Leadless welding alloy and its applicationTechnical field
The invention belongs to lead-free solder technical fields, more particularly, to the lead-free solder group for glass of environment-friendly typeClose object.
Background technique
The windscreen and wind shield glass wind shield of automobile will often carry some necessary functions, for example, demisting defrosting and nothingThe functions such as line electricity antenna.
In order to provide the function of these types to vehicle window, it is necessary first to which metal coating (main component is silver paste) to be printed onOn glass, as electrical contact surface, electric signal transmission function is played；It also needs to provide stable voltage to windowpane simultaneously, justThere is corresponding electrical connector as weld to electrical contact surface.
Initially, electrical connector is all by there is kupper solder to be welded on electrical contact surface.Due to there is kupper solder that there is welderingTin good fluidity, welding equipment require low, cheap advantage, are widely used in electrical connector and glass (metal coating)Between welding.However, European Union puts into effect 2000/53/EG regulation, to electronics member device in vehicle since it is related to environmental problemThe harmful substances such as the lead in solder, mercury, cadmium and chromium that part and electrical connections use clearly are limited.Japan, South Korea all issuesThe similar regulation of cloth, Chinese related bill is in drawing up, it is contemplated that implement in full in the year two thousand twenty, therefore, there is kupper solder quiltLead-free solder, which replaces, becomes a kind of trend.
Known leadless welding alloy, mostlys come from electronics industry, and mainstream is tin silver system alloy.On the one hand, these nothingsKupper solder alloy is easily fabricated and cheap, to become the first choice of lead-free solder；On the other hand, these leadless welding alloysWith poor plastic deformation characteristics, it is easy to produce biggish welding stress, for example, glass and electrical connector (mostly copper material)Belong to thermal expansion coefficient and distinguish very big two kinds of materials, leadless welding alloy passes through glass and electronic component after high-temperature fusionConnector weld together after, in subsequent cooling procedure, due to the solder have poor plastic deformation, cannot offsetThe stress generated between the connector and glass of electronic component, in relatively large temperature fluctuation or external force strikesIn the case of glass can be caused to rupture, connector falls off.
In this field, need to develop it is a kind of be resistant to environment temperature required by automobile industry, and be able to satisfy garageThe environment-friendly type lead-free solder that industry all properties require.
Summary of the invention
The present invention provides two kinds of environmentally friendly leadless welding alloys, liquidus temperature with higher and solidus temperature,In the case where bearing higher operating ambient temperature, good mobility can also be kept in welding, finally realized splendidWeld strength.
First aspect present invention provides two kinds of leadless welding alloys, and by mass percentage, the technical solution of use is distinguishedIt is as follows:
The first leadless welding alloy contains indium 60%~95%, and surplus is tin and inevitable impurity.
In preferred embodiment, the mass percent of the indium is 75~91%
In preferred embodiment, the mass percent of the tin is 9~25%,
It can further include 1%~4.5% silver in preferred embodiment,
It can further include 0.3%~2% copper in preferred embodiment,
It can further include 0.03%~1% iron in preferred embodiment,
It can further include 0.03%~1% aluminium in preferred embodiment,
It can also further include 0~1% nickel, 0~1% zinc, 0~1% bismuth in preferred embodiment.
Second of leadless welding alloy contains tin 70%~95%, and surplus is indium and inevitable impurity.
In preferred embodiment, the mass percent of the tin is 75%~85%
In preferred embodiment, the mass percent of the indium is 15%~25%,
It can further include 4.5%~10% silver in preferred embodiment,
It can further include 0.3%~2% copper in preferred embodiment,
It can further include 0.5%~2% iron in preferred embodiment,
It can further include 0.5%~1.5% aluminium in preferred embodiment,
It can also further include 0~1% nickel, 0~1% zinc, 0~1% bismuth in preferred embodiment.
Second aspect of the present invention provides the application of leadless welding alloy described above, and the leadless welding alloy is used for willThe connector of electronic component is welded to the electrical contact surface on glass.
Third aspect present invention provides a kind of glass assembly, glass matrix, lead-free solder including having electrical contact surfaceLayer and electronic component, the connector of the electronic component are fixedly welded on the electrical contact table by the Pb-free coating bed of materialFace, the material of the Pb-free coating bed of material are the first described above or second of leadless welding alloy.
