TWI539014B - Low lead ingot - Google Patents
Low lead ingot Download PDFInfo
- Publication number
- TWI539014B TWI539014B TW100139572A TW100139572A TWI539014B TW I539014 B TWI539014 B TW I539014B TW 100139572 A TW100139572 A TW 100139572A TW 100139572 A TW100139572 A TW 100139572A TW I539014 B TWI539014 B TW I539014B
- Authority
- TW
- Taiwan
- Prior art keywords
- weight
- alloy
- eds
- content
- alloys
- Prior art date
Links
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 title description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 264
- 239000000956 alloy Substances 0.000 claims description 264
- 229910052717 sulfur Inorganic materials 0.000 claims description 63
- 239000010949 copper Substances 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 46
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 45
- 239000011701 zinc Substances 0.000 claims description 43
- 239000011593 sulfur Substances 0.000 claims description 42
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 37
- 229910052802 copper Inorganic materials 0.000 claims description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 24
- 239000000155 melt Substances 0.000 claims description 24
- 229910052718 tin Inorganic materials 0.000 claims description 21
- 229910052725 zinc Inorganic materials 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 239000011572 manganese Substances 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 239000002893 slag Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 2
- 230000006698 induction Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 2
- PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 claims 1
- 230000001939 inductive effect Effects 0.000 claims 1
- 239000012071 phase Substances 0.000 description 59
- 239000011135 tin Substances 0.000 description 43
- 238000009826 distribution Methods 0.000 description 33
- 238000010586 diagram Methods 0.000 description 30
- 238000005266 casting Methods 0.000 description 26
- 239000002245 particle Substances 0.000 description 21
- 229910001369 Brass Inorganic materials 0.000 description 19
- 239000010951 brass Substances 0.000 description 19
- 238000009472 formulation Methods 0.000 description 19
- 229910000521 B alloy Inorganic materials 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 14
- 150000004763 sulfides Chemical class 0.000 description 13
- 230000003287 optical effect Effects 0.000 description 12
- 229910000881 Cu alloy Inorganic materials 0.000 description 11
- 229910052797 bismuth Inorganic materials 0.000 description 11
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 229910052984 zinc sulfide Inorganic materials 0.000 description 9
- 229910000906 Bronze Inorganic materials 0.000 description 8
- 239000010974 bronze Substances 0.000 description 7
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 7
- 230000008014 freezing Effects 0.000 description 7
- 238000007710 freezing Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 229910017518 Cu Zn Inorganic materials 0.000 description 6
- 229910017752 Cu-Zn Inorganic materials 0.000 description 6
- 229910017943 Cu—Zn Inorganic materials 0.000 description 6
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 238000003754 machining Methods 0.000 description 6
- 238000010587 phase diagram Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 5
- 229910000581 Yellow brass Inorganic materials 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000010955 niobium Substances 0.000 description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 5
- 238000007528 sand casting Methods 0.000 description 5
- 229910052711 selenium Inorganic materials 0.000 description 5
- 239000011669 selenium Substances 0.000 description 5
- 229910001339 C alloy Inorganic materials 0.000 description 4
- 229910000978 Pb alloy Inorganic materials 0.000 description 4
- 239000005083 Zinc sulfide Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052950 sphalerite Inorganic materials 0.000 description 4
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 4
- 229910001257 Nb alloy Inorganic materials 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- -1 transition metal sulfide Chemical class 0.000 description 3
- 238000007514 turning Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910017755 Cu-Sn Inorganic materials 0.000 description 2
- 229910017927 Cu—Sn Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 240000006829 Ficus sundaica Species 0.000 description 2
- 229910001370 Se alloy Inorganic materials 0.000 description 2
- 229910007609 Zn—S Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005242 forging Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910017888 Cu—P Inorganic materials 0.000 description 1
- 229910001340 Leaded brass Inorganic materials 0.000 description 1
- KWEGYAQDWBZXMX-UHFFFAOYSA-N [Au]=[Se] Chemical compound [Au]=[Se] KWEGYAQDWBZXMX-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005058 metal casting Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000010120 permanent mold casting Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 208000034100 susceptibility to 1 basal cell carcinoma Diseases 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/0006—Adding metallic additives
-
- 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
- C22C9/02—Alloys based on copper with tin 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
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
Description
本申請案請求2010年10月29日申請之美國臨時專利申請案第61/408518號案及2010年11月5日申請之美國臨時專利申請案第61/410752號案之優先權。此等申請案在此完整併入本案以為參考資料。The present application claims priority to U.S. Provisional Patent Application Serial No. 61/408, 518, filed on Jan. 29, 2010, and to U.S. Provisional Patent Application No. 61/410,752, filed on Nov. 5, 2010. These applications are hereby incorporated by reference in their entirety into this application.
本發明係有關於低鉛鑄錠。The present invention relates to low lead ingots.
現今配管材料典型上係自含鉛之銅合金製造。一標準之黃銅合金配製物於此項技藝係稱為C84400或“81,3,7,9”合金(由81%之銅，3%之錫、7%之鉛，及9%之鋅所構成)(此處於後係“81合金”)。雖然由於健康及環境問題(部份係由美國環保署對用於飲用水應用之銅合金之最大鉛含量之規定)及成本原因，需降低配管配件所含之鉛，但鉛之存在對於達成合金之所欲性質係持續需要。例如，黃銅合金中之鉛存在提供所欲機械特性及助於鑄造物之機械加工及最後加工。簡單地移除鉛或降至低於某些程度係大量降低鑄造物之機械加工性及結構完整性，且係不實用。Today's piping materials are typically made from lead-containing copper alloys. A standard brass alloy formulation in this technology is called C84400 or "81,3,7,9" alloy (from 81% copper, 3% tin, 7% lead, and 9% zinc) Composition) (hereafter "81 alloy"). Although the lead contained in the piping fittings needs to be reduced due to health and environmental problems (some of which are stipulated by the US Environmental Protection Agency for the maximum lead content of copper alloys for drinking water applications) and cost, the presence of lead for alloying The desired nature is a constant need. For example, lead in brass alloys provides the desired mechanical properties and aids in the machining and finishing of the casting. Simply removing the lead or reducing it to below a certain extent is a significant reduction in the machinability and structural integrity of the casting and is not practical.
自黃銅合金移除或降低鉛先前已被嘗試。此項技藝先前嘗試以其它元素替代而取代鉛於包括主要鑄造、主要機械加工、次要機械加工、拋光、電鍍，及機械組合之製造方法中造成主要之機械加工及最後加工之問題。Removal or reduction of lead from brass alloys has previously been tried. This art has previously attempted to replace lead with other elements to cause major mechanical and final processing problems in manufacturing processes including primary casting, primary machining, secondary machining, polishing, electroplating, and mechanical combinations.
數種低或無鉛之配製物先前已被描述。見，例如，以商品名SeBiLOY®或EnviroBrass®、Federalloy®，及Eco Brass®出售之產品，與美國專利第7,056,396及6,413,330號案。第1圖係包括以銅發展協會(Copper Development Association)之註冊為主之數種已知合金之配製物之表。現存之以低鉛或無鉛之銅為主之鑄造物之技藝係由二主要種類所構成：以矽為主之材料及鉍/硒材料。 Several low or lead-free formulations have been previously described. See, for example, under the trade name SeBiLOY ® or EnviroBrass ®, Federalloy ®, Eco Brass ® and sale of the product, and US Patent No. 6,413,330 and 7,056,396 the first case. Figure 1 is a table of formulations of several known alloys based on the registration of the Copper Development Association. The existing art of castings based on low-lead or lead-free copper consists of two main types: bismuth-based materials and bismuth/selenium materials.
但是，需要提供具有與現今銅/鉛合金相似性質而不會降低機械性質或化學性質與因為材料中之鉛取代造成切割工具及最終加工問題之顯著干擾製造方法之低鉛溶液。 However, there is a need to provide low lead solutions having similar properties to today's copper/lead alloys without degrading mechanical or chemical properties and significant interference with the manufacturing process due to cutting tools and final processing problems caused by lead substitution in the materials.
本發明之一實施例係有關於一種半紅黃銅，其具有約83%至約91%之銅，約0.1%至約0.8%之硫，約2.0%至約4.0%之錫，少於約0.09%之鉛，約4.0%至約14.0%之鋅，及約1.0%至約2.0%之鎳之一組成物。 One embodiment of the invention relates to a semi-red brass having from about 83% to about 91% copper, from about 0.1% to about 0.8% sulfur, from about 2.0% to about 4.0% tin, less than about 0.09% lead, from about 4.0% to about 14.0% zinc, and from about 1.0% to about 2.0% nickel.
本發明之一實施例係有關於一種錫青銅，其具有約86%至約89%之銅，約0.1%至約0.8%之硫，約7.5%至約8.5%之錫，少於0.09%之鉛，約1.0%至約5.0%之鋅，及約1.0%之鎳之一組成物。 One embodiment of the invention relates to a tin bronze having from about 86% to about 89% copper, from about 0.1% to about 0.8% sulfur, from about 7.5% to about 8.5% tin, less than 0.09% Lead, about 1.0% to about 5.0% zinc, and about 1.0% nickel.
本揭露內容之另外特徵、優點，及實施例可自考量下列詳細說明、圖式，及申請專利範圍而闡述。再者，需瞭解本揭露內容之先前概要及下列詳細說明係例示且意欲於未進一步限制所請求之本揭露內容的範圍而提供進一步解釋。Additional features, advantages, and embodiments of the present disclosure can be set forth in the description of the following detailed description, drawings, and claims. In addition, it is to be understood that the foregoing general description of the disclosure and the following detailed description are intended to provide a further explanation of the scope of the disclosure.
本揭露內容之先前及其它之目的、方面、特徵，及優點藉由參考結合所附圖式之下列說明會變得更明顯及更佳瞭解，其中：The foregoing and other objects, aspects, features and advantages of the present disclosure will become more apparent and appreciated by
第1圖提供列示數種已知市面上銅合金之配製物之第1表。Figure 1 provides a first table listing the formulations of several known copper alloys on the market.
第2圖提供列示依據本發明實施例之合金族群之配製物之第2表。Figure 2 provides a second table listing the formulations of the alloy population in accordance with an embodiment of the present invention.
第3A圖提供以其個別鑄造熱列示I-A族群之機械性質範例之合金配製物之第3表。第3B圖提供以其個別鑄造熱列示I-A族群之平均機械性質測試之結果之第4表。Figure 3A provides a third table of alloy formulations showing examples of mechanical properties of the I-A group with their individual casting heats. Figure 3B provides a fourth table showing the results of the average mechanical property test of the I-A population with its individual casting heat.
第4A圖提供以其個別鑄造熱列示I-B族群機械性質範例之合金配製物之第5表。第4B圖提供列示I-B族群之平均機械性質測試之結果之第6表。Figure 4A provides a fifth table of alloy formulations showing examples of mechanical properties of the I-B group with their individual casting heats. Figure 4B provides a sixth table showing the results of the average mechanical property test of the I-B population.
第5A圖提供以其個別鑄造熱列示II-A族群機械性質範例之合金配製物之第7表。第5B圖提供列示II-A族群之平均機械性質測試之結果之第8表。Figure 5A provides a seventh table of alloy formulations showing examples of the mechanical properties of Group II-A groups with their individual casting heats. Figure 5B provides an eighth table showing the results of the average mechanical properties test for the II-A population.
第6圖提供列示本發明之某些合金族群之實施例所觀察之典型及最小性質及諸如第1表(第1圖)中者之可購得合金所報導之性質之第9表。Figure 6 provides a ninth table listing the typical and minimal properties observed for the examples of certain alloy populations of the present invention and the properties reported for commercially available alloys such as those in Table 1 (Figure 1).
第7圖提供列示用於SEM/EDS測試之合金組成物之第10表。Figure 7 provides a table 10 listing the alloy compositions used for SEM/EDS testing.
第8A及8B圖例示合金I-A-10a中之硫的元素映像(0.16% S)。 Figures 8A and 8B illustrate the elemental map of sulfur in alloy I-A-10a (0.16% S).
第9A圖係合金I-A-10a之SEM；第9B-H圖例示元素映像；第9B圖係Sn之EDS；第9C圖係Zn之EDS；第9D圖係Cu之EDS；第9E圖係Fe之EDS；第9F圖係Ni之EDS；第9G圖係P之EDS；第9H圖係S之EDS。 9A is an SEM of alloy IA-10a; 9B-H is an illustration of an elemental image; 9B is an EDS of Sn; 9C is an EDS of Zn; 9D is an EDS of Cu; and 9E is a Fe of EDS; 9F is the EDS of Ni; 9G is the EDS of P; and 9H is the EDS of S.
第10A圖係合金I-A-10a之顯微照片，且區域1，2，及3被標記；第10B-D圖顯示Cu2S、ZnS及Cu-Zn介金屬相存在；第10B圖係區域1之EDS光譜；第10C圖係區域2之EDS光譜；第10D圖係區域3之EDS光譜。 Figure 10A is a photomicrograph of alloy IA-10a, and regions 1, 2, and 3 are labeled; 10B-D shows the presence of Cu2S, ZnS, and Cu-Zn intermetallic phases; and 10B is the EDS for region 1 Spectrum; 10C is the EDS spectrum of region 2; and 10D is the EDS spectrum of region 3.
