CN114293066A - Lead-free low-temperature solder alloy material containing Ni and preparation method thereof - Google Patents
Lead-free low-temperature solder alloy material containing Ni and preparation method thereof Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 127
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- 239000002245 particle Substances 0.000 claims abstract description 40
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- 229910017984 Ag—Ni Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
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Abstract
The invention discloses a lead-free low-temperature solder alloy material containing Ni and a preparation method thereof, wherein the lead-free low-temperature solder alloy consists of Sn, Bi, Ag and Ni, and the solder alloy consists of 35-37 wt% of Bi, 1 wt% of Ag, 0.5 wt% of Ni and the balance of Sn. The preparation method comprises the following steps: weighing corresponding particle raw materials according to the weight percentage, uniformly mixing, putting into a quartz tube, vacuumizing, sealing, and putting into a well type furnace for smelting. The Ni-containing lead-free low-temperature solder alloy greatly improves the wettability of Sn-Bi-Ag series solder alloy, has no obvious influence on the melting point and the mechanical property, improves the aging service strength of a photovoltaic solder strip coating, and can meet the development requirements of miniaturization and light development of a photovoltaic module, thinning of a battery piece and low temperature of the soldering temperature of a solder strip. The preparation method of the invention not only solves the problem of easy oxidation in the alloy smelting process, but also effectively improves the performance of the solder.
Description
Technical Field
The invention belongs to the technical field of solder alloys for photovoltaic solder strip coatings, and particularly relates to a lead-free low-temperature solder alloy material containing Ni and a preparation method thereof.
Background
The photovoltaic solder strip is formed by coating a layer of binary or multi-element tin-containing alloy on the surface of a copper strip with a set specification. The solar cell module is used as a hinge part in the solar cell module, and the key function of the solar cell module is to connect the cell pieces and transmit the current generated by the cell pieces. For a long time, Sn-Pb solder has been the first choice of the coating solder for the photovoltaic solder strip because of the advantages of low cost, strong conductivity, good manufacturability and the like. The Sn-Pb eutectic composition is 40 wt.% Pb, with the remainder being Sn, and has a melting point of about 183 ℃. With the implementation of the RoHS and WEEE directive in the european union, lead-free manufacturing products are becoming global trend, and photovoltaic modules are also moving toward miniaturization and lightening, and the thinner the cell, the lower the welding temperature of the solder strip. Therefore, the development of lead-free low-temperature solder-strip-coated solders is a necessary trend in photovoltaic solder strip development.
At present, a material worker has conducted extensive research on a solder-strip-coated lead-free low-temperature solder, and has replaced Pb in an Sn-Pb alloy with another component, and the research systems include Sn-Ag systems, Sn-Bi systems, and the like. The Sn-3.5Ag binary eutectic solder alloy has higher mechanical property, but the melting point is up to 221 ℃, and the alloy per se is easy to form coarse brittle Ag3Sn phase, resulting in reduced solder joint reliability and reduced service life of the photovoltaic module. Therefore, attempts have been made to improve the problems of high melting point, poor wettability, etc. of solder by adding trace elements and to reduce the Ag content to reduce the cost. For example, In patent CN105397329A, a Sn-Ag-Cu low-silver lead-free solder containing Nd, Re and In, while adding trace amounts of Nd, Re and In elements can improve the wettability and mechanical properties of the solder and reduce the melting point of the solder, the mechanical properties of the solder still far fail to meet the use requirements, and the conductivity of the solder is also poor.
The Sn-Bi lead-free solder can be prepared into alloy within the melting temperature range of 138-232 ℃, and the melting temperature is obviously reduced along with the increase of the Bi content, so that the control of the Bi content is an effective means for adjusting the melting temperature of the solder. The melting point (138 ℃) of the Sn-58Bi binary eutectic solder alloy is far lower than that of Sn-40Pb solder (183 ℃), and the low melting point makes the Sn-58Bi binary eutectic solder alloy have the advantage in the trend of low-temperature soldering development of the photovoltaic solder strip. But the brittleness of the Bi phase and the problem of Bi phase coarsening and Bi element segregation at the welding spot interface appear in the long service of the Sn-Bi solder, the shearing strength drop impact resistance service life of the welding spot is seriously reduced, and great potential safety hazard is brought to the service reliability of the photovoltaic module. At present, the research results for comprehensively improving the comprehensive performance of the Sn-Bi solder alloy are few and few.