Further, the glass assembly is vehicle glass component.
Technical solution provided by the invention has the following beneficial effects:
1, harmful human health such as lead, antimony and ecological environment are not added in two kinds of leadless welding alloy environmental protection of the inventionComponent.
2, two kinds of leadless welding alloys of the invention, the superior performance in terms of intensity, ductility and electric conductivity are not being addedIn the case where the component that lead, antimony etc. are easy and tin combines, still has a good welding performance, when welding has preferably flowingProperty and wellability, caking property are good.By the detection of pulling capacity and shearing force after welding, the performance of the lead-free solder can with it is existingThere is kupper solder to compare favourably, performance is close, and welding stress is small, especially suitable for the welding on vehicle glass.And have kupper solderPerformance comparison is shown in 201810574013.8 1 text of Chinese Patent Application No. that this department submits.
3, the connector of electronic component is welded to the electrical contact of glass using two kinds of leadless welding alloys of the inventionWhen surface, simple welding procedure can be used to implement.Such as electric iron technique, resistance-welding process, hot gas welding etc.,Without special welding equipment, welding surroundings requirement is low, can carry out in air；And the solder alloy can bear 120 DEG C withOn higher operating ambient temperature and it is non-fusible.
Detailed description of the invention
Fig. 1 is the planar structure schematic diagram for having used a kind of glass assembly of leadless welding alloy of the invention.
Fig. 2 is Section A-A schematic diagram in Fig. 1.
Description of symbols:
90-glass assembly 900-glass matrix, 920-electrical contact surfaces
930-800-electronic components of argentiferous 980-heating work of heater strip region
840-power supply line 850-connector, 700-Pb-free coating bed of materials
Specific embodiment
For a better understanding of the technical solution of the present invention, illustrating the present invention in detail further below.
Two kinds of leadless welding alloys of the invention, ingredient all contain tin, indium, optionally also containing silver and/or copper and/orIron and/or aluminium and/or nickel and/or zinc and/or bismuth.According to mass percent meter:
The first leadless welding alloy ingredient contains, indium 60%~95%, and surplus is tin and inevitable impurity, can be withFurther includes 0%~10% silver, 0%~5% copper, 0%~2.5% iron, 0%~2% aluminium, 0%~1%Nickel, 0%~1% zinc, the one or more of 0~1% bismuth.
Second of leadless welding alloy ingredient contains, tin 70%~95%, and surplus is indium and inevitable impurity, can be withFurther includes 0%~10% silver, 0%~5% copper, 0%~2.5% iron, 0%~2% aluminium, 0%~1%Nickel, 0%~1% zinc, the one or more of 0%~1% bismuth.
Without using poisonous components such as lead, antimony in leadless welding alloy formula of the invention.Lead-free solder of the invention is matchedSide, by elements such as tin, indiums according to the mutual cooperation of specific proportion, has good welding on the basis of not using lead, antimonyPerformance, solder fluidity and wellability are good, are easy to welding procedure；The lead-free solder can also bear 120 DEG C or more of work simultaneouslyMake environment temperature and non-fusible, and weld strength is high, is easy to combine with electrical contact surface and electronic component；In addition, usingThe alloy malleability and ductility of inventive formulation add, and are easy to be processed into various specifications shape, and good conductivity, performanceStablize.
" the inevitable impurity " refers to inevitable existing during melting leadless welding alloyTrace element, such as when the melting alloy, each metallic element such as indium, tin of addition or alloy range such as sn-ag alloy excessively carry out meltingWhen two kinds of leadless welding alloys of the invention, the purity of used each metallic element is up to 99.99%, it is inevitable there may beSome non-required trace elements, these trace elements are referred in the art to inevitable impurity.
