TWI609974B - 新穎產物及彼等之用途 - Google Patents

新穎產物及彼等之用途 Download PDF

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TWI609974B
TWI609974B TW102145979A TW102145979A TWI609974B TW I609974 B TWI609974 B TW I609974B TW 102145979 A TW102145979 A TW 102145979A TW 102145979 A TW102145979 A TW 102145979A TW I609974 B TWI609974 B TW I609974B
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powder
metal
alloyed
mns
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西爾立 卡默斯
賽納德 迪達
歐威 瑪斯
菲利浦 沙柏
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好根那公司
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Abstract

本發明係關於一種欲用於金屬部件之表面塗覆的新穎預合金化金屬基粉末。該粉末係利用例如雷射披覆或轉移式電漿電弧焊接(PTA)，或熱噴霧(例如HVOF)而沈積。該粉末可用於減少該沈積塗層之摩擦及改進其減耗性。該等塗層亦可改進切削性。就減摩或減耗組分而言，可在該預合金化粉末中使用硫化錳或硫化鎢內含物。

Description

新穎產物及彼等之用途
本發明係關於一種欲用於金屬部件之表面塗覆的新穎預合金化金屬基粉末。該粉末係利用例如雷射披覆或轉移式電漿電弧焊接(PTA)，或熱噴霧(例如HVOF)而沈積。該粉末可用於減少該沈積塗層之摩擦及改進其減耗性。該等塗層亦可改進切削性。就減摩及減耗組分而言，可在該預合金化粉末中使用硫化錳或硫化鎢內含物。
熱表面加工(即熱噴塗及堆焊粉料)係廣泛用於組件表面之塗覆以抵抗磨耗及腐蝕。已知Fe-、Ni-及Co-基料根本上改進曝露於磨耗及/或腐蝕之組件的壽命。然而，仍然存在需要改進組件壽命的大量應用。此外，Ni及Co在全球市場上之高價格及有限的可利用性亦需要更長壽命改進。最後，新穎塗覆沈積法(例如雷披射覆、冷噴霧及高速噴霧)之發展開啟合金化、塗覆法之更精密控制及更高自動化的新可能性，因此需要其他類型的粉末。
一種改進摩擦及磨耗性之潛在途徑可為在熱表面加工料中併入固體潤滑劑，使得該沈積塗層包括減摩及減耗物質，同時維持可接受水平的抗腐蝕性及硬度。
固體潤滑劑為可減少兩個表面之間相對彼此滑動的摩擦及磨耗而無需液體介質的軟固相材料。視為固體潤滑劑的材料需要滿足至少下列標準：黏附接觸表面-黏著性：低剪切強度-低固有摩擦；低硬度- 低磨蝕度及對於預定環境之熱化學穩定性。固體潤滑劑之實例為滑石、石墨、硫化錳(MnS)、二硫化鉬(MoS2)或二硫化鎢(WS2)。固體潤滑劑之使用可提供以下優勢：在極低或極高溫度下的穩定性；在極端環境(諸如冷或熱環境，或具有高輻射水平的環境)下的穩定性；機械設計問題(更輕設計，低臨界速度)或可攜帶極端的負載。
長久以來，於熱表面加工中使用固體潤滑劑已成為棘手問題，原因在於大量固體潤滑劑為金屬硫化物且即使焊縫中之微量的硫亦可導致斷裂及/或腐蝕。
Skarvelis等人；ASME J.Tribol.132(2010)031302-1-031302-8,Surf.& Coat.Techn.203(2009)1384-1394，及Trib.Int.42(2009)1765-1770描述MnS粉末與金屬粉末混合的用途及在(例如)PTA(轉移式電漿電弧焊接)中使用所得粉末混合物。
然而，固體潤滑劑可具有高摩擦係數(與油或油脂相比)；當不可更新時固體潤滑劑膜之有限的磨耗壽命；無或有限的冷卻性能(與油或油脂相比)，或具有碎屑或殘留顆粒引起堵塞的傾向。
