Formation of （Ca n-x, Na x）Pm Compounds in Eutectic Al--Si Piston Alloys and Invalidation of Phosphorus Modification Effect

利用金相和电子探针微量分析仪(EPMA)等手段研究了共晶型Al-Si(ZL109)合金熔体中Ca或(和)Na对Al-P中间合金变质效果的影响，含磷化合物的组成与磷变质的关系．结果表明，合金中Ca或(和)Na能使磷变质失效，甚至出现反常的Na变质效果；Ca或(和)Na促使AlP分解，并与磷形成比AlP更稳定的(Can-x，Nax)Pm化合物，从而抑制了磷变质作用的发挥；C2C16精炼可使(Can-x，Nax)Pm化合物的组成和结构发生转化，形成了能作为初晶Si结晶核心的(Al5，Mg0．85，Ca0．15)P3．4化合物，从而使磷变质效果得以恢复．     

锶对铝硅合金磷变质的影响

利用金相和电子探针微成分分析仪(EPMA)等手段研究了共晶Al-Si(ZL109)合金熔体中Sr对P变质效果的影响。结果表明:Sr的加入量小于0.175%时,对P变质没有影响。分析表明:在Al-Si合金中心仍是作为核心的AlP,其周围是Sr与P、Al、Ca、Mg生成的多元化合物,此多元化合物与初晶硅的晶格结构相似。     

Mg对共晶Al-Si合金磷变质效果的影响

研究结果表明,经过磷变质处理的共晶Al-Si合金中加入1.2%的Mg后,磷变质效果变差,甚至出现类似钠变质处理的特征.分析认为:Mg能与合金熔体中P形成比AlP更稳定的化合物,抑制了磷变质作用的发挥;在加入Mg再进行变质处理的情况下,变质效果良好.     

微量元素对铸造Al-Si合金中Sr变质行为的毒化效应

铸造Al-Si合金在生产、使用、回收及再生过程中往往添加、积累了一定量合金化元素和杂质元素。某些微量元素(Ca、B、Bi、Sb、RE等)往往会和Sr反应形成复杂金属间化合物,减少了参与变质的Sr的含量,降低了Sr的变质效果。Sr在加入到不同合金中,首先要中和微量元素对Sr变质共晶Si的毒化效应,即只要熔体中Sr的含量足够高,仍能够产生良好的变质效果。     

新型Al-P-N晶种合金及其对过共晶Al-Si系合金组织和性能的影响

研究了Al-P-N晶种合金及其对过Al-Si合金组织和性能的影响。结果表明:AlP和AlN粒子在Al-P-N晶种合金中形成,AlN粒子存在于AlP粒子的周围,因此抑制了AlP粒子的长大,使AlP得到了细化。与Al-P合金相比,Al-P-N合金中AlP粒子数目多、尺寸小,从而提高了Al-Si熔体对P的吸收率。过共晶Al-Si合金经Al-P-N合金细化,可以减少P的添加量达到与Al-P合金相同的细化效果,且室温极限拉伸性能得到显著提高。在提高P吸收率的基础上,提出了Al-Si熔体中AlN粒子对P原子的吸附模型。     

Al-20％Si中间合金对Al-Si合金共晶Si变质行为的影响

研究了Al-20％Si中间合金对铸造Al-Si合金显微组织的影响.结果表明:向Al-Si合金熔体中加入1％的Al-20％Si中间合金,Al-7％Si合金中的共晶Si由粗大的板片状变为细密的纤维状或点状,变质效果较好,而对共晶Al- 12％Si合金的变质效果较弱;浇注温度对合金显微组织影响较大,适当降低浇注温度,有利于铸件组织的细化;变质温度越低越有利于颗粒状Si相成为形核核心,抑制枝晶组织的形成长大;在变质温度为650℃时,Al-20％Si中间合金对Al-7％Si合金变质有效时间是3h左右.     

Al-10Ce中间合金对ZL102合金的变质研究

用光学显微镜(OM)等分析研究Al-10Ce中间合金对ZL102共晶铝硅合金的变质处理效果.结果表明.Al-10Ce中间合金用量、熔体中的杂质以及冷却速度对变质效果的影响很大.Al-10Ce中间合金用量为0.9%左右时达到最佳变质效果,用量少变质效果差,用量过多则形成过变质.通过提高Al-Si的纯度可以获得变质组织.冷却速度超过70℃/min时才具有明显的变质效果.由于冷却强度不同,铸棒中心部位变质效果比边部差.Al-10Ce中间合金对共晶铝硅合金变质处理时间较短.     

