TWI760567B - 適於熱加工工具的鋼 - Google Patents

適於熱加工工具的鋼 Download PDF

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TWI760567B
TWI760567B TW107135411A TW107135411A TWI760567B TW I760567 B TWI760567 B TW I760567B TW 107135411 A TW107135411 A TW 107135411A TW 107135411 A TW107135411 A TW 107135411A TW I760567 B TWI760567 B TW I760567B
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steel
powder
satisfies
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hardness
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瑟班天 彥傑馬克
克里斯多夫 歐伊倫姆
歐羅夫 托恩伯格
凡卡達 施恩佳 卡拉姆都
理查 歐維爾
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瑞典商伍德赫爾恩股份有限公司
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Abstract

本發明係關於用於製備熱加工工具之鋼,鋼由以下以重量%(wt.%)計的組分組成:
Figure 107135411-A0202-11-0001-1
餘量為視需要選用元素、雜質以及Fe。
本發明亦關於由該合金製備之預合金粉末以及由該粉末製成的AM物件。

Description

適於熱加工工具的鋼
本發明關於適於熱加工工具(諸如模子以及模具)之鋼。特別的是,本發明關於沉澱硬化鋼,其適於製備需要高硬度以及高耐回火性之熱加工工具。
對熱加工應用而言,通常使用不同種類熱加工工具鋼,特別是5% Cr鋼如H11及H13是此類型的優質熱加工工具。Uddeholm DIEVAR®為此類型之優質熱加工工具。它是由ESR製造之高性能鉻鉬釩鋼。它含有如WO9950468 A1所述平衡之碳以及釩含量。
儘管由ESR製造的釩合金工具鋼在諸多性質上相對於習知製造的工具鋼具有更好的性質,但需要進一步改良以降低熱加工工具故障的風險。此外,進一步改良熱加工工具鋼的熱強度及耐回火性會是有利的,以延長使用壽命。
將麻時效鋼(maraging steels)用於熱加工應用亦為習知。麻時效鋼通常為不生鏽的且包括17-7PH、17-4 PH、15-5 PH、PH 15-7Mo、PH 14-8Mo以及PH 13-8Mo。後述鋼也命名為1.4534、X3CrNiMoAl13-8-2以及S13800。
本發明係關於改良熱加工工具鋼。特別的是,本發明係關於具有 高硬度以及高耐回火性之熱加工工具鋼。
本發明目的係提供一種鋼,其具有用於熱加工之改良性質輪廓。特別的是,本發明目標為提供沉澱硬化模子鋼,其具有高強度及韌度以及高清潔度、優良研磨性以及均勻性質也為大尺寸。除此之外,本發明目標為提供呈粉末型式之鋼,特別的是,但不限於,適於增材製造(AM)之鋼粉末。
進一步目的為提供物件,其係藉由增材製造方法由使用本發明粉末而形成。
上述目的以及額外的優點係藉由提供如申請專利範圍所定義之鋼實現至顯著的程度。
本發明係如申請專利範圍所定義。
一般目的係藉由提供鋼而解決,該鋼由以下所述組成(以重量%計):
Figure 107135411-A0202-12-0002-5
視需要選用
Figure 107135411-A0202-12-0002-6
Figure 107135411-A0202-12-0003-8
餘量Fe以及雜質。
以下簡要說明各個元素及其相互作用的重要性以及所請合金之化學成分之限制。在整個說明書中,鋼之化學組成之所有百分比係以重量%(wt.%)提供。相之量係以體積%(vol.)提供。個別元素的上限及下限可在申請專利範圍所說明的限制內自由組合。數值的算術精度可以增加一位數。因此,給出的值例如是0.1%也可表示為0.10%。
(0.01%-0.08%)
