Lead-free Sn-based/MW-CNTs nanocomposite soldering: effects of reinforcing content, Ni-coating modification, and isothermal ageing treatment

  • N. Shahamat Javid
  • R. Sayyadi
  • F. KhodabakhshiEmail author


In this article, soldering of sheet-form copper substrates in a lap-joint design by using the newly developed lead-free nanocomposite solders based on the ternary eutectic system of Sn–3.5Ag–0.7Cu (in wt%) alloy reinforced with multi-walled carbon nano-tubes (MW-CNTs) was assessed. Different weight percentages of MW-CNTs (0.05, 0.1, 0.15, and 0.2 wt%) were incorporated within the SAC solder matrix by using the powder mixture system and employing of mechanical alloying (MA) processing route. The main object was controlling the formation morphology and growth kinetics of intermetallic compounds (IMCs) layer at the interface with the Cu substrate during soldering process. Also, to improve the compatibility of reinforcing MW-CNTs and solder alloy, decoration of nickel particles on the surface of nanotubes by using the electroless plating system was considered. The results showed that by increasing the amount of reinforcing nanotubes and implementation of Ni-coating on the surface of MW-CNTs, the thickness of IMC layer at the interface between Cu substrate and solder alloy is continuously refined. This important issue yielded to a continuous and significant improvement of tensile strength up to ~ 50%, as compared to the un-reinforced SAC solder alloy, despite of considerable ductility reduction. In following, the influence of post isothermal ageing treatment at a temperature of 150 °C with a holding time up to ~ 100 h on the microstructural characteristics and mechanical property of the soldered joints was elaborated. Employing of such isothermal ageing treatment revealed very effective in more elevating the mechanical strength of soldered joints (to attain the tensile strength of up to ~ 30 MPa). Furthermore, a simultaneous improvement of the elongation to failure more than ~ 22% was noted caused by increasing the thickness of the IMC layer at the interface. To this end, acceleration in the solid-state diffusion of elements played the main role.


  1. 1.
    J. Keller, D. Baither, U. Wilke, G. Schmitz, Mechanical properties of Pb-free SnAg solder joints. Acta Mater. 59(7), 2731–2741 (2011)Google Scholar
  2. 2.
    Y. Yang, J.N. Balaraju, Y. Huang, H. Liu, Z. Chen, Interface reaction between an electroless Ni–Co–P metallization and Sn–3.5Ag lead-free solder with improved joint reliability. Acta Mater. 71, 69–79 (2014)Google Scholar
  3. 3.
    Y. Yao, J. Fry, M.E. Fine, L.M. Keer, The Wiedemann–Franz–Lorenz relation for lead-free solder and intermetallic materials. Acta Mater. 61(5), 1525–1536 (2013)Google Scholar
  4. 4.
    F. Khodabakhshi, R. Sayyadi, N.S. Javid, Lead free Sn–Ag–Cu solders reinforced by Ni-coated graphene nanosheets prepared by mechanical alloying: microstructural evolution and mechanical durability. Mater. Sci. Eng. A 702, 371–385 (2017)Google Scholar
  5. 5.
    M. Huang, F. Yang, Size effect model on kinetics of interfacial reaction between Sn–xAg–yCu solders and Cu substrate. Sci. Rep. 4, 7117 (2014)Google Scholar
  6. 6.
    L. Zhang, K.N. Tu, Structure and properties of lead-free solders bearing micro and nano particles. Mater. Sci. Eng. R 82(1), 1–32 (2014)Google Scholar
  7. 7.
    S.M.L. Nai, J. Wei, M. Gupta, Interfacial intermetallic growth and shear strength of lead-free composite solder joints. J. Alloys Compd. 473(1–2), 100–106 (2009)Google Scholar
  8. 8.
    T. Fouzder, Q. Li, Y.C. Chan, D.K. Chan, Interfacial microstructure and hardness of nickel (Ni) nanoparticle-doped tin-silver-copper (Sn–Ag–Cu) solders on immersion silver (Ag)-plated copper (Cu) substrates. J. Mater. Sci. - Mater. Electron. 25(9), 4012–4023 (2014)Google Scholar
  9. 9.
    N. Zhao, Y. Zhong, M.L. Huang, H.T. Ma, W. Dong, Growth kinetics of Cu6Sn5 intermetallic compound at liquid-solid interfaces in Cu/Sn/Cu interconnects under temperature gradient. Sci. Rep. 5, 13491 (2015)Google Scholar
  10. 10.
