MX2008001874A

MX2008001874A - Solder composition

Info

Publication number: MX2008001874A
Application number: MX/A/2008/001874A
Authority: MX
Inventors: John Pereira
Original assignee: Antaya Technologies Corporation; John Pereira
Priority date: 2005-08-12
Filing date: 2008-02-07
Publication date: 2008-09-02

Abstract

A solder composition having a mixture of elements including tin, indium, silver, and bismuth, and can include about 30%to 85%tin and about 15%to 65%indium.

Description

WELDING COMPOSITION RELATED REQUESTS This Application is a partial continuation of U.S. Application No. 11 / 359,876, filed on February 22, 2006 and U.S. Application No. 11 / 359,864, filed on February 22, 2006, which are partial continuations of U.S. Application No. 11 / 202,640, filed August 12, 2005. All ideas of the above applications are incorporated herein by reference. BACKGROUND Electric connectors are typically used to make electrical connections to devices such as antennas and deicers, which are incorporated or embedded within a car glass. Electrical connectors are usually welded to the glass with a solder containing lead. Due to environmental issues, most industries are currently using or planning to use low lead or lead-free solders for various welding applications. A common unleaded solder used in some industries contains a high content of tin (Sn), for example 95% tin. However, difficulties arise when welding automobile glass devices that do not exist in other fields. Automotive glass tends to be brittle, and common lead-free, high-tin solders that are suitable for use in other applications can typically cause fissures in automotive glass. While it might seem that materials such as ceramics and silicon are similar in some respects to automotive glass, some solders that are suitable for welding to ceramic or silicon devices are not suitable for automotive glass welding. SUMMARY The present invention provides a welding article which may be suitable for automotive glass welding and which may be lead-free. The welding article can be a multilayer solder-hard article that includes a layer of a lead-free first solder for bonding to an electrically conductive material. A layer of a second lead-free solder may be in the layer of the first weld. The second weld may have a lower melting temperature than the first weld. The melting temperature of the second weld may be less than about 310 ° F (154 ° C). In particular embodiments, the second weld may be suitable for automobile glass welding and may be a softer material than the first weld. The first weld can have a melting temperature of about 465 ° F (241 ° C) and the second weld can have a melting temperature of about 250 ° F (121 ° C). The first solder may be a tin and silver composition having approximately 70% or more of tin, and the second solder may have an indium, tin, silver and copper composition of at least about 40% indium and less than about 55 % tin. In some embodiments, the second weld may have a composition of about 50% or more of indium, a maximum of about 30% tin, about 3% to 5% silver, and about 0.25% to 0.75. % coppermade. In one embodiment, the first solder may be about 95% tin and about 5% silver, and the second solder may be about 65% indium, about 30% tin, about 4.5% silver and about 0, 5% copper The layers of the first and second welds may have a combined thickness of the order of between about 0.007 and 0.040 inches (0.177-1.016 mm), and in some embodiments, they may be about 0.013 to 0.015 inches (0.33-0, 38 mm). The layer of the first weld can range from about 0.005 to 0.010 inch (0.127-0.254 mm) thick. The layer of the second weld may be in the range of between about 0.001 and 0.008 inches (0.0254-0.203 mm) thick, and in some embodiments, it can be in the range of between approximately 0.005 and 0.008 inches (0.203-0.025 mm) thick. The layers of the first and second welds may be joined to a base substrate formed of electrical conductive material. The base substrate can be made of metal foil such as a copper band. The multilayer welding article can be an electrical device such as an electrical connector. An electrical device in the present invention may include a base formed of electrical conductive material. At the base there may be a layer of a first lead-free solder. A layer of a second lead-free solder can be in the first weld layer. The second weld may have a lower melting temperature than the first weld. The melting temperature of the second weld may be less than about 310 ° F (154 ° C). The present invention also provides a method of making a multilayer weld article including providing a layer of a lead-free first weld. A layer of a second unleaded solder can be bonded against the first cold-rolled solder layer of the first and second solder layers together between a pair of rollers. The layer of the second weld may have a lower melting temperature than the layer of the first weld. The melting temperature of the second solder layer may be less than about 310 ° F (154 ° C). In particular embodiments, the first weld layer may be formed on a surface of a base substrate formed of a sheet of electrically conductive material. A sheet of the first weld can be applied to the surface of the base substrate and melted to the base substrate with a heat source. The first weld may be a band that is applied to a band of the base substrate. Flux can be applied between the first weld and the base substrate. The first weld can be cut to a desired dimension in the base substrate. A band of the second weld can be cold rolled on the first weld. The cold rolling of the second weld against the first weld can be carried out without requiring pretreatment of the coupling surfaces of the first and second welds. The combined thickness of the layers of the first and second welds can be reduced approximately from 30% to 50% during cold rolling. The welding layers can be heated with a heat source after cold rolling. The first and second welds can be aligned with one another before cold rolling within a guide device, which can be stationary. The second weld can be selected so that it is softer than the first weld. The first weld can have a melting temperature of about 465 ° F (241 ° C) and the second weld can have a melting temperature of about 250 ° F (121 ° C). The first solder may have tin and a solder composition having approximately 70% or more of tin, and the second solder may have an indium, tin, silver and copper composition of at least about 40% indium and less than about 55 % tin. In some embodiments, the second weld may have a composition of 50% or more of indium, a maximum of about 30% tin, about 3% to 5% silver, and about 0.25% to 0.75% copper . In one embodiment, the first solder may be about 95% tin and about 5% silver, and the second solder may be about 65% indium, about 30% tin, about 4.5% silver and about 0, 5% copper The base substrate can be formed of a metal foil such as a copper band. The multi-layer welding article can also be formed in an electrical device such as an electrical connector. The layers of the first and second welds can have a combined thickness of the order of between about 0, 007 and 0.040 inches (0.177-1.016 mm), and in some embodiments may be approximately 0.013 to 0.015 inches (0.33-0.38 mm). The layer of the first weld may be in the range of about 0.005 to 0.010 inches (0.127-0.254 mm) thick. The layer of the second weld may be in the range of about 0.001 to 0.008 inches (0.0254-0.203 mm) thick, and in some embodiments it may be in the range of between about 0.005 and 0.008 inches (0.203-0.025 mm) of thick. The present invention further provides a method of welding an electric device to automotive glass including providing a layer of a first lead-free solder in the electrical device. A layer of a second lead-free solder is disposed on the first weld layer. The second weld may have a lower melting temperature than the first weld. The melting temperature of the second weld may be less than about 310 ° F (154 ° C). The electrical device can be oriented relative to the automotive glass to place the layer of the second weld against the glass. A preselected amount of heat can be applied to the second weld to melt the second weld layer without substantively melting the first weld layer to weld the electrical device to the automotive glass. The layer of the first weld can be disposed on a metal base of the electrical device which can be formed of copper. The first and second welds can have configurations, dimensions, compositions and properties similar to those indicated above. The present invention also provides an electrical device including a base formed of electrical conductive material, and a layer of a first leadless solder on the base. In the layer of the first weld there is a layer of a second solder without lead. The second weld may have a composition including tin, indium, silver and copper. The second weld has a lower melting temperature than the first weld. In particular embodiments, the second weld may have a melting temperature of less than about 360 ° F (182 ° C). In some embodiments, the second weld may have a melting temperature of less than about 315 ° F (157 ° C), and in other embodiments the second weld may have a melting temperature of less than about 310 ° F (154 ° C). ). The second weld may have a composition comprising at least about 50% tin, at least about 10% indium, about 1% to 10% silver, and about 0.25% to 0.75% copper . In one embodiment, the second weld may include about 60% tin, about 35% indium, about 4.5% silver, and about 0.5% copper. The second weld can have a melting temprature of about 300 ° F (149 ° C). The first weld may include tin and silver, with approximately 70% or more of tin. The first weld may include about 95% tin and about 5% silver. The first weld can have a melting temperature of approximately 465 ° F (241 ° C). The base can be made of metal foil such as copper. The electrical device can be an electrical connector. The present invention further provides a multilayer welding article including a layer of a lead-free first solder for bonding to an electrically conductive material, and a layer of a second lead-free solder in the first solder layer. The second weld may have a composition including tin, indium, silver and copper. The second weld may have a lower melting temperature than the first weld and may be suitable for automotive glass welding. In particular embodiments, the first and second welds can be as described herein. further, the article may further include a base substrate formed of an electrically conductive material in which the layers of the first and second welds are joined. The base substrate can be made of metal foil such as a copper band. The present invention can also provide a method of making a multilayer weld article including providing a layer of a lead-free first weld, and attaching a layer of a second lead-free weld against the first weld layer by cold-rolling the layers of the welds. first and second welds together between a pair of rollers. The second weld may have a composition including tin, indium, silver and copper. The layer of the second weld has a lower melting temperature than the layer of the first weld. The present invention can also provide a method of welding an electrical device to automotive glass including providing a layer of a first leadless solder in the electrical device. A layer of a second leadless solder is disposed in the layer of the first weld. The second weld may have a composition including tin, indium, silver and copper. The second weld has a lower melting temperature than the first solder. The electrical device can be oriented relative to the automotive glass to place the layer of the second weld against the glass. A preselected amount of heat can be applied to the second weld to melt the second weld layer without substantially melting the first weld layer to weld the electrical device to the automotive glass. In particular embodiments, the first and second welds may be as described. The present invention can also provide a solder composition having a mixture of elements including tin, indium, silver, and bismuth, and can include about 30% to 85% tin and about 15% to 65% indium. In particular embodiments, the solder-hard composition may further include copper. The composition may include about 1% to 10% silver, about 0.25% to 6% bismuth, and about 0.25% to 0.75% copper. In some embodiments, the composition may include from about 1% to 6% silver, from about 0.25% to 4% bismuth, and from about 0.25% to 0.75% copper. The composition may include about 50% to 83% tin, and about 15% to 45% indium. The composition may have a solid temperature below about 315 ° F (157 ° C). The present invention can also provide a solder composition having a mixture of elements including tin, indium, silver, and bismuth, and may include about 30% to 85% tin, about 13% to 65% indium, and approximately 0.25% to 4% bismuth. In particular embodiments, the composition may include copper. The composition may include about 1% to 10% silver, and about 0.25% to 0.75% copper. In some embodiments, the composition may include from about 1% to 6% silver, from about 0.25% to 4% bismuth, and from about 0.25% to 0.75% copper. The composition may include about 50% to 83% tin, and about 13% to 45% indium. In some embodiments, the composition may include about 15% to 45% indium. The composition may have a solid temperature below about 315 ° F (157 ° C).