第11A-B圖係合金I-A-10a於低(第11A圖)及高放大倍率(第11B圖)之光學影像。 Fig. 11A-B is an optical image of the alloy I-A-10a at low (Fig. 11A) and high magnification (Fig. 11B).
第12A圖係合金I-B-10a之SEM，且第12B圖係例示合金I-B-10a內之硫之元素映像(0.31% S)。 Fig. 12A is a SEM of alloy I-B-10a, and Fig. 12B illustrates an elemental map of sulfur (0.31% S) in alloy I-B-10a.
第13A圖係合金I-B-10a之SEM；第13B-H圖例示1000x放大倍率之元素映像；第13B圖係Sn之EDS；第13C圖係Zn之EDS；第13D圖係Cu之EDS；第13E圖係Fe之EDS；第13F圖係Ni之EDS；第13G圖係P之EDS；第13H圖係S之EDS。 Fig. 13A is an SEM of alloy IB-10a; Fig. 13B-H illustrates an elemental map of 1000x magnification; Fig. 13B is an EDS of Sn; Fig. 13C is an EDS of Zn; and Fig. 13D is an EDS of Cu; The figure is the EDS of Fe; the 13F is the EDS of Ni; the 13G is the EDS of P; the 13H is the EDS of S.
第14A圖係合金I-B-10b之SEM(0.13% S)；第14B-I圖例示5000x放大倍率之元素映像；第14B圖係Si之EDS；第14C圖係S之EDS；第14D圖係Fe之EDS；第14E圖係Cu之EDS；第14F圖係Zn之EDS；第14G圖係Sn之EDS；第14H圖係Pb之EDS；第14I圖係Ni之EDS。 Figure 14A is a SEM (0.13% S) of alloy IB-10b; Figure 14B-I illustrates an elemental map of 5000x magnification; Figure 14B is an EDS of Si; Figure 14C is an EDS of S; Figure 14D is a Fe EDS; 14E is the EDS of Cu; 14F is the EDS of Zn; 14G is the EDS of Sn; 14H is the EDS of Pb; and 14I is the EDS of Ni.
第15A-B圖係合金I-B-10a(0.31% S)於低(第15A圖)及 高放大倍率(第15B圖)之光學影像。 Figure 15A-B shows that the alloy I-B-10a (0.31% S) is low (Figure 15A) and Optical image with high magnification (Fig. 15B).
第16A及16B圖例示合金II-A-10a內之硫之元素映像(0.30% S)。 Figures 16A and 16B illustrate the elemental map of sulfur in the alloy II-A-10a (0.30% S).
第17A圖係合金II-A-10a之SEM；第17B-H圖例示元素映像；第17B圖係Sn之EDS；第17C圖係Zn之EDS；第17D圖係Cu之EDS；第17E圖係Fe之EDS；第17F圖係Ni之EDS；第17G圖係P之EDS；第17H圖係S之EDS。 Figure 17A is an SEM of Alloy II-A-10a; Figure 17B-H is an illustration of an elemental image; Figure 17B is an EDS of Sn; Figure 17C is an EDS of Zn; Figure 17D is an EDS of Cu; EDS of Fe; 17F is EDS of Ni; 17G is EDS of P; and 17H is EDS of S.
第18A圖係合金II-A-10b(0.19% S)之SEM；第18B-I圖例示於1000x放大倍率之元素映像；第18B圖係Si之EDS；第18C圖係S之EDS；第18D圖係Fe之EDS；第18E圖係Cu之EDS；第18F圖係Zn之EDS；第18G圖係Sn之EDS；第18H圖係Pb之EDS；第18I圖係Ni之EDS。 Figure 18A is an SEM of Alloy II-A-10b (0.19% S); Figure 18B-I is an elemental image at 1000x magnification; Figure 18B is an EDS of Si; Figure 18C is an EDS of S; 18D The figure is the EDS of Fe; the 18E is the EDS of Cu; the 18F is the EDS of Zn; the 18th is the EDS of Sn; the 18H is the EDS of Pb; the 18I is the EDS of Ni.
第19A-B圖係合金II-A於低(第19B圖)及高放大倍率(第19A圖)之光學影像。 19A-B is an optical image of Alloy II-A at low (Fig. 19B) and high magnification (Fig. 19A).
第20A及20B圖例示合金III-A內之硫之元素映像(0.011% S)。 Figures 20A and 20B illustrate the elemental map of sulfur in alloy III-A (0.011% S).
第21A圖係合金III-A之SEM；第21B-H圖例示元素映像；第21B圖係Sn之EDS；第21C圖係Zn之EDS；第21D圖係Cu之EDS；第21E圖係Fe之EDS；第21F圖係Ni之EDS；第21G圖係P之EDS；第21H圖係S之EDS。 21A is an SEM of Alloy III-A; 21B-H is an illustration of an elemental image; 21B is an EDS of Sn; 21C is an EDS of Zn; 21D is an EDS of Cu; and 21E is a Fe of EDS; 21F is the EDS of Ni; 21G is the EDS of P; and 21H is the EDS of S.
第22A-B圖係合金III-A於低(第22A圖)及高放大倍率(第22B圖)之光學影像。 Fig. 22A-B is an optical image of alloy III-A at low (Fig. 22A) and high magnification (Fig. 22B).
第23圖係I-A、I-B及II-A族群合金中形成之主要硫化物之硫自由能圖。Figure 23 is a graph showing the sulfur free energy of the main sulfides formed in the I-A, I-B and II-A alloys.
第24圖係Cu-Sn-Zn-S合金之不同合金之垂直截面。Figure 24 is a vertical section of a different alloy of Cu-Sn-Zn-S alloy.
第25A圖係使用Scheil冷卻之合金I-A-11a之相分佈圖，第25B圖係此相分佈圖之一放大部份，其顯示次要相之相對量。Fig. 25A is a phase distribution diagram using Scheil cooled alloy I-A-11a, and Fig. 25B is an enlarged portion of the phase distribution diagram showing the relative amount of the secondary phase.
第26A圖係使用Scheil冷卻之合金I-A-11b之相分佈圖，第26B圖係此相分佈圖之一放大部份，其顯示次要相之相對量。Fig. 26A is a phase distribution diagram using Scheil cooled alloy I-A-11b, and Fig. 26B is an enlarged portion of the phase distribution diagram showing the relative amount of the secondary phase.
第27A圖係使用Scheil冷卻之合金I-A-11c之相分佈圖，第27B圖係此相分佈圖之一放大部份，其顯示次要相之相對量。Figure 27A is a phase distribution diagram using Scheil cooled alloy I-A-11c, and Figure 27B is an enlarged portion of the phase distribution diagram showing the relative amounts of the secondary phases.
第28A圖係使用Scheil冷卻之合金I-A-11d之相分佈圖，第28B圖係此相分佈圖之一放大部份，其顯示次要相之相對量。Figure 28A shows the phase distribution of the Scheil cooled alloy I-A-11d, and Figure 28B shows an enlarged portion of the phase distribution showing the relative amount of the secondary phase.
第29A圖係使用Scheil冷卻之合金I-A-11e之相分佈圖，第29B圖係此相分佈圖之一放大部份，其顯示次要相之相對量。Fig. 29A is a phase distribution diagram using Scheil cooled alloy I-A-11e, and Fig. 29B is an enlarged portion of the phase distribution diagram showing the relative amount of the secondary phase.
第30A圖係使用Scheil冷卻之C83470市面上之合金(第1表，第1圖)之相分佈圖，第30B圖係此相分佈圖之一放大部份，其顯示次要相之相對量。Figure 30A shows the phase distribution of the alloy on the C83470 market (Table 1, Figure 1) using Scheil cooling, and Figure 30B is an enlarged portion of the phase distribution showing the relative amount of the secondary phase.
第31圖係I-A族群之垂直截面之相圖。Figure 31 is a phase diagram of the vertical section of the I-A group.
第32A圖係I-A族群之Scheil相組合圖，第32B圖係I-A族群之放大Scheil相組合圖。Fig. 32A is a Scheil combination diagram of the I-A group, and Fig. 32B is an enlarged Scheil combination diagram of the I-A group.
第33圖係I-B族群之垂直截面。Figure 33 is a vertical section of the I-B group.
第34A圖係I-B族群之Scheil相組合圖，第34B圖係I-B族群之放大Scheil相組合圖。 Figure 34A is a Scheil combination diagram of the I-B group, and Figure 34B is an enlarged Scheil combination diagram of the I-B group.
第35圖係II-A族群之垂直截面。 Figure 35 is a vertical section of the II-A group.
第36A圖係II-A族群之Scheil相組合圖，第36B圖係II-A族群之放大Scheil相組合圖。 Fig. 36A is a Scheil combination diagram of the II-A group, and Fig. 36B is a magnified Scheil combination diagram of the II-A group.
第37圖係顯示以其CDA數指示之與數種已知合金相比之I-A合金族群之各種熱之極限抗拉強度(UTS)圖。 Figure 37 is a graph showing the various thermal ultimate tensile strength (UTS) plots for the I-A alloy population compared to several known alloys, indicated by their CDA numbers.
第38圖係顯示以其CDA數指示之與數種已知合金相比之I-A合金族群之各種熱之屈服強度圖。 Figure 38 is a graph showing the various yield strengths of the I-A alloy populations as indicated by their CDA numbers compared to several known alloys.
第39圖係顯示以其CDA數指示之與數種已知合金相比之I-A合金族群之各種熱之伸長率圖。 Figure 39 is a graph showing various heat elongations for the I-A alloy population as indicated by its CDA number compared to several known alloys.
第40圖係顯示以其CDA數指示之與數種已知合金相比之I-B合金族群之各種熱之極限抗拉強度(UTS)圖。 Figure 40 is a graph showing the various thermal ultimate tensile strength (UTS) of the I-B alloy population as indicated by its CDA number compared to several known alloys.
第41圖係顯示以其CDA數指示之與數種已知合金相比之I-B合金族群之各種熱之屈服強度圖。 Figure 41 is a graph showing the various yield strengths of the I-B alloy population compared to several known alloys as indicated by their CDA numbers.
第42圖係顯示以其CDA數指示之與數種已知合金相比之I-B合金族群之各種熱之伸長率圖。 Figure 42 is a graph showing various heat elongations for the I-B alloy population as indicated by its CDA number compared to several known alloys.
第43圖係顯示以其CDA數指示之與數種已知合金相比之II-A合金族群之各種熱之極限抗拉強度(UTS)圖。 Figure 43 is a graph showing the various thermal ultimate tensile strength (UTS) plots for the II-A alloy population compared to several known alloys, indicated by their CDA numbers.
第44圖係顯示以其CDA數指示之與數種已知合金相比之II-A合金族群之各種熱之屈服強度圖。 Figure 44 is a graph showing the various yield strengths of the II-A alloy population compared to several known alloys as indicated by their CDA numbers.
第45圖係顯示以其CDA數指示之與數種已知合金相比之II-A合金族群之各種熱之伸長率圖。 Figure 45 is a graph showing various heat elongations for the II-A alloy population compared to several known alloys, indicated by their CDA numbers.
第46A圖例示一市面上之硫黃銅，BiwaliteTM(C83470)，之硫化物顆粒尺寸，且第46B圖顯 示I-B合金族群(0.13S-4.45Zn-3.63Sn)之顆粒尺寸之顯微照片。 46A shows an illustration of the market of sulfur brass, Biwalite TM (C83470), the particle size of the sulfide, and FIG 46B shows a photomicrograph of Alloy IB group (0.13S-4.45Zn-3.63Sn) of the particle size.
專利或申請案檔案含有至少一以彩色製作之圖。具有彩色圖之此專利或專利申請公開案之影本於請求及付必要費用時會由局方提供。 A patent or application file contains at least one picture made in color. A copy of this patent or patent application publication with a color map will be provided by the Administrator upon request and payment of the necessary fee.
於下列詳細說明，係參考為此說明一部份之所附圖式。除文中作其它指示外，於圖式中，相似符號典型上係視為相似組件。詳細說明、圖式，及申請專利範圍中說明之例示實施例並非用於作限制。於未偏離此處呈現之主題的精神或範圍，其它實施例可被使用，且其它改變可被進行可輕易瞭解如此處所概述及於圖式中所例示之本揭露之各方面可以廣泛之各種不同組態作安排、取代、組合，及設計，所有者皆係被明確地考量且作為此揭露內容之一部份。 In the following detailed description, reference is made to the accompanying drawings in this section. In the drawings, similar symbols are typically considered to be similar components, unless otherwise indicated herein. The exemplified embodiments described in the detailed description, drawings, and claims are not intended to be limiting. Other embodiments may be utilized, and other changes may be made without departing from the spirit or scope of the subject matter presented herein. The various aspects of the present disclosure as outlined herein and illustrated in the drawings can be readily understood. The configuration, arrangement, replacement, combination, and design of the owner are explicitly considered and part of this disclosure.
