CN101830098B - Polymer-matrix composite material with super-hydrophobic surface and preparation method thereof - Google Patents
Polymer-matrix composite material with super-hydrophobic surface and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of a super-hydrophobic composite material and a preparation method thereof and specifically discloses a polymer-matrix composite material with a super-hydrophobic surface and a preparation method thereof. The polymer-matrix composite material comprises a composite material body and a super-hydrophobic coating coated thereon, wherein, the composite material body is a carbon fiber or glass fiber reinforced composite material, and a microgranitic structure with the diameter of 10 mu m-30mu m is distributed on the super-hydrophobic coating; and the contact angle between the surface of the super-hydrophobic coating and water is 150-160 degrees, and the roll angle of water drops on the surface is below 10 degrees. The preparation method comprises the following steps: firstly preprocessing the surface of the composite material body; painting and flattening a resin system on the surface; spraying metallic oxide nano-powder on the surface of the resin system; and finally heating and curing, and then self-assembling in stearic acid ethanol solution or other similar solutions to obtain the composite material. The polymer-matrix composite material of the invention has the advantages of strong self-cleanness, strong anti-moisture absorption property, strong anti-freezing property, long service life, stable hydrophobic property and the like.
Description
Technical field
The present invention relates to a kind of composite and preparation method thereof, relate in particular to a kind of process super-hydrophobic composite of handling and preparation method thereof that comes to the surface.
Background technology
Polymer matrix composite has received widely and having paid close attention to because of it has characteristics such as designability, specific strength are high, in light weight, in each association areas such as blade of wind-driven generator, big aircrafts very important application is arranged all.Yet; Present business-like polymer matrix composite surface does not have self-cleaning property, and long-term out of doors the use is prone to the accumulation dust, influences attractive in appearance; Splash on the polymer matrix composite surface and when in time not wiping, tend to stay tangible pollution vestige on the surface when sewage drips.In addition, a lot of epoxy resin-base composite materials all have the certain moisture characteristic, tend to cause mechanical strength to reduce after the moisture absorption and influence serviceability.Therefore, develop the polymer matrix composite that has water proofing property and self-cleaning property simultaneously concurrently and have very important using value and practical significance.
In recent years, inspired by " lotus leaf effect ", become new material and forward position, sufacing field research topic greater than 150 °, roll angle less than 5 ° super hydrophobic surface with water contact angle.The characteristic feature of super hydrophobic surface is: when light water or sewage drip to the surface, can form the glistening spherical globule; The globule can not stably stop at super hydrophobic surface; Slight is uneven perhaps under the effect of gentle breeze; The globule can tumble fast at once and not stay any vestige, can also take away all contaminations of surface deposition simultaneously, and this makes super hydrophobic surface not only have very strong self-cleaning property; Can also not receive the influence of water and keep long-term drying, thereby avoid polymer matrix composite in wet environment, to descend because of moisture absorption causes performance.Yet; Also there is not relevant report at present both at home and abroad about polymer matrix composite super hydrophobic surface and technology of preparing thereof; Therefore the super hydrophobic surface technology is extended the polymer matrix composite field that is applied to, significant to the performance of optimizing polymer matrix composite.
Summary of the invention
The technical problem that the present invention will solve is the deficiency that overcomes prior art; Provide that a kind of self-cleaning property is splendid, anti-moisture absorption property is strong, anti-freezing performance is strong, long service life, the stable polymer matrix composite with super hydrophobic surface of hydrophobic performance, and the preparation method of a kind of simple to operate, convenient in application, cost is little, industrialization prospect the is wide polymer matrix composite with super hydrophobic surface also is provided.
For solving the problems of the technologies described above; The technical scheme that the present invention proposes is a kind of polymer matrix composite with super hydrophobic surface; Said polymer matrix composite comprises the super-hydrophobic coat that applies on composite body and the composite body; Said composite body is carbon fiber or glass fibre reinforced composion, is distributed with the little flower-like structure of diameter at 10 μ m～30 μ m on the said super-hydrophobic coat; Said super-hydrophobic coat surface is 150 °～160 ° with the contact angle of water, and water droplet is below 10 ° in the roll angle on said super-hydrophobic coat surface.
