, be less than approximately 0.1%) with the impurity form, and by 12%-20%Zn, 10%-17%Mn and 0.5%-2.5%Fe form.It more preferably contains 15%-18%Zn, 14%-17%Mn and 0.5%-1.5%Fe.
According to the present invention, the copper alloy of white also is being provided, it comprises the highest 30% zinc by weight, the highest 20% manganese, the highest 6% nickel, the highest 4% iron and the copper of surplus.This alloy more preferably contains the zinc of 6%-25%, the manganese of 4%-17%, the nickel of 0.1%-5%, the iron of 0.05%-2.5% and the copper of surplus.Surplus copper in alloy can also contain with lower at least a: the highest 0.5% be selected from least a of Sn, Si, Co, Ti, Cr, Mg, Zr and Ag; And the highest 0.1% be selected from least a of P, B, Ca, Ge, Se, Te.This alloy preferably contains 12%-20%Zn, 10%-17%Mn, 0.5%-3.5%Ni and 0.1%-1%Fe.It more preferably contains 13%-16%Zn, 14%-17%Mn, 1.5%-2.5%Ni and 0.2%-0.6%Fe.This alloy can also contain the highest 1.0% Al.
According to the present invention, the copper alloy of white also is being provided, it is greater than the specific conductivity of 2.5%IACS under 60kHz-480kHz that this alloy has in the ededy current gauge excitation frequency, this alloy comprises the highest 30% zinc by weight, the highest 20% manganese, the highest 10% nickel, the highest 4% iron, the highest 1% zirconium and the copper of surplus.This alloy more preferably contains the zinc of 6%-25%, the manganese of 4%-17%, the nickel of 0.1%-9%, the highest 2.5% iron, the copper of the highest 0.5%Zr and surplus.Surplus copper in alloy can also contain with lower at least a: the highest 0.5% be selected from least a of Sn, Si, Co, Ti, Cr, Mg and Ag; And the highest 0.1% be selected from least a of P, B, Ca, Ge, Se, Te.This alloy preferably contains 10%-18%Zn, 4%-7%Mn, 4%-9%Ni and 0.05%-0.2%Zr.It more preferably contains 12%-16%Zn, 4%-6%Mn, 5%-9%Ni and 0.05%-0.15%Zr; This combination has the specific conductivity of 4%IACS-7%IACS.
Description of drawings
Fig. 1 illustrates the known attribute for the CIELAB color diagram of lightness (lightness), tone (hue) and colourity (chroma) of prior art.
Fig. 2 has shown and has been drawn in the alloy of the present invention that shows the required color scope on 2 Vc IELAB color diagram, and comparative alloy.
Fig. 3 has shown the data identical with Fig. 2, but pays close attention to required " white visual appearance " scope.
Fig. 4 has shown the anti-microbial effect of alloy of the present invention.
Definition
Be the purpose of following listed claim, will use following definition:
All compositions that provide by weight percentage.The composition of listing take Cu-18Zn-17Ni means nominal value as the Zn of 18% weight, the Ni of 17% weight and the copper of surplus and inevitable impurity.Can understand other composition of listing with similar form by this embodiment of analogy.
After this " copper base alloy " is defined as: have the copper of minimum 50% weight and the alloy of one or more elementary compositions, perhaps many components alloy, wherein the per-cent of Cu is greater than any other component.
After this " white visual appearance " is defined as: color (adopt the spectrophotometer of d/8 spherical geometry (comprising the minute surface inverse), measure with D65 twinkler and 10 ° of observers) is at CIE1976L *a *b *(CIELAB) upper satisfied-2≤a of scale (scale) *≤ 3 and-2≤b *≤ 10.
After this " effectively antimicrobial " is defined as: be placed on the bacterium in suspension on uncoated surface, 99.9% will be inactivated in exposing 120 minutes.
After this will " complete the time of deactivation " is defined as: place from the teeth outwards until the time that 99.9% bacterium is inactivated from bacterium.
After this " anti-variable color " is defined as: do not contact with human skin or body fluid, after exposing 30 days under 20-25 ℃ in air, the colour-change Δ E between initial color and final color CMC(as defined in ASTM D2244-07, pp.2-3) less than 1.
After this " variable color of the temperature of anti-raising " is defined as: after exposing 24 hours under 150 ℃ in air, the colour-change Δ E between initial color and final color CMC(as defined in ASTMD2244-07, pp.2-3) less than 20.
Detailed Description Of The Invention
Can measure (alloy or other material) color with spectroscope or other objective means.As X-Rite Inc. (Grand Rapids, MI) or those the instrument that provides of Hunter Associates Laboratory Inc. (Reston, VA) according to two color attributes " tone " and " colourity " and the lightness attribute that is called " value (value) ", color is quantized.Tone is color perception, and Target Recognition is red, green, yellow, blue etc.Colourity is color depth (intensity or saturation ratio), and scope is that ash is to pure hue.Value is the tolerance of the lightness of color luminosity (tone), and scope is pure white to black.Being combined in of these values provides unique position in the polar coordinates color space, represent color of light degree (position, angle) with tone in Fig. 1, chrominance representation intensity (radial position), and value representation lightness (vertical position).
The alternative method of specified color is by the CIELAB scale.CIE represents that Commission Internationale de 1 ' Eclairage (International Commission on Illumination) and LAB represent the L on this scale *, a *, b *Coordinate; Therefore CIELAB is CIE 1976 L *a *b *The abbreviation of colour scale.On this scale, tone represents (color pair) with the term color, use+a *Expression is red ,-a *Expression is green ,+b *Expression is yellow ,-b *Expression is blue.Colourity (intensity or saturation ratio) is expressed as center from coordinate system (0 is grey) to the value at the full strength of ± 60 color component.The higher expression color of the value of any component is stronger, and is worth the measured material of lower expression more close to colourless.Brightness value L *For from 0 (black) to 100 (pure white).Again, L *, a *, b *Unique position in color space and concrete color, saturation ratio and lightness have been determined in the concrete combination of value.
