CN102189354A - Adhesive special for melting and glue welding of magnesium-aluminum dissimilar metals and preparation method thereof - Google Patents
Adhesive special for melting and glue welding of magnesium-aluminum dissimilar metals and preparation method thereof Download PDFInfo
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- CN102189354A CN102189354A CN2011101016925A CN201110101692A CN102189354A CN 102189354 A CN102189354 A CN 102189354A CN 2011101016925 A CN2011101016925 A CN 2011101016925A CN 201110101692 A CN201110101692 A CN 201110101692A CN 102189354 A CN102189354 A CN 102189354A
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Abstract
The invention relates to an adhesive special for the melting and glue welding of magnesium-aluminum dissimilar metals and a preparation method thereof. The adhesive is added with a large quantity of metal powder and other solid particles, so that the content of organic matters and oxygen in the adhesive can be obviously reduced, gas generated by decomposition in the welding process can be correspondingly reduced, and the trend of generating a gas hole in a welding joint can be obviously reduced. By optimizing the components of the conventional adhesive, the adhesive can eliminate the adverse effect of a magnesium-aluminum intermetallic compound on the joint in the melting and glue welding process of the magnesium-aluminum dissimilar metals, and improves the whole performance of a melting and glue welding test piece; and tests prove that the performance of the melting and glue welding test piece obtained by connecting the magnesium-aluminum dissimilar metals through the special adhesive is 20 to 30 percent higher than that of a test piece obtained by using the general adhesive under the same structure condition.
Description
Technical field
The present invention relates to field of material engineering technology, relate to the connection material that uses in the welding method of dissimilar metal, specially refer to the special-purpose adhesive that in fusing glue weldering process, uses of a kind of magnesium alloy and aluminium alloy.
Background technology
Magnesium alloy and aluminium alloy are the most widely used two kinds of alloy in lightweight in industrial production at present.Along with automobile lightweight technology rapid development magnesium alloy and aluminium alloy must be more widely used in auto industry manufacturing field.The good connection that realizes magnalium special metal then will better promote the application of these two kinds of metals, and then effectively realize the automobile lightweight, promote the realization of target for energy-saving and emission-reduction.
The method of attachment of magnalium special metal at present mainly contains methods such as Diffusion Welding, friction stir welding, laser weld.Because forming the magnalium intermetallic compound that enbrittles in welding process has influenced the performance of welding point and then the connection between the magnalium special metal is well solved as yet.Both at home and abroad in the report document, adopt Diffusion Welding magnalium xenogenesis jointing performance can reach 80Mpa (Scripta Materialia, 2008,58:283-286), adopt independent laser weld joint shear strength can reach 48Mpa (Science andTechnology of Advanced Materials, 2005,6:199-204), adopt friction stir welding to carry out magnalium special metal connection banjo fixing butt jointing performance and be 132MPa (Materials Letters to the maximum, 2008,62:3827-3829), magnalium xenogenesis lap joint (40mm is long) maximum tension shear-type load is 3.64KN (ScriptaMaterialia, 2008,58:433-436); Above-mentioned research contents shows above-mentioned method of attachment, still can not satisfy the practical engineering application demand of magnalium dissimilar materials.
Fusing glue welding technology is a kind of novel interconnection technique that high energy beam welding and splicing are compounded to form mutually, and wherein the high energy beam welding heat source mainly refers to laser, electron beam and beam-plasma.In this technology, can effectively improve the performance of whole jointing by the mutual organic effect of high energy beam welding and splicing.Adopt fusing glue welding technology successfully to realize the magnalium special metal connection at present, under the condition that obtains the good welds joint, the adding of adhesive can effectively improve switching performance (Scripta Materialia, 2007,56 (4): 473-476) of magnalium special metal joint.But at present in fusing glue weldering process, because the adhesive that uses all is commercial construction adhesive commonly used in the splicing process, the gas that adhesive decomposes can not suppress the formation of magnalium intermetallic compound fully, therefore cause still having the existence of compound between magnalium special metal in welding point inside, and then can produce harmful effect to the performance of welding point, often cause weld defects such as occurring pore, crackle in the welding process, make the reliability of property of welded joint and durability be subjected to obvious influence.Therefore need be at the special-purpose sqtructural adhesive of fusing glue welding technology exploitation.
