201102445 六、發明說明： w 【發明所屬之技術領域】 ^ 本發0系關於—種環保铸造黃銅合金及其物件之制 法尤，、无本^明係關於一種低錯黃銅合金及 製法。 、干之 t 【先前技術】201102445 VI. Description of the invention: w [Technical field of invention] ^ This is a system of environmentally-friendly cast brass alloys and their articles, and there is no such thing as a low-error brass alloy and its preparation method. . , dry t [previous technology]
黃銅之主要成份為銅與鋅，兩者之比例通常 或6:4,此外通常包含少量雜質。為了改善黃銅性.3 知黃銅係含錯（多為^ wt%)以達到產業所欲之機j 性，並因此成為卫業上重要材料，廣泛應用於管線、= 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, usually in the ratio of 6:4, and usually contain small amounts of impurities. In order to improve the brassiness. 3 know that the brass system contains the wrong (mostly ^ wt%) to achieve the desired function of the industry, and thus become an important material in the health industry, widely used in pipelines, = head, water supply / drainage Products such as metal devices or metal valves in the system.
然而，隨著環保意識抬頭，重金屬對於人體健康的^ 響及對環❹染的問題逐漸受到重視，ϋ此，限制含錯: 金的使用係為目前的趨勢，日本、美國等_續修訂^ 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ΠΠ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。因此 業界亟欲開發無錯1C銅材料，尋找可替代含錯黃鋼，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。 目前已有許多無鉛銅合金配方被報導，例如以石夕（Si) 為主要成分而取代錯添加於黃銅合金中，例如 TW421674 、 US7354489 、 US20070062615 、 US20060078458、US2004023441等所揭露之無错銅合金配 111287 3 201102445 方，但該些習知技術之缺點是切削性不佳。另外’無鉛銅 合金配方例如CN10144045揭示以鋁、矽、磷為主要合金 元素，雖然可用於鑄造，但切削性較差，加工效率遠低於 鉛黃銅，不適於大批量產；CN101285138、CN101285137 揭示以磷為主要合金元素，但其用於鑄造則容易產生裂 紋，夾潰等缺陷。 或，亦有文獻以鉍（Bi)為主要成分而取代鉛添加於黃 銅合金中，例如 US7297215、US6974509、US6955378、 US6149739、US5942056、US5653827、US5487867、 US5330712 > US20060005901 、 US20040094243 、 US5637160、US20070039667等，上述合金配方之鉍含量 約涵蓋0.5 wt%至7 wt%之範圍，且除了絲之外，各自包 不同的元素成分及特定比例。又，US6413330係揭露同時 包含銀、矽及其他成分之無鉛銅合金配方，CN101440444 亦揭露高鋅矽無鉛黃銅合金，然而，因其含矽量高但含銅 里較低，合金之溶湯流動性差，在金屬模中比較難充慢型 腔易產生洗不足專每造缺陷。而CN101403056係揭露以 鉍及錳代替鉛之無鉛黃銅合金，然而，高鉍含量易產生裂 紋、夾渣等缺陷，而鉍低錳高則硬度高，不易斷屑，切削 性差。 由於鉍的資源稀少、價格昂貴，以較高量之鉍代替鉛 會造成無鉛黃銅的製造成本過高，不利於商業化。且上述 黃銅合金配方仍存在有鑄造性能差、㈣脆化未能有效改 善。 111287 4 201102445 另外，亦有文獻揭示無鉛銅合金之製程或洗鉛製程之 。 改良，例如US5904783係揭露以鈉、鉀金屬在高溫下處理 . 黃銅合金以減少鉛濾出到供給液的方法；TW491897係揭 露含有1-2.6 wt%之叙之黃銅合金之製法；然而，習知洗 鉛製程僅能在含鉛產品在浸入水中時，減少與水接觸表面 的鉛析出，無法將生產原料成分中鉛含量降低至0.3 wt% 以下。 【發明内容】 籲 有鑑於此，本發明之目的係為開發低鉛黃銅合金材料 以及改良製程。 為達上述及其他目的，本發明係提供一種低船的環保 黃銅合金，包括：〇.〇5至0.3重量％(wt%)之錯（pb) ; 0.3 至0.8重量％之鋁（A1) ; 0.01至〇·4重量％之鉍（Bi) ; 〇 ] 至0.15重量％之微量元素；以及97.5重量％以上之銅（Cu) 與鋅(Zn)，其中，該銅於該低錯黃鋼合金中之含量為至 • 70重量％。 於一態樣中，本發明之低鉛黃鋼合金中所包含之銅與 鋅之總含量係為97.5-99.54 wt% ’較佳為98wt%以上。於 悲樣中，該銅之含量為該低錯！鋼合金總重量之5 8-70 wt%，此範圍之含量之銅可提供合金良好的韌性，和良好 的加工性。於較佳實施例中，該鋼之含量較佳為62_65 wt 於本發明之低鉛黃銅合金中，該鉛之含量為〇〇5 〇3 Wt%。‘於較佳實施例中，鉛之含量為〇 1〇 25 wt%，更佳 111287 5 201102445 為 0.15-0.25%。 於本發明之低鉛黃銅合金中，該鋁之含量為0.3-0.8 wt %。於較佳實施例中，鋁之含量為0.4-0.7 wt%，更佳為 0.5-0.65 wt%。添力υ適量之铭可增加銅水之流動性，並改 善該合金材料之鑄造性能。 於本發明之低鉛黃銅合金中，該鉍之含量為0.4 wt% 以下。於較佳實施例中，鉍之含量為0.01_0.4 wt%，較佳 為 0.05-0.3 wt%，更佳為 0.1-0.2 wt%。 本發明之低鉛黃銅合金中所包含之0.1-0.15 wt%之微 量元素可為稀土元素及/或不可避免之雜質，其中，該稀土 元素係包括鈽、銃、釔、鑭系元素等，該稀土元素可單獨 使用或組合使用。添加適量之稀土元素（例如飾（Ce))可 強烈地細化合金材料之鑄態組織，並可使重結晶退火後之 <2、yS相之相對量及結晶形貌(morphology)發生變化，且 可與鉛等元素形成顆粒狀雜質，因而改善合金材料中雜質 之分佈，並改善合金之物理性質及加工性質。於一態樣中， 該稀土元素為飾，其含量為0.1-0.15wt%。 本發明之低鉛黃銅合金復包括0.8 wt%以下之磷 (P)。於較佳實施例中，磷之含量為0.4-0.8 wt%。添加適 量之磷能可以提高熔體之流動性，改善銅及合金之焊接性 能。磷在銅中固溶度大，CuP的表面能低，故能降低銅的 表面張力，促使鉍以顆粒狀析出。 於本發明中，以Bi代替Pb，是爲了保持黃銅的易切 削性能。Pb相為面心立方晶格，晶格常數為4.949x10_1Qm， 6 111287 201102445However, with the rise of environmental awareness, heavy metals have gradually received attention for human health and the problem of ring-dyeing. Therefore, the limitation is limited: the use of gold is the current trend, Japan, the United States, etc. Regulations, which strive to reduce the lead content in the environment, covering lead-containing alloy materials used in household appliances, automobiles, and water-producing areas. In particular, it is not required to dissolve lead from the product to drinking water, and lead pollution must be avoided in the processing. . Therefore, the industry is eager to develop error-free 1C copper materials and look for alloy formulations that can replace castings with wrong yellow steel, but still have to take into account casting properties, machinability, corrosion resistance, and mechanical properties. At present, many lead-free copper alloy formulations have been reported, for example, using Shi Xi (Si) as a main component instead of being added to brass alloys, such as TW421674, US7354489, US20070062615, US20060078458, US2004023441, etc. 111287 3 201102445 square, but the disadvantages of these prior art techniques are poor machinability. In addition, 'lead-free copper alloy formulations such as CN10144045 reveal aluminum, tantalum and phosphorus as the main alloying elements. Although they can be used for casting, they have poor machinability and are far less efficient than lead brass. They are not suitable for mass production; CN101285138 and CN101285137 disclose Phosphorus is the main alloying element, but it is prone to cracks, pinching and the like when it is used for casting. Or, there is also a literature in which bismuth (Bi) is used as a main component instead of lead added to brass alloys, for example, US7297215, US6974509, US6955378, US6149739, US5942056, US5653827, US5487867, US5330712 > US20060005901, US20040094243, US5637160, US20070039667, etc. The cerium content of the above alloy formulation covers a range of about 0.5 wt% to 7 wt%, and each has a different elemental composition and a specific ratio in addition to the filament. Moreover, US6413330 discloses a lead-free copper alloy formulation containing silver, bismuth and other components, and CN101440444 also discloses a high-zinc bismuth-free brass alloy. However, due to its high strontium content but low copper content, the alloy has poor fluidity. In the metal mold, it is more difficult to refill the cavity and it is easy to produce insufficient defects. CN101403056 discloses a lead-free brass alloy in which lead and manganese are replaced by lead. However, the high bismuth content is liable to cause defects such as cracks and slag inclusions, while the low manganese content is high in hardness, is not easily broken, and has poor machinability. Because of its scarce resources and high price, replacing lead with a higher amount of lead will result in too high manufacturing cost of lead-free brass, which is not conducive to commercialization. Moreover, the above brass alloy formulations still have poor casting properties, and (4) embrittlement has not been effectively improved. 