The color of all alloys is analyzed with the SP-62 spectrophotometer that X-Rite Inc. (Grand Rapids, MI) makes.Analysis condition is d/8 spherical geometry (comprising the minute surface inverse), use D65 twinkler and 10 ° of observers.With CIE 1976 L *a *b *(CIELAB) scale report all colours is measured.For initial color measuring, be to have identical surface smoothness (6-18Ra with sample preparation; Measuring of surfaceness), and clean to remove oxide on surface, this oxide compound can affect the analysis of initial color measuring and the discolouration of anti-atmosphere the subsequently.List in table 1 according to chemical constitution and the color of alloy of the present invention, in company with showing contrast copper alloy and selected stainless identical data.Alloy according to the present invention is classified I1, I2, I3 etc. as in table.The contrast copper alloy is classified C1 as, C2, C3 etc.The comparative alloy (carbon steel and stainless steel, zinc and aluminium alloy, the pure metal except copper etc.) that is not based on copper is classified S1 as, S2, and S3, etc.
Table 1. chemical constitution and original (real metal) color
Table 1. chemical constitution and color
Figure GDA00002479058900101
Figure GDA00002479058900111
One of difficulty that produces " white " copper base alloy is that what is " white " in definite determining.The many early stage application of these alloys is alloys of the lower cost of monetization, dish and holloware, therefore desired color and the color similarity of Stirling (sterling) and silver coin.Recently, just " white " copper alloy is considered as the brush nickel surface layer processed (brushed nickel finishes) that substitutes stainless steel or building metalwork and Application in Building, in order to can obtain the antimicrobial properties of copper alloy, and the outward appearance similar to stainless modern appearance.Analyzed several traditional " white " copper alloys and the color of other alloy, these other alloys show slight but the obvious color of little red or little yellow.Also analyzed stainless steel and carbon steel, and pure nickel, zinc and tin as finding on the surface of white plated product.These materials have been contrasted to determine in the CIELAB value physical constraints to white alloy.A with measurement *And b *Value almost shows colourless close to zero material and therefore at identical whole lightness (L *) value is lower has higher a than those *Or b *The material of value is whiter.Be the copper alloy of 6-18Ra for surperficial oxide-free and surfaceness, lightness (L *) value is typically 75-86; For all measured copper alloys, from bright orange cartridge brass (alloy C2, Cu-30Zn) to the cupronickel (alloy C5) of red fine copper (alloy C1) to the American currency of circulation strong white used, this is all real.
In order to determine the purpose of required white, after this be no longer initial white and begin to become with the obvious position definition a of the white of red color tone at the visual appearance of copper alloy *The upper limit.This transition from white to the redness a of alloy C31 (Cu-15Ni) *The value definition.Alloy C31 has 2.9 a *Value.The copper alloy (alloy C4, Cu-10Ni-1Fe) that is purchased of contrast is evident as blush and has 3.7 a *Value.Be purpose of the present invention, consider to have a less than 3 *Value and the suitable b that is white in color *Value (on the CIELAB scale) is suitable.
For the copper alloy with white visual appearance, be no longer initial white and the obviously position definition b of yellow white of yellow hue (or with) that begins to become at copper alloy *The upper limit.This transition from white to the yellow b of comparative alloy C3 (Cu-12Zn-7Mn-4Ni) *The value definition.This is with the patent alloy of " golden visual appearance " (at US 6,432, discussing in 556 B1 as Brauer etc.), and the white that is configured to especially the color that the represents alloy C5 more used than the American currency of circulation is more near the 18K gold.This alloy has the b of 10.2 measurement *Value.We set b *On be limited to 10, in order to be only acceptable unlike the alloy of alloy C3 Huang.
a *And b *Lower limit based on pure zinc (alloy C35, a *-1.7, b *-1.9) color settings.The subjective white that is shown as of pure zinc, although on the surface of just cleaning and preparation visible weak pale blue and pale green color.Therefore, a *And b *Lower limit all be set as-2, in order to comprise zinc in the white alloy zone.Measured copper alloy all has CIELAB value a in our research *＞-1.5 and b *＞1.5.
For being considered as white, copper alloy must satisfy a listed above *And b *Restricted condition; That is to say a *Preferably between approximately-2 to approximately+3, b simultaneously *Preferably between approximately-2 peace treaties+10.More preferably a *Between approximately-2 to approximately+2, and b *Simultaneously between approximately-2 peace treaties+8.A most preferably *Between approximately-2 to approximately+1, and b *Simultaneously between approximately-2 peace treaties+7.Satisfy one or the other rather than the alloy that satisfies simultaneously is not considered as white.For example, alloy C2 (Cu-30Zn) has CIELAB a *, b *Value is (1.5,21.5); Although it has fallen into a for white *Scope (low redness), but it has exceeded the maximum admissible b that is considered as white *, therefore, alloy C2 is yellow copper alloy.Another embodiment is alloy C4 (Cu-10Ni-1Fe), has CIELAB a *, b *Value is (3.7,8.2); Although b *Value is in white range (low yellow), but it has exceeded admissible a *Value, and be visually to be blush.And, consider the scope with endpoint value in above-mentioned discussion scope, even do not set forth especially these endpoint values or scope.For example, a *The value range of value can have lower end points-1.9, and-1.8 ,-1.7 etc., to+2.7 ,+2.8 ,+2.9, and upper extreme point can be+2.9 ,+2.8 ,+2.7 etc., to-1.7 ,-1.8 ,-1.9.Also imagined value b *Similar end points.Also imagined a *Any scope and b *The combination of any scope.For example, a *The scope of value can be-2～+ 2, and b *The scope of value can be-2～approximately+10.