Summary of the invention
In view of existing in prior technology the problems referred to above, the present invention is intended to propose a kind of magnalium special metal fusing and glueds joint the special-purpose adhesive that uses in the welding technology, optimization by traditional adhesive component, can eliminate the harmful effect that the butt joint of magnalium intermetallic compound brings, and the pore that produces in the reduction welding process, be mingled with, weld defect such as crackle, thereby improve the overall performance of fusing glue weldering test specimen, reach the durability of optimization magnalium dissimilar metal jointing and the purpose of reliability.
Adopt this kind special-purpose adhesive, under the same structure condition, use this special-purpose adhesive to carry out magnalium special metal and connect the fusing glue weldering test specimen performance obtain and use the test specimen performance of all-purpose gum stick can improve 20～30%.
Technical solution of the present invention is achieved in that
A kind of magnalium special metal fusing glue weldering special-purpose adhesive, according to the composition and the configuration of quality proportioning of following table:
| Composition | The quality component |
| Bisphenol A type epoxy resin | 100～120 |
| Polysulfone resin (toughness reinforcing) | 50～60 |
| Dicyandiamide (curing agent of hiding) | 11～15 |
| Dimethylformamide (solvent) | 25 |
| Toluene (solvent) | 120～130 |
| Gas-phase silica (thixotropic agent) | 10～15 |
| Reduced iron powder | 100-120 |
| Reduction zinc powder | 20～30 |
| |
5～10 |
| Aluminium oxide | 20～30 |
| |
10 |
Each component role in adhesive specifically is described below:
Bisphenol A type epoxy resin: epoxide number is 0.48-0.52, as the main component of adhesive, plays the effect that connects magnesium alloy and aluminium alloy, requires its purity more than 99%, and granularity is more than 300 orders.
Polysulfone resin: have another name called bisphenol a polysulfone,, have good toughness reinforcing performance, can improve the toughness and the peeling resistance of adhesive as flexibilizer.
Dicyandiamide:, when being heated to uniform temperature, promote epoxy resin cure as the curing agent of hiding.
Dimethylformamide:, require its water content below 1% as organic solvent.
Toluene:, require its water content below 1% as organic solvent.
Gas-phase silica: be commonly called as aerosil,, require its purity more than 99% in order to improve the viscosity and the uniformity of adhesive.
Reduced iron powder: a kind of high-purity iron powder that adopts oxide-reduction method at high temperature to prepare, the powder particle size is more than 300 orders, and purity is greater than 99%.Iron powder does not react with magnesium alloy and does not dissolve each other yet in welding process, thereby can become a phase counterdiffusion between the isolation strip minimizing magnalium at the iron powder of magnalium heterogeneous interface, and then reduces the existence of metallic compound between magnalium.
Reduction zinc powder: adopt the oxide-reduction method preparation, require its granularity more than 300 orders, purity is greater than 99%.Be mainly used in and improve the solid solubility of aluminium element in iron, reduce the formation of short iron Al intermetallic, improve the feature that combines between magnesium alloy and the iron, improve the switching performance of iron powder and magnesium alloy.
Rare earth powder: rare earth composition is mainly based on cerium oxide, and purity reaches more than 90%, requires its granularity more than 300 orders.After adhesive has added reduced iron powder, owing to existing reduced iron powder, preparation technology's reason subregion mixes uneven phenomenon, iron powder can not intercept the reaction between the magnalium fully, utilize rare earth powder that the intermetallic compound disperse is distributed, optimize the structure of organizational interface, improve the performance of whole welding joints.
Alumina powder: mainly as filler, play fire-retardant effect, purity requirement is more than 99%, more than granularity requirements 300 orders.
A large amount of metal dusts and other solid particles have been added in the described adhesive, organic content and oxygen content will obviously reduce in the adhesive, in welding process, decompose corresponding the reducing of gas meeting that produces, and then will significantly reduce the trend that produces pore in the welding point.
