TWI392751B - Low-lead copper alloy - Google Patents
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Description
本發明係關於一種銅合金，尤其是，本發明係關於一種低鉛黃銅合金。This invention relates to a copper alloy, and more particularly to a low lead brass alloy.
黃銅之主要成份為銅與鋅，兩者之比例通常為約7:3或6:4，此外通常包含少量雜質。為了改善黃銅性質，習知黃銅係含鉛(多為1-3wt%)以達到產業所欲之機械特性，並因此成為工業上重要材料，廣泛應用於管線、水龍頭、供水/排水系統之金屬裝置或金屬閥等製品。The main components of brass are copper and zinc, which are usually about 7:3 or 6:4, and usually contain small amounts of impurities. In order to improve the properties of brass, conventional brass is lead-containing (up to 1-3% by weight) to achieve the desired mechanical properties of the industry, and thus has become an important industrial material, which is widely used in pipelines, faucets, water supply/drainage systems. Products such as metal devices or metal valves.
然而，隨著環保意識抬頭，重金屬對於人體健康的影響及對環境污染的問題逐漸受到重視，因此，限制含鉛合金的使用係為目前的趨勢，日本、美國等國陸續修訂相關法規，極力推動降低環境中的含鉛率，涵蓋用於家電、汽車、水週邊產品之含鉛合金材料，特別要求不可從該產品溶出鉛至飲用水，且在加工製程中必須避免鉛污染。However, with the rise of environmental awareness, the impact of heavy metals on human health and the problem of environmental pollution are gradually being taken seriously. Therefore, limiting the use of lead-containing alloys is the current trend, and countries such as Japan and the United States have successively revised relevant regulations to promote Reducing the lead content in the environment, including lead-containing alloy materials used in household appliances, automobiles, and water peripheral products, in particular, it is not allowed to dissolve lead to drinking water from the product, and lead pollution must be avoided in the processing.
另外，當黃銅中的鋅含量超過20重量%時易發生脫鋅(dezincification)之腐蝕現象，由於脫鋅作用會嚴重破壞黃銅合金之結構，使黃銅製品的表層強度降低，甚或導致黃銅管穿孔，大幅縮短黃銅製品的使用壽命，並造成應用上的問題。In addition, when the zinc content in the brass exceeds 20% by weight, dezincification corrosion is likely to occur, and the dezincification effect may seriously damage the structure of the brass alloy, thereby lowering the surface strength of the brass product, or even causing yellow The perforation of the copper tube greatly shortens the service life of the brass product and causes problems in application.
針對上述高含鉛量及脫鋅問題，業界持續開發銅合金配方，除了銅及鋅之必要成分外，例如US6413330、US7354489、US20070062615、US20060078458、US2004023441揭露無鉛銅合金配方，上述合金切削性不佳、加工效率低、不適於大批量產、裂紋、夾渣等缺陷。另外，例如US7297215、US6974509、US6955378、US6149739、US5942056、US5653827、US5487867、US5330712、US20060005901、US20040094243、US5637160、US20070039667等揭露含鉍之無鉛或低鉛黃銅合金配方，上述配方之鉍含量約涵蓋0.5wt%至7wt%之範圍，然而，高鉍含量易產生裂紋、夾渣等缺陷，致使加工效率低。In view of the above-mentioned problems of high lead content and dezincification, the industry continues to develop copper alloy formulations, in addition to the necessary components of copper and zinc, such as US6413330, US7354489, US20070062615, US20060078458, US2004023441, which disclose a lead-free copper alloy formulation, which has poor machinability. Low processing efficiency, not suitable for mass production, cracks, slag inclusion and other defects. In addition, for example, US Pat. No. 7,297,215, US 6,974, 509, US Pat. No. 6,955,378, US Pat. No. 6,149,739, US Pat. No. 5, 092, 056, US Pat. No. 5, 565, 827, US Pat. No. 5, 487, 867, US Pat. No. 5,307, 712, US Pat. In the range of up to 7 wt%, however, the high niobium content is liable to cause defects such as cracks and slag inclusions, resulting in low processing efficiency.
