最新镁合金制造技术手册(繁).doc

最新鎂合金製造技術手冊 林順藍編著2001年8月28日目 錄一、 鎂合金的發展史第2頁二、 ASTM-B275鎂合金命名規則 第3頁 三、 AZ91D之三演變 第3頁四、 各種規格性能表之應用（美國ASTM有關鎂合金材料的規範）第412頁五、 鎂合金鑄件成形方法第1319頁六、 機械制程與模具控制第2025頁七、 各種技術參數及作業安全第2627頁八、 NB鎂合金壓鑄件主要訴求與問題對策 第2829頁九、 提升鎂合金產品良品率之秘訣第30頁十、 鎂合金後處理制程第3136頁十一、 鎂合金清洗步驟流程 第37頁十二、 X-835鹼性脫脂清洗液 第38頁十三、 X-695酸性清洗液 第39頁十四、 X-24皮膜處理液第40頁十五、 X-2000皮膜處理液第41頁十六、 藥水管理 第42頁十七、 藥水自動監控系統 第43頁十八、 藥劑使用量計算 第44頁十九、 藥劑使用量及補給 第45頁二十、 塗料特性及應用 第46頁二十一、 粉體特徵(1)(2)(3)第47頁二十二、 粉體塗料編號 第48頁二十三、 粉體塗料色板 第49頁二十四、 環保廢水處理 第50頁二十五、 測試標準 第51頁二十六、 模具界的革命溶射塗層之應用 第5256頁一、 鎂合金的發展史：德國是一次大戰前鎂合金的唯一生產國，最早用於軍事用途。由於軍用規格的嚴格要求，才促成鎂合金在新合金製造技術及設計產品技術上有極大的進展。在軍事用途的考量中往往只考慮性能，較少考慮成本，而于民生用途不只須考慮性能也必須考慮成本的競爭。民生應用始於美國及法國的研究發展，目前美、英、法、挪威、義大利、德國、日本和俄國、經過40餘年的應用發展對於鎂合金應用可達成合理性能及成本都有相當的瞭解，尤其近年後來居上的中國大陸，由於白雲石礦含高量磷鎂礦產豐富，給於優勢，是主要世界上的供應國。鎂的提煉：一是海水(鹽水)電解法成本較高、純度較好中國雲海及挪威海德魯是典型代表。二是皮江法mgco2+caco3 11001300 mgo+cao+co2將白雲石破碎成適度塊狀送入回轉窖煆燒溫度為11001300成鍛白再與矽鐵粉、熒石粉、混勻經微機配料混勻球磨，立壓成球狀包裝入還原管罐中，在11501200高溫真空下還原，週期10小時反映成為：Mgo+Cao+SiCasio+mg（粗鎂）鎂呈蒸汽狀成爐料中逸出，於還原罐前端冷卻器成冷凝結晶成粗鎂。粗鎂再精煉鑄錠表面即得之。大致上 1.Mgoco3+Caco3白雲石1214T(噸) 2.無煙煤C(煤炭)1012T(噸) 3.Fe/si矽鐵及熒石1.21.5T(噸)以上1-3項可提煉1T(噸)鎂所需的主要材料依據IMA彙整世界需求2003年預估需求50萬8000噸壓鑄38%輕金屬延壓34.3%脫硫用12.9%。在壓鑄用途中汽車部門將擴大需求、電動車及輕量化省油的期待下，下世紀代汽車公共開發（簡稱PNGV）皆積極的朝耐衝撞性能提高零件輕量化邁進此乃趨勢。二、 ASTM-B275鎂合金命名規則A E Q I D ASTM登記序號區分主要 合金元素含量相同之不同合金 主要合金元素 次要元素 主要合金元素 次要合金元素鋁ALUMINUM 鋅EINC 含量百分比 含量百分比 合金元素略號 A-第1種標準成分 Q-Silver A-Aluminum B-第2種標準成分 S-Silicon E-Rare Eartt C-第3種標準成分 E-Eine H-Thorium D-高純度合金 K-Eirconium E-高抗蝕性合金 M-Eirconium XI-未在ASTM登記合金三、 AZ9ID之演變Mg合金中AL，ZN是重要合金，AZ91-91之意思即A19%ZN1%的成分含量存在於Mg合金錠，因此才有AZ91名稱之產生後發展初期依序AZ91A，AZ91B，AZ91C等，用於輕型構造物中。早期是以砂模鑄造厚件之構件，然後依據使用範圍的增加，即要求抗腐蝕能力耐氧化程度及形狀較複雜的薄件而發展出AZ91D及AZ91HP（High purity）之產生。時到今日各種鑄件廠所面臨的共同問題(一)超薄件1.0m/m的生產、產品強度和耐蝕能力，(二)良品率的提升，(三)低雜值及氣孔產生。三大問題其實有方法的，只是業者沒抓到要點。首先在鎂合金技術領域，CL的控制氯的含量在鎂合金冶煉過程因助溶劑和造渣劑的添加造成氯含量的存在，而CL又是無法以光譜分析儀能檢驗出來的非金屬元素，因此AZ91D或AZ91HP規範中加入CL的含量控制及CU，Ni，Fe,控制皆為重要控制因素，各大精煉廠莫不對此下很大功夫。然而機械設備製造商流程忽略了一點鍋材鎳的反映為什麼Thxomolding在非半固態，成型較熱室、冷室好的原因下，因與螺管壁反映時間較短，但停頓下來比熱室嚴重許多，且螺筒及螺杆損耗更利害。如螺杆及筒壁材質上鎳含量更多，滯留殘量之鎂合金更久，則越造成不良更多。其實半固態成型要達成薄件要看物件結構否則也是難達成所需，所以溫度一直提高到630多以上才能成型，解決之道業者應趕快噴塗一層高溫陶磁層以杜絕熱金屬反應氣體產生以外，依據美國四、 美國ASTM有關鎂合金材料的規範（英文原文） Designation Standard Specifiation for Magnesium-Alloy Die CastingsThis standard is issued under the fixed designation B94: the number immediately following the designation indicates the year of original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates year of last reapproval. A superseript epsilon indicates an editorial change since the revision or reapproval.1. Scope*1.1 This specification covers magnesium-alloy die castings. Four alloy compositions are specified. Designated as shown in Table 1.21.2 The values stated in inch-pound units are standard The SI values in parentheses are provided for information only.2. Referenced Documents2.1 The following documents of the issue in effect on date of order acceptance form a part of this specification to the extent referenced herein:2.2 ASTM