In some embodiments of the first leadless welding alloy, the mass percent of indium is preferably 70-94%, furtherPreferably 75-91% is still more preferably 85-91%；Less dosage, example can be used in terms of the usage amount of tin simultaneouslyThe usage amount of tin can such as be reduced to 15% hereinafter, such as 9-25%, 9-15%.Such as in some embodiments, the matter of indiumAmount percentage be 85-91%, tin 9-15%, the solder that this formula combination obtains, liquidus temperature reach 140 DEG C withOn, solidus temperature reaches 129 DEG C or more, Morse hardness 1-1.5, when welding mobility more preferably, high temperature after being welded on glassTolerance is enhanced, and solidus temperature and liquidus temperature are improved；And it is provided simultaneously with higher adhesion strength, with glassCaking property gets a promotion between the electrical contact surface of matrix and the connector of electronic component.
The silver of preferable amount, silver-colored dosage can be further used in the formula system of the first leadless welding alloyIn 0%-10%, preferably in 1%-4.5%, silver is combined with each other with other components with corresponding proportion, can reduce lead-free solderThe thermal expansion coefficient of alloy, while improving the combination of solder and electrical contact surface.
The copper of preferable amount, the dosage of copper can be further used in the formula system of the first leadless welding alloyIt is preferred that use the copper of preferable amount in formula system in 0.3%-2%, be combined with each other with other components with corresponding proportion,Can effectively improve solder alloy can forgeability, while improving the combination of solder and electronic component.
The iron of preferable amount, the dosage of iron can be further used in the formula system of the first leadless welding alloyIt is preferred that in 0.03%-1%, to improve the compatibility with the electrical contact surface on glass matrix, solder and electrical contact surface itBetween form adhesive interface, prevent silver-colored precipitation, further enhance weld strength；
The aluminium of preferable amount, the dosage of aluminium can be further used in the formula system of the first leadless welding alloyIt is preferred that aluminium element and other elements combine 0.03%~1%, it is possible to prevente effectively from mesophase alloy (such as Ag6Sn andAg3Sn solder becomes fragile and is hardened caused by appearance).However if the content of aluminium is too many, it will cause the appearance of solder paste,Reduce the usability of solder；
Component nickel, zinc, bismuth can be further increased in the formula system of the first leadless welding alloy, improve infiltrationProperty, liquidus curve and solidus section are narrowed, while also further reducing cost.
In some embodiments of second of leadless welding alloy, the mass percent of tin is preferably 75-85%；Exist simultaneouslyLess dosage can be used in terms of the usage amount of indium, such as the usage amount of indium can be reduced to 25% hereinafter, such as 15-25%.Such as in some embodiments, the mass percent of tin is 75-85%, indium 15-25%, this formula combination obtainsSolder, liquidus temperature reaches 175 DEG C or more, and solidus temperature reaches 135 DEG C or more, Morse hardness 1.7-2.0, weldingHigh temperature resistance after on to glass compared to the first leadless welding alloy formula further increases, solidus temperature and liquid phaseLine temperature is further enhanced；And it is provided simultaneously with higher weld strength, the electrical contact surface and electronics with glass matrixSwitching performance is better between the connector of component.
The silver of preferable amount, silver-colored dosage can be further used in the formula system of second of leadless welding alloyIn 0%-10%, preferably between 4.5%-10%, it is combined with each other with other components with corresponding proportion, Pb-free coating can be reducedExpect the thermal expansion coefficient of alloy, reduces stress and generate, while improving the combination of solder and electrical contact surface.
The copper of preferable amount, the dosage of copper can be further used in the formula system of second of leadless welding alloyPreferably 0.3%-2% is used the copper of preferable amount in formula system, is combined with each other with other components with corresponding proportion,Can effectively improve solder alloy can forgeability, while improving the combination of solder and electronic component.
The iron of preferable amount, the dosage of iron can be further used in the formula system of second of leadless welding alloyIt is preferred that in 0.5%-2%, to improve the compatibility with the electrical contact surface on glass matrix, between solder and electrical contact surfaceAdhesive interface is formed, silver-colored precipitation is prevented, further enhances weld strength；
The aluminium of preferable amount, the dosage of aluminium can be further used in the formula system of second of leadless welding alloyIt is preferred that aluminium element and other elements combine 0.5%~1.5%, it is possible to prevente effectively from mesophase alloy (such as Ag6Sn andAg3Sn solder becomes fragile and is hardened caused by appearance).However if the content of aluminium is too many, it will cause the appearance of solder paste,Reduce the usability of solder；
Component nickel, zinc, bismuth can be further increased in the formula system of second of leadless welding alloy, improve infiltrationProperty, liquidus curve and solidus section are narrowed, while also further reducing cost.
