CN105745345A - 无钛合金 - Google Patents

无钛合金 Download PDF

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CN105745345A
CN105745345A CN201580002649.XA CN201580002649A CN105745345A CN 105745345 A CN105745345 A CN 105745345A CN 201580002649 A CN201580002649 A CN 201580002649A CN 105745345 A CN105745345 A CN 105745345A
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maximum
alloy
weight
resistance
titanium
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CN105745345A8 (zh
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J·罗森比尔格
J·克勒沃
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VDM Metals GmbH
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VDM Metals GmbH
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Priority claimed from DE102014002402.4A external-priority patent/DE102014002402A1/de
Priority claimed from DE102014002693.0A external-priority patent/DE102014002693A1/de
Application filed by VDM Metals GmbH filed Critical VDM Metals GmbH
Priority to CN202110894371.9A priority Critical patent/CN114000032A/zh
Publication of CN105745345A publication Critical patent/CN105745345A/zh
Publication of CN105745345A8 publication Critical patent/CN105745345A8/zh
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Abstract

无钛合金，所述无钛合金具有高的耐点状腐蚀性和耐裂缝腐蚀性以及冷作硬化状态下的高的屈服极限，具有(以重量％计)最多0.02％的C，最多0.01％的S，最多0.03％的N，20.0-23.0％的Cr，39.0-44.0％的Ni，0.4-<1.0％的Mn，0.1-<0.5％的Si，>4.0-<7.0％的Mo，最多0.15％的Nb，>1.5-<2.5％的Cu，0.05-<0.3％的Al，最多0.5％的Co，0.001-<0.005％的B，0.005-<0.015％的Mg，余量为Fe以及由熔炼造成的杂质。

