CN101712765B - Method for bonding aluminum or aluminum alloy surface with resin material - Google Patents
Method for bonding aluminum or aluminum alloy surface with resin material Download PDFInfo
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- CN101712765B CN101712765B CN2009102190796A CN200910219079A CN101712765B CN 101712765 B CN101712765 B CN 101712765B CN 2009102190796 A CN2009102190796 A CN 2009102190796A CN 200910219079 A CN200910219079 A CN 200910219079A CN 101712765 B CN101712765 B CN 101712765B
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Abstract
The invention discloses a method for bonding an aluminum or aluminum alloy surface with a resin material. The method comprises the following steps of: firstly, self-assembling high-polymer nano-membranes on the aluminum or aluminum alloy surface bonded with the resin material and on the surface of the resin material; spraying low-concentration organic peroxide and auxiliary vulcanizing agent solution on the surface of the high-polymer nano-membrane so as to modify the surface; and realizing high-intensity bonding of the aluminum or aluminum alloy and the resin material by heating and compressing. The invention adopts a self-assembly dipping method, so that the method can treat materials and components with complex shapes and can realize bonding aluminum or aluminum alloy with complex shapes and the resin material. The method belongs to an environment-friendly formula and has simple and convenient operation process. Moreover, the method realizes high bonding intensity between the aluminum or aluminum alloy and the resin material and high stability.
Description
Technical field
The invention belongs to the modification technology field of metallic surface, relate to the bonding of metallic surface and resin material, particularly a kind of aluminum or aluminum alloy surface and the bonding method of resin material.
Background technology
The novel production of 21st century should be the production (two-supremes one is low) of high yield, high-performance and low environmental load.Since over half a century, as a kind of main surface treatment technology of material, the chromium passivating process quilt is widely used in different industrial circles, like automobile, aircraft and shipping industry etc.Yet, contained Cr in the chromium compounds
6+The continuation that seriously hindered this technology of toxicity and carinogenicity use.Along with the reinforcement of people's environmental consciousness in recent years, it is imperative to develop " green process for treating surface ".
At present, bonding between the differing materials generally is to spread upon material surface through caking agent to realize bonding.But in the process of bonding interface coating adhesive, be difficult to guarantee the even of adhesive coating, especially for special, the baroque component of surface shape, this method is difficult to guarantee omnibearing good bonding especially.Caking agent commonly used simultaneously is generally the organic solvent type material, and is bigger to environment and human harm, and most of caking agent also has infection to metallic surface, so develops new pollution-freely, and the adhesive technology that cementability is good is imperative.
Some new environmental friendliness top coat Study on Technology is mixed nanometer rete technology like organic and inorganic in recent years, electrically conductive polyaniline erosion shield technology, self-assembled nanometer membrane technique.Wherein the self-assembled nanometer membrane technique is the novel organic superthin membrane technique that grew up in recent years, is a kind of metal surface treating method of alternative chromium passivating of tool potentiality.
Yet,, therefore comparatively difficult at its surface preparation self-assembled nanometer film owing to iron, zinc, aluminium etc. belong to the very easily oxidation of its surface, active metal; For the lower non-polar resin materials surface of surface energy, the formation of self-assembled nanometer film is also very difficult simultaneously.And the high strength bond of these two types of storerooms also is a more scabrous problem.
Reported the adhering method of some metals and resin material at present, but in bonding strength, complex-shaped device, aspects such as environmental protection still exist certain defective.
Summary of the invention
The problem that the present invention solves is to provide the adhering method of a kind of aluminum or aluminum alloy and resin material, through the preparation and then the binder-treatment of material surface functional nano film, realizes the good bonding of aluminium and duraluminum and resin material.
The present invention realizes through following technical scheme:
A kind of aluminum or aluminum alloy surface and the bonding method of resin material may further comprise the steps:
1) will treat that respectively bonding aluminum or aluminum alloy surface and resin material are immersed in the self-assembly solution, are self-assembled into the high molecular nanometer film in its surface;
The solvent of described self-assembly solution is the ethanol of volume(tric)fraction 75～95%, and solute is the alkoxysilane compound containing trialkylsilyl group in molecular structure that has reactive sulfydryl, and its concentration is 1.0～10.0mmol/L;
The processing condition that are self-assembled into the high molecular nanometer film are:
After treating that self-assembly solution is heated, under 90～170 ℃ of temperature, solidify 5～20min, each self-assembly time is 10～30min, self-assembly 1～5 time;
2) surface is formed bonding the aluminum or aluminum alloy surface and the resin material treated of the thick high molecular nanometer film of 10～40nm; The mixing solutions of spraying organo-peroxide and cocuring agent; Wherein, the mass ratio of organo-peroxide and cocuring agent is 1: 1～1.2, and its mass concentration is 1～5%;
3) aluminum or aluminum alloy surface that treating of crossing of spray treatment is bonding and after resin material contacts, putting into behind the thermocompressor at pressure is that 5～15M Pa, temperature are to compress 1～5min under 90～180 ℃ the condition, naturally cools to room temperature after the taking-up.