The alloy that the present invention includes is the highest 30% zinc, the highest 20% manganese, and the highest 5% nickel and the copper of surplus, by weight.These alloys more preferably contain the zinc of 6%-25%, the manganese of 4%-17%, the nickel of 0.1%-3.5% and the copper of surplus.In alloy, the copper of surplus can also contain with lower at least a: the highest 0.5% be selected from least a of Sn, Si, Co, Ti, Cr, Fe, Mg, Zr and Ag; And the highest 0.1% be selected from least a of P, B, Ca, Ge, Se, Te.These alloys preferably contain 12%-20%Zn, 10%-17%Mn, 0.5%-3.5%Ni.It more preferably contains 13%-16%Zn, 14%-17%Mn, 1.5%-2.5%Ni.These alloys can also contain the highest 0.3% Zr by weight.In the most preferred embodiment, the alloy of above-mentioned composition is also white copper base alloy; That is to say, in the CIELAB value that they have, a *Preferably between approximately-2 peace treaties+3, b simultaneously *Preferably between approximately-2 peace treaties+10.More preferably, a *Between approximately-2 peace treaties+2, and while b *Between approximately-2 peace treaties+8.Most preferably, a *Between approximately-2 peace treaties+1, and while b *Between approximately-2 peace treaties+7.Having imagined composition discussed above can be in conjunction with each scope of CIELAB value discussed above.
The alloy that the present invention includes is the highest 30% zinc, the highest 20% manganese, and the highest 4% iron and the copper of surplus, by weight.These alloys more preferably contain the zinc of 6%-25%, the manganese of 4%-17%, the iron of 0.1%-2.5% and the copper of surplus.In alloy, the copper of surplus can also contain with lower at least a: the highest 0.5% be selected from least a of Sn, Si, Co, Ti, Cr, Ni, Mg, Zr and Ag; And the highest 0.1% be selected from least a of P, B, Ca, Ge, Se, Te.These alloys are preferred only contains nickel (namely, less than approximately 0.1%) with the form of impurity, and contains 12%-20%Zn, 10%-17%Mn and 0.5%-2.5%Fe.These alloys more preferably contain 15%-18%Zn, 14%-17%Mn and 0.5%-1.5%Fe.In the most preferred embodiment, the alloy of above-mentioned composition is also white copper base alloy; That is to say, in the CIELAB value that they have, a *Preferably between approximately-2 peace treaties+3, b simultaneously *Preferably between approximately-2 peace treaties+10.More preferably, a *Between approximately-2 peace treaties+2, and while b *Between approximately-2 peace treaties+8.Most preferably, a *Between approximately-2 peace treaties+1, and while b *Between approximately-2 peace treaties+7.Having imagined composition discussed above can be in conjunction with each scope of CIELAB value discussed above.
The alloy that the present invention includes is the highest 30% zinc, the highest 20% manganese, and the highest 6% nickel, the highest 4% iron and the copper of surplus, by weight.This alloy more preferably contains the zinc of 6%-25%, the manganese of 4%-17%, the nickel of 0.1%-5%, the iron of 0.05%-2.5% and the copper of surplus.Surplus copper in alloy can also contain with lower at least a: the highest 0.5% be selected from least a of Sn, Si, Co, Ti, Cr, Mg, Zr and Ag; And the highest 0.1% be selected from least a of P, B, Ca, Ge, Se, Te.These alloys preferably contain 12%-20%Zn, 10%-17%Mn, 0.5%-3.5%Ni and 0.1%-1%Fe.These alloys more preferably contain 13%-16%Zn, 14%-17%Mn, 1.5%-2.5%Ni and 0.2%-0.6%Fe.These alloys can also contain the highest 1.0%Al.In the most preferred embodiment, the alloy of above-mentioned composition is also white copper base alloy; That is to say, in the CIELAB value that they have, a *Preferably between approximately-2 peace treaties+3, b simultaneously *Preferably between approximately-2 peace treaties+10.More preferably, a *Between approximately-2 peace treaties+2, and while b *Between approximately-2 peace treaties+8.Most preferably, a *Between approximately-2 peace treaties+1, and while b *Between approximately-2 peace treaties+7.Having imagined composition discussed above can be in conjunction with each scope of CIELAB value discussed above.
In another embodiment of the invention, it is greater than the specific conductivity of 2.5%IACS under 60kHz-480kHz that this alloy has in the ededy current gauge excitation frequency, this alloy is the highest 30% zinc, the highest 20% manganese, the highest 10% nickel, the highest 4% iron, the copper of the highest 1%Zr and surplus, by weight.These alloys more preferably contain the zinc of 6%-25%, the manganese of 4%-17%, the nickel of 0.1%-9%, the highest 2.5% iron, the copper of the highest 0.5%Zr and surplus.Surplus copper in alloy can also contain with lower at least a: the highest 0.5% be selected from least a of Sn, Si, Co, Ti, Cr, Mg and Ag; And the highest 0.1% be selected from least a of P, B, Ca, Ge, Se, Te.These alloys preferably contain 10%-18%Zn, 4%-7%Mn, 4%-9%Ni and 0.05%-0.2%Zr.This alloy more preferably contains 12%-16%Zn, 4%-6%Mn, 5%-9%Ni and 0.05%-0.15%Zr.In a more preferred embodiment, each of composition discussed above has the specific conductivity of 4%IACS-7%IACS.In the most preferred embodiment, the alloy of above-mentioned composition is also white copper base alloy; That is to say, in the CIELAB value that they have, a *Preferably between approximately-2 peace treaties+3, b simultaneously *Preferably between approximately-2 peace treaties+10.More preferably, a *Between approximately-2 peace treaties+2, and while b *Between approximately-2 peace treaties+8.Most preferably, a *Between approximately-2 peace treaties+1, and while b *Between approximately-2 peace treaties+7.Having imagined composition discussed above can be in conjunction with each scope of CIELAB value discussed above and in conjunction with each of specific conductivity feature discussed above.
Some specific embodiments of contemplated composition comprise:
1) zinc of 6-25%, the manganese of 4-17%, the nickel of 0.1-3.5% and the Cu of surplus; And
2) with 1) identical, have 0.5% Sn, Si, Co, Ti, Cr, Fe, Mg, Zr or Ag, and the highest 0.1% P, B, Ca, Ge, Se or Te's is at least a.
3) with 1) or 2) identical, the iron of 0.1-2.5% had.
4) with 1) or 2) identical, the nickel of 0.1-5% and the iron of 0.05-2.5% had.