111287 4 201102445 In addition, there are also literatures on the process of lead-free copper alloys or lead-washing processes. Improvements, for example, US 5,904,783 discloses the treatment of sodium and potassium metals at high temperatures. Brass alloys are used to reduce the filtration of lead to the feed liquid; TW491897 discloses a method for the production of brass alloys containing 1-2.6 wt%; however, The conventional lead-washing process can only reduce lead precipitation on the surface in contact with water when the lead-containing product is immersed in water, and cannot reduce the lead content in the raw material component to less than 0.3 wt%. SUMMARY OF THE INVENTION In view of the above, the object of the present invention is to develop a low-lead brass alloy material and to improve the process. To achieve the above and other objects, the present invention provides a low-vessel environmentally friendly brass alloy comprising: 〇.〇5 to 0.3% by weight (wt%) of the error (pb); 0.3 to 0.8% by weight of aluminum (A1) 0.01 to 重量·4% by weight of bismuth (Bi); 〇] to 0.15% by weight of a trace element; and more than 97.5% by weight of copper (Cu) and zinc (Zn), wherein the copper is in the low-error yellow steel The content in the alloy is up to 70% by weight. In one aspect, the total content of copper and zinc contained in the low-lead yellow steel alloy of the present invention is from 97.5 to 99.54 wt%', preferably 98 wt% or more. In the sadness, the copper content is the low mistake! The total weight of the steel alloy is 5 8-70 wt%. Copper in this range provides good toughness and good processability. In a preferred embodiment, the steel content is preferably 62-65 wt% in the low-lead brass alloy of the present invention, and the lead content is 〇〇5 〇3 Wt%. In the preferred embodiment, the lead content is 〇 1 〇 25 wt%, more preferably 111287 5 201102445 is 0.15-0.25%. In the low-lead brass 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 the right amount of hydrazine can increase the fluidity of the copper water and improve the casting properties of the alloy material. In the low-lead brass alloy of the present invention, the content of the niobium is 0.4 wt% 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. The trace element of 0.1-0.15 wt% contained in the low-lead brass alloy of the present invention may be a rare earth element and/or an unavoidable impurity, wherein the rare earth element includes lanthanum, cerium, lanthanum, lanthanoid, and the like. The rare earth elements may be used singly or in combination. Adding an appropriate amount of rare earth elements (such as garnish (Ce)) can strongly refine the as-cast microstructure of the alloy material, and can change the relative amount of the <2, yS phase and the crystal morphology after recrystallization annealing. And can form particulate impurities with elements such as lead, thereby improving the distribution of impurities in the alloy material, and improving the physical properties and processing properties of the alloy. In one aspect, the rare earth element is a decoration having a content of 0.1 to 0.15 wt%. The low-lead brass alloy of the present invention comprises phosphorus (P) of 0.8 wt% or less. In a preferred embodiment, the phosphorus content is from 0.4 to 0.8 wt%. Adding an appropriate amount of phosphorus can improve the fluidity of the melt and improve the weldability of copper and alloys. Phosphorus has a large solid solubility in copper, and the surface energy of CuP is low, so that the surface tension of copper can be lowered, and the ruthenium is precipitated in the form of particles. In the present invention, Bi is substituted for Bi in order to maintain the easy cutting performance of brass. The Pb phase is a face-centered cubic lattice with a lattice constant of 4.949x10_1Qm, 6 111287 201102445
Pb在Cu之固溶度均極小，因此，Pb在Cu合金中常以單 質相之方式存在。Bi相為菱方晶格，晶格常數為4.7457X 10 1()m ’晶車由間爽角a =57 14.2’ ’ Cu於Bi在固態基本上 均不互溶，因此，少量Bi就會在組織中出現單獨之Bi相。 B i常呈連續之脆性薄版分佈在育銅晶界上，既產生熱脆 性，又產生冷脆性。Bi偏析於晶界之兩種機制，如第8圖 所示。 造成B i偏析於晶界之機制疋由兩種數學模型來解 _釋，第8A圖係由麥克林模式（McLean Model)及霍氏模式 (Hofmann-ErteweinModel)來解釋其機制。第8A圖為體 積擴散之模型，原理為Bi原子藉由從塊材擴散至晶界，即 為一般s忍知之非克定律（Fick s Law );第8B圖可由位錯 管擴散模式（Dislocation-pipe diffusion Model)來解釋其 機制，原理為液態Bi先流入差排’而差排如同輸送管將液 態Bi送進晶界，為差排擴散機制。此兩種擴散機制，後者 鲁擴散速度為前者之105倍。當Bi析出由差排擴散機制主 導，此機制主導則會造成（Cu)固體溶液+L(液態Bi)雙相區 產生，造成所謂之薄膜狀Bi產生，材料之脆裂性大幅提 升。為改善此狀況，當溫度降至75〇ΐ以下時，採用加速 冷卻之方式，使雙相區之差排擴散消失，則Bi不會呈薄膜 偏析至晶界，將可避免材料脆裂之產生。 於本發明中，藉由進一步加入磷元素至該黃鋼合金配 方以減y汽鋼合金的表面張力。使黃銅合金的異相之間夾 角之表面張力與同相之間夾角之表面張力的比值趨近於 111287 7 201102445 0.5，若雙面角（dihedral angle)大於60度，則使該黃銅合金 配方中之Bi形成顆粒狀Bi析出。從而提高該合金材料之 切削性，不致於產生鑄造缺陷。 於一態樣中，本發明之低鉛黃銅合金係包括：〇.〇5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0.15重量％之微量元素（即，稀土元素及/ 或不可避免之雜質）；0.8 wt%以下之磷；以及98至99.54 重量％之銅與鋅，其中，該銅於該低錯黃銅合金中之含量 為58至70重量％。 於一態樣中，本發明之低錯黃銅合金係包括62-65 wt % 之銅、0.05-0.25 wt% 之錯、0.5-0.75 wt% 之I呂、0.2-0.3 wt %之麵、0.8 wt%以下之填（且紹與構之總含量為1.4 wt %以下）、0.1-0.15 wt%之鈽及餘量鋅，且不可避免之雜質 含量係為0.1 wt%以下。 