CN115815872A - Lead-free and antimony-free reinforced solder alloy and preparation method thereof - Google Patents
Lead-free and antimony-free reinforced solder alloy and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a lead-free and antimony-free reinforced solder alloy and a preparation method thereof, wherein the lead-free and antimony-free reinforced solder alloy comprises the following components in percentage by weight: bi:2% -5%; ag:3% -5%; cu:0.4% -0.8%; ni:0.001% -0.5%; and the balance Sn. The solder alloy does not contain lead and antimony, wherein Bi, sn, ag, cu and Ni enhance the second phase and refine crystal grains to strengthen the high-temperature mechanical property, so that the lead-free and antimony-free strengthened solder can bear higher load and ambient temperature; meanwhile, the lead-free reinforced solder has good plasticity, forming and processing capacity and wetting property, low welding voidage, small melting point change and longer service life, does not need to change the existing welding process, and has strong replaceability. The preparation method comprises the steps of preparing Sn-Zr intermediate alloy, sn-Cu-Zr intermediate alloy and ZrH 2 The lead-free reinforced solder alloy is prepared from the powder or the Cu-Zr intermediate alloy, so that the smelting temperature is reduced, the serious oxidation of Sn is avoided, other new impurities are not introduced, the quality of the product is improved, and the cost is reduced.
Description
Technical Field
The invention belongs to the technical field of electronic assembly, packaging and power semiconductor packaging, and particularly relates to a lead-free and antimony-free reinforced solder alloy and a preparation method thereof.
Background
With the wide application of electronic products, the reliability of electronic products is valued by people, especially in the fields of aviation, aerospace, military, monitoring, finance, communication and the like, and once failure and invalidation occur, huge loss is caused. The integrated circuit industry in the field of electronic packaging requires smaller and smaller solder joint sizes to bear electricity, gas, heat and force, and higher packaging densities, and can be in service in higher-frequency power cycles, higher vibration levels, high humidity, more severe temperature cycles and higher temperature environments. The conventional SAC305 is a lead-free solder alloy containing 96.5% tin, 3% silver and 0.5% copper. The conventional foreign SAC305 strengthened brazing filler metal alloy has high tensile strength, but sacrifices plasticity and wettability. The solder alloy has wettability which affects the welding voidage, and when the welding voidage is high, the shear strength of a welding spot is low, so that the high-temperature creep life of the welding spot is affected, and therefore the solder alloy not only needs high tensile strength, but also needs good wettability. Therefore, the mechanical properties of the SAC305 solder alloy have not met the increasingly demanding requirements of the industry.
Although the existing Sn-Pb solder is widely used due to its low price and excellent wettability, pb and Pb-containing compounds have toxicity, and thus, electronic and electrical equipment (WEEE) directive of the united states environmental protection agency and restriction of certain hazardous substances (RoHS) by the european union prohibit lead-containing electronic products, respectively, from 7/1/2006. In addition, in some special applications where the cooling rate of package soldering is slow, the addition of Sb may cause the specific gravity segregation of SnSb phase, forming coarse SnSb phase, and at the same time, the properties such as solder forming ability, wettability, thermal expansion coefficient, etc. may be affected, and the package reliability of electronic products may be affected, so that the research on novel lead-free and antimony-free solder alloys is urgent.
The reliability of the electronic device is evaluated, and accelerated tests are usually adopted in the early stage packaging link verification, so that the service life is estimated or weak links are determined in the conditions of higher-frequency power cycle, higher vibration level, high humidity, harsher temperature cycle and higher temperature environment, wherein the most typical and important accelerated tests are accelerated temperature cycle tests. It has been demonstrated that the creep deformation behavior of lead-free solders at temperatures close to or above 0.5 times the melting point plays a very important role if the loading rate is slow enough for creep deformation to occur. Creep response can be considered to be the dominant deformation in the use of a weld. Therefore, in solder development, the evaluation of creep performance plays a decisive role in solder joint reliability.
Therefore, in order to meet the increasing performance requirements for solder alloys and to meet environmental or health requirements, there is a need for an enhanced high creep performance lead-free and antimony-free solder alloy that meets the high reliability of electronic assembly, packaging and power semiconductor packaging.
Disclosure of Invention
In order to overcome the defects of the prior art, the first object of the invention is to provide a lead-free and antimony-free reinforced solder alloy, which does not contain lead, and the solder joint formed by welding has the characteristics of long creep life, no sacrifice of wettability and forming capability, and suitability for large-scale production of enterprises.
The second purpose of the invention is to provide a lead-free and antimony-free reinforced solder alloy and a preparation method thereof.