碳有效用於改良鋼之強度及硬度。然而,如果含量太高,鋼在從熱加工冷卻之後難以加工。C應以最小含量0.01%存在,較佳至少0.02%。碳之 上限為0.08%。上限可為0.07%、0.06%、0.055%或0.05%。標稱(nominal)含量約為0.030%。低碳含量改良成形性且賦予強度以及韌度之優良組合。
(0.05%-0.6%)
矽係用於脫氧。Si也為強肥粒鐵(ferrite)形成體。因此Si受限於0.6%。上限可為0.55%、0.50%、0.40%、0.35%、0.34%、0.33%、0.32%、0.31%、0.30%、0.29%或0.28%。下限可為0.10%、0.12%、0.14%、0.16%、0.18%或0.20%。較佳範圍為0.15-0.40%以及0.20%-0.35%。
(0.1%-0.8%)
錳有助於改良鋼之硬化性。如果含量太低,則硬化性可能太低。在較高之硫含量下,錳防止鋼中的紅脆性。因此,錳應以最小含量0.10%存在、較佳至少0.15%、0.20%、0.25%或0.30%。鋼應包含最大含量0.8% Mn、較佳最大為0.75%、0.70%、0.65%、0.60%、0.50%、0.45%、0.40%或0.35%。較佳範圍為0.20%-0.40%。
(3.9%-6.1%)
鉻係至少3.9%含量存在以提供優良硬化性以及耐腐蝕性。下限可為4.0%、4.1%、4.2%、4.3%、4.4%或4.5%。如果鉻含量太高,可能導致形成不想要的相。因此,上限為6.1%且可設定為6.0%、5.9%、5.8%、5.7%、5.6%或5.5%。
(1%-3%)
鎳為沃斯田鐵安定劑,會抑制形成delta肥粒鐵。鎳賦予鋼優良硬化性以及韌度。鎳也對鋼之機械加工性以及研磨性有利。然而,過量添加Ni會導致保留之沃斯田鐵量太高。下限可設定為1.1%、1.2%、1.3%、1.4%或1.5%。上限可設定為2.9%、2.8%、2.7%、2.6%或2.5%。
(7.0%-9.0%)
已知呈固體溶液之Mo對硬化性具有非常有利的影響。鉬為強的碳化物形成元素且也為強肥粒鐵形成體。Mo在本發明老化期間沉澱硬化形成時所必要者。基於此理由,Mo之量應為7%-9%。下限可為7.1%、7.2%、7.3%或7.4%。上限可為8.9%、8.8%、8.7%、8.6%、或8.5%。
(9.0%-12.5%)
鈷係溶於麻時效鋼內之基質中,且不參與沉澱。然而,鈷通常提高Ms溫度,因此增加其他老化-硬化元素之容許量而不會留下太多的保留沃斯田鐵。鈷降低鉬在麻田散鐵中之固體溶解度且促進鉬接觸顆粒更強的沉澱而導致硬度提高。然而,非常高Co含量可能降低具有高含量Mo之麻時效鋼之Ms溫度。因此,Co被限制到12.5%,且上限可為12.4%、12.3%、12.2%、12.1%、12.0%、11.9%、11.8%或11.7%。下限可為9.5%、9.7%、9.9%、10.1%、10.2%、10.3%、10.4%或10.5%。
(0.01%-0.15%)
氮為強沃斯田鐵形成體且也為強氮化物形成體。氮為以0.01%-0.15%,較佳0.02%-0.07%之範圍存在。下限可為0.01%、0.02%或0.03%。因此,上限可為0.10%、0.09%、0.08%、0.07%、或0.06%。
本發明發明人已令人驚訝地發現,可以在不損害研磨性的情況下故意地將氮添加到鋼中。
(0.2%-6.5%)
Cu為有助於增加鋼的硬度及耐腐蝕性的元素。若在老化期間形成之ε-Cu相不僅藉由沉澱硬化使鋼補強,也會影響金屬間相之沉澱動力學。除此之外,似乎添加Cu會導致在較高加工溫度下金屬間相生長緩慢。Cu之上限可為6.0%、5.5%、4.5%、4.0%、3.5%、3.0%、2.5%或2.0%。Cu之下限可為0.2%、0.3%、0.4%、0.5%、0.6%、0.75、0.8%或0.9%。
(0.002%-0.0008%)
硼為視需要選用元素,可少量使用以增加硬化性且改良不鏽鋼之熱加工性。則,上限可設定為0.007%、0.006%、0.005%或0.004%。
(0.01%-0.25%)
可視需要選用添加S以改良鋼之機械加工性。如果為此目的而使用S,則故意將0.01%-0.25%量之S加入鋼。較高硫含量會有紅脆性風險。再者,高硫含量可能會對鋼之疲勞性質以及研磨性有負面影響。因此,上限應為0.25%、較佳0.1%、最佳為0.03%。較佳範圍為0.015%-0.030%。然而,如果不是故意添加,則S之量被限制為如以下提出之雜質含量。