依據本發明之目的，本發明提供一種低鉛黃銅合金之 物件之製造方法，係包括下列步驟： (a) 將該低鉛黃銅合金及回爐料預熱至400°C至500 °C ； (b) 將該低鉛黃銅合金及該回爐料熔解至沸騰以形成 熔解銅液； (c) 將模具預熱至200°C後，將砂芯置於該模具中； (d) 將該熔解銅液澆鑄至該模具中，其中，該澆鑄之 溫度介於1010至1060°C之間；以及 (e) 將所得到之鑄件脫模。 8 111287 201102445 本發明之方法可復包括製備該砂芯之步驟，係將選自 - 由粒徑為40至7〇目、50至100目及70至140目之圓型 - 砂所組成群組之—種或多種圓型砂、樹脂以及固化劑予以 混合而製備砂芯，其中，該樹脂係為尿醛樹脂及/或呋喃樹 脂。用於本發明方法之砂芯必須充分乾燥，以降低氣孔缺 陷0 於一態樣中，該回爐料於預熱前係經洗紗處理，俾以 移除砂及鐵線。 於一態樣中，本發明之步驟(1))之無鉛銅錠及回爐料之 重量比為6.1至9:1，較佳之無鉛銅錠及回爐料之重量 比為6 : 1至8 : 1，更佳為7 : 1。 本發明之步驟(b)可復包括添加精鍊清渣劑’其中，該 精鍊清渣劑於添加前係先預熱至4〇(rc以上。於一實施例 中，該精鍊清_之添加量係為無錯賊及回爐料之總重 之（U-0.5 wt%，較佳為〇.15_〇 3㈣，更佳為〇 2㈣。The solid solubility of Pb in Cu is extremely small. Therefore, Pb is often present as a single phase in Cu alloy. The Bi phase is a rhombohedral lattice, and the lattice constant is 4.7457X 10 1()m 'The crystal car has a resilience angle of a =57 14.2' 'Cu. Bi is basically immiscible in the solid state. Therefore, a small amount of Bi will be in A separate Bi phase appears in the tissue. B i is often distributed in a continuous brittle thin plate on the copper grain boundary, which produces both hot brittleness and cold brittleness. Bi is the mechanism of segregation in the grain boundary, as shown in Figure 8. The mechanism that causes Bi to segregate at the grain boundary is solved by two mathematical models. The 8A map is explained by the McLean model and the Hofmann-Ertewein Model. Fig. 8A is a model of volumetric diffusion. The principle is that Bi atoms diffuse from the bulk to the grain boundary, which is the general s-negative Fick s Law; the 8th graph can be distorted by the dislocation tube (Dislocation- Pipe diffusion Model) to explain the mechanism, the principle is that the liquid Bi first flows into the difference row' and the difference is like the delivery tube sends the liquid Bi into the grain boundary, which is a diffusion mechanism. These two diffusion mechanisms, the latter, are 105 times faster than the former. When Bi precipitation is dominated by the differential diffusion mechanism, this mechanism dominates the (Cu) solid solution + L (liquid Bi) two-phase region, resulting in the so-called film-like Bi generation, and the brittleness of the material is greatly increased. In order to improve this condition, when the temperature drops below 75 ,, the accelerated cooling is used to make the difference between the two-phase regions disappear, and Bi does not segregate to the grain boundary, which will avoid the occurrence of brittle cracking of the material. . In the present invention, the surface tension of the yoke steel alloy is reduced by further adding a phosphorus element to the yellow steel alloy formulation. The ratio of the surface tension between the opposite phases of the brass alloy to the surface tension between the in-phase angles is close to 111287 7 201102445 0.5, and if the dihedral angle is greater than 60 degrees, the brass alloy formulation is made Bi forms a granular Bi precipitate. Thereby, the machinability of the alloy material is improved without causing casting defects. In one aspect, the low-lead brass alloy of the present invention comprises: 〇. 5 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 0.15% by weight of a trace element (ie, a rare earth element and/or an unavoidable impurity); a phosphorus of 0.8 wt% or less; and 98 to 99.54 wt% of copper and zinc, wherein the content of the copper in the low-loss brass alloy is 58 Up to 70% by weight. In one aspect, the low-error brass alloy of the present invention comprises 62-65 wt% copper, 0.05-0.25 wt% error, 0.5-0.75 wt% Ilu, 0.2-0.3 wt% face, 0.8. The wt% or less (and the total content of the structure is 1.4 wt% or less), 0.1-0.15 wt% of the niobium and the balance zinc, and the unavoidable impurity content is 0.1 wt% or less. In accordance with the purpose of the present invention, the present invention provides a method for producing a low lead brass alloy article comprising the steps of: (a) preheating the low lead brass alloy and the recycled material to 400 ° C to 500 ° C; (b) melting the low-lead brass alloy and the recycled material to boiling to form a molten copper liquid; (c) after preheating the mold to 200 ° C, placing the sand core in the mold; (d) The molten copper solution is cast into the mold, wherein the casting temperature is between 1010 and 1060 ° C; and (e) the resulting casting is demolded. 8 111287 201102445 The method of the present invention may further comprise the step of preparing the sand core, which is selected from the group consisting of - round-shaped sand having a particle size of 40 to 7 mesh, 50 to 100 mesh, and 70 to 140 mesh. The sand core is prepared by mixing one or more kinds of round sand, a resin and a curing agent, wherein the resin is a urea resin and/or a furan resin. The sand core used in the method of the present invention must be sufficiently dried to reduce the porosity defect in a state in which the material is subjected to yarn washing before preheating to remove sand and iron wire. In one aspect, the weight ratio of the lead-free copper ingot and the recycled material of the step (1) of the present invention is 6.1 to 9:1, and preferably the weight ratio of the lead-free copper ingot to the recycled material is 6:1 to 8:1. More preferably 7: 1. The step (b) of the present invention may further comprise adding a refining slag agent, wherein the refining slag agent is preheated to 4 〇 or more before being added. In one embodiment, the refining amount is added. It is the total weight of the error-free thief and the recycled material (U-0.5 wt%, preferably 〇.15_〇3 (four), more preferably 〇2 (four).