於一實施例，本發明係有關於一物料組成物及其製造方法。此物料組成物係一以銅為主之合金，其係具有與熟習與飲用水接觸之腔體裝置(包括，例如，配管設備)之技藝者所瞭解般之”低”含量之鉛。鉛量係低於一般用於賦予合金用於大部份應用所需之諸如抗拉強度、伸長率、機械加工性，及氣壓密閉性之有利性質者。習知技藝之作為含鉛黃銅之無鉛另類物典型上需要對用於砂磨鑄造之金屬供料作改變，以便產生足夠之氣壓密閉性(諸如，不具材料多孔 性)。本發明之合金包括特殊含量之硫，且於某些實施例，硫係經由一較佳方法添加，以賦予因降低鉛而損失之有利性質。 In one embodiment, the invention relates to a material composition and a method of making the same. The material composition is a copper-based alloy having a "low" content of lead as understood by those skilled in the art of contact with drinking water (including, for example, piping equipment). The amount of lead is lower than that which is generally used to impart alloys for most applications such as tensile strength, elongation, machinability, and gas tightness. Conventional art as a lead-free alternative to lead-containing brass typically requires a change in the metal feed for sand casting to produce sufficient gas tightness (eg, without material porosity) Sex). The alloys of the present invention comprise a particular level of sulfur, and in certain embodiments, the sulfur is added via a preferred method to impart advantageous properties for loss due to reduced lead.
本發明之合金一般係有關於適合之半紅黃銅、錫青銅，及黃色黃銅之配製物。某些實施例係配製成主要用於砂模鑄造應用、永久模鑄造應用，或鍛造應用。 The alloys of the present invention are generally formulated with suitable semi-red brass, tin bronze, and yellow brass. Certain embodiments are formulated primarily for use in sand casting applications, permanent mold casting applications, or forging applications.
第2表(第2圖)係例示依據本發明之一族群之合金。每一合金之特徵至少部份係相對較低量之鉛(約0.09%或更少)及硫之存在(約0.1%至0.8%)。提供三族群之半紅黃銅，標記為I-A合金族群、I-B合金族群，及I-C合金族群。於一實施例，此等半紅黃銅合金係適於砂模鑄造。提供三族群之錫青銅，標記為II-A合金族群、II-B合金族群，及II-C合金族群。於一實施例，此等錫青銅合金係適於砂模鑄造。提供六族群之黃色黃銅，標記為III-A合金族群、III-B合金族群、III-C合金族群、IV-A合金族群、IV-B合金族群，及IV-C合金族群。於一實施例，III合金族群之合金係適於永久模鑄造。於一實施例，IV合金族群之合金係適於鍛造應用。 The second table (Fig. 2) illustrates an alloy of a group according to the present invention. Each alloy is characterized, at least in part, by a relatively low amount of lead (about 0.09% or less) and the presence of sulfur (about 0.1% to 0.8%). A semi-red brass of the triad group is provided, labeled as an I-A alloy group, an I-B alloy group, and an I-C alloy group. In one embodiment, the semi-red brass alloys are suitable for sand casting. Three groups of tin bronze are provided, labeled as II-A alloy group, II-B alloy group, and II-C alloy group. In one embodiment, the tin bronze alloys are suitable for sand casting. Six groups of yellow brass are provided, labeled III-A alloy group, III-B alloy group, III-C alloy group, IV-A alloy group, IV-B alloy group, and IV-C alloy group. In one embodiment, the alloy of the III alloy group is suitable for permanent die casting. In one embodiment, the alloy of the IV alloy population is suitable for forging applications.
本發明之合金包含銅、鋅、錫、硫、鎳，及磷。於某些實施例，係包括錳、鋯、硼、鈦，及/或碳之一或多者。非IV族群之鍛造黃色黃銅之實施例亦包括銻、錫、鎳、磷、鋁，及矽之一或多者。 The alloy of the present invention contains copper, zinc, tin, sulfur, nickel, and phosphorus. In certain embodiments, one or more of manganese, zirconium, boron, titanium, and/or carbon are included. Embodiments of the non-IV group of forged yellow brass also include one or more of bismuth, tin, nickel, phosphorus, aluminum, and antimony.
此等合金包含作為一主要組份之銅。銅提供此合金基本性質，包括抗微生物性質及耐腐蝕性。純銅具有相對較 低之屈服強度及抗拉強度，且相對於其一般合金種類之青銅及黃銅，並非極硬。因此，所欲地係經由合金化改良用於許多應用之銅性質。銅典型上係以一基本鑄錠添加。此基本鑄錠之組成物純度會依來源礦物及採礦後之加工而改變。因此，需瞭解鑄錠化學會改變，因此，於一實施例，基本鑄錠之化學被考量。例如，基本鑄錠之鋅含量係於決定多少額外之鋅被添加以達到合金之所欲最終組成物時被考量。基本鑄錠需被選擇以提供合金所欲之銅，同時考量基本鑄錠內之次要元素及於最終合金內之意欲存在，因為小含量之諸如鐵之各種雜質係普遍且對於所欲性質不具實質作用。 These alloys contain copper as a major component. Copper provides the basic properties of this alloy, including antimicrobial properties and corrosion resistance. Pure copper has a relatively high Low yield strength and tensile strength, and not very hard relative to the bronze and brass of its general alloy type. Therefore, it is desirable to improve the copper properties for many applications via alloying. Copper is typically added as a basic ingot. The purity of the composition of this basic ingot will vary depending on the source mineral and the processing after mining. Therefore, it is to be understood that the ingot chemistry will change, and therefore, in one embodiment, the chemistry of the basic ingot is considered. For example, the zinc content of the basic ingot is taken into account when determining how much additional zinc is added to achieve the desired final composition of the alloy. The basic ingot needs to be selected to provide the desired copper for the alloy, taking into account the secondary elements in the basic ingot and the intended presence in the final alloy, since small amounts of impurities such as iron are common and do not have the desired properties. Substantial effect.
鉛典型上被包括作為銅合金之一組份，特別是於機械加工性係一重要因素之諸如配管之應用。相對於銅合金之普遍的許多其它元素，鉛具有低熔點。因此，於熔融物冷卻時，於銅合金內之鉛易遷移至樹枝狀或顆粒狀邊界區域。鉛於樹枝狀或顆粒狀邊界區域之存在會大量改良機械加工性及氣壓密閉性。但是，於最近數十年，鉛之嚴重不利衝擊使鉛於許多銅合金應用係非所欲的。特別地，鉛於樹枝狀或顆粒狀邊界區域之存在，改良機械加工性之普遍被接受之特徵，係鉛會非所欲地輕易自銅合金漏出之部份原因。 Lead is typically included as a component of a copper alloy, particularly for applications such as piping, which is an important factor in mechanical processing. Lead has a low melting point relative to many other elements common to copper alloys. Therefore, when the melt is cooled, the lead in the copper alloy easily migrates to the dendritic or granular boundary region. The presence of lead in dendritic or granular boundary regions greatly improves machinability and airtightness. However, in recent decades, the severe adverse effects of lead have made lead unsuitable for many copper alloy applications. In particular, the presence of lead in dendritic or granular boundary regions, a generally accepted feature of improved machinability, is partly responsible for the fact that lead can easily escape from copper alloys as desired.
硫添加至本發明合金以克服使用含鉛銅合金之某些缺點。存在於熔融物之硫典型上會與亦存在於熔融物之過渡金屬反應形成過渡金屬硫化物。例如，硫化銅及硫化鋅會形成，或對於其中錳存在之實施例，會形成硫化錳。第23圖例示會於本發明實施例形成之數種過渡金屬硫化物之自由能圖。硫化銅之熔點係1130℃，硫化鋅係1185℃，硫化錳係1610℃，且硫化錫係832℃。因此，未限制本發明之範圍，基於形成之自由能，相信大量之硫化物形成對於不具錳之實施例會係硫化鋅。相信於銅固化因而於熔融物形成樹脂狀物後固化之硫化物係聚集於樹枝狀區域或顆粒邊界。Sulfur is added to the alloys of the present invention to overcome some of the disadvantages of using lead-containing copper alloys. The sulfur present in the melt typically reacts with the transition metal also present in the melt to form a transition metal sulfide. For example, copper sulfide and zinc sulfide may form, or for embodiments in which manganese is present, manganese sulfide may be formed. Figure 23 illustrates a free energy diagram of several transition metal sulfides formed in the examples of the present invention. The melting point of copper sulfide is 1130 ° C, zinc sulfide is 1185 ° C, manganese sulfide is 1610 ° C, and tin sulfide is 832 ° C. Thus, without limiting the scope of the invention, it is believed that a large amount of sulfide formation will be zinc sulfide for embodiments that do not have manganese based on the free energy of formation. It is believed that the sulfide which solidifies after the copper solidifies and forms a resin after the melt forms agglomerates on a dendritic region or a particle boundary.
硫提供與鉛所賦予銅合金者相似之性質，而無與鉛有關之健康顧慮。硫形成硫化物，其被認為係易聚集於樹枝狀或顆粒邊界區域。硫化物之存在提供金屬結構破壞，及於顆粒邊界區域形成屑片之位置，及改良機械加工潤滑性，能改良整體機械加工性。本發明合金中大量之硫化物提供潤滑性。硫化物之良好分佈改良氣壓密閉性及機械加工性。Sulfur provides properties similar to those imparted to lead alloys by lead without the health concerns associated with lead. Sulfur forms sulfides which are believed to accumulate in dendritic or grain boundary regions. The presence of sulfides provides metal structure damage, where the chips are formed in the boundary regions of the particles, and improved mechanical processing lubricity, which improves overall machinability. A large amount of sulfide in the alloy of the present invention provides lubricity. Good distribution of sulfides improves airtightness and machinability.
相信於某些實施例中之錫存在藉由固體溶液強化及藉由形成諸如Cu3Sn之Cu-Sn介金屬相而增加強度及硬性但降低延展性。其亦增加固化範圍。鑄造流動性隨錫含量而增加。錫亦增加耐腐蝕性。但是，現今，相較於其它組份，Sn係極昂貴。Believed to certain embodiments of the present embodiments tin by the solid solution strengthening and by formation of Cu 3 Sn Cu-Sn intermetallic phase such as increasing the strength but reduces the ductility and hard. It also increases the curing range. Casting fluidity increases with tin content. Tin also increases corrosion resistance. However, today, Sn is extremely expensive compared to other components.
有關於鋅，相信Zn之存在係相似於Sn，但係較少程度，於某些實施例，有關於如上所述特性之上述改良，約2%之Zn係約略相等於1%之Sn。Zn係藉由固化溶液硬化而增加強度及硬性。但是，Cu-Zn合金具有一短的冷凍範圍。Zn係比Sn更不昂貴。Regarding zinc, it is believed that the presence of Zn is similar to Sn, but to a lesser extent, and in some embodiments, with respect to the above-described improvements in properties as described above, about 2% of the Zn is about a little equal to 1% of Sn. Zn is hardened by a curing solution to increase strength and hardness. However, the Cu-Zn alloy has a short freezing range. The Zn system is less expensive than Sn.
有關於某些實施例，鐵被認為係於熔融及傾倒操作期間自攪拌桿、漏杓等取得之雜質，或為基本鑄錠內之雜質。此等種類之雜質對於合金性質不具實質作用。With respect to certain embodiments, iron is believed to be an impurity obtained from a stirring rod, a skimmer, or the like during a melting and pouring operation, or an impurity in a substantially ingot. These types of impurities have no substantial effect on the properties of the alloy.
對於紅黃銅及錫青銅，銻可被認為係所述合金內之雜質。典型上，銻係自較差廠牌之錫、碎削及差品質之鑄錠及碎削取得。但是，銻係蓄意地添加至於一永久模具內之黃色黃銅以增加耐脫鋅性。For red brass and tin bronze, tantalum can be considered as an impurity in the alloy. Typically, the bismuth is obtained from the poorly produced tin, broken and poor quality ingots and chips. However, the lanthanide is deliberately added to the yellow brass in a permanent mold to increase the resistance to dezincification.
於某些實施例，鎳被包含以增加強度及硬性。再者，鎳助於硫化物顆粒於合金內之分佈。於一實施例，添加鎳助於在鑄造物冷卻處理期間之硫化物沉澱。硫化物沉澱係所欲的，因為懸浮之硫化物作為鉛之取代物，以於鑄造後之機械加工操作期間供屑片破裂及機械加工潤滑。以較低之鉛含量，相件硫化物沉澱會使降低之機械加工性之作用達最小。In certain embodiments, nickel is included to increase strength and stiffness. Furthermore, nickel assists in the distribution of sulfide particles within the alloy. In one embodiment, the addition of nickel aids in the precipitation of sulfide during the casting cooling process. Sulfide precipitation is desirable because the suspended sulfide acts as a substitute for lead for chip rupture and mechanical lubrication during the post-cast machining operations. With a lower lead content, the precipitation of phase sulfides minimizes the effect of reduced machinability.