Described treat the adhering resin material aluminum or aluminum alloy surface before being self-assembled into the high molecular nanometer film, pass through pre-treatment with resin material, described pre-treatment is:
Be self-assembled into the high molecular nanometer film before through pre-treatment on aluminum or aluminum alloy surface to be glued and resin material, described pre-treatment is:
At first treat bonding aluminum or aluminum alloy surface and resin material ultrasonic washing 15～30min with organic solvent, the SK-144 alkaline solution with mass concentration 10% carries out oil removal treatment at 60 ℃ to it again, and is dry after water cleans;
Treat bonding aluminum or aluminum alloy surface and resin material with low-temperature plasma electrical source then and carry out Corona discharge Treatment.
The described alkoxysilane compound containing trialkylsilyl group in molecular structure that has reactive sulfydryl is:
Wherein, R
1Be one of following functional group:
H、CH
3、C
2H
5、n-C
3H
7、CH
2＝CHCH
2、n-C
4H
9、C
6H
5、n-C
6H
13、n-C
8H
17、i-C
8H
17；
R
2Be one of following functional group:
CH
2CH
2、CH
2CH
2CH
2、CH
2CH
2CH
2CH
2CH
2、CH
2CH
2SCH
2CH
2、
CH
2CH
2CH
2SCH
2CH
2CH
2、CH
2CH
2NHCH
2CH
2CH
2、
(CH
2CH
2)
2NCH
2CH
2CH
2、CH
2CH
2OCONHCH
2CH
2CH
2、
CH
2CH
2NHCONHCH
2CH
2CH
2、(CH
2CH
2)
2CHOCONHCH
2CH
2CH
2；
X is one of following functional group:
H、CH
3、C
2H
5、n-C
3H
7、i-C
3H
7、n-C
4H
9、i-C
4H
9、t-C
4H
9；
Y is one of following functional group:
CH
3O、C
2H
5O、n-C
3H
7O、i-C
3H
7O、n-C
4H
9O、i-C
4H
9O、t-C
4H
9O；
M is one of following atom:
Li、Na、K；
N described in the functional group, i, t are respectively: just, different, uncle.
The described alkoxysilane compound containing trialkylsilyl group in molecular structure that has reactive sulfydryl is:
Z-R-SiX
3-nY
n；
Wherein, Z is one of following functional group:
SH、SNa、SK、NH
2、CSOH、CSSNa、CSSK；
R is one of following functional group:
CH
3、C
2H
5、n-C
3H
7、n-C
4H
9、n-C
8H
17、n-C
10H
21、n-C
12H
25；
X is one of following functional group:
H、CH
3、C
2H
5、n-C
3H
7、n-C
4H
9、
Y is one of following functional group:
CH
3O、C
2H
5O、n-C
3H
7O-；
N described in the functional group is for just.
Described duraluminum is aluminum magnesium alloy, aluminium-zinc alloy, aluminum-copper alloy, alumal or aluminum-manganese-iron alloy.
Described organo-peroxide is: Di Cumyl Peroxide 99, BPO or Diisopropyl azodicarboxylate
Described cocuring agent is: bismaleimides
Described resin material is: high density polyethylene(HDPE) (HDPE), new LDPE (film grade) (LDPE), Vestolen PP 7052 (PP) or acrylonitrile-butadiene-styrene resin (ABS resin).
Described treat that self-assembly solution is heated after, 5～20min is solidified in the aluminum or aluminum alloy surface under 120～160 ℃ of temperature.
Described treat that self-assembly solution is heated after, resin material solidifies 5～20min under 90～120 ℃ of temperature.
Compare with existing adhesive technology, the present invention has following beneficial technical effects:
1, the present invention has realized the fastening bonding of in active metal aluminum or aluminum alloy surface and non-polar resin materials surface, and the scheme step that realizes is succinct, the prescription environmental protection.
2, the present invention will treat the adhering resin material aluminum or aluminum alloy surface and resin material after the self-assembly liquid of reactive sulfydryl organoalkoxysilane is handled; The process heating cure has formed with material at material surface and has combined firm high molecular nanometer film, and this high molecular nanometer film can be used as the resist of material;
Spray the organo-peroxide and the cocuring agent solution of lower concentration then, make and between the nano thin-film of sulfydryl organoalkoxysilane covering chemical reaction has been taken place, formed new covalent linkage, make its surface-treated change.
3, the present invention has realized aluminum or aluminum alloy that surperficial generation modification changes and the high strength bond between the resin material after through warming and pressurizing; Under 20 ℃ of constant temperatures, the stripping strength of measuring bonding sample through Elongation test reaches 5.2～7.2KN/m
2, and observed the destruction of Vilaterm face.
4, because the present invention adopts is the method for self-assembly dipping, thereby can handle, can realize the bonding of complicated shape aluminum or aluminum alloy and resin material the material and the parts of complicated shape.
5, the self-assembly solution that the present invention relates to does not contain environment and the healthy poisonous and harmful element of human body, has the characteristics of nontoxic non-environmental-pollution, belongs to the environment-friendly type prescription.