Standards.B93/B93M Specification for Magnesium Alloys in Ingot Form for Sand Castings. Permanent Mold Castings, and Die Castings3.1.This specification is under the jurisdiction of ASIM Committee B-7on Light Metals and Alloys. And is the direct responsibility ofSubcommittee B07.04 on Magnesium Alloys Cast and Wrought Products.Current edition approved Feb.15.1994. Published April 1994.Originally Published as B94-34 T. Last Previous edition B94-93.2.SAE specifications No.501 and 501 A conform to the requirements for Alloy AZ91A and AZ91B respectively.3. Terminology3.1 Definition:3.1.1 die casting-a metal object produced by the introduction of moltenmetal under substantial pressure into a metal die and characterizedby a hight degree of fidelity to the die cavity.TABLE Chemical RequirementsA.B.C.DElementcompositionUNS M10600(Alloy AM60A)UNS M1041(Alloy AM41)UNS M10412(Alloy AS41B)UNS M11910(Alloy AZ91A)UNS M1191(Alloy AZ91B)MagnesiumAluminumManganeseZincSiliconCopperNickelIron.maxOther metallicImpuritiesmax.eachRemainder5.5-6.50.13-0.60.220.500.350.03Remainder3.5-5.00.20-0.500.120.50-1.50.060.03Remainder3.5-5.00.35-0.7E0.120.50-1.50.020.0020.0035E0.02Remainder8.3-9.70.13-0.500.35-1.00.500.100.03Remainder8.3-9.70.13-0.500.35-1.00.500.350.03UNS M11916(Alloy AZ91D)UNS M10602(Alloy AM60B)UNS M10500(Alloy AM50A)MagnesiumAluminumManganeseZincSiliconCopperNickelIron.maxOther metallicImpuritiesmax.eachRemainder8.3-9.70.15-0.05E0.35-1.00.100.0300.0020.005E0.02Remainder5.5-6.50.24-0.6E0.22max0.100.0100.0020.005E0.02Remainder4.4-5.40.26-0.6E0.220.100.0100.0020.004E0.02A. Analysis shall regularly be made only for the elements specifically mentioned in this table. If however, the presence of other elements is suspected or indicated in the course of routine analysis further analysis shall be made to determine that these other elements are not in excess 0.3%.B. The following applies to all specified limits in this table: For purposes of acceptance and rejection an observed value or a calculated value obtained from analysis should be rounded to the nearest unit in the last right-hand place of figures used in expressing the specified limit in accordance with the rounding procedure prescribed in Section 3 of Practice E 29.C. Where single units are shown these indicate the maximum amounts permitted.D. ASTM alloy designations were established in accordance with Practice B 275. UNS designations were established in accordance with Practice E 527.E. In alloys AS41B. AM60B. and AZ91D. if either the minimum manganese limit or the maximum iron limit not met. Then the iron/manganese ratio shall not exceed 0.010. 0.015. 