The concrete preparation method of described adhesive is as follows:
One, raw material is handled: detect the purity of raw material, guarantee that water content that organic solvent comprises below 1%, guarantees that needing to add pressed powder comprise that the granularity of reduced iron powder, reduction zinc powder, rare earth powder, alumina powder and asbestos fibre is more than 300 orders; Remove the impurity that mixes in the raw material, make its purity more than 99%;
Two, course of dissolution: organic solvent is comprised 120～130 parts of 25 parts of dimethylformamides and toluene and 100～120 parts of bisphenol A type epoxy resins, 50～60 parts of polysulfone resins, 11～15 parts of dicyandiamides, putting into reactor mixes mutually, the control reaction temperature is 30～40 ℃, makes above-mentioned organic matter uniform dissolution;
(3) whipping process: adopt 60r/min to stir 10min the organic matter that mixes in the step (2); Stopping stirring adding continuation stirring 5～10min in reactor mixes; Stir 10～15min with 200r/min again; The control reaction temperature is 30～40 ℃ in this process.
Three, whipping process: at first the organic solvent that mixes in the step (2) is adopted stirring than low velocity of 60r/min, the control temperature stirred 10 minutes at 30～40 ℃; Stop stirring adding pressed powder in reactor then and comprise 100～120 parts of reduced iron powders, 20～30 parts of reduction zinc powders, 5～10 parts of rare earth powders, 20～30 parts of alumina powders, 10 parts of asbestos fibres, 10～15 parts of gas-phase silicas, temperature-resistant, stirred again 5～10 minutes, note bigger in this process as configuration amount, metal dust to be joined in the organic solvent gradually, prevent to mix uneven; When metal dust is basic mix with organic substance after the raising rotating speed, it is 200 rev/mins, stirred 10～15 minutes, temperature remains unchanged, if find in the whipping process that adhesive viscosity is too high, then suitably increases organic solvent, if viscosity is low excessively, then slightly improve temperature, make the volatilization of part organic solvent.
Finished product packing and storage: the adhesive for preparing is injected metal bucket or Plastic Drum, preserve with the Instant cement sealing then, the adhesive storage temperature is between 5 ℃～20 ℃, and the shelf-life of adhesive is 3 months.If adhesive viscosity is higher when using, can suitably heat or add a small amount of spirit solvent, reduce viscosity and be convenient to brushing.
Use the adhesive of aforementioned formula preparation, room temperature places an order and overlaps the thick aluminum alloy joint shear strength 〉=20Mpa of 2mm, and the tensile shear standard is referring to GB/T7124-2008.
Compared with prior art, adhesive of the present invention, by optimization to traditional adhesive component, make it in magnalium special metal fusing glue weldering process, can eliminate the harmful effect that the butt joint of magnalium intermetallic compound brings, improve the overall performance of fusing glue weldering test specimen, evidence, under the same structure condition, use this special-purpose adhesive to carry out magnalium special metal and connect the fusing glue weldering test specimen performance obtain and use the test specimen performance of all-purpose gum stick can improve 20～30%.