The first purpose of the invention can be achieved by adopting the following technical scheme:
a lead-free and antimony-free reinforced solder alloy comprises the following components in percentage by weight:
Bi：2%-5%；
Ag：3%-5%；
Cu：0.4%-0.8%；
Ni：0.001%-0.5%；
Zr：0.001%-0.5%；
and Sn:91.2% -94.598%;
and (Ag-3.5%) 2 +（Bi-3%) 2 ≤0.0002；Zr+Ni<0.5%。
Furthermore, the material also comprises 0.001 to 0.1 weight percent of Ge.
Further, one or more of Ti, co, in, P, ga, B, au, ta, V, nb, hf, ta, mn, al, zn and Si elements are contained, and the content of each element does not exceed the content of Ni.
The second purpose of the invention can be achieved by adopting the following technical scheme:
a preparation method of a lead-free and antimony-free reinforced solder alloy comprises the following steps:
in the atmospheric environment, at the temperature of above 650 ℃, intermediate alloy and/or ZrH of Sn elementary metal, ni elementary metal, cu elementary metal, ag elementary metal, ge elementary metal and Zr 2 Sequentially adding powder and Bi elementary metal for smelting;
wherein the intermediate alloy of Zr is one or the combination of two of Sn-Zr and Sn-Cu-Zr intermediate alloy.
Further, the mass percent of Zr in the Sn-Zr intermediate alloy is 0.01-16.9%; the melting point of the Sn-Zr intermediate alloy is 232-1142 ℃.
A preparation method of a lead-free and antimony-free reinforced solder alloy comprises the following steps:
under the protection atmosphere or vacuum environment, sn elementary substance metal, ni elementary substance metal, cu elementary substance metal, ag elementary substance metal, ge elementary substance metal, intermediate alloy of Bi elementary substance metal and Zr and/or ZrH are/is added at the temperature of more than 885 DEG C 2 Adding the powder for smelting;
wherein the intermediate alloy of Zr is Cu-Zr intermediate alloy;
the pressure of the protective atmosphere is 0.1-7kPa higher than the atmospheric pressure; the air pressure of the vacuum environment is 0.81-100Pa.
Further, the mass percent of Zr in the Cu-Zr intermediate alloy is 1-79%.
Compared with the prior art, the invention has the beneficial effects that:
1. compared with the traditional SAC305 solder alloy, the lead-free and antimony-free strengthened solder alloy disclosed by the invention has the advantages that the mechanical property is remarkably improved, the creep life at normal temperature and high temperature is greatly prolonged, the cost is lower, the lead-free and antimony-free strengthened solder alloy meets the industrial large-scale production and application, has excellent exchangeability, and meets the requirements of various electronic components such as PCB assembly, automobile accessory modules, chip modules, power supply modules and the like on solder; the strengthened solder alloy does not contain lead and antimony, so that the damage to the environment and the influence on the biological health are reduced, the generation of a coarse SnSb phase by the solder can be thoroughly avoided, the high-temperature creep life of the solder is prolonged, and the packaging reliability is improved.
2. According to the preparation method of the lead-free reinforced solder alloy, zr is added in the form of intermediate alloy, the adding sequence of each component is limited, the melting temperature is reduced, the funds for purchasing high-temperature melting equipment, consuming power in high-temperature melting and the like are saved, and the cost is reduced; the alloy can be smelted in the atmospheric environment, so that the serious oxidation of Sn is avoided, other new impurities are not introduced, and the quality of the product is improved.
Drawings
FIG. 1 is a metallographic structure diagram of a metallographic structure of a sample 9 Sn92.249Ag4Cu0.7Bi3Ni0.05Zr0.001.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the specific embodiments. It is to be understood that the described embodiments are merely some embodiments of the invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The service life of the traditional SAC305 brazing filler metal under high temperature and high load is short, so that the invention provides the lead-free and antimony-free reinforced brazing filler metal alloy which has higher tensile strength and longer creep life, does not sacrifice wettability and forming capability, is suitable for large-scale production and application of enterprises, and solves the problem that the service life of the traditional SAC305 brazing filler metal under high temperature and high load is short.
A lead-free and antimony-free reinforced solder alloy comprises the following components in percentage by weight:
bi:2 to 5 percent; ag:3% -5%; cu:0.4% -0.8%; ni:0.001% -0.5%; zr:0.001% -0.5%; and Sn:91.2% -94.598%; and (Ag-3.5%) 2 +（Bi-3%) 2 ≤0.0002；Zr+Ni<0.5%。
The micro-mechanism of creep deformation is mainly 3: the main requirements for improving the creep life are to control the dislocation climbing speed and the grain boundary sliding, namely to control the atom diffusion process in the crystal and the grain boundary. For this reason, it is considered that the addition of the second strengthening phase resists creep deformation by hindering dislocation glide, refining grain-strengthening grain boundary strength, and the like.
