CN110832093A - 用于添加剂技术的铝合金 - Google Patents
用于添加剂技术的铝合金 Download PDFInfo
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- 239000000654 additive Substances 0.000 title claims abstract description 14
- 230000000996 additive effect Effects 0.000 title claims abstract description 11
- 238000005516 engineering process Methods 0.000 title claims abstract description 11
- 229910000838 Al alloy Inorganic materials 0.000 title description 9
- 239000000956 alloy Substances 0.000 claims abstract description 35
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 34
- 239000000843 powder Substances 0.000 claims abstract description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 20
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 13
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000004411 aluminium Substances 0.000 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011575 calcium Substances 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 238000005275 alloying Methods 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 4
- 238000000889 atomisation Methods 0.000 claims description 3
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 claims description 2
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 238000010894 electron beam technology Methods 0.000 claims 1
- 238000004781 supercooling Methods 0.000 claims 1
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 238000010309 melting process Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910018125 Al-Si Inorganic materials 0.000 description 1
- 229910003407 AlSi10Mg Inorganic materials 0.000 description 1
- 229910018520 Al—Si Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000274 aluminium melt Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- RGKMZNDDOBAZGW-UHFFFAOYSA-N aluminum calcium Chemical compound [Al].[Ca] RGKMZNDDOBAZGW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及冶金学，更具体地涉及用于由铝基合金制造部件坯体和成品部件的组合物和方法，包括但不限于使用选择性激光熔融工艺。所提出的包含镁、锆和钪的铝基合金用于由其雾化得到铝粉、然后通过添加剂技术制造成品部件，该合金具有减少的钪含量，并且还包含具有受限尺寸的氧化物膜和水含量的氧和钙。
Description
本发明涉及冶金学，更具体地涉及用于由铝基合金制造部件坯体和成品部件的组合物和方法，包括但不限于使用选择性激光熔融(SLM)工艺。
目前，基于Al-Si和Al-Mg-Sc体系的铝合金被广泛用于使用添加剂技术制造各种部件。
已知AlSi10Mg铝合金以粉末形式使用，以利用添加剂技术制造成品部件。尽管所述合金具有良好的加工性并且允许获得铸造合金水平上的机械性能，但这种特性水平不足以与高强度锻造合金竞争。
含钪材料可以实现至多500MPa-550MPa的强度，使得这些材料可以找到更广泛的应用。然而，目前钪的高成本导致设计者和工艺工程师对使用这些材料的兴趣较低。
因此，存在开发用于添加剂技术的高强度且价格合理的新材料的实际需求。
已知一种用于通过添加剂技术来制造部件的铝合金，其包含(以重量％计)：
Zn–4～10；
Mg–1～3.5；
Zr–0～0.5；
Cu–0～2.5；
Sc–0～1.25；