出人意料地，發明者已注意到，當以內含物形式存在於預合金化金屬粉末中時，固體潤滑劑展示比當該固體潤滑劑以粉末組分形式存在於粉末混合物中時更佳的潤滑效果。本發明係關於一種經固體潤滑劑(例如MnS或WS2)預合金化之金屬粉末，及該金屬粉末於塗覆基板表面的用途。根據本發明利用固體潤滑劑的主要益處在於曝露於磨耗及/或腐蝕之組件的更長壽命。
圖1 藉由利用與金屬合金粉末預混合之MnS-粉末製造之塗層的摩擦係數(COF)及磨耗。
圖2 藉由利用具有MnS內含物之預合金化金屬粉末製造之塗層的 摩擦係數(COF)及磨耗。
圖3 經1525-30 SP570+5% MnS預合金化之粉末之顆粒的SEM顯微圖。深灰色區域為包含MnS之內含物。
圖4 板上之滑塊磨耗。不鏽鋼板上之滑塊摩擦接觸、正常負載10N、滑動速度0.36m/s、乾燥(未經潤滑)。Y軸顯示摩擦係數，及X軸顯示滑動距離。
本發明者已表明硫化錳MnS為一種適宜的固體潤滑劑。結果表明與金屬粉末預合金化之Mn及S具有減摩及減耗的潛力。經Mn及S預合金化之粉末尤其相當適合用於焊接披覆法，諸如雷射披覆或PTA。此外，熱噴霧，例如火焰噴霧、HVOF、HVAF、冷噴霧、電漿噴霧等亦可為適宜的應用。與不含固體潤滑劑內含物之金屬合金相比，自具有MnS內含物之預合金化金屬粉末製得之合金化料之切削性未改變，該切削性係經由平面研磨測試而評定。
文中之所有百分比為重量%。
在一個態樣中，本發明提供一種包括硫化錳(MnS)或硫化鎢(WS2)內含物之預合金化金屬粉末的組合物。如文中所使用，術語「預合金化」表示金屬粉末(其粉末顆粒具有例如MnS及/或WS2內含物(即Mn及/或W及S))已在製備預合金化粉末時被併入熔體中。
適合根據本發明之用途的金屬粉末合金一般基於鎳、鐵或鈷。
因此，本發明之一個實施例為一種預合金化鎳基金屬粉末合金的組合物，其包含下列或由其組成：C，0.05-0.4%；Si，2.0-3.1%；B，0.6-1.5%；Cr，2.6-3.6%；Fe，1.2-2.5%；Al，0.2-0.7%；MnS內含物，4-15%；餘量為Ni。
本發明之另一實施例為一種預合金化鈷基金屬粉末合金的組合物，其包含下列或由其組成：C，0.05-0.4%；Si，2.0-3.1%；B，0.6- 1.5%；Cr，2.6-3.6%；Fe，1.2-2.5%；Al，0.2-0.7%；MnS內含物，4-15%；餘量為Co。
本發明之另一實施例為一種預合金化鐵基金屬粉末合金的組合物，其包含下列或由其組成：C，1-1.3%；Cr，22-27%；Mn，4-5%；Ni，3-5%；Si，3-4%；Mo，1.5-2.5%；MnS內含物，4-15%；餘量為Fe。
本發明之另一實施例為一種預合金化鎳基金屬粉末合金的組合物，其包含下列或由其組成：C，0.05-0.2%；Si，2.2-2.9%；B，0.8-1.3%；Cr，2.8-3.45%；Fe，1.4-2.3%；Al，0.3-0.5%；MnS內含物，4-15%；餘量為Ni。
本發明之另一實施例為一種預合金化鈷基金屬粉末合金的組合物，其包含下列或由其組成：C，0.05-0.2%；Si，2.2-2.9%；B，0.8-1.3%；Cr，2.8-3.45%；Fe，1.4-2.3%；Al，0.3-0.5%；MnS內含物，4-15%；餘量為Co。
本發明之另一實施例為一種預合金化鐵基金屬粉末的組合物，其包含下列或由其組成：C，1.2%；Cr，25%；Mn，4.5%；Ni，4%；Si，3.3%；Mo，2%；MnS內含物，4-15%；餘量為Fe。
在一個實施例中，呈內含物形式之MnS及/或WS2的含量為4-8重量%，或5-8重量%。
該預合金化鎳、鐵或鈷基粉末較佳係藉由包括Mn或W、S及選自由C、Si、B、Cr、Fe、Al、Ni、Co及V組成之群的其他合金元素的熔體的水或氣體霧化而製造。
該預合金化粉末合金的粒度一般為10μm至800μm，或10μm至200μm，或較佳為15-150μm，或50-150μm。
該固體潤滑劑(例如MnS或WS2)係呈內含物形式存在。此等內含物係藉由將該固體潤滑劑(例如MnS或WS2)本身添加至熔融金屬而製 造，或者，可將FeS與適量FeMn混合及接著添加至熔融金屬。