In the above-mentioned technical scheme; Said composite body can be existing known various types of carbon fibers or glass fibre reinforced composion, for example carbon fiber or fibre-glass reinforced polyester based composites, carbon fiber or glass fiber reinforced polyester urethano composite etc.Through our experiment, the matrix material of said composite body is preferably the epoxy resin compounds, because epoxy resin is easy to get relatively, cost is lower, uses wider.
In the above-mentioned technical scheme; The host material of said super-hydrophobic coat mainly is meant the material as binding agent; The binding agent that can super-hydrophobic coat and composite body effectively be combined into one, so known all can being suitable for of those skilled in that art at the binding agent that composite material surface plays better bond effect.Preferably; The host material of said super-hydrophobic coat should be identical with the matrix material of composite body; Promptly when the matrix material of said composite body is preferably epoxy resin compounds (or polyesters compound); The host material of said super-hydrophobic coat also is preferably epoxy resin compounds (or polyesters compound), because it can not only reach bond effect preferably, and can make polymer matrix composite keep good whole property and homogeneity.
In above-mentioned each technical scheme, the thickness of said super-hydrophobic coat is preferably 20 μ m～3mm.The main component of the little flower-like structure that distributes on the said super-hydrophobic coat is the mixture that metallic oxide nano powder and the self assembly of stearic acid ethanolic solution form, but is not limited to the combination of metallic oxide nano powder and stearic acid ethanolic solution.In fact, said stearic acid ethanolic solution also the ethanolic solution of ethanolic solution or the 17 fluorine trimethoxy Ethoxysilanes of available perfluorinated aliphatic acid substitute.Said metallic oxide nano powder is preferably cupric oxide nanometer power, bitter earth nano powder or zinc oxide nano-powder; Because the preparation of these several kinds of powders is simple; Wide material sources, cost is lower, but is not limited to these three kinds; The metal oxide that can carry out self assembly with stearic acid ethanolic solution or perfluorinated aliphatic acid ethanolic solution or 17 fluorine trimethoxy Ethoxysilane ethanolic solutions etc. well known in the art is also applicable to the present invention, for example calcium oxide, zirconia etc.The particle diameter of said metallic oxide nano powder is preferably 20nm～1000nm, because through our experiment repeatedly, and the size of metallic oxide nano powder or too mostly be difficult to form super hydrophobic surface.
As a total technical conceive; The present invention also provides a kind of preparation method with polymer matrix composite of super hydrophobic surface; May further comprise the steps: at first; Take carbon fiber or glass fibre reinforced composion as the composite body, and polished and clean in the surface of this composite body; Take the resin system of forming by binding agent and curing agent, with surface and the strickling of this resin system brushing at said composite body; Then, take metallic oxide nano powder and it evenly is sprayed on the good resin system surface of brushing; Spraying is carried out vacuum solidification with whole material system after accomplishing; Place the ethanolic solution of stearic acid ethanolic solution or perfluorinated aliphatic acid or the ethanolic solution of 17 fluorine trimethoxy Ethoxysilanes to carry out self assembly the semi-finished product after the vacuum solidification at last, obtain having the polymer matrix composite of super hydrophobic surface after self assembly is accomplished.
Among the preparation method of above-mentioned polymer matrix composite with super hydrophobic surface; Said metallic oxide nano powder is preferably the cupric oxide nanometer power of particle diameter at 20nm～1000nm; The concrete preparation method of said cupric oxide nanometer power can for: at first; Getting mol ratio is 1: 2 copper chloride and NaOH, and be dissolved in the water the respectively copper chloride solution of formation 0.01～4mol/L and the sodium hydroxide solution of 0.01～4mol/L; Then; Said copper chloride solution and sodium hydroxide solution are mixed; In mixed solution, drip polyethylene glycol (mixed solution of general 2L drips 10 μ L～80 μ L and gets final product); Again this solution is placed under 80 ℃～120 ℃ the condition and heat 1h～5h, filter, wash (3～6 times get final product) then, the atrament in the filter residue is carried out dry back (dry 3h～10h gets final product in 100 ℃～120 ℃ the baking oven) obtain cupric oxide nanometer power.Said cupric oxide nanometer power is not limited to the product that above-mentioned method for optimizing prepares, and the particle diameter that adopts any other known method to prepare all can be realized the object of the invention at the cupric oxide nanometer power of 20nm～1000nm.