5) 12-20%Zn, 10-17%Mn, and the Cu of 0.5-3.5%Ni and surplus.
6) 13-16%Zn, 14-17%Mn, and the Cu of 1.5-2.5%Ni and surplus.
7) with 1) identical, have the highest 0.3%Zr.
8) 12-20%Zn, 10-17%Mn, and the Cu of 0.5-2.5%Fe and surplus.
9) 15-18%Zn, 14-17%Mn, and the Cu of 0.5-1.5%Fe and surplus.
10) 13-16%Zn, 14-17%Mn, 1.5-2.5%Ni, and the Cu of 0.2-0.6%Fe and surplus.
11) zinc of 6-25%, the manganese of 4-17%, the nickel of 0.1-9.0%, and the Cu of surplus.
12) with 11) identical, have the highest 0.3%Zr.
13) 10-18%Zn, 4-7%Mn, 4-9%Ni, the Cu of 0.05-0.20%Zr and surplus.
14) 12-16%Zn, 4-6%Mn, 5-9%Ni, the Cu of 0.05-0.15%Zr and surplus.
All these embodiment can with a *And b *Any combination of value and any scope of specific conductivity combine.
For all components in forming, also imagined the scope with endpoint value in the scope of above-mentioned discussion, although do not set forth especially these endpoint values or scope.For example, the scope of Zn value can have lower end points 6.1%, 6.2%, 6.3% and wait until 24.7%, 24.8% and 24.9%, and upper extreme point can be that 24.9%, 24.8%, 24.7% waits until 6.3%, 6.2% and 6.1%.Also imagined the similar end points of the scope of other component.The Zn scope of equally, also having imagined any special elaboration combines with the scope of other component of any special elaboration.For example, the zinc of 6%-25% can combine with the Mn of 10%-17% and the Ni of 0.5%-3.5%.
Feature of the present invention is that this alloy contains Zn and Mn and than the lower level Ni of traditional " white " copper base alloy.This stems from the synergistic effect of alloy element, and wherein the combination of many components has provided with the unavailable result of simple binary alloy.
Nickel is potential whitening agent in copper alloy.Add that 10% Ni (alloy C4) provides light color in the Cu but still with little red-alloy of purple color and luster.Interpolation 15% (alloy C31) or more Ni provide obvious white, and along with Ni content increases to 30% (alloy C6), alloy becomes more near colourless.The Ni that increases helps the discolouration of anti-the atmosphere, stops the formation of dark copper oxide.Regrettably, Ni also than Cu more expensive (usually 2-3 doubly cost) significantly, therefore has strong economic interests with the alloy of growth phase like outward appearance, but with still less nickel.Low-alloyed anti-microbial effect also falls in higher Ni interpolation, therefore Ni should be remained on the minimum consistence of required color and discoloration-resistant.Show that also nickel is the principal element of metallic contact dermatitis, promoted the European Community to be used for the like product of jewelry, glasses and " directly also contacting with human body skin for a long time " without the nickelalloy legislation, referring to EP 0 635 564 B1 (Ammannati); " Copper-zinc-manganese alloy for the production of articles coming into direct and prolonged contact with the human skin "; On December 1st, 2000; Title, pg.1-2.
Manganese is also the effective whitening agent in copper alloy, although binary alloy is because low strength, be difficult to ingot casting and hot rolling and the low and inconsistent toughness relevant to short range order and almost there is no commercial significance.Add in the copper 12% or more Mn provide alloy (alloy the C30, [a of white relatively *, b *]=[5.05,8.27]), but this is the binary alloy medium or short range significant scope that becomes in order wherein.Manganese is generally used for containing in the more complicated copper alloy of Al, Zn, Si, Ni or these combinations to be strengthened with low-level.These low-level Mn add casting and the hot rolling characteristic that also can improve these alloys.
Add Zn in the copper alloy and change consumingly color, but alloy does not become " white " or colourless; But Cu-Zn alloy (" brass ") is along with content is increased to～the 30%Zn yellow that aurifies.Surpass 33%Zn, along with forming new crystalline structure, it is little red that alloy becomes again.Mock platina also shows short range order under certain conditions, and this can limit toughness and can cause performance change in use.When brightening copper base alloy (basis of " nickeline " Cu-Ni-Zn alloy), zinc can reduce the demand of Ni.Outward appearance is close to the Cu-Ni alloy of white, due to Zn content a little with yellow mixture.
Low solubility has limited in copper and has added iron.Fe greater than 3.5% has the solid phase miscibility gap, stops the casting of higher Fe alloy.By suitable thermal treatment, the Fe of 0.5-2.5% can remain in sosoloid, and with the Ni of par be same effectively whitening agent almost.Fe can also be potential reinforcer, directly and by reacting with P (phosphorus) forms precipitated phase in alloy.
With regard to relating to color, zinc is similar with aluminium in copper alloy, but Al is more effective significantly on acquisition gold-yellow color.Add 6%Al (alloy C32) and provide the color similar to Cu-15Zn (alloy C29).Pass in time, Cu-Al alloy (comprising that those have other element such as Zn, Mn and Fe) forms fine and close indifferent oxide film, and this film is of value to discoloration-resistant and erosion resistance.This identical impact has reduced the anti-microbial effect of the Cu alloy with Al, therefore Al should be kept minimum quantity for antimicrobial application.Because with the interaction of many other alloy elements, the hot and cold of aluminium-containing alloy roll and thermal treatment more complicated than those alloys without Al.
One of basic purpose of the present invention is to provide white visual appearance but has the copper alloy that reduces Ni content.The alloying additive has pointed out to obtain the method for this target on the top description of the impact of copper base alloy color.By the Ni with the Zn Substitute For Partial, have can produce the alloy that reduces nickel content, although color is tending towards becoming more yellow than the Cu-Ni alloy of identical total Cu content.By substituting further some remaining Ni with Mn, containing significantly, the alloy of lower Ni content can have the outward appearance of white (colourless) basically.We find, and the reservation of low-level Ni (with special total alloy content) helps to keep required white colour and with regard to the discolouration of anti-the atmosphere with to reduce with regard to polluting be also useful, this pollutes owing to the fluid contact from human body skin.Therefore, the Ni by in the alternative conventional alloys of the combination of Zn and Mn together with keeping low-level Ni to improve color and discoloration-resistant, has found the copper alloy of white visual appearance.
