CN110181171A - Pass through the method for laser processing control polymer matrix composites surface hydrophilic and hydrophobic - Google Patents
Pass through the method for laser processing control polymer matrix composites surface hydrophilic and hydrophobic Download PDFInfo
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- CN110181171A CN110181171A CN201910443448.3A CN201910443448A CN110181171A CN 110181171 A CN110181171 A CN 110181171A CN 201910443448 A CN201910443448 A CN 201910443448A CN 110181171 A CN110181171 A CN 110181171A
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- polymer matrix
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/352—Working by laser beam, e.g. welding, cutting or boring for surface treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/16—Composite materials, e.g. fibre reinforced
Abstract
The present invention relates to a kind of methods by laser processing control polymer matrix composites surface hydrophilic and hydrophobic.This method comprises: carrying out surface cleaning to polymer matrix composites surface, surface attachments are removed；Laser emission is carried out to the polymer matrix composites surface under assist gas environment, the content of oxygen in intensity and auxiliary gas by controlling laser, the modified resin base composite material surface of different contact angles is obtained, to realize the control to polymer matrix composites surface hydrophilic and hydrophobic；Wherein, when oxygen content ratio changes from 0 to 100% in auxiliary gas, the contact angle on the polymer matrix composites surface is from 150 ° to 0 ° variations are greater than, and correspondingly, the polymer matrix composites surface changes from super-hydrophobicity to Superhydrophilic.The polymer matrix composites surface hydrophilic and hydrophobic stability of this method preparation is preferable, and without additional coating, and the change of composite material surface chemical property is smaller.
Description
Technical field
The present invention relates to technical field of material surface treatment, multiple by laser processing control resin base more particularly to one kind
The method of condensation material surface hydrophilic and hydrophobic.
Background technique
The hydrophilic and hydrophobic control of material is always the hot issue of many application fields, and hydrophilicity and hydrophobicity influences material surface
With the interaction between contactant (reinforcing material, surface covering, catalyst, solvent, the adsorbate of such as composite material), in turn
Influence application performance.Polymer matrix composites have that light-weight, modulus is high, specific strength is big, thermal expansion coefficient is low, thermal shock, resistance to
The series of advantages such as burn into absorbing is good, application cover the fields such as aerospace, automobile, strategic weapon.Resin base is multiple
Condensation material surface characteristic is applied to have a major impact, especially polymer matrix composites surface is cementing, coating, it is anti-freeze, from
Fields, the surface hydrophilicity and hydrophobicities such as cleaning have important meaning.
Existing close and distant water surface preparation method includes physical method and chemical method.Physical method is referred mainly to through cold plasma
The physical techniques such as body, radiation, coating, chemical method refer mainly to using chemical reagent or chemical reaction material surface is performed etching or
Grafting.During physical method surface is modified, normal pressure plasma surface processing technique is high with treatment effeciency, low energy consumption, equipment is simple
Etc. advantages.Suitable atmosphere is chosen, surface hydrophilic and hydrophobic surface can be prepared by adjusting discharge voltage and processing time.Disadvantage
It is that performance is unstable, there is timeliness.Passed through in chemical method using technologies such as corona treatment, surface grafting, chemical etchings
The group for introducing low-surface-energy or high surface energy achievees the purpose that surface hydrophobe.However, chemical method changes surfacing
Matter, certainly will change the chemical property of material surface, to influence service performance.Surface cladding process can not change matrix properties
In the case where obtain surface hydrophilicity and hydrophobicity, utilize the technologies such as chemical gas-phase method, electrophoretic deposition, physical sputtering and collosol and gel
One layer of hydrophilic and hydrophobic coating with certain bond strength can be formed on the surface of the material, so that it is modified to reach surface hydrophobe
Purpose.But surface cladding process is not particularly suited for polymer matrix composites surface itself and needs coating or the application neck such as cementing
Domain.
Therefore, it is based on the shortcomings of the prior art, is inventor provided a kind of multiple by laser processing control resin base
The method of condensation material surface hydrophilic and hydrophobic.