In the tin alloy, trace elements of Zr and Ni can form Sn with Sn 2 Zr、Ni 3 Sn 4 The high-temperature refractory compound can play a role in non-spontaneous nucleation in the molten liquid, so that finally solidified crystal grains are fine and have a large number of crystal grains. And the finer the crystal grains, the more crystal boundaries are formed, so that the dislocation motion can be effectively blocked, the plastic deformation can be resisted, and the time for the alloy to fracture due to creep can be prolonged. At the same time, sn 2 Zr、Ni 3 Sn 4 Sn as a dispersed phase capable of strongly inhibiting dislocation movement 2 Zr、Ni 3 Sn 4 The particle hardness is higher, the stability is better under high temperature, and the strengthening effect is better. And the strengthening effect of a plurality of elements is better than that of a single element, so trace elements Zr and Ti are added into Sn to form the alloy.
In the tin alloy, bi is added, a part of Bi can form a solid solution beta-Sn, and a part of Bi forms a Bi crystal structure to be pinned in a matrix, so that solute atoms and dislocations interact to block dislocation movement, and the material strength is improved. After the Bi is added, the Bi element does not form a high-melting-point second phase with Sn, ag and Cu elements, and eutectic, homogeneous crystal and other reactions occur, so that the melting point of each element can be reduced; thus enabling the use of lead-free and antimony-free strengthened solder alloys to replace the SAC305 solder alloy at conventional soldering process temperatures; besides, bi can improve the integral wettability of the solder and reduce the welding void ratio.
Therefore, the invention strengthens the matrix alloy solder by adding Bi, ni and Zr, improves the high-temperature creep life of the welding spot and further improves the service life of the module.
As an embodiment of the invention, the Ge is further contained in an amount of 0.001 to 0.1% by weight.
The oxidation of the Sn solder alloy in the using processes of smelting, casting, forming and welding can be reduced by adding trace Ge element. When a trace amount of Ge element, ga is added into Sn solder alloy 3+ The complex oxysalt is enriched on the surface of the Sn solder alloy, can be preferentially oxidized to form a compact oxide film, and prevents Sn from being directly oxidized to Sn 4+ Or a dense oxide film formed to prevent further oxidation of Sn.
Wherein the chemical composition satisfies the following formula (1):
（Ag-3.5%） 2 +（Bi-3%) 2 ≤0.0002 （1）
in the formula (1), ag and Bi respectively represent the weight percentage of the chemical components of the alloy.
The addition of Ag changes the creep property, the creep property of the solder with the content of 3.5 percent reaches the best, meanwhile, sn-3.5Ag is a eutectic structure, and the solder with the silver content of more than 3.5 percent is a hypereutectic structure, so that the Ag can be caused 3 Sn is coarse and brittle intermetallic compounds having a size of several tens of micrometers are fatal to reliability of solder joints, so that excessive use of Ag should be avoided. When the silver content is small, the solder strength per se and brittle Cu to the solder joint 3 Sn、Cu 6 Sn 5 The growth inhibition capability of the IMC layer is weakened, and the mechanical property and reliability of the welding spot are influenced. The addition of Bi contributes to the wetting and strength improvement, and the solder joint tensile strength reaches the maximum at 3%, and the use of excessive Bi makes the solder itself more brittle and the plasticity worse, making the processing more difficult. Therefore, the weight percentage of the chemical components of Ag and Bi satisfies the formula (Ag-3.5%) 2 +（Bi-3%) 2 The creep property, plasticity, wettability and strength of the solder can be optimized only when the solder is less than or equal to 0.0002.
Wherein the chemical composition satisfies the following formula (2):
Zr+Ni<0.5 % （2）
in the formula (2), zr and Ni respectively represent the weight percentage of the chemical components of the alloy.
The addition of Zr and Ni can improve the high-temperature creep life of the solder alloy, and the creep life is increased along with the increase of Zr and Ni within a certain range, but the creep life is reduced on the contrary after the addition exceeds a certain range. Research shows that when the chemical component contents of Zr and Ni exceed a certain range, the wettability and the welding voidage of the brazing filler metal alloy are influenced, and the high-temperature creep life is further influenced. Therefore, in the application scene that the soldering flux cannot be coated, when the weight percentage of the chemical components of Zr and Ni meets the formula Zr + Ni <0.5%, the creep life of the solder can be prolonged.
In one embodiment of the present invention, the alloy further contains one or a combination of two or more of elements selected from the group consisting of Ti, co, in, P, ga, B, au, ta, V, nb, hf, ta, mn, al, zn and Si, and the content of each element does not exceed the content of Ni.