於該步驟(b)巾，該精鍊清_可為—次添加或分次添加。 於柄月之步驟⑹中’炫解銅液之洗鎮可為重力洗 鎮。對於步驟⑷之洗鎢溫度需維持於胁腦。c。針對 該洗每步驟’其中，該潘德 ^ a&曰—& Λ澆鉍你从抵次的方式進行，且該澆 以及澆鑄之時間為3至 鑄之洗鑄置母次約1至2公斤， 秒0 *日:本方法中’該脫模係於完成該澆鑄後10至 不呈現紅熱狀態下進行。於較佳實施例 中，元成餘之麵件係以自然降溫冷卻。 9 111287 201102445 本發明之方法可復包括於步驟(e)後，冷卻該模具，使 該模具之溫度維持在180至220°C之間；以及清理模具（例 如以壓縮空氣吹淨模具表面），將少許石墨水噴塗於模具表 面（例如以噴霧器噴灑），以供下一次澆鑄使用。 於一態樣中，係以石墨水冷卻該模具，進行方式係將 該模具係浸入該石墨水中3至8秒。該石墨水之溫度較佳 為維持於25-40°C之間，而石墨水之比重係為1.02-1.10。 【實施方式】 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内容暸解本 發明之其他優點與功效。 於本說明書中，除非另有說明，否則低鉛黃銅合金所 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。 本案發明人發現，當以習知高含量之鉍（1 wt%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 成錢之液態薄膜，最後於晶界偏析而產生連續片狀的叙：， 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0.4 wt%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 10 111287 201102445 及應用上極具優勢。 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0.05-0.3 wt%，符合對於與水接觸之管線 材料之錯含量之國際規定。因此，依據本發明之低錯黃銅 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。 於實施例中，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0.15重量％之微量元素（即，稀土元素及/或不可 避免之雜質）稀土元素及不可避免之雜質；以及97.5至 99.54重量％之銅與鋅，其中，該銅於該低錯黃銅合金中 之含量為58至70重量％。 以下，將以例示性實施例詳細闡述本發明。 實施例1 : 在此較佳實施例1中，本發明之低鉛黃銅合金之成分 ^ (單位為重量百分比）如下：In the step (b), the refining _ may be added in time or in portions. In the step (6) of the stalk month, the washing of the copper liquid can be used for gravity washing. The temperature of the tungsten washing in step (4) needs to be maintained in the brain. c. For each step of the washing, the Pand ^ a & 曰 - & Λ Λ 铋 铋 铋 铋 从 从 从 从 从 从 从 从 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , Kilograms, seconds 0 *day: In the present method, the demolding is carried out 10 after completion of the casting to a state where no red heat is present. In the preferred embodiment, the surface of the element is cooled by natural cooling. 9 111287 201102445 The method of the present invention may be further included in step (e), cooling the mold to maintain the temperature of the mold between 180 and 220 ° C; and cleaning the mold (for example, blowing the mold surface with compressed air), A small amount of graphite water is sprayed onto the surface of the mold (for example, sprayed with a sprayer) for the next casting. In one aspect, the mold is cooled with graphite water by immersing the mold in the graphite water for 3 to 8 seconds. The temperature of the graphite water is preferably maintained between 25 and 40 ° C, and the specific gravity of the graphite water is between 1.02 and 1.10. [Embodiment] The embodiments of the present invention are described by way of specific examples, and those skilled in the art can understand the other advantages and effects of the present invention from the disclosure of the present disclosure. In the present specification, unless otherwise stated, the components contained in the low-lead brass alloy are based on the total weight of the alloy and expressed in weight percent (wt%). The inventors of the present invention found that when a high content of niobium (1 wt% or more) is added to a brass alloy, microscopically, a liquid film of money is easily formed in the crystal grains of the brass alloy, and finally segregated at the grain boundary. Producing a continuous sheet-like shape: shielding the grain boundary, causing the mechanical strength of the alloy to collapse, which increases the hot brittleness and cold brittleness of the alloy, causing cracking of the material. However, according to the low-lead brass alloy formulation of the present invention, only 0.4 wt% or less of niobium 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 an advantage in commercial production of 10 111287 201102445 and application. 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 the faulty content of pipeline materials in contact with water. Therefore, the low-error 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. In an 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 lanthanum; 0.1 to 0.15% by weight of trace elements (ie a rare earth element and/or an unavoidable impurity) a rare earth element and an unavoidable impurity; and 97.5 to 99.54% by weight of copper and zinc, wherein the copper is contained in the low-error brass alloy in an amount of 58 to 70% by weight. . Hereinafter, the present invention will be described in detail by way of illustrative embodiments. Example 1: In the preferred embodiment 1, the component (in terms of weight percent) of the low-lead brass alloy of the present invention is as follows:
Cu ： 62.51Cu : 62.51
Zn ： 35.72Zn : 35.72
Pb ： 0.177 Bi ： 0.154 A1 ： 0.478 P ： 0.52 Sn ： 0.183Pb : 0.177 Bi : 0.154 A1 : 0.478 P : 0.52 Sn : 0.183
Ce ： 0.114 11 111287 201102445 經過掃描式電子顯微鏡（Scanning electron microscopy，SEM)和 X-ray 能譜儀（Energy Dispersive Spectrdmeter，EDS)分析依此製得之環保鑄造黃銅試片之 形貌、成分以及形成機制，其結果如第1圖、第2圖及表 1所示。於第2圖之電顯圖中，A點為α相，銅含量較高， 並於晶粒内部具有少量鉍；Β點為^相，鋅含量較高，一 般不含鉍；以及C點為晶界，有較多的鉍於此處析出，形 成易斷屑軟質點，可提高材料切削性能。該低鉍無鉛黃銅 試片之A、Β、C點之成分分析如表」所示。 表1、能譜分析結果（原子百分比） A( a ) B(/3) C Cu 63. 03 51. 91 61. 09 Zn 24. 31 42. 87 35.1 Bi 〇. 09 0 2. 37 Pb 〇. 25 0. 17 0. 04 A1 〇. 67. 0. 53 0. 1 P 8. 01 1. 76 0. 26 試驗例1 : 於相同製程及相同操作條件下，分別以本發明之低鉛 頁銅合金（實施例2_4)、鉍無鉛黃銅（比較例丨·#)、H59 錯頁銅（比較例5-6)、及高磷含量之鉛黃銅（比較例7) 為材料進行相同之產品鑄造，並比較各合金之加工特性 及各階段之製程良率’其中，製程良率定義如下所示： 12 111287 201102445 生產良率-良品數/全部產品數χ1〇〇〇/〇 • 製程之生產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。 表2、產品試作統計表 ----- 高磷含 項目 絲無金 〗黃銅 鉛黃銅 量船黃 銅 本發明之低船黃銅 比較 比較 比較 比較 比較 比較 比較 實施 實施 實施 ----- 例1 例2 例3 例4 例5 例6 例7 例2 例3 例4 Cu含量 實測(％) 62.48 62.57 63.01 61.96 61,5 61.1 62.29 63.35 61.12 62.51 A1含量 ^¾%)^ 0.513 0.556 0.563 0.555 0.607 0.589 0.537 0.515 0.531 0.524 Pb含量 實測(％) 0.0075 0.0042 0.0067 0.0047 1.47 1.54 0.117 0.182 0.151 0.143 Bi含量 tm%) 0,762 0.549 0.312 0.147 0.0119 0.0089 0.125 0.117 0.149 0.116 p含量實 0.0024 0.0083 0.0074 0.0041 0.0002 0.0002 0.947 0.435 0.584 0.721 鱗造 良率 71% 78% 85% 88% 96% 95% 83% 93% 92% 92% 機加 良率 84% 82% 81% 77% 99% 99% 97% 98% 99% 97% 抛光良 率 89% 88% 90% 91% 92% 94% 94% 96% 95% 95% 總良率 53.1% 56.3% 62.0% 61.7% 87.4% 88.4% 75.7% 87.5% 86.5% 84.8% 13 111287 201102445 由表2可知，以無船叙黃銅為材料進行產品鑄造時， 所得產品之鑄造缺陷較多，故產品之生產總良率低於70 %，且鉍含量越高則良率越低。