Using the leadless welding alloy of two kinds of formula systems of the invention, possess that environmental protection, ductility is good, moderate strength, welderingScoop out that power is small, can bear 120 DEG C or more of operating ambient temperature, performance can all compare favourably with there is kupper solder, be suitable for automobileThe advantages that being welded on glass.Unlike, the first leadless welding alloy formula can have about 124-142 DEG C of solidus temperatureDegree and about 135 DEG C to about 154 DEG C of liquidus temperature, Mohs' hardness reach 1-1.5；Second leadless welding alloy formula can be withLiquidus temperature with about 135-177 DEG C of solidus temperature and about 189-206 DEG C, Mohs' hardness reach 1.7-2.0.
With specific embodiment, further the present invention will be described below.
The case study on implementation of the first lead-free solder:
Embodiment 1
The component and its mass percent of the leadless welding alloy of the present embodiment are as follows:
Indium In:73.6%, surplus are tin and inevitable impurity.
The fusing point or liquidus temperature of the leadless welding alloy are 134.06 DEG C, and solidus temperature is 121.14 DEG C.
Embodiment 2
The component and its mass percent of the leadless welding alloy of the present embodiment are as follows:
Indium In:84.2%, silver-colored Ag:3.2%, copper Cu:0.5%, surplus are tin and inevitable impurity.
The fusing point or liquidus temperature of above-mentioned leadless welding alloy are 140.01 DEG C, and solidus temperature is 129.04 DEG C.
Embodiment 3
The component and its mass percent of the leadless welding alloy of the present embodiment are as follows:
Indium In:84.2%, silver-colored Ag:3.2%, copper Cu:0.5%, iron Fe:1.1%, surplus are tin and inevitably miscellaneousMatter.
The fusing point or liquidus temperature of above-mentioned leadless welding alloy are 140.01 DEG C, and solidus temperature is 129.04 DEG C.
Embodiment 4
The component and its mass percent of the leadless welding alloy of the present embodiment are as follows:
Indium In:85%, silver-colored Ag:4.5%, surplus is tin and inevitable impurity.
The fusing point or liquidus temperature of above-mentioned leadless welding alloy are 140.13 DEG C, and solidus temperature is 129.22 DEG C.
Embodiment 5
The component and its mass percent of the leadless welding alloy of the present embodiment are as follows:
Indium In:90%, silver-colored Ag:3%, surplus is tin and inevitable impurity.
The fusing point or liquidus temperature of above-mentioned leadless welding alloy are 145.26 DEG C, and solidus temperature is 133.24 DEG C.
Embodiment 6
The component and its mass percent of the leadless welding alloy of the present embodiment are as follows:
Indium In:90%, copper Cu:1%, surplus are tin and inevitable impurity.
The fusing point or liquidus temperature of above-mentioned leadless welding alloy are 144.26 DEG C, and solidus temperature is 132.14 DEG C.
Embodiment 7
The component and its mass percent of the leadless welding alloy of the present embodiment are as follows: indium In:93%, silver-colored Ag:2%, copper Cu:0.3%, iron Fe:0.1%, aluminium Al:0.5%, surplus are tin and inevitable impurity.
The fusing point or liquidus temperature of above-mentioned leadless welding alloy are 147.02 DEG C, and solidus temperature is 135.21 DEG C.
The case study on implementation of second of lead-free solder:
Embodiment 8
The component and its mass percent of the leadless welding alloy of the present embodiment are as follows:
Tin Sn:73%, silver-colored Ag:5%, copper Cu:0.5%, iron Fe:0.3%, aluminium Al:0.2%, surplus is indium and can not keep awayThe impurity exempted from.
The fusing point or liquidus temperature of the leadless welding alloy are 188.3 DEG C, and solidus temperature is 134.62 DEG C.
Embodiment 9
The component and its mass percent of the leadless welding alloy of the present embodiment are as follows:
Tin Sn:73.6%, silver-colored Ag:6%, surplus is indium and inevitable impurity.