0.021. and 0.032.respectively.AEMP公司提供的SSFOD Work方式，生產所得產品之金相及鑄件結構各方面良品率高氣孔少物性好，業者可參考How Does SSFOD WorkNear Net-Shape partSemi-solid slag(Non-Dendritic)Ciguid AlloycooledHigh-PressurrestirredCasting以下附件圖性質單位AZ91DABSHi-HeatPET30%glassPET30%glassNylon30%伸長率 Elongation%316.54.536降服強度 Yield strengthMpa16039152117172抗拉強度Tensile strengthMpa24043193172193彈性模數 Elastic modulesGpa452.18.310.38.9密度 Densityg/cm31.811.071.611.721.38比強度Yield/weight ratio1004310878143吸水性Water absorption%nil0.330.050.070.7熱傳導率Thermal conductiviryW/mk510.280.280.290.33熔點Melting temp598260260260260熱膨脹係數Thermal exp Coeffm/m26.076.527.025.034.5比剛性1007.8212426鎂合金AZ91D與塑膠之機性及物性表壓鑄鎂合金與鋁，鋅合金之物性及機性表 鎂 合 金 鋁 合 金 鋅 合 金性質AZ91D(Mg)AM60B(Mg)A380(AI)(ADC10)Zemak3(Zn)密度 g/cm2(Density)1.81.82.76.6比熱cal/g/(Specific heat)0.250.250.23熱膨脹率m/.m/.20-100(Thermal expansion)26262227.4熱轉道率,cal/cm/ses/(Thermal conducrivity)0.250.250.23熔解範圍. (Melting range)468596（128）540615（75）521588（67）382388（6）潛熱 cal/g(Latent heat)893.72KJ/kg89372KJ/kg9324導電率,% of copper standard(Electric conductivity)11142327制震能力,%,345kg/cm2(Specific damping capacity)2540汽車用、手工具用118抗拉強度, ksi UTS(Ultimate tensile strength)34354841降服強度, ksi YS(Yield strength)233C用、汽車用2224伸長率, %(Elongation)310汽車用、工具310比強度(Strength Y.S. to weight ratio)13139剪力強度, ksi(Shear strength)202731衝擊值, ft-lbs Charpy-unnotched(Impact toughness)511443疲勞強度, ksi Moore 5103cyc(Fartigue strength)14216.9硬度, HB(Hardness Brinell)63618082彈性模數, psiModmus of eiasticity6.51066.510610.3106剪變模數, psi(Shear modulus)2.41062.41063.9106Poissons ratio0.350.350.33潛變強度, ksi, 0.5% strain(Creep strength)100 day.21100 hr. 21100 hr. 93100 hr. 121100 hr. 15020251375202524272321207113.5壓 鑄 常 用 鎂 合 金 的 主 要 成 分合 金 元 素Nimax0.0020.0020.010.010.002Cumax0.0100.020.080.250.030Fe0.0050.00350.005Zn0.22max0.12max0.45-0.90.45-0.90.35-1.0Si0.1max0.5-1.50.20max0.20max0.10maxMn0.24-0.60.35-0.70.15min0.15min0.15-0.5Al5.5-6.53.5-5.08.3-9.78.3-9.78.3-9.7Mgrem.rem.rem.rem.rem.合金系列AM60BAS41BAZ91AAZ91BAZ91D鎂 合 金 的 材 料 特 征AZ-91D Mg合金240160370451713897機械性質抗拉強度（Mpa）降伏強度（Mpa）伸長率%硬度（HB）抗拉彈性係數（Gpa）抗剪扭彈性係數（Gpa）抗剪強度（Mpa）疲勞強度（Mpa）AZ-91D Mg合金595470261.8151（20）170111050（20）373物理性質液相溫度（）固體溫度（）熱膨脹率（um/m.K）密度（g/cm3）熱傳導率（W/m。K）電阻（n。m）導電率（IACS）比熱（(J/kg.K)熔解熱（kJ/kg）AS211.76632420-43526.13701.028410.8AS411.77617420-43526.13701.0268nmAM201.75638420-43526.03701.029413.1AM501.77620420-43526.03701.02659.1AM601.80615420-43526.03701.0261nmAZ91D1.81598420-43526.03701.02516.6Temp.o2020-100202020UnitG/cm3 m/m.KKJ/kgKJ/kg*KW/K*mMS/mPropertyDensityLiquidus tempIncipient melting tempLin.thermal.exp.coeffSpecific heat of fusionSpecific heatThermal conductivityElectrical conductivityAS2117511011094517555AS4121514014064517604AM2019090901245174518AM502101251251045176018AM60225130130845176517AZ91D24016016034517706UnitMpaMpaMpa%GpaGpaHBS1/5JPropertyUltimate TensileTensile YieldCompressive YieldElongationElastic Mod.(Ten.)Elastic Mod. (Shr.)Brinell HardnessImpact Strength(charpy un-notched)THIXO-MOLDING, CHAMBER DIE CAST 與 COLD CHAMBER DIE CAST的比較備註因鑄件不同及充填方案設計不同而有差異COLD CHAMBERDIE CAST0.81155%30秒/SHOT必須作熔煉對策1.9%1.01.2mm0.50.6%650HOT CHAMBERDIE CAST11160%20秒/SHOT必須作熔煉對策1.8%0.70.8mm0.50.6%630THIXO-MOLDING1.811.260%80秒/SHOT無熔煉問題初期USD 50，000每台機台 USD 100，0001.5%0.50.6mm0.4%450機台價格模具價格原料價格成品率週期時間安全對策技術費含氣量（鑄件體積比）平均厚度收縮率射出溫度五、 鎂合金鑄件成形方法目前鎂成形大致分為壓鑄成形及觸變成形（搖溶成形）二種。