Description

无钛合金
本发明涉及无钛合金，所述无钛合金具有高的耐点状腐蚀性和耐裂缝腐蚀性以及冷作硬化状态下的高的屈服极限和强度。
高耐腐蚀性材料Alloy825主要用于化学工业和海洋技术。其以材料编号2.4858销售并且具有如下化学组成：≤0.025％的C、≤0.015％的S、19.5-23.5％的Cr、28-46％的Ni、≤1％的Mn、≤0.5％的Si、2.5-3.5％的Mo、0.6-1.2％的Ti、1.5-3％的Cu、≤0.2％的Al、≤1％的Co，余量为Fe。
对于在石油工业和天然气工业中的新用途，耐点状腐蚀性和耐裂缝腐蚀性(问题1)以及屈服极限和强度(问题2)过低。
鉴于低的铬含量和钼含量，Alloy825仅具有相对低的耐点蚀当量(PRE＝1x％Cr+3.3x％Mo)。耐点蚀当量PRE被本领域技术人员理解为耐点蚀当量。
合金Alloy825为钛稳定的材料。然而钛特别是在连续铸造时可能造成问题，因为其与铸造粉末的SiO2反应(问题3)。希望避免元素钛，然而这造成边缘裂缝倾向的明显升高。
JP61288041A1涉及具有如下组成的合金：<0.045％的C、<0.03％的S、0.005-0.2％的N、14-26％的Cr、<1％的Mn、<1％的Si、<8％的Mo、<2％的Cu、<25％的Fe、<2％的Al、0.001-0.1％的B、0.005-0.5％的Mg，余量为Ni。Nb的含量通过公式产生。还可以以≤2的含量包含至少一种元素Ti、Al、Zr、W、Ta、V、Hf。
US2,777,766公开了具有如下组成的合金：<0.25％的C、18-25％的Cr、35-50％的Ni、2-12％的Mo、0.1-5％的Nb、至多2.5％的Cu、至多5％的W，余量为Fe(最少15％)。
本发明所基于的目的是提供替代Alloy825的合金，所述合金克服上述问题并且
-无钛，
-具有提高的耐点状腐蚀性和耐裂缝腐蚀性，
-在冷作硬化状态下具有更高的屈服极限，
-其热成形性和可焊接性至少同样好，
还应当提供制备所述合金的方法。
通过无钛合金实现所述目的，所述无钛合金具有高的耐点状腐蚀性并且具有(以重量％计)
最多0.02％的C
最多0.01％的S
最多0.03％的N
20.0-23.0％的Cr
39.0-44.0％的Ni
0.4-<1.0％的Mn
0.1-<0.5％的Si
>4.0-<7.0％的Mo
最多0.15％的Nb
>1.5-<2.5％的Cu
0.05-<0.3％的Al
最多0.5％的Co
0.001-<0.005％的B
0.005-<0.015％的Mg
余量为Fe以及由熔炼造成的杂质。
根据本发明的合金的优选实施方案取自具体的从属权利要求。
根据本发明的合金的有利的实施方案具有如下组成(以重量％计)
最多0.015％的C
最多0.005％的S
最多0.02％的N
21.0-<23％的Cr
>39.0-<43.0％的Ni
0.5-0.9％的Mn
0.2-<0.5％的Si
>4.5-6.5％的Mo
最多0.15％的Nb
>1.6-<2.3％的Cu
0.06-<0.25％的Al
最多0.5％的Co
0.002-0.004％的B
0.006-0.015％的Mg
余量为Fe以及由熔炼造成的杂质。
铬的含量还可以根据需要如下改变：
>21.5-<23％的Cr
22.0-<23％的Cr
镍含量还可以根据需要如下改变：
>39.0-<42％的Ni
>39.0-<41％的Ni
钼含量还可以根据需要如下改变：
>5-<6.5％的Mo
>5-<6.2％的Mo
铜的含量还可以根据需要如下调节：
>1.6-<2.0％的Cu
还可以根据需要在合金中加入如下含量(以重量计)的元素V
>0-1.0％的V
0.2-0.7％的V。
根据本发明的合金中的铁含量应当>22％。
由于省略元素钛，因此在轧制时产生(如上所述)边缘裂缝。可以通过50-150ppm数量级的镁积极影响裂缝倾向。表1中显示了相关/研究的实验室熔体。
关于Alloy825的耐腐蚀性的耐点蚀当量PRE为PRE33，相比于其它合金极低。表2中显示了根据现有技术的耐点蚀当量PRE。
Alloy Ni Fe Cr Mo 其它 PRE
Duple×2205 5,5 Rest 22 3 0,15N 37
825 40 31 23 3,2 33
28 31 35 27 3,5 1,3Cu 38
926 25 Rest 19 6 0,16N 47
表2：对应于现有技术的不同合金的耐点蚀当量PRE
通过提高钼含量，耐点蚀当量升高，因此耐腐蚀性升高。PRE＝1x％Cr+3.3x％Mo(耐点蚀当量)。
表3显示了各种点蚀研究的结果。降低的钛含量对点蚀温度没有负面影响。升高的钼含量具有积极作用。
T℃ Ni Cr Mo N Ti PRE
LB 2316 35 39,2 22,4 3,1 0,04 ＜0,04 33
LB 2317 40 40,1 22,5 4,2 0,03 ＜0,04 36
LB 2318 50 39,8 22,8 5,2 0,04 ＜0,04 40
LB 2319 55 38,8 22,9 6,1 0,04 ＜0,04 43
LB 2320 50 39 22,1 6,2 0,1 ＜0,03 43
LB 2321 50 40,2 22,6 6,2 0,04 0,4 43
LB 2322 40 40 23,1 6,3 0,1 0,4 44
Alloy 825参照 30 40 23 3,2 ＜0,02 0,8 33
表3：在6％FeCl3+1％HCL中72小时的临界点蚀温度(ASTMG-48方法C)
其它腐蚀研究同样显示了临界裂缝腐蚀温度相比于Alloy825的改进。其显示于表4。
Alloy CPT℃ CCT℃ Ni Cr Mo V Ti PRE
825＊ 30 ＜5 33
PV661 40 15 40 23 3,3 ＜0,002 0,8 34
PV662 50 20 40 23 5,9 ＜0,002 ＜0,002 42
PV663 50 20 39 23 5,8 0,4 ＜0,002 42
表4：临界点蚀温度(CPT)和临界裂缝腐蚀温度(CCT)
通过15和30-％的冷成形，可以升高屈服极限和强度。下表中显示了各个实验室合金的相关研究结果。
表5：室温下的拉伸试验
下图1和2中显示了拉伸试验的结果，一方面是参照合金Alloy825，另一方面是替代合金。
室温下的拉伸试验的结果(平均值)取决于状态的图表。
钼对屈服极限和强度起积极作用。图3和4中说明了钼的积极作用。
室温下的拉伸试验的结果(平均值)取决于钼含量的图表。
借助于PVR试验(编程-变形-裂缝试验)研究Ni基础合金Alloy825的热裂敏感性。通过在WIG焊接过程中设置线性升高的拉伸速度，确定临界拉伸速度VKr。下图中显示了研究结果。拉伸速度越高并且热裂倾向越低，材料的可焊接性越好。高钼含量的无钛变体形式(PV506和PV507)显示比标准合金(PV942)更少的裂缝。
Alloy 825/PV·编号 942-1 506-1 507-1 942-0 507-0 942-2 506-2 507-2 942-3 506-3
L0[mm] 185 185 185 110 110 110 110 110 110 110
Vkr[mm/min] 45 45 45 45 45 60 60 60 75 75
WB WG LG LG WG LG WG LG LG WG LG
第一个热裂缝的类型 WAR WAR WAR WAR WAR WAR WAR WAR WAR WAR
LG＝固溶退火
WG＝软化退火
图5显示了Alloy825的第一个热裂缝(PT和立体显微镜检查)的独立于裂缝类型的临界变形速度。
表6(以重量％计的化学组成)
还通过制备具有根据具体权利要求所述的组成的合金的方法实现所述目的，其中
a)以连续铸造或铸锭铸造的方式开放熔炼合金，
b)为了消除由于升高的钼含量造成的偏析，将形成的扁锭/棒锭在1150-1250℃下进行均质化退火15至25小时，其中
c)均质化退火特别在第一次热成形之后进行。
任选也可以通过ESU/VAR熔炼形成合金。
根据本发明的合金应当优选用作石油工业和天然气工业中的构件。
适合的产品形式为板材、带材、管材(纵向无缝焊接)、棒材或锻件。
表6对比了Alloy825(标准)、两个根据本发明的合金。
表6(以重量％计的化学组成)