The fusing point or liquidus temperature of the leadless welding alloy are 189.2 DEG C, and solidus temperature is 135.22 DEG C.
Embodiment 10
The component and its mass percent of the leadless welding alloy of the present embodiment are as follows:
Tin Sn:78%, surplus are indium and inevitable impurity.
The fusing point or liquidus temperature of the leadless welding alloy are 193.82 DEG C, and solidus temperature is 142.06 DEG C.
Embodiment 11
The component and its mass percent of the leadless welding alloy of the present embodiment are as follows:
Tin Sn:80%, silver-colored Ag:5%, copper Cu:1.3%, aluminium Al:0.3%, surplus is indium and inevitable impurity.
The fusing point or liquidus temperature of the leadless welding alloy are 196.82 DEG C, and solidus temperature is 148.66 DEG C.
Embodiment 12
The component and its mass percent of the leadless welding alloy of the present embodiment are as follows:
Tin Sn:80%, silver-colored Ag:5%, copper Cu:1.2%, surplus are indium and inevitable impurity.
The fusing point or liquidus temperature of the leadless welding alloy are 196.42 DEG C, and solidus temperature is 147.38 DEG C.
Embodiment 13
The component and its mass percent of the leadless welding alloy of the present embodiment are as follows:
Tin Sn:83.2%, silver-colored Ag:6.2%, copper Cu:0.5%, nickel: 0.5%, surplus be indium and inevitably it is miscellaneousMatter.
The fusing point or liquidus temperature of above-mentioned leadless welding alloy are 200.28 DEG C, and solidus temperature is 160.74 DEG C.
Embodiment 14
The component and its mass percent of the leadless welding alloy of the present embodiment are as follows:
Tin Sn:83%, silver-colored Ag:5%, surplus is indium and inevitable impurity.
The fusing point or liquidus temperature of above-mentioned leadless welding alloy are 199.65 DEG C, and solidus temperature is 160.34 DEG C.
Embodiment 15
The component and its mass percent of the leadless welding alloy of the present embodiment are as follows:
Tin Sn:85%, silver-colored Ag:5%, copper Cu:0.3%, nickel: 0.5%, zinc Zn:0.5%, surplus are indium and can not keep awayThe impurity exempted from.
The fusing point or liquidus temperature of above-mentioned leadless welding alloy are 203.55 DEG C, and solidus temperature is 171.94 DEG C.
Embodiment 16
The component and its mass percent of the leadless welding alloy of the present embodiment are as follows:
Tin Sn:85%, silver-colored Ag:5%, copper Cu:0.5%, surplus are indium and inevitable impurity.
The fusing point or liquidus temperature of above-mentioned leadless welding alloy are 202.42 DEG C, and solidus temperature is 170.22 DEG C.
Embodiment 17
The component and its mass percent of the leadless welding alloy of the present embodiment are as follows:
Tin Sn:90%, copper Cu:1%, surplus are indium and inevitable impurity.
The fusing point or liquidus temperature of above-mentioned leadless welding alloy are 208.55 DEG C, and solidus temperature is 188.94 DEG C.
Embodiment 18
The component and its mass percent of the leadless welding alloy of the present embodiment are as follows:
Tin Sn:95%, surplus are indium and inevitable impurity.
The fusing point or liquidus temperature of above-mentioned leadless welding alloy are 214.08 DEG C, and solidus temperature is 209.04 DEG C.
The electrical contact being welded to the connector of electronic component using the leadless welding alloy of above-described embodiment on glassSurface.In use, making its fusing using heating devices heat leadless welding alloy, the leadless welding alloy of fusing is placed in electricityBetween electrical contact surface on the connector and glass matrix of sub- component, weld the electrical contact surface of electronic component and glassIt connects in succession, leadless welding alloy forms the Pb-free coating bed of material.Specifically, glass can be vehicle glass, such as windshield etc..OneIn kind specific embodiment, forming glass assembly by the welding process may refer to Fig. 1-2.Fig. 1 be used it is of the inventionA kind of planar structure schematic diagram of glass assembly of leadless welding alloy, Fig. 2 are Section A-A schematic diagram in Fig. 1.