铝–基础成分(参见美国专利申请20170233857，2017年8月17日公开，C22F1/053；B33Y10/00；B33Y70/00；B33Y80/00；C22C21/10)。
该已知铝合金的缺点在于高含量(4重量％～10重量％)的锌，其在通过添加剂技术制造成品部件的过程中蒸发。此外，需要淬火来实现高水平的拉伸性能，这可能在热处理期间引起各种变形并导致制造成品部件的时间更长。
已知一种用于通过添加剂技术制造部件坯体的铝合金(参见美国专利申请2017121794，2017年5月4日公开，C22C21/08；B22F1/00；C22F1/05；C23C4/08)，其包含(以重量％计)：
Mg–3～6；
Si–1～4；
Ti–0.005～0.2；
Sc–0.1～0.75；
Zr–0.01～0.375；
Hf,Mo,Tb,Nb,Gd,Er,V–0～0.5；
Be–0～0.004；
铝–基础成分；
其中，锆含量或锆和钛的集合含量小于钪含量的50％。
该合金的缺点是硅含量高(1重量％至4重量％)，这大大改善了铸造性能，但导致形成了粗过剩相，其由于与铝基体的结合性差而降低了材料的可塑性特性。
与所提出的发明最接近的现有技术是美国专利申请20170165795(2017年6月15日公开，B23K35/28；C22C21/08)所述的合金，该专利申请公开了一种铝粉合金，其包含(重量％)：
Mg–0.5～10；
Sc–0.1～30；
Zr–0.05～1.5；
Mn–0.01～1.5；
Zn–0～2.0；
Ti–0.01～0.2；
Ce≦0.25；
Be–0～0.004；
B–0～0.008；
Si≦0.25；
Fe≦0.25；
Hf≦0.5；
至少一种选自由除Ce外的镧系元素、Y、Ga、Nb、Ta、W、V、Ni、Co、Mo、Li、Th、Ag组成的组的元素，其中这些元素的比例为最多0.5；和
作为剩余部分的铝。
上述铝合金的缺点是由于钪(至多30重量％)和其它稀有元素的含量高而导致材料成本高；此外，材料的过合金化导致较低的可塑性和疲劳特性。
本发明要解决的技术问题是开发一种铝粉，其用于通过添加剂技术制造高强度且价格合理的部件坯体和成品部件。
本发明的技术效果在于制造一种具有高强度性能(极限拉伸强度至少为470MPa)和至少11％的增加的伸长率水平的铝合金，以及用于通过添加剂技术制造部件坯体和成品部件的该铝合金的粉末。由于其与最接近的现有技术相比具有优化的组成和更低浓度的昂贵元素，一个突出特点是粉末成本低，使得成品部件的制造成本因使用较廉价的原料而可以大幅降低。该粉末可用于生产高负荷的成品部件，尤其用于在暴露于要求提高强度和塑性特性的冲击载荷时使用。
通过制备具有如下提出的化学组成(以重量％计)的粉末，解决所述问题并实现了所述效果：
Mg 4.0～6.5；
Zr 0.5～1.0；
Sc 0.2～0.6；
O 0.001～0.2；
Ca 0.005～0.2；
其余为Al和不可避免的杂质。
该合金中的镁含量是有限的，因为必须提供窄的结晶范围以改善加工性，因为制品和部件通过选择性激光熔融来制造。镁含量高于合金的6.5重量％将导致耐腐蚀性下降的不良效果，因为Al3Mg2相倾向于在晶界处成核，这导致因应力腐蚀开裂而造成的碎裂。钪含量是有限的，因为它在室温下的最大溶解度为0.02重量％，且其最大溶解度不超过0.8重量％，这使得可以确保避免在粉末本身和在所制造的成品部件中形成初级金属间化合物。采用钪和锆一起合金化使得可以使钪被部分地替换，从而形成Al3(Sc,Zr)相，其具有增加的耐热性并且在正确选择的热处理参数下高效地硬化该材料。
氧是提供所需球形度和降低粉末反应性所必需的。氧含量增加至超过0.2重量％将导致颗粒表面品质降低和球形形状被破坏。钙的添加防止了在反复再熔融过程中沿着合成材料的边界形成氧化铝。另外，在随后的热处理过程中，形成了Al4Ca型相以能够获得晶粒细化效果，由此使得微晶粒尺寸变小并且改善强度特性。
由于与最接近的现有技术相比具有少量过渡金属的该材料的整体合金化水平，提供了改进的伸长率特性。此外，进一步的效果在于防止镁在熔体制备和喷雾过程中烧尽。
作为用于生产合金的原料，通常使用纯度等级不低于GOST 11069A5的铝(铝含量不低于99.5％)。存在于金属中的杂质低于其最大溶解度的极限，并且对最终样品的特性没有显著影响，因为其存在于固溶体中或者作为体积比小于0.1％的金属间化合物存在。
重要的是，所提出的合金不含锰和钛添加剂，因为带有这些过渡金属(TM)的铝固溶体的老化所能实现的硬化表现得远远小于因锆和钪固溶体在铝中的瓦解所能实现的硬化。此外，这些添加剂的改性效果表现得比引入锆的情形更低，这使得引入这些添加剂不切实际。合金中增加的金属间化合物含量也会降低它们对点蚀的抗性。
附图说明
图1显示了铝粉颗粒的照片。
图2是在选择性激光合金化平台上的样品排布的数字3D模型。
图3显示了用所提出的合金的粉末制备的用于测定孔隙率的金相样品的照片。
图4显示了用所提出的合金的粉末制备的样品的硬度与在单步退火中的退火时间和温度之间的关系。
具体实施方式
实施例1
如下获得铝粉：在850℃～950℃，向等级不低于GOST 11069-A7的铝熔体中分批添加作为合金元素的钪和锆，以避免该熔体过冷却至低于740℃的温度。在钪和锆溶解后，加入作为合金元素的钙。
在铝-钙母合金完全溶解后，在不高于820℃的温度加入镁，选择熔体样品并调节化学组成。
在雾化之前即刻，最终检查化学组成，并在适当时进行额外的合金化。
在获得所需的化学组成后，使用含有0.2％～1.0％氧气的氮气-氧气或氩气-氧气混合物以不低于5·104K/s的冷却速率使熔体雾化，以产生过饱和固溶体。将熔体在高出液相点160℃～250℃的温度喷雾，以避免在熔体中存在细小的锆和钪初级金属间化合物。一旦制成，分离粉末以根据需要筛出低于20μm和高于63μm或高于130μm的级分。