Description of drawings
Fig. 1 is magnalium special metal fusing glue weldering (laser thermal source) welding point magnalium heterogeneous interface institutional framework scanning electron microscope image; Among the figure,
C1 place element ratio: Mg (96.3%), Al (2.71%), Zn (0.99%), Fe (0.00%)
C2 place element ratio: Mg (0.42%), Al (19.23%), Fe (80.35%)
C3 place element ratio: Mg (0.00%), Al (95.16%), Fe (3.21%), Zn (1.36%)
Fig. 2 is magnalium special metal fusing glue weldering (laser thermal source) Welding Structure sketch; Among the figure,
1, pulse laser; 2, magnesium alloy; 3, adhesive; 4, aluminium alloy; 5, protection gas
Fig. 3 a) is vertical view, b) side view for magnalium special metal fusing glue weldering (laser thermal source) tensile and shear property test test specimen structure chart; Among the figure,
2, magnesium alloy; 3, adhesive; 4, aluminium alloy; 6, welding point; 61, weld seam
The specific embodiment
With E-51 epoxy resin 100g, polysulfone resin 50g, dicyandiamide 11g, dimethylformamide 25g, toluene 120g puts into reactor and mixes mutually, the control temperature is 30～40 ℃ of fully dissolvings, behind the speed stirring 5min with 60r/min, puts into reduced iron powder 100g then, reduction zinc powder 20g, rare earth powder 8g, alumina powder 20g, asbestos fibre 10g, and then stirred 5 minutes with the speed of 60r/min, after treating evenly to mix, improve mixing speed to 200r/min, stir 10min, package encapsulation.Adhesive splicing this moment room temperature strength reaches 20.8MPa.Adopt this adhesive to carry out the weldering of magnalium special metal fusing glue, as shown in Figure 2, the magnalium laser that obtains glueds joint the heterogeneous interface conjunctive tissue structure of plumb joint, as shown in Figure 1, by adopting ESEM the zones of different analysis is found, the adding of iron powder has effectively suppressed the formation of intermetallic compound between magnalium, and then has improved the overall performance of joint.The ratio of iron powder slightly change mainly be according to the welding magnalium special metal composition difference adjust accordingly, in general the aluminium content in the magnesium alloy is high more, the also corresponding raising of the ratio of iron powder.Welding on Properties of Welding Joint is carried out the tensile shear test, and as shown in Figure 3, result of the test proves that special-purpose adhesive proposed by the invention is used in welding in the same way, and its joint load can reach 4.5KN; Use other to have the commercial adhesive of identical adhesive property, its performance is about about 3.5KN.
With E-51 epoxy resin 120g, polysulfone resin 55g, dicyandiamide 15g, dimethylformamide 25g, toluene 125g puts into reactor and mixes mutually, the control temperature is 30～40 ℃ of fully dissolvings, behind the speed stirring 5min with 60r/min, puts into reduced iron powder 105g then, reduction zinc powder 25g, rare earth powder 10g, alumina powder 20g, asbestos fibre 10g, and then stir 5min with the speed of 60r/min, after treating evenly to mix, improve mixing speed to 200r/min, stir 12min, package encapsulation.Adhesive splicing this moment room temperature strength reaches 21.5MPa.Adopt this adhesive to carry out the weldering of magnalium special metal fusing glue, as shown in Figure 2; Same Welding on Properties of Welding Joint is carried out the tensile shear test, and as shown in Figure 3, result of the test proves that special-purpose adhesive proposed by the invention is used in welding in the same way, and its joint load can reach 4.6KN; And use other commercial adhesive with identical adhesive property, its performance is about about 3.5KN.
With E-51 epoxy resin 115g, polysulfone resin 50g, dicyandiamide 12g, dimethylformamide 25g, toluene 130g puts into reactor and mixes mutually, the control temperature is 30～40 ℃ of fully dissolvings, behind the speed stirring 5min with 60r/min, puts into reduced iron powder 110g then, reduction zinc powder 30g, rare earth powder 10g, alumina powder 25g, asbestos fibre 10g, and then stir 5min with the speed of 60r/min, after treating evenly to mix, improve mixing speed to 200r/min, stir 15min, package encapsulation.Adhesive splicing this moment room temperature strength reaches 20.6MPa.Adopt this adhesive to carry out the weldering of magnalium special metal fusing glue, as shown in Figure 2; Same Welding on Properties of Welding Joint is carried out the tensile shear test, and as shown in Figure 3, result of the test proves that special-purpose adhesive proposed by the invention is used in welding in the same way, and its joint load can reach 4.4KN; Use other to have the commercial adhesive of identical adhesive property, its performance is about about 3.5KN.
The above; only be the preferable specific embodiment of the present invention; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; be equal to replacement or change according to technical scheme of the present invention and inventive concept thereof, all should be encompassed within protection scope of the present invention.
Claims (2)
1. a magnalium special metal fusing glue welds special-purpose adhesive, it is characterized in that its composition and quality proportioning are as follows:
And the organic solvent in the mentioned component is that the water content of dimethylformamide and toluene is below 1%; Pressed powder comprises the granularity of reduced iron powder, reduction zinc powder, rare earth powder, alumina powder and asbestos fibre more than 300 orders, and purity is more than 99%.