另外，針對抗脫鋅之配方，除了銅及鋅之必要成分外，目前已有US4417929揭露包含鐵、鋁及矽等成分；US5507885及US6395110揭露包含磷、錫及鎳等成分；US5653827揭露包含鐵、鎳及鉍等成分；U 6974509揭露包含錫、鉍、鐵、鎳及磷之成分；US6787101揭露同時包含磷、錫、鎳、鐵、鋁、矽及砷；以及US6599378及US5637160等專利揭露以硒及磷等成分添加至黃銅合金以達到抗脫鋅效果。然而，習知抗脫鋅黃銅含鉛量通常較高(多為1-3wt%)，俾利於黃銅材料之冷/熱加工，但不符合環保要求，鉛溶出量高，且易於製程中產生鉛污染。In addition, in addition to the necessary components of copper and zinc, US Pat. No. 4,417,929 discloses the inclusion of iron, aluminum and bismuth, and US Pat. No. 5,507,885 and US Pat. No. 6,395,110 disclose compositions containing phosphorus, tin and nickel. Compositions of nickel and ruthenium; U 6974509 discloses components comprising tin, antimony, iron, nickel and phosphorus; U.S. Patent 6,787,101 discloses phosphorus, tin, nickel, iron, aluminum, bismuth and arsenic; and US 6,599,378 and US Pat. No. 5,637,160 disclose selenium and Phosphorus and other ingredients are added to the brass alloy to achieve dezincification resistance. However, conventional anti-dezincification brass has a high lead content (mostly 1-3wt%), which is beneficial to the cold/hot processing of brass materials, but does not meet environmental requirements, high lead dissolution, and is easy to process. Lead pollution is produced.
因此，業界亟欲開發新的黃銅材料，尋找可替代含鉛黃銅，並可達到抗脫鋅腐蝕性，但仍須兼顧鑄造性能、切削性、耐腐蝕性、與機械性質之合金配方。Therefore, the industry is eager to develop new brass materials, to find alternatives to lead-containing brass, and to achieve dezincification resistance, but still have to consider the casting properties, machinability, corrosion resistance, and mechanical properties of the alloy formulation.
為達上述及其他目的，本發明係提供一種低鉛銅合金，包括：0.05至0.3重量%(wt%)之鉛(Pb)；0.3至0.8重量%之鋁(Al)；0.01至04重量%之鉍(Bi)；0.1至2重量%之鎳(Ni)；以及96.5重量%以上之銅(Cu)與鋅(Zn)，其中，該銅於該低鉛銅合金中之含量為58至70重量%。To achieve the above and other objects, the present invention provides a low-lead copper alloy comprising: 0.05 to 0.3% by weight (wt%) of lead (Pb); 0.3 to 0.8% by weight of aluminum (Al); 0.01 to 04% by weight (Bi); 0.1 to 2% by weight of nickel (Ni); and more than 96.5% by weight of copper (Cu) and zinc (Zn), wherein the copper is present in the low-lead copper alloy in an amount of 58 to 70 weight%.
本發明之低鉛銅合金係為黃銅合金，銅與鋅之總含量可達96.5重量%以上。於實施例中，該銅之含量為58至70重量%，此範圍之含量之銅可提供合金良好的韌性，俾利於合金材料後續加工。於較佳實施例中，該銅之含量為62至65重量%。The low-lead copper alloy of the present invention is a brass alloy, and the total content of copper and zinc can be more than 96.5 wt%. In the embodiment, the copper content is 58 to 70% by weight, and the copper in the range can provide good toughness of the alloy, which is beneficial to the subsequent processing of the alloy material. In a preferred embodiment, the copper content is from 62 to 65% by weight.
於本發明之銅合金中，該鋁之含量為0.3至0.8重量%。於較佳實施例中，鋁之含量為0.4至0.7重量%，更佳為0.5至0.65重量%。添加適量之鋁可增加銅水之流動性，並改善該合金材料之鑄造性能。In the copper alloy of the present invention, the aluminum content is from 0.3 to 0.8% by weight. In a preferred embodiment, the aluminum content is from 0.4 to 0.7% by weight, more preferably from 0.5 to 0.65% by weight. Adding an appropriate amount of aluminum increases the fluidity of the copper water and improves the casting properties of the alloy material.
於本發明之銅合金中，該鉍之含量為0.4重量%以下。於較佳實施例中，鉍之含量為0.01至0.4重量%，較佳為0.05至0.3重量%，更佳為0.1至0.2重量%。In the copper alloy of the present invention, the content of the cerium is 0.4% by weight or less. In a preferred embodiment, the content of cerium is from 0.01 to 0.4% by weight, preferably from 0.05 to 0.3% by weight, more preferably from 0.1 to 0.2% by weight.