Claims (7)

1.无钛合金，所述无钛合金具有高的耐点状腐蚀性和耐裂缝腐蚀性以及冷作硬化状态下的高的屈服极限，具有(以重量％计)
最多0.02％的C
最多0.01％的S
最多0.03％的N
20.0-23.0％的Cr
39.0-44.0％的Ni
0.4-<1.0％的Mn
0.1-<0.5％的Si
>4.0-<7.0％的Mo
最多0.15％的Nb
>1.5-<2.5％的Cu
0.05-<0.3％的Al
最多0.5％的Co
0.001-<0.005％的B
0.005-<0.015％的Mg
余量为Fe以及由熔炼造成的杂质。
2.根据权利要求1所述的合金，具有(以重量％计)
最多0.015％的C
最多0.005％的S
最多0.02％的N
21.0-<23％的Cr
>39.0-<43.0％的Ni
0.5-0.9％的Mn
0.2-<0.5％的Si
>4.5-6.5％的Mo
最多0.15％的Nb
>1.6-<2.3％的Cu
0.06-<0.25％的Al
最多0.5％的Co
0.002-0.004％的B
0.006-0.015％的Mg
余量为Fe以及由熔炼造成的杂质。
3.根据权利要求1或2所述的合金，具有(以重量％计)
>21.5-<23％的Cr
>39.0-<42％的Ni
>5-<6.5％的Mo
>1,-<2.2％的Cu。
4.根据权利要求1至3任一项所述的合金，所述合金根据需要具有(以重量％计)>0-1.0％，特别是0.2-0.7％的V。
5.制备具有根据权利要求1至4任一项所述的组成的合金的方法，其中
a)以连续铸造或铸锭铸造的方式开放熔炼合金，
b)为了消除由于升高的钼含量造成的偏析，将形成的扁锭/棒锭在1150-1250℃下进行均质化退火15至25小时，其中
c)均质化退火特别在第一次热成形之后进行。
6.根据权利要求1至4任一项所述的合金作为石油工业和天然气工业中的构件的用途。
7.根据权利要求6所述的用途，其中构件以板材、带材、管材(纵向缝焊接和无缝)、棒材的生产形式或者以锻件形式存在。
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