Another feature of the present invention is that Fe can substituting or replenishing to improve the whiteness of Cu-Zn-Mn alloy as Ni.When measuring the color of business Cu-Ni alloy, we find that some whiteness in these alloys is than from desired good of independent Ni content.Find that described alloy contains the Fe of significant quantity, add its casting and hot and cold processing characteristics to improve these alloys.The Cu-Fe alloy studies show that further although it still is evident as redness due to low total alloy content, they (have lower a than Cu-Zn or the desired more approaching white of Cu-Mn of identical alloy content on the CIELAB scale *Value).Based on this, we are added into many 2.5% Fe in alloy of the present invention, and find that the whiteness of improving even is maintained until total alloy content and surpasses 30%.In addition, we find that the existence of Ni do not interfere the impact of Fe, therefore any one or two kinds of whiteness that may be used to improve the Cu-Zn-Mn alloy.We also find to help to keep the white colour of expectation and with regard to the discolouration of anti-the atmosphere and to reduce with regard to polluting be also useful at the Fe that exists in (with special total alloy content) sosoloid of alloy, this pollute owing to fluid contact from human body skin, similar in appearance to the impact of low-level Ni on these performances.These impacts have also been found when with the independent Ni of the combination replacement of Fe or Fe and Ni.Therefore, by with the Ni in the combination replacement conventional alloys of Zn and Mn, to improve color and discoloration-resistant, found the copper alloy of white visual appearance together with the combination that keeps low-level Ni or Fe or Ni and Fe.
Important factor in selecting copper base alloy for outward appearance (as the metalwork of building and building) is outward appearance stability in time.In the time of in being exposed to atmosphere, stainless steel does not significantly change outward appearance; This is because form the oxide skin of inertia, and this layer stops visible variable color and corrosion and be why they are considered to the reason of " stainless ".Regrettably, can not obtain stainless steel in the color that can obtain with copper base alloy and photometric range, stainless steel does not have the antimicrobial properties of suitably prepd copper alloy yet.Traditionally, add Ni to improve the discolouration of anti-the atmosphere in copper alloy, because Ni forms the oxide skin of inertia in the surface, be similar to stainless inactive surfaces on function.We have found to formulate the chemical constitution with the white copper alloy that reduces Ni content, and the higher Ni white copper base alloy with traditional is identical basically to provide, and has the alloy of required white appearance and the discolouration of anti-the atmosphere.
Variable color in copper alloy is to form in time the result of oxide film with reacting from the oxygen in atmosphere.It is shown as the surface of darkening usually, compares different color harmony colourity from the original appearance of material although the different colours of the oxide compound that is formed by base mateiral (and interference-effect layer) also can cause.Color before and after exposing by contrast, the value of variable color can quantize and carry out objective contrast between different alloys.
The color distortion that has between the sample of CIELAB value of measurement is easy to calculate; At ASTM standard D2244-07 ε 1" Standard Practice for Calculation of Color Tolerances and Color Differences from Instrumentally Measured Color Coordinates "; ASTM International; Shades of colour difference and color tolerances equation have been provided in 1 day May in 2007.At each all with L *, a *, b *Total color distortion Δ E between two kinds of colors that provide * abCan be calculated as:
ΔE * ab＝[(ΔL *) 2+(Δa *) 2+(Δb *) 2] 1/2
Δ E * abThe size of color distortion is provided, but does not provide the indication of the feature of difference, because it does not indicate relative populations and the direction of tone, colourity and lightness difference.(ASTM standard D2244-07 ε 1, the 6.2.2 part).This is the most useful when color change is easily understood by the character of the domination of one of three factors and color change, but this is more not useful when two or three components significantly contribute to the color change of measurement.Also can be with L *, a *, b *Rectangular coordinates is converted to L *, C *, H *Cylindrical coordinates is understood lightness L with better *, chrominance C *With tone H *Relative different.Total color distortion equation of equivalence is so:
ΔE * ab＝[(ΔL *) 2+(ΔC *) 2+(ΔH *) 2] 1/2
The color distortion Δ E of substituting calculating CMC(defining as Colour Measurement Committee (CMC) of the Society of Dyers and Colourists in England) is intended to pass through equation (also by ASTM D2244-07 as the odd number projection ε 1Definition).It is developed as based on the tolerance system of CIELCH cylindrical coordinates and the definition ellipsoid around Standard Colors (at color space specific), in its scope, with the difference of standard be acceptable for the application of expectation.By the following color distortion Δ E that provides CMC:
ΔE * CMC＝cf[(ΔL */(1·S L)) 2+(ΔC */(c·S C)) 2+(ΔH */(S H)) 2] 1/2
Parameter interpretation in equation spectrum sensitivity and the lightness difference with respect to the relative importance of colourity and tone, therefore feel to have better consistence between visually-acceptable actual color scope in numerical value tolerance and the mankind.Particularly, business factor cf can change to mate for the desired scope of given application.Suppose Δ E cmcThe color distortion that=1 representative just perceives.
In order to contrast the purpose of the anti-color change that causes because of atmospheric exposure, based on (time=0) before exposing with at the calculating of the actual color difference between sample Δ E after preset time and temperature exposure CMCΔ E CMCMore low value (the less color change due to exposure) be considered to measuring of the excellent discolouration of anti-the atmosphere.