於本發明之銅合金中，該鎳之含量為0.1至2重量%。於較佳實施例中，鎳之含量為0.5至1重量%。添加適量之鎳於該銅合金中可作為高熔點元素，鎳於合金結晶時作為非自發形成核的異質核心，使成核點增多而能細化合金晶粒；且鎳可淨化銅基體及晶界，俾提高該銅合金之力學性能和耐腐蝕性。In the copper alloy of the present invention, the content of the nickel is from 0.1 to 2% by weight. In a preferred embodiment, the nickel content is from 0.5 to 1% by weight. Adding an appropriate amount of nickel in the copper alloy can be used as a high melting point element. Nickel acts as a heterogeneous core that does not spontaneously form nuclei when the alloy is crystallized, which increases the number of nucleation sites and refines the alloy grains; and the nickel can purify the copper matrix and crystal Boundary, 俾 improve the mechanical properties and corrosion resistance of the copper alloy.
本發明銅合金所包含之鉛含量極低，為0.3重量%以下。於實施例中，該鉛含量為0.05至0.3重量%，較佳為0.1至0.25重量%，更佳為0.15至0.20重量%。而該合金中亦可能具有雜質，該等不可避免之雜質含量係為0.1重量%以下。The copper alloy of the present invention contains an extremely low lead content of 0.3% by weight or less. In the embodiment, the lead content is 0.05 to 0.3% by weight, preferably 0.1 to 0.25% by weight, more preferably 0.15 to 0.20% by weight. The alloy may also have impurities, and the unavoidable impurity content is 0.1% by weight or less.
本發明銅合金可替代習知含鉛黃銅，而更能達到環保及降低鉛污染的效果，亦具備抗脫鋅腐蝕性，並可同時兼顧合金的鑄造性能、切削性、耐腐蝕性、與機械性質等優點。The copper alloy of the invention can replace the conventional lead-containing brass, and can better achieve environmental protection and reduce the effect of lead pollution, and is also resistant to dezincification corrosion, and can simultaneously take into consideration the casting property, machinability, corrosion resistance of the alloy, and Mechanical properties and other advantages.
以下係藉由特定的具體實施例說明本發明之實施方式，熟習此技藝之人士可由本說明書所揭示之內容瞭解本發明之其他優點與功效。The embodiments of the present invention are described by way of specific examples, and those skilled in the art can understand the advantages and advantages of the present invention as disclosed in the present disclosure.
於本說明書中，除非另有說明，否則抗脫鋅銅合金所包含之成分皆以該合金總重量為基準，並以重量百分比(wt%)表示。In the present specification, unless otherwise stated, the components contained in the dezincification-resistant copper alloy are based on the total weight of the alloy and expressed in weight percent (wt%).
當以習知高含量之鉍(1wt%以上)添加入黃銅合金時，在微觀上，易於黃銅合金的晶粒中形成鉍之液態薄膜，最後於晶界偏析而產生連續片狀的鉍，遮蔽晶界，使得合金的機械強度潰散而使合金的熱脆性及冷脆性提高，造成材料開裂。然而，依據本發明之低鉛黃銅合金配方，僅需使用0.4wt%以下之鉍，不但可解決材料開裂之缺陷且仍可達到鉛黃銅(如習知之H59鉛黃銅)所具備之材料特性(如切削性等)，且不易產生裂紋或夾雜等產品缺陷。因此，本發明之低鉛黃銅合金可大幅降低鉍用量，有效降低低鉛黃銅合金之生產成本，對於商業量產及應用上極具優勢。When a high content of ruthenium (1 wt% or more) is added to a brass alloy, microscopically, a liquid film of ruthenium is easily formed in the crystal grains of the brass alloy, and finally segregated at the grain boundary to produce a continuous sheet-like ruthenium. The grain boundary is shielded, so that the mechanical strength of the alloy is broken, and the hot brittleness and cold brittleness of the alloy are improved, causing cracking of the material. However, according to the low-lead brass alloy formulation of the present invention, only 0.4% by weight or less of bismuth is required, which not only solves the defects of material cracking but also can reach the material of lead brass (such as the conventional H59 lead brass). Characteristics (such as machinability, etc.), and are not susceptible to product defects such as cracks or inclusions. Therefore, the low-lead brass alloy of the present invention can greatly reduce the amount of bismuth, and effectively reduce the production cost of the low-lead brass alloy, and has great advantages for commercial mass production and application.