(
Figure 107135411-A0202-12-0006-28
1%)
Nb為強碳化物及氮化物形成體。因此,此元素含量應被限制,以避免形成不欲之碳化物及氮化物。因此,Nb最大量為1%。一般情況不會故意添加Nb。可容許雜質含量可被設定為0.05%、0.03%、0.01%或0.005%。
Ti、Zr、Ta、Hf以及Y(
Figure 107135411-A0202-12-0006-29
2%)
此等元素可與C、B、N及/或O形成化合物。它們可被用於生產氧化物分散强化型(ODS)或氮化物分散强化型(NDS)合金。則此等元素每一者之上限為2%。上限可為1.5%、1.0%、0.5%或0.3%。然而,如果不是故意添加此等元素以製造ODS合金,則上限可為0.1%、0.05%、0.01%或0.005%。
Ca、Mg、O以及REM(稀土金屬)
基於不同理由,此等元素可視需要選用以所請之量添加至鋼。此等元素通常被用於改良非金屬夾雜物及/或以進一步改良鋼機械加工性、熱加功性及/或可焊性。則氧含量較佳被限為0.03%。然而,如果氧被用於形成氧化物分散强化型(ODS)合金,則上限可為高至0.80%。氧化物可混合以原位形成之粉末,例如藉由氣態霧化,特別的是藉由使用氣態霧化反應合成(GARS)或在增材製造 (AM)方法期間、特別的是經由液態金屬沉積(LMD)中之大氣反應而形成。
雜質元素
P、S及O為主要的雜質,其可能對鋼的機械性質具有負面影響。因此,P可限制為0.05%、0.04%、0.03%、0.02%或0.01%。
如果不故意添加硫,則S雜質含量可限制為0.05%、0.04%、0.003%、0.001%、0.0008%、0.0005%或甚至0.0001%。
在一個具體實例中,鋼滿足以下條件中至少一者:
Figure 107135411-A0202-12-0007-9
在另一個具體實例中,鋼滿足以下條件中至少一者:
Figure 107135411-A0202-12-0007-10
Figure 107135411-A0202-12-0008-11
及/或其中基質包含
Figure 107135411-A0202-12-0008-30
80vol.%麻田散鐵及/或
Figure 107135411-A0202-12-0008-31
20vol.%沃斯田鐵及/或基質硬度為45-58HRC,及/或其中鋼具有至少100mm之厚度且根據ASTM E10-01量測在厚度方向與平均勃氏硬度(Brinell hardness)值HBW10/3000最大偏差小於5%,且其中壓痕中心距試樣邊緣或另一壓痕邊緣的最小距離應至少為壓痕直徑的2.5倍,最大距離不應超過壓痕直徑的4倍及/或鋼的清潔度符合以下ASTM E45-97方法A規定的微渣的最大要求:
Figure 107135411-A0202-12-0008-12
在一較佳具體實例中,鋼滿足以下條件:
Figure 107135411-A0202-12-0008-13
N 0.02-0.06。
本發明合金可藉任何適合方法生產。適合方法之非限制性實例包含:
a)習用熔融冶金,隨後為鑄造及熱加工。
b)粉末冶金(PM)。
c)大於103℃/s之快速凝固。
PM粉末可藉由預合金鋼之習用氣態-或水-霧化加以生產。
如果粉末應用於AM,則氣體霧化是較佳的霧化方法,因為使用產生具有高圓度和低量衛星繞射點(satellites)的粉末顆粒的技術是重要的。特別的是,緊耦合氣體霧化方法可用於此目的。
較佳至少80%的氣態霧化粉末顆粒的尺寸在5至150μm的範圍內。AM的粉末顆粒的最大尺寸為150μm,較佳的尺寸範圍為10-100μm,平均尺寸為約25-45μm。
主要關注的AM方法是液態金屬沉積(LMD)、選擇性雷射熔化(SLM)以及電子束熔化(EBM)。粉末特性對AM也很重要。根據ISO 4497,使用Camsizer測量的粉末尺寸分佈應滿足以下要求(以μm為單位):5
Figure 107135411-A0202-12-0009-32
D10
Figure 107135411-A0202-12-0009-33
35
20
Figure 107135411-A0202-12-0009-34
D50
Figure 107135411-A0202-12-0009-35
55
D90
Figure 107135411-A0202-12-0009-36
80。