觀察以完全無鉛之鉍黃銅 為材料的鑄件的主要缺陷為：氣孔、夾渣、裂紋、澆不飽、 縮鬆，具有該等缺陷之不良品占全部不良品的72%。具體 而言，無錯錢黃銅之溶解銅液之流動性差，且對模具之填 充性差，鑄件易產生澆不飽的狀況；鑄件容易產生裂紋， 一些微小裂紋到最後拋光階段才能被發現；鑄件易發生夾 潰和氣孔的現象；且完全無錯的银黃銅切削性較差，容易 產生振刀、粘刀等問題，造成後續機械加工的良率偏低。 而依據本發明之低鉛黃銅為原料之試作組，良率最好 (可達90%以上），其材料流動性接近習知之H59鉛黃 銅，對鑄造工藝進行優化後，在鑄件凝固時形成具有低脆 裂敏感度成等軸樹枝狀晶相組織，在保障切削性的同時， 又不易產生裂紋等缺陷，使材料完全可以滿足生產之需 求。其中，由於高含量的鱗易使黃銅合金產生鑄造缺陷， 並降低良率，因此，本發明之低鉛黃銅之磷含量不宜超過 0.8%。另外，本發明之低錯黃銅之财钱性也較比較例1及 2之高鉍無鉛銅顯著改善。 試驗例2 : 將黃銅材料之試片於光學金相顯微鏡下檢視材料之 組織分佈，其放大100倍之結果如第3圖所示。 貫施例1之低錯黃銅之成分貫測值為Cu . 63 ·35 wt %、A1 : 0.515 wt %、Pb : 0.182 wt %、Bi : 0.117 wt %、P : 14 111287 201102445 0.435 wt %。其組織分佈如第3A圖所示，會形成等軸樹枝 狀晶相組織，因晶粒呈樹枝狀相，會使材料較易斷屑而可 . 提供良好切削性；又具有低脆裂敏感度，故不易產生裂紋 等缺陷。 第3B圖為比較例1之組織分佈，鉍無鉛黃銅主要成 分之實測為：Cu : 62.48 wt %、A1 : 0.513 wt %、Pb : 0.0075 wt %、Bi : 0.762 wt %、P : 0.0024 wt %。鉍含量高時，會 造成異質成核點多且成核速率快，而α相組成過冷越大， 鲁形成的晶粒多呈現枝蔓臂形狀且極少呈塊狀。因此，鉍會 於晶界偏析而產生連續片狀的鉍，使得材料的機械強度潰 散、熱脆性及冷脆性提高，而易造成材料開裂。 第3C圖則為比較例6之組織分佈，Η59鉛黃銅主要 成分之實測值為：Cu : 61.1 wt %、Α1 : 0.589 wt %、Pb : 1.54 wt %、Bi : 0.0089wt %、P : 0.0002 wt %。合金 α:相 圓粒狀形態，有良好的韌性，不易產生裂紋等缺陷。 • 其中，比較例1之高紐無船黃銅試片在鑄造後發生自 然開裂，試片之開裂情況如第4Α圖所示，於立體顯微鏡 下之觀察結果係如第4Β圖所示，鉍含量較高者，易沿著 晶界方向產生較大之裂隙，而降低機械強度。 試驗例3 . 以實施例3及比較例4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》標准進行。腐蝕實驗前用酚醛樹臘鑲樣·使 其暴露面積為100 mm2，所有試片均經過600#金相砂紙研 15 111287 201102445 磨平整，並用蒸餾水洗淨、烘乾。試驗溶液為現配的以之 CuCl2溶液’試驗溫度為75±2<t。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 微鏡觀祭’結果如第5圖所示。 、 比較例4之低鉍無鉛黃銅（Bi:0.147%)之平均脫辞深 度為324.08mm，如第5A圖所示。本發明之低鉛黃鋼 (Bi:0.149%)之平均脫鋅深度為125 36mm，如第5B圖所 示。上述結果證實本發明之低鉛黃銅之抗脫鋅腐蝕性 試驗例4 : 依照IS06998-1998《金屬材料室溫拉伸實驗》標準進 行育銅合金之機械性能測試，結果如下表3所示： 表3、 機械性能 ~Ί H竹 抗 拉強义 (Mpa) 伸長率（％) 1 2 3 4 5 平均 1 2 3 4 5 ----, 平均 實施 例1 372 358 349 367 375 364.2 15 14 11 12 10 —,! J 12.4 比較 例5 356 337 363 374 367 359.6 12 11 13 13 12 12.2 從表3可知，本發明之低鉛黃鋼合金的抗拉強度和伸 長率與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，確實可以取代H59鉛黃鋼 而用於製造產品。 H1287 16 201102445 試驗例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4所示： 表4、 元素 上限之 標準值 (ug/L) 比較例 5 比較例5 (經洗鉛處理） 實施例1 鉛 5. 0 19. 173 0. 462 0. 281 银 50. 0 0. 011 0. 006 0. 023 鋁 5. 0 0. 093 0. 012 0. 146 如表4所示，本發明之低船黃銅之各金屬析出量皆低 於上限標準值，符合NSF 61-2007a SPAC之要求。且本發 明之低錯黃銅在重金屬錯的析出量更明顯低於H5 9錯黃銅 之析出量，亦低於經過洗錯處理的H5 9錯黃銅，更符合環 保要求，且有利於人體健康。 試驗例6 . 分別以實施例1之低鉛黃銅、比較例1之鉍無鉛黃 銅、及比較例5之H5 9錯黃銅在車床上進行切削性測試。 切削性測試之條件設定為進刀量為2 mm，轉速為950 rpm，進給量0.21 mm/rev，結果如第6圖及表5所示。。 17 111287 201102445 表 項目 比較例1 比較例5 1# 2# 1# 816J2 100. 54 切削能u(N/mm2) 979. 84 998. 32 809. 93 切削阻 力 Ff (N) 178.34 162.49 95.47 Fp(N) 42. 72 37.23 23.31 -----—. 21.72 Fc(N) 349. 31 336. 89 212.97 231.83 切削形態 捲曲狀’屬於連續 切屑 ----— 針狀，崩碎切屑Ce : 0.114 11 111287 201102445 The morphology and composition of environmentally-friendly cast brass test pieces obtained by Scanning electron microscopy (SEM) and X-ray energy dispersive spectrometer (EDS) were analyzed. The formation mechanism is shown in Fig. 1, Fig. 2, and Table 1. In the electric map of Fig. 2, point A is α phase, copper content is high, and there is a small amount of ruthenium inside the grain; Β point is ^ phase, zinc content is high, generally does not contain bismuth; and point C is At the grain boundary, there are more defects deposited here, which form a soft point that is easy to break and can improve the cutting performance of the material. The composition analysis of the A, Β, and C points of the low-lead lead-free brass test piece is shown in the table. Table 1. Results of energy spectrum analysis (atomic percent) A( a ) B(/3) C Cu 63. 03 51. 91 61. 09 Zn 24. 31 42. 87 35.1 Bi 〇. 09 0 2. 37 Pb 〇. 25 0. 17 0. 04 A1 〇. 67. 0. 53 0. 1 P 8. 01 1. 76 0. 26 Test Example 1: Under the same process and the same operating conditions, respectively, the low lead copper of the present invention Alloy (Example 2_4), bismuth-free lead-free brass (Comparative Example 丨·#), H59-lead copper (Comparative Example 5-6), and lead-brass with high phosphorus content (Comparative Example 7) The same product was used for the material. Casting, and comparing the processing characteristics of each alloy and the process yield at each stage', the process yield is defined as follows: 12 111287 201102445 Production yield - number of good products / total number of products χ 1 〇〇〇 / 〇 • Production of process The yield is reflected in the quality stability of the production process, and the quality is stable - the higher the quality - to ensure normal production. Table 2, product trial statistics table ----- high phosphorus containing project silk no gold〗 brass lead brass volume boat brass The low ship brass of the present invention is comparatively comparatively comparative implementation implementation ----- - Example 1 Example 2 Case 3 Case 4 Case 5 Case 6 Case 7 Case 2 Case 3 Case 4 Cu content measured (%) 62.48 62.57 63.01 61.96 61,5 61.1 62.29 63.35 61.12 62.51 A1 content ^3⁄4%)^ 0.513 0.556 0.563 0.555 0.607 0.589 0.537 0.515 0.531 0.524 Pb content measured (%) 0.0075 0.0042 0.0067 0.0047 1.47 1.54 0.117 0.182 0.151 0.143 Bi content tm%) 0,762 0.549 0.312 0.147 0.0119 0.0089 0.125 0.117 0.149 0.116 p content 0.0024 0.0083 0.0074 0.0041 0.0002 0.0002 0.947 0.435 0.584 0.721 Scale yield 71% 78% 85% 88% 96% 95% 83% 93% 92% 92% Machine plus yield 84% 82% 81% 77% 99% 99% 97% 98% 99% 97% Polished Rate 89% 88% 90% 91% 92% 94% 94% 96% 95% 95% Total yield 53.1% 56.3% 62.0% 61.7% 87.4% 88.4% 75.7% 87.5% 86.5% 84.8% 13 111287 201102445 From Table 2 It can be seen that when the product is cast from the shipless brass, the product is produced. The casting defects more, so the total production of the product yield less than 70%, and the bismuth content the higher the lower the yield. The main defects of the castings which are made of completely lead-free bismuth brass are: pores, slag inclusions, cracks, insufficient filling, shrinkage, and defective products with such defects account for 72% of all defective products. Specifically, the fluidity of the dissolved copper liquid of the error-free brass is poor, and the filling property of the mold is poor, and the