另外，依據本發明之低鉛黃銅合金配方，可以使合金之鉛含量降低至0.05-0.3wt%，符合對於與水接觸之管線材料之鉛含量之國際規定。因此，依據本發明之低鉛黃銅合金有利於製造水龍頭及衛浴零組件、自來水管線、供水系統等之應用。In addition, the low lead brass alloy formulation according to the present invention can reduce the lead content of the alloy to 0.05-0.3 wt%, in accordance with international regulations for lead content in pipeline materials in contact with water. Therefore, the low-lead brass alloy according to the present invention is advantageous for the manufacture of faucets and sanitary components, water pipes, water supply systems and the like.
於一實施例中，本發明之低鉛黃銅合金包括：0.05至0.3重量%之鉛；0.3至0.8重量%之鋁；0.01至0.4重量%之鉍；0.1至2重量%之鎳；以及96.5至99.54重量%之銅與鋅，其中，該銅於該低鉛黃銅合金中之含量為58至70重量%。In one embodiment, the low-lead brass alloy of the present invention comprises: 0.05 to 0.3% by weight of lead; 0.3 to 0.8% by weight of aluminum; 0.01 to 0.4% by weight of bismuth; 0.1 to 2% by weight of nickel; and 96.5 Up to 99.54% by weight of copper and zinc, wherein the copper is contained in the low-lead brass alloy in an amount of 58 to 70% by weight.
於另一實施例中，本發明之含鎳低鉛黃銅合金係包括：0.1至0.25重量%之鉛；0.4至0.7重量%之鋁；0.05至0.3重量%之鉍；0.5至1重量%之鎳；58至70重量%之銅；以及餘量鋅；且不可避免之雜質含量係為0.1重量%以下。In another embodiment, the nickel-containing low-lead brass alloy of the present invention comprises: 0.1 to 0.25% by weight of lead; 0.4 to 0.7% by weight of aluminum; 0.05 to 0.3% by weight of bismuth; and 0.5 to 1% by weight of Nickel; 58 to 70% by weight of copper; and the balance zinc; and the unavoidable impurity content is 0.1% by weight or less.
於又一實施例中，本發明之含鎳低鉛黃銅合金係包括：0.15至0.20重量%之鉛；0.5至0.65重量%之鋁；0.1至0.2重量%之鉍；0.5至1重量%之鎳；62至65重量%之銅；以及餘量鋅；且不可避免之雜質含量係為0.1重量%以下。In still another embodiment, the nickel-containing low-lead brass alloy of the present invention comprises: 0.15 to 0.20% by weight of lead; 0.5 to 0.65% by weight of aluminum; 0.1 to 0.2% by weight of bismuth; and 0.5 to 1% by weight of Nickel; 62 to 65% by weight of copper; and the balance zinc; and the unavoidable impurity content is 0.1% by weight or less.
以下，將以例示性實施例詳細闡述本發明。Hereinafter, the present invention will be described in detail by way of illustrative embodiments.
用於後述試驗例之本發明低鉛銅合金之成分，係如下所述，其中，各成分之比例係以合金總重為基準：The components of the low-lead copper alloy of the present invention used in the test examples described later are as follows, wherein the ratio of each component is based on the total weight of the alloy:
實施例1：Example 1:
Cu：61.54wt% Al：0.457wt%Cu: 61.54 wt% Al: 0.457 wt%
Bi：0.197wt% Ni：0.584wt%Bi: 0.197 wt% Ni: 0.584 wt%
Pb：0.144wt% Zn：餘量Pb: 0.144wt% Zn: balance
實施例2：Example 2:
Cu：62.72wt% Al：0.634wt%Cu: 62.72wt% Al: 0.634wt%
Bi：0.126wt% Ni：0.853wt%Bi: 0.126 wt% Ni: 0.853 wt%
Pb：0.178wt% Zn：餘量Pb: 0.178wt% Zn: balance
實施例3：Example 3:
Cu：62.45wt% Al：0.582wt%Cu: 62.45 wt% Al: 0.582 wt%
Bi：0.159wt% Ni：0.696wt%Bi: 0.159 wt% Ni: 0.696 wt%
Pb：0.156wt% Zn：餘量Pb: 0.156wt% Zn: balance
試驗例1：Test Example 1:
以圓型砂、尿醛樹脂、呋喃樹脂及固化劑為原料以射芯機製備砂芯，並以發氣性試驗機測量樹脂發氣量。所得砂芯須於5小時內使用完畢，否則需以烘箱烘乾。The sand core was prepared by a core shooting machine using round sand, urine aldehyde resin, furan resin and curing agent as raw materials, and the gas generating amount of the resin was measured by a gas generating tester. The obtained sand core must be used within 5 hours, otherwise it needs to be dried in an oven.