磷可被添加至提供去氧化作用。添加磷降低液體合金內之氣體含量。移除氣體一般係藉由降低熔融物內之氣體含量及降低完成合金內之多孔性而提供較高品質之鑄造物。但是，過量的磷會促成金屬-模具反應，產生低機械品質及多孔性鑄造物。Phosphorus can be added to provide deoxidation. The addition of phosphorus reduces the gas content in the liquid alloy. Removal of the gas generally provides a higher quality casting by reducing the gas content within the melt and reducing the porosity within the finished alloy. However, excess phosphorus contributes to the metal-mold reaction, resulting in a low mechanical quality and porous casting.
於某些實施例，諸如，半紅黃銅及錫青銅，鋁係作為雜質而處理。於此等實施例，鋁對於氣壓密閉性及機械性質係具有有害之作用。但是，黃色黃銅鑄造物內之鋁可選擇性地改良鑄造流動性。相信鋁於此等實施例係促進精細羽毛狀樹枝結構。In certain embodiments, such as semi-red brass and tin bronze, aluminum is treated as an impurity. In these embodiments, aluminum has a detrimental effect on gas tightness and mechanical properties. However, the aluminum in the yellow brass casting selectively improves the casting fluidity. It is believed that the embodiments of aluminum promote fine feather-like branch structures.
矽亦被認為係雜質。於具多種合金之鑄造廠，以矽為主之材料於非含矽之合金會導致矽污染。小量之殘餘矽會污染半紅黃銅合金，使多種合金之生產變幾乎不可能。此外，矽之存在會降低半紅黃銅合金之機械性質。It is also considered to be an impurity. In foundries with multiple alloys, bismuth-based materials can cause bismuth contamination in non-containing alloys. A small amount of residual ruthenium can contaminate the semi-red brass alloy, making the production of a variety of alloys almost impossible. In addition, the presence of niobium reduces the mechanical properties of the semi-red brass alloy.
錳於某些實施例可被添加。錳被認為係助於硫化物之分佈。特別地，錳之存在被認為助於硫化鋅於熔融物內之形成及滯留。於一實施例，添加小量之錳以改良氣壓密閉性。於一實施例，錳係以MnS添加。Manganese can be added in certain embodiments. Manganese is believed to contribute to the distribution of sulfides. In particular, the presence of manganese is believed to contribute to the formation and retention of zinc sulfide in the melt. In one embodiment, a small amount of manganese is added to improve airtightness. In one embodiment, the manganese is added as MnS.
鋯或硼係個別(非結合地)添加以產生一細微顆粒結構，其於拋光期間改良鑄造物之表面精製度。Zirconium or boron is added individually (unbound) to produce a fine particle structure that improves the surface finish of the casting during polishing.
碳於某些實施例可被添加以改良氣壓密閉性，降低多孔性，及改良機械加工性。Carbon may be added in certain embodiments to improve gas tightness, reduce porosity, and improve machinability.
鈦可與碳，諸如，以石墨型式，結合地添加。雖不限制本發明範圍，但相信鈦係助於碳顆粒與銅基質之結合，特別是對於原料石墨。對於使用以碳塗覆之銅之實施例，鈦對於碳之分佈可能沒用。Titanium can be added in combination with carbon, such as in graphite form. While not limiting the scope of the invention, it is believed that the titanium system aids in the bonding of carbon particles to the copper matrix, particularly for the raw graphite. For embodiments using carbon coated copper, titanium may not be useful for carbon distribution.
於一實施例，本發明之合金係以使得許多之個別的硫/硫化物之顆粒以一般呈均勻之方式分佈於整個鑄造物之方式固化。此等非金屬之硫顆粒用以改良潤滑性及碎化於以此新合金鑄造之零件之機械加工期間發展出之屑片，藉此改良機械加工性，且顯藉或完全降低鉛含量。雖不限制本發明範圍，但硫化物被認為改良潤滑性。In one embodiment, the alloy of the present invention is cured in such a manner that a plurality of individual sulfur/sulfide particles are distributed throughout the casting in a generally uniform manner. These non-metallic sulphur particles are used to improve lubricity and fragmentation of chips developed during machining of parts cast from the new alloy, thereby improving machinability and thereby reducing or completely reducing lead content. Although not limiting the scope of the invention, sulfides are considered to improve lubricity.
所述合金之較佳實施例維持諸如“81”合金或相似含鉛合金之現今合金之機械加工性優點。再者，相信由於相對較小量之某些涉及材料，鑄錠合金之較佳實施例之成本會相當地少於現今被倡導用以替代諸如“81”之含鉛黃銅合金之以鉍及/或硒合金化黃銅者。硫於此處所述之某些實施例係以硫化物存在，其可溶於熔融物，但於合金以一件式零件固化及其後冷卻期間係以硫化物沉澱。此沉澱之硫能藉由作為相似於諸如”81”之合金及於鉍及硒合金中之鉛之功能之屑片破碎劑而改良機械加工性。於鉍及/或硒合金之情況，鉍化物或硒化物之形成與某些金屬鉍一起完成與此新穎之含硫合金相似之目的。機械加工性之改良可以增加之工具壽命、改良之機械加工表面、降低之工具力等顯示。此新穎概念亦提供產業低鉛之黃銅/青銅，此於現今環境係考量任何數量之管理機關法侓限制於配管配件內可含之鉛含量。 The preferred embodiment of the alloy maintains the machinability advantages of today's alloys such as "81" alloys or similar lead-containing alloys. Furthermore, it is believed that the cost of a preferred embodiment of an ingot alloy will be considerably less than the cost of a relatively small amount of material involved in the replacement of a leaded brass alloy such as "81". / or selenium alloyed brass. Certain embodiments of sulfur described herein are in the form of sulfides that are soluble in the melt but are precipitated as sulfides during solidification of the alloy in a one-piece part and subsequent cooling. This precipitated sulfur can improve machinability by acting as a chip breaker similar to the function of an alloy such as "81" and lead in niobium and selenium alloys. In the case of niobium and/or selenium alloys, the formation of telluride or selenide is similar to the treatment of this novel sulfur-containing alloy with certain niobium alloys. Improvements in machinability can be shown by increased tool life, improved machined surfaces, and reduced tooling. This novel concept also provides the industry's low-lead brass/bronze, which is considered by the current environmental regulations to limit the amount of lead that can be contained in piping fittings.
再者，添加鉛之合金造成固化作用發生之溫度範圍增加，一般係更難以生產於配管配件係重要之密封鑄造物。但是，鉛偏析至固化之最後區域，因此，密封發生之樹枝狀及顆粒邊界收縮。此密封樹枝狀或顆粒邊界多孔性於含硫/硫化物之合金未被完全。於鉍及/或硒侣金亦未被完成。雖然鉍於元素週期表中係相似於鉛，且於固化期間膨脹，但與諸如”81”之傳統合金中之鉛含量相比，使用之鉍含量係較小。Bi典型上係以元素型式存在於市面上之合金中。 Furthermore, the addition of a lead alloy causes an increase in the temperature range in which the curing action occurs, and it is generally more difficult to produce a seal casting which is important in piping fittings. However, lead segregates to the last region of solidification, and therefore, the dendritic and particle boundaries of the seal shrink. This sealed dendritic or grain boundary porosity is not complete with the sulfur/sulfide containing alloy. Yu Yu and/or Selenium Gold has not been completed. Although it is similar to lead in the periodic table and expands during curing, it has a smaller content of tantalum than conventional lead alloys such as "81". Bi is typically present in the alloy on the market in elemental form.
熟習此項技藝者會瞭解超出本發明合金之性能性質之另外利益。與鉍及硒相比，本發明之合金大量發現之元素，而鉍及硒係相對較有限供應；且黃銅鑄造物轉變成此等材料會顯著增加對此等有限供應材料之需求。此外，鉍具有與其於配管設備之使用有關之某些健康顧慮，部份係由於其接近週期表上為重金屬之鉛。再者，於某些實施例，本發明之合金使用比習知技藝之鉍及硒組成物較低百分率之銅。Those skilled in the art will appreciate additional benefits beyond the performance properties of the alloys of the present invention. Compared to niobium and selenium, the alloys of the present invention are found in large quantities, while niobium and selenium are relatively limited in supply; and the conversion of brass castings into such materials significantly increases the demand for such limited supply materials. In addition, 铋 has certain health concerns associated with its use in piping equipment, in part because it is close to the lead metal of the heavy metal. Moreover, in certain embodiments, the alloys of the present invention use a lower percentage of copper than conventional techniques and selenium compositions.
觀察到使用硫作為鉛之替代物，而非矽，提供較佳之“每一熔融物之產率”。與矽相比，其每一熔融物可產生40至60%，藉由硫，每一熔融物之產率範圍係70至80%。一般之含鉛黃銅合金依處理效率而定係產生70至80%。如熟習此項技藝者所瞭解，此一產率增加反映物品差異之大量成本。因此，金屬鑄造設備之能力藉由使用以矽為主之材料係明顯降低。再者，本發明之某些實施例具有比以矽為主之習知技藝合金(其一般含有多於30%之鋅，會由於鋅及水之交互作用產生腐蝕而導致外漏)更低之鋅含量。相對於此等以矽為主之合金，本發明之較低的鋅降低脫鋅作用之趨勢。再者，若典型上產品欲以一鍍鉻表面精製，以矽為主之材料於電鍍前需要銅或錫刮平，此增加電鍍成本。本發明之合金無需此另外步驟(及其相關成本)而能鍍鉻。The use of sulfur as a substitute for lead, rather than helium, was observed to provide a preferred "yield per melt". Each melt can produce 40 to 60% compared to ruthenium, and the yield of each melt ranges from 70 to 80% by sulfur. Typical lead-containing brass alloys produce 70 to 80% depending on the processing efficiency. As will be appreciated by those skilled in the art, this increase in yield reflects the substantial cost of item differences. Therefore, the ability of the metal casting equipment is significantly reduced by the use of a material system based on ruthenium. Furthermore, certain embodiments of the present invention have lower specificity than conventional art alloys based on bismuth (which generally contain more than 30% zinc, which can cause corrosion due to corrosion of zinc and water interaction). Zinc content. The lower zinc of the present invention tends to reduce the dezincification effect relative to such bismuth-based alloys. Furthermore, if the product is typically refined on a chrome-plated surface, the bismuth-based material requires copper or tin to be flattened prior to plating, which increases plating costs. The alloy of the present invention can be chrome plated without this additional step (and its associated cost).
於一實施例，於加熱前將石墨置於坩鍋之底部。於一實施例，碳化矽或黏土石墨坩鍋可用於此熔融。相信使用石墨降低加熱期間之鋅損失，且不會實質上併入完成之合金內。於一實施例，約兩杯之石墨被用於90至95磅容量之坩鍋。對於此處使用之範例，B-30坩鍋被用於此熔融，其具有90至95磅合金之容量。In one embodiment, the graphite is placed at the bottom of the crucible prior to heating. In one embodiment, a tantalum carbide or clay graphite crucible can be used for melting. It is believed that the use of graphite reduces the loss of zinc during heating and does not substantially incorporate into the finished alloy. In one embodiment, about two cups of graphite are used in a crucible having a capacity of 90 to 95 pounds. For the examples used herein, a B-30 crucible is used for this melting, which has a capacity of 90 to 95 pounds of alloy.
以所欲之最終合金配製物為基準，所需之基本鑄錠置於坩鍋內，且將爐起動。使基本鑄錠達約2,100℉之溫度以形成一熔融物。於一實施例，使用傳統之燃氣爐，且於另一者，係使用感應爐。然後，爐被關掉，即，熔融物不再加熱。然後，於一實施例，除硫及磷外之添加劑於15至20秒之間投入熔融物內，以達所欲量之Zn、Ni及Sn。添加劑包含用以達到特定基本鑄錠之最後所欲合金組成物所需之材料。於一實施例，添加劑包含欲存在於最終合金內之元素型式之此等元素。然後，一部份量之熔渣自熔融物之頂部撇除。Based on the desired final alloy formulation, the required basic ingot is placed in a crucible and the furnace is started. The base ingot is brought to a temperature of about 2,100 °F to form a melt. In one embodiment, a conventional gas furnace is used, and in the other, an induction furnace is used. The furnace is then turned off, ie the melt is no longer heated. Then, in one embodiment, the additive other than sulfur and phosphorus is introduced into the melt between 15 and 20 seconds to achieve the desired amount of Zn, Ni and Sn. The additive contains the materials needed to achieve the final desired alloy composition of the particular base ingot. In one embodiment, the additive comprises such elements of the elemental form that are intended to be present in the final alloy. Then, a portion of the slag is removed from the top of the melt.