The patent CN10669515A discloses a low-melting-point lead-free solder, which reduces the Bi content to 16-18 wt%, and improves the comprehensive mechanical property and wetting spreadability of the solder by adding alloy elements such as Ag, Fe and the like, but the melting point of the solder is 178-192 ℃, and the Bi content is too low, so that the molten solder is easier to form Bi segregation in the cooling process; patent CN108374104A discloses a low melting point Sn-Bi-Al series lead-free solder alloy material and a preparation method thereof, wherein the alloy comprises the following components by weight percent, wherein Bi: 15-25%; al: 0.5-2%; the balance being Sn. The patent utilizes a planetary ball mill to prepare the solder alloy, so that Al particles are uniformly distributed in the solder and the alloy, the technical problem that Al and Sn-Bi alloy are not easy to mutually melt is solved, the mechanical property of the solder is effectively improved, and the wettability of the solder on a Cu substrate is not researched.
When the actual solder strip is applied to the photovoltaic module, the mechanical property of the solder basically can meet the requirement, and the more concerned indexes are the pressure which can be born after the solder strip is combined with the main grid and whether the solder strip is easy to weld, namely the wettability. Because a small amount of Ni is usually added into a hot-dip galvanizing zinc pool, on one hand, the fluidity of zinc liquid can be improved, on the other hand, the brightness of a coating can be improved, and in addition, the photovoltaic welding strip prepared by a hot-dip galvanizing method is similar to that of hot-dip galvanizing. Therefore, the patent proposes that a trace amount of Ni element is added on the basis of Sn-Bi-Ag solder, and the addition of the trace amount of Ni is found to greatly improve the wettability of the solder and has no obvious influence on the melting point of the solder. Although the mechanical property of the Sn-Bi-Ag solder can be reduced by adding Ni, the addition of Ni is still better than that of Sn-40Pb solder alloy, so that the addition of the trace Ni element into the Sn-Bi-Ag solder disclosed by the patent is more in line with the development of solder for solder strip coating in the low-temperature photovoltaic industry.
Disclosure of Invention
The technical scheme adopted by the invention for solving the technical problems is as follows: the lead-free low-temperature solder alloy containing Ni comprises the following raw material components in percentage by weight: bi: 35% -37%, Ag: 1%, Ni: 0.5% and the balance Sn.
Further, the method comprises the following steps: the solder alloy comprises the following components in percentage by weight: bi: 35% and Ag: 1%, Ni: 0.5% and the balance Sn.
Further, the method comprises the following steps: the solder alloy comprises the following components in percentage by weight: bi: 37%, Ag: 1%, Ni: 0.5% and the balance Sn.
Furthermore, the purities of the raw materials Bi, Ag, Ni and Sn are all more than or equal to 99.99%.
The invention also discloses a preparation method of the Ni-containing lead-free low-temperature solder alloy material, which comprises the following steps of:
s1, weighing raw materials, and respectively weighing Sn particles, Bi particles, Ag particles and Ni particles in corresponding amounts according to the weight percentage of each raw material component;
s2, uniformly mixing the Sn particles, the Bi particles, the Ag particles and the Ni particles weighed in the step S1, putting the mixture into a quartz tube, and vacuumizing the quartz tube by using a vacuum unit, wherein the vacuum degree is 5.0 x 10-3Pa; argon (99.99% high purity argon at one standard atmosphere) was introduced, followed by vacuum pumping and repeating for 6 times.
S3, based on the step S2, the quartz tube is vacuumized for 7 times until the vacuum degree reaches 5.0 x 10-3The water fuel oxyhydrogen machine is opened after Pa, and the gas production reaches 720m3And sealing the quartz tube by using an oxyhydrogen flame gun after the reaction is carried out for h.