將本發明之低鉛黃銅合金及回爐料預熱15分鐘，使溫度達400℃以上，再將兩者以重量比為7：1之比例以感應爐進行熔煉，並添加0.2wt%之精鍊清渣劑，待該黃銅合金達到一定的熔融狀態(下稱熔解銅液)，以金屬型重力鑄造機配合砂芯及重鑄模具進行澆鑄，復以溫度監測系統控制，使澆鑄溫度維持於1010-1060℃之間。澆鑄之每次投料量以1-2kg為宜，澆鑄時間控制在3-8秒內。The low-lead brass alloy and the reclaimed material of the present invention are preheated for 15 minutes to have a temperature of 400 ° C or higher, and then smelted in an induction furnace at a weight ratio of 7:1, and 0.2% by weight of refining is added. The slag-removing agent is subjected to a certain molten state (hereinafter referred to as melting copper liquid), and is cast by a metal gravity casting machine with a sand core and a recasting mold, and is controlled by a temperature monitoring system to maintain the casting temperature at Between 1010-1060 °C. The casting amount is preferably 1-2kg per casting, and the casting time is controlled within 3-8 seconds.
待模具冷卻凝固後開模卸料清理澆冒口，監測模具溫度，使模具溫度控制在200-220℃中並形成鑄件，隨後進行鑄件脫模。每模鑄件取出後，清潔模具，確保芯頭位置乾淨，噴石墨於模具表面後再行浸水冷卻。用以冷卻模具之石墨水之溫度為30-36℃為宜，比重為1.05～1.06。After the mold is cooled and solidified, the mold is unloaded to clean the pouring riser, the mold temperature is monitored, the mold temperature is controlled at 200-220 ° C and a casting is formed, and then the casting is demolded. After each molded part is taken out, the mold is cleaned to ensure that the core position is clean, and the graphite is sprayed on the surface of the mold and then immersed in water for cooling. The temperature of the graphite water used to cool the mold is preferably from 30 to 36 ° C, and the specific gravity is from 1.05 to 1.06.
將冷卻的鑄件進行自檢並送入清砂機滾筒陶砂清理。接著，進行毛胚處理(鑄造坯件的熱處理(清除應力退火)，以消除鑄造產生的內應力)。將坯件進行後續機械加工及拋光，俾使鑄件內腔不附有砂、金屬屑或其他雜質。進行品檢分析並計算生產總良率：The cooled castings are self-tested and sent to the sander drum for cleaning. Next, the blank processing (heat treatment of the cast blank (clearing stress annealing) is performed to eliminate the internal stress generated by the casting). The blank is subsequently machined and polished so that the interior of the casting is free of sand, metal shavings or other impurities. Conduct quality inspection analysis and calculate total production yield:
生產總良率=良品數/全部產品數×100%Total production yield = number of good products / total number of products × 100%
製程之生產總良率係反映生產製程品質穩定性，品質穩定性越高，才能保證正常生產。The total production yield of the process reflects the quality stability of the production process, and the higher the quality stability, the normal production can be guaranteed.
另以高鎳無鉛黃銅及習知H59鉛黃銅作為比較例，以與上述相同之製程製備物件。各合金之成分、加工特性及生產總良率如表1所示，其中，鉛含量低於0.05wt%之黃銅材料即視為無鉛黃銅。In addition, high nickel lead-free brass and conventional H59 lead brass were used as comparative examples to prepare articles in the same manner as described above. The composition, processing characteristics and total production yield of each alloy are shown in Table 1, wherein a brass material having a lead content of less than 0.05% by weight is regarded as a lead-free brass.