通过扫描电子显微镜研究粉末形态。所制造的铝粉颗粒的照片如图1所示。
使用Leco气体分析仪根据载气混合物中的氧含量来研究粉末中的氧含量。氧含量在0.2％至2％之间变化。
获得了以下结果：
| 氮气中的氧含量,％ | 粉末中的氧含量,重量％ |
| 0.2 | 0.003 |
| 0.6 | 0.08 |
| 1.0 | 0.19 |
| 2.0 | 0.36 |
使用激光衍射来确定铝粉的分散度。获得了以下结果：d10＝12.7μm，d50＝33.1μm，d90＝59.8μm。
实施例2
通过选择性激光熔融，用实施例1的上述粉末制备了部件坯体。
使用CAD(Solid Works，Catia，Creo，NX，Compas 3D)生成制品的数字3D模型(例如，用于拉伸测试的样品，如图2所示)，然后存储为STL文件。然后将生成的文件加载到计算机。使用特殊的软件包将该3D模型分成多层(每层厚度为30μm)。基于这些层来制备来自金属粉末的制品。
将一定量的粉末从另外的平台或从料斗转移到主操作平台。该平台包括可移除的金属板。该板由具有类似于所述粉末的基础成分的材料制成以用于打印。利用特殊的支持结构体(图2中用红色标出)将所要制造的部件连接到该板上。打印后移除所述支持结构体。
利用特殊的刮刀将粉末平铺在整个平台上，刮刀可包括圆柱刮刀、金属刮刀或陶瓷刮刀。
通过暴露于180瓦的激光辐射，使粉末颗粒沿预定的轮廓熔化。然后通过反复施加粉末层并使其沿着预定轮廓合金化来进行打印过程。
一旦打印过程完成，从室中除去过量的粉末。将带有打印部件的板从机器中取出。
以机械手段或通过放电切割从平台上切割出部件。
图3显示了根据上述方法生长的金相样品的照片。孔隙率水平不超过0.35％。
图4显示了由本发明的铝基合金粉末制备的样品的硬度与在不同退火温度下的均热时间之间的关系。基于曲线数据分析，确定了热处理模式，从而根据GOST 1497的要求进行圆柱形样品的拉伸测试。
表1显示了所研究的粉末的化学组成。
表2显示了在400℃进行单步退火后测定的拉伸性能。
表1
表2
从上表中可以看出，氧含量的增加导致伸长率的某种降低，这是由合金材料中氧化物相的存在引起的，所述氧化物相足够精细以保持硬化效果，但对铝基质没有亲合力。
粉末成本是根据所需部分的35％的产率和以下原料的使用而计算出的：
-A7铝锭；
-Mg95镁锭；
-铝-2％钪母合金；
-铝-10％锆母合金；
-铝-10％钇母合金；
-Z0级锌金属；
-铝-6％钙母合金；
-铝-5％钛母合金。
所提出的合金与原型相比的估算制造成本节约如下表3所示。
表3
由于将钪含量降低至了0.2重量％～0.6重量％，并且将铝-2％钪初始合金的成本降至了50美元/公斤，因此与原型(US20170165795)相比，每吨合金的成本节约了7,500美元至17,500美元。同时，所提出的合金在拉伸强度方面与其高钪含量的原型相似，同时伸长率值高出20％～30％，因此它可用于制造能够承受严重应变的结构元件。在这方面，所要求保护的发明的工程性能和经济性能远高于原型。
Claims (6)
1.一种由铝基合金制造铝粉的方法，其特征在于，在850℃至950℃的温度，向铝熔体中分批添加作为合金元素的钪和锆，以避免所述熔体过冷却至低于750℃的温度；在钪溶解后，添加钙作为母合金；而后添加镁，然后用氮气-氧气或氩气-氧气混合物使所述熔体雾化以得到铝粉，同时在雾化前保持熔体组成成分为下述以重量％计的比例：
其余为Al和不可避免的杂质。
2.如权利要求1所述的方法，其中，在高出合金液相点160℃～250℃的温度在氧气含量为0.2％～1.0％时将所述熔体喷雾。
3.一种包含镁、锆和钪的铝基合金，其用于由其雾化得到铝粉、然后通过添加剂技术来制造成品部件，其特征在于，所述合金具有减少的钪含量并且还包含以重量％计的以下成分比例的氧和钙：
其余为Al和不可避免的杂质。
4.用权利要求1或2所述的方法制造的球形粉末，其粒径为20μm至150μm，优选为20μm至63μm。
5.由权利要求3所述的合金制造的球形粉末，其粒径为20μm至150μm，优选为20μm至63μm。
6.通过选择性激光合金化或电子束合金化方法由权利要求4或5所述的球形粉末制造的成品部件。
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| CA3050947A1 (en) | 2019-11-21 |
| US20220205067A1 (en) | 2022-06-30 |
| CA3050947C (en) | 2022-01-11 |
| KR102422213B1 (ko) | 2022-07-18 |
| KR20200087857A (ko) | 2020-07-21 |
| US20210246535A1 (en) | 2021-08-12 |
| CN110832093B (zh) | 2022-05-17 |
| RU2717441C1 (ru) | 2020-03-23 |
| EP3623488B1 (en) | 2021-05-05 |
| JP2021507088A (ja) | 2021-02-22 |
| WO2019226063A1 (ru) | 2019-11-28 |
| EP3623488A1 (en) | 2020-03-18 |
| PL3623488T3 (pl) | 2021-10-25 |
| US11802325B2 (en) | 2023-10-31 |
| JP6880203B2 (ja) | 2021-06-02 |
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