Table 2 atmosphere variable color table-room temperature
Table 2 atmosphere variable color-room temperature
Figure GDA00002479058900211
Table 2 has provided because the color change that the atmosphere variable color causes.After at room temperature 30 days, many comparative alloy without nickel (alloy C11-C24) show Δ E CMC＞1.Nickeliferous comparative alloy C 3-C8 (Ni content＞4%) shows less color change, and Δ E CMC＜1.Alloy of the present invention (alloy I1-I9) also demonstrates Δ E CMC＜1, even for Ni＜3.5%.With alloy C16 and alloy I8 contrast, expect and to find that adding 1%Fe (in the Cu-Zn-Mn alloy of color balance) will not reduce discoloration-resistant and can make visual appearance more near colourless.Similarly with alloy I7 and alloy C16 contrast, expect and to find that adding 3%Ni also can provide whiter alloy and improve significantly discoloration-resistant.Expect that interpolation Ni and Fe (alloy I9) show that the color of two kinds of elements and the benefit of variable color are separate and can mutually interfere.
The temperature of table 3 atmosphere variable color-raising
Figure GDA00002479058900221
For the purpose of research oxidation or corrosion, the temperature of raising is through being usually used in simulating long-term exposure.It is important selecting temperature-time range, the character of oxide compound or corrosion product under this temperature-time be identical under simulated conditions.For example, at the temperature of medium raising (200 ℃ or more than), compare the red Cu that changes subsequently CuO in air 2O, the preferred black CuO that directly forms; This affects the character of the color change with regard to all three components (tone, colourity and lightness) during the atmosphere variable color.These expose and show also how (as the plate of kitchen goods) maybe will respond when being used for automatic dishwasher or autoclave sterilization circulation time material when being used for the temperature of medium raising.
Be displayed in Table 3 because the color change that the atmospheric exposure of the temperature that improves causes.Clean and prepare by the operation alloy sample (also referred to as sample) identical with the sample of other color, and carry out the CIELAB color measuring before exposure.The color of reappraising after exposure is also calculated Δ E CMCAfter 150 ℃ of lower stoves were processed 7 hours or 24 hours, alloy of the present invention (alloy I2-I9) showed the identical or color change still less of any contrast copper alloy (alloy C 3-C26) listed with table 3.The preferred embodiments of the invention (alloy I7-I9) have shown minimum color change in any listed copper alloy.Interested especially is contrast between alloy C16 and these preferred embodiments.Alloy C16 is basically identical with these embodiments, but there is no Ni or Fe; At 150 ℃ after lower 24 hours, color change Δ E CMC=15.6.For (alloy I8) same alloy with 1%Fe, Δ E CMC=11.9, the interpolation that shows Fe has not only improved the whiteness of alloy but also has improved the discoloration-resistant of alloy.Alloy I7 and I9 (Δ E CMC=9.1-9.9) be also identical situation (but more like this); Add the whiteness that Ni (or Ni adds Fe) improves discoloration-resistant and alloy significantly in basic Cu-Zn-Mn alloy.
Surface in contact (handrail, door metalwork, table top, utensil plate, hospital equipment etc.) contacts the part as they functions repeatedly with water, sweat, sebum film and other body fluid.These body fluid contain complicated substance mixture, and many in them have significant corrodibility to copper and copper alloy.The assessment that how to change for the outward appearance that repeatedly contacts rear these alloys with human body skin is not only important for selecting these alloys that are used for the surface in contact purposes, and for determining that necessary cleaning frequency is also useful to keep its outward appearance.From the angle of function, for stainless steel and similar hospital with the surface, recommend the cleaning and disinfection circulation for from weekly to every day repeatedly so that the crossed contamination under health care facility minimize.
Table 4. contact variable color-room temperature
Interested alloy sample is cleaned and be prepared with the surface smoothness (6-18Ra) of expecting.With any contact of human body skin and/or fluid before determine initial color.Sample is all contacted every day, determine and calculated color change to be used for contrast.The results are shown in Table 4.After 3 days repetitious skin contact, all white alloies almost show difference on resistance to crocking; Δ E CMCBe 1.2-2.8.As if the content of this and any special alloy element or element combinations without any strong contacting.After repeatedly exposing in 7 days, although total color change larger, but the difference between alloy is even less; Δ E CMCBe 2.9-4.4.Although the content of Ni and/or Fe is markedly inferior to the Ni content of conventional white copper base alloy, to change for color alloy of the present invention poor unlike conventional alloy with regard to contacting with human body skin and/or body fluid because of opposing.
Many application of copper base alloy relate to conductivity or resist this conduction.For example, controlled specific conductivity or resistivity are used as security feature, the special combination of desired color and electrical property herein in distinguishing legal currency or fractional currency and invalid " tinsel ".Also used as the activity of controlling electric equipment such as safety fuse and circuit breaker.Mainly control specific conductivity by alloy content; To cause specific conductivity reduction more or less to the middle different-alloy element that adds of fine copper (having 100% IACS specific conductivity).Listed comparative alloy in table 1 and according to the specific conductivity of alloy of the present invention.
With alloy C29 (Cu-15Zn, 37%IACS), alloy C31 (Cu-15Ni, 9.15%IACS) and alloy C30 (Cu-12Mn, 4.15%IACS) contrast, we see that different alloy elements has different impacts on specific conductivity.Utilize this point, but the specific specific conductivity of alloy design is kept special visual appearance simultaneously.Alloy I1 has the similar of white visual appearance and specific conductivity (5.1%IACS) and alloy C5, but it only contains 6% Ni, C5 contains 24.5% Ni by contrast, uses if substitute in the American currency of circulation, and this will cause significant cost savings.
One of advantage of the present invention is, the copper base alloy of white of the present invention has antimicrobial properties.Copper and many copper base alloys when suitably being prepared, have reduced the vitality of the bacterium that is exposed on these alloy surfaces and other microorganism.The effect of alloy surface deactivation bacterium and the chemical constitution of alloy and other factor analysis, for example surfaceness, apply for as shown in PCT/US2007/069413 as PCT.On the deactivation surface 99.9% bacterium required open-assembly time be consider that the useful of antimicrobial properties of alloy measure, and use based on this test procedure and their open numerical value in the research of being subsidized by copper development association (Wilks etc.) in November, 2003 and compare.