在一個態樣中，本發明提供一種藉由沈積技術(諸如雷射披覆或PTA(轉移式電漿電弧)；熱噴霧法(諸如HVOF(高速氧燃料噴霧)、HVAF(高速乙炔燃料噴霧)或電漿噴霧))；或藉由漿液法(諸如離心鑄造)，以上述金屬粉末表面塗覆金屬部件的方法。
在一個實施例中，本發明提供根據以上之用途，其中該金屬粉末包含4-10%，或4-8%，或5-7重量%之MnS或WS2作為內含物。
在另一態樣中，本發明亦提供藉由上述製造且適合藉由用於機械中之乾摩擦接觸的本發明粉末塗覆的金屬部件，諸如例如工業閥門、金屬薄板成形(SMF)工具、鐵廠中之輸送輥、裁紙刀，及玻璃模子。
實例
實例1
預合金化粉末之製法
按如下方式製備一種金屬粉末；一種具有以下組成的金屬粉末：C，0.05-0.2%；Si，2.2-2.9%；B，0.8-1.3%；Cr，2.8-3.45%；Fe，1.4-2.3%；Al，0.3-0.5%；MnS，4-15%；餘量為Ni，其係藉由使包含該等含量之以上元素的熔體霧化而製備。所得粉末包含MnS作為金屬合金基質中之內含物。此粉末在文中表示為「粉末A」。
實例2
藉由在普通粉末混合器中混合具有下列組成的預合金化金屬粉末與5重量% MnS粉末來完成預混合粉末的製備：C，0.05-0.2%；Si，2.2-2.9%；B，0.8-1.3%；Cr，2.8-3.45%；Fe，1.4-2.3%；Al，0.3-0.5%。此粉末在文中表示為「粉末B」。
實例3
藉由利用PTA之沈積之粉末施加
按如下方式將預合金化或預混合粉末施加至測試樣本；藉由其中參數經設置以容許稀釋5-15%之PTA(轉移式電漿電弧)將粉末A沈積在S235JRG(基礎結構鋼)基板上。
實例4
在與基板熔合之前，用手將粉末B鋪散在基板上。
實例5
亦可藉由雷射披覆將本發明粉末施加至基板。固體潤滑劑(MnS)內含物出現在來自粉末A及粉末B之塗層中。來自粉末A之塗層比彼等來自粉末B者似乎產生更精細的MnS內含物尺寸。
實例6
磨耗測試
進行磨耗測試，且表明粉末A於金屬表面塗層或包層中之有益效果。樣本為硬面矩形塊，其中該基體金屬為常用的低碳結構鋼(EN S235 JRG，ASTM A570 Gr.36)且該表面層在成品測量中至少為1mm厚。該測試表面具有藉由雙平面研磨製得之表面粗糙度Ra為0.3-0.4μm的精磨加工。計數器
Figure TWI609974BD00001
60/CR100 x 17環係由AISI 316L(EN X2CrNiMo17 12 2)或AISI 304L(EN X2CrNi19-9)不鏽鋼製造。摩擦測試為未經潤滑的(即乾燥的)，且在測試之前，藉由乙醇仔細清潔測試樣本及去油脂。磨耗測試係類似於標準ASTM G77中所述之測試。最大測試赫茲(Hertzian)接觸壓力為180MPa，角速度為0.36m/s及總滑動距離為594m。
實例7
板上之滑塊磨耗測試
進行板上之滑塊磨耗測試，且表明粉末A於金屬表面塗層或包層中之有益效果。樣本為圓柱形環
Figure TWI609974BD00002
50/CR5 mx 10mm，其中該基體金屬為常用的低碳結構鋼(EN S235 JRG，ASTM A570 Gr.36)且該表面層 在成品測量中至少為0.5mm厚。該測試表面具有藉由雙OD研磨製得之表面粗糙度Ra為0.3-0.4μm的精磨加工。計數器板1000 x 1000 x 1.5mm係由AISI 316L(EN X2CrNiMo17 12 2)不鏽鋼製造。摩擦測試為未經潤滑的(即乾燥的)，且在測試之前，藉由乙醇仔細清潔測試樣本及去油脂。正常測試負載為10N，滑動速度為0.36m/s及總滑動距離為3m。結果顯示於圖4中。
實例8
腐蝕測試
根據ISO 16701，進行鹽噴霧腐蝕測試的結果。在12、15、30及39天之後的各間隔中巨觀照相該等部件。然後，完成SEM(掃描式電子顯微術)研究。來自粉末B之塗層在39天之後顯示50μm銹堆陣列。在12天結束時，辨識到銹引發。來自粉末A之塗層出現類似的銹類型，但銹堆的數目少得多，且此等之尺寸更小。利用圖像分析軟體(諸如Adobe Photoshop)，藉由使SEM-微型圖像素化可完成結果之量化。

Claims (8)

  1. 一種預合金化金屬粉末，其包含下列或由其組成：C，0.05-0.2%；Si，2.2-2.9%；B，0.8-1.3%；Cr，2.8-3.45%；Fe，1.4-2.3%；Al，0.3-0.5%；MnS內含物，4-15%；餘量為Ni，該粉末係適用於熱表面加工。
  2. 一種預合金化金屬粉末，其包含下列或由其組成：C，0.05-0.2%；Si，2.2-2.9%；B，0.8-1.3%；Cr，2.8-3.45%；Fe，1.4-2.3%；Al，0.3-0.5%；MnS內含物，4-15%；餘量為Co，該粉末係適用於熱表面加工。
  3. 一種預合金化金屬粉末，其包含下列或由其組成：C，1.2%；Cr，25%；Mn，4.5%；Ni，4%；Si，3.3%；Mo，2%；MnS內含物，4-15%；餘量為Fe，該粉末係適合用於熱表面加工。
  4. 如請求項1至3中任一項之預合金化金屬粉末，其中該MnS之含量為4-8重量%，或5-7重量%。
  5. 如請求項1至3中任一項之預合金化金屬粉末，其具有45μm至200mm或50至150μm之粒度。
  6. 一種表面塗覆金屬部件的方法，其係藉由雷射披覆或PTA(轉移式電漿電弧)之方式，利用如請求項1至5中任一項之預合金化金屬粉末，因而製造經金屬塗覆之組件。
  7. 一種經金屬塗覆之組件，其係藉由如請求項6之方法製造。
  8. 如請求項7之經金屬塗覆之組件，其中該組件係選自由工業閥門、金屬薄板成形(SMF)工具、鐵廠中之輸送輥、裁紙刀及玻璃模子組成之群。
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