Among the preparation method of above-mentioned polymer matrix composite with super hydrophobic surface, said metallic oxide nano powder can also be magnesia or the zinc oxide nano-powder of particle diameter at 20nm～1000nm.The preparation method of this magnesia or zinc oxide nano-powder and the preparation method of above-mentioned cupric oxide powder are basic identical; Only need with the raw material copper chloride correspondingly replace with magnesium chloride, zinc chloride gets final product; What but prepare at last according to the preparation method of above-mentioned cupric oxide nanometer power is the presoma of magnesia and zinc oxide; Need just can obtain bitter earth nano powder and zinc oxide nano-powder with this presoma at 250 ℃～500 ℃ temperature lower calcination 3h～10h at last.
Among the preparation method of above-mentioned polymer matrix composite with super hydrophobic surface; The matrix material of said composite body is preferably epoxy resin compounds or polyesters compound; Said matrix material is identical with the binder material of said resin system, and said composite body preferably adopts the vacuum molding method to prepare.Yet; Compound mass of the present invention is not limited to above-mentioned two types matrix material; Also be not limited to the prepared composite that obtains of above-mentioned preferred vacuum mold platen press, the carbon fiber of any other types well known in the art or prepared by other or glass fibre reinforced composion (for example existing hand is stuck with paste the fibre reinforced composites of preparations such as method, resin transfer moulding method or injection moulding) all can be used for the method for preparing polymer matrix composite with super hydrophobic surface of the present invention.
Among the preparation method of above-mentioned polymer matrix composite with super hydrophobic surface, the said temperature that is heating and curing preferably is controlled at 80 ℃～120 ℃, and the said time that is heating and curing is preferably 3h～6h.
Among the preparation method of above-mentioned polymer matrix composite with super hydrophobic surface, the mass concentration of the ethanolic solution of the ethanolic solution of said stearic acid ethanolic solution or perfluorinated aliphatic acid or 17 fluorine trimethoxy Ethoxysilanes all is preferably 0.5%～5%; The time of said self assembly is preferably 1h～5h.
Compared with prior art, the invention has the advantages that: the polymer matrix composite with super hydrophobic surface of the present invention has fabulous self-cleaning property, and the performance that can avoid polymer matrix composite in wet environment, to cause because of moisture absorption descends; Meanwhile; On polymer matrix composite, make up super hydrophobic surface and can also effectively improve the anti-freezing performance of its waterproof; Its anti-freezing performance is much higher than the non-super hydrophobic material with same composition and character; These characteristics all help increasing substantially the serviceability of polymer matrix composite, prolong its service life.The superhydrophobic property of the polymer matrix composite with super hydrophobic surface of the present invention is stable, is that 0 ℃～40 ℃, relative humidity are to place 3 months in 20%～90% the environment in temperature range, and superhydrophobic property does not change.
In addition; The present invention also provides a kind of preparation method simple and that be easy to industrialization to prepare the polymer matrix composite with super hydrophobic surface of the present invention; This preparation method not only operating procedure is simple, favorable reproducibility, and need not any expensive device; Do not need the complex chemical treatment process yet, have wide industrial applications prospect.
Description of drawings
Polymer matrix composite with super hydrophobic surface surperficial sem photograph of Fig. 1 for making in the embodiment of the invention 1.
Fig. 2 is the polymer matrix composite surface with super hydrophobic surface that makes in the embodiment of the invention 1 contact angle resolution chart with water.
Fig. 3 is the polymer matrix composite surface with super hydrophobic surface that makes in the embodiment of the invention 2 contact angle resolution chart with water.
Fig. 4 is the polymer matrix composite surface with super hydrophobic surface that makes in the embodiment of the invention 3 contact angle resolution chart with water.