The present invention can also provide a solder composition having a mixture of elements including tin, indium, silver, bismuth and copper, and can include about 30% to 85% tin and about 13% to 65% tin. Indian. In particular embodiments, the composition may include about 1% to 10% silver, about 0.25% to 6% bismuth, and about 0.25% to 0.75% copper. In some embodiments, the composition can include about 1% to 6% silver, about 0.25% to 4% bismuth, and about 0.25% to 0.75% copper. The composition may include about 50% to 83% tin, and about 13% to 45% indium. In some embodiments, the composition may include about 15% to 45% indium. In other embodiments, the composition may include about 66% to 85% tin, and about 13% to 26% indium. The composition may have a solid temperature below about 315 ° F (157 ° C). In other embodiments, the composition may include about 70% to 80% tin, and about 15% to 26% indium. In one embodiment, the composition may include about 70% to 74% tin, about 18% to 26% indium, about 1% to 6% silver, about 0.25% to 4% bismuth, and approximately 0.25% to 0.75% copper. In another embodiment, the composition may include about 73% to 78% tin, about 17% to 22% indium, about 1% to 6% silver, about 0.25% to 4% bismuth, and approximately 0.25% to 0.75% copper. In another embodiment, the composition may include about 78% to 85% tin, about 13% to 16% indium, about 1% to 6% silver, about 0.25% to 4% bismuth, and approximately 0.25% to 0.75% copper. The present invention can also provide a solder composition including tin, indium and silver, and which has more than about 60% tin and a solid temperature below about 330 ° F (165 ° C). In particular embodiments, the temperature of the solid may be less than about 315 ° F (157 ° C). The composition may also include bismuth, and some embodiments may also include copper. The present invention can also provide a method of forming a solder composition including mixing together tin, indium, silver, and bismuth, and including about 30% to 85% tin, and about 15% to 65% indium. The present invention can also provide a method of forming a composition including mixing together tin, indium, silver, and bismuth, and including about 30% to 85% tin, about 13% to 65% indium, and about from 0.25% to 4% bismuth. The present invention can also provide a method of forming a solder composition including mixing together tin, indium, silver, bismuth and copper, and including about 30% to 85% tin, and about 13% to 65% indium. The present invention can also provide a method of forming a solder composition including jointly mixing tin, indium and silver, including more than about 60% tin, and providing the composition with a solid temperature below about 330 ° F (165 °). C). The present invention can also provide a method of welding including providing a solder composition having a mixture of elements including tin, indium, silver and bismuth, and including from about 30% to 85% tin, and from about 15% to 65%. % of Indian The welding composition is subsequently melted with a welding device. BRIEF DESCRIPTION OF THE DRAWINGS The foregoing and other objects, features and advantages of the invention will be apparent from the following more specific description of particular embodiments of the invention., as illustrated in the accompanying drawings in which analogous reference characters refer to the same parts in all the different views. The drawings are not necessarily to scale, with emphasis being placed on illustrating the principles of the invention. Figure 1 is a schematic drawing of an embodiment of an apparatus for forming a multilayer weld article. Fig. 2 is a front view of an embodiment of a device or rolling mill illustrated in Fig. 1. Fig. 3 is a front view of an embodiment of a guide for guiding material to the laminator. Figure 4 is a cross-sectional view of a coating strip having a base substrate coating with a layer of a first or higher melting temperature weld. Fig. 5 is a schematic drawing of an embodiment of a process and apparatus for forming the cover band of Fig. 4. Fig. 6 is a cross-sectional view of an embodiment of a multilayer welding article including a base substrate having a multilayer weld with a layer of a first weld or higher melting temperature and a layer of a second weld or lower melting temperature covering the first weld. Figure 7 is a schematic drawing of an electrical connector having a multilayer weld before automotive glass welding. Figure 8 is a schematic drawing of the device of Figure 7 after automotive glass welding. Figure 9 is an interior view of a rear window of an automobile including an electric defroster. Figure 10 is a side view of an electrical connector welded to an electrical contact in the rear window of Figure 9, the rear window, electrical contact and welding representing in section. DETAILED DESCRIPTION Figure 1 illustrates an embodiment of an apparatus 10 for forming a multilayer welding article 24 (Figure 6). The multilayer weld article 24 may have a multilayer weld 15 which may include a first weld 13 and a second weld 16. When forming the multilayer weld article 24, a tape, strip, belt or cover band 12 (Fig. 4), having an electrically conductive base substrate 11 and a layer of a first weld 13 on a surface, can be removed from a roll 12a in an unwinding station. The first weld 13 can be a higher temperature or melting point solder. The base substrate 11 may be a tape, strip, belt or sheet metal strip suitable for forming electrical devices, such as electrical connectors, by stamping. The cover band 12 can pass through a guide 20 to align the cover band 12 with a device or laminator 14 (Figure 2). A tape, strip, belt or band 16b of a second or lower temperature or melting point solder 16 can be pulled out of a roll 16a into an unwinding station to place it in or on the higher melting temperature solder 13. The second weld 16 may be softer or more ductile than the first weld 13. The web 16b of the second weld 16 may be passed through the guide 20 (Figure 3) for alignment with the cover band 12 and the mill 14 The guide 20 can align the strip 16b of the second weld 16 relative to or with the first weld 13 and the base substrate 11.