6, operating procedure of the present invention is easy, and the bonding strength between aluminum or aluminum alloy/resin material is big, and stability is high, has highly application value.
Embodiment
The adhering method of aluminum or aluminum alloy provided by the invention and resin material; At first respectively the adhering resin material aluminum or aluminum alloy surface and resin material surface be self-assembled into the high molecular nanometer film; Then at organo-peroxide and cocuring agent solution to high molecular nanometer film surface spraying lower concentration; Make its surface-treated change, again through realizing the high strength bond between aluminum or aluminum alloy and the resin material after the warming and pressurizing.
Below through concrete embodiment the present invention is done further elaboration, need to prove that following embodiment is that the present invention is not limited to these embodiment for those skilled in the art better understands the present invention.
Embodiment 1
Treat that bonding metal parts is the fine aluminium substrate that is of a size of 50 * 30 * 0.2 (mm), treat that bonding resin material is new LDPE (film grade) (LDPE), realize fastening bonding through following steps:
Step 1): surface and LDPE surface in the fine aluminium substrate are self-assembled into the high molecular nanometer film:
The solvent of self-assembly solution is an absolute ethyl alcohol: water=95: 5 (volume ratio), and the alkoxysilane compound containing trialkylsilyl group in molecular structure that has reactive sulfydryl is:
Concentration is 1.0mmol/L; The curing time of assembled solution is 24h;
The layoutprocedure of described self-assembly solution is: at first put into volumetric flask according to the alkoxysilane compound containing trialkylsilyl group in molecular structure of the reactive sulfydryl of the strength of solution weighing that will dispose, in 95: 5 ratio elder generation adding absolute ethyl alcohol, add deionized water more then;
Described being assembled into: the material that will handle is put into the solution that is disposed, clear and definite through a class formation of non-covalent interaction formation between alkoxysilane compound containing trialkylsilyl group in molecular structure molecule in the solution and the material surface of handling, as to stablize, have specific function molecule nano film.
Described being cured as: between the molecule that passes through hydrogen bond action of base material surface self-assembly, take off water molecules, thereby obtain the process of the high molecular nanometer film of cross-linked state through the mode of heating.
The fine aluminium substrate is immersed in assembles 10min in the assembled solution, be heated to 160 ℃ then and solidify 10min;
LDPE is immersed in assembles 10min in the assembled solution, be heated to branch then and solidify 10min for 90 ℃; Respectively at fine aluminium substrate surface and the surperficial high molecular nanometer film that forms about 10nm of LDPE;
Step 2) spraying of organo-peroxide and cocuring agent:
In the fine aluminium substrate surface spraying concentration that forms the high molecular nanometer film is 1.0% the organo-peroxide and the mixing solutions of cocuring agent;
Organo-peroxide is: Di Cumyl Peroxide 99, concentration are 1.0%; Cocuring agent be between the penylene bismaleimides, concentration is 1.0%; Solvent is an acetone.
The step 3) warming and pressurizing is bonding:
With the fine aluminium substrate surface that sprayed organo-peroxide and cocuring agent with put into thermocompressor after LDPE contacts, be 5MPa at pressure, temperature be 140 ℃ with condition under compress 1min, naturally cool to room temperature after the taking-up.
Under 20 ℃ of constant temperatures, measure the stripping strength of bonding sample through Elongation test.Test result shows that the stripping strength of bond reaches 5.8KN/m
2, and observed the destruction of Vilaterm face.
Embodiment 2
Treat that bonding metal parts is the aluminium-zinc alloy substrate that is of a size of 50 * 30 * 0.3 (mm), treat that bonding resin material is Vestolen PP 7052 (PP), realize fastening bonding through following steps:
Step 1): pre-treatment
At first, use the pure acetone solvent respectively, Vestolen PP 7052 is carried out ultrasonic washing 20min with absolute ethyl alcohol to the aluminium-zinc alloy substrate, dry after the washing;
Then, carry out oil removal treatment with the 10%SK-144 alkaline solution on 60 ℃ of surfaces to the aluminium-zinc alloy substrate, drying is also carried out to it in flushing with clean water surface;
With low-temperature plasma electrical source the surface and the polypropylene surface of aluminium-zinc alloy substrate are carried out Corona discharge Treatment 20s again.
Step 2): surface and polypropylene surface in the aluminium-zinc alloy substrate are self-assembled into the high molecular nanometer film:
The solvent of self-assembly solution is an absolute ethyl alcohol: water=90: 10, and the alkoxysilane compound containing trialkylsilyl group in molecular structure that has reactive sulfydryl is:
Concentration is 5.0mmol/L; The curing time of assembled solution is 24h;
The aluminium-zinc alloy substrate is immersed in assembles 5min in the assembled solution, be heated to 140 ℃ then and solidify 10min; Solidify after the completion, the base material of assembling is joined new assembling liquid again assemble once more again, solidify 5min once more.