By taking such as Fig. 1 as an example, glass assembly 90 is described by further examples.The glass assembly 90 is specially a kind of glass of automobileGlass component, the windscreen assembly for example, installed on compartment.In this specific embodiment, which has heating functionCan, certainly in practical applications, it is also possible to the glass assembly with other function.The glass matrix 900 of the glass assembly 90It is equipped with heating work region 980, specially the heating work region 980 of argentiferous heater strip 930.It is set in heating work regionThere is argentiferous heater strip 930, these argentiferous heater strips 930 are specifically located on the surface of glass matrix 900, and number can be according to realityBorder needs and increases and decreases, for example, 13.
On the surface of glass matrix 900 be equipped with electrical contact surface 920, the both ends of every argentiferous heater strip 930 respectively withElectrical contact surface 920 is electrically connected, and is welded with electronic component 800 on each electrical contact surface 920.Specifically, electronics is firstDevice 800 is equipped with connector 850, such as can be the electrical connections such as antenna terminal, heater strip tongue piece, braid over braid, electronicsComponent 800 is weldingly fixed on electrical contact surface 920 especially by connector 850, is powered by power supply line 840.Connector850 are welded on the electrical contact surface of glass matrix by leadless welding alloy, form Pb-free coating after leadless welding alloy weldingThe bed of material 700.Using the leadless welding alloy of above embodiments of the present invention, in the welding process, solder fluidity and wetability are equalVery well, welding stress is small；In the welding process, glass matrix is non-breakable, and in the glass assembly subsequent heat course of workIn or in exceedingly odious hot environment (such as 120 DEG C), leadless welding alloy is also not easy to melt.The glass assembly canIt is good by property, ageing-resistant related request can be met.
Below to utilization embodiment 4, embodiment 5, the glass group of the leadless welding alloy preparation of embodiment 9 and embodiment 12Part carries out the endurance test that following mainly U.S.'s vehicle factor requires:
1, room temperature is tested: sample is placed in baking oven (no power) according to entrucking angle, hangs the load of 0.45kg, ifIt sets 23 DEG C to test 500 hours, restores to check appearance, energization performance, the positive pull test of shearing force to room temperature after the completion, it is desirable that >=100N。
2, hot test: being placed in baking oven (no power) according to entrucking angle for sample, hang the load of 0.45kg, ifIt sets 105 DEG C to test 500 hours, restores to check appearance, energization performance, the positive pull test of shearing force to room temperature after the completion, after testPulling tension requirements >=100N.
3, low-temperature test: being placed in baking oven (no power) according to entrucking angle for sample, hang the load of 0.45kg, ifIt sets -40 DEG C to test 500 hours, restores to check appearance, energization performance, the positive pull test of shearing force to room temperature after the completion, it is desirable that >=100N。
4, high humidity test: sample is placed in enviromental cycle case (no power) according to entrucking angle, hangs 0.45kg'sLoad is arranged 50 DEG C of 90%RH and tests 336 hours, restores to check appearance, energization performance, the positive pulling force of shearing force to room temperature after the completionTest, it is desirable that >=100N.
5, high/low temperature cyclic test: sample is placed in enviromental cycle case (no power) according to entrucking angle, -40In DEG C -90 DEG C of temperature (20 DEG C/0 minute → -40 DEG C/60 minutes → -40 DEG C/150 minutes → 20 DEG C/210 minutes → 90 DEG C/300 minutes → 90 DEG C/410 minutes → 20 DEG C/480 minutes) hanging 0.45kg load, be arranged environment above cyclic test 30Circulation is restored to check appearance, energization performance, the positive pull test of shearing force to room temperature after the completion, it is desirable that >=100N.
6, low temperature energizing test: sample is placed in enviromental cycle case according to entrucking angle, and -40 DEG C of tests are arranged and are powered- 40 DEG C are replied afterwards within 10 minutes (14V), recycled 1000 times, restore checking appearance, energization performance, shearing force just to room temperature after the completionPull test, it is desirable that >=100N.