Summary of the invention
Demand for polymer matrix composites to surface hydrophilicity and hydrophobicity, the embodiment of the invention provides one kind by swashing
Polymer matrix composites surface may be implemented from super hydrophilic in the method for light machining control polymer matrix composites surface hydrophilic and hydrophobic
To super-hydrophobic controllable preparation, solve that hydrophilic and hydrophobic stabilizability in surface of the existing technology is poor and surface chemistry
The problem of performance is changed greatly, influences service performance.
The embodiment of the present invention proposes a kind of by laser machining control polymer matrix composites surface hydrophilic and hydrophobic
Method, this method comprises:
Step S110 carries out surface cleaning to polymer matrix composites surface, removes surface attachments；
Step S120 carries out laser emission to the polymer matrix composites surface under assist gas environment, passes through control
The content of oxygen, obtains the modified resin base composite material surface of different contact angles in the intensity and auxiliary gas of laser processed,
To realize the control to polymer matrix composites surface hydrophilic and hydrophobic；Wherein, when in auxiliary gas oxygen content ratio from 0
To when 100% variation, the contact angle on the polymer matrix composites surface changes from being greater than 150 ° to 0 °, correspondingly, the tree
Resin-based composite surface changes from super-hydrophobicity to Superhydrophilic.
Further, the polymer matrix composites be using carbon fiber as reinforcing material, using resin as basis material and
The carbon fiber enhancement resin base composite material being compounded to form, described matrix material use thermosetting resin, described matrix material packet
Include unsaturated poly-vinegar resin, epoxy resin, phenolic resin, bimaleimide resin or polyimide resin.
Further, in the step S120, using the laser process equipment with auxiliary blowing function, pass through laser
The beam mode coaxial with auxiliary gas carries out laser emission to the polymer matrix composites surface.
Further, the pulse width of the laser is 800fs~800ps, and wavelength is 800nm~2000nm, and power is
0.1w to 100w, frequency are 1kHZ~100kHZ, and the focal beam spot diameter of laser beam is 50 μm~500 μm.
Further, the auxiliary gas is the mixture of oxygen and nitrogen or oxygen and inert gas, wherein described
Inert gas is one of helium, neon, argon, krypton and xenon or a variety of.
Further, the auxiliary gas is coaxially blown out by the nozzle of laser beam with laser beam, air pressure for 0.1MPa~
0.5MPa。
Further, the resin after the step S120, using dehydrated alcohol or acetone to obtained hydrophilic and hydrophobic
Based composites carry out surface cleaning, and are dried up with cold wind.
Further, after the polymer matrix composites for obtaining hydrophilic and hydrophobic, deionized water is drawn using microsyringe, it will
It contacts or drops onto polymer matrix composites surface, and the test of static contact angle is then carried out with angle tester, based on contact
The size at angle judges the hydrophilic and hydrophobic of polymer matrix composites.
To sum up, the method for the invention by laser processing control polymer matrix composites surface hydrophilic and hydrophobic, utilizes control
Oxygen content and laser intensity can by the severe degree of laser and polymer matrix composites interaction in system auxiliary gas
With realize polymer matrix composites surface from super hydrophilic (0 ° of contact angle) to super-hydrophobic (150 ° of contact angle >) continuous controllable preparation,
Compared with physical method (cold plasma, radiation, coating etc.), stability is preferable, and without additional applicator.With chemical method (wait from
Daughter processing, surface grafting, chemical etching etc.) it compares, polymer matrix composites surface chemistry changes smaller.This method is outstanding
The demand of cementing, surface covering, anti-freeze, automatically cleaning to surface hydrophilicity and hydrophobicity that it is suitable for polymer matrix composites.In addition,
By auxiliary gas and laser surface modelling process in the present invention, control while to surface topography and hydrophilicity and hydrophobicity can be realized
System.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, will make below to required in the embodiment of the present invention
Attached drawing is briefly described, it should be apparent that, drawings described below is only some embodiments of the present invention, for
For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings other
Attached drawing.
Fig. 1 is a kind of method flow by laser processing control polymer matrix composites surface hydrophilic and hydrophobic of the invention
Figure.