Vestolen PP 7052 is immersed in assembles 5min in the assembled solution, be heated to 110 ℃ then and solidify 10min; Solidify to accomplish to assemble for the first time afterwards and accomplish, and then assembling once;
Form the high molecular nanometer film of about 15nm respectively in aluminium-zinc alloy substrate surface and polypropylene surface;
The spraying of step 3) organo-peroxide and cocuring agent:
In the aluminium-zinc alloy substrate surface spraying concentration that forms the high molecular nanometer film is 2.0% the organo-peroxide and the mixing solutions of cocuring agent;
Organo-peroxide is: BPO, concentration are 2.0%; Cocuring agent is to the penylene bismaleimides, and concentration is 2.0%; Solvent is an acetone.
The step 4) warming and pressurizing is bonding:
With the aluminium-zinc alloy substrate surface that sprayed organo-peroxide and cocuring agent with put into thermocompressor after Vestolen PP 7052 contacts, be 10MPa at pressure, temperature be 170 ℃ with condition under compress 3min, naturally cool to room temperature after the taking-up.
Under 20 ℃ of constant temperatures, measure the stripping strength of bonding sample through Elongation test.Test result shows that the stripping strength of bond reaches 6.2KN/m
2, and observed the destruction of Vilaterm face.
Embodiment 3
Treat that bonding metal parts is the aluminum magnesium alloy substrate that is of a size of 50 * 30 * 0.3 (mm), treat that bonding resin material is high density polyethylene(HDPE) (HDPE), realize fastening bonding through following steps:
Step 1): pre-treatment
At first, use the pure acetone solvent respectively, HDPE is carried out ultrasonic washing 15min with absolute ethyl alcohol to the aluminum magnesium alloy substrate, dry after the washing;
Then, carry out oil removal treatment with the aqueous solution of 10%SK-144 alkaline solution on 70 ℃ of surfaces to the aluminum magnesium alloy substrate, drying is also carried out to it in the flushing with clean water surface;
With low-temperature plasma electrical source Corona discharge Treatment 20s is carried out on the surface and the HDPE surface of aluminum magnesium alloy substrate again.
Step 2): surface and HDPE surface in the aluminum magnesium alloy substrate are self-assembled into the high molecular nanometer film:
The solvent of self-assembly solution is an absolute ethyl alcohol: water=90: 10, and the alkoxysilane compound containing trialkylsilyl group in molecular structure that has reactive sulfydryl is:
Concentration is 1mmol/L; The curing time of assembled solution is 12h;
The aluminum magnesium alloy substrate is immersed in assembles 15min in the assembled solution, be heated to 150 ℃ then and solidify 10min; Solidify to accomplish to assemble for the first time afterwards and accomplish, and then assemble twice;
HDPE is immersed in assembles 5min in the assembled solution, be heated to branch then and solidify 5min for 100 ℃; Solidify to accomplish to assemble for the first time afterwards and accomplish, and then assemble twice;
Respectively at aluminum magnesium alloy substrate surface and the surperficial high molecular nanometer film that forms about 20nm of HDPE;
The spraying of step 3) organo-peroxide and cocuring agent:
In the aluminum magnesium alloy substrate surface spraying concentration that forms the high molecular nanometer film is 1.5% the organo-peroxide and the mixing solutions of cocuring agent;
Organo-peroxide is: Diisopropyl azodicarboxylate, concentration are 1.5%; Cocuring agent is to the penylene bismaleimides, and concentration is 1.8%; Solvent acetone.
The step 4) warming and pressurizing is bonding:
With the aluminum magnesium alloy substrate surface that sprayed organo-peroxide and cocuring agent with put into thermocompressor after HDPE contacts, be 8MPa at pressure, temperature be 90 ℃ with condition under compress 2min, naturally cool to room temperature after the taking-up.
Under 20 ℃ of constant temperatures, measure the stripping strength of bonding sample through Elongation test.Test result shows that the stripping strength of bond reaches 5.6KN/m
2, and observed the destruction of Vilaterm face.
Embodiment 4
Treat that bonding metal parts is the aluminum-copper alloy substrate that is of a size of 50 * 30 * 0.3 (mm), treat that bonding resin material is acrylonitrile-butadiene-styrene resin (ABS resin), realize fastening bonding through following steps:
Step 1): pre-treatment
At first, use the pure acetone solvent respectively, ABS is carried out ultrasonic washing 20min with absolute ethyl alcohol to the aluminum-copper alloy substrate, dry after the washing;
Then, carry out oil removal treatment with the 10%SK-144 alkaline solution on 70 ℃ of surfaces to the aluminum-copper alloy substrate, drying is also carried out to it in flushing with clean water surface;
With low-temperature plasma electrical source Corona discharge Treatment 20s is carried out on the surface and the ABS surface of aluminum-copper alloy substrate again.