    B. Li, Y. Shi, Y. Lei, F. Guo, Z. Xia, B. Zong, Effect of rare earth element addition on the microstructure of Sn–Ag–Cu solder joint. J. Electron. Mater. 34(3), 217–224 (2005)Google Scholar
  11. 11.
    Y.W. Wang, C.C. Chang, C.R. Kao, Minimum effective Ni addition to SnAgCu solders for retarding Cu3Sn growth. J. Alloys Compd. 478(1), L1–L4 (2009)Google Scholar
  12. 12.
    M. Sobhy, A.M. El-Refai, M.M. Mousa, G. Saad, Effect of ageing time on the tensile behavior of Sn-3.5 wt% Ag-0.5 wt% Cu (SAC355) solder alloy with and without adding ZnO nanoparticles. Mater. Sci. Eng. A 646, 82–89 (2015)Google Scholar
  13. 13.
    G. Chen, H. Peng, V.V. Silberschmidt, Y.C. Chan, C. Liu, F. Wu, Performance of Sn–3.0Ag–0.5Cu composite solder with TiC reinforcement: Physical properties, solderability and microstructural evolution under isothermal ageing. J. Alloys Compd. 685, 680–689 (2016)Google Scholar
  14. 14.
    A. Lee, K.N. Subramanian, Development of nano-composite lead-free electronic solders. J. Electron. Mater. 34(11), 1399–1407 (2005)Google Scholar
  15. 15.
    M.H. Obaidat, O.T. Al Meanazel, M.A. Gharaibeh, H.A. Almomani, Pad cratering: reliability of assembly level and joint level. Jordan J. Mech. Ind. Eng. 10(4), 271–277 (2016)Google Scholar
  16. 16.
    Y. Fujiwara, H. Enomoto, T. Nagao, H. Hoshika, Composite plating of Sn–Ag alloys for Pb-free soldering, Surf. Coat. Technol. 169–170 (2003) 100–103Google Scholar
  17. 17.
    S.Y. Hwang, J.W. Lee, Z.H. Lee, Microstructure of a lead-free composite solder produced by an in-situ process. J. Electron. Mater. 31(11), 1304–1308 (2002)Google Scholar
  18. 18.
    J.W. Lee, Z.H. Lee, H.M. Lee, Formation of intermetallic compounds in the Ni bearing lead free composite solders. Mater. Trans. 46(11), 2344–2350 (2005)Google Scholar
  19. 19.
    N.H. Cao-Luu, Q.T. Pham, Z.H. Yao, F.M. Wang, C.S. Chern, Synthesis and characterization of poly(N-isopropylacrylamide-co-acrylamide) mesoglobule core–silica shell nanoparticles. J. Colloid Interface Sci. 536, 536–547 (2019)Google Scholar
  20. 20.
    J. Li, J. Ma, S. Chen, Y. Huang, J. He, Adsorption of lysozyme by alginate/graphene oxide composite beads with enhanced stability and mechanical property. Mater. Sci. Eng. C 89, 25–32 (2018)Google Scholar
  21. 21.
    M. Ma, Y. Yang, W. Li, R. Feng, Z. Li, P. Lyu, Y. Ma, Gold nanoparticles supported by amino groups on the surface of magnetite microspheres for the catalytic reduction of 4-nitrophenol. J. Mater. Sci. 54(1), 323–334 (2019)Google Scholar
  22. 22.
    G. Wu, Y. Cheng, Z. Yang, Z. Jia, H. Wu, L. Yang, H. Li, P. Guo, H. Lv, Design of carbon sphere/magnetic quantum dots with tunable phase compositions and boost dielectric loss behavior. Chem. Eng. J. 333, 519–528 (2018)Google Scholar
  23. 23.
    G. Wu, Z. Jia, Y. Cheng, H. Zhang, X. Zhou, H. Wu, Easy synthesis of multi-shelled ZnO hollow spheres and their conversion into hedgehog-like ZnO hollow spheres with superior rate performance for lithium ion batteries. Appl. Surf. Sci. 464, 472–478 (2019)Google Scholar
  24. 24.
    S.R. Bakshi, D. Lahiri, A. Agarwal, Carbon nanotube reinforced metal matrix composites—a review. Int. Mater. Rev. 55(1), 41–64 (2013)Google Scholar
  25. 25.
    J. Mittal, K.L. Lin, The formation of electric circuits with carbon nanotubes and copper using tin solder. Carbon 49(13), 4385–4391 (2011)Google Scholar
  26. 26.