Fig. 2 is that the super hydrophilic bismaleimide resin base that obtains after being processed by Laser Assisted Gas of the embodiment of the present invention 1 is compound
Material surface scanning electron microscope (SEM) photograph.
Fig. 3 is super hydrophilic bismaleimide resin based composites surface static contact angle (0 °) side view of embodiment 1.
Fig. 4 is the super-hydrophobic bismaleimide resin based composites table obtained after being processed by Laser Assisted Gas of embodiment 2
Surface scan electron microscope.
Fig. 5 is super-hydrophobic bismaleimide resin based composites surface static contact angle (153 °) side view of embodiment 2.
Specific embodiment
Embodiments of the present invention are described in further detail with reference to the accompanying drawings and examples.Following embodiment it is detailed
Thin description and attached drawing cannot be used to limit the scope of the invention for illustratively illustrating the principle of the present invention, i.e., of the invention
It is not limited to described embodiment, covers part, component and connection type under the premise of without departing from the spirit of the present invention
Any modification, replacement and improvement.
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.The application is described in detail below with reference to accompanying drawings and in conjunction with the embodiments.
Fig. 1 is by the method flow diagram of laser processing control polymer matrix composites surface hydrophilic and hydrophobic, such as Fig. 1 institute
Show, this method has included at least following steps S110~step S120:
Step S110 carries out surface cleaning to polymer matrix composites surface, removes surface attachments, obtain clean tree
Resin-based composite surface.
Step S120 carries out laser emission to the polymer matrix composites surface under assist gas environment, passes through control
The content of oxygen, obtains the modified resin base composite material surface of different contact angles in the intensity and auxiliary gas of laser processed,
To realize the control to polymer matrix composites surface hydrophilic and hydrophobic；Wherein, when in auxiliary gas oxygen content ratio from 0
To when 100% variation, the contact angle on the polymer matrix composites surface changes from being greater than 150 ° to 0 °, correspondingly, the tree
Resin-based composite surface changes from super-hydrophobicity to Superhydrophilic.
Above by the method for laser processing control polymer matrix composites surface hydrophilic and hydrophobic, oxygen in gas is assisted to contain
From 0 to 100%, polymer matrix composites surface from super-hydrophobic (150 ° of contact angle >) to super hydrophilic (0 ° of contact angle) connects amount ratio
Continuous variation, i.e., with the increase of oxygen content in auxiliary gas, polymer matrix composites surface contact angle gradually lowers.In addition, swashing
Certain surface roughness can be improved resin surface hydrophilicity and hydrophobicity after light and resin material interaction, and water-wetted surface is thick
Rugosity will increase contact area and infiltration during increasing, so that hydrophily is improved, and after hydrophobic surface roughening, due to connecing
The reduction of contact can further promote hydrophobicity.
Wherein, the polymer matrix composites refer to carbon fiber enhancement resin base composite material, are using carbon fiber as increasing
Strong material is compounded to form using resin as basis material, and the basis material of the polymer matrix composites uses thermosetting resin,
Described matrix material includes unsaturated poly-vinegar resin, epoxy resin, phenolic resin, bimaleimide resin or polyimides tree
Rouge.
In the step s 120, using the laser process equipment with auxiliary blowing function, using laser beam and auxiliary gas
Coaxial mode carries out laser emission to the polymer matrix composites surface.Pass through laser and polymer matrix composites phase interaction
Severe degree can obtain the modified resin base composite material surface of different contact angles.
Wherein, the pulse width of the laser is 800fs~800ps, and wavelength is 800nm~2000nm, power 0.1w
To 100w, frequency is 1kHZ~100kHZ, and the focal beam spot diameter of laser beam is 50 μm~500 μm.Assist gas be oxygen and
The mixed gas of nitrogen or oxygen and inert gas, oxygen proportion from 0 to 100%, inert gas include helium, neon, argon, krypton and
The gases such as xenon, using coaxial blowing method secondary process, specifically, auxiliary gas is coaxial by the nozzle and laser beam of laser beam
Blowout, coaxial air blowing air pressure are 0.1MPa-0.5MPa.Under assist gas environment, laser and polymer matrix composites phase interaction
With polymer matrix composites surface generates irreversible change after laser irradiation, to obtain the modified resin base of different contact angles
Composite material surface, in practice, with the severe degree of laser single sweep operation removal amount characterization interaction.