Fig. 5 is the polymer matrix composite surface with super hydrophobic surface that makes in the embodiment of the invention 4 contact angle resolution chart with water.
Fig. 6 is the polymer matrix composite surface with super hydrophobic surface that makes in the embodiment of the invention 5 contact angle resolution chart with water.
The specific embodiment
Embodiment 1
A kind of polymer matrix composite with super hydrophobic surface of the present invention as shown in Figure 1; This polymer matrix composite comprises the super-hydrophobic coat that applies on composite body and the composite body; The composite body is a carbon cloth reinforced epoxy based composites; The thickness of super-hydrophobic coat is 30 μ m, is distributed with the little flower-like structure (see figure 1) of diameter at 10 μ m～30 μ m on this super-hydrophobic coat; The host material of super-hydrophobic coat is an epoxy resin; The main component of little flower-like structure is the mixture that burning copper nano body and stearic acid ethanolic solution (or ethanolic solution of the ethanolic solution of perfluorinated aliphatic acid or 17 fluorine trimethoxy Ethoxysilanes) self assembly form; The particle diameter of this cupric oxide nanometer power is 20nm～100nm, and average grain diameter is about 60nm.This super-hydrophobic coat surface is 156 ° ± 1.8 ° (see figure 2)s with the contact angle of water, and water droplet is 4 ° in the roll angle on super-hydrophobic coat surface.
The polymer matrix composite with super hydrophobic surface of above-mentioned present embodiment specifically is to adopt following method step to prepare:
1. the preparation of cupric oxide nanometer power
At first; Take by weighing 13.5g copper chloride and 8g NaOH; And be dissolved in formation copper chloride solution and sodium hydroxide solution in the 1L water respectively, and then copper chloride solution and sodium hydroxide solution are mixed, in mixed solution, drip the polyethylene glycol of 10 μ L; Again this solution is placed under 80 ℃ the condition and heat 1h; Solution after will heating then filters and washs three time, places the atrament on the filter paper 120 ℃ the dry 3h of baking oven again, obtains the cupric oxide nanometer power that average grain diameter is about 60nm.
2. the preparation of composite body (die pressing)
2.1 material is prepared: take carbon cloth, and be cut into 10cm * 15cm size, be ready to Composite Preparation and use mould, wait until subsequent use; Take by weighing 20g E51 type epoxide-resin glue and 2g diethylenetriamine, obtain basic resin system after stirring;
2.2 lay applies: mould is polished and coated releasing agent; The carbon cloth that cuts is positioned on the processing release paper; On carbon cloth, coat the basic resin system for preparing again; Then another piece carbon cloth is covered on it, three times so repeatedly (3 times～10 times all can) obtain the carbon fiber/epoxy resin preform;
2.3 mold pressing: the carbon fiber/epoxy resin preform that obtains in the step 2.2 is positioned in the mould; (solidify 3h (3h～20h), slowly obtain tabular composite body after the cooling under 0.1MPa～0.6MPa), 80 ℃ the temperature conditions at the pressure of 0.5MPa.
3. the preparation that has the polymer matrix composite of super hydrophobic surface
3.1 surface preparation: the tabular composite body surface to preparation in the above-mentioned steps 2 is polished with sand paper, to remove the defective on surface, blows off with the impurity such as dust of hair dryer with the surface then, and is subsequent use;
3.2 gluing: take by weighing 10g E51 epoxide-resin glue and 0.8g diethylenetriamine, after mixing the coating resin system for preparing is brushed through above-mentioned pretreated composite body surface equably, and use doctor blade;
3.3 dust: the cupric oxide nanometer power for preparing in the above-mentioned steps 1 is sprayed on equably on the glue-line of composite body surface;
3.4 self assembly: the whole composite system after will dusting is placed in the vacuum drying chamber; Under 80 ℃ of temperature, solidifying 3h (3h～6h all can) back takes out; Self assembly 1h in 1% stearic acid ethanolic solution then obtains the polymer matrix composite with super hydrophobic surface of present embodiment.