The web 16b of the second weld 16 and the cover band 12 can be cold rolled together with the first or top roller 18a and second or lower rollers 18b of a roller system 18. The cold roll can be combined or joining the second weld 16 with the first weld 13 to form the multilayer weld article 24. A heating station 26 can be located after the mill 14 to heat the multilayer weld article 24 in order to ensure a sufficient junction. between the first weld 13 and the second weld 16, but without melting the welds 13 or 16. The heating station 26 can be a flame heater placed below the base substrate 11 as depicted, or in other embodiments, it can be a furnace , hot air gun, etc. The multi-layer welding article 24 (FIG. 6) can subsequently be wound onto a roll 24a in a winding station. In particular embodiments, the guide 20 may be attached to the laminator 14 near the rollers 18a / 18b. The position of the guide 20 can be adjusted with an adjustment device 22 (FIG. 1). The guide 20 may include a first or upper portion 32 and a second or lower portion 34 that are shaped and fixed together to form a longitudinal passage 36 through the guide 20 (Figure 3). The lower portion 34 may have a groove 34a which is dimensioned to guide the base substrate 11 through the guide 20 and the upper portion 32 may have a groove 32a which is dimensioned and positioned to guide the strip 16b of the second weld 16 in alignment with the first weld 13 in the base substrate 11. The guide 20 can begin to combine the second weld 16 with the first weld 13 and the base substrate 11. The downward end of the guide 20 can be contoured in a manner tapered or curved so as to be placed closely between and adjacent rollers 18a and 18b. In one embodiment, the slot 34a may be approximately 0.01 inch (0.254 mm) wider and 0.004 inch (0.101 mm) taller than the width and thickness of the base substrate 11. Furthermore, the slot 32a may be approximately 0.025 inch (0.025 mm) wider than the width of the weld 13 on the base substrate 11 and about 0.010 inch (0.254 mm) higher than the combined height or thickness of the first weld 13 and the strip 16b of the second weld 16 With reference to Figures 1 and 2, the laminator 14 may include a frame 30 in which the rollers 18a and 18b are rotatably mounted about first or upper axes 17a and second or lower 17b, respectively. A gear system 28 can be connected to the roller system 18 to make the rollers 18a and 18b rotate in unison. The gear system 28 may include a first or upper gear 28a which is fixed to roll 18a along axis 17a, and a second or lower gear 28b which is fixed to roll 18b along axis 17b. The gears 28a and 28b can be engaged or meshed with each other. The laminator 14 can be moved by a moving unit 29, or it can be rotated by the movement of the covering band 12 and the second weld 16 passing between the rollers 18a and 18b. The space 35 between the rollers 18a and 18b can be adjusted with an adjusting fitting 33 to provide the desired amount of pressure in the recovery band 12 and the weld 16 during the rolling process in order to join the second weld 16 to the first welding 13 by cold rolling. In some embodiments, the space 35 between the rollers 18a and 18b may be set to reduce the combined initial height or thickness of the first weld 13 and the second weld 16 of approximately 30% to 50%. The adjustment adapter 33 may include a pair of cylinders 31, for example, hydraulic or pneumatic cylinders, for positioning the roller 18a and the shaft 17a relative to the roller 18b and the shaft 17b, and provide laminate pressure. The cylinders 31 can be fixed to an adjustable plate 37, which can be adjusted, for example, with adjusting screws (not shown) to change the position of the cylinders 31. Cold rolling can be performed with the rolling mill 14 without requiring pretreatment of the coupling surfaces of the first 13 and second 16 welds (for example, the removal of contaminants such as oxides, by chemical, energy or mechanical means). The reduction of the thickness and the deformation of the material of the first and second welds 16 during the cold rolling process can provide sufficient pressure, heat or material changes for bonding between the first and second weld layers 16 to occur. In some embodiments, the heating station 26 can be omitted. In other embodiments, the base substrate 11 may be omitted so that the first 13 and second 16 welds are combined only by the laminator 14 to form a multilayer weld article. The guide 20 can be modified to accommodate the omission of the base substrate 11. The web 9 of the first weld 13 can initially be approximately 0.016 inches (0.40 mm) thick and the thickness of the first weld 13 can be reduced to approximately 0.005 to 0.010 inches (0.127-0.254 mm) thick by cutting, machining or deburring. The reduction in thickness may also include cold rolling. The web 16b of the second weld 16 may initially be about 0.010 inch (0.254 mm) thick and the thickness of the second weld 16 may be reduced to about 0.005 to 0.008 inch (0.127-0.203 mm) thick by cut-out and / or cold rolled. The total thickness of the multilayer weld 15 may be approximately 0.013 to 0.015 inches (0.33-0.38 mm) thick. In some embodiments, the multilayer weld 15 may be approximately 0.007 to 0.040 inches (0.177-1.016 mm) thick. In other embodiments, the weld 13 may be even finer or omitted, and the layer of the second weld 16 may be in the range of between about 0.001 and 0.008 inches (0.0254-0.203 mm) thick. Depending on the application in question, the thicknesses may be even higher or lower than those described above. The second weld 16 may be softer and more ductile than the first weld 13. In particular embodiments, the multilayer weld 15 may be formed from generally lead-free compositions which are suitable for cold rolling by the laminator 14 of the apparatus 10. .

With reference to Figure 4, the cover band 12 can be preformed before being processed by the apparatus 10. This can be done with the embodiments of the apparatus 8 illustrated in Figure 5 where a moving band of the base substrate 11 can have flux 46a applied to a surface of the base substrate 11 in a flux station 46, such as by a brush, roller dispenser, etc. A belt, strip, belt or band 9 of the first or highest melting temperature solder 13 can be applied with a roller 48 on the flux 46a and against the base substrate 11. The strip 9 of the first weld 13 can be melted then or flowing in a heating station 50, such as by flame, furnace, hot air gun, etc., to melt and bond the web 9 to the base substrate 11 as reflow solder 9a. If desired, a recessing or trimming station 52 may be included to trim the reflow solder 9a and / or the base substrate 11 resulting in a cover band 12 with a cutout layer 9b of the first weld or melting temperature. highest 13 to desired dimensions. The desired dimensions can be the thickness and / or the width. The trimming can also be done in a separate processing magic. The cover band 12 can be wound onto a roll 12a for processing in the apparatus 10. In some embodiments, the cover band 12 can be fed directly to the laminator 14 to combine it with the web 16b of the second weld 16. Although flux 46a has been discussed for treating the surfaces so that the first weld 13 can be attached to the base substrate 11, other suitable treatments can be employed. With reference to Figure 6, the multilayer welding article 24 produced by the apparatus 10 (Figure 1) may have a multilayer weld 15 where the first or highest melting temperature solder 13 may be placed or bonded against the base substrate 11. and the second or higher melting temperature solder 16 may be attached to the first weld 13. The multilayer weld 15 may be a narrower strip than the base substrate 11 and may be located along a longitudinal axis of the weld. base substrate 11, for example, the central longitudinal axis. As a result, only a portion of the base substrate 11 can be covered by the multilayer weld 15 so that the lateral margins of the base substrate 11 are exposed. The base substrate 11 can be made of a material, such as metal foil, which is suitable to convert it into electrical devices. In one embodiment, the base substrate 11 can be made of copper, for example, C110 which is approximately 0.031 inches (0.78 mm) thick and approximately 1.812 inches (46.02 mm) wide. The base substrate 11 can be cut to a width of approximately 1.56 inches (39.62 mm). The multilayer weld 15 can be about 0, 620 inches (15,74 mm) wide and centered on the base substrate 11 with margins of about 0.448 inch (11.37 mm) on each side. Depending on the situation in question, other materials such as steel may be employed, and the base substrate 11 and / or multilayer weld 15 may have other suitable dimensions. In some embodiments, the width of the base substrate 11 can be trimmed before starting stamping. The base substrate 11 can be cut out in a cutting station 52, in the apparatus 8, the apparatus 10, or in a separate processing machine. The multilayer weld 15 can also be trimmed to the desired configurations and dimensions in the trimming station 52 in the apparatus 10, or in a separate processing magna. For example, the width and / or thickness of the multilayer weld 15 can be trimmed. In addition, the layer of the first weld 13 can be made narrower than the layer of the second weld 16 to reduce the possibility of the first weld 13 contacting welding surfaces. Alternatively, a second weld 16 wider than the first weld 13 on the first weld 13 can also be cold-rolled. Referring to FIG. 7, the multilayer weld article 24 can be converted into electric weld coating devices of various configurations , including an electrical connector 40, such as by stamping processes, feeding the roll 24a to the appropriate processing machinery. The electrical connector 40 may include a connection portion 38 that is formed from the base substrate 11 in a desired configuration, for example, to engage a coupling connector. The multilayer weld 15 can be located in the electrical connector 40 in a suitable position to weld the electrical connector 40 to a surface, such as in a base 39. The first or highest melting temperature solder layer 13 can be interleaved between the base 39 of the connecting portion 38 and the second weld or lower melting temperature layer 16.