壓鑄成形是以柱塞等將完全溶融狀態之鎂合金從溶湯射出至模具內的方式，鋁及鎂各種類似金屬合金也可進行。但可分為冷室方式及熱室方式原料則為錠，觸變方式原料為碎片(Chip)置入汽缸內，以螺杆間摩擦熱來進行加熱混煉配合加熱來使其成為溶融狀態觸變後再將其射出至模具內的成形方法。超薄射出溫度已達溶融狀態，其實半固態此處有待爭議。依US A AEMP實驗結果其實半固態真正的成形。無論材質品質各方面是最好的。只要均勻及溫度控制模具條件等控制得當，不良品幾乎沒有。茲將各種方式圖示及比較如下：（以下附圖面）觸變成形機（THHIXO-MOLDING）熱室機（HOT CHAMBER DIE CAST）冷室機（COLD CHANBER DIE CAST）55- -EinsatzDoppeltiegelofen zum Schmelzen, Warmhalten und Dosier von Magnesium-Legierungen, vorwiegend in Druckgie Bereien.Die Anlage ist fur die Fertigung von hochwertigen Mg-GuBteilen im Kaltkammer-DruckgieBverfahren konzipiert.BeschreibungSchmelz- und Warmhalteteil sind raumlich voneinander getrennt, um eine metallurgisch einwandfreie Schmelze- und Temperaturfuhrung zu gewahrleisten.Das trockene Blockmaterial wird durch die pneumatisch betatigte Chargieroffnung manuell oder automatisch zugefuhrt. Das Fullniveau wird im Warmhalteteil pneumatisch abgetastet und als Signal fur den NachchargierprozeB verwendet oder angezeigt. Der Flussigmetalltransport zwischen den Tiegeln erfolgt uber ein Syphonrohr und vermeidet so das Einbringen von ,Sumpf / Schlamm“ in den Warmhalteteil.Hierdurch werden im Warmhalte- und Dosiertiegel Seigerungen verhindert und die grobtmogilche Temperaturkonstanz erreicht.Die Metallentnahme erfolgt durch das Schopfen von Hand oder eine Dosierpumpe.ApplicationDouble crucible furnace for melting, holding and dosing of magnesium alloys, mainly in diecasting foundries.The plant is designed for the production of high quality Mg castings in cold chamber diecasting.DescriptionMelting and holding sections are specifically separated from one another in order to guarantee a metallurgically perfect melt purity and temperature process.The dry ingot material is led through the automized charging door either manually or automatically. The liquid metal level is scanned pneumatically in the holding area and is then indicated or used as a signal for the charging process. The metal transport between the crucibles ensues through a siphon tube and prevents the carry over of ,sump /sludge“ in the holding part. As a result, segregations are avoided in the holding and dosing crucible and a high temperature constancy is obtained.The metal distribition is made through a hand ladie or a dosing pump.Komstruktive MerkmaleGetrennte Schmelz- und Warmhaltezone fur eine metallurglsch einwandfreie Schmelzefuhrung.Sysphonrohr zur oxidtrennenden Metalluberfuhrung vom Schmelz- zum Warmhaltetell.12parallel geschaltete Heizelemente im Schmelzteil und 6 parallel geschaltete Heizelemente im Warmhaltetell sorgen fur eine hohe Verfugharkelt.Der Austall eines Heizelementes vermindert die Leistung nur um 1/12 bzw. 1/6Alle Heizelemente sind von auben leich zuganglich und ohne Tiegelausbau austauschbar.Gute Warmedammung durch Einsata hochwertiger lsollerstoffe.Die Feuerfestzustellung bestent aus lsolier- materialien ohne freies SIOz (Weichisolierstofle mit freiem SiO2 fuhren zu heftigen exothermen Reaktionen bei Beruhrung