Elements such as Ti, co, in, P, ga, B, au, ta, V, nb, hf, ta, mn, al, zn, si and the like are added into the Sn matrix to form a solid solution, so that the solid solution strengthening is realized, the stacking fault can be reduced, the extended dislocation is easier to form, and the dislocation is difficult to generate secant order, cross slip and climb; meanwhile, solute atoms and solvent atoms have stronger bonding force, and the diffusion activation energy is increased, which are beneficial to the improvement of creep life.
The invention relates to a preparation method of a lead-free and antimony-free reinforced solder alloy, which comprises the following steps:
in the atmospheric environment, at the temperature of above 650 ℃, intermediate alloy and/or ZrH of Sn elementary metal, ni elementary metal, cu elementary metal, ag elementary metal, ge elementary metal and Zr 2 Sequentially adding powder and Bi elementary metal for smelting;
wherein the intermediate alloy of Zr is one or the combination of two of Sn-Zr and Sn-Cu-Zr intermediate alloy.
The preparation method comprises the following steps of smelting according to Sn elementary metal, ni elementary metal, cu elementary metal, ag elementary metal and Ge elementary metalMetal, zr master alloy and/or ZrH 2 Sequentially adding powder and Bi elementary metal; the smelting can be carried out at the temperature of more than 650 ℃, the smelting temperature is reduced, the smelting can be carried out in the atmospheric environment, the serious oxidation of Sn can be avoided, other new impurities cannot be introduced, the product quality can be improved, the capital for protecting the atmosphere, purchasing high-temperature smelting equipment, consuming power for high-temperature smelting and the like is saved, and the cost is reduced.
The melting point of Zr element is 1852 deg.C, the melting point of Sn is 231.9 deg.C, if it depends on high temperature to break the metal bond of zirconium crystal, sn will be oxidized seriously. Although the vacuum melting possibly solves the problem of tin high-temperature oxidation, the melting cannot be carried out due to the fact that the boiling point of Sn is far lower than the melting point of zirconium under low pressure, and therefore Sn-Cu-Zr intermediate alloys and Sn-Zr intermediate alloys are provided for preparing the lead-free and antimony-free reinforced solder alloy.
In one embodiment of the present invention, the mass percentage of Zr in the Sn — Zr intermediate alloy is 0.01 to 16.9%; the melting point of the Sn-Zr intermediate alloy is 232-1142 ℃.
The intermediate alloy of Zr is Sn-Cu-Zr intermediate alloy, because the melting point of the Cu-Zr intermediate alloy is 885-1115 ℃, and the melting point of 885-1115 ℃ belongs to a high-temperature melting point, the Cu-Zr intermediate alloy is smelted in an atmospheric environment, and the oxidation of Sn, sb and Bi is serious, so that the Cu-Zr intermediate alloy is prepared into the Sn-Cu-Zr intermediate alloy, and the melting point temperature of the intermediate alloy is further reduced.
As an embodiment of the invention, zr component in the lead-free and antimony-free reinforced solder alloy is ZrH 2 Is added as raw material.
In the chemical addition of zirconium atoms, sn itself cannot reduce Zr 4+ Is a zirconium monomer and therefore cannot be added by redox reaction, and therefore can only be decomposed by pyrolysis reaction, zrH 2 At 700 ℃, the zirconium atoms are decomposed into hydrogen and zirconium atoms, a part of the zirconium atoms enter into the molten liquid, and when the zirconium atoms are solidified, the zirconium atoms and Sn, ag, cu and Bi atoms in the liquid generate compounds, and the compounds are decomposed to generate gas without introducing impurities. Thus, the invention uses ZrH 2 Used as a raw material of Zr in the lead-free and antimony-free reinforced solder alloy.
The invention relates to a preparation method of a lead-free and antimony-free reinforced solder alloy, which comprises the following steps:
under the protection atmosphere or vacuum environment, sn elementary substance metal, ni elementary substance metal, cu elementary substance metal, ag elementary substance metal, ge elementary substance metal, intermediate alloy of Bi elementary substance metal and Zr and/or ZrH are/is added at the temperature of more than 885 DEG C 2 Adding powder and smelting;
wherein the Zr intermediate alloy is Cu-Zr intermediate alloy.
The preparation method comprises the step of smelting intermediate alloy and/or ZrH of Sn elementary metal, ni elementary metal, cu elementary metal, ag elementary metal, ge elementary metal and Zr 2 Adding powder and Bi elementary metal, and smelting at a temperature of more than 885 ℃; the charging sequence is not required to be controlled, and charging and smelting are carried out in a protective atmosphere or a vacuum environment, so that oxidation of Sn by high-temperature smelting can be avoided, and smelting at a higher temperature is realized.