S4, putting the quartz tube filled with the raw materials in the step S3 into a shaft furnace for smelting. The temperature of the furnace is set to 380 ℃, the temperature of the furnace is kept for 12 hours after the furnace reaches the set temperature, and the quartz tube is inverted and shaken up and down every 30 minutes so as to ensure that the components are uniform in the melting process.
And S5, taking out the solder alloy melted in the step S4 by using crucible tongs, and then quickly putting the solder alloy into a cold water bucket for cooling.
And S6, completely cooling to obtain the Sn-Bi-Ag-Ni lead-free low-temperature solder alloy.
The invention has the beneficial effects that: the invention adds trace Ni element on the basis of the known Sn-Bi-Ag solder alloy to form a new Sn-Bi-Ag-Ni solder alloy. The method has the advantages that the addition of the Ni element with stronger trace fluidity greatly improves the wettability of the lead-free solder alloy, has no obvious influence on the melting point, and has mechanical property still superior to that of the traditional Sn-40Pb solder; during preparation, the quartz tube filled with the raw materials is subjected to vacuum pumping sealing packaging by using a vacuum unit and a water fuel oxyhydrogen machine, and then the solder is smelted, so that the problem that Sn is easy to oxidize is solved, the components of the solder alloy in the melting process are uniform, a better microstructure can be obtained, the performance of the solder alloy is effectively improved, and the service life of the photovoltaic module is prolonged.
Drawings
FIG. 1 is a structural diagram of a Sn-Bi-Ag based solder alloy according to a comparative example of the present application.
FIG. 2 is a structural diagram of a Sn-Bi-Ag-Ni based solder alloy according to the present application.
FIG. 3 is a graph showing a comparison of contact angle curves of a Sn-Bi-Ag-Ni based solder alloy in the present application and those of a Sn-Bi-Ag based solder alloy in a comparative example.
FIG. 4 is a graph showing a comparison between the tensile strength of the Sn-Bi-Ag-Ni based solder alloy of the present application and the tensile strength of the Sn-Bi-Ag based solder alloy of the comparative example.
FIG. 5 is a graph showing a comparison between the melting point of the Sn-Bi-Ag-Ni based solder alloy of the present application and the melting point of the Sn-Bi-Ag based solder alloy of the comparative example.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
It will be understood that when an element is referred to as being "secured to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The invention discloses a lead-free low-temperature solder alloy material containing Ni, which consists of 35-37 wt% of Bi, 1 wt% of Ag, 0.5 wt% of Ni and the balance of Sn.
Specifically, the content of Bi may be 35%, 36%, 37%, or the like.
Specifically, the purities of the raw materials Bi, Ag, Ni and Sn are all more than or equal to 99.99%.
The invention adds trace Ni element on the basis of the known Sn-Bi-Ag solder alloy to form a new Sn-Bi-Ag-Ni solder alloy. The method has the advantages that the addition of the Ni element with stronger trace fluidity greatly improves the wettability of the lead-free solder alloy, has no obvious influence on the melting point, and has mechanical property still superior to that of the traditional Sn-40Pb solder
The invention also discloses a preparation method of the Ni-containing lead-free low-temperature solder alloy material, which comprises the following steps:
s1, weighing raw materials, and respectively weighing Sn particles, Bi particles, Ag particles and Ni particles in corresponding amounts according to the weight percentage of each raw material component;
s2, uniformly mixing the Sn particles, the Bi particles, the Ag particles and the Ni particles weighed in the step S1, putting the mixture into a quartz tube, and vacuumizing the quartz tube by using a vacuum unit, wherein the vacuum degree is 5.0 x 10-3Pa; argon (99.99% high purity argon at one standard atmosphere) was introduced, followed by vacuum pumping and repeating for 6 times.
S3, based on the step S2, the quartz tube is vacuumized for 7 times until the vacuum degree reaches 5.0 x 10-3The water fuel oxyhydrogen machine is opened after Pa, and the gas production reaches 720m3And sealing the quartz tube by using an oxyhydrogen flame gun after the reaction is carried out for h.