As a preferred implementation manner, after the step S120, can also using dehydrated alcohol or acetone to
The polymer matrix composites of the hydrophilic and hydrophobic arrived carry out surface cleaning, and are dried up with cold wind.
As another preferred embodiment, the polymer matrix composites of the dry hydrophilic and hydrophobic of surface cleaning are being obtained
Afterwards, deionized water is drawn using microsyringe, is contacted or dropped onto polymer matrix composites surface, is then tested with angle
Instrument carries out the test of static contact angle, and the size based on contact angle judges the hydrophilic and hydrophobic of polymer matrix composites.
Specifically, in order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, below by way of
Technical solution of the present invention is described in detail in embodiment 1 and embodiment 2.Experimental method described in following embodiments, such as nothing
Specified otherwise is conventional method；The reagent and material commercially obtain unless otherwise specified.
Embodiment 1:
The present embodiment provides a kind of by laser machining the method for controlling bismaleimide resin based composites surface hydrophilic and hydrophobic,
Super hydrophilic bismaleimide resin based composites surface can be prepared in this method, include the following steps:
(1) necessary cleaning is carried out to bismaleimide resin based composites surface, removes surface attachments, obtain clean pair
Horse resin based composites surface.
(2) using the picosecond laser process equipment with auxiliary blowing function, in auxiliary gas (oxygen content 100%)
Laser irradiation, laser pulse width 3ps, wavelength 1030nm are carried out to bismaleimide resin based composites surface under environment, power is
0.24W, frequency 75kHZ, focal beam spot diameter are 100 μm.It is processed using auxiliary gas and the coaxial blowing method of laser beam, gas
Body pressure be 0.1MPa, laser single parallel sweep bismaleimide resin based composites surface, 100 μm of sweep span.
(4) surface clean is carried out with dehydrated alcohol to the bismaleimide resin based composites surface after processing and is blown with cold wind
It is dry.
(5) deionized water of 4 μ L is drawn using microsyringe, the bismaleimide resin base after contacting or dropping onto processing is compound
Material surface makes aqueous contact material surface, and the test of static contact angle (CA) is then carried out with angle tester, and the water of test connects
Feeler is 0 °, obtains ultra-hydrophilic surface at this time, referring to figs. 2 and 3.
Embodiment 2:
The present embodiment provides a kind of by laser machining the method for controlling bismaleimide resin based composites surface hydrophilic and hydrophobic,
Super-hydrophobic bismaleimide resin based composites surface can be prepared, include the following steps:
(1) necessary cleaning is carried out to bismaleimide resin based composites surface, removes surface attachments, obtains clean ring
Epoxy resin-based composite surface.
(2) using the picosecond laser process equipment with auxiliary blowing function, in auxiliary gas (oxygen content 0%, nitrogen
Gas content is 100%) to carry out laser irradiation, laser pulse width 3ps, wavelength to bismaleimide resin based composites surface under environment
1030nm, power 0.24W, frequency 75kHZ, focal beam spot diameter are 100 μm.Using auxiliary gas with laser beam is coaxial blows
Gas mode is processed, gas pressure 0.1MPa, laser single sweep operation bismaleimide resin based composites surface.
(4) surface clean is carried out with dehydrated alcohol to the bismaleimide resin based composites surface after processing and is blown with cold wind
It is dry.
(5) deionized water of 4 μ L is drawn using microsyringe, the bismaleimide resin base after contacting or dropping onto processing is compound
Material surface makes aqueous contact material surface, and the test of static contact angle (CA) is then carried out with angle tester, and the water of test connects
Feeler is 153 °, obtains super hydrophobic surface at this time, referring to fig. 4 and Fig. 5.