The melting point of Zr is 1852 ℃, the melting point of Sn is 231.9 ℃, the melting points of Sn and Zr are greatly different, if the metallic bond between zirconium crystals is damaged, the temperature is raised to the melting point to provide sufficient energy to break the metallic bond, so that Zr atoms are in a short-range ordered and long-range disordered state, atomic groups with short-range ordered are not fixed, but are structural fluctuation which is easy to eliminate, is instantaneously changeable and is unstable in size, and Zr atoms can be combined with Sn, ag, cu and Bi atoms in a phase diagram proportion to generate intermetallic compounds during solidification. However, sn, ag, cu, bi, etc. are oxidized at high temperature, and therefore, when zirconium atoms are generated from the zirconium compound as a raw material, it is necessary to reduce the energy for breaking chemical bonds, that is, to lower the melting point of the master alloy. Under the premise of not introducing other impurities, after the metallic bond of the Zr crystal is broken at 1852 ℃, the Zr crystal and the Zr atom are combined into Sn, ag, cu and Bi of intermetallic compounds, and considering that the Sn and the Bi are seriously oxidized, the Zr crystal is not suitable for being used as an intermediate alloy with zirconium; the melting point of silver is 960.5 ℃, the oxidation is serious, and the silver belongs to noble metal, so the silver is not suitable for being used as intermediate alloy with zirconium. Therefore, cu-Zr is selected as the intermediate alloy, the chemical composition of the intermediate alloy is 1-79 percent of Zr and the balance of Cu according to weight percentage, and the melting point is 885-1115 ℃.
In one embodiment of the present invention, the mass percentage of Zr in the Cu — Zr intermediate alloy is 1 to 79%.
Because the melting point of the Cu-Zr intermediate alloy is 885-1115 ℃, and the melting point of 885-1115 ℃ belongs to a high-temperature melting point, the oxidation of Sn, sb and Bi is still serious when the Cu-Zr intermediate alloy is smelted in an atmospheric environment, so that the charging smelting is carried out in a protective atmosphere or a vacuum environment, and the oxidation of other elements is avoided.
As an embodiment of the present invention, the pressure of the protective atmosphere is 0.1 to 7kPa greater than the atmospheric pressure; the air pressure of the vacuum environment is 0.81-100Pa.
The following will explain further by way of specific examples.
Example 1
Sequentially adding Sn elemental metal, ni elemental metal, cu elemental metal, ag elemental metal and Bi elemental metal according to the proportion of alloy components, and smelting at the temperature of 600 ℃ in an atmospheric environment to prepare the lead-free and antimony-free strengthened solder alloy, wherein the lead-free and antimony-free strengthened solder alloy comprises the following components in percentage by weight: 3% of Ag, 0.5% of Cu0.5%, 3% of Bi, 0.05% of Ni0%, and the balance of Sn and inevitable impurities.
Example 2
Sequentially adding Sn elemental metal, ni elemental metal, cu elemental metal, ag elemental metal and Bi elemental metal according to the proportion of alloy components, and smelting at the temperature of 600 ℃ in an atmospheric environment to prepare the lead-free and antimony-free strengthened solder alloy, wherein the lead-free and antimony-free strengthened solder alloy comprises the following components in percentage by weight: 5% of Ag, 0.8% of Cu0.8%, 2% of Bi, 0.001% of Ni0%, and the balance of Sn and inevitable impurities.
Example 3
Sequentially adding Sn elemental metal, ni elemental metal, cu elemental metal, ag elemental metal and Bi elemental metal according to the proportion of alloy components, and smelting at 650 ℃ in an atmospheric environment to prepare the lead-free and antimony-free reinforced solder alloy, wherein the lead-free and antimony-free reinforced solder alloy comprises the following components in percentage by weight: 4% of Ag, 0.4% of Cu0.4%, 5% of Bi, 0.5% of Ni0%, and the balance of Sn and inevitable impurities.
Example 4
Sequentially adding Sn elemental metal, ni elemental metal, cu elemental metal, ag elemental metal and Bi elemental metal according to the proportion of alloy components, and smelting at 650 ℃ in an atmospheric environment to prepare the lead-free and antimony-free reinforced solder alloy, wherein the lead-free and antimony-free reinforced solder alloy comprises the following components in percentage by weight: 4% of Ag, 0.5% of Cu0.5%, 3% of Bi, 0.2% of Ni0%, and the balance of Sn and inevitable impurities.
Example 5
Sequentially adding Sn elemental metal, ni elemental metal, cu elemental metal, ag elemental metal and Bi elemental metal according to the proportion of alloy components, and smelting at 650 ℃ in an atmospheric environment to prepare the lead-free and antimony-free strengthened solder alloy, wherein the lead-free and antimony-free strengthened solder alloy comprises the following components in percentage by weight: 3% of Ag, 0.6% of Cu0.05% of Bi, 0.05% of Ni0, and the balance of Sn and inevitable impurities.