較佳地,至少90%的粉末顆粒具有10至100μm範圍的尺寸,較佳地,粉末應滿足以下尺寸條件中的至少一者(以μm計):10
Figure 107135411-A0202-12-0009-37
D10
Figure 107135411-A0202-12-0009-38
30
25
Figure 107135411-A0202-12-0009-39
D50
Figure 107135411-A0202-12-0009-40
45
D90
Figure 107135411-A0202-12-0009-41
70
又更佳地,粗粒級(coarse size fraction)D90限於
Figure 107135411-A0202-12-0010-42
60μm或甚至
Figure 107135411-A0202-12-0010-43
55μm。
粉末之球度應較高。球度(SPHT)可藉由Camsizer量測且定義在ISO 9276-6中。SPHT=4πA/P2,其中A為由顆粒投影所覆蓋之量測面積,且P為顆粒投影之量測周長/圓周。平均SPHT應為至少0.80且較佳可為至少0.85、0.90、0.91、0.92、0.93、0.94或甚至0.95。此外,不大於5%之顆粒應具有
Figure 107135411-A0202-12-0010-44
0.70之SPHT。除SPHT之外,縱橫比可用於對粉末顆粒進行分類。縱橫比定義為b/l,其中b為顆粒投影之最短寬度且l為最長直徑。平均縱橫比較佳應為至少0.85或更佳0.86、0.87、0.88、0.89或0.90。
本發明合金為具有麻田散鐵之沉澱可硬化鋼。
可藉任何適合PM-方法諸如PIM、MIM、ROC、HIP以及習用壓製及燒結,由本發明預合金粉末形成物件。較佳地,使用增材製造(AM)方法。AM物件應滿足以下條件中至少一者:基質包含
Figure 107135411-A0202-12-0010-45
80vol.%麻田散鐵、基質包含
Figure 107135411-A0202-12-0010-46
20vol.%沃斯田鐵、基質硬度為34-56HRC、垂直於構建方向的夏比V-缺口值為
Figure 107135411-A0202-12-0010-47
5J、垂直於構建方向的抗張強度Rm
Figure 107135411-A0202-12-0010-48
1600MPa、垂直於構建方向的降伏強度c0.2
Figure 107135411-A0202-12-0010-49
1500MPa、垂直於構建方向的壓縮降伏強度Rc0.2比抗張降伏強度Rp0.2至少高10%。
可根據EN 10045-1、ISO 148及/或ASTM A370並使用標準試片尺寸10mm x10 mm x 55mm進行夏比衝擊試測。可使用X射線繞射(XRD)及/或電子背散射繞射儀(EBSD)in the SEM量測沃斯田鐵含量。
實施例
在此實施例中,二個本發明合金與優質熱加工鋼Uddeholm Dievar®比較。
合金具有以下標稱組成(wt.%):
Figure 107135411-A0202-12-0011-14
餘量之鐵及雜質。
將本發明鋼熔化且鑄造成為重量約100克之小鑄錠。在冷卻至室溫後,使這些鋼在620℃經受回火二次達2小時(2x2h)。
比較鋼係以習用方式製備,並在真空爐中於1020℃經受沃斯田鐵化,隨後在800-500℃範圍(t8/5=100s)以氣淬100秒之時間。在冷卻至室溫後,讓比較鋼在615℃經受回火二次達2小時(2x2h)。
隨後,在600℃溫度下檢視合金耐回火性。結果如表1所示。
Figure 107135411-A0202-12-0012-15
雖然本發明二種鋼在試測開始具有較高起始硬度,從表1明顯可看出本發明鋼相較於比較鋼Uddeholm Dievar®具有顯著較佳耐回火性。本發明鋼暴露於600℃達100小時之後硬度減少約5HRC,而比較性鋼約14HRC。據上所述,結論為本發明鋼不僅具有顯著高之起始硬度,也具有優異耐回火性。
產業利用性
本發明鋼特別有用於需要高且均勻硬度以及高耐回火性之模子。本發明鋼也非常適合作為用於PM以及用於藉AM製造物件之粉末。

Claims (9)