For embodiments of the electrical connector 40 which are suitable for automotive glass welding 42, the first weld 13 may have a composition which is suitable for attachment to the material of the connecting portion 38, eg, copper, and the second weld 16 may having a composition suitable for attachment to a terminal adapter 44 on the surface of the automotive glass 42. The first or highest melting temperature solder 13 may be a solder (Sn) and silver (Ag) solder, for example , which has approximately 70% or more tin, by weight. For example, in one embodiment, the weld 13 may be a tin and silver solder having a composition of about 95% tin and about 5% silver, by weight (95Sn 5Ag). In other embodiments, the solder 13 may have several different amounts of tin, such as about 97Sn 3Ag, 90Sn lOAg, 80Sn 20Ag, etc. In addition, part of the silver can be replaced by other elements. While the first weld 13 is suitable for joining the connecting portion 38, the first weld 13 may not be suitable for welding to the automobile glass 42, and could produce fissures of the glass 42. The Applicant has observed that the welds of High tin content typically produces fissures in automobile glass. On the other hand, the second or lower melting temperature solder 16 can have a lower tin content (Sn) and high indium content (In) so that it can be welded to automotive glass 42 without cracking the glass 42. The second weld 16 can be placed in the base 39 of the connecting portion 38 in contact with the automotive glass 42 and also to prevent contact of the first weld 13 with the glass 42. The second weld 16 can have an indium composition (In), tin (Sn), silver (Ag) and copper (Cu) with at least about 40% indium, less than about 55% tin, and the balance being about 3% to 5% silver and from 0.25% to 0.75% copper, by weight. Some embodiments of the weld 16 may have at least about 50% indium and about 45% or less tin. For example, the weld 16 can have a composition of more than 50% indium, a maximum of about 30% tin, about 3% to 5% silver and about 0.25% to 0.75% coppermade. In one embodiment, the weld 16 may be about 65% indium, about 30% tin, about 4.5% silver and about 0.5% copper, by weight. The content of indium can even be higher than 65%, thus reducing the percentage of tin more. An example of a welding composition suitable for welding 16 is disclosed in U.S. Patent No. 6,253,988, issued July 3, 2001, the ideas of which are incorporated herein by reference. The multi-layer welding article can be formed with the desired welding compositions, and then, if desired, it can be converted into electric devices or electrical connectors 40. The welding 13 and the welding 16 can include silver to avoid or reduce the Silver sweep of automobile glass 42. With reference to Figures 7 and 8, when welding electrical device 40 to automobile glass 42, a welding device 54 can apply a selected or programmed amount of heat 56 to weld the electrical device 40 to terminal adapter 44 of automobile glass 42. The welding device 54 can be controlled by microprocessor and the amount of heat required can be pre-selected or preprogrammed, for example, in watts / second. Such a welding device can be purchased on the market from Antaya Technologies Corporation, in Cranston, Rhode Island. The amount of programmed heat 56 can melt the second or lower melting temperature solder 16 to weld the electrical device 40 to the glass 42 without substantially melting the first or highest melting temperature solder 13. Preferably, the first or highest melting temperature solder 13 does not melt completely, but a slight melting is allowed, provided that there is not too much mixing of the two welding layers 13 and 16. If the tin content next to the glass 42 is increased too much by the migration of tin from the layer of the first weld 13 to the layer of the second weld 16, figuration of the glass 42 can occur. In one embodiment, the multi-layer weld article 24 and electrical device or electrical connector 40 may have a first weld 13 having a composition of 95 Sn 5 Ag, and a second weld 16 having a composition of 65 In 30 Sn 4, 5 Ag 0.5 Cu. The melting point or melting temperature (liquid) of a first weld of 95Sn 5Ag 13 is approximately 465 ° F (241 ° C), and the solid is approximately 430 ° F (221 ° C). The melting point or melting temperature (liquid) of a second weld of 65In 30Sn 4,5Ag 0.5Cu 16 is about 250 ° F (121 ° C), and the solid is about 245 ° F (118 ° C). As can be seen, the difference in melting temperatures between the first weld 13 of 95Sn 5Ag and the second weld 16 of 65In 30Sn 4.5Ag 0.5Cu can be about 215 ° F (102 ° C). Such a difference between the two melting temperatures can allow the second weld 16 to melt without substantially melting the first weld 13. When the weld 13 has a composition of 95 Sn 5Ag and the weld 16 has a composition of 65In 30Sn 4, 5Ag 0, 5 Cu, approximately 500 to 650 watts / second of heat 56 may be a suitable range for melting the second weld 16, but not the first weld 13. The amount of heat applied may differ depending on the size and thickness of the connection 38 and the welding volume 16. In other embodiments, approximately 650 to 750 watts / second may be suitable. With the second weld 16 having a melting temperature of less than about 310 ° F (154 ° C), for example about 250 ° F (121 ° C), welding of the second weld 16 to the automobile glass 42 at said low temperature can minimize the thermal stress on the automotive glass 42. In addition, the degree of cooling that the second weld 16 experiences while cooling from the melting temperature to room temperature (e.g., less than about 70 ° F (21 ° C). C)) can be of only a temperature drop of 180 ° F (82 ° C). Therefore, the amount of thermal shrinkage experienced by the second weld 16 can be kept to a minimum due to the temperature drop, thereby minimizing the differential shrinkage between the second weld 16 and the automobile glass 42. The glass of automobile 42 has a very low coefficient of thermal expansion relative to the weld 16, and does not shrink as much as the weld 16 during cooling. In addition, including a high content of indium, the weld 16 can be sufficiently soft or ductile to absorb the differences in thermal expansion between the weld 16 and the automotive glass 42 without cracking the glass 42. One or more of these factors can allowing the second weld 16 to be welded to automobile glass 42 without cracking the glass 42. In other embodiments, the melting temperatures of the first 13 and second 16 welds can vary depending on the situation in question and the compositions chosen. The melting temperature of the first weld 13 can be less than 465 ° F (241 ° C), for example, about 350 ° F (177 ° C), or it can be higher, for example, higher than 500 ° F (260 ° C), and even up to approximately 650 ° F (343 ° C). The melting temperature of the second weld may be less than 250 ° F (121 ° C), for example, only 135 ° F, or may be greater than 310 ° F (154 ° C), for example 500 ° F (260 ° C) to 550 ° F (288 ° C). The compositions chosen for the first 13 and second 16 welds should have at least about 100 ° F (38 ° C) difference in melting temperature so that the second weld 16 can be melted more easily without substantially melting the first weld 13. It may be possible to have more glued differences in the melting temperature depending on the accuracy to which the heat 56 can be distributed and of the compositions employed.

It has been found by other tests that the additional embodiments of the second weld 16 can have a greater range of tin and indium and be compatible or suitable for automotive glass welding without cracking or deconfiguring the glass. Additional embodiments of the second weld 16 can have a composition with 55% or more of tin (Sn) and 40% or less of indium (In). The composition of the second weld 16 can have less than 90% tin (Sn) and more than 10% indium (In), which in comparison with a high tin solder, such as 95 Sn 5 Ag, has lower Tin content and high indium content. The equilibrium can be about 1% to 10% silver (Ag) (often about 1% to 6%), and about 0.25% to 0.75% copper (Cu). Embodiments of the second weld 16 can have a melting temperature of about 360 ° F (182 ° C) to lower, and often about 320 ° F (160 ° C) and lower. In some embodiments, the melting temperature may be less than about 315 ° F (157 ° C) and in other embodiments may be less than about 310 ° F (154 ° C). In one embodiment, the second weld 16 may be about 60% tin (Sn), about 35% indium (In), about 4.5% silver (Ag) and about 0.5% copper (Cu). ). The exact percentages may vary slightly due to normal manufacturing variations, eg, from about 59% to 61% Sn, about 34% to 36% In, about 4% to 5% Ag, and about 0, 4% to 0.6% Cu. The melting point or melting temperature (liquid) can be about 300 ° F (149 ° C) and the solid can be about 235 ° F (113 ° C). In another embodiment, the second weld 16 may be about 50% Sn, about 46% In, about 3.5% Ag, and about 0.5% Cu. The exact percentages may vary slightly due to normal manufacturing variations, for example, approximately 49% to 52% Sn, approximately 45% to 47% In, approximately 3% to 4% Ag, and approximately 0.4 % to 0.6% Cu. The melting point or melting temperature (liquid) can be about 240 ° F (116 ° C) and the solid can be about 235 ° F (113 ° C). These compositions of the second weld 16 can be used with a first weld 13 having 95 Sn 5 Ag, as well as other suitable compositions, including those previously described. A common range of the compositions of the additional embodiments of the second weld 16 may be at least about 50% tin, at least about 10% indium, from 1% to 10% silver (often about 2% to 6%). %), and approximately 0.25% to 0.75% copper. In some situations, it is understood that other elements may also be included in the composition of the second weld 16 in addition to tin, indium, silver and copper, typically, a relatively small percentage compared to tin and indium. The present invention also provides another lead-free solder composition that may be suitable for soldering automotive glass electrical components for electrical connection to electrical devices within or on glass, as well as suitable for use as the second weld 16 of a multilayer weld. With reference to Figure 9, the glass of the rear window 60 of a car is used as an illustrative example for welding electrical components to automotive glass. The glass of the automobile window 60 may include a window defroster 62 which consists of electric resistance defrosting lines 64 embedded within or deposited on the interior surface of the window 60. The defrosting lines 64 may be electrically connected to a pair. of electrical contacts 66 located on the interior surface of the glass 60. The electrical contacts 66 may consist of a conductive coating deposited on the interior surface of the glass 60. Often, the electrical contacts 66 are made of silver. With reference to Figure 10, the welding composition 70 can be used to weld an electrical connector 72 to each electrical contact 66 on the glass 60. Power lines 74 can then be electrically connected to electrical connectors 72 to supply power to the de-icer. window 62 (figure 9). The welding of the electrical connectors 72 to the electrical contacts 66 in the glass 60 with the welding composition 70 can be carried out by resistance welding. Alternatively, any conventional welding apparatus can be used to melt the welding composition 70, for example, a welding wire. The solder composition 70 may include tin (Sn), indium (In), silver (Ag), and bismuth (Bi). The solder composition 70 may have a lower amount of tin than there may be in common high tin solder compositions. This can help prevent cracking and / or chipping of automobile glass 60 during welding. A sufficient amount of indium may provide the solder composition 70 with a relatively low melting point or temperature (liquefied) as well as mechanical properties which can prevent cracking and / or chipping of the automotive glass 60. Aungue too much bismuth can By debonding the weld composition 70, the appropriate amount of bismuth in combination with the other elements can provide the solder composition 70 with a sufficiently low temperature of the solid which can also help to avoid cracking and / or chipping of the automotive glass 60, without making the weld composition 70 too guebradiza. The bis-muto can provide a range of paste between the temperatures of solid and solid which can be only about 30 ° F (1 ° C) and up to about 140 ° F (60 ° C). An appropriate amount of bismuth can maintain the solid temperature below about 330 ° F (165 ° C), commonly less than about 315 ° F (157 ° C). Some embodiments of the solder composition 70 may have a solid temperature of about 310 ° F (154 ° C) and less, for example, about 305 ° F (152 ° C) and less. The silver in the solder composition 70 can prevent the solder composition 70 from stripping the silver from the electrical contact 66 to the solder composition 70. Finally, copper (Cu) can be included within the solder composition 70 to improve wetting .