使爐達約2,140℉之溫度。燃後，爐關掉，且硫添加物投入。對於具有添加磷之某些實施例，諸如，用於熔融物除氣，爐再次加熱至約2,150℉，且磷以Cu-P母合金投入熔融物內。其次，較佳地，所有熔渣係上坩鍋頂部撇除。用於壓力測試及機械加工性及電鍍評估之測試鑄造物、用於化學分析之底部物、楔形物及小鑄錠，及用於抗拉測試之網桿係個別於約2100、約2040，及約2000 F澆注。於一實施例，對於I-A及I-B合金族群，爐係點火至約2,140℉。於另一實施例，對於II-A合金族群，爐係點火至約2,050℉。The furnace was allowed to reach a temperature of about 2,140 °F. After the combustion, the furnace is turned off and the sulfur additive is put in. For certain embodiments with the addition of phosphorus, such as for degassing the melt, the furnace is again heated to about 2,150 °F and phosphorus is introduced into the melt as a Cu-P master alloy. Secondly, preferably, all of the slag is removed from the top of the crucible. Test castings for pressure testing and machinability and plating evaluation, bottoms for chemical analysis, wedges and small ingots, and nets for tensile testing are individually at about 2100, about 2040, and Casting about 2000 F. In one embodiment, for the I-A and I-B alloy populations, the furnace is ignited to about 2,140 °F. In another embodiment, for the II-A alloy population, the furnace is ignited to about 2,050 °F.
本申請案所述之機械加工性測試係使用下列方法實施。零件係藉由冷卻劑餵食，2軸，CNC Turning Center機械加工。切割工具係一碳化物嵌件。機械加工性係以於上述CNC Turning Center上車削期間使用之能量比率為基準。計算公式可寫為如下：The machinability test described in this application was carried out using the following method. Parts are fed by coolant, 2-axis, CNC Turning Center machining. The cutting tool is a carbide insert. Machinability is based on the energy ratio used during turning on the CNC Turning Center described above. The calculation formula can be written as follows:
CF=(E1/E2) x 100C F = (E 1 /E 2 ) x 100
CF=切割力C F = cutting force
E1=新合金車削期間使用之能量E 1 = energy used during new alloy turning
E2=“已知”合金C 36000(CDA)車削期間使用之能量E 2 = "known" alloy C 36000 (CDA) energy used during turning
供應速率=.005 IPRSupply rate = .005 IPR
心軸速度=1,500 RPMMandrel speed = 1,500 RPM
切割深度=徑向切割深度=0.038英吋Cutting depth = radial cutting depth = 0.038 inches
一電表被用以測量切割工具於負載下之電拉取(electrical pull)。此拉取係經由毫安培測量捕集。An electric meter is used to measure the electrical pull of the cutting tool under load. This pull is measured by milliamperes.
本發明合金之各種實施例之機械性質被測試。第3A-6圖係相對應於I-A合金族群、I-B合金族群，及II-A合金族群之特定測試配製物及相對應結果。The mechanical properties of various embodiments of the alloys of the present invention were tested. Figures 3A-6 correspond to specific test formulations and corresponding results for the I-A alloy population, the I-B alloy population, and the II-A alloy population.
第3A及3B圖係相對應於I-A合金族群之特定測試配製物及相對應結果。依據上述方法製備達成I-A族群合金之八個樣品加熱物被測試極限抗拉強度(“UTS”)、屈服強度(“YS”)、伸長百分率(“E%”)、Brinnell硬度(“BHN”)，及彈性模量(“MoE”)。八個I-A合金族群之合金的平均值，極限抗拉強度係40.25 ksi，屈服強度係17.1 ksi，伸長百分率係47，Brinnell硬度係63，且彈性模量係13.5Mpsi。 Figures 3A and 3B correspond to specific test formulations and corresponding results for the I-A alloy population. According to the above method, the eight sample heating materials for the IA group alloy were tested for ultimate tensile strength ("UTS"), yield strength ("YS"), percent elongation ("E%"), and Brinnell hardness ("BHN"). And elastic modulus ("MoE"). The average of the alloys of the eight I-A alloy groups, the ultimate tensile strength was 40.25 ksi, the yield strength was 17.1 ksi, the elongation percentage was 47, the Brinnell hardness was 63, and the elastic modulus was 13.5 Mpsi.
第4A及4B圖係相對應於I-B合金族群之特定測試配製物及相對應結果。依據上述方法製備達成I-B族群合金之七個樣品加熱物被測試極限抗拉強度、屈服強度、伸長百分率、Brinnell硬度，及彈性模量。七個I-B合金族群之合金之平均值，極限抗拉強度係38.1ksi，屈服強度係17.5ksi，伸長百分率係32，Brinnell硬度係64，且彈性模量係13.8Mpsi。 Figures 4A and 4B correspond to specific test formulations and corresponding results for the I-B alloy population. The seven sample heaters which achieved the I-B group alloy were tested according to the above method to be tested for ultimate tensile strength, yield strength, percent elongation, Brinnell hardness, and modulus of elasticity. The average of the alloys of the seven I-B alloy groups, the ultimate tensile strength was 38.1 ksi, the yield strength was 17.5 ksi, the elongation percentage was 32, the Brinnell hardness was 64, and the elastic modulus was 13.8 Mpsi.
第5A及5B圖係相對應於II-A合金族群之特定測試配製物及相對應結果。依據上述方法製備達成II-A族群合金之八個樣品加熱物被測試極限抗拉強度、屈服強度、伸長百分率、Brinnell硬度，及彈性模量。八個II-A合金族群之合金的平均值，極限抗拉強度係43.8ksi，屈服強度係23ksi，伸長百分率係17，Brinnell硬度係80，且彈性模量係15.0Mpsi。 Figures 5A and 5B correspond to specific test formulations and corresponding results for the II-A alloy population. The eight sample heaters which achieved the II-A group alloy were tested according to the above method to be tested for ultimate tensile strength, yield strength, percent elongation, Brinnell hardness, and modulus of elasticity. The average of the alloys of the eight II-A alloy groups, the ultimate tensile strength was 43.8 ksi, the yield strength was 23 ksi, the elongation percentage was 17, the Brinnell hardness system was 80, and the elastic modulus was 15.0 Mpsi.
第9表(第6圖)例示對本發明合金及數種已知市面上合金之以實驗決定之機械性質範圍。 Table 9 (Fig. 6) illustrates experimentally determined ranges of mechanical properties for the alloys of the present invention and several known alloys on the market.
此等結果指示合金I-A之最小及典型之UTS值，個別地相對於C89520、C89836，及C83470，對於最小者係高50%、18%，及34%，且對於典型者係高30%、9%，及12%。相似地，個別地相對於C89520、C89836，及C83470，E%對於最小者係高550%、95%，及129%，且對於典型者係高370%、57%，及88%。I-A之YS係比BiwaliteTM(C83470)高8%。 These results indicate the minimum and typical UTS values for Alloy IA, individually relative to C89520, C89836, and C83470, 50%, 18%, and 34% for the smallest, and 30%, 9 for typical models. %, and 12%. Similarly, individually relative to C89520, C89836, and C83470, E% is 550%, 95%, and 129% higher for the smallest, and 370%, 57%, and 88% for the typical. The IA system high YS 8% Biwalite TM (C83470).
有關於I-B，個別地相對於C89520、C89836，及BiwaliteTM(C83470)合金，此等值對於最小UTS係40%、11%，及26%，對於典型UTS係24%、4%，及7%；對於最 小E%係350%、35%，及59%，且對於典型E%係220%、7%，及28%。 About the IB, individually with respect to C89520, C89836, and Biwalite TM (C83470) alloy, the UTS system equivalent to a minimum of 40%, 11% and 26%, 24% for typical UTS system, 4% and 7% For the minimum E% is 350%, 35%, and 59%, and for typical E% is 220%, 7%, and 28%.
第37至45圖係例示I-A族群(第37至39圖)、I-B族群(第40至42圖)，及II-A族群(第43至45圖)之每一者內之各種熱間之變化。機械數據亦對三種可購得之合金，C84400(描述為---)、C89836(描述為-)，及C89520(描述為---)提供以用於比較目的。本發明之個別合金族群之數據亦以由一實線連接之點顯示。 Figures 37 to 45 illustrate the variation of various heats in each of the IA group (Figures 37 to 39), the IB group (Figures 40 to 42), and the II-A group (Figures 43 to 45). . Mechanical data is also provided for three commercially available alloys, C84400 (described as ---), C89836 (depicted as -), and C89520 (described as ---) for comparison purposes. The data for the individual alloy populations of the present invention are also shown as points joined by a solid line.
有關於I-A族群，第37圖顯示觀察到之UTS係一致性地高於市面上之合金。第38圖顯示觀察到之YS係一致性地高於除C89520(含有昂貴稀元素鉍之合金)外之所有市面上之合金。第39圖顯示觀察到之伸長率係一致性地遠高於所有市面上之合金。對於I-A族群，伸長率確實展現隨熱之變化性。 Regarding the I-A population, Figure 37 shows that the observed UTS is consistently higher than the alloys on the market. Figure 38 shows that the observed YS is consistently higher than all commercially available alloys except C89520 (an alloy containing expensive rare element bismuth). Figure 39 shows that the observed elongation is consistently much higher than all commercially available alloys. For the I-A population, the elongation does exhibit variability with heat.
有關於I-B族群，第40圖顯示觀察到之UTS係一致性地高於市面上之合金。第41圖顯示觀察到之YS係再次地一致地高於除C89520(含有昂貴稀元素鉍之合金)外之所有市面上之合金。第42圖顯示觀察到之伸長率係一致地高於所有市面上之合金。對於I-B族群，伸長率確實展現隨熱之顯著變化性。 Regarding the I-B population, Figure 40 shows that the observed UTS is consistently higher than the alloys on the market. Figure 41 shows that the observed YS is again consistently higher than all commercially available alloys except C89520 (alloy containing expensive rare element bismuth). Figure 42 shows that the observed elongation is consistently higher than all commercially available alloys. For the I-B group, the elongation does exhibit significant variability with heat.
除如先前探討使用之市面上合金外，II-A族群之合金亦與含鉛合金C90300(描述為---)比較。有關於II-A族群，第43圖顯示觀察到之UTS係一致地高於市面上之合金，包含些微高於C90300。第44圖顯示觀察到之YS係一致地高於包括 C89520之所有市面0之合金。第45圖顯示觀察到之伸長率係一致地高於所有市面上之合金。對於II-A族，伸長率確實展現隨熱之顯著變化性。 In addition to the commercially available alloys previously discussed, the alloys of Group II-A are also compared to leaded alloy C90300 (described as ---). Regarding the Group II-A, Figure 43 shows that the observed UTS is consistently higher than the alloy on the market, including slightly higher than C90300. Figure 44 shows that the observed YS is consistently higher than the included All alloys of the market of C89520. Figure 45 shows that the observed elongation is consistently higher than all commercially available alloys. For Group II-A, the elongation does exhibit significant variability with heat.
第10表(第7圖)列示本發明之五種合金，合金I-A-10、合金I-B-10、合金II-A-10、合金II-B-10，及合金III-A-10，之組成，其係使用裝設能量分散光譜儀之掃瞄式電子顯微鏡(SEM/EDS)分析。第10表之每一合金之樣品被置放，依據已知方法金相式製備，然後，以光學及使用SEM/EDS檢測。為了比較，BiwaliteTM(C83470)合金被熔融且於相似於合金I-A之條件下鑄造，且用於評估及比較微結構。 Table 10 (Fig. 7) lists the five alloys of the present invention, Alloy IA-10, Alloy IB-10, Alloy II-A-10, Alloy II-B-10, and Alloy III-A-10, The composition was analyzed using a scanning electron microscope (SEM/EDS) equipped with an energy dispersive spectrometer. Samples of each of the alloys of Table 10 were placed, prepared in a metallographic manner according to known methods, and then examined optically and using SEM/EDS. For comparison, Biwalite TM (C83470) and the alloy is melted under conditions similar to the IA alloy casting, and for evaluating and comparing microstructure.
第8A及8B圖例示合金I-A-10內之硫之元素映像(0.16%S)。第9A圖係合金I-A-10a之SEM；第9B-H圖例示元素映像；第9B圖係Sn之EDS；第9C圖係Zn之EDS；第9D圖係Cu之EDS；第9E圖係Fe之EDS；第9F圖係Ni之EDS；第9G圖係P之EDS；第9H圖係S之EDS；第10A圖係合金I-A-10a之顯微照片，具有標記之區域1、2，及3；第10B-D圖顯示Cu2S、ZnS及Cu-Zn介金屬相之存在；第10B圖係區域1之EDS光譜；第10C圖係區域2之EDS光譜；第10D圖係區域3之EDS光譜。第11A-B圖係合金I-A-10a於低(第11A圖)及高放大倍率(第11B圖)之光學影像。元素被見到係廣泛分佈，但硫除外，其看起來係被收集於被認為係樹枝狀區域或顆粒邊界。 Figures 8A and 8B illustrate the elemental map of sulfur in the alloy I-A-10 (0.16% S). 9A is an SEM of alloy IA-10a; 9B-H is an illustration of an elemental image; 9B is an EDS of Sn; 9C is an EDS of Zn; 9D is an EDS of Cu; and 9E is a Fe of EDS; 9F is the EDS of Ni; the 9th is the EDS of P; the 9th is the EDS of S; the 10A is the photomicrograph of the alloy IA-10a, with the marked areas 1, 2, and 3; 10B-D shows the presence of Cu2S, ZnS and Cu-Zn intermetallic phases; 10B shows the EDS spectrum of region 1; 10C shows the EDS spectrum of region 2; and 10D shows the EDS spectrum for region 3. Fig. 11A-B is an optical image of the alloy I-A-10a at low (Fig. 11A) and high magnification (Fig. 11B). The elements are widely distributed, except for sulfur, which appears to be collected in a dendritic region or particle boundary.