2. the preparation method of an adhesive as claimed in claim 1 comprises the steps:
(1) prepare raw material: detect the purity of raw material, organic solvent comprises that the water content of dimethylformamide and toluene is below 1%; Pressed powder comprises the granularity of reduced iron powder, reduction zinc powder, rare earth powder, alumina powder and asbestos fibre more than 300 orders, and purity is more than 99%;
(2) organic matter uniform dissolution process: organic solvent is comprised 120～130 parts of 25 parts of dimethylformamides and toluene and 100～120 parts of bisphenol A type epoxy resins, 50～60 parts of polysulfone resins, 11～15 parts of dicyandiamides, putting into reactor mixes mutually, the control reaction temperature is 30～40 ℃, makes above-mentioned organic matter uniform dissolution;
(3) whipping process: adopt 60r/min to stir 10min the organic matter that mixes in the step (2); Stop stirring adding pressed powder in reactor and comprise 100～120 parts of reduced iron powders, 20～30 parts of reduction zinc powders, 5～10 parts of rare earth powders, 20～30 parts of alumina powders, 10 parts of asbestos fibres, 10～15 parts of gas-phase silicas, continue to stir 5～10min and mix; Stir 10～15min with 200r/min again; The control reaction temperature is 30～40 ℃ in this process.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110101692A CN102189354B (en) | 2011-04-22 | 2011-04-22 | Adhesive special for melting and glue welding of magnesium-aluminum dissimilar metals and preparation method thereof |
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|---|---|---|---|
| CN201110101692A CN102189354B (en) | 2011-04-22 | 2011-04-22 | Adhesive special for melting and glue welding of magnesium-aluminum dissimilar metals and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105195916A (en) * | 2015-11-05 | 2015-12-30 | 广东轻工职业技术学院 | Lead-free solder alloy soldering paste |
| CN105238312A (en) * | 2015-09-21 | 2016-01-13 | 烟台德邦科技有限公司 | Structural adhesive used for automobile and preparation method thereof |
| CN114633015A (en) * | 2022-05-17 | 2022-06-17 | 太原科技大学 | Aluminum-magnesium dissimilar metal and static shaft shoulder friction stir welding process and device thereof |
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| CN1880008A (en) * | 2005-06-03 | 2006-12-20 | 国家淀粉及化学投资控股公司 | Fluxing compositions |
| CN101709448A (en) * | 2009-11-10 | 2010-05-19 | 大连理工大学 | Magnalium special metal coating and preparation method thereof |
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Patent Citations (5)
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| JP2000344870A (en) * | 1999-06-02 | 2000-12-12 | Toray Ind Inc | Epoxy resin composition, prepreg, and fiber-reinforced composite material |
| CN1579698A (en) * | 2003-08-08 | 2005-02-16 | 株式会社东芝 | Thermal-setting welding-assistant, welding paste and welding method |
| US20070221712A1 (en) * | 2003-08-08 | 2007-09-27 | Kabushiki Kaisha Toshiba | Thermosetting flux and solder paste |
| CN1880008A (en) * | 2005-06-03 | 2006-12-20 | 国家淀粉及化学投资控股公司 | Fluxing compositions |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105238312A (en) * | 2015-09-21 | 2016-01-13 | 烟台德邦科技有限公司 | Structural adhesive used for automobile and preparation method thereof |
| CN105238312B (en) * | 2015-09-21 | 2017-12-19 | 烟台德邦科技有限公司 | A kind of automobile using structure glue and preparation method thereof |
| CN105195916A (en) * | 2015-11-05 | 2015-12-30 | 广东轻工职业技术学院 | Lead-free solder alloy soldering paste |
| CN105195916B (en) * | 2015-11-05 | 2017-06-16 | 广东轻工职业技术学院 | A kind of leadless welding alloy solder(ing) paste |
| CN114633015A (en) * | 2022-05-17 | 2022-06-17 | 太原科技大学 | Aluminum-magnesium dissimilar metal and static shaft shoulder friction stir welding process and device thereof |
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