电解Al-Si合金自变质显微组织及力学性能

电解Al-Si合金是一种符合我国矿产资源特点,能耗少、能减轻环境污染的轻质金属。电解Al-Si合金具有自变质的特性,Si相、Fe相及Ti相细小弯曲,共晶合金也具有相当数量的初生Al枝晶。合金组织对冷却速度不敏感,具有遗传性,合金具有良好的韧性和塑性。电解Al-Si合金熔体为均质熔体,凝固时出现大的过冷度是形成变质组织的原因。     

熔体温度处理及变质对Al-20%Si合金凝固组织的影响

采用熔体温度处理(包括熔体混合及过热处理)工艺研究Al-20%Si(质量分数)合金凝固组织,并结合化学变质法进一步细化初生硅相。结果表明,当熔体经混合后过热至900℃时,初生硅的尺寸约为34μm;添加变质剂后再进行熔体混合可以使Al-20%Si中的初生硅相进一步细化,特别是在Al-10%Si和Al-30%Si中分别添加0.2%Al-5Ti-C-3Ce和0.4%Cu-10%P后,再进行熔体过热处理,合金中的初生硅呈小块状弥散分布,且尺寸在10μm以下,材料基体呈现出典型的复合材料特征。熔体温度处理与添加化学变质剂方法对初生硅相有显著的多重变质细化作用;在熔体混合时α(Al)的重新熔化和熔体化学键的重组,增大了合金液在凝固时的过冷度,使初生硅相得到细化;对混合熔体再进行过热处理时,混合熔体中的Si相发生熔断、增殖,从而使合金中初生硅相得到进一步细化。添加细化剂或变质剂会明显增强熔体温度处理对Al-Si合金中初生硅的细化效果。     

A1—Si合金稀土氟盐变质剂研究

试验研究的结果表明,当添加适当的熔剂时,氟化稀土对金属型和砂型铸造Al-Si合金均有良好的变质效果,理论分析表明,该变质剂通过和熔体作用,产生稀土元素,从而起到变质作用。     

Relationship of Ca, B, and AlP in Al–12.6Si alloy

P modification has been widely used in Al-Si piston industry, but trace of Ca element has great influence on the P modification efficiency. In this work, it is found that primary Si can be heterogeneously nucleated by AlP in near eutectic Al-12.6Si alloy, but Ca element may destroy the P modification efficiency, whereas the addition of B can recover the P modification efficiency in near eutectic Al-12.6Si alloy with high Ca containing. The microstructure transformation was related to the reaction of Ca, B, and AlP. According to the thermodynamic calculation, Ca may react with AlP and form Ca3P2 compound in Al-Si alloy, whereas, when B was added into the melt, AlP could be reformed. The reaction of Ca, B, and AlP can be shown as follows: 2AlP +3Ca→Ca3P2+2Al; Ca3P2+18B+2Al→3CaB6+2AlP. In addition, with B added into the Al-12.6Si alloy with Ca and P addition, the mechanical properties were improved compared with single Ca and/or P addition.     

铝硅合金晶粒细化剂Al-Ti-C-P的研制

采用自蔓延＋熔铸法制备了Al-Ti—C-P晶粒细化剂，探讨了其对共晶铝硅合金的变质效果。通过扫描电镜（SEM）、光学显微镜（OM）、能谱分析（EDS）和X射线衍射仪（XRD）等手段，研究了Al—Ti—C—P晶粒细化刺的显微组织。结果表明：Al—Ti—C—P晶粒细化剂的主要相组成为TiAl3、TiC、AlP，对共晶铝硅合金具有优良的变质效果。晶粒细化剂中的TiAl2和TiC颗粒促进了AlP时共晶铝硅合金的变质效果。     

Al-Si-P master alloy and its modification and refinement performance on Al-Si alloys

An Al-Si-P master alloy has been developed by an in-situ reaction and the electron probe microanalyzer (EPMA) results show that there are many pre-formed AlP particles contained in the master alloy. Silicon introduced into the system plays an important role in remarkably im-proving the distribution and content of AlP particles due to their similar crystal structure and lattice parameters. ZL109 alloys have shown fast modification response to the addition of 0.5% Al-15Si-3.SP master alloy at 720℃, with a mass of primary Si precipitating in size of about 15 μm. Also, coarse primary Si grains in Al-30Si alloy can be refined dramatically from 150 μm to 37 μm after the addition of 2.0% Al- 15Si-3.5P master alloy at 850℃. The P recovery of the Al-15Si-3.5P master alloy is much higher than that of a Cu-8.SP master alloy due to the pre-formed AlP particles.     