And S4, putting the quartz tube filled with the raw materials in the step S3 into a well type furnace for smelting, wherein the temperature of the furnace is set to 380 ℃, keeping the temperature for 12 hours after the furnace reaches the set temperature, and during the process, the quartz tube is inverted and shaken up and down every 30 minutes to ensure that the components in the melting process are uniform.
And S5, taking out the solder alloy melted in the step S4 by using crucible tongs, and then quickly putting the solder alloy into a cold water bucket for cooling.
By adopting the preparation method, the vacuum unit and the water fuel oxyhydrogen machine are utilized to carry out vacuum pumping sealing packaging on the quartz tube filled with the raw materials during preparation, and then the solder is smelted, so that the problem that Sn is easy to oxidize is solved, the components of the solder alloy in the melting process are uniform, a better microstructure can be obtained, the performance of the solder alloy is effectively improved, and the service life of the photovoltaic module is prolonged.
The formulations of the solders of the specific examples of the present invention and the comparative examples are shown in table 1:
TABLE 1
The specific preparation methods of the above examples and comparative examples are as follows:
example 1:
(1) the Sn particles, Bi particles, Ag particles and Ni particles described in example 1 in Table 1 were weighed and mixed in percentage by weight, and then placed in a quartz tube, and the quartz tube was evacuated by a vacuum unit at a vacuum degree of 5.0 x 10-3Pa; argon (99.99% high purity argon at one standard atmosphere pressure) is introduced,then, vacuum was applied again and the process was repeated 6 times.
(2) Performing 7 times of vacuum pumping on the quartz tube on the basis of the step (1), and keeping the vacuum degree to 5.0 x 10-3The water fuel oxyhydrogen machine is opened after Pa, and the gas production reaches 720m3And sealing the quartz tube by using an oxyhydrogen flame gun after the reaction is carried out for h.
(3) And (3) putting the quartz tube filled with the raw materials in the step (2) into a well type furnace for smelting. The temperature of the furnace is set to 380 ℃, the temperature of the furnace is kept for 12 hours after the furnace reaches the set temperature, and the quartz tube is inverted and shaken up and down every 30 minutes so as to ensure that the components are uniform in the melting process.
(4) And (4) taking out the solder alloy melted in the step (3) by using crucible tongs, and then quickly putting the solder alloy into a cold water bucket for cooling.
(5) After complete cooling, the Sn-35Bi-1Ag-0.5Ni lead-free low-temperature solder alloy can be obtained.
(6) The prepared solder alloy is subjected to metallographic treatment, and then the microstructure morphology is analyzed by a scanning electron microscope, and the mechanical property test, the wetting property test and the melting point test are carried out.
Example 2:
(1) the Sn particles, Bi particles, Ag particles and Ni particles described in example 2 in Table 1 were weighed and mixed in percentage by weight, and then placed in a quartz tube, and the quartz tube was evacuated by a vacuum unit at a vacuum degree of 5.0 x 10-3Pa; argon (99.99% high purity argon at one standard atmosphere) was introduced, followed by vacuum pumping and repeating for 6 times.
(2) Performing 7 times of vacuum pumping on the quartz tube on the basis of the step (1), and keeping the vacuum degree to 5.0 x 10-3The water fuel oxyhydrogen machine is opened after Pa, and the gas production reaches 720m3And sealing the quartz tube by using an oxyhydrogen flame gun after the reaction is carried out for h.
(3) And (3) putting the quartz tube filled with the raw materials in the step (2) into a well type furnace for smelting. The temperature of the furnace is set to 380 ℃, the temperature of the furnace is kept for 12 hours after the furnace reaches the set temperature, and the quartz tube is inverted and shaken up and down every 30 minutes so as to ensure that the components are uniform in the melting process.
(4) And (4) taking out the solder alloy melted in the step (3) by using crucible tongs, and then quickly putting the solder alloy into a cold water bucket for cooling.
(5) After complete cooling, the Sn-37Bi-1Ag-0.5Ni lead-free low-temperature solder alloy can be obtained.