該高鎳無鉛黃銅的硬度較高，因此，欲對高鎳無鉛黃銅進行機械加工較為困難。當將上述三種黃銅材料以相同的進刀量及相同的切削速度時，該高鎳無鉛黃銅製品之表面容易留下刀痕，且表面粗糙度達不到要求(即Ra值為3.2μm)，因此，生產良率較低。The high nickel lead-free brass has a high hardness, so it is difficult to machine high nickel lead-free brass. When the above three kinds of brass materials have the same feed amount and the same cutting speed, the surface of the high-nickel lead-free brass product is likely to leave a knife mark, and the surface roughness is not required (ie, the Ra value is 3.2 μm). ), therefore, the production yield is low.
而依據本發明之低鉛黃銅為原料之試作組，生產良率高，可達85%以上，與習知H59鉛黃銅相當，確實可作為替代黃銅材料。而本發明之低鉛黃銅可大幅降低合金中的鉛含量，有效避免製程中所產生的鉛污染，並降低使用該鑄造物件時的鉛釋出量，在兼顧材料特性的同時更可達到環保的要求。According to the test group of the low lead brass according to the present invention, the production yield is high, up to 85% or more, which is equivalent to the conventional H59 lead brass, and can be used as an alternative brass material. The low-lead brass of the invention can greatly reduce the lead content in the alloy, effectively avoid lead pollution generated in the process, and reduce the amount of lead released when the cast object is used, and achieve environmental protection while taking into consideration material properties. Requirements.
試驗例2：Test Example 2:
將本發明之低鉛銅合金(實施例1)、高鎳無鉛黃銅(比較例1)、H59鉛黃銅(比較例3)、低鎳無鉛黃銅(比較例5)之試片於光學金相顯微鏡下檢視材料之組織分佈，放大100倍之結果，分別如第1A-1C圖所示。A test piece of the low lead copper alloy (Example 1), high nickel lead-free brass (Comparative Example 1), H59 lead brass (Comparative Example 3), and low nickel lead-free brass (Comparative Example 5) of the present invention was optically observed. The tissue distribution of the material under the metallographic microscope was magnified 100 times as shown in Fig. 1A-1C.
實施例1之含鎳低鉛黃銅之成分實測值為Cu：61.54wt%、Al：0.457wt%、Pb：0.144wt%、Bi：0.197wt%、Ni：0.584wt%。其金相組織分佈如第1A圖所示，會形成細小之晶粒，晶粒之粒徑尺寸約15-25μm，俾提供較佳之材料韌性，故不易產生裂紋等缺陷。與比較例相較，實施例1之α相之晶粒更細小，組織更為緻密，表示材料具有良好機械性能。The composition of the nickel-containing low-lead brass of Example 1 was found to be Cu: 61.54 wt%, Al: 0.457 wt%, Pb: 0.144 wt%, Bi: 0.197 wt%, and Ni: 0.584 wt%. The metallographic structure distribution, as shown in Fig. 1A, forms fine grains, and the grain size of the crystal grains is about 15-25 μm. The niobium provides better material toughness, so that defects such as cracks are less likely to occur. Compared with the comparative example, the α phase of the embodiment 1 has finer crystal grains and a denser structure, indicating that the material has good mechanical properties.
比較例1之高鎳無鉛黃銅成分實測值為Cu：61.01wt%、Al：0.574wt%、Pb：0.0067wt%、Bi：0.134wt%、Ni：2.324wt%。其金相組織分佈如第1B圖所示，晶粒呈細小粒狀，故可提供材料較高的硬度。The measured value of the high nickel lead-free brass composition of Comparative Example 1 was Cu: 61.01 wt%, Al: 0.574 wt%, Pb: 0.0067 wt%, Bi: 0.134 wt%, and Ni: 2.324 wt%. The metallographic structure distribution is as shown in Fig. 1B, and the crystal grains are fine-grained, so that the material has a high hardness.