By providing the solder composition 70 with a relatively low melting temperature, the thermal stress exerted on the automotive glass 60 can be minimized. Furthermore, by providing the solder composition with a relatively low solid temperature, the degree can be minimized. of cooling that the solder composition 70 experiences while cooling from the solid temperature to room temperature. Therefore, the amount of thermal shrinkage experienced by the solder composition 70 after solidification can be kept to a minimum due to a relatively sticky temperature drop, thereby minimizing differential shrinkage and stresses between the solder composition 70 and automotive glass 60. As previously mentioned, including a sufficient content of indium, the weld composition 70 may be sufficiently ductile or soft to absorb differences in thermal expansion between the weld composition 70 and the automobile glass. 60 without cracking and / or flaking the glass 60. A common compositional range for the weld composition 70 may be approximately 30% to 85% tin, approximately 13% to 65% indium (often approximately 15% a 65%), approximately 1% to 10% silver, and approximately 0.25% to 6% bismuth, by weight. Some embodiments may include about 50% to 85% tin (often about 50% to 83%), and about 13% to 45% indium (often about 15% to 45%). Additional embodiments may include about 66% to 85% tin (often about 66% to 83%), and about 13% to 26% indium (often about 15% to 26%). Particular embodiments may include about 70% to 80% tin, and about 15% to 26% indium. Other embodiments may include copper, for example 0.25% to 0.75%. In some embodiments there may be about 1% to 6% silver, about 0.25% to 4% bismuth and about 0.25% to 0.75% copper. To make the solder composition 70, indium, tin, silver, bismuth and copper ingots can be melted and mixed. Alternatively, the elements may be melted from the powder form or a desired combination of ingots, powder and / or existing solder compositions. The blended solder composition 70 can be melted, extruded or subsequently rolled into a suitable form for welding, for example, a tape, wire, etc. If desired, the solder composition 70 may be in the form of a paste.

In one embodiment, the solder composition 70 may include about 51% tin, about 42% indium, about 3.5% silver, about 3% bismuth and about 0.5% copper. The final percentages may vary slightly due to normal manufacturing variations, for example about 49% to 52% tin, about 40% to 44% Indian, about 1% to 6% silver, about 0.25% to 4% bismuth, and approximately 0.25% to 0.75% copper. The melt-point or temperature (liquefied) may be approximately 253 ° F (123 ° C) and the solid may be approximately 223 ° F (106 ° C), resulting in a paste range of approximately 30 ° F (1 C) . In another embodiment, the solder composition 70 may include about 60% to 63% tin, about 28% to 33% indium, about 1% to 6% silver, about 0.25% at 4% bismuth, and approximately 0.25% to 0.75% copper. For example, the solder composition 70 may include about 62% tin, about 30% indium, about 5% silver, about 2.5% bismuth, and about 0.5% copper. The melting point or temperature (liguid) may be approximately 311 ° F (155 ° C) and the solid may be approximately 226 ° F (108 ° C), resulting in a paste range of approximately 85 ° F (30 ° C). In another example, the solder composition 70 may include about 62% tin, about 32% indium, about 4.5% silver, about 1% bismuth, and about 0.5% copper. The melting point or temperature (liquid) may be approximately 336 ° F (169 ° C) and the solid may be approximately 199 ° F (93 ° C), resulting in a paste range of approximately 137 ° F (58 ° C). C). The coefficient of thermal expansion (CET) can be approximately Ilxl0 ~ 6 / ° F (19,7x10" In another embodiment, the solder composition 70 may include about 68% tin, about 24% indium, about 6% silver, about 1.5% bismuth, and about 0.5% copper. Actual percentages may vary slightly, for example, from about 66% to 69% tin, about 22% to 26% Indian, about 1% to 7% silver, about 0.25% to 4% bismuth, and approximately 0.25% to 0.75% copper. The melting point or temperature (liguid) may be approximately 360 ° F (182 ° C) and the solid may be approximately 235 ° F (113 ° C), resulting in a range of pulp of approximately 125 ° F (52 ° C). C). The coefficient of thermal expansion (CET) can be approximately 10.9x106 / ° F (19.6x10 ~ 6 / ° C). In another embodiment, the solder composition 70 may include about 70% to 74% tin, about 18% to 26% indium, about 1% to 6% silver, about 0.25% at 4% bismuth, and approximately 0.25% to 0.75% copper. For example, the solder composition 70 may include about 72% tin, about 19% indium, about 5% silver, about 3.5% bismuth and about 0.5% copper. The melting point or temperature (liquid) can be about 370 ° F (188 ° C) and the solid can be about 273 ° F (134 ° C), resulting in a paste range of about 97 ° F (36 ° C) C). The thermal expansion coefficient (CET) can be about 10.8 x 10"6 / ° F (19.5 × 10 ~ 6 / ° C.) In another example, the welding composition 70 can include about 72% tin, approximately 24% indium, approximately 2% silver, approximately 1.5% bismuth and approximately 0.5% copper.The melting point or temperature (liquid) may be in the range of approximately 379 ° F (193 ° C) ) at 385 ° F (196 ° C) with an average of approximately 382 ° F (194 ° C), and the solid can be in the range of approximately 221 ° F (105 ° C) to 233 ° F (112 ° C) ) with an average of approximately 227CF (108 ° C) This can result in a medium paste range of approximately 155 ° F (69CC) .The coefficient of thermal expansion (CET) can have an average of approximately 12.5x10" 6 / ° F (22.5x10"6 / ° C.) In another embodiment, the solder composition 70 may include approximately 73% to 78% tin, approximately 17% to 22% indium, approximately from 1% to 6% silver, approximately 0.25% to 4% bismuth, and approximately 0.25% to 0.75% copper. For example, the solder composition 70 may include about 75% tin, about 19% indium, about 3.5% silver, about 2% bismuth, and about 0.5% copper. The melting point or temperature (liquefied) can be about 381 ° F (194 ° C) and the solid can be about 284 ° F (140 ° C), resulting in a paste range of about 97 ° F (36 ° C) C). The coefficient of thermal expansion (CET) can be approximately 10x10 ~ 6 / ° F (18x10"6 / ° C) and the density can be approximately 7.4 g / cm 3. In another example, the welding composition 70 can include approximately 75% tin, approximately 20.5% indium, approximately 2.5% silver, approximately 1.5% bismuth and approximately 0.5% copper.The melting point or temperature (liquid) can be about 372 ° F (189 ° C) and the solid can be approximately 278 ° F (137 ° C), giving rise to a paste range of about 9 ° F (34 ° C). In another example, the solder composition 70 may include about 77% tin, about 18% indium, about 3% silver, about 1.5% bismuth, and about 0.5% copper. The melting point or temperature (liquefied) can be about 379 ° F (193 ° C) and the solid can be about 297 ° F (147 ° C), giving rise to a paste range of about 82 ° F (28 ° C) C). The coefficient of thermal expansion (CET) can be approximately 8, 8x10"7 ° F (15.9x10" 6 / ° C). In another embodiment, the solder composition 70 may include from about 78% to 85% tin, about 13% to 16% indium, about 1% to 6% silver, about 0.25% a 4% bismuth, and approximately 0.25% to 0.75% copper. For example, the solder composition 70 may include about 80% tin, about 15% indium, about 3.5% silver, about 1% bismuth and about 0.5% copper. The melting point or temperature (liguid) can be about 390 ° F (199 ° C) and the solid can be about 304 ° F (151 ° C), resulting in a pas-ta range of about 86 ° F ( 30 ° C). The coefficient of thermal expansion (CET) can be approximately 8.5x10"6 / ° F (15.3x10" d / ° C). In another example, the solder composition 70 may also include about 83% tin, about 13% indium, about 2.5% silver, about 1% bismuth, and about 0.5% copper. The melting point or temperature (liquefied) can be about 399 ° F (204 ° C) and the solid can be about 305 ° F (152 ° C), resulting in a paste range of about 94 ° F (34 ° C) C). The coefficient of thermal expansion (CTE) can be approximately 7,6x10"6 / ° F (13.7x10" 6 / ° C). In some situations, the content of indium may be approximately 12% to 16%. While this invention has been shown and described in particular with references to its particular embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention encompassed by the claims. annexes. For example, the apparatus 10 can be used to join more than two layers of welding together, resulting in a multi-layer welding article, electrical device or electrical connector having more than two layers of welding.