(6) The prepared solder alloy is subjected to metallographic treatment, and then the microstructure morphology is analyzed by a scanning electron microscope, and the mechanical property test, the wetting property test and the melting point test are carried out.
Comparative example 1:
(1) the Sn particles, Bi particles and Ag particles described in comparative example 1 in Table 1 were weighed and mixed in percentage by weight, and then placed in a quartz tube, and the quartz tube was evacuated by a vacuum unit at a vacuum degree of 5.0 x 10-3Pa; argon (99.99% high purity argon at one standard atmosphere) was introduced, followed by vacuum pumping and repeating for 6 times.
(2) Performing 7 times of vacuum pumping on the quartz tube on the basis of the step (1), and keeping the vacuum degree to 5.0 x 10-3The water fuel oxyhydrogen machine is opened after Pa, and the gas production reaches 720m3And sealing the quartz tube by using an oxyhydrogen flame gun after the reaction is carried out for h.
(3) And (3) putting the quartz tube filled with the raw materials in the step (2) into a well type furnace for smelting. The temperature of the furnace is set to 300 ℃, the furnace is kept warm for 12 hours after reaching the set temperature, and the quartz tube is inverted and shaken up and down every 30 minutes to ensure that the components are uniform in the melting process.
(4) And (4) taking out the solder alloy melted in the step (3) by using crucible tongs, and then quickly putting the solder alloy into a cold water bucket for cooling.
(5) The prepared Sn-35Bi-1Ag solder alloy is subjected to metallographic treatment, and then the microstructure morphology is analyzed by a scanning electron microscope, and the mechanical property test, the wetting property test and the melting point test are carried out.
Comparative example 2:
(1) the Sn particles, Bi particles and Ag particles described in comparative example 2 in Table 1 were weighed and mixed in percentage by weight, and then placed in a quartz tube, and the quartz tube was evacuated by a vacuum unit at a vacuum degree of 5.0 x 10-3Pa; argon (99.99% high purity argon at one standard atmosphere) was introduced, followed by vacuum pumping and repeating for 6 times.
(2) Performing 7 times of vacuum pumping on the quartz tube on the basis of the step (1), and keeping the vacuum degree to 5.0 x 10-3The water fuel oxyhydrogen machine is opened after Pa, and the gas production reaches 720m3And sealing the quartz tube by using an oxyhydrogen flame gun after the reaction is carried out for h.
(3) And (3) putting the quartz tube filled with the raw materials in the step (2) into a well type furnace for smelting. The temperature of the furnace is set to 300 ℃, the furnace is kept warm for 12 hours after reaching the set temperature, and the quartz tube is inverted and shaken up and down every 30 minutes to ensure that the components are uniform in the melting process.
(4) And (4) taking out the solder alloy melted in the step (3) by using crucible tongs, and then quickly putting the solder alloy into a cold water bucket for cooling.
(5) The prepared Sn-37Bi-1Ag solder alloy is subjected to metallographic treatment, and then the microstructure morphology is analyzed by a scanning electron microscope, and the mechanical property test, the wetting property test and the melting point test are carried out.
Comparative example 3:
(1) since Pb has toxicity, a large amount of lead vapor is easy to escape in the process of manufacturing Sn-Pb solder, which is harmful to human health, and lead-rich solder waste residue generated in the production can cause irreversible pollution to the environment. In view of this, the Sn-40Pb solder alloy required in comparative example 3 of this patent was purchased from Sn-40Pb alloy products produced in the Yunnan tin industry.