Al-5Ti-1B对Al-Si合金磷变质行为影响机理的研究

研究了熔炼条件及Al-5Ti-1B中间合金加入量对P变质ZL109合金凝固组织的影响，并着重对其影响机理进行了探讨。结果发现在中频感应炉熔炼条件下，加入适量Al-5Ti-1B对初晶硅有明显的细化作用，而在静置炉（电阻炉）熔炼条件下，这种作用却不明显；同时发现，无论是在电阻炉还是感应炉熔炼条件下，加入过量的Al-5Ti-1B都会使合金中的初晶硅粗化。EPMA分析发现，加入Al-5Ti-1B后合金的初晶硅中心有Ti元素富集。分析认为Al-5Ti-1B中的TiB：粒子对AlP质点具有吸附作用，从而对Al-P中间合金的变质效果产生影响。     

Effects of P+Cr complex modification and solidification conditions on microstmcture of hypereutectic Al-Si alloys by wedge-shaped copper mould casting

Large and segregated primary Si particles may drastically decrease the mechanical properties of Al-Si alloys. To solve this problem, a P-Cr complex modif ier was added into the alloy, and the effects of P-Cr complex modification and solidification conditions on the microstructure of hypereutectic Al-Si alloys casting produced in wedge-shaped copper mould were studied. The thermal analysis technique was applied to calculate the cooling rate during solidification. The microstructures were observed by means of optical and scanning electron microscopies. Results showed that the primary Si segregates in the as-cast hypereutectic Al-Si alloys. The segregation of primary Si can be inhibited by adding a P+Cr complex modif ier and increasing the cooling rate during solidif ication. The ref inement of primary Si particles by P+Cr complex modif ication is due to the formation of CrS i2 and AlP particles which act as the heterogeneous nuclei for the primary Si phase. The segregation of Si was also inhibited through the adherence of heavier CrS i2 particles to the primary Si particles.     

变形处理Al—P中间合金对Al—Si合金变质作用的影响

将Al-2.5%P中间合金锭挤压成丝材能显著改善中间合金中AIP颗粒的分布形态,增加AIP的表面自由能。比较了Al-2.5%P中间合金锭和丝材对Al-Si合金的变质时间,发现采用Al-2.5%P中间合金丝能缩短变质时间,约15min即能使Al-Si合金获得良好的变质效果,更符合实际生产的要求。     

稀土Sm对Al-7Si-0.3Mg合金微观组织的影响

采用金相显微镜(OM)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射仪(XRD)和差示扫描量热法(DSC)等研究不同含量稀土Sm对Al-7Si-0.3Mg合金微观组织的影响。结果表明:添加Sm元素之后,合金的二次枝晶间距相比基础合金的明显减小;稀土Sm可以显著细化片层状的共晶硅,Sm元素主要形成Al2Si2Sm相。从能量角度,Sm可优先与P形成SmP相,可能会抑制AlP相的形成,减弱其促进共晶硅形核的效能。随着Sm元素含量的增加,Al-Si共晶反应的过冷度逐渐增大。     

Effects of individual and combined additions of phosphorus, boron and cerium on primary and eutectic silicon in an Al-30Si alloy

The modification of silicon in an Al-30Si alloy was studied using optical microscopy, electron probe micro-analysis, transmission electron microscopy and differential scanning calorimetry. It is found that phosphorus master alloys combined with boron master alloys have good modification effect on primary silicon but no evident modification effect on eutectic silicon, while boron combined with cerium has good modification effect on eutectic silicon. The results of differential scanning calorimetry show that phosphorus, boron or cerium addition and their combined addition have different undercooling effects on eutectic silicon. Many scholars thought that AlP particles were the nuclei of eutectic silicon when phosphorus was enough in the alloy. Our results show that β-(Al,Si,Fe) can still be the nucleus of plate-like eutectic silicon while AlP is the nucleus of primary silicon when there is enough phosphorus in the melt. In addition, the mechanism about the modification was also discussed.