第12A及12B圖例示合金I-B-10a內之硫之元素映像(0.31% S)。第13A圖係合金I-B-10之SEM；第13B-H圖例示元素映像；第13B圖係Sn之EDS；第13C圖係Zn之EDS；第13D圖係Cu之EDS；第13E圖係Fe之EDS；第13F圖係Ni之EDS；第12G圖係P之EDS；第13H圖係S之EDS。第14A圖係合金I-B-10b之SEM(0.13%S)；第14B-H圖例示5000x放大倍率之元素映像；第14B圖係Si之EDS；第14C圖係S之EDS；第14D圖係Fe之EDS；第14E圖係Cu之EDS；第14F圖係Zn之EDS；第14G圖係Sn之EDS；第14H圖係Pb之EDS；第14I圖係Ni之EDS。第15A-B圖係合金I-B-10a於低(第15A圖)及高放大倍率(第15B)圖之光學影像。元素被見到係廣泛分佈，但硫除外，其看起來係被收集於被認為係樹枝狀區域或顆粒邊界。較高體積分率之硫化物由於高硫含量係明顯的。此等硫化物之一些由EDS數據係明顯為ZnS。此等硫化物係比BiwaliteTM(C83470)觀察到者更精細，，見第46A圖。Cu-Zn介金屬相之存在亦明顯。 Figures 12A and 12B illustrate the elemental map of sulfur in the alloy IB-10a (0.31% S). Fig. 13A is an SEM of alloy IB-10; Fig. 13B-H is an illustration of an elemental map; Fig. 13B is an EDS of Sn; Fig. 13C is an EDS of Zn; Fig. 13D is an EDS of Cu; and Fig. 13E is an E of Fe EDS; Fig. 13F is the EDS of Ni; Fig. 12G is the EDS of P; and Fig. 13H is the EDS of S. Fig. 14A is a SEM (0.13% S) of alloy IB-10b; Fig. 14B-H illustrates an elemental map of 5000x magnification; 14B is an EDS of Si; 14C is an EDS of S; Fig. 14D is a Fe EDS; 14E is the EDS of Cu; 14F is the EDS of Zn; 14G is the EDS of Sn; 14H is the EDS of Pb; and 14I is the EDS of Ni. 15A-B is an optical image of the alloy IB-10a at low (Fig. 15A) and high magnification (Fig. 15B). The elements are widely distributed, except for sulfur, which appears to be collected in a dendritic region or particle boundary. Sulfides with higher volume fractions are evident due to the high sulfur content. Some of these sulfides are clearly ZnS from the EDS data system. These sulfide than that observed Biwalite TM (C83470) by a finer to ,, see section 46A of FIG. The presence of the Cu-Zn intermetallic phase is also evident.
第16A及16B圖例示合金II-A內之硫之元素映像(0.30% S)。第17A圖係合金II-A之SEM；第17B-H圖例示元素映像；第15B圖係Sn之EDS；第17C圖係Zn之EDS；第17D圖係Cu之EDS；第17E圖係Fe之EDS；第17F圖係Ni之EDS；第17G圖係P之EDS；第17H圖係S之EDS。第18A圖係合金II-A-10b之SEM(0.19% S)；第18B-H圖例示1000x放大倍率之元素映像；第18B圖係Si之EDS；第18C圖係S之EDS；第18D圖係Fe之EDS；第18E圖係Cu之EDS；第18F圖係Zn之EDS；第 18G圖係Sn之EDS；第18H圖係Pb之EDS；第18I圖係Ni之EDS。第19A-B圖係合金II-A於低(第19B圖)及高放大倍率(第19A圖)之光學影像。元素被見到係廣泛分佈，但硫除外，其看起來係被收集於被認為係樹枝狀區域或顆粒邊界。此等圖式顯示Cu2S、ZnS與Cu-Sn及Cu-Zn之介金屬相之存在。 Figures 16A and 16B illustrate the elemental map of sulfur in the alloy II-A (0.30% S). Figure 17A is an SEM of Alloy II-A; Figure 17B-H is an illustration of an elemental image; Figure 15B is an EDS of Sn; Figure 17C is an EDS of Zn; Figure 17D is an EDS of Cu; EDS; 17F is an EDS of Ni; 17G is an EDS of P; and 17H is an EDS of S. Figure 18A is an SEM (0.19% S) of Alloy II-A-10b; Figure 18B-H illustrates an elemental map of 1000x magnification; Figure 18B is an EDS of Si; Figure 18C is an EDS of S; Figure 18D EDS of Fe; 18E is EDS of Cu; 18F is EDS of Zn; 18G is the EDS of Sn; the 18th is the EDS of Pb; and the 18I is the EDS of Ni. 19A-B is an optical image of Alloy II-A at low (Fig. 19B) and high magnification (Fig. 19A). The elements are widely distributed, except for sulfur, which appears to be collected in a dendritic region or particle boundary. These patterns show the presence of Cu2S, ZnS and Cu-Sn and Cu-Zn intermetallic phases.
第20A及20B圖例示合金III-A內之硫之元素映像(0.011% S)。第21A圖係合金III-A之SEM；第121B-H圖例示元素映像；第21B圖係Sn之EDS；第21C圖係Zn之EDS；第21D圖係Cu之EDS；第21E圖係Fe之EDS；第21F圖係Ni之EDS；第21G圖係P之EDS；第21H圖係S之EDS。第22A-B圖係合金III-A於低(第22A圖)及高放大倍率(第22B圖)之光學影像。元素被見到係廣泛分佈，但硫除外，其看起來係被收集於被認為係樹枝狀區域或顆粒邊界。 Figures 20A and 20B illustrate the elemental map of sulfur in alloy III-A (0.011% S). 21A is an SEM of Alloy III-A; 121B-H is an illustration of an elemental image; 21B is an EDS of Sn; 21C is an EDS of Zn; 21D is an EDS of Cu; and 21E is a Fe of EDS; 21F is the EDS of Ni; 21G is the EDS of P; and 21H is the EDS of S. Fig. 22A-B is an optical image of alloy III-A at low (Fig. 22A) and high magnification (Fig. 22B). The elements are widely distributed, except for sulfur, which appears to be collected in a dendritic region or particle boundary.
相資訊係對第11表內之合金收集。合金I-A-1至1-A-5與合金I-B-1及II-A-1係依據本發明配製及製造。合金C83470係一已知合金，其完整組成物係列示於第1表(第1圖)。合金1-B-11a及II-A-11a個別係I-B及II-A合金族群之公稱組成物。為了比較，可購得之合金C83470(BiwaliteTM)之公稱組成物亦包括於第11表內。 The phase information is collected on the alloy in Table 11. Alloys IA-1 to 1-A-5 and alloys IB-1 and II-A-1 are formulated and manufactured in accordance with the present invention. Alloy C83470 is a known alloy, and its complete composition series is shown in Table 1 (Fig. 1). The alloys 1-B-11a and II-A-11a are the nominal compositions of the IB and II-A alloy groups. For comparison, the commercially available alloy C83470 (Biwalite TM) of nominal composition also included in the table 11.
為瞭解此等合金之強化機構，具有及不具有Mn之Cu-Zn-Sn-S系統之相圖係使用平衡及非平衡之冷卻(Scheil 冷卻)條件決定。需注意砂模鑄造一般係相對應於非平衡冷卻。存在於此等合金之相已使用微組份系統之垂直區段研究。 To understand the strengthening mechanism of these alloys, the phase diagram of the Cu-Zn-Sn-S system with and without Mn is determined using balanced and unbalanced cooling (Scheil cooling) conditions. It should be noted that sand casting is generally equivalent to non-equilibrium cooling. The presence of such alloy phases has been studied using vertical sections of the microcomponent system.
使用傳統技術進行之分析被實施以決定於室溫存在於第11表之合金之相的相對量。於第一相研究，I-A合金族群之五個特別配製物被測試以觀察合金族群內之相的變化。一已知傳統合金，C83470，亦被研究作為參考。第12表係以百分率例示每一合金之相。C83470展現比I-A或II-A族之合金更少之β相。 Analysis using conventional techniques was performed to determine the relative amount of phase present in the alloy of Table 11 at room temperature. In the first phase study, five special formulations of the I-A alloy population were tested to observe changes in the phases within the alloy population. A known conventional alloy, C83470, has also been studied as a reference. The 12th table exemplifies the phase of each alloy in percentage. C83470 exhibits fewer beta phases than alloys of Groups I-A or II-A.
第24圖繪製第12表之合金於銅/鋅/錫相圖之位置。合金係從左邊之最高百分率之銅及鋅行進至右邊之最低銅及鋅。使用Scheil冷卻之I-A-11a(第25A及25B圖)、I-A-11b(第26A及26B圖)、I-A-11c(第27A及27B圖)、I-A-11d(第28A及28B圖)、I-A-11e(第29A及29B圖)之相分佈圖被顯示。第31、32A，及32B圖係相對應於合金I-A-12f。第33、34A，及34B圖係相對應於合金I-B-12a。第35、36A，及36B圖係相對應於合金II-A-12a。具有FCC、液體、BCC1、BCC2,、Cu2S，及Cu3Sn之熔融物與溫度相關之相對量係顯示於第26A、26B、27A及27B圖(圖26B及27B被放大以顯示次要相之分佈)。 Figure 24 plots the position of the alloy of Table 12 in the copper/zinc/tin phase diagram. The alloy travels from the highest percentage of copper and zinc on the left to the lowest copper and zinc on the right. Using Scheil cooled IA-11a (Figures 25A and 25B), IA-11b (Figures 26A and 26B), IA-11c (Figures 27A and 27B), IA-11d (Figures 28A and 28B), IA- The phase distribution map of 11e (Figs. 29A and 29B) is shown. Figures 31, 32A, and 32B correspond to alloy IA-12f. Figures 33, 34A, and 34B correspond to alloy IB-12a. Figures 35, 36A, and 36B correspond to Alloy II-A-12a. The temperature-dependent relative amounts of the melts with FCC, liquid, BCC 1 , BCC 2 , Cu 2 S, and Cu 3 Sn are shown in Figures 26A, 26B, 27A, and 27B (Figures 26B and 27B are enlarged to show Distribution of secondary phases).
第30A-30B圖例示與第25A-29圖相似系列之相分佈，但係對於現存市面上之合金，C83470。第30A圖係使用Scheil冷卻之C83470合金之相分佈圖。第30B圖係此相分佈圖之放大部份，其顯示次要相之相對量。Figures 30A-30B illustrate phase distributions similar to those of Figures 25A-29, but for existing alloys on the market, C83470. Figure 30A is a phase diagram of a C83470 alloy cooled using Scheil. Figure 30B is an enlarged portion of the phase distribution diagram showing the relative amounts of the secondary phases.
相分佈圖顯示可預期之相及其等開始出現之溫度。每一相之相對量亦可自此等圖評估。第12圖係以對非平衡冷卻顯示者之相為基準，其係β(BCC1)相(其係Cu及Zn之介金屬化合物)，其係促進合金之強度。但是，強度增加犧牲延展性。Sloan Green合金顯示高強度及延展性。其高延展性可能係由於良好熔融品質、低氣體含量，及良好均質性。除促進氣壓密閉性及機械加工性外，硫化物之較細微分佈亦促進高強度及高延展性。The phase diagram shows the expected phase and the temperature at which it begins to appear. The relative amount of each phase can also be evaluated from these figures. Figure 12 is a reference to the phase of the non-equilibrium cooled display, which is a beta (BCC1) phase (which is a metal compound of Cu and Zn) which promotes the strength of the alloy. However, the increase in strength sacrifices ductility. Sloan Green alloy exhibits high strength and ductility. Its high ductility may be due to good melt quality, low gas content, and good homogeneity. In addition to promoting airtightness and machinability, the finer distribution of sulfides also promotes high strength and high ductility.