Example 6
Sequentially adding Sn elemental metal, ni elemental metal, cu elemental metal, ag elemental metal and Bi elemental metal according to the proportion of alloy components, and smelting at 650 ℃ in an atmospheric environment to prepare the lead-free and antimony-free strengthened solder alloy, wherein the lead-free and antimony-free strengthened solder alloy comprises the following components in percentage by weight: ag3.5%, cu0.5%, bi4.5%, ni0.05%, and the balance of Sn and unavoidable impurities.
Example 7
Sequentially adding Sn elemental metal, ni elemental metal, cu elemental metal, ag elemental metal and Bi elemental metal according to the proportion of alloy components, and smelting at 650 ℃ in an atmospheric environment to prepare the lead-free and antimony-free strengthened solder alloy, wherein the lead-free and antimony-free strengthened solder alloy comprises the following components in percentage by weight: 5% of Ag, 0.5% of Cu0.5%, 3% of Bi, 0.05% of Ni0%, and the balance of Sn and inevitable impurities.
Example 8
And smelting the Sn elementary metal and the Cu-47.4Zr intermediate alloy at the temperature of 885 ℃ in an argon protective atmosphere according to the alloy component proportion to prepare the Sn-3.32Cu-3Zr intermediate alloy. Wherein the argon protective atmosphere is kept 0.01-7kPa higher than the atmospheric pressure.
Sequentially adding Sn elementary metal, ni elementary metal, cu elementary metal, ag elementary metal, sn-3.32Cu-3Zr intermediate alloy and Bi elementary metal according to the proportion of alloy components, and smelting at 650 ℃ in an atmospheric environment to prepare the lead-free and antimony-free strengthened solder alloy, wherein the lead-free and antimony-free strengthened solder alloy comprises the following components in percentage by weight: 3% of Ag, 0.6% of Cu0.6%, 4% of Bi, 0.05% of Ni0.5%, and the balance of Zr0.5%, and unavoidable impurities.
Example 9
Sequentially adding Sn elementary substance metal, ni elementary substance metal, cu elementary substance metal, ag elementary substance metal, sn-1Zr intermediate alloy and Bi elementary substance metal according to the proportion of alloy components, and smelting at 650 ℃ in an atmospheric environment to prepare the lead-free and antimony-free strengthened solder alloy, wherein the lead-free and antimony-free strengthened solder alloy comprises the following components in percentage by weight: 4% of Ag, 0.7% of Cu0.7%, 3% of Bi, 0.05% of Ni0.001%, and the balance of Sn and inevitable impurities.
Example 10
Adding Sn elementary substance metal, ni elementary substance metal, cu elementary substance metal, ag elementary substance metal, cu-47.4Zr intermediate alloy and Bi elementary substance metal according to the proportion of alloy components, and smelting at the temperature of 885 ℃ and under the condition that the pressure of an argon protective atmosphere is kept to be 0.1-7kPa higher than the atmospheric pressure to prepare the lead-free and antimony-free reinforced solder alloy, wherein the lead-free and antimony-free reinforced solder alloy comprises the following components in percentage by weight: 4% of Ag, 0.5% of Cu0.5%, 3% of Bi, 0.2% of Ni0.2%, and Zr0.2% of the balance of Sn and inevitable impurities.
Example 11
Sequentially adding Sn elemental metal, ni elemental metal, cu elemental metal, ag elemental metal, ge elemental metal and Bi elemental metal according to the proportion of alloy components, and smelting at 650 ℃ in an atmospheric environment to prepare the lead-free and antimony-free reinforced solder alloy, wherein the lead-free and antimony-free reinforced solder alloy comprises the following components in percentage by weight: 3% of Ag, 0.5% of Cu0.5%, 3% of Bi, 0.05% of Ni0.02% of Ge0.02% of the balance Sn and inevitable impurities.
Example 12
Adding Sn elementary metal, ni elementary metal, cu elementary metal, ag elementary metal, ge elementary metal, cu-47.4Zr intermediate alloy and Bi elementary metal according to the proportion of alloy components, smelting at the temperature of 885 ℃ and under the condition that the pressure of an argon protective atmosphere is kept 0.1-7kPa higher than the atmospheric pressure, and preparing the lead-free and antimony-free reinforced solder alloy, wherein the lead-free and antimony-free reinforced solder alloy comprises the following components in percentage by weight: 5% of Ag, 0.5% of Cu0.5%, 3% of Bi, 0.05% of Ni0.01%, zr0.01%, 0.1% of Ge0%, and the balance of Sn and inevitable impurities.