Below to utilization embodiment 4, embodiment 5, the glass group of the leadless welding alloy preparation of embodiment 9 and embodiment 12Part carries out the endurance test that following mainly European vehicle factor requires:
1, temperature cycling test: sample is placed in temperature environment case according to entrucking angle, at -40 DEG C -105 DEG C (20DEG C/0 minute → -40 DEG C/60 minutes → -40 DEG C/150 minutes → 20 DEG C/210 minutes → 105 DEG C/300 minutes → 105 DEG C/420Minute → 20 DEG C/480 minutes) temperature in, environment above cyclic test 60 circulations are set, it is whole logical in the last one circulationElectric (14+/- 0.2V) restores to check the positive pulling force >=50N of shearing force to room temperature after the completion.
2, high temperature energizing test: sample being placed in temperature environment case according to entrucking angle, hangs the load of 6N, setting105 DEG C are tested 96 hours, and whole process is powered (14+/- 0.2V), restore to check the positive pulling force >=50N of shearing force to room temperature after the completion.
3, high temperature shelf test: being placed in temperature environment case (no power) for sample, is arranged 120 DEG C and stores 24 hours,Restore to check the positive pulling force >=50N of shearing force to room temperature after the completion.
4, high temperature energization endurance test: sample is placed in temperature environment case according to entrucking angle, whole process energization (14+/- 0.2V), it is arranged 105 DEG C and tests 500 hours, restores to check the positive pulling force >=50N of shearing force to room temperature after the completion.
5, thermal shock test: being placed in enviromental cycle case (no power) for sample, 105 DEG C of tests 1 hour is arranged, thenSample is completely submerged in cold water (about 23 DEG C or lower).After each cycle, sample is dried with hair dryer.Respectively 5After secondary circulation and after 10 circulations, restore to check the positive pulling force >=50N of shearing force to room temperature.
6, high humidity test: sample is placed in enviromental cycle case according to entrucking angle, is arranged 80 DEG C of constant temperature, and humidity >96%RH, after 10 hours on-tests, be powered 15 minutes (14+/- 0.2V), is powered 15 minutes within every 24 hours, until full 500 is smallWhen, restore to check the positive pulling force >=50N of shearing force to room temperature after the completion.
7, room temperature resistance to cleaning test: simulation windshield cleaning fluid by 69.5% water, 20% ethyl alcohol, 10% isopropanol,0.09%, which receives alkyl sulfate, 0.05% ethylene glycol, mixes, and sample is immersed in the simulation cleaning solution, cleaning solution temperatureIt is taken out after 23 DEG C, 24 hours, checks the positive pulling force >=50N of shearing force.
8, salt spray test: test specimen is exposed in salt fog 96 hours in chamber, and concentration of saline fog is set as 5%, pHValue is 6.5 to 7.2.Salt fog temperature is set as 35 ± 2 DEG C, and air pressure is taken out after being 16 to 18psi, 96 hours and checks shearing forcePositive pulling force >=50N.
Leadless welding alloy of the invention is not limited in the welded connecting used in glass matrix and electronic component, may be used alsoTo be used in other be similar between two kinds of materials that coefficient of expansion difference is big between glass matrix and electronic component connectorWelded connecting.
Using embodiment 4, embodiment 5, the figure that the leadless welding alloy of embodiment 9 and embodiment 12 is prepared as solderGlass assembly shown in 1, carries out test item required by vehicle factor, and pulling capacity and shearing force after detection test all meet wholeDepot's requirement of experiment, and the problems such as not will lead to cracking glasses.The experimental result of remaining embodiment through detecting, testing result withEmbodiment 4, embodiment 5, embodiment 9 is similar with 12 result of embodiment, does not do and repeats one by one.
Example above primarily illustrates leadless welding alloy of the invention and its preparation method and application, using the Pb-free coatingExpect the glass assembly of alloy.Although only some of embodiments of the present invention are described, the common skill in this fieldArt personnel are it is to be appreciated that the present invention can implemented without departing from its spirit in range in many other form.Therefore, institute's exhibitionThe example shown is considered as illustrative and not restrictive with embodiment, is not departing from as defined in appended claimsIn the case where spirit and scope of the present invention, the present invention may cover various modification and replacement.