此等系統之熱研究係使用DSC-2400 Setaram Setsys差式掃瞄量熱術實施。DSC之溫度校正係使用7種純金屬：In、Sn、Pb、Zn、Al、Ag，及Au進行，溫度範圍橫跨156至1065℃。樣品經切割及機械式拋光以移除任何可能之污染表面層。其後，以乙醇清理且置於一石墨坩鍋內，且以蓋子覆蓋以限制可能之蒸發及保護此裝置。為避免氧化，分析腔室係抽空至10-2毫巴，然後，充滿氬氣。DSC測量係於流動之氬氣氛圍下進行。每一樣品之三個複製品被測試。樣品重量係62~78毫克。 Thermal studies of these systems were performed using the DSC-2400 Setaram Setsys differential scanning calorimetry. The DSC temperature calibration system uses seven pure metals: In, Sn, Pb, Zn, Al, Ag, and Au, with a temperature range of 156 to 1065 °C. The sample is cut and mechanically polished to remove any possible contaminated surface layers. Thereafter, it was cleaned with ethanol and placed in a graphite crucible and covered with a lid to limit possible evaporation and protect the device. To avoid oxidation, the analytical chamber was evacuated to 10 -2 mbar and then filled with argon. The DSC measurement was carried out under a flowing argon atmosphere. Three replicates of each sample were tested. The sample weight is 62 to 78 mg.
樣品從室溫加熱至1080℃。然後，冷卻至800℃，且於此溫度保持10分鐘，600s。此係稱為“第一加熱及冷卻周期”。於第二及第三周期，樣品加熱至1080℃，然後，冷卻至800℃，進行兩次。最後，樣品冷卻至室溫。5℃/分鐘之固定速率被用於所有加熱及冷卻。具二個空石墨坦鍋之基線實驗係使用相同實驗程序進行。對於操作係扣除基線。溫度及焓之分析係對此等經基線調整之溫度記錄圖進行。 The sample was heated from room temperature to 1080 °C. It was then cooled to 800 ° C and maintained at this temperature for 10 minutes, 600 s. This is referred to as the "first heating and cooling cycle." In the second and third cycles, the sample was heated to 1080 ° C and then cooled to 800 ° C for two passes. Finally, the sample was cooled to room temperature. A fixed rate of 5 ° C / min was used for all heating and cooling. Baseline experiments with two empty graphite pans were performed using the same experimental procedure. For the operating system, the baseline is deducted. The analysis of temperature and enthalpy is performed on these baseline-adjusted temperature maps.
第二及第三周期之結果被用於決定相關之熱參數，即，熔融之T開始、固化之T起始，及熔融與固化T峰值，與熔融及固化之焓，E。通常，T開始(加熱)及T峰值(冷卻)係取為TS(固相)及TL(液相)。 The results of the second and third periods are determined for the parameters related to heat, i.e., the T starts melting, the curing initiation of T, and T peak melting and solidified, and enthalpy of melting and solidified, E. Generally, T start (heating) and T peak (cooling) are taken as T S (solid phase) and T L (liquid phase).
液相研究結果指示與含鉛合金相比(第13表)，引入硫化物看起來係降低液相溫度及冷凍範圍。於A-I族群之合金，當Zn含量增加時，液相溫度及冷凍範圍減少。 The results of the liquid phase study indicate that the introduction of sulfides appears to lower the liquidus temperature and the freezing range compared to lead-containing alloys (Table 13). For alloys of the A-I group, as the Zn content increases, the liquidus temperature and the freezing range decrease.
有關於冷凍範圍，BiwaliteTM(C83470)具有中間之冷凍範圍。第13表之合金具有廣冷凍範圍。相反地，以BiwaliteTM(C83470)，可認為於冒口內之深管，其延伸至鑄造物產生收縮多孔性。藉由廣冷凍範圍合金，多孔性可適當分佈於鑄造物。此外，其可藉由使用適當之冒口設計及/或藉由使用金屬冷卻而減到最小/去除。在某種程度，第13表之I-A、I-B，及II-A合金可較不易受收縮多孔性影響。此會導致如所觀察到之較佳強度及伸長率值。 About freezing range, Biwalite TM (C83470) intermediate the freezing range. The alloy of Table 13 has a wide freezing range. In contrast to Biwalite TM (C83470), it may be considered in depth within the riser pipe, which extends to produce a porous casting contraction. Porosity can be appropriately distributed in the cast by the extensive freezing range alloy. In addition, it can be minimized/removed by using a suitable riser design and/or by using metal cooling. To some extent, the IA, IB, and II-A alloys of Table 13 are less susceptible to shrinkage porosity. This results in better strength and elongation values as observed.
進行第14表中合金與第10表中選擇之合金之硫化物顆粒尺寸之研究。第15表列示此等合金之最小、最大，及平均之顆粒尺寸。此外，對二市面上之合金，C83470及C90300，檢查顆粒尺寸。本發明之合金平均上係提供比C83470更小之顆粒尺寸，及比市面上之合金C90300更小之最小顆粒尺寸。第46A-46B圖例示與I-B族群合金(I-B-14a)相比之市面上C83470之顯微照片。 A study was conducted on the size of the sulfide particles of the alloys in Table 14 and the alloys selected in Table 10. Table 15 lists the minimum, maximum, and average particle sizes of these alloys. In addition, for the alloys on the market, C83470 and C90300, check the particle size. The alloy of the present invention provides on average a smaller particle size than C83470 and a smaller particle size than the commercially available alloy C90300. Figures 46A-46B illustrate photomicrographs of C83470 on the market compared to Group I-B alloys (I-B-14a).
先前之例示實施例說明已呈現用以例示及說明。關於所揭露之精確型式，非意欲修詳盡或作限制，且改變及變化基於上述教示係可能，或可自所揭露實施例而獲得。本發明之範圍係意欲藉由所附之申請專利範圍及其等化物而界定。The previous illustrative embodiment has been presented for purposes of illustration and description. The precise type disclosed is not intended to be exhaustive or limiting, and variations and modifications are possible based on the above teachings, or may be obtained from the disclosed embodiments. The scope of the invention is intended to be defined by the scope of the appended claims and their equivalents.
第1圖提供列示數種已知市面上銅合金之配製物之第1表。Figure 1 provides a first table listing the formulations of several known copper alloys on the market.
第2圖提供列示依據本發明實施例之合金族群之配製物之第2表。Figure 2 provides a second table listing the formulations of the alloy population in accordance with an embodiment of the present invention.
第3A圖提供以其個別鑄造熱列示I-A族群之機械性質範例之合金配製物之第3表。第3B圖提供以其個別鑄造熱列示I-A族群之平均機械性質測試之結果之第4表。Figure 3A provides a third table of alloy formulations showing examples of mechanical properties of the I-A group with their individual casting heats. Figure 3B provides a fourth table showing the results of the average mechanical property test of the I-A population with its individual casting heat.
第4A圖提供以其個別鑄造熱列示I-B族群機械性質範例之合金配製物之第5表。第4B圖提供列示I-B族群之平均機械性質測試之結果之第6表。Figure 4A provides a fifth table of alloy formulations showing examples of mechanical properties of the I-B group with their individual casting heats. Figure 4B provides a sixth table showing the results of the average mechanical property test of the I-B population.
第5A圖提供以其個別鑄造熱列示II-A族群機械性質範例之合金配製物之第7表。第5B圖提供列示II-A族群之平均機械性質測試之結果之第8表。Figure 5A provides a seventh table of alloy formulations showing examples of the mechanical properties of Group II-A groups with their individual casting heats. Figure 5B provides an eighth table showing the results of the average mechanical properties test for the II-A population.
第6圖提供列示本發明之某些合金族群之實施例所觀察之典型及最小性質及諸如第1表(第1圖)中者之可購得合金所報導之性質之第9表。Figure 6 provides a ninth table listing the typical and minimal properties observed for the examples of certain alloy populations of the present invention and the properties reported for commercially available alloys such as those in Table 1 (Figure 1).
第7圖提供列示用於SEM/EDS測試之合金組成物之第10表。Figure 7 provides a table 10 listing the alloy compositions used for SEM/EDS testing.
第8A及8B圖例示合金I-A-10a中之硫的元素映像(0.16% S)。 Figures 8A and 8B illustrate the elemental map of sulfur in alloy I-A-10a (0.16% S).
第9A圖係合金I-A-10a之SEM；第9B-H圖例示元素映像；第9B圖係Sn之EDS；第9C圖係Zn之EDS；第9D圖係Cu之EDS；第9E圖係Fe之EDS；第9F圖係Ni之EDS；第9G圖係P之EDS；第9H圖係S之EDS。 9A is an SEM of alloy IA-10a; 9B-H is an illustration of an elemental image; 9B is an EDS of Sn; 9C is an EDS of Zn; 9D is an EDS of Cu; and 9E is a Fe of EDS; 9F is the EDS of Ni; 9G is the EDS of P; and 9H is the EDS of S.
第10A圖係合金I-A-10a之顯微照片，且區域1，2，及3被標記；第10B-D圖顯示Cu2S、ZnS及Cu-Zn介金屬相存在；第10B圖係區域1之EDS光譜；第10C圖係區域2之EDS光譜；第10D圖係區域3之EDS光譜。 Figure 10A is a photomicrograph of alloy IA-10a, and regions 1, 2, and 3 are labeled; 10B-D shows the presence of Cu2S, ZnS, and Cu-Zn intermetallic phases; and 10B is the EDS for region 1 Spectrum; 10C is the EDS spectrum of region 2; and 10D is the EDS spectrum of region 3.
第11A-B圖係合金I-A-10a於低(第11A圖)及高放大倍率(第11B圖)之光學影像。 Fig. 11A-B is an optical image of the alloy I-A-10a at low (Fig. 11A) and high magnification (Fig. 11B).
第12A圖係合金I-B-10a之SEM，且第12B圖係例示合金I-B-10a內之硫之元素映像(0.31% S)。 Fig. 12A is a SEM of alloy I-B-10a, and Fig. 12B illustrates an elemental map of sulfur (0.31% S) in alloy I-B-10a.
第13A圖係合金I-B-10a之SEM；第13B-H圖例示1000x放大倍率之元素映像；第13B圖係Sn之EDS；第13C圖係Zn之EDS；第13D圖係Cu之EDS；第13E圖係Fe之EDS；第13F圖係Ni之EDS；第13G圖係P之EDS；第13H圖係S之EDS。 Fig. 13A is an SEM of alloy IB-10a; Fig. 13B-H illustrates an elemental map of 1000x magnification; Fig. 13B is an EDS of Sn; Fig. 13C is an EDS of Zn; and Fig. 13D is an EDS of Cu; The figure is the EDS of Fe; the 13F is the EDS of Ni; the 13G is the EDS of P; the 13H is the EDS of S.
第14A圖係合金I-B-10b之SEM(0.13% S)；第14B-I圖例示5000x放大倍率之元素映像；第14B圖係Si之EDS；第14C圖係S之EDS；第14D圖係Fe之EDS；第14E圖係Cu之EDS；第14F圖係Zn之EDS；第14G圖係Sn之EDS；第14H圖係Pb之EDS；第14I圖係Ni之EDS。 Figure 14A is a SEM (0.13% S) of alloy IB-10b; Figure 14B-I illustrates an elemental map of 5000x magnification; Figure 14B is an EDS of Si; Figure 14C is an EDS of S; Figure 14D is a Fe EDS; 14E is the EDS of Cu; 14F is the EDS of Zn; 14G is the EDS of Sn; 14H is the EDS of Pb; and 14I is the EDS of Ni.
第15A-B圖係合金I-B-10(0.31% S)於低(第15A圖)及高放大倍率(第15B圖)之光學影像。 15A-B is an optical image of alloy I-B-10 (0.31% S) at low (Fig. 15A) and high magnification (Fig. 15B).
第16A及16B圖例示合金II-A-10a內之硫之元素映像(0.30% S)。 Figures 16A and 16B illustrate the elemental map of sulfur in the alloy II-A-10a (0.30% S).
第17A圖係合金II-A-10a之SEM；第17B-H圖例示元素映像；第17B圖係Sn之EDS；第17C圖係Zn之EDS；第17D圖係Cu之EDS；第17E圖係Fe之EDS；第17F圖係Ni之EDS；第17G圖係P之EDS；第17H圖係S之EDS。 Figure 17A is an SEM of Alloy II-A-10a; Figure 17B-H is an illustration of an elemental image; Figure 17B is an EDS of Sn; Figure 17C is an EDS of Zn; Figure 17D is an EDS of Cu; EDS of Fe; 17F is EDS of Ni; 17G is EDS of P; and 17H is EDS of S.
第18A圖係合金II-A-10b(0.19% S)之SEM；第18B-I圖例示於1000x放大倍率之元素映像；第18B圖係Si之EDS；第18C圖係S之EDS；第18D圖係Fe之EDS；第18E圖係Cu之EDS；第18F圖係Zn之EDS；第18G圖係Sn之EDS；第18H圖係Pb之EDS；第18I圖係Ni之EDS。 Figure 18A is an SEM of Alloy II-A-10b (0.19% S); Figure 18B-I is an elemental image at 1000x magnification; Figure 18B is an EDS of Si; Figure 18C is an EDS of S; 18D The figure is the EDS of Fe; the 18E is the EDS of Cu; the 18F is the EDS of Zn; the 18th is the EDS of Sn; the 18H is the EDS of Pb; the 18I is the EDS of Ni.
第19A-B圖係合金II-A於低(第19B圖)及高放大倍率(第19A圖)之光學影像。 19A-B is an optical image of Alloy II-A at low (Fig. 19B) and high magnification (Fig. 19A).