Step 2): surface and ABS surface in the aluminum-copper alloy substrate are self-assembled into the high molecular nanometer film: the solvent of self-assembly solution is an absolute ethyl alcohol: water=75: 25, and the alkoxysilane compound containing trialkylsilyl group in molecular structure that has reactive sulfydryl is:
Concentration is 7.0mmol/L; The curing time of assembled solution is 8h;
The aluminum-copper alloy substrate is immersed in assembles 10min in the assembled solution, be heated to 150 ℃ then and solidify 10min; Solidify to accomplish to assemble for the first time afterwards and accomplish, and then assembling once;
ABS is immersed in assembles 10min in the assembled solution, be heated to branch then and solidify 10min for 120 ℃; Solidify to accomplish to assemble for the first time afterwards and accomplish, and then assembling once;
Respectively at aluminum-copper alloy substrate surface and the surperficial high molecular nanometer film that forms about 20nm of ABS;
The spraying of step 3) organo-peroxide and cocuring agent:
In the aluminum-copper alloy substrate surface spraying concentration that forms the high molecular nanometer film is 2.5% the organo-peroxide and the mixing solutions of cocuring agent;
Organo-peroxide is: BPO, concentration are 2.5%; Cocuring agent be between the penylene bismaleimides, concentration is 2.75%; Solvent is an acetone.
The step 4) warming and pressurizing is bonding:
With the aluminum-copper alloy substrate surface that sprayed organo-peroxide and cocuring agent with put into thermocompressor after ABS contacts, be 15MPa at pressure, temperature be 180 ℃ with condition under compress 5min, naturally cool to room temperature after the taking-up.
Under 20 ℃ of constant temperatures, measure the stripping strength of bonding sample through Elongation test.Test result shows that the stripping strength of bond reaches 7.2KN/m
2, and observed the destruction of Vilaterm face.
Embodiment 5
Treat that bonding metal parts is the alumal substrate that is of a size of 50 * 30 * 0.3 (mm), treat that bonding resin material is LDPE, realize fastening bonding through following steps:
Step 1): pre-treatment
At first, use the pure acetone solvent respectively, LDPE is carried out ultrasonic washing 20min with absolute ethyl alcohol to the alumal substrate, dry after the washing;
Then, carry out oil removal treatment with the 10%SK-144 alkaline solution on 70 ℃ of surfaces to the alumal substrate, drying is also carried out to it in flushing with clean water surface;
With low-temperature plasma electrical source Corona discharge Treatment 20s is carried out on the surface and the LDPE surface of alumal substrate again.
Step 2): surface and LDPE surface in the alumal substrate are self-assembled into the high molecular nanometer film:
The solvent of self-assembly solution is an absolute ethyl alcohol: water=75: 25, and the alkoxysilane compound containing trialkylsilyl group in molecular structure that has reactive sulfydryl is:
Concentration is 10.0mmol/L; The curing time of assembled solution is 6h;
The alumal substrate is immersed in assembles 10min in the assembled solution, be heated to 160 ℃ then and solidify 20min; Solidify to accomplish to assemble for the first time afterwards and accomplish, and then assemble twice;
LDPE is immersed in assembles 10min in the assembled solution, be heated to branch then and solidify 10min for 90 ℃; Solidify to accomplish to assemble for the first time afterwards and accomplish, and then assemble twice;
Respectively at aluminium manganese substrate surface and the surperficial high molecular nanometer film that forms about 30nm of LDPE;
The spraying of step 3) organo-peroxide and cocuring agent:
In the alumal substrate surface spraying concentration that forms the high molecular nanometer film is 5% the organo-peroxide and the mixing solutions of cocuring agent;
Organo-peroxide is: Diisopropyl azodicarboxylate, concentration are 5%; Cocuring agent be between the penylene bismaleimides, concentration is 5%; Solvent acetone.
The step 4) warming and pressurizing is bonding:
With the alumal substrate surface that sprayed organo-peroxide and cocuring agent with put into thermocompressor after LDPE contacts, be 7.5MPa at pressure, temperature be 145 ℃ with condition under compress 2min, naturally cool to room temperature after the taking-up.
Under 20 ℃ of constant temperatures, measure the stripping strength of bonding sample through Elongation test.Test result shows that the stripping strength of bond reaches 7.2KN/m
2, and observed the destruction of Vilaterm face.
Embodiment 6
Treat that bonding metal parts is the fine aluminium substrate that is of a size of 50 * 30 * 0.2 (mm), treat that bonding resin material is LDPE, realize fastening bonding through following steps:
Step 1): pre-treatment
At first, use the pure acetone solvent respectively, LDPE is carried out ultrasonic washing 15min with absolute ethyl alcohol to the fine aluminium substrate, dry after the washing;
Then, carry out oil removal treatment with the aqueous solution of 10%SK-144 alkaline solution on 70 ℃ of surfaces to the fine aluminium substrate, drying is also carried out to it in the flushing with clean water surface;
With low-temperature plasma electrical source Corona discharge Treatment 15s is carried out on the surface and the LDPE surface of aluminum magnesium alloy substrate again.