Prepare before exposure and the interested alloy sample (～22mm is square) of sterilizing.Sample through preparation will be placed in training Ti Shi culture dish on the filter paper of sterilization.The equal portions suspension of the activated bacterial culture with 5-20 μ l in nutrient broth (intestinal bacteria, American type culture collection [ATCC] strain 11229, gram-feminine gender) is applied to the surface of sample; Contain minimum 10 in this inoculum 6-10 8Every milliliter of colony forming unit (CFU/ml).After the open-assembly time of expectation, sample is placed in the test tube of Butterfield ' the s damping fluid that contains 20ml sterilization (at 3.1 * 10 of the deionization that filters/reverse osmosis laboratory rank water -4M K 2HPO 4) and 5 minutes bacterium colonies with any survival that suspends from specimen surface of excusing from death stirring.Suspension serial dilution four times (1/10,1/100,1/1000 and 1/10000) to the survival bacterium colony.Every kind of diluent of this original suspension of 20 μ l equal portions and 20 μ l equal portions is coated on nutrient agar medium and 35-37 ℃ of lower incubation 48 hours with the enumeration to survival.In order to check baseline (being exposed to the colony number in the primitive bacteria nutrient solution on sample), the primitive bacteria nutrient solution of 20 μ l equal portions is placed directly in test tube and is not exposed on test button, contain 20ml sterilization damping fluid in this test tube, then it is adopted the mode that is equal to suspension from the survival thing of sample to process (ultrasonic agitation, dilute, be placed on agar disks and carry out incubation before counting).Expose duplicate (duplicate) sample and with diluent plating (plated) on duplicate finally to obtain statistical variations general in biological test.Count and calculate at former baseline with from every milliliter of colony forming single-digit (CFU) of the suspension of exposed sample being present in colony number on each agar disks, explain all diluents.The plate that only represents the 5-400 bacterium colony is used for final calculating, in order to significant difference is minimized.Bacterial count (3log in CFU 10Reduce) to reach for 99.9% time that reduces required open-assembly time and complete deactivation be mainly measuring of anti-microbial effect.
Listed the anti-microbial test result of the alloy of the present invention that is subject to the intestinal bacteria attack in table 5 and Fig. 4.Comprise that hereinafter the public information of the commercial alloy that is subject to intestinal bacteria (from Wilks and Keevil) attack is to be used for contrast.
The antimicrobial effect of table 5 copper alloy
Figure GDA00002479058900271
Comparative alloy C32 (Cu-10Zn) shows that after exposing 90-105 minute 99.9% bacterial count reduced and completed deactivation after 105 minutes.Alloy C4 (Cu-10Ni-1Fe) has the essentially identical effect with alloy C32.Similar alloy with high alloy content more (C2[Cu-30Zn] with C5[Cu-25Ni-0.5Fe]) demonstrates slightly poor effect, has 99.9% minimizing and only completes deactivation after 120 minutes in 90-105 minute.Alloy C8 (Cu-17Zn-18Ni) is being medium between these alloys on chemical constitution, and demonstrates medium anti-microbial effect, and is only slightly poor than C22000 alloy C 32 and alloy C4.Commercial money alloy (from the Y90 of Olin Brass, comparative alloy C3, Cu-12Zn-4Ni-7Mn) also contains Mn as alloy of the present invention, have " golden visual appearance " but be balanced to turn to, rather than white basically of the present invention.The anti-microbial effect of C3 is slightly better than the alloy that there is no Mn, has 99.9% minimizing and completed deactivation after 120 minutes near the exposures of 90 minutes.Alloy C1 (business fine copper) shows exposure minimizing of 99.9% in bacterial count after 75-90 minute, completes deactivation after 90 minutes.
Based on these disclosed results, we expect that the anti-microbial effect of alloy of the present invention is similar in appearance to the anti-microbial effect of alloy C3 (Y90).Zinc slightly higher (this makes it compare with alloy C2 with alloy C32, and the time is longer) and nickel slightly low (this makes it compare with alloy C5 with alloy C4, and the time is shorter).With alloy C8 and C3 contrast, Mn seems the combating microorganisms effect does not have strong impact, although more relax and more Zao decline than the sharp-pointed decline of seeing with most of alloys in bacterial count.Unexpectedly that initial test shows that 99.9% in CFU counting is reduced to 45-60 minute (than other alloy fast 40%) and complete deactivation (fast 40-50%) after 60 minutes.Test subsequently shows that 99.9% minimizing is as short as 10 minutes or still less and to complete deactivation be 15-30 minute, and the analog result that uses the same alloy that same sample preparation method and operation attack with gram positive bacterium gold-coloured staphylococci [ATCC 6538].As if the mechanism of explaining the kill ratio that increases in the higher Mn alloy of our modification is unclear, although it is relevant to the inhibition of the passive oxide layer that exists on the Cu alloy with Zn and Ni.
Obviously, according to the invention provides copper alloy, it satisfies target of the present invention in this paper, feature and advantage fully.Unite when describing when the present invention and specific embodiment, obviously have based on the many of these specification sheetss and substitute, improve and change, these are clearly for those skilled in the art.Therefore, the present invention is intended to comprise that all these substitute, improve and change, as long as it falls into the wide in range spirit and scope of claims, and is not limited to the specific embodiment that this paper proposes.
What further illustrate is, the function of a plurality of components or step or structure can be integrated with independent component or step, and perhaps function or the structure of step or component can be split into a plurality of steps or component.The present invention imagines all these combinations.Unless otherwise stated, the size of different structure as herein described and severally why not be intended to limit the scope of the invention, and other size or be also possible how much.Can provide a plurality of structure components or step by single integrated structure or step.As an alternative, single integrated structure or step can be divided into a plurality of components or the step of separation.In addition, when feature of the present invention is only described in the context of one of cited embodiment, can combine with the more than one further feature of other embodiment for any given this feature of application.Also consist of the method according to this invention from the preparation and the operation thereupon that above it will also be appreciated that this paper unique texture.The present invention also comprises from the centre of the method for this paper and final product.Also consider " comprising " used or " comprising " embodiment of " basically being consisted of by the feature of narrating " or " being consisted of by the feature of narrating ".