第20A及20B圖例示合金III-A內之硫之元素映像(0.011% S)。 Figures 20A and 20B illustrate the elemental map of sulfur in alloy III-A (0.011% S).
第21A圖係合金III-A之SEM；第21B-H圖例示元素映像；第21B圖係Sn之EDS；第21C圖係Zn之EDS；第21D圖係Cu之EDS；第21E圖係Fe之EDS；第21F圖係Ni之EDS；第21G圖係P之EDS；第21H圖係S之EDS。 21A is an SEM of Alloy III-A; 21B-H is an illustration of an elemental image; 21B is an EDS of Sn; 21C is an EDS of Zn; 21D is an EDS of Cu; and 21E is a Fe of EDS; 21F is the EDS of Ni; 21G is the EDS of P; and 21H is the EDS of S.
第22A-B圖係合金III-A於低(第22A圖)及高放大倍率(第22B圖)之光學影像。 Fig. 22A-B is an optical image of alloy III-A at low (Fig. 22A) and high magnification (Fig. 22B).
第23圖係I-A、I-B及II-A族群合金中形成之主要硫化物之硫自由能圖。 Figure 23 is a graph showing the sulfur free energy of the main sulfides formed in the I-A, I-B and II-A alloys.
第24圖係Cu-Sn-Zn-S合金之不同合金之垂直截面。Figure 24 is a vertical section of a different alloy of Cu-Sn-Zn-S alloy.
第25A圖係使用Scheil冷卻之合金I-A-11a之相分佈圖，第25B圖係此相分佈圖之一放大部份，其顯示次要相之相對量。Fig. 25A is a phase distribution diagram using Scheil cooled alloy I-A-11a, and Fig. 25B is an enlarged portion of the phase distribution diagram showing the relative amount of the secondary phase.
第26A圖係使用Scheil冷卻之合金I-A-11b之相分佈圖，第26B圖係此相分佈圖之一放大部份，其顯示次要相之相對量。Fig. 26A is a phase distribution diagram using Scheil cooled alloy I-A-11b, and Fig. 26B is an enlarged portion of the phase distribution diagram showing the relative amount of the secondary phase.
第27A圖係使用Scheil冷卻之合金I-A-11c之相分佈圖，第27B圖係此相分佈圖之一放大部份，其顯示次要相之相對量。Figure 27A is a phase distribution diagram using Scheil cooled alloy I-A-11c, and Figure 27B is an enlarged portion of the phase distribution diagram showing the relative amounts of the secondary phases.
第28A圖係使用Scheil冷卻之合金I-A-11d之相分佈圖，第28B圖係此相分佈圖之一放大部份，其顯示次要相之相對量。Figure 28A shows the phase distribution of the Scheil cooled alloy I-A-11d, and Figure 28B shows an enlarged portion of the phase distribution showing the relative amount of the secondary phase.
第29A圖係使用Scheil冷卻之合金I-A-11e之相分佈圖，第29B圖係此相分佈圖之一放大部份，其顯示次要相之相對量。Fig. 29A is a phase distribution diagram using Scheil cooled alloy I-A-11e, and Fig. 29B is an enlarged portion of the phase distribution diagram showing the relative amount of the secondary phase.
第30A圖係使用Scheil冷卻之C83470市面上之合金(第1表，第1圖)之相分佈圖，第30B圖係此相分佈圖之一放大部份，其顯示次要相之相對量。Figure 30A shows the phase distribution of the alloy on the C83470 market (Table 1, Figure 1) using Scheil cooling, and Figure 30B is an enlarged portion of the phase distribution showing the relative amount of the secondary phase.
第31圖係I-A族群之垂直截面之相圖。Figure 31 is a phase diagram of the vertical section of the I-A group.
第32A圖係I-A族群之Scheil相組合圖，第32B圖係I-A族群之放大Scheil相組合圖。Fig. 32A is a Scheil combination diagram of the I-A group, and Fig. 32B is an enlarged Scheil combination diagram of the I-A group.
第33圖係I-B族群之垂直截面。Figure 33 is a vertical section of the I-B group.
第34A圖係I-B族群之Scheil相組合圖，第34B圖係I-B族群之放大Scheil相組合圖。Figure 34A is a Scheil combination diagram of the I-B group, and Figure 34B is an enlarged Scheil combination diagram of the I-B group.
第35圖係II-A族群之垂直截面。 Figure 35 is a vertical section of the II-A group.
第36A圖係II-A族群之Scheil相組合圖，第36B圖係II-A族群之放大Scheil相組合圖。 Fig. 36A is a Scheil combination diagram of the II-A group, and Fig. 36B is a magnified Scheil combination diagram of the II-A group.
第37圖係顯示以其CDA數指示之與數種已知合金相比之I-A合金族群之各種熱之極限抗拉強度(UTS)圖。 Figure 37 is a graph showing the various thermal ultimate tensile strength (UTS) plots for the I-A alloy population compared to several known alloys, indicated by their CDA numbers.
第38圖係顯示以其CDA數指示之與數種已知合金相比之I-A合金族群之各種熱之屈服強度圖。 Figure 38 is a graph showing the various yield strengths of the I-A alloy populations as indicated by their CDA numbers compared to several known alloys.
第39圖係顯示以其CDA數指示之與數種已知合金相比之I-A合金族群之各種熱之伸長率圖。 Figure 39 is a graph showing various heat elongations for the I-A alloy population as indicated by its CDA number compared to several known alloys.
第40圖係顯示以其CDA數指示之與數種已知合金相比之I-B合金族群之各種熱之極限抗拉強度(UTS)圖。 Figure 40 is a graph showing the various thermal ultimate tensile strength (UTS) of the I-B alloy population as indicated by its CDA number compared to several known alloys.
第41圖係顯示以其CDA數指示之與數種已知合金相比之I-B合金族群之各種熱之屈服強度圖。 Figure 41 is a graph showing the various yield strengths of the I-B alloy population compared to several known alloys as indicated by their CDA numbers.
第42圖係顯示以其CDA數指示之與數種已知合金相比之I-B合金族群之各種熱之伸長率圖。 Figure 42 is a graph showing various heat elongations for the I-B alloy population as indicated by its CDA number compared to several known alloys.
第43圖係顯示以其CDA數指示之與數種已知合金相比之II-A合金族群之各種熱之極限抗拉強度(UTS)圖。 Figure 43 is a graph showing the various thermal ultimate tensile strength (UTS) plots for the II-A alloy population compared to several known alloys, indicated by their CDA numbers.
第44圖係顯示以其CDA數指示之與數種已知合金相比之II-A合金族群之各種熱之屈服強度圖。 Figure 44 is a graph showing the various yield strengths of the II-A alloy population compared to several known alloys as indicated by their CDA numbers.
第45圖係顯示以其CDA數指示之與數種已知合金相比之II-A合金族群之各種熱之伸長率圖。 Figure 45 is a graph showing various heat elongations for the II-A alloy population compared to several known alloys, indicated by their CDA numbers.
第46A圖例示一市面上之硫黃銅BiwaliteTM(C83470)，之硫化物顆粒尺寸，且第46B圖顯示I-B合金族群(0.13S-4.45Zn-3.63Sn)之顆粒尺寸之顯微照片。 Figure 46A illustrates a commercially available sulfur brass BiwaliteTM (C83470) having a sulfide particle size, and Figure 46B shows a photomicrograph of the particle size of the I-B alloy population (0.13S-4.45Zn-3.63Sn).
Claims (17)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US40851810P | 2010-10-29 | 2010-10-29 | |
| US41075210P | 2010-11-05 | 2010-11-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201221661A TW201221661A (en) | 2012-06-01 |
| TWI539014B true TWI539014B (en) | 2016-06-21 |
Family
ID=46047929
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW100139572A TWI539014B (en) | 2010-10-29 | 2011-10-31 | Low lead ingot |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US20120121455A1 (en) |
| TW (1) | TWI539014B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9181606B2 (en) | 2010-10-29 | 2015-11-10 | Sloan Valve Company | Low lead alloy |
| US9050651B2 (en) * | 2011-06-14 | 2015-06-09 | Ingot Metal Company Limited | Method for producing lead-free copper—bismuth alloys and ingots useful for same |
| US20130115128A1 (en) * | 2011-11-07 | 2013-05-09 | Nibco Inc. | Sulfur-rich corrosion-resistant copper-zinc alloy |
| US9829122B2 (en) * | 2011-11-07 | 2017-11-28 | Nibco Inc. | Leach-resistant leaded copper alloys |
| US8991787B2 (en) | 2012-10-02 | 2015-03-31 | Nibco Inc. | Lead-free high temperature/pressure piping components and methods of use |
| WO2014066631A1 (en) * | 2012-10-26 | 2014-05-01 | Sloan Valve Company | White antimicrobial copper alloy |
| CN102952967A (en) * | 2012-11-20 | 2013-03-06 | 无锡常安通用金属制品有限公司 | Copper alloy |
| CN103045901B (en) * | 2013-01-16 | 2014-11-26 | 苏州金仓合金新材料有限公司 | Lead-free environmentally-friendly alloy bar and preparation method thereof |
| US10519528B2 (en) | 2013-09-04 | 2019-12-31 | Hunan Terry New Materials Company Ltd. | Lead-free, high-sulphur and easy-cutting copper-manganese alloy and preparation method thereof |
| CA2926331A1 (en) * | 2013-10-07 | 2015-04-16 | Sloan Valve Company | White antimicrobial copper alloy |
| AT520560B1 (en) * | 2018-01-29 | 2019-05-15 | Miba Gleitlager Austria Gmbh | Multilayer plain bearing element |
| WO2020136772A1 (en) * | 2018-12-26 | 2020-07-02 | 株式会社明石合銅 | Bronze alloy for casting use, and sliding member comprising said bronze alloy |
| AT522440B1 (en) | 2019-05-07 | 2020-11-15 | Miba Gleitlager Austria Gmbh | Multi-layer plain bearing element |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6136104A (en) * | 1998-07-08 | 2000-10-24 | Kobe Steel, Ltd. | Copper alloy for terminals and connectors and method for making same |
| US6471792B1 (en) * | 1998-11-16 | 2002-10-29 | Olin Corporation | Stress relaxation resistant brass |
| US9181606B2 (en) * | 2010-10-29 | 2015-11-10 | Sloan Valve Company | Low lead alloy |
| WO2013166454A1 (en) * | 2012-05-03 | 2013-11-07 | Sloan Valve Company | Antimony-modified low-lead copper alloy |
-
2011
- 2011-10-28 US US13/317,785 patent/US20120121455A1/en not_active Abandoned
- 2011-10-31 TW TW100139572A patent/TWI539014B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| TW201221661A (en) | 2012-06-01 |
| US20120121455A1 (en) | 2012-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI539014B (en) | Low lead ingot | |
| US9181606B2 (en) | Low lead alloy | |
| JP6177441B2 (en) | Antibacterial white copper alloy | |
| JP6359523B2 (en) | Antimony-modified low-lead copper alloy | |
| JP6783314B2 (en) | Lead-free free-cutting brass alloy with excellent castability, its manufacturing method, and its applications | |
| CA1208042A (en) | Rhenium-bearing copper-nickel-tin alloys | |
| CA2816320C (en) | Low lead ingot | |
| US10385425B2 (en) | White antimicrobial copper alloy | |
| US10507520B2 (en) | Copper-based alloys, processes for producing the same, and products formed therefrom | |
| CN106987737A (en) | Have the unleaded of excellent founding and cut brass alloys and its manufacture method and purposes soon | |
| Acar et al. | Producing non-dendritic A356 and A380 feedstocks: evaluation of the effects of cooling slope casting parameters | |
| WO1994004712A1 (en) | Lead-free copper base alloys | |
| Shakya et al. | Study of Hardness and Wear Analysis in AL-SI Alloy (AL-5% SI, AL-11% SI and AL-17% SI) Along With Microstructural Analysis | |
| Egole et al. | Effect of Aluminium Addition and Grain Refinement on the Microstructure, Mechanical and Physical Properties of Leaded Brass Alloys | |
| JP3949557B2 (en) | Wear-resistant aluminum alloy for casting and cast aluminum alloy | |
| HYPOEUTECTIC | EFFECTS OF Sr ON THE MICROSTRUCTURE OF ELECTROMAGNETICALLY STIRRED SEMI SOLID HYPOEUTECTIC Al-Si ALLOYS G. Eisaabadi B. ¹*, M. Nouri², R. Beygi¹, M. Zarezadeh Mehrizi¹, A. Nouri¹, M. Ebrahimi³'Department of Materials Science and Engineering, Faculty of Engineering, Arak University | |
| CN114717454A (en) | Al-Si series aluminum alloy liquid and preparation method thereof | |
| MXPA99005252A (en) | Composition of strontium base alloys that have a reduced fusion temperature and method to manufacture the mi | |
| BRPI0805451B1 (en) | Production process of Al-Si-Mg-Cu alloys, Al-Si-Mg-Cu alloys obtained by the process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |