CN101823188B - High-temperature amorphous solder for soldering Si3N4 ceramics - Google Patents
High-temperature amorphous solder for soldering Si3N4 ceramics Download PDFInfo
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- CN101823188B CN101823188B CN2010101674959A CN201010167495A CN101823188B CN 101823188 B CN101823188 B CN 101823188B CN 2010101674959 A CN2010101674959 A CN 2010101674959A CN 201010167495 A CN201010167495 A CN 201010167495A CN 101823188 B CN101823188 B CN 101823188B
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Abstract
The invention discloses high-temperature amorphous solder for soldering Si3N4 ceramics, belonging to the technical field of soldering materials. The high-temperature amorphous solder of the invention for soldering the Si3N4 ceramics comprises the following components by weight percent: 35.0% to 45.0% of Ti, 20% to 30% of Zr, 0.1% to 0.3% of B and Cu in balancing amount, wherein the melting temperature of the solder ranges from 1,100K to 1,200K, and the soldering temperature thereof is 1,223K to 1,373K. The Si3N4 ceramics is prepared by vacuum-soldering the Ti-Zr-Cu-B high-temperature active amorphous solder on the basis of the rapid solidification technology, and the maximal room-temperature strength of the Si3N4 ceramics reaches 245MPa; and the high-temperature performance thereof is much higher than that of the Ag-Cu-Ti solder and Ti-Zr-Ni-Cu solder, particularly, the high-temperature bending strength of the ceramic connector is 165.5MPa at the testing temperature of 673K.
Description
Technical field:
The invention belongs to technical field of soldering materials.Relate to a kind of soldering Si
3N
4The high-temperature amorphous solder of pottery more particularly, relates to a kind of Ti-Zr-Cu-B high temperature active amorphous brazing filler metal.
Background technology:
Si
3N
4Pottery is a kind of up-and-coming engineering structure ceramic material, and its main application fields is hot machine, wear parts and heat exchanger etc., is the important materials of making the new ceramics engine.Research and development to it has caused showing great attention to of people.Because the part that poor processability, ductility and impact toughness are low, heat-resistant impact ability is low and manufacturing dimension is big and complex-shaped of pottery is shortcoming such as difficulty comparatively, need form that composite construction is used with metal material usually or realize the manufacturing of complex parts through being connected between the pottery.Therefore, realize between the pottery or pottery is important prerequisite and the assurance that high performance structure ceramic is able to wide range of industrial applications with reliable connection between the metal.
Over nearly 20 years, people have carried out research extensively and profoundly to multiple method of attachment, and diffusion connects and active soldering is two kinds of comparatively successful methods of attachment.The active soldering technology is simple with its technology, bonding strength is high, as a result wide adaptability, good seal performance, the relative cost of good reproducibility, joint dimension and shape low, be fit to series of advantages such as industrial-scale production and become the one preferred technique that metal/ceramic connects.
The research and development of active solder are important contents of the ceramic soldering of development.The active element of empirical tests mainly contains elements such as Ti, Zr, Hf, Nb, V, Ta, Al, B, Si, and wherein secondly Ti the most effectively is Zr and Hf.The disadvantage of active soldering is that high-temperature behavior is poor, and this mainly is to be determined by active solder., Al basic isoreactivity solder basic like Ag base, Sn is because the restriction of solder fusing point, and the serviceability temperature of its joint generally is lower than 573K; This obvious and Si
3N
4The excellent high performance of pottery is incompatible.Though and the high-temperature behavior that Cu is basic, the basic solder of Ni can improve solder owing to need to add a large amount of active element Tis in the solder, increases solder embrittlement, room temperature strength reduces, and more crucial is, and the sheet that can't laminate is used, big limitations its practical application.Therefore, adopting the amorphous technology of preparing to develop practical high temperature active solder paper tinsel has and important theory and using value for pottery/pottery, ceramic/metal soldering field.The high-temperature amorphous solder of report mainly is a Ti-Zr-Ni-Cu system both at home and abroad at present, but alloying element Ti and Ni very easily form the Ni-Ti frangible compounds, reduces the activity of active element Ti in the solder, increases the fragility of solder and joint.
Summary of the invention:
Technical problem: the objective of the invention is in order to solve present soldering Si
3N
4Problems such as the Ag-Cu-Ti solder high-temperature behavior difference of pottery and Ti-Zr-Ni-Cu brazing filler metal fragility are big, the activity of Ti is low provide a kind of soldering Si
3N
4The high-temperature amorphous solder of pottery.The present invention adopts the Ti-Zr-Cu-B amorphous brazing filler metal of flash set technology preparation to connect Si
3N
4Pottery through adjustment solder composition and soldering processes, increases substantially Si
3N
4The room temperature of ceramic joint and high temperature bend strength.
Technical scheme: to achieve these goals, soldering Si of the present invention
3N
4The high-temperature amorphous solder of pottery, it is characterized in that: the component of this solder and content (by mass percentage) are: Ti:35.0～45.0%; Zr:20～30%; B:0.1～0.3%; All the other are Cu, and total amount is 100%.
The Cu of the above is the electrolysis copper billet, and its purity is more than 99.9%;
The Ti of the above is a titanium sponge, and its purity is more than 99.9%;
The Zr of the above is a sponge zirconium, and its purity is 99.99%;
The B of the above is the technical grade Cu-B alloy, and wherein the mass fraction of B is 13.45%.
Soldering Si of the present invention
3N
4The high-temperature amorphous solder of pottery is by following step and prepared.
(1) with electrolysis copper billet (Cu), titanium sponge (Ti) is after sponge zirconium (Zr) and Cu-B alloy raw material are pulverized respectively, according to above-mentioned prescription weighing raw materials;
(2) will place WK type high vacuum Ar atmosphere protection non-consumable arc furnace by the batching of above-mentioned prescription, electric arc furnaces has 5 copper crucibles, puts a pure Ti sample in one of them crucible, and all the other four crucibles can be put four kinds of batchings with prescription or different formulations simultaneously;
(3) before the melting, be evacuated to 10 earlier in the stove
-2Pa after applying argon gas prepurging 3-4 time, is evacuated to 10
-2Pa, applying argon gas is to-0.06MPa once more;
(4) before the formal melting, pure Ti sample of melt back is with residual oxygen in the further removal atmosphere;
(5) during the melting sample, even in order to make cast alloy, melt back 3-4 time under function composite by electromagnetic stirring of the sample in the water jacketed copper crucible, and use the stirring rod sample that overturns;
(6) behind the electric arc melting, sample is carried out weighing, the weightlessness of finding sample can think that alloy actual constituent and nominal composition basically identical, the sample after the melting promptly are the foundry alloys of preparation amorphous brazing filler metal in 0.1%;
(7) with after the foundry alloy pulverizing, the single roller of the HVDS-II high vacuum of packing into gets rid of in the quartz glass tube of band machine.The quartz ampoule nozzle is rectangle, and its length is a=6-8mm; Width b=0.5-1mm;
(8) quartz glass tube is installed in the induction heating circle that gets rid of the band machine, and its nozzle to copper roller surface spacing is adjusted to b
n=0.8-1.5mm is dull and stereotyped stream with the liquid that guarantees to be injected on the copper roller, and forms condition of steady flow;
(9) close fire door, adopt mechanical pump to be evacuated to 6.5 * 10
-1Pa, molecular pump pumping high vacuum to 7.5 * 10
-4Pa, cavity is full of high-purity Ar gas to 100-200mbar then;
(10) open high frequency electric source, to fully even fusion, it melts and sprays temperature T=1273-1573K with the foundry alloy high-frequency induction heating in the quartz glass tube, insulation superheated melt 0.5～1 minute;
(11) open motor, make copper roller rotating speed u
s=32-40m/s (the copper roller diameter is 230mm, and copper roller width is 40mm);
(12) the Ar atmospheric pressure is transferred to p=48kPa, with the cooling copper roller surface of the superheated melt continuous injection in the quartz glass tube to rotation at a high speed, liquid metal forms the paper tinsel band shape owing to receive chilling, thereby obtains amorphous brazing filler metal of the present invention with the high pressure argon gas.
Beneficial effect: adopting the chilling solder paper tinsel tape thickness of above-mentioned prepared is 0.040 ± 0.002mm, and any surface finish, and both sides are smooth, have good plasticity and toughness.
The fusion temperature scope of this solder is 1100～1200K, and brazing temperature is 1223～1373K, and temperature retention time is 10～60min.Before the soldering, amorphous paper tinsel band solder is with 800
#Abrasive paper for metallograph polishes, with solder and Si
3N
4Pottery carries out ultrasonic waves for cleaning 5～10min respectively in acetone soln, taking-up dries up, and presses Si
3N
4/ solder/Si
3N
4Assembled in sequence in brazing jig, put into vacuum drying oven and carry out soldering.Connection procedure vacuum is not less than 9.5 * 10
-3Pa, heating rate are 10 ℃/min, accomplish the connection back and reduce to 600 ℃ with the cooling velocity of 8 ℃/min, cool to room temperature at last with the furnace.Adopt this amorphous brazing filler metal vacuum brazing Si
3N
4Pottery, its room temperature strength is up to 245MPa; High-temperature behavior is much higher than Ag-Cu-Ti solder and Ti-Zr-Ni-Cu brazing filler metal.When probe temperature was 673K, the joint high temperature bend strength was 165.5MPa.
The advantage that the present invention has:
(1) the amorphous high temperature active solder paper tinsel that adopts flash set technology to obtain is compared with the solder of conventional melting technique preparation; Following characteristics are arranged: a) easy to use; The composition adjustable is strong: the solder that is used for the ceramic high temperature soldering of developmental research at present, how constitute by nonmetalloids such as animal migration element such as active element Ti and Ni, Fe, Cr, Cu, Al and Si, B, P, and this type alloy is all very crisp; Be difficult to the shape that laminates; Often process sheet or directly adopt laminated, use very inconvenience with line cutting etc., and also difficulty very of adjustment solder composition.And armorphous paper tinsel shape material only needs to prepare by design mix foundry alloy remelting on the amorphous state device for making of component ratio, and directly spray forms, and the solder paper tinsel of processing has pliability preferably; B) wetability is good: because amorphous structure is unsettled, near fusing the time, the tendency of separating out crystal is arranged, so can emit a large amount of heat melting moment.Under the influence of this exothermic reaction, the atom in the solder moves aggravation, thereby has improved the wettability of solder; C) heat resisting temperature of joint does not reduce after the soldering: because amorphous foil is in case fusing will generate common alloy crystalline texture during condensation, therefore again. and the brazing filler metal layer can not melt as armorphous paper tinsel at a lower temperature.Therefore the amorphous brazing filler metal paper tinsel is for Si
3N
4The high temperature brazing of pottery has great importance; D) improve the soldered fitting performance: the amorphous filler metal chemical composition is even, and impurity content is few, has not both had crystal grain, does not have eutectic phase again and separates out, and fusing is even, and the diffusivity of alloying element is strong, forms uniform brazed seam easily.In addition, amorphous filler metal can make the brazing filler metal gap further reduce, and the fusion temperature scope is extremely narrow, and fusing time is short, thereby has good moment flowability, can give full play to the capillary adsorption function, thereby can obtain the fine and close high-strength joint of brazing filler metal layer.
(2) active element Ti is Si
3N
4The pottery soldering is necessary, and alloy element Zr is as its active Ti that is not so good as of active element, but adding Zr can improve the amorphous formation ability of alloy greatly.Improve solder flowability and plasticity through adding alloying element cu, compare, owing to there is not alloying element Ni with the Ti-Zr-Ni-Cu brazing filler metal; Avoided the formation of Ni-Ti frangible compounds; Improved the activity of alloying element Ti, under identical active element Ti content, the Ti-Zr-Cu solder is at Si
3N
4Wetability on the pottery and room temperature strength of joint are better than the Ti-Zr-Ni-Cu solder.
(3) the micro-B that adds in the solder can further improve the wetability and the high-temperature behavior of solder.
The specific embodiment:
Embodiment 1:
Component formula: the component of solder and content are by mass percentage: Ti is: 40.0%; Zr is: 25%; B is: 0.2%; All the other are Cu.