  1. 一種用於製備熱加工工具之鋼,該鋼由以下所述組成(以重量%計):C 0.01-0.08,Si 0.05-0.6,Mn 0.1-0.8,Cr 3.9-6.1,Ni 1.0-3.0,Mo 7.0-9.0,Co 9.0-12.5,Cu 0.4-6.5,N 0.01-0.15,視需要選用B <0.008,S <0.25,V <2,Nb <1,Ti <2,Zr <2,Ta <2,Hf <2,Y <2,Ca <0.009,Mg <0.01, REM <0.2,餘量為Fe以及雜質。
  2. 根據申請專利範圍第1項之鋼,其滿足以下條件中至少一者:C 0.01-0.06,Si 0.1-0.5,Mn 0.1-0.6,Cr 4.0-6.0,Ni 1.2-2.9,Mo 7.1-8.9,Co 9.5-12.0,Cu 0.4-5.0,N 0.02-0.08。
  3. 根據申請專利範圍第1或2項之鋼,其滿足以下條件中至少一者:C 0.02-0.04,Si 0.2-0.4,Mn 0.2-0.6,Cr 4.5-5.5,Ni 1.5-2.5,Cr+Ni 6.0-8.0,Mo 7.5-8.5,Co 10.5-11.7,Cu 0.4-4.0,N 0.02-0.06,該基質包含
    Figure 107135411-A0305-02-0016-5
    80vol.%麻田散鐵, 該基質包含
    Figure 107135411-A0305-02-0017-6
    20vol.%沃斯田鐵,該基質硬度為45-58 HRC,及/或其中該鋼具有至少100mm之厚度且根據ASTM E10-01量測在厚度方向與平均勃氏硬度(Brinell hardness)值HBW10/3000最大偏差小於5%,且其中壓痕中心距試樣邊緣或另一壓痕邊緣的最小距離應至少為壓痕直徑的2.5倍,最大距離不應超過壓痕直徑的4倍,及/或鋼的清潔度符合以下ASTM E45-97方法A規定的微渣的最大要求:
    Figure 107135411-A0305-02-0017-1
  4. 根據申請專利範圍第1項之鋼,其滿足以下條件:C 0.025-0.055,Si 0.15-0.40,Mn 0.15-0.50,Cr 4.5-5.5,Ni 1.5-2.5,Mo 7.5-8.5,Co 10.5-11.7,Cu 0.4-4.0,N 0.02-0.06。
  5. 一種預合金鋼粉末,其具有根據申請專利範圍第1至4項中任一項之鋼之組成。
  6. 根據申請專利範圍第5項之預合金鋼粉末,其中該粉末係藉由氣態霧化製備,至少80%該粉末之顆粒具有5至150μm範圍之尺寸且其中該粉末滿足以下條件中至少一者:
    Figure 107135411-A0305-02-0018-3
    其中SPHT=4πA/P2,其中A為由顆粒投影所覆蓋之量測面積,且P為顆粒投影之量測周長/圓周,且球度(SPHT)係根據ISO 9276-6藉由Camsizer量測,且其中b為顆粒投影之最短寬度且1為最長直徑。
  7. 根據申請專利範圍第6項之預合金鋼粉末,其中至少90%該粉末之顆粒具有10至100μm範圍之尺寸且其中該粉末滿足以下條件中至少一者:
    Figure 107135411-A0305-02-0018-4
  8. 一種使用根據申請專利範圍第5至7中任一項之預合金鋼粉末藉由增材製造方法形成之物件,其中該物件滿足以下條件中至少一者:該基質包含
    Figure 107135411-A0305-02-0018-7
    80vol.%麻田散鐵、該基質包含
    Figure 107135411-A0305-02-0018-8
    20vol.%沃斯田鐵、該基質硬度為34-56 HRC、垂直於構建方向的夏比V-缺口值為
    Figure 107135411-A0305-02-0018-9
    5J、 垂直於構建方向的抗張強度Rm
    Figure 107135411-A0305-02-0019-10
    1600MPa、垂直於構建方向的降伏強度Rc0.2
    Figure 107135411-A0305-02-0019-11
    1500MPa、垂直於構建方向的壓縮降伏強度Rc0.2比抗張降伏強度Rp0.2至少高10%。
  9. 根據申請專利範圍第8項之物件,其中該物件在620℃老化2小時二次之後具有在室溫下至少52 HRC之硬度且其中在該物件暴露於600℃溫度50小時後該硬度至少為50 HRC。
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