The explanation that this paper occurs and explanation are intended to make other technician of the technical field of the invention to know its principle and its practical application.When its can be best be applied to the requiring of application-specific the time, those skilled in the art can adapt to and use the present invention with several forms.Therefore, the particular of the present invention that proposes is not intended to be limit of the present invention or restriction.Therefore scope of the present invention should not determine with reference to above-mentioned specification sheets, but should be with reference to described claim, and is equal to the four corner that these claims give and determines.Disclosing of all clauses and reference comprises patent application and open, for all purposes are incorporated into by reference.

Claims (24)

1. effective antimicrobial copper alloy, have similar in appearance to the visual appearance of one of stainless steel and " nickeline ", and this copper alloy comprises:
A) zinc of 6-25% (Zn)
B) manganese of 4-17% (Mn),
C) nickel of 0.1-3.5% (Ni),
D) be essentially the surplus of Cu; And
E) combination of a-d shows white visual appearance and is effectively antimicrobial.
2. the copper alloy of claim 1, the surplus that wherein is essentially Cu also contain at the most with lower at least a:
At least a in lower group of 0.5%: Sn, Si, Co, Ti, Cr, Fe, Mg, Zr, Ag; And
At least a in lower group of the highest 0.1%: P, B, Ca, Ge, Se, Te;
And described alloy has and is less than the inactivation time of completing of 60 minutes.
3. similar in appearance to the copper alloy of stainless steel with the white visual appearance of one of " nickeline ", this copper alloy is comprised of following basically:
A) zinc of 6-25% (Zn)
B) manganese of 4-17% (Mn),
C) iron of 0.1-2.5% (Fe),
D) be essentially the surplus of Cu; And
E) wherein the combination of a-d shows white visual appearance and is effectively antimicrobial.
4. the copper alloy of claim 3, the surplus that wherein is essentially Cu also contain with lower at least a:
At least a in lower group of the highest 0.5%: Sn, Si, Co, Ti, Cr, Ni, Mg, Zr, Ag, and
At least a in lower group of the highest 0.1%: P, B, Ca, Ge, Se.
5. similar in appearance to the copper alloy of stainless steel with the white visual appearance of one of " nickeline ", this copper alloy is comprised of following basically:
A) zinc of 6-25% (Zn)
B) manganese of 4-17% (Mn),
C) nickel of 0.1-5% (Ni),
D) iron of 0.05-2.5% (Fe), and
E) be essentially the surplus of Cu;
F) wherein the combination of a-e is effectively antimicrobial and have a white visual appearance.
6. the copper alloy of claim 5, it also contains with lower at least a:
At least a in lower group of the highest 0.5%: Sn, Si, Co, Ti, Cr, Mg, Zr, Ag, and
At least a in lower group of the highest 0.1%: P, B, Ca, Ge, Se, Te.
7. the copper alloy of claim 1, it is combined in room temperature and is exposed in air anti-variable color and has and be less than the inactivation time of completing of 60 minutes.
8. the copper alloy of claim 7, it contains 12-20%Zn, 10-17%Mn, and 0.5-3.5%Ni.
9. the copper alloy of claim 8, it contains 13-16%Zn, 14-17%Mn, and 1.5-2.5%Ni, and the wherein said inactivation time of completing is less than 20 minutes.
10. the copper alloy of claim 1, it contains the highest 0.3% Zr by weight.
11. the copper alloy of claim 3, it is effectively antimicrobial and only contain Ni with the impurity form.
12. the copper alloy of claim 11, it contains 12-20%Zn, 10-17%Mn, and 0.5-2.5%Fe.
13. the copper alloy of claim 12, it contains 15-18%Zn, 14-17%Mn, and 0.5-1.5%Fe.
14. the copper alloy of claim 5, the variable color of the temperature of its anti-raising.
15. the copper alloy of claim 14, it contains 12-20%Zn, 10-17%Mn, 0.5-3.5%Ni and 0.1-1.0%Fe.
16. the copper alloy of claim 15, it contains 13-16%Zn, 14-17%Mn, 1.5-2.5%Ni and 0.2-0.6%Fe.
17. the copper alloy of claim 14, it contains with lower at least a:
The highest 1.0%Al; With
And at least a:
At least a in lower group of the highest 0.5%: Sn, Si, Co, Ti, Cr, Mg, Zr, Ag, and
At least a in lower group of the highest 0.1%: P, B, Ca, Ge, Se, Te.
Use to be used for currency 18. copper alloy, this copper alloy are white visual appearance and contact resistance variable color, as directly substituting of C713, this copper alloy contains:
A) zinc of 6-25% (Zn)
B) manganese of 4-17% (Mn),
C) nickel of 0.1-9.0% (Ni),
D) be essentially the surplus of Cu; And
E) combination that has a described a-d of white visual appearance is effectively antimicrobial, and has under ededy current gauge excitation frequency 60kHz-480kHz the specific conductivity greater than 2.5%IACS.
19. the copper alloy of claim 18, the surplus that wherein is essentially Cu also contain at the most with lower at least a:
At least a in lower group of 0.5%: Sn, Si, Co, Ti, Cr, Fe, Mg, Zr, Ag; And
At least a in lower group of the highest 0.1%: P, B, Ca, Ge, Se, Te.
20. the copper alloy of claim 19, wherein said specific conductivity are 4%IACS-7%IACS; And have and be less than the inactivation time of completing of 60 minutes.
21. the copper alloy of claim 19 contains the highest 0.3% Zr by weight; And
Be less than the inactivation time of completing of 30 minutes.
22. the copper alloy of claim 21 contains 10-18%Zn, 4-7%Mn, 4-9%Ni and 0.05-0.20%Zr; And
Complete inactivation time and be less than 20 minutes.
23. the copper alloy of claim 22, it contains 12-16%Zn, 4-6%Mn, 5-9%Ni and 0.05-0.15%Zr; And
Complete inactivation time and be less than 15 minutes.
24. the copper alloy of claim 18, it is molded is disk.
CN200980134815.6A 2008-09-10 2009-09-08 White-colored copper alloy with reduced nickel content Expired - Fee Related CN102149834B (en)

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US10627508P 2008-10-17 2008-10-17
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