Example 13
Sequentially adding Sn elemental metal, ni elemental metal, cu elemental metal, ag elemental metal, ge elemental metal, sn-1Zr intermediate alloy and Bi elemental metal according to the alloy component proportion, and smelting at the temperature of 650 ℃ in an atmospheric environment to prepare the lead-free and antimony-free strengthened solder alloy, wherein the lead-free and antimony-free strengthened solder alloy comprises the following components in percentage by weight: 3% of Ag, 0.6% of Cu0.6%, 4% of Bi, 0.05% of Ni0.5%, 0.001% of Zr0.5%, and the balance of Sn and inevitable impurities.
Example 14
Sequentially adding Sn elemental metal, ni elemental metal, cu elemental metal, ag elemental metal, ge elemental metal, sn-1Zr intermediate alloy and Bi elemental metal according to the alloy component proportion, and smelting at the temperature of 650 ℃ in an atmospheric environment to prepare the lead-free and antimony-free strengthened solder alloy, wherein the lead-free and antimony-free strengthened solder alloy comprises the following components in percentage by weight: 4% of Ag, 0.5% of Cu0.5%, 3% of Bi, 0.5% of Ni0.5%, 0.5% of Zr0.02%, and the balance of Sn and inevitable impurities.
Example 15
Adding Sn elementary metal, ni elementary metal, cu elementary metal, ag elementary metal, ge elementary metal, cu-47.4Zr intermediate alloy and Bi elementary metal according to the proportion of alloy components, smelting at the temperature of 885 ℃ and under the condition that the pressure of an argon protective atmosphere is kept 0.1-7kPa higher than the atmospheric pressure, and preparing the lead-free and antimony-free reinforced solder alloy, wherein the lead-free and antimony-free reinforced solder alloy comprises the following components in percentage by weight: 4% of Ag, 0.5% of Cu0.5%, 3% of Bi, 0.01% of Ni0.1%, 0.02% of Zr0%, and the balance of Sn and inevitable impurities.
Comparative example 1
A traditional SnAgCu solder alloy comprises the following components in percentage by weight: 3% of Ag, 0.5% of Cu0.5%, and the balance of Sn and inevitable impurities.
The present inventors conducted a series of performance tests on the above-described lead-free and antimony-free strengthened solder alloy examples and comparative examples, and evaluated the replaceability of the lead-free strengthened solder alloy for SAC305, mainly from the melting point, workability, solder voidage, and creep life, as shown in Table 1.
The melting point test mode is a differential scanning calorimeter test using NETZSCH 200F 3. The melting point test range is 210-230 ℃, and the product is judged to be replaceable, otherwise, the product is judged to be non-replaceable.
The workability takes the 'unilateral maximum edge cracking' as a judgment standard, the consistent thickness of each solder alloy before rolling is 8mm, the width is 50mm, the length is 120mm, the same rolling reduction per pass is 0.5mm, 15 times of rolling passes and 0.25mm of final rolling reduction are adopted, and the uniform thickness is 0.25mm after rolling. And then measuring the single-side maximum cracked edge of the brazing alloy strip, and grading the sizes of the cracked edges, wherein the size of the single-side maximum cracked edge is less than 5mm and is I grade, the size of the single-side maximum cracked edge is 5-10mm and is II grade, and the size of the single-side maximum cracked edge is more than 10mm and is III grade. Wherein, the I grade is judged as substitutable, and the II grade and the III grade are judged as irreplaceable.
TABLE 1 Performance test Table for examples and comparative examples
The solder voidage was measured using a Sonoscan D9600Z Sonoscan microscope, and was consistent with a vacuum formic acid reflow solder process using a 20mm by 20mm solder coupon made from each of the examples and comparative lead-free solder alloys and two 20mm by 20mm DBC boards, using a UNITEMP RSS450-160. And classifying the welding voidage, wherein the welding voidage is grade I when the welding voidage is less than 1%, the welding voidage is grade II when the welding voidage is 1% -10%, and the welding voidage is grade III when the welding voidage is more than 10%. Wherein, the I grade is judged as substitutable, and the II grade and the III grade are judged as irreplaceable.
The creep life was measured by preparing a weld shear specimen according to Japanese Industrial Standard JISZ3198, and testing with an electronic creep relaxation tester model RWS30 from Middlekto, inc., under 90 ℃ and 15MPa. Among them, the creep life exceeds 3h and is judged as substitutable, and if not exceeds 3h, it is judged as irreplaceable.
In table 1, those that satisfy expressions (1) and (2) and are alternatively represented by "√" and those that do not satisfy expressions (1) and (2) and are not alternatively represented by "×".