In addition, the coupling surfaces of the welds 13/16 can be pre-treated for bonding purposes. In embodiments where the multilayer weld article does not have a base substrate 11, the multilayer weld article can be attached or placed later in relation to products that require welding. A rolling process can also be used to join the first weld 13 to the base substrate 11. Although the multilayer weld article 24 has been shown and described so that it is formed using cold laminating processes, alternatively, article 24 and / or the electrical device or connector 40 can be formed using other processes, for example, deposition or reflow processes. Ultrasound or resistance welding devices can also be used to join together the desired layers of material. For example, the welds can be applied to the base substrate 11 by welding processes. Although particular solder compositions have been described for the first 13 and second 16 solders, other solder compositions may alternatively be used for various applications, including lead containing compositions. The embodiments of the resulting apparatuses and articles, electrical devices, electrical connectors represented and described, may also be intended for non-automotive applications. The first welding layer 13 can be used to compensate uneven surfaces and can be omitted when there are very flat surfaces. Aungue welding compositions for automotive glass welding have been described, alternatively, the welding compositions can be used for welding to other types of glass such as those used in buildings or any other material where a low-level weld is desirable. melting point or solid. In addition, given solid and solid temperatures have been indicated, such temperatures may vary depending on the elements present and the percentages of the elements. In addition, in some embodiments, additional elements can be added to the welding compositions or replace elements of the welding compositions, for example, antimony, zinc, nickel, iron, gallium, germanium, cadmium, titanium, tellurium, platinum, etc. .