casting is liable to cause insufficient filling; the casting is prone to cracks, and some micro cracks can be found until the final polishing stage; It is prone to pinch and pores; and the silver-brass with no error is inferior in machinability, which is prone to problems such as vibrating knives and sticking knives, resulting in low yield of subsequent machining. According to the low-lead brass of the present invention, the yield is the best (up to 90%), and the material fluidity is close to the conventional H59 lead brass. After the casting process is optimized, when the casting is solidified. The formation of equiaxed dendritic crystal structure with low brittle fracture sensitivity, while ensuring machinability, is not easy to produce cracks and other defects, so that the material can fully meet the production needs. Among them, since the high content of scales easily causes casting defects in the brass alloy and lowers the yield, the phosphorus content of the low-lead brass of the present invention should not exceed 0.8%. In addition, the money of the low-error brass of the present invention is also significantly improved compared to the high-grade lead-free copper of Comparative Examples 1 and 2. Test Example 2: The test piece of the brass material was examined under the optical metallographic microscope for the microstructure distribution of the test piece, and the result of magnification was 100 times as shown in Fig. 3. The composition of the low-error brass of Example 1 was Cu. 63 · 35 wt %, A1 : 0.515 wt %, Pb: 0.182 wt %, Bi: 0.117 wt %, P : 14 111287 201102445 0.435 wt %. Its tissue distribution, as shown in Figure 3A, will form an equiaxed dendritic phase structure. Because the crystallites are dendritic, the material will be more easily broken and can provide good machinability and low brittle fracture sensitivity. Therefore, defects such as cracks are less likely to occur. Fig. 3B is the tissue distribution of Comparative Example 1, and the main components of the lead-free brass are: Cu: 62.48 wt%, A1: 0.513 wt%, Pb: 0.0075 wt%, Bi: 0.762 wt%, P: 0.0024 wt % . When the content of strontium is high, it will cause more heterogeneous nucleation sites and faster nucleation rate, while the α phase composition is too cold, and the grains formed by Lu are mostly in the shape of branch arms and rarely block. Therefore, niobium segregates at the grain boundary to produce a continuous sheet-like flaw, which causes the mechanical strength of the material to collapse, the hot brittleness and the cold brittleness to be improved, and the material is easily cracked. The 3C graph is the tissue distribution of Comparative Example 6, and the measured values of the main components of Η59 lead brass are: Cu: 61.1 wt%, Α1: 0.589 wt%, Pb: 1.54 wt%, Bi: 0.0089 wt%, P: 0.0002 Wt %. Alloy α: The phase is round and granular, has good toughness, and is not susceptible to cracks and other defects. • Among them, the high-rise non-ship brass test piece of Comparative Example 1 naturally cracks after casting, and the cracking of the test piece is as shown in Figure 4, and the observation under the stereo microscope is as shown in Figure 4, 铋The higher the content, the larger the crack along the grain boundary direction, and the lower the mechanical strength. Test Example 3. Dezincification tests were carried out using the brass alloys of Example 3 and Comparative Example 4 to examine the corrosion resistance of brass. The dezincification test was carried out in accordance with the Australian AS2345-2006 "copper alloy anti-dezincification" standard. Before the corrosion test, the phenolic wax was mounted and the exposed area was 100 mm2. All the test pieces were ground through 600# metallographic sandpaper 15 111287 201102445, and washed and dried with distilled water. The test solution was a ready-to-use CuCl2 solution. The test temperature was 75 ± 2 < t. The test piece and the CuCl2 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 the digital phase electron microscope was used to observe the result. Figure 5 shows. The average unpeeled depth of the low-lead unleaded brass (Bi: 0.147%) of Comparative Example 4 was 324.08 mm, as shown in Fig. 5A. The low lead yellow steel of the present invention (Bi: 0.149%) has an average dezincification depth of 125 36 mm as shown in Fig. 5B. The above results confirmed the anti-dezincification corrosion test of the low-lead brass of the present invention. Example 4: The mechanical properties of the copper-plated alloy were tested in accordance with the IS06998-1998 "Metal Material Room Temperature Tensile Test" standard, and the results are shown in Table 3 below: Table 3, Mechanical Properties ~ Ί H Bamboo Tensile Strength (Mpa) Elongation (%) 1 2 3 4 5 Average 1 2 3 4 5 ----, Average Example 1 372 358 349 367 375 364.2 15 14 11 12 10 —,! J 12.4 Comparative Example 5 356 337 363 374 367 359.6 12 11 13 13 12 12.2 As can be seen from Table 3, the tensile strength and elongation of the low lead yellow steel alloy of the present invention are comparable to those of H59 lead brass, indicating The low-lead brass alloy of the present invention has mechanical properties equivalent to that of H59 lead brass, and can be used for manufacturing products instead of H59 lead yellow steel. H1287 16 201102445 Test Example 5 · According to NSF 61-2007a SPAC single product metal allowable precipitation standard. Test to verify the metal precipitation of brass alloy in the environment in contact with water Test results are shown in Table 4 below: 4. Standard value of element upper limit (ug/L) Comparative Example 5 Comparative Example 5 (Lead-washed treatment) Example 1 Lead 5. 0 19. 173 0. 462 0. 281 Silver 50. 0 0. 011 0. 006 0. 023 Aluminium 5. 0 0. 093 0. 012 0. 