比較例3之H59鉛黃銅主要成分之實測值為：Cu：59.7wt%、Al：0.521wt%、Pb：2.16wt%、Bi：0.0074wt%、Ni：0.0103wt%。其金相組織分佈如第1C圖所示，呈α相合金，晶粒為圓粒狀形態，粒徑尺寸約30-40μm，具良好韌性。The measured values of the main components of H59 lead brass of Comparative Example 3 were: Cu: 59.7 wt%, Al: 0.521 wt%, Pb: 2.16 wt%, Bi: 0.0074 wt%, and Ni: 0.0103 wt%. The metallographic structure distribution is as shown in Fig. 1C, and it is an α-phase alloy. The crystal grains are in a round granular form with a particle size of about 30-40 μm and good toughness.
另以低鎳含量之無鉛黃銅作為比較例5，其主要成分之實測值為：Cu：63.28wt%、Al：0.597wt%、Pb：0.037wt%、Bi：0.114wt%、Ni：0.063wt%，其中，比較例5之鎳含量低於0.1%。其金相組織分佈如第1D圖所示，晶粒較狹長、粗大，晶粒之尺寸約40-50μm，顯示低鎳無鉛黃銅並無細化晶粒之作用。Another lead-free brass with a low nickel content was used as Comparative Example 5, and the measured values of the main components were: Cu: 63.28 wt%, Al: 0.597 wt%, Pb: 0.037 wt%, Bi: 0.114 wt%, Ni: 0.063 wt. %, wherein the nickel content of Comparative Example 5 was less than 0.1%. The metallographic structure distribution is as shown in Fig. 1D. The crystal grains are narrow and large, and the size of the crystal grains is about 40-50 μm, indicating that the low-nickel lead-free brass has no effect of refining crystal grains.
試驗例3：Test Example 3:
以實施例3及比較例3之黃銅合金進行脫鋅測試，以檢測黃銅的耐蝕性。脫鋅測試是按照澳洲AS2345-2006《銅合金抗脫鋅》標準進行。腐蝕實驗前用酚醛樹臘鑲樣‧使其暴露面積為100mm2 ，所有試片均經過600#金相砂紙研磨平整，並用蒸餾水洗淨、烘乾。試驗溶液為現配的1%之CuCl2 溶液，試驗溫度為75±2℃。將試片與CuCl2 溶液置於恆溫水浴槽中作用24±0.5小時，取出後沿縱向切開，將試片之剖面拋光後，測量其腐蝕深度並以數位金相電子顯微鏡觀察，結果如第2A及2B圖所示。Dezincification tests were carried out using the brass alloys of Example 3 and Comparative Example 3 to detect the corrosion resistance of brass. The dezincification test is carried out in accordance with the Australian AS2345-2006 "copper alloy anti-dezincification" standard. Before the corrosion test, the phenolic wax was used to mount ‧ so that the exposed area was 100 mm 2 . All the test pieces were ground and smoothed by 600# metallographic sandpaper, and washed and dried with distilled water. The test solution was a 1% CuCl 2 solution, and the test temperature was 75 ± 2 °C. The test piece and the CuCl 2 solution were placed in a constant temperature water bath for 24±0.5 hours, and then taken out and cut longitudinally. After the cross section of the test piece was polished, the corrosion depth was measured and observed by a digital phase electron microscope. The result was as follows 2A. And 2B shown.
實施例3之本發明低鉛黃銅之平均脫鋅深度為141.72μm，如第2A圖所示。比較例3之H59鉛黃銅之平均脫鋅深度為307.94μm，如第2B圖所示。上述結果證實，本發明之低鉛黃銅具有更佳的抗脫鋅能力。The average dezincification depth of the low lead brass of the present invention of Example 3 was 141.72 μm as shown in Fig. 2A. The average dezincification depth of the H59 lead brass of Comparative Example 3 was 307.94 μm as shown in Fig. 2B. The above results confirmed that the low-lead brass of the present invention has better resistance to dezincification.
試驗例4：Test Example 4:
本實施例依照ISO6998-1998《金屬材料室溫拉伸實驗》標準進行機械性能的測試，結果如下表2所示。In this embodiment, the mechanical properties were tested in accordance with the ISO 6998-1998 "Metal Material Room Temperature Tensile Test" standard, and the results are shown in Table 2 below.