Step 2): surface and LDPE surface in the fine aluminium substrate are self-assembled into the high molecular nanometer film:
The solvent of self-assembly solution is an absolute ethyl alcohol: water=85: 15, and the alkoxysilane compound containing trialkylsilyl group in molecular structure that has reactive sulfydryl is:
Concentration is 5.0mmol/L; The curing time of assembled solution is 18h;
The fine aluminium substrate is immersed in assembles 15min in the assembled solution, be heated to 170 ℃ then and solidify 10min; Solidify to accomplish to assemble for the first time afterwards and accomplish, and then assemble twice;
LDPE is immersed in assembles 5min in the assembled solution, be heated to branch then and solidify 10min for 95 ℃; Solidify to accomplish to assemble for the first time afterwards and accomplish, and then assemble twice;
Respectively at fine aluminium substrate surface and the surperficial high molecular nanometer film that forms about 20nm of LDPE;
The spraying of step 3) organo-peroxide and cocuring agent:
In the fine aluminium substrate surface spraying concentration that forms the high molecular nanometer film is 1.0% the organo-peroxide and the mixing solutions of cocuring agent;
Organo-peroxide is: Di Cumyl Peroxide 99, concentration are 1.0%; Cocuring agent is to the penylene bismaleimides, and concentration is 1.2%; Solvent is an acetone.
The step 4) warming and pressurizing is bonding:
With the fine aluminium substrate surface that sprayed organo-peroxide and cocuring agent with put into thermocompressor after LDPE contacts, be 8MPa at pressure, temperature be 135 ℃ with condition under compress 3min, naturally cool to room temperature after the taking-up.
Under 20 ℃ of constant temperatures, measure the stripping strength of bonding sample through Elongation test.Test result shows that the stripping strength of bond reaches 5.3KN/m
2, and observed the destruction of Vilaterm face.
Embodiment 7
Treat that bonding metal parts is the aluminium-zinc alloy substrate that is of a size of 50 * 30 * 0.3 (mm), treat that bonding resin material is Vestolen PP 7052 (PP), realize fastening bonding through following steps:
Step 1): pre-treatment
At first, use the pure acetone solvent respectively, Vestolen PP 7052 is carried out ultrasonic washing 15min with absolute ethyl alcohol to the aluminium-zinc alloy substrate, dry after the washing;
Then, carry out oil removal treatment with the 10%SK-144 alkaline solution on 60 ℃ of surfaces to the aluminium-zinc alloy substrate, drying is also carried out to it in flushing with clean water surface;
With low-temperature plasma electrical source the surface and the polypropylene surface of aluminium-zinc alloy substrate are carried out Corona discharge Treatment 20s again.
Step 2): surface and polypropylene surface in the aluminium-zinc alloy substrate are self-assembled into the high molecular nanometer film:
The solvent of self-assembly solution is an absolute ethyl alcohol: water=75: 25, and the alkoxysilane compound containing trialkylsilyl group in molecular structure that has reactive sulfydryl is:
Concentration is 4.5mmol/L; The curing time of assembled solution is 48h;
The aluminium-zinc alloy substrate is immersed in assembles 5min in the assembled solution, be heated to 150 ℃ then and solidify 10min; Solidify after the completion, the base material of assembling is joined new assembling liquid again, assembling is once solidified 10min once more more again.
Vestolen PP 7052 is immersed in assembles 5min in the assembled solution, be heated to 110 ℃ then and solidify 10min; Solidify to accomplish to assemble for the first time afterwards and accomplish, and then assembling once;
Form the high molecular nanometer film of about 18nm respectively in aluminium-zinc alloy substrate surface and polypropylene surface;
The spraying of step 3) organo-peroxide and cocuring agent:
In the aluminium-zinc alloy substrate surface spraying concentration that forms the high molecular nanometer film is 1.5% the organo-peroxide and the mixing solutions of cocuring agent;
Organo-peroxide is: BPO, concentration are 1.5%; Cocuring agent is to the penylene bismaleimides, and concentration is 1.5%; Solvent is an acetone.
The step 4) warming and pressurizing is bonding:
With the aluminium-zinc alloy substrate surface that sprayed organo-peroxide and cocuring agent with put into thermocompressor after Vestolen PP 7052 contacts, be 10MPa at pressure, temperature be 165 ℃ with condition under compress 4min, naturally cool to room temperature after the taking-up.
Under 20 ℃ of constant temperatures, measure the stripping strength of bonding sample through Elongation test.Test result shows that the stripping strength of bond reaches 5.9KN/m
2, and observed the destruction of Vilaterm face.
Embodiment 8
Treat that bonding metal parts is the aluminum magnesium alloy substrate that is of a size of 50 * 30 * 0.3 (mm), treat that bonding resin material is LDPE, realize fastening bonding through following steps:
Step 1): pre-treatment
At first, use the pure acetone solvent respectively, LDPE is carried out ultrasonic washing 15min with absolute ethyl alcohol to the aluminum magnesium alloy substrate, dry after the washing;
Then, carry out oil removal treatment with the aqueous solution of 10%SK-144 alkaline solution on 70 ℃ of surfaces to the aluminum magnesium alloy substrate, drying is also carried out to it in the flushing with clean water surface;
With low-temperature plasma electrical source Corona discharge Treatment 15s is carried out on the surface and the LDPE surface of aluminum magnesium alloy substrate again.