146 As shown in Table 4, the metal precipitation of the low ship brass of the present invention is lower than the upper limit standard and meets the requirements of NSF 61-2007a SPAC. Moreover, the amount of precipitation of the heavy metal in the low-error brass of the present invention is significantly lower than that of the H5 9-brown brass, and is also lower than that of the H5 9-brown brass which has been subjected to the mishandling treatment, which is more environmentally friendly and beneficial to the human body. health. Test Example 6. The machinability test was carried out on a lathe by the low-lead brass of Example 1, the lead-free yellow copper of Comparative Example 1, and the H5 9-br or brass of Comparative Example 5, respectively. The machinability test conditions were set to an infeed amount of 2 mm, a rotational speed of 950 rpm, and a feed rate of 0.21 mm/rev. The results are shown in Fig. 6 and Table 5. . 17 111287 201102445 Table item comparison example 1 Comparative example 5 1# 2# 1# 816J2 100. 54 Cutting energy u(N/mm2) 979. 84 998. 32 809. 93 Cutting resistance Ff (N) 178.34 162.49 95.47 Fp(N 42. 72 37.23 23.31 -----.. 21.72 Fc(N) 349. 31 336. 89 212.97 231.83 Cutting shape curled 'belongs to continuous chips----- needle-like, chipping chips
於切削性測試中，在轴向（Ff)、徑向（Fp)、法向（Fc) 三方向之切削阻力以鉍無鉛黃銅為最大，而本發明之低鉛 黃銅與習知H59鉛黃銅比較接近。切削能亦以鉍無鉛黃銅 為最大，而本發明之低鉛黃銅與習知H59鉛黃銅比較接近。 另外’從第6圖之可知，H59鉛黃鋼因為鉛以軟質點 形式瀰散分佈在黃銅基體上，故切屑呈崩碎粒狀或針狀， 切削性好（第6B圖）；本發明之低鉛黃銅切屑（第6C圖） 與H59錯黃鋼切屑類似；而鉍無鉛黃銅（第6A圖）切屑 呈片狀，切削性差。 由上述各試驗例可證實，鉍無鉛黃銅材料切削性較習 知H59錯黃鋼差’且容易產生振刀、粘刀等問題，造成後 續機械加工的良率偏低，不適合作為取代鉛黃銅之合金。 且以秘無錯黃鋼材料製作產品時，鑄件容易產生夾渣、氣 孔及裂紋’且裂紋常須至拋光階段才能被發現，且生產成 18 111287 201102445 本較高，因此，不利於產業應用。 本發明之低鉛黃銅合金具有與H59鉛黃銅相當之機 械性能（例如切削性），甚至更優異於習知H5 9錯黃銅（例 如抗拉強度及深長性）；在鑄造產品之製程良率、機械加工 良率亦為良好；且本發明之低鉛黃銅合金大幅降低鉛析出 量，極適合作為取代習知錯黃銅之合金材料。 試驗例7 · 以本發明之環保鑄造黃銅製備水龍頭之製程如第7圖 鲁所示。 首先以40-70目、50-100目及70-140目之圓型砂、尿 酸樹脂、°夫B南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小時内 使用完畢，否則需以烘箱烘乾。 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°C以上，再將兩者以重量比為7 : 1之比例以感 φ應爐進行熔煉，待該黃銅合金達到一定的熔融狀態（下稱 炼解銅液），進行分析取樣銅合金試塊，並用直讀式光譜儀 器進行成分分析，確認銅合金化學成分符合要求後，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°C之間。 於澆鑄過程中，為了避免溫度變化過大，每次投料量 以1-2 kg為宜，澆鑄時間控制在3-8秒内，如此可減少鑄 造缺陷。每次投料後清理熔解銅液表面和澆勺，目視檢查 熔解銅液表面以避免過多雜質漂浮，檢查澆勺以避免過多 19 111287 201102445In the machinability test, the cutting resistance in the axial (Ff), radial (Fp), and normal (Fc) directions is the largest in the lead-free brass, while the low-lead brass of the present invention and the conventional H59 lead Brass is closer. The cutting energy is also the largest in the lead-free brass, and the low-lead brass of the present invention is relatively close to the conventional H59 lead brass. In addition, as can be seen from Fig. 6, H59 lead yellow steel is dispersed in the form of soft spots on the brass base, so the chips are broken or acicular, and the machinability is good (Fig. 6B); Low-lead brass chips (Fig. 6C) are similar to H59 yellow-steel steel chips; while 铋 lead-free brass (Fig. 6A) chips are sheet-like and have poor machinability. It can be confirmed from the above test cases that the machinability of the lead-free brass material is worse than that of the conventional H59 yellow steel, and it is easy to cause problems such as vibrating knives and sticking knives, resulting in low yield of subsequent machining, and is not suitable as a substitute for lead yellow. Copper alloy. When the product is made of the secret-free yellow steel material, the casting is prone to slag inclusions, pores and cracks, and the cracks are often found until the polishing stage, and the production is higher than 18 111287 201102445, which is not conducive to industrial applications. The low-lead brass alloy of the present invention has mechanical properties (e.g., machinability) comparable to those of H59 lead brass, and is even superior to conventional H5 9-brown brass (e.g., tensile strength and depth); The yield and the mechanical processing yield are also good; and the low-lead brass alloy of the present invention greatly reduces the amount of lead precipitation, and is highly suitable as an alloy material for replacing the misplaced brass. Test Example 7 The process for preparing a faucet from the environmentally-friendly cast brass of the present invention is shown in Fig. 7. Firstly, 40-70 mesh, 50-100 mesh and 70-140 mesh round sand, uric acid resin, °fu B-resin and curing agent are used as raw materials to prepare sand cores by core shooting machine and the resin is measured by gas generating tester. Gas production. The resulting sand core must be used within 5 hours, otherwise it should be dried in an oven. The low-lead brass alloy and the recycled material of the present invention are preheated for 15 minutes to make the temperature reach 400 ° C or higher, and then the two are smelted in a ratio of 1:1 by weight to the furnace. The alloy reaches a certain molten state (hereinafter referred to as copper smelting solution), and the copper alloy test block is analyzed and sampled, and the component analysis is performed by a direct reading spectroscopy instrument. After confirming that the chemical composition of the copper alloy meets the requirements, the metal gravity casting machine is used with the sand. The core and the recast mold are cast and controlled by a temperature monitoring system to maintain the casting temperature between 1010-1060 °C. In the casting process, in order to avoid excessive temperature changes, it is advisable to feed 1-2 kg each time, and the casting time is controlled within 3-8 seconds, thus reducing casting defects. Clean the molten copper surface and the pouring spoon after each feeding, visually inspect the molten copper surface to avoid excessive impurities floating, check the pouring spoon to avoid excessive 19 111287 201102445