從表2可知，實施例1的抗拉強度和伸長率與比較例3之習知H59鉛黃銅相當，表示本發明之低鉛黃銅合金具備相當於H59鉛黃銅之機械性能；但本發明之低鉛黃銅的含鉛量低，符合環保要求，確實可以取代H59鉛黃銅而用於製造產品。As can be seen from Table 2, the tensile strength and elongation of Example 1 are comparable to those of the conventional H59 lead brass of Comparative Example 3, indicating that the low-lead brass alloy of the present invention has mechanical properties equivalent to H59 lead brass; The low-lead brass of the invention has low lead content and meets environmental protection requirements, and can be used to manufacture products by replacing H59 lead brass.
雖然比較例1之高鎳無鉛黃銅的強度及硬度較高，但高硬度不利於合金切削加工，冷加工之難度提高，且成本亦增加，不適於量產製造衛浴產品。Although the high nickel lead-free brass of Comparative Example 1 has high strength and hardness, the high hardness is not conducive to alloy cutting processing, the difficulty of cold working is increased, and the cost is also increased, which is not suitable for mass production of sanitary products.
試驗例5：Test Example 5:
依照NSF 61-2007a SPAC單產品金屬允許析出量標準進行測試，檢驗在與水接觸之環境中之黃銅合金之金屬析出量，測試結果如下表3所示：According to NSF 61-2007a SPAC single product metal allowable precipitation standard test, the metal precipitation of brass alloy in the environment of contact with water is tested. The test results are shown in Table 3 below:
比較例3之材料在未經洗鉛處理時，鉛含量大幅超過標準值，僅有實施例1無須經洗鉛處理即符合標準，且本發明之低鉛黃銅合金之重金屬鉛的析出量仍顯著低於經過洗鉛處理的H59鉛黃銅，更符合環保，且有利於人體健康。When the material of Comparative Example 3 was not subjected to lead washing treatment, the lead content greatly exceeded the standard value, and only Example 1 did not need to be subjected to lead washing treatment, which met the standard, and the precipitation amount of heavy metal lead of the low lead brass alloy of the present invention was still Significantly lower than lead-treated H59 lead brass, it is more environmentally friendly and beneficial to human health.
綜上述，本發明之低鉛黃銅合金具有細化之晶粒結構、良好的合金強度及韌性，不易產生裂紋或夾雜等缺陷，不致於產生鑄造缺陷，可達到鉛黃銅所具備之材料特性，俾利於合金材料應用於後續製程。本發明之低鉛銅合金無須進行洗鉛處理即具有低鉛析出之效果，可降低製程之生產成本，對於商業量產及應用上極具優勢。In summary, the low-lead brass alloy of the present invention has a refined grain structure, good alloy strength and toughness, is not susceptible to defects such as cracks or inclusions, and does not cause casting defects, and can achieve material properties of lead brass. The use of alloy materials in subsequent processes. The low-lead copper alloy of the invention has the effect of low lead precipitation without the need of lead-washing treatment, can reduce the production cost of the process, and has great advantages for commercial mass production and application.
上述實施例僅例示性說明本發明之低鉛銅合金，而非用於限制本發明。任何熟習此項技藝之人士均可在不違背本發明之精神及範疇下，對上述實施例進行修飾與改變。因此，本發明之權利保護範圍如後述申請專利範圍所載。The above examples are merely illustrative of the low lead copper alloys of the present invention and are not intended to limit the invention. Modifications and variations of the above-described embodiments can be made by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, the scope of the invention is set forth in the appended claims.
第1A圖為本發明低鉛銅合金試片之金相組織分佈圖；1A is a metallographic structure distribution diagram of a low lead copper alloy test piece of the present invention;
第1B圖為高鎳無鉛黃銅試片之金相組織分佈圖；Figure 1B is a metallographic structure of a high nickel lead-free brass test piece;
第1C圖為H59鉛黃銅試片之金相組織分佈圖；Figure 1C is a metallographic structure of the H59 lead brass test piece;
第1D圖為低鎳無鉛黃銅試片之金相組織分佈圖；Figure 1D is a metallographic structure of a low nickel lead-free brass test piece;
第2A圖為本發明低鉛銅合金試片之抗脫鋅腐蝕測試之金相組織分佈圖；以及2A is a metallographic structure distribution diagram of the anti-dezincification corrosion test of the low-lead copper alloy test piece of the present invention;
第2B圖為H59鉛黃銅試片之抗脫鋅腐蝕測試之金相組織分佈圖。Figure 2B is a metallographic structure map of the anti-dezincification test of the H59 lead brass test piece.
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