The above description is only an example of the present application, is not restricted to the application.The scope of the present invention is not being departed from
In the case where to those skilled in the art, various changes and changes are possible in this application.It is all in spirit herein and
Any modification, equivalent replacement, improvement and so within principle, should be included within the scope of claims hereof.
Claims (8)
1. passing through the method for laser processing control polymer matrix composites surface hydrophilic and hydrophobic characterized by comprising
Step S110 carries out surface cleaning to polymer matrix composites surface, removes surface attachments；
Step S120 carries out laser emission to the polymer matrix composites surface under assist gas environment, is swashed by controlling
The content of oxygen, obtains the modified resin base composite material surface of different contact angles in the intensity and auxiliary gas of light, thus
Realize the control to polymer matrix composites surface hydrophilic and hydrophobic；Wherein, when auxiliary gas in oxygen content ratio from 0 to
When 100% variation, the contact angle on the polymer matrix composites surface changes from being greater than 150 ° to 0 °, correspondingly, the resin
Based composites surface changes from super-hydrophobicity to Superhydrophilic.
2. the method according to claim 1 by laser processing control polymer matrix composites surface hydrophilic and hydrophobic,
It is characterized in that, the polymer matrix composites are to be compounded to form using carbon fiber as reinforcing material using resin as basis material
Carbon fiber enhancement resin base composite material, described matrix material use thermosetting resin, described matrix material include unsaturation
Poly-vinegar resin, epoxy resin, phenolic resin, bimaleimide resin or polyimide resin.
3. the method according to claim 1 by laser processing control polymer matrix composites surface hydrophilic and hydrophobic,
It is characterized in that, in the step S120, using the laser process equipment with auxiliary blowing function, passes through laser beam and auxiliary
The coaxial mode of gas carries out laser emission to the polymer matrix composites surface.
4. the method according to claim 1 or 3 by laser processing control polymer matrix composites surface hydrophilic and hydrophobic,
It is characterized in that, the pulse width of the laser is 800fs~800ps, wavelength is 800nm~2000nm, and power arrives for 0.1w
100w, frequency are 1kHZ~100kHZ, and the focal beam spot diameter of laser beam is 50 μm~500 μm.
5. the method according to claim 1 or 3 by laser processing control polymer matrix composites surface hydrophilic and hydrophobic,
It is characterized in that, the auxiliary gas is the mixture of oxygen and nitrogen or oxygen and inert gas, wherein the indifferent gas
Body is one of helium, neon, argon, krypton and xenon or a variety of.
6. the method according to claim 3 by laser processing control polymer matrix composites surface hydrophilic and hydrophobic,
It is characterized in that, the auxiliary gas is coaxially blown out by the nozzle of laser beam with laser beam, and air pressure is 0.1MPa~0.5MPa.
7. the method according to claim 1 by laser processing control polymer matrix composites surface hydrophilic and hydrophobic,
It is characterized in that, after the step S120, using dehydrated alcohol or acetone to the resin base composite wood of obtained hydrophilic and hydrophobic
Material carries out surface cleaning, and is dried up with cold wind.
8. the method according to claim 1 by laser processing control polymer matrix composites surface hydrophilic and hydrophobic,
Be characterized in that, after obtaining the polymer matrix composites of hydrophilic and hydrophobic, using microsyringe draw deionized water, contacted or
Polymer matrix composites surface is dropped onto, the test of static contact angle is then carried out with angle tester, the size based on contact angle
Judge the hydrophilic and hydrophobic of polymer matrix composites.
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| CN110423523A (en) * | 2019-09-05 | 2019-11-08 | 中国航空制造技术研究院 | A kind of super-hydrophobic deicing composite coating and preparation method thereof |
| CN114406485A (en) * | 2022-02-25 | 2022-04-29 | 西南交通大学 | Preparation method of wear-resistant super-hydrophobic antibacterial surface in nitrogen atmosphere |
| CN114670430A (en) * | 2022-03-29 | 2022-06-28 | 吉林大学 | Method for carrying out wettability modification on polyarylether composite material |
| CN114769848A (en) * | 2022-03-01 | 2022-07-22 | 山东大学 | Processing method and application of striped hydrophilic-hydrophobic heterogeneous surface |
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