氧i化物附著。甚4皇W 辩件為鋼模，於洗鑄5-8模後淮并κ 理爐渣作業，若+ 误便進订一次清 ^ 為銅松鑄件則以20模為一次。 每板鱗件取出後，以 乾淨，噴石Ε於描’诉心頭位置 、* 、权具表面後再行浸水冷卻。用以冷卻桓且 之石墨水之痒1、，A » ? P挨八 ，皿度以、准持於3〇_36。〇為宜，並於 以比重計測量石墨水潔 澆鑄則 、主 辰度，使其控制在比重1.05〜1.06之 3並‘理水㈣之㈣，以減 石墨水係以中央β#丄 丨辦职該 、“卩錄集+冷卻，再通過管道將冷卻水 刀配至各重力澆鑄機水 卻效果。 [财再_具以水槽*達到冷 ^具冷卻凝固後開模卸料清理Μ口，監測模具溫 ^使具溫度控制在·_22代中並形成鑄件，隨後進 亍铸件脫_⑽彳叫須嚴格遵守輕拔輕放，避輯件在红 熱狀態下被損壞。 ' …待感應爐中炼解鋼液全部洗鑄完畢後，將冷卻的鑄件 進行自檢並送人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 的内應力）。將坯件進行後續機械加工及拋光，俾使鑄件内 腔不附有砂、金屬屑或其他雜質。再進行坯件全封閉，在 水中試驗殼體密封和隔板密封性檢驗。最後經過品檢分析 及檢驗分類入庫。 通過本製程’將無鉛銅重力鑄造生產從6M(Man、 Machine ' Material' Method ' Measurement' Mother Nature) 角度進行全面考量，將溫度，時間等生產條件進行嚴格的 111287 20 201102445 規範，使得各項異變因數都得到有效的控制。將產品發生 * 的不良狀況減少到最低。 . 綜上述，本發明低鉛黃銅合金可改善材料之鑄造性 能，具有良好韌性，切削性佳，不致於產生鑄造缺陷，可 達到習知鉛黃銅所具備之材料特性，俾利於合金材料應用 鵪 於後續製程。且本發明低鉛黃銅合金材料不易產生裂紋或 夾雜等缺陷，並可大幅降低鉍用量，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。 • 另外，利用本發明之製程可提高無鉛黃銅產品之產率 及良率。 上述實施例僅例示性說明本發明之低鉛黃銅合金與 其物件製備方法，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。 Φ 【圖式簡單說明】 第1圖係為本發明低鉛黃銅自熔解之液態凝固之示意 圖； 第2圖係為本發明低鉛黃銅試片於掃描式電子顯微鏡 (SEM)下之微觀形貌(morphology)及用X-ray能譜儀（EDS ) 對微觀區域元素成分進行定量分析。 第3A圖係為本發明低鉛黃銅試片之金相組織分佈； 第3B圖係為鉍無鉛黃銅試片之金相組織分佈； 第3C圖係為H59鉛黃銅試片之金相組織分佈； 21 111287 201102445 第4A圖係為鉍無鉛黃銅試片之材料開裂情況； 第4B圖係為鉍無鉛黃銅試片之裂紋放大圖； 第5A圖係為鉍無鉛黃銅試片之抗脫鋅腐蝕測試之金 相組織分佈， 第5B圖係為本發明低鉛黃銅試片之抗脫鋅腐蝕測試 之金相組織分佈； 第6A圖係為鉍無鉛黃銅之切屑； 第6B圖係為H59鉛黃銅之切屑； 第6C圖係為本發明低鉛黃銅之切屑； 第7圖係為製造本發明之低鉛黃銅之產品之製程示意 圖；以及 第8A及8B圖係說明合金中之鉍偏析於晶界之機制。 【主要元件符號說明】 無。 22 111287The oxygen oxide is attached. The 4th Emperor W is a steel mold. After the 5-8 mold is washed and cast, the slag is processed. If the fault is +, the order is cleared once. For the copper loose casting, the 20 mold is used once. After each scale is taken out, it is cleaned, and the stone is sprayed on the surface of the heart, and the surface of the right arm is immersed in water. It is used to cool the itch of graphite water 1, A » ? P 挨 eight, the degree of the dish, and the standard is held at 3 〇 _36. 〇 is suitable, and the graphite is cleaned and casted by the specific gravity meter, and the main brightness is controlled to be 3 in the specific gravity of 1.05~1.06 and 'Lishui (4) (4), to reduce the graphite water system to the central β# The job, "卩 集 + + cooling, and then through the pipeline to the cooling water knife to the gravity casting machine water but the effect. [财再_ With the sink * to achieve cooling ^ mold cooling and solidification after the mold discharge uncleaning mouth, Monitor the temperature of the mold so that the temperature is controlled in the _22 generation and form the casting, and then the casting is removed. _(10) The squeaking must strictly follow the light pull and the escaping piece is damaged in the red hot state. After all the molten steel in the medium-smelting solution is completely cast, the cooled castings are self-tested and sent to the sand cleaning machine for cleaning the sand. Then, the blank processing (heat treatment of the casting blank (clearing stress annealing) is performed to eliminate the casting Internal stress generated). The blank is subjected to subsequent machining and polishing, so that the inner cavity of the casting is not attached with sand, metal scraps or other impurities. Then the blank is completely closed, and the seal of the casing and the seal of the separator are tested in water. Inspection. Finally, after quality inspection analysis and inspection Class warehousing. Through the process of 'lead-free copper gravity casting production from the perspective of 6M (Man, Machine 'Material ' Method ' Measurement ' Mother Nature), the temperature, time and other production conditions are strictly 111287 20 201102445 specifications, making All the variable factors are effectively controlled. The adverse conditions of product occurrence* are minimized. In summary, the low-lead brass alloy of the present invention can improve the casting property of the material, has good toughness, and has good machinability. Casting defects can be achieved to achieve the material characteristics of the conventional lead brass, which is beneficial to the application of the alloy material in subsequent processes. The low-lead brass alloy material of the present invention is less prone to cracks or inclusions, and can greatly reduce the amount of bismuth. Effectively reducing the production cost of low-lead brass alloys, which has great advantages for commercial mass production and application. • In addition, the process of the present invention can improve the yield and yield of lead-free brass products. The above embodiments are merely illustrative. The invention discloses a low-lead brass alloy of the present invention and a method for preparing the same, and is not intended to limit the present invention. The above embodiments may be modified and changed without departing from the spirit and scope of the present invention. Therefore, the scope of the present invention is as set forth in the appended claims. Φ [Simple description of the drawings 1 is a schematic diagram of liquid solidification of the low-lead brass self-melting solution of the present invention; FIG. 2 is a micromorphology of the low-lead brass test piece of the present invention under a scanning electron microscope (SEM) and The X-ray energy spectrometer (EDS) was used to quantitatively analyze the elemental composition of the microscopic region. Fig. 3A is the metallographic structure distribution of the low lead brass test piece of the invention; Fig. 3B is the unleaded brass test piece of the bismuth Metallographic structure distribution; 3C is the metallographic structure of H59 lead brass test piece; 21 111287 201102445 Fig. 4A is the material cracking condition of 铋 lead-free brass test piece; Figure 4B is 铋 lead-free brass The crack of the test piece is enlarged; the 5A is the metallographic structure of the anti-dezincification test of the lead-free brass test piece, and the 5B is the anti-zinc corrosion test of the low-lead brass test piece of the invention. Metallographic organization distribution; Figure 6A is 铋 lead-free Brass chip; Fig. 6B is the chip of H59 lead brass; Fig. 6C is the chip of the low lead brass of the invention; Fig. 7 is a schematic view of the process for manufacturing the low lead brass product of the invention; And Figures 8A and 8B illustrate the mechanism by which the ruthenium in the alloy segregates at the grain boundaries. [Main component symbol description] None. 22 111287