    S. Berber, Y.K. Kwon, D. Tománek, Unusually high thermal conductivity of carbon nanotubes. Phys. Rev. Lett. 84(20), 4613–4616 (2000)Google Scholar
  27. 27.
    J.N. Coleman, U. Khan, W.J. Blau, Y.K. Gun’ko, Small but strong: a review of the mechanical properties of carbon nanotube–polymer composites. Carbon 44(9), 1624–1652 (2006)Google Scholar
  28. 28.
    S.M.L. Nai, M. Gupta, J. Wei, Evelopment of novel lead-free solder composites using carbon nanotube reinforcements. Int. J. Nanosci. 4(4), 423–429 (2005)Google Scholar
  29. 29.
    S.M.L. Nai, J. Wei, M. Gupta, Lead-free solder reinforced with multiwalled carbon nanotubes. J. Electron. Mater. 35(7), 1518–1522 (2006)Google Scholar
  30. 30.
    S.M.L. Nai, J. Wei, M. Gupta, Improving the performance of lead-free solder reinforced with multi-walled carbon nanotubes. Mater. Sci. Eng. A 423(1–2), 166–169 (2006)Google Scholar
  31. 31.
    E.K. Choi, K.Y. Lee, T.S. Oh, Fabrication of multiwalled carbon nanotubes-reinforced Sn nanocomposites for lead-free solder by an electrodeposition process. J. Phys. Chem. Solids 69(5–6), 1403–1406 (2008)Google Scholar
  32. 32.
    K.M. Kumar, V. Kripesh, A.A.O. Tay, Single-wall carbon nanotube (SWCNT) functionalized Sn–Ag–Cu lead-free composite solders. J. Alloys Compd. 450(1–2), 229–237 (2008)Google Scholar
  33. 33.
    V.L. Niranjani, B.S.S.C. Rao, V. Singh, S.V. Kamat, Influence of temperature and strain rate on tensile properties of single walled carbon nanotubes reinforced Sn–Ag–Cu lead free solder alloy composites. Mater. Sci. Eng., A 529(1), 257–264 (2011)Google Scholar
  34. 34.
    S.M.L. Nai, J. Wei, M. Gupta, Effect of carbon nanotubes on the shear Strength and electrical resistivity of a lead-free solder. J. Electron. Mater. 37(4), 515–522 (2008)Google Scholar
  35. 35.
    S.M.L. Nai, J. Wei, M. Gupta, Using carbon nanotubes to enhance creep performance of lead free solder. Mater. Sci. Technol. 24(4), 443–448 (2008)Google Scholar
  36. 36.
    S. Chantaramanee, S. Wisutmethangoon, L. Sikong, T. Plookphol, Development of a lead-free composite solder from Sn–Ag–Cu and Ag-coated carbon nanotubes. J. Mater. Sci. - Mater. Electron. 24(10), 3707–3715 (2013)Google Scholar
  37. 37.
    Z. Yang, W. Zhou, P. Wu, Effects of Ni-coated Carbon Nanotubes addition on the electromigration of Sn–Ag–Cu solder joints. J. Alloys Compd. 581, 202–205 (2013)Google Scholar
  38. 38.
    S.H. Kim, M.S. Park, J.P. Choi, C. Aranas Jr., Improved electrical and thermo-mechanical properties of a MWCNT/In–Sn–Bi composite solder reflowing on a flexible PET substrate. Sci. Rep. 7(1), 13756 (2017)Google Scholar
  39. 39.
    V. Gopee, O. Thomas, C. Hunt, V. Stolojan, J. Allam, S.R. Silva, Carbon nanotube interconnects realized through functionalization and sintered silver attachment. ACS Appl. Mater. Interfaces 8(8), 5563–5570 (2016)Google Scholar
  40. 40.
    S. Xu, X. Hu, Y. Yang, Z. Chen, Y.C. Chan, Effect of carbon nanotubes and their dispersion on electroless Ni–P under bump metallization for lead-free solder interconnection. J. Mater. Sci. - Mater. Electron. 25(6), 2686–2691 (2014)Google Scholar
  41. 41.
    K. Mehrabi, F. Khodabakhshi, E. Zareh, A. Shahbazkhan, A. Simchi, Effect of alumina nanoparticles on the microstructure and mechanical durability of meltspun lead-free solders based on tin alloys. J. Alloys Compd. 688, 143–155 (2016)Google Scholar
  42. 42.
    G. Zeng, S. McDonald, K. Nogita, Development of high-temperature solders: review. Microelectron. Reliab. 52(7), 1306–1322 (2012)Google Scholar
  43. 43.