As can be seen from Table 1, the lead-free reinforced solder alloy according to formula (1) has a melting point within the range of 210-230 ℃, a single maximum crack edge of less than 5mm, a melting point and processability replaceability.
As can be seen from table 1, the lead-free brazing filler metal alloy conforming to both the formula (1) and the formula (2) has a welding void ratio of less than 1%, and has a replaceability of the welding void ratio.
As can be seen from Table 1, after Bi, ni, zr and Ge elements are added, the high-temperature creep life of the solder alloy is improved, and the alloy with replaceability, which is improved by more than 15 times and exceeds 3 hours, is required to conform to the formula (1) and the formula (2) at the same time. Among them, the high temperature creep life was improved by 23 times as much as that of example 9. As can be seen from table 1, the alloy compositions satisfying both formula (1) and formula (2) have excellent substitutability, while the alloy compositions not satisfying formula (1) and formula (2), or satisfying only formula (1) or formula (2) do not have excellent substitutability.
FIG. 1 is a metallographic structure of a sample of 9 Sn92.249Ag4Cu0.7Bi3Ni0.05Zr0.001, and it is apparent from FIG. 1 that Ag 3 Sn、Bi、Cu 6 Sn 5 The alloy is uniformly distributed in the alloy, so that dislocation movement is strongly hindered, the deformation resistance of the solder is improved, the integral wettability of the solder is improved, and the welding void ratio is reduced. At the same time, sn 2 Zr、Ni 3 Sn 4 The dispersion phase is used as a dispersion phase to strongly hinder dislocation movement, and the hardness of the dispersion phase particles is higher, the stability at high temperature is better, and the strengthening effect is better. And the strengthening effect of a plurality of elements is better than that of a single element, which is the reason for adding Zr and Ni simultaneously. In conclusion, the lead-free reinforced solder alloy provided by the invention has remarkably improved high-temperature mechanical properties, is compared with the existing Sn96.5Ag3Cu0.5 solder, does not need to greatly change the existing forming and processing technology and welding technology when in use, accords with industrial large-scale production, and can be widely applied to various electronic component welding and semiconductor packaging technologies such as PCBs, automobile accessory modules, chip modules, power supply modules and the like.
The above embodiments are only preferred embodiments of the present invention, and the scope of the present invention should not be limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Claims (7)
1. The lead-free and antimony-free reinforced solder alloy is characterized by comprising the following components in percentage by weight:
Bi：2%-5%；
Ag：3%-5%；
Cu：0.4%-0.8%；
Ni：0.001%-0.5%；
Zr：0.001%-0.5%；
and Sn:91.2% -94.598%;
and (Ag-3.5%) 2 +（Bi-3%) 2 ≤0.0002；Zr+Ni<0.5%。
2. The lead-free and antimony-free reinforced solder alloy as claimed in claim 1, further comprising 0.001-0.1% by weight of Ge.
3. The lead-free and antimony-free strengthened solder alloy according to claim 1 or 2,
also comprises one or more of Ti, co, in, P, ga, B, au, ta, V, nb, hf, ta, mn, al, zn and Si elements, and the content of each element does not exceed the content of Ni.
4. A method of making a lead-free and antimony-free strengthened solder alloy as claimed in any one of claims 1 to 3, comprising the steps of:
in the atmospheric environment, at the temperature of above 650 ℃, intermediate alloy and/or ZrH of Sn elementary metal, ni elementary metal, cu elementary metal, ag elementary metal, ge elementary metal and Zr 2 Sequentially adding powder and Bi elementary metal for smelting;
wherein the intermediate alloy of Zr is one or the combination of two of Sn-Zr and Sn-Cu-Zr intermediate alloy.
5. The method of claim 4, wherein the solder alloy is a lead-free and antimony-free solder alloy,
the mass percent of Zr in the Sn-Zr intermediate alloy is 0.01-16.9%; the melting point of the Sn-Zr intermediate alloy is 232-1142 ℃.
6. A method of making a lead-free and antimony-free strengthened solder alloy as claimed in any one of claims 1 to 3, comprising the steps of:
under the protection atmosphere or vacuum environment, sn elementary substance metal, ni elementary substance metal, cu elementary substance metal, ag elementary substance metal, ge elementary substance metal, intermediate alloy of Bi elementary substance metal and Zr and/or ZrH are/is added at the temperature of more than 885 DEG C 2 Adding powder and smelting;
wherein the intermediate alloy of Zr is Cu-Zr intermediate alloy;
the pressure of the protective atmosphere is 0.1-7kPa higher than the atmospheric pressure; the air pressure of the vacuum environment is 0.81-100Pa.
7. The method of claim 6, wherein the solder alloy is a lead-free and antimony-free solder alloy,
the mass percent of Zr in the Cu-Zr intermediate alloy is 1-79%.
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