Sample detection:
(1) and (3) comparing the structural morphology of the solder alloy:
the Sn-Bi-Ag solder alloys obtained in comparative examples 1 to 2 and the Sn-Bi-Ag-Ni solder alloys obtained in examples 1 to 2 were examined to obtain texture and morphology comparison graphs, as shown in FIGS. 1 and 2, wherein graphs a and b in FIG. 1 are texture and morphology graphs of Sn-35Bi-1Ag and Sn-37Bi-1Ag solder alloys, respectively, and graphs a and b in FIG. 2 are texture and morphology graphs of Sn-35Bi-1Ag-0.5Ni and Sn-37Bi-1Ag-0.5Ni solder alloys, respectively. As can be seen from FIG. 1, the gray substrate phase with low contrast is (Sn), the phase with high contrast is (Bi), and a small amount of Ag is present3The Sn phase is dispersed and distributed on the (Sn) matrix. As can be seen from FIG. 2, the gray substrate phase with low contrast is (Sn), the phase with high contrast is (Bi), and a small amount of dark gray Ag3Sn phase is distributed on (Sn) matrix, and multilateral phase also appearsNi of shape3Sn4And (4) phase(s).
(2) And (3) wettability testing:
0.25g of each of the Sn-Bi-Ag solder alloys obtained in comparative examples 1 to 2 and the Sn-Bi-Ag-Ni solder alloys obtained in examples 1 to 2 was weighed, and then subjected to a wettability test using a high temperature wettability tester at a heating temperature of 170 ℃. The whole dripping process is recorded by a CCD high-speed camera, after the experiment is finished, a picture is captured from a video recorded by the camera, the ADSA software is used for vectorizing the alloy liquid image so as to extract contour data, and finally the SESDROPD software is used for fitting, calculating and analyzing the data so as to obtain a contact angle. In the test, the wetting property of the solder alloy is judged by adopting the contact angle of the alloy liquid when the alloy liquid drops on the Cu plate for 5s, and the smaller the contact angle is, the better the wettability of the alloy is.
FIG. 3 is a graph comparing the contact angle curves of the solder alloys of examples 1-2 with those of comparative examples 1-2. Comparing the contact angles of example 1 and comparative example 1, and example 2 and comparative example 2 respectively, it can be seen that the magnitude of the contact angle of the Sn-Bi-Ag-Ni solder alloy obtained in examples 1-2 is significantly smaller than that of the solder alloy of comparative examples 1-2, indicating that the wettability of the Sn-Bi-Ag-Ni solder alloy of the examples is significantly better than that of the Sn-Bi-Ag solder alloy of the comparative examples. The contact angles of the solder alloys of examples 1 to 2 were 65.82 ° and 42.67 °, respectively; the solder alloy contact angles of comparative examples 1 to 2 were 98.68 ° and 75.15 °, respectively, and it is clear from the above that the solder wettability of the alloys of examples 1 to 2 was better.
(3) And (3) detecting the tensile strength:
the Sn-Bi-Ag solder alloys obtained in comparative examples 1 to 2, the conventional Sn-40Pb solder alloy obtained in comparative example 3, and the Sn-Bi-Ag-Ni solder alloys obtained in examples 1 to 2 were prepared into I-shaped tensile specimens, and the widths and thicknesses of the tensile specimens were measured with a vernier caliper. And then, respectively stretching the alloy by using an electronic universal testing machine WDT-3030KN, and calculating the tensile strength of the solder alloy.
FIG. 4 is a graph comparing the tensile strength of the solder alloys of examples 1-2 with the tensile strength of the solder alloys of comparative examples 1-2. It can be seen that the solder alloys obtained in comparative examples 1 to 2 and examples 1 to 2 both exhibited a tendency that the tensile strength decreased with the increase in the Bi content. Although the tensile strengths of the Sn-Bi-Ag-Ni solder alloys obtained in examples 1 to 2 are all lower than those of the Sn-Bi-Ag solder alloys of the comparative examples, the tensile strengths of the Sn-Bi-Ag-Ni solder alloys obtained in examples 1 to 2 are still much higher than those of the conventional Sn-40Pb solder of comparative example 3, i.e., still better than those of the conventional solder. The tensile strengths of the solder alloys of examples 1 to 2 were 76.52MPa and 72.29MPa, respectively; the tensile strengths of the solder alloys of comparative examples 1 to 2 were 83.376MPa and 77.73MPa, respectively; the tensile strength of the conventional Sn-40Pb solder alloy of comparative example 3 was 59.26MPa, and it is understood from the above that the alloy solder of the present invention has a slightly reduced tensile strength after Ni is added, but still higher than that of the conventional solder.