Claims

CLAIMS 1. A solder composition having a mixture of elements including tin, indium, silver, and bismuth, and including about 30% to 85% tin and about 15% to 65% indium.
2. The solder composition of claim 1 further including copper.
3. The solder composition of claim 2 wherein the composition includes about 1% to 10% silver, about 0.25% to 6% bismuth, and about 0.25% to 0.75%. coppermade.
4. The welding composition of claim 3 wherein the composition includes about 1% to 6% silver, about 0.25% to 4% bismuth, and about 0.25% to 0, 75% copper
5. The solder composition of claim 1 wherein the composition includes about 50% to 83% tin.
6. The solder composition of claim 5 wherein the composition includes about 15% to 45% indium.
7. The solder composition of claim 1 wherein the composition has a solid temperature below about 315 ° F (157 ° C).
8. A solder composition having a mixture of elements including tin, indium, silver, and bismuth, and, including about 30% to 85% tin, about 13% to 65% indium, and about 0.25% to 4% bismuth.
9. The solder composition of claim 8 further including copper.
The welding composition of claim 9 wherein the composition includes about 1% to 10% silver, and about 0.25% to 0.75% copper.
11. The solder composition of claim 10 wherein the composition includes about 1% to 6% silver, about 0.25% to 4% bismuth, and about 0.25% to 0, 75% copper
12. The solder composition of claim 8 wherein the composition includes from about 50% to 83% tin.
13. The solder composition of claim 12 wherein the composition includes about 13% to 45% indium.
14. The solder composition of claim 12 wherein the composition includes about 15% to 45% indium.
15. The solder composition of claim 8 wherein the composition has a solid temperature below about 315 ° F (157 ° C).
16. A solder composition having a mixture of elements including tin, indium, silver, bismuth and copper, and including from about 30% to 85% tin and about 13% to 65% indium.
The welding composition of claim 16 wherein the composition includes about 1% to 10% silver, about 0.25% to 6% bismuth, and about 0.25% to 0.75% coppermade.
18. The solder composition of claim 17 wherein the composition includes from about 1% to 6% silver, from about 0.25% to 4% bismuth, and from about 0.25% to 0.75% coppermade.
19. The solder composition of claim 16 wherein the composition includes from about 50% to 83% tin.
The solder composition of claim 19 wherein the composition includes about 13% to 45% indium.
21. The solder composition of claim 20 wherein the composition includes about 15% to 45% indium.
22. The solder composition of claim 18 wherein the composition includes about 66% to 85% tin, and about 13% to 26% indium.
23. The solder composition of claim 16 wherein the composition has a solid temperature below about 315 ° F (157 ° C).
24. The solder composition of claim 16 wherein the composition includes about 70% to 80% tin, and about 15% to 26% indium.
25. The solder composition of claim 16 wherein the composition includes about 70% to 74% tin, about 18% to 26% indium, about 1% to 6% silver, about 0.25% to 4% bismuth and about 0.25% to 0.75% copper.
26. The solder composition of claim 16 wherein the composition includes about 73% to 78% tin, about 17% to 22% indium, about 1% to 6% silver, about 0.25% to 4% bismuth, and approximately 0.25% to 0.75% copper.
27. The solder composition of claim 16 wherein the composition includes about 78% to 85% tin, about 13% to 16% indium, about 1% to 6% silver, about 0, 25% to 4% bismuth, and approximately 0.25% to 0.75% copper.
28. A solder composition including tin, in-dio and silver, and including more than about 60% tin, the composition having a solid temperature below about 330 ° F (165 ° C).
29. The solder composition of claim 28 wherein the solid temperature is less than about 315 ° F (157 ° C).
30. The solder composition of claim 29 further including bismuth.
31. The solder composition of claim 30 further including copper.
32. A method of forming a solder composition including mixing tin, indium, silver, and bismuth together, and including about 30% to 85% tin and about 15% to 65% indium.
33. The method of claim 32 further including mixing copper.
34. The method of claim 33 further comprising mixing about 1% to 10% silver, about 0.25% to 6% bismuth, and about 0.25% to 0.75% copper.
35. The method of claim 34 further comprising mixing about 1% to 6% silver, about 0.25% to 4% bismuth, and about 0.25% to 0.75% copper.
36. The method of claim 32 further comprising mixing from about 50% to 83% tin.
37. The method of claim 36 further comprising mixing about 15% to 45% indium.
38. The method of claim 32 further comprising providing the composition with a solid temperature below about 315 ° F (157 ° C).
39. A method of forming a solder composition including mixing tin, indium, silver, and bismuth jointly, and including about 30% to 85% tin, about 13% to 65% indium, and about 0 , 25% to 4% bismuth.
40. The method of claim 39 further including mixing copper.
41. The method of claim 40 further comprising mixing about 1% to 10% silver, and about 0.25% to 0.75% copper.
42. The method of claim 41 further comprising mixing about 1% to 6% silver, about 0.25% to 4% bismuth, and about 0.25% to 0.75% copper.
43. The method of claim 39 further comprising mixing from about 50% to 83% tin.
44. The method of claim 42 further comprising mixing about 13% to 45% indium.
45. The method of claim 43 further comprising mixing about 15% to 45% indium.
46. The method of claim 39 further comprising providing the composition with a solid temperature below about 315 ° F (157 ° C).
47. A method of forming a solder composition including mixing tin, indium, silver, bismuth and copper together, and including about 30% to 85% tin and about 13% to 65% indium.
48. The method of claim 47 further comprising mixing about 1% to 10% silver, about 0.25% to 6% bismuth, and about 0.25% to 0.75% copper.
49. The method of claim 48 further comprising mixing from about 1% to 6% silver, from about 0.25% to 4% bismuth, and about 0, 25% to 0.75% copper.
50. The method of claim 47 further including mixing about 50% to 83% tin.
51. The method of claim 50 further comprising mixing about 13% to 45% indium.
52. The method of claim 51 further comprising mixing about 15% to 45% indium.
53. The method of claim 49 further comprising mixing from about 66% to 85% tin and from about 13% to 26% indium.
54. The method of claim 47 further comprising providing the composition with a solid temperature below about 315 ° F (157 ° C).
55. The method of claim 47 further comprising mixing about 70% to 80% tin, and about 15% to 26% indium.
56. The method of claim 47 further comprising mixing about 70% to 74% tin, about 18% to 26% indium, about 1% to 6% silver, about 0.25% to 4% of bismuth, and approximately 0.25% to 0.75% copper.
57. The method of claim 47 further comprising mixing from about 73% to 78% tin, from about 17% to 22% indium, about 1% to 6% silver, about 0.25% at 4% bismuth, and approximately 0.25% to 0.75% copper.
58. The method of claim 47 further comprising mixing from about 78% to 85% tin, about 13% to 16% indium, about 1% to 6% silver, about 0.25 to 4% silver. bismuth, and approximately 0.25% to 0.75% copper.
59. A method of forming a solder composition including mixing together tin, indium and silver, including more than about 60% tin, and providing the composition with a solid temperature below about 330 ° F (165 ° C). .
60. The method of claim 59 further comprising providing a solid temperature below about 315 ° F (157 ° C).
61. The method of claim 60 further including mixing bismuth.
62. The method of claim 61 further including mixing copper.
63. A method of welding including: providing a solder composition having a mixture of elements including tin, indium, silver, and bismuth, and including from about 30% to 85% tin and from about 15% to 65% of Indian; and melting the welding composition with a welding device.
64. An electrical device comprising: a base formed of electrical conductive material; a layer of a first solder without lead in the base; a layer of a second unleaded solder on the first weld layer, the second weld having a lower melting temperature than the first weld, and the second weld having a solid temperature less than about 315 ° F (157 ° C) ).
65. A multi-layer welding article including: a layer of a first lead-free solder for bonding to an electrically conductive material; and a layer of a second unleaded solder on the first weld layer, the second weld having a lower melting temperature than the first weld, and the second weld having a solid temperature below about 315 ° F ( 157 ° C) and suitable for automotive glass welding.
66. A method of making a multi-layer welding article including: providing a layer of a first lead-free solder; joining a layer of a second unleaded solder against the first weld layer by cold-laminating the first and second weld layers together between a pair of rollers, the second weld layer having a lower melting temperature than the layer of the first weld, and the second weld having a solid temperature below about 315 ° F (157 ° C).
67. A method of welding an electric device to automotive glass including: providing a layer of a first lead-free solder in the electrical device; provide a layer of a second leadless solder on the first weld layer, the second weld having a melt temperature below the first weld, and the second weld having a solid temperature less than about 315 ° F (157 ° C); orienting the electrical device in relation to the automotive glass to place the layer of the second weld against the glass; and applying a preselected amount of heat to the second weld to melt the layer of the second weld without substantially melting the layer of the first weld to weld the electrical device to the automotive glass.
68. An electrical device including: a base formed of electrical conductive material; a layer of a first solder without lead in the base; a layer of a second unleaded solder on the first solder layer, the second solder having a composition including tin, indium, silver and copper, the second solder having a lower melting temperature than the first solder.
69. The electrical device of claim 68 wherein the second weld has a melting temperature of less than about 360 ° F (182 ° C).
70. The electrical device of claim 69 wherein the second weld has a melting temperature of less than about 315 ° F (157 ° C).
71. The electrical device of claim 70 wherein the second weld has a melting temperature of less than about 310 ° F (154 ° C).
72. The electrical device of claim 68 wherein the second weld has a composition comprising at least about 50% tin, at least about 10% indium, about 1% to 10% silver, and about 0.25 % to 0.75% copper.
73. The electrical device of claim 72 wherein the second weld includes about 60% tin, about 35% indium, about 4.5% silver and about 0.5% copper.
74. The electrical device of claim 73 wherein the second weld has a melting temperature of about 300 ° F (149 ° C).
75. The electrical device of claim 68 wherein the first weld includes tin and silver with about 70% or more of tin.
76. The electrical device of claim 75 wherein the first weld includes about 95% tin and about 5% silver.
77. The electrical device of claim 76 wherein the first weld has a melting temperature of about 465 ° F (241 ° C).
78. The electrical device of claim 68 wherein the base is made from metal to metal.
79. The electrical device of claim 78 wherein the base is made of copper.
80. The electrical device of claim 79 wherein the electrical device is an electrical connector.
81. A multilayer welding article including: a layer of a first lead-free solder for bonding to an electrically conductive material; and a layer of a second unleaded solder on the layer of the first weld, the second weld having a composition including tin, indium, silver and copper, the second weld having a melting temperature lower than the first weld and suitable for automotive glass welding.
82. The article of claim 81 wherein the second weld has a melting temperature of less than about 360 ° F (182 ° C).
83. The article of claim 82 wherein the second weld has a melting temperature of less than about 315 ° F (157 ° C).
84. The article of claim 83 wherein the second weld has a melting temperature of less than about 310 ° F (154 ° C).
85. The article of claim 81 wherein the second weld has a composition comprising at least about 50% tin, at least about 10% indium, about 1% to 10% silver and about 0, 25% to 0.75% copper.
86. The article of claim 85 wherein the second weld includes about 60% tin, about 35% indium, about 4.5% silver and about 0.5% copper.
87. The article of claim 86 wherein the second weld has a melting temperature of about 300 ° F (149 ° C).
88. The article of claim 81 in which the first weld includes tin and silver with approximately 70% or more of tin.
89. The article of claim 88 in which the first weld it includes approximately 95% tin and approximately 5% silver.
90. The article of claim 89 wherein the first weld has a melting temperature of about 465 ° F (241 ° C).
91. The article of claim 81 further including a base substrate formed of electrically conductive material in which the layers of the first and second welds are joined.
92. The article of claim 91 wherein the base substrate is made of metal foil.
93. The article of claim 92 wherein the base substrate includes a copper band.
94. A method of making a multilayer weld article including: providing a layer of a first weld without plo-rao; joining a layer of a second lead-free weld against the first weld layer by cold-laminating the first and second weld layers together between a pair of rollers, the second weld having a composition including tin, indium, silver and copper , the layer of the second weld having a melting temperature lower than the layer of the first weld.
95. The method of claim 94 further comprising providing the second weld with a melting temperature of less than about 360 ° F (182 ° C).
96. The method of claim 95 further comprising providing the second weld with a melting temperature of less than about 315 ° F (157 ° C).
97. The method of claim 96, further comprising providing the second weld with a melting temperature of less than about 310 ° F (154 ° C).
98. The method of claim 94 further comprising providing the second weld with a composition comprising at least about 50% tin, at least about 10% indium, about 1% to 10% silver and about 0, 25% to 0.75% copper.
99. The method of claim 98 further comprising providing the second weld with a composition comprising about 60% tin, about 35% indium, about 4.5% silver and about 0.5% copper.
100. The method of claim 99 further comprising providing the second weld with a melting temperature of about 300 ° F (149 ° C).
101. The method of claim 94 further comprising providing the first solder with a composition including tin and silver with approximately 70% or more of tin.
102. The method of claim 101 further comprising providing the first weld with a composition comprising about 95% tin and about 5% silver.
103. The method of claim 102 further including providing the first weld with a melting temperature of about 465 ° F (241 ° C).