Step 2): surface and LDPE surface in the aluminum magnesium alloy substrate are self-assembled into the high molecular nanometer film:
The solvent of self-assembly solution is an absolute ethyl alcohol: water=95: 5, and the alkoxysilane compound containing trialkylsilyl group in molecular structure that has reactive sulfydryl is:
HS-(CH
2)
3-Si-(OCH
3)
3
Concentration is 2.5mmol/L; The curing time of assembled solution is 24h;
The aluminum magnesium alloy substrate is immersed in assembles 15min in the assembled solution, be heated to 160 ℃ then and solidify 10min; Solidify to accomplish to assemble for the first time afterwards and accomplish, and then assemble twice;
LDPE is immersed in assembles 5min in the assembled solution, be heated to branch then and solidify 10min for 90 ℃; Solidify to accomplish to assemble for the first time afterwards and accomplish, and then assemble twice;
Respectively at aluminum magnesium alloy substrate surface and the surperficial high molecular nanometer film that forms about 17nm of LDPE;
The spraying of step 3) organo-peroxide and cocuring agent:
In the aluminum magnesium alloy substrate surface spraying concentration that forms the high molecular nanometer film is 3.5% the organo-peroxide and the mixing solutions of cocuring agent;
Organo-peroxide is: Di Cumyl Peroxide 99, concentration are 3.5%; Cocuring agent be between the penylene bismaleimides, concentration is 3.5%; Solvent acetone.
The step 4) warming and pressurizing is bonding:
With the aluminum magnesium alloy substrate surface that sprayed organo-peroxide and cocuring agent with put into thermocompressor after LDPE contacts, be 7MPa at pressure, temperature be 140 ℃ with condition under compress 5min, naturally cool to room temperature after the taking-up.
Under 20 ℃ of constant temperatures, measure the stripping strength of bonding sample through Elongation test.Test result shows that the stripping strength of bond reaches 5.2KN/m
2, and observed the destruction of Vilaterm face.
Embodiment 9
Treat that bonding metal parts is the aluminum magnesium alloy substrate that is of a size of 50 * 30 * 0.3 (mm), treat that bonding resin material is acrylonitrile-butadiene-styrene resin (ABS), realize fastening bonding through following steps:
Step 1): pre-treatment
At first, use the pure acetone solvent respectively, LDPE is carried out ultrasonic washing 15min with absolute ethyl alcohol to the aluminum-copper alloy substrate, dry after the washing;
Then, carry out oil removal treatment with the aqueous solution of 10%SK-144 alkaline solution on 75 ℃ of surfaces to the aluminum-copper alloy substrate, drying is also carried out to it in the flushing with clean water surface;
With low-temperature plasma electrical source Corona discharge Treatment 15s is carried out on the surface and the ABS surface of aluminum-copper alloy substrate again.
Step 2): surface and ABS surface in the aluminum-copper alloy substrate are self-assembled into the high molecular nanometer film:
The solvent of self-assembly solution is an absolute ethyl alcohol: water=80: 20, and the alkoxysilane compound containing trialkylsilyl group in molecular structure that has reactive sulfydryl is:
NaS-(CH
2)
8-Si-CH
2-(OC
2H
5)
2
Concentration is 3mmol/L; The curing time of assembled solution is 24h;
The aluminum-copper alloy substrate is immersed in assembles 10min in the assembled solution, be heated to 160 ℃ then and solidify 5min; Solidify to accomplish to assemble for the first time afterwards and accomplish, and then assemble twice;
ABS is immersed in assembles 5min in the assembled solution, be heated to branch then and solidify 20min for 100 ℃; Solidify to accomplish to assemble for the first time afterwards and accomplish, and then assemble twice;
Respectively at aluminum-copper alloy substrate surface and the surperficial high molecular nanometer film that forms about 15nm of ABS;
The spraying of step 3) organo-peroxide and cocuring agent:
In the aluminum-copper alloy substrate surface spraying concentration that forms the high molecular nanometer film is 3.5% the organo-peroxide and the mixing solutions of cocuring agent;
Organo-peroxide is: BPO, concentration are 3.5%; Cocuring agent be between the penylene bismaleimides, concentration is 3.5%; Solvent is an acetone.
The step 4) warming and pressurizing is bonding:
With the aluminum magnesium alloy substrate surface that sprayed organo-peroxide and cocuring agent with put into thermocompressor after ABS contacts, be 6MPa at pressure, temperature be 100 ℃ with condition under compress 1min, naturally cool to room temperature after the taking-up.
Under 20 ℃ of constant temperatures, measure the stripping strength of bonding sample through Elongation test; Test result shows that the stripping strength of bond reaches 5.2KN/m
2, and observed the destruction of Vilaterm face.