    X.D. Liu, Y.D. Han, H.Y. Jing, J. Wei, L.Y. Xu, Effect of graphene nanosheets reinforcement on the performance of Sn–Ag–Cu lead-free solder. Mater. Sci. Eng. A 562, 25–32 (2013)Google Scholar
  44. 44.
    K. Prakash, T. Sritharan, Interface reaction between copper and molten tin–lead solders. Acta Mater. 49(13), 2481–2489 (2001)Google Scholar
  45. 45.
    A. Agarwal, S.R. Bakshi, D. Lahiri, Carbon Nanotubes: Reinforced Metal Matrix Composites (CRC Press, Boca Raton, 2016)Google Scholar
  46. 46.
    Y.D. Han, H.Y. Jing, S.M.L. Nai, L.Y. Xu, C.M. Tan, J. Wei, Interfacial reaction and shear strength of Ni-coated carbon nanotubes reinforced Sn–Ag–Cu solder joints during thermal cycling. Intermetallics 31, 72–78 (2012)Google Scholar
  47. 47.
    M. Kouzeli, A. Mortensen, Size dependent strengthening in particle reinforced aluminium. Acta Mater. 50(1), 39–51 (2002)Google Scholar
  48. 48.
    F. Khodabakhshi, A. Simchi, A.H. Kokabi, P. Švec, F. Simančík, A.P. Gerlich, Effects of nanometric inclusions on the microstructural characteristics and strengthening of a friction-stir processed aluminum–magnesium alloy. Mater. Sci. Eng. A 642, 215–229 (2015)Google Scholar
  49. 49.
    F. Khodabakhshi, A.P. Gerlich, P. Švec, Reactive friction-stir processing of an Al-Mg alloy with introducing multi-walled carbon nano-tubes (MW-CNTs): Microstructural characteristics and mechanical properties. Mater. Charact. 131, 359–373 (2017)Google Scholar
  50. 50.
    F. Khodabakhshi, M. Nosko, A.P. Gerlich, Influence of CNTs decomposition during reactive friction-stir processing of an Al–Mg alloy on the correlation between microstructural characteristics and microtextural components. J. Microsc. 271(2), 188–206 (2018)Google Scholar
  51. 51.
    G.E. Dieter, D.J. Bacon, Mechanical Metallurgy (McGraw-Hill, New York, 1986)Google Scholar
  52. 52.
    Y.D. Han, S.M.L. Nai, H.Y. Jing, L.Y. Xu, C.M. Tan, J. Wei, Development of a Sn–Ag–Cu solder reinforced with Ni-coated carbon nanotubes. J. Mater. Sci. - Mater. Electron. 22(3), 315–322 (2011)Google Scholar
  53. 53.
    Y.D. Han, H.Y. Jing, S.M.L. Nai, L.Y. Xu, C.M. Tan, J. Wei, Creep mitigation in Sn–Ag–Cu composite solder with Ni-coated carbon nanotubes. J. Mater. Sci. - Mater. Electron. 23(5), 1108–1115 (2011)Google Scholar
  54. 54.
    T.K. Lee, T.R. Bieler, C.U. Kim, H. Ma, Fundamentals of Lead-Free Solder Interconnect Technology (Springer, New York, 2015)Google Scholar
  55. 55.
    F. Gao, T. Takemoto, H. Nishikawa, Effects of Co and Ni addition on reactive diffusion between Sn–3.5 Ag solder and Cu during soldering and annealing. Mater. Sci. Eng. A 420(1–2), 39–46 (2006)Google Scholar
  56. 56.
    S. Tay, A. Haseeb, M.R. Johan, P. Munroe, M.Z. Quadir, Influence of Ni nanoparticle on the morphology and growth of interfacial intermetallic compounds between Sn–3.8 Ag–0.7 Cu lead-free solder and copper substrate. Intermetallics 33, 8–15 (2013)Google Scholar
  57. 57.
    A.A. El-Daly, A.M. El-Taher, T.R. Dalloul, Improved creep resistance and thermal behavior of Ni-doped Sn–3.0Ag–0.5Cu lead-free solder. J. Alloys Compd. 587, 32–39 (2014)Google Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  • N. Shahamat Javid
    • 1
  • R. Sayyadi
    • 1
  • F. Khodabakhshi
    • 2
    Email author
  1. 1.Department of Materials Science and Engineering, School of EngineeringShiraz UniversityShirazIran
  2. 2.School of Metallurgical and Materials Engineering, College of EngineeringUniversity of TehranTehranIran

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