mit flussigem Magnesium).Mechanische Schraubenpumpe fur die Metall- dosierung alternativ pneumatische Dosierpumpen erhaltlich.Beheizte Dosierrinne mit Schutzgaszufuhrung.Mechanisierte Chargieroffnung fur die Massel zufuhrung in den Schmelztiegel, auch fur eine automatisierte Beschickung geeignet.Technische DatenFassung: 2300kg MgHeizlelstung Schmelzbereich(12 Elemente) 74kwheizeistung Warmhaltebereich(6 Elemente):Elektrische Anschlu Bleistunggesamt 120kvaSchmelz- und Dosledeistung: 215kg/hSpez EnergieverbrauchSchmelzen und Warmhalten: 0.36kwh/kgSpez EnergieverbrauchWarmhalten: 12kwh/hDosiergewichte: 0.55kgMax. Metalltemperatur 720Schutzgas(emptohen): trock Luft(N2)+ Ca. 0.3%SF6Schutzgasverbrauch Schmelz- 500l/hUnd Warmbhaltebereich ca: MischgasAbmessung oa: L=2200,B=1350 H=1600Gewicht ca: 2.5tConstructive CharacteristivcsSeparate melting and holding areas for a perfect metallurgical melt handling process.Siphon tube ton metal transport from melting to holding section with oxide separation.12parallelly connected heating elements in melting section and 6 parallely connected heating elements in holding section provide a high availabllity. The breakdown of one heating eiement reduces the capacity only to 1/12 resp 1/6.All heating elements can be easily reached and replaced from the outside.Good heat insulation through use of high-quality insulating materials.The refractory materials are without free of SiO2- (Soft insulation materials contain free SiO2 and lead to strong exothermal reactions when in contact with liquid magnesium.)Mechanical propeller pump for metal dosing elternatively. Pneumatic dosing pumps available.Heated dosing launders with additional prolective gas supply.Mechanical charging door for the delivery pt ingots into the melting crucible; also suitable for an automized charging.Technical DataCapacity: 2300kg mgHeating capacity melting area(12 elements) 74kwHeating capacity holding area(6 elements): 37kwElectrical connection capacity in total: 120kvaMelting and dosing capacity: 215kg/hSpec energy consumptionmelting and holding: 0.36kwh/kgSpec. Energy consumptionHolding 12kwh/hDosing weights: 0.55kgMax. metal temperature: 720Protective gas (recommended): dry air(N2)+abt0.3% SF6protective gas consumption 500l/h minedmelting and holding area abt: gasDimensions abt: L=2200 B=1350 H=1600Weight abt: 2.5tKaltkammer DrukgieBmaschine Cold chamber diecasting machineMachine a couler sous pression a chamber froideDAK 800SDAK800S DAK800S 六、 機械制程與模具控制首先必須瞭解鎂合金材料特徵及其主要成分如附件（二）物理性質要瞭解以AZ-91D鎂合金液相溫度595固相溫度在470溶解熱373熱膨脹率在26um/m.K密度1.81gcm3熱傳導20時51w/m.k及比熱20時是1050J/kg.K這些資料要記牢，因為溫度對鎂合金來講，控制它非常重要，各元素反應亦得瞭解如下：Ce易氧化腐蝕，造成產品變色發黑Ni易吸熱生鋼成硬點塊，造成加工破裂Si易急聚熱收縮和造成爐溫提高影響偏析形成結構鬆散氣泡增升使製品破損Cu多則吸熱生冷裂，少則吸熱生熱裂Fe加速碎裂外成品雖經皮膜塗處理，依然埋下潛在的氣化腐蝕因數，造成日後生銹脫皮危機。此外尚有接觸的模具，爐體金屬等的化學反應造成的氯化物氣體、氧化物體等添加物及禦制SF6 & SO2氣體等等。內在外在因素要徹底瞭解。其次就制程與模具，以冷室方式COLD CHAMBE DiE CAST鎂錠預熱150去除濕氣，投入爐中方式上入料差異度就有關係了，橫放立放差異也大，關於均勻度主要靠高周波回流熱熔混均，但很慢不符生產所需鎂氣化損耗大，再以Hot Chamber DiE