Claims (6)
1. the surperficial and bonding method of resin material of aluminum or aluminum alloy is characterized in that, may further comprise the steps:
1) will treat that respectively bonding aluminum or aluminum alloy surface and resin material are immersed in the self-assembly solution, are self-assembled into the high molecular nanometer film in its surface;
The solvent of described self-assembly solution is the ethanol of volume(tric)fraction 75～95%, and solute is the alkoxysilane compound containing trialkylsilyl group in molecular structure that has reactive sulfydryl, and its concentration is 1.0～10.0mmol/L;
The processing condition that are self-assembled into the high molecular nanometer film are:
After treating that self-assembly solution is heated, 5～20min is solidified in the aluminum or aluminum alloy surface under 120～160 ℃ of temperature, and resin material solidifies 5～20min under 90～120 ℃ of temperature, and each self-assembly time is 10～30min, self-assembly 1～5 time;
2) surface is formed bonding the aluminum or aluminum alloy surface and the resin material treated of the thick high molecular nanometer film of 10～40nm; The mixing solutions of spraying organo-peroxide and cocuring agent; Wherein, the mass ratio of organo-peroxide and cocuring agent is 1: 1～1.2, and its mass concentration is 1～5%; Described cocuring agent is a bismaleimides;
3) aluminum or aluminum alloy surface that treating of crossing of spray treatment is bonding and after resin material contacts, putting into behind the thermocompressor at pressure is that 5～15MPa, temperature are to compress 1～5min under 90～180 ℃ the condition, naturally cools to room temperature after the taking-up.
2. aluminum or aluminum alloy as claimed in claim 1 surface and the bonding method of resin material is characterized in that the described alkoxysilane compound containing trialkylsilyl group in molecular structure that has reactive sulfydryl is:
Wherein, R
1Be one of following functional group:
H、CH
3、C
2H
5、n-C
3H
7、CH
2＝CHCH
2、n-C
4H
9、C
6H
5、n-C
6H
13、n-C
8H
17、i-C
8H
17；
R
2Be one of following functional group:
CH
2CH
2、CH
2CH
2CH
2、CH
2CH
2CH
2CH
2CH
2、CH
2CH
2SCH
2CH
2、
CH
2CH
2CH
2SCH
2CH
2CH
2、CH
2CH
2NHCH
2CH
2CH
2、
CH
2CH
2OCONHCH
2CH
2CH
2、CH
2CH
2NHCONHCH
2CH
2CH
2；
X is one of following functional group:
H、CH
3、C
2H
5、n-C
3H
7、i-C
3H
7、n-C
4H
9、i-C
4H
9、t-C
4H
9；
Y is one of following functional group:
CH
3O、C
2H
5O、n-C
3H
7O、i-C
3H
7O、n-C
4H
9O、i-C
4H
9O、t-C
4H
9O；
M is one of following atom:
Li、Na、K；
N described in the functional group, i, t are respectively: just, different, uncle.
3. aluminum or aluminum alloy as claimed in claim 1 surface and the bonding method of resin material is characterized in that the described alkoxysilane compound containing trialkylsilyl group in molecular structure that has reactive sulfydryl is:
Z-R-SiX
3-nY
n；
Wherein, Z is one of following functional group:
SH、SNa；
R is one of following functional group:
n-C
3H
6、n-C
8H
16；
X is one of following functional group:
H、CH
3、n-C
3H
7；
Y is one of following functional group:
CH
3O、C
2H
5O；
N described in the functional group is for just.
4. aluminum or aluminum alloy as claimed in claim 1 surface and the bonding method of resin material is characterized in that described duraluminum is aluminum magnesium alloy, aluminium-zinc alloy, aluminum-copper alloy, alumal or aluminum-manganese-iron alloy.
5. aluminum or aluminum alloy as claimed in claim 1 surface and the bonding method of resin material is characterized in that described organo-peroxide is Di Cumyl Peroxide 99 or BPO.
6. aluminum or aluminum alloy as claimed in claim 1 surface and the bonding method of resin material is characterized in that described resin material is: high density polyethylene(HDPE), new LDPE (film grade), Vestolen PP 7052 or acrylonitrile-butadiene-styrene resin.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102190796A CN101712765B (en) | 2009-11-20 | 2009-11-20 | Method for bonding aluminum or aluminum alloy surface with resin material |
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| CN101914797B (en) * | 2010-08-11 | 2012-07-11 | 西北农林科技大学 | Method for preparing composite nano film on metal surface |
| CN102358946B (en) * | 2011-08-05 | 2013-11-13 | 华南理工大学 | Preparation method for metal material surface antifriction and antiwear nano-composite film |
| CN103525317B (en) * | 2013-10-10 | 2014-10-15 | 青岛科技大学 | Method for indirectly fixing polymer thin sample to ultra-thin slicer sample holder |
| CN104742312A (en) * | 2014-11-12 | 2015-07-01 | 深圳富泰宏精密工业有限公司 | Preparation method of heterogeneous material composition and composition prepared by adopting method |
| CN105441965A (en) * | 2015-12-01 | 2016-03-30 | 烟台柳鑫新材料科技有限公司 | Aluminum foil for cover plate and processing method for aluminum foil |
| CN106905863A (en) * | 2015-12-23 | 2017-06-30 | 上海邦中高分子材料有限公司 | A kind of fiberglass surfacing method Nian Jie with resin material |
| CN111057089B (en) * | 2019-12-19 | 2023-06-02 | 湖北新蓝天新材料股份有限公司 | Adhesive and preparation method thereof |
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