The preparation method:
(1) with electrolysis copper billet (Cu), after titanium sponge (Ti), raw material such as sponge zirconium (Zr) and Cu-B alloy are pulverized, on electronic balance according to above-mentioned prescription weighing raw materials;
(2) will place WK type high vacuum Ar atmosphere protection non-consumable arc furnace by the batching of above-mentioned prescription, electric arc furnaces has 5 copper crucibles, puts a pure Ti sample in one of them crucible, and all the other four crucibles can be put four kinds of batchings with prescription or different formulations simultaneously;
(3) before the melting, be evacuated to 10 earlier in the stove
-2Pa after applying argon gas prepurging 3-4 time, is evacuated to 10
-2Pa, applying argon gas is to-0.06MPa once more;
(4) before the formal melting, pure Ti sample of melt back is with residual oxygen in the further removal atmosphere;
(5) during the melting sample, even in order to make cast alloy, melt back 3-4 time under function composite by electromagnetic stirring of the sample in the water jacketed copper crucible, and use the stirring rod sample that overturns;
(6) behind the electric arc melting, sample is carried out weighing, the weightlessness of finding sample can think that alloy actual constituent and nominal composition basically identical, the sample after the melting promptly are the foundry alloys of preparation amorphous brazing filler metal in 0.1%;
(7) with after the foundry alloy pulverizing, the single roller of the HVDS-II high vacuum of packing into gets rid of in the quartz glass tube of band machine.The quartz ampoule nozzle is rectangle, and its length is a=6-8mm; Width b=0.5-1mm;
(8) quartz glass tube is installed in the induction heating circle that gets rid of the band machine, and its nozzle to copper roller surface spacing is adjusted to b
n=0.8-1.5mm is dull and stereotyped stream with the liquid that guarantees to be injected on the copper roller, and forms condition of steady flow;
(9) close fire door, adopt mechanical pump to be evacuated to 6.5 * 10
-1Pa, molecular pump pumping high vacuum to 7.5 * 10
-4Pa, cavity is full of high-purity Ar gas to 100-200mbar then;
(10) open high frequency electric source, to fully even fusion, it melts and sprays temperature T=1273-1573K with the foundry alloy high-frequency induction heating in the quartz glass tube, insulation superheated melt 0.5～1 minute;
(11) open motor, make copper roller rotating speed u
s=32-40m/s (the copper roller diameter is 230mm, and copper roller width is 40mm);
(12) the Ar atmospheric pressure is transferred to p=48kPa, with the cooling copper roller surface of the superheated melt continuous injection in the quartz glass tube to rotation at a high speed, liquid metal forms the paper tinsel band shape owing to receive chilling, thereby obtains amorphous brazing filler metal of the present invention with the high pressure argon gas.
The fusion temperature scope of this solder is 1125～1188K, adopts this amorphous brazing filler metal vacuum brazing Si
3N
4Ceramic joint room temperature bending strength is 245MPa; High temperature bend strength is: 145MPa (673K).
Embodiment 2:
Component formula: the component of solder and content are by mass percentage: Ti is: 35.0%; Zr is: 30%; B is: 0.3%; All the other are Cu.
Preparation method: identical with embodiment 1 preparation method.
The fusion temperature scope of this solder is 1102～1130K, adopts this amorphous brazing filler metal vacuum brazing Si
3N
4Ceramic joint room temperature bending strength is 184MPa; High temperature bend strength is: 123MPa (673K).
Embodiment 3:
Component formula: the component of solder and content are by mass percentage: Ti is: 45.0%; Zr is: 20%; B is: 0.1%; All the other are Cu.
Preparation method: identical with embodiment 1 preparation method.
The fusion temperature scope of this solder is 1109～1139K, adopts this amorphous brazing filler metal vacuum brazing Si
3N
4Ceramic joint room temperature bending strength is 201MPa; High temperature bend strength is: 136MPa (673K).
Claims (5)
1. soldering Si
3N
4The high-temperature amorphous solder of pottery, it is characterized in that: the component of this solder and mass percentage content are: Ti:35.0～45.0%; Zr:20～30%; B:0.1～0.3%; All the other are Cu, and total amount is 100%.
2. soldering Si as claimed in claim 1
3N
4The high-temperature amorphous solder of pottery, it is characterized in that: described Cu is a cathode copper, and its purity is more than 99.9%.
3. soldering Si as claimed in claim 1
3N
4The high-temperature amorphous solder of pottery, it is characterized in that: described Ti is a titanium sponge, and its purity is more than 99.9%.
4. soldering Si as claimed in claim 1
3N
4The high-temperature amorphous solder of pottery, it is characterized in that: described Zr is a sponge zirconium, its purity is 99.99%.
5. soldering Si as claimed in claim 1
3N
4The high-temperature amorphous solder of pottery, it is characterized in that: described B is the Cu-B alloy of technical grade, wherein the mass fraction of B is 13.45%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101674959A CN101823188B (en) | 2010-05-10 | 2010-05-10 | High-temperature amorphous solder for soldering Si3N4 ceramics |
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| CN2010101674959A CN101823188B (en) | 2010-05-10 | 2010-05-10 | High-temperature amorphous solder for soldering Si3N4 ceramics |
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| CN101823188A CN101823188A (en) | 2010-09-08 |
| CN101823188B true CN101823188B (en) | 2012-05-23 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102390132A (en) * | 2011-07-11 | 2012-03-28 | 江苏科技大学 | Composite middle layer component connecting Si3N4 ceramic samples and connecting method thereof |
| CN102351412B (en) * | 2011-07-11 | 2013-11-06 | 江苏科技大学 | Interlayer assembly for connecting Si3N4 ceramics and method |
| CN102615442A (en) * | 2012-04-20 | 2012-08-01 | 江苏科技大学 | Semi brazing and semi diffusion welding connecting method |
| CN102689108A (en) * | 2012-06-20 | 2012-09-26 | 哈尔滨工业大学 | Composite brazing material for connecting Si3N4 ceramic and 42CrMo steel and brazing method by using same |
| CN103173654A (en) * | 2013-04-01 | 2013-06-26 | 中南大学 | Alloy for braze welding of high-intensity graphite and titanium alloy and preparation method thereof |
| CN103752973B (en) * | 2014-02-14 | 2015-11-04 | 常州工学院 | A kind of connection Si 3n 4the mid-tier component of pottery and method |
| CN104858561B (en) * | 2015-03-20 | 2017-03-08 | 江苏科技大学 | Zirconium-based high-temperature alloy solder and preparation method thereof |
| CN105081606A (en) * | 2015-09-09 | 2015-11-25 | 钢铁研究总院 | Strap-shaped brazing filler for rare earth cobalt-based permanent magnet and preparing method of strap-shaped brazing filler |
| CN105057919B (en) * | 2015-09-16 | 2017-04-05 | 江苏科技大学 | For Si3N4The material and preparation method of ceramic surface metallization and soldering processes |
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|---|---|---|---|---|
| CN101157567A (en) * | 2007-09-11 | 2008-04-09 | 江苏科技大学 | Boron-containing titanium-based amorphous solder for braze welding Si3N4 ceramic and preparation method thereof |
| CN101172880A (en) * | 2007-09-21 | 2008-05-07 | 江苏科技大学 | Titanium group high temperature amorphous solder of hard solder Si*N* ceramic and method for producing the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63169348A (en) * | 1986-12-29 | 1988-07-13 | Teikoku Piston Ring Co Ltd | Amorphous alloy foil for jointing ceramics |
| EP0350735A1 (en) * | 1988-07-11 | 1990-01-17 | Lonza Ag | Cu-Zr brazing foil |
| JPH07187840A (en) * | 1993-12-27 | 1995-07-25 | Toho Titanium Co Ltd | Cement for titanium substrate and ceramics and joining method |
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2010
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157567A (en) * | 2007-09-11 | 2008-04-09 | 江苏科技大学 | Boron-containing titanium-based amorphous solder for braze welding Si3N4 ceramic and preparation method thereof |
| CN101172880A (en) * | 2007-09-21 | 2008-05-07 | 江苏科技大学 | Titanium group high temperature amorphous solder of hard solder Si*N* ceramic and method for producing the same |
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