(4) And (3) melting point detection:
40mg samples of the Sn-Bi-Ag solder alloys obtained in comparative examples 1 to 2 and the Sn-Bi-Ag-Ni solder alloys obtained in examples 1 to 2 were weighed, and then subjected to melting point measurement using a differential scanning calorimeter (DSC 404F3A00) at a temperature increase rate of 5 ℃/Min.
FIG. 5 is a graph comparing the melting points of the solder alloys of examples 1-2 with the melting points of the solder alloys of comparative examples 1-2. Comparing the melting points of example 1 and comparative example 1, and example 2 and comparative example 2, respectively, it can be seen that the melting points of the Sn-Bi-Ag-Ni solder alloys obtained in examples 1-2 are not much different from those of comparative examples 1-2, and are all within 1 ℃, and the melting points are much lower than those of the conventional Sn-40Pb solder alloy. In actual production, the method cannot cause substantial change due to the influence of factors such as errors. The melting points of the solder alloys of examples 1 to 2 were 163.8 ℃ and 162.7 ℃, respectively; the melting points of the solder alloys of comparative examples 1 to 2 were 164.1 ℃ and 162.4 ℃, respectively; the melting point of the conventional Sn-40Pb solder alloy of comparative example 3 was 183 ℃ and, as can be seen from the above, the alloy solder of the present invention had no effect on the melting point after Ni was added.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A lead-free low-temperature solder alloy material containing Ni is characterized in that: the solder alloy consists of 35-37 wt% of Bi, 1 wt% of Ag, 0.5 wt% of Ni and the balance of Sn.
2. The Ni-inclusive lead-free low-temperature solder alloy material as set forth in claim 1, wherein: the solder alloy comprises the following components in percentage by weight: bi: 35% and Ag: 1%, Ni: 0.5% and the balance Sn.
3. The Ni-inclusive lead-free low-temperature solder alloy material as set forth in claim 1, wherein: the solder alloy comprises the following components in percentage by weight: bi: 37%, Ag: 1%, Ni: 0.5% and the balance Sn.
4. The Ni-inclusive lead-free low-temperature solder alloy material as set forth in claim 1, wherein: the purities of the raw materials Bi, Ag, Ni and Sn are all more than or equal to 99.99%.
5. A preparation method of the Ni-containing lead-free low-temperature solder alloy material comprises the proportioning of the Ni-containing lead-free low-temperature solder alloy material as claimed in any one of claims 1 to 4, and is characterized in that: the preparation method comprises the following steps:
s1, weighing raw materials, and respectively weighing Sn particles, Bi particles, Ag particles and Ni particles in corresponding amounts according to the weight percentage of each raw material component;
s2, uniformly mixing the Sn particles, the Bi particles, the Ag particles and the Ni particles weighed in the step S1, putting the mixture into a quartz tube, and vacuumizing the quartz tube by using a vacuum unit, wherein the vacuum degree is 5.0 x 10-3Pa; argon gas was introduced again, followed by vacuum pumping and repeating the process 6 times.
S3, based on the step S2, the quartz tube is vacuumized for 7 times until the vacuum degree reaches 5.0 x 10-3The water fuel oxyhydrogen machine is opened after Pa, and the gas production reaches 720m3And sealing the quartz tube by using an oxyhydrogen flame gun after the reaction is carried out for h.
And S4, putting the quartz tube filled with the raw materials in the step S3 into a well type furnace for smelting, wherein the temperature of the furnace is set to 380 ℃, keeping the temperature for 12 hours after the furnace reaches the set temperature, and during the process, the quartz tube is inverted and shaken up and down every 30 minutes to ensure that the components in the melting process are uniform.
And S5, taking out the solder alloy melted in the step S4 by using crucible tongs, and then quickly putting the solder alloy into a cold water bucket for cooling.
And S6, completely cooling to obtain the Sn-Bi-Ag-Ni lead-free low-temperature solder alloy.
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