104. The method of claim 94 further comprising forming the first weld layer on a surface of a base substrate formed of a sheet of electrically conductive material.
105. The method of claim 104 further comprising forming the metal foil base substrate.
106. The method of claim 105 further comprising forming the base substrate of a copper band.
107. The method of claim 106 further comprising forming the article in the form of an electrical device.
108. The method of claim 107 further including forming the article in the form of an electrical connector.
109. A method of welding an electric device to automotive glass including: providing a layer of a first lead-free solder in the electrical device; providing a layer of a second leadless solder on the first solder layer, the second solder having a composition including tin, indium, silver and copper, the second solder having a lower melting temperature than the first solder; orienting the electrical device in relation to the automotive glass to place the layer of the second weld against the glass; and applying a preselected amount of heat to the second weld to melt the second weld layer without substantially melting the first weld layer to weld the electrical device to the automotive glass.
110. The method of claim 109 further including providing the second weld with a melting temperature less than about 360 ° F (182 ° C).
111. The method of claim 110 further comprising providing the second weld with a melting temperature of less than about 315 ° F (157 ° C).
112. The method of claim 111 further comprising providing the second weld with a melting temperature of less than about 310 ° F (154 ° C).
113. The method of claim 109 further comprising providing the second weld with a composition comprising at least about 50% tin, at least about 10% indium, about 1% to 10% silver and about 0, 25% to 0.75% copper.
114. The method of claim 113 further comprising providing the second weld with a composition comprising about 60% tin, about 35% indium, about 4.5% silver and about 0.5% copper.
115. The method of claim 114 further including providing the second weld with a melting temperature of about 300 ° F (149 ° C).
116. The method of claim 109 further comprising providing the first solder with a composition including tin and silver with approximately 70% or more of tin.
117. The method of claim 116 further comprising providing the first weld with a composition comprising about 95% tin and about 5% silver.
118. The method of claim 117 further comprising providing the first weld with a melting temperature of about 465 ° F (241 ° C).
119. An electrical device including: a base formed of electrical conductive material; a layer of a first solder without lead on the base; a layer of a second unleaded solder on the first weld layer, the second weld having a lower melting temperature than the first weld, the melting temperature of the second weld being less than about 310 ° F (154 ° C) ).
120. The electrical device of claim 119 wherein the second weld is a softer material than the first weld.
121. The electrical device of claim 119 wherein the first weld has a melting temperature of about 465 ° F (241 ° C).
122. The electrical device of claim 121 wherein the second weld has a melting temperature of about 250 ° F (121 ° C).
123. The electrical device of claim 119 wherein the first weld is a tin and silver composition having approximately 70% or more of tin, and the second weld has an indium, tin, silver and copper composition of at least about 40% indium and less than about 55% tin.
124. The electrical device of claim 123 wherein the second weld has a composition of about 50% or more of indium, a maximum of about 30% tin., approximately 3% -5% of silver and approximately of 0.25% to 0.75% of copper.
125. The electrical device of claim 124 wherein the first weld is about 95% tin and about 5% silver.
126. The electrical device of claim 125 wherein the second weld is about 65% indium, about 30% tin, about 4.5% silver and about 0.5% copper.
127. The electrical device of claim 119 wherein the base is made of metal foil.
128. The electrical device of claim 127 wherein the base is made of copper.
129. The electrical device of claim 128 wherein the electrical device is an electrical connector.
130. The electrical device of claim 119 wherein the layers of the first and second welds have a combined thickness in the range of about 0.013 to 0.015 inches (0.33-0.38 mm).
131. The electrical device of claim 130 wherein the layer of the first weld is in the range of about 0.005 to 0.010 inches (0.127-0.254 mm) thick.
132. The electrical device of claim 130 wherein the layer of the second weld is in the range of about 0.001 to 0.008 inches thick.
133. The electrical device of claim 132 wherein the layer of the second weld is in the range of between about 0.005 and 0.008 inches (0.203-0.025 mm) thick.
134. A multi-layer welding article including: a layer of a first lead-free solder for attachment to an electrically conductive material; and a layer of a second unleaded solder on the first weld layer, the second weld having a lower melting temperature than the first weld, the melting temperature of the second weld being less than about 310 ° F (154 °). C) and suitable for welding to automotive glass.
135. The article of claim 134 wherein the second weld is a softer material than the first weld.
136. The article of claim 134 wherein the first weld has a melting temperature of about 465 ° F (241 ° C).
137. The article of claim 136 wherein the second weld has a melting temperature of about 250 ° F (121 ° C).
138. The article of claim 134 wherein the first weld is a tin and silver composition having approximately 70% or more of tin, and the second weld has an indium, tin, silver and copper composition of at least about 40% Indian and less than about 55% tin.
139. The article of claim 138 wherein the second weld has a composition of about 50% or more of indium, a maximum of about 30% tin, about 3% to 5% silver and about 0.25% to 0.75% copper.
140. The article of claim 139 wherein the first weld is about 95% tin and about 5% silver.
141. The article of claim 140 wherein the second weld is about 65% indium, about 30% tin, about 4.5% silver and about 0.5% copper.
142. The article of claim 134 further including a base substrate formed of electrically conductive material in which the layers of the first and second welds are joined.
143. The article of claim 142 wherein the base substrate is made of metal foil.
144. The article of claim 143 wherein the base substrate includes a copper band.
145. The article of claim 134 wherein the layers of the first and second welds have a combined thickness of the order of between about 0.013 to 0.015 inches (0.33-0.38 mm).
146. The article of claim 145 wherein the first weld layer is in the range of between about 0.005 and 0.010 inches (0.127-0.254 mm) thick.
147. The article of claim 145 wherein the layer of the second weld is in the range between about 0.001 to 0.008 inches (0.0254-0.203 mm) thick.
148. The article of claim 147 wherein the layer of the second weld is in the range of between about 0.005 and 0.008 inches (0.203-0.025 mm) thick.
149. A method of making a multi-layer welding article including: providing a layer of a first lead-free solder; joining a layer of a second lead-free weld against the first weld layer by cold-laminating the first and second weld layers together between a pair of rollers, the second weld layer having a melting temperature lower than the layer of the first weld, the melting temperature of the second weld being less than about 310 ° F (154 ° C).
150. The method of claim 149 further comprising forming the first weld layer on a surface of a base substrate formed of a sheet of electrically conductive material.
151. The method of claim 150 further comprising: applying a sheet of the first weld to the surface of the base substrate; and melting the sheet of the first solder on the base substrate with a heat source.
152. The method of claim 151 further including applying a web of the first weld onto a web of the base substrate.
153. The method of claim 152 further including applying flux between the first weld and the base substrate.
154. The method of claim 152 further including cutting the first weld to a desired dimension on the base substrate.
155. The method of claim 154 further including cold laminating a band of the second weld onto the first weld.
156. The method of claim 155 further including cold-rolling the second weld against the first weld without pre-treating the mating surfaces of the first and second welds.
157. The method of claim 155 further including reducing the combined thickness of the first and second weld layers by about 30% to 50% during cold rolling.
158. The method of claim 157 further including heating the weld layers with a heat source after cold rolling.
159. The method of claim 155 further including aligning the first and second welds with one another within a guide device prior to cold rolling.
160. The method of claim 159 further including aligning the first and second welds within a stationary guide device.
161. The method of claim 149 further including selecting the second weld so that it is a softer material than the first weld.
162. The method of claim 149 further comprising providing the first weld with a melting temperature of about 465 ° F (241 ° C).
163. The method of claim 162 further including providing the second weld with a melting temperature of about 250 ° F (121 ° C).
164. The method of claim 149 further comprising: providing the first solder with a tin and silver composition having approximately 70% or more of tin; and providing the second solder with an indium, tin, silver and copper composition of at least about 40% indium and less than about 55% tin.
165. The method of claim 164 further comprising providing the second weld with a composition of about 50% or more of indium, a maximum of about 30% tin, about 3% to 5% silver and about 0.25% to 0.75% copper.
166. The method of claim 165 further comprising providing the first weld with about 95% tin and about 5% silver.
167. The method of claim 166 further including providing the second weld with about 65% indium, about 30% tin, about 4.5% silver and about 0.5% copper.
168. The method of claim 150 further including forming the sheet metal base substrate.
169. The method of claim 168 further comprising forming the base substrate of a copper band.
170. The method of claim 169 further including forming the article in the form of an electrical device.
171. The method of claim 170 further comprising forming the article in the form of an electrical connector.
172. The method of claim 149 further comprising forming the layers of the first and second welds so that they have a combined thickness of the order of between about 0.013 to 0.015 inches (0.33-0.38 mm).
173. The method of claim 172 further comprising forming the first weld layer in the range of between about 0, 005 and 0.010 inches (0.127-0.254 mm) thick.
174. The method of claim 172 further comprising forming the second weld layer in the range of about 0.001 to 0.008 inches (0.0254-0.203 mm) thick.
175. The method of claim 174 further comprising forming the second weld layer in the range of between about 0.005 and 0.008 inches (0.203-0.025 mm) thick.
176. A method of welding an electrical device to automotive glass including: providing a layer of a first lead-free solder in the electrical device; providing a layer of a second unleaded weld on the first weld layer, the second weld having a lower melting temperature than the first weld, the melting temperature of the second weld being less than about 310 ° F (154 °) C); orienting the electrical device in relation to the automotive glass to place the layer of the second weld against the glass; and applying a preselected amount of heat to the second weld to melt the layer of the second weld without substantially melting the layer of the first weld to weld the electrical device to the automotive glass.
177. The method of claim 176 further comprising providing the first weld layer on a metal base of the electrical device formed of copper.
178. The method of claim 176 further including selecting the second weld so that it is a softer material than the first weld.
179. The method of claim 176 further including providing the first weld with a melting temperature of about 465 ° F (241 ° C).
180. The method of claim 179 further comprising providing the second weld with a melting temperature of approximately 250 ° F (121 ° C).
181. The method of claim 176 further comprising: providing the first solder with a tin and silver composition having approximately 70% or more of tin; and providing the second solder with an indium, tin, silver and copper composition of at least about 40% indium and less than about 55% tin.
182. The method of claim 181 further comprising providing the second weld with a composition of about 50% or more of indium, a maximum of about 30% tin, about 3% to 5% silver and about 0, 25% to 0.75% copper.
183. The method of claim 182 further including providing the first weld with about 95% tin and about 5% silver.
184. The method of claim 183 further comprising providing the second weld with about 65% indium, about 30% tin, about 4.5% silver and about 0.5% copper.
185. The method of claim 176 further comprising providing the first and second weld layers with a combined thickness in the range of about 0.013 to 0.015 inches (0.33-0.38 mm).
186. The method of claim 185 further comprising providing the first weld layer with a thickness of the order of between about 0.005 and 0.010 inches (0.127-0.254 mm).
187. The method of claim 185 further comprising providing the second weld layer with a thickness of the order of between about 0.001 and 0.008 inches (0.0254-0.203 mm).
188. The method of claim 187 further comprising providing the second weld layer with a thickness of the order of between about 0.005 and 0.008 inches (0.203-0.025 mm).
189. The solder composition of claim 16, wherein the composition includes from about 49% to 52% tin, from about 40% to 44% indium, from about 1% to 6% silver, of about 0 , 25% to 4% bismuth, and from about 0.25% to 0.75% copper.
190. The solder composition of claim 16, wherein the composition includes from about 60% to 63% tin, from about 28% to 33% of indium, of about 1% to 6% of silver, of about 0.25. % to 4% bismuth, and from about 0.25% to 0.75% copper.
191. The solder composition of claim 16, wherein the composition includes from about 66% to 69% tin, from about 22% to 26% indium, from about 1% to 7% silver, from about 0.25% to 4% bismuth, and from about 0.25% to 0.75% copper.
192. The method of claim 47, further comprising mixing from about 49% to 52% tin, from about 40% to 44% indium, from about 1% to 6% silver, from about 0.25% to 4%. % bismuth, and from about 0.25% to 0.75% copper.
193. The method of claim 47, further comprising mixing from about 60% to 63% tin, from about 28% to 33% indium, from about 1% to 6% silver, from about 0.25% to about 4%. % bismuth, and from about 0.25% to 0.75% copper.
194. The method of claim 47, further comprising mixing from about 66% to 69% tin, from about 22% to 26% indium, from about 1% to 7% silver, from about 0.25% to 4%. % bismuth, and from about 0.25% to 0.75% copper.