Sem test is the result show; (as shown in Figure 1) formed by a large amount of " little flower " shape structures in the polymer matrix composite super-hydrophobic coat surface that the present embodiment method prepares; The contact angle test result shows that this super-hydrophobic coat surface and the contact angle of water are 156 ° ± 1.8 °, and the super-hydrophobic coat surface is 4 ° with the roll angle of water.
Embodiment 2
A kind of polymer matrix composite with super hydrophobic surface of the present invention; This polymer matrix composite comprises the super-hydrophobic coat that applies on composite body and the composite body; The composite body is a carbon cloth reinforced epoxy based composites; The thickness of super-hydrophobic coat is 50 μ m, is distributed with the little flower-like structure of diameter at 10 μ m～30 μ m on this super-hydrophobic coat; The host material of super-hydrophobic coat is an epoxy resin; The main component of little flower-like structure is the mixture that burning copper nano body and the self assembly of stearic acid ethanolic solution form; The particle diameter of this cupric oxide nanometer power is 20nm～100nm, and average grain diameter is about 70nm.This super-hydrophobic coat surface is 155 ° ± 1.9 ° (see figure 3)s with the contact angle of water, and water droplet is 5 ° in the roll angle on super-hydrophobic coat surface.
The polymer matrix composite with super hydrophobic surface of above-mentioned present embodiment specifically is to adopt following method step to prepare:
1. the preparation of cupric oxide nanometer power
At first; Take by weighing 27g copper chloride and 16g NaOH; And be dissolved in formation copper chloride solution and sodium hydroxide solution in the 1L water respectively, and then copper chloride solution and sodium hydroxide solution are mixed, in mixed solution, drip the polyethylene glycol of 15 μ L; Again this solution is placed under 100 ℃ the condition and heat 2h; Solution after will heating then filters and washs three time, places the atrament on the filter paper 100 ℃ the dry 4h of baking oven again, obtains the cupric oxide nanometer power that average grain diameter is about 70nm.
2. the preparation of composite body (die pressing)
2.1 material is prepared: take carbon cloth, and be cut into 20cm * 20cm size, be ready to Composite Preparation and use mould, wait until subsequent use; Take by weighing 20g E51 type epoxide-resin glue and 2g diethylenetriamine, obtain basic resin system after stirring;
2.2 lay applies: mould is polished and coated releasing agent; The carbon cloth that cuts is positioned on the processing release paper; On carbon cloth, coat the basic resin system for preparing again; Then another piece carbon cloth is covered on it, five times so repeatedly, obtain the carbon fiber/epoxy resin preform;
2.3 mold pressing: the carbon fiber/epoxy resin preform that obtains in the step 2.2 is positioned in the mould, under the pressure of 0.3MPa, 80 ℃ temperature conditions, solidifies 5h, slowly obtain tabular composite body after the cooling.
3. the preparation that has the polymer matrix composite of super hydrophobic surface
3.1 surface preparation: the tabular composite body surface to preparation in the above-mentioned steps 2 is polished with sand paper, to remove the defective on surface, blows off with the impurity such as dust of hair dryer with the surface then, and is subsequent use;
3.2 gluing: take by weighing 20g E51 epoxide-resin glue and 1.6g diethylenetriamine, after mixing the coating resin system for preparing is brushed through above-mentioned pretreated composite body surface equably, and use doctor blade;
3.3 dust: the cupric oxide nanometer power for preparing in the above-mentioned steps 1 is sprayed on equably on the glue-line of composite body surface;
3.4 self assembly: the whole composite system after will dusting is placed in the vacuum drying chamber; After solidifying 4h under 80 ℃ of temperature, take out; Self assembly 2h in 1% stearic acid ethanolic solution then obtains the polymer matrix composite with super hydrophobic surface of present embodiment.
Sem test is the result show; The polymer matrix composite super-hydrophobic coat surface that the present embodiment method prepares is made up of a large amount of " little flower " shape structures; The contact angle test result shows that this super-hydrophobic coat surface and the contact angle of water are 155 ° ± 1.9 °, and the super-hydrophobic coat surface is 5 ° with the roll angle of water.
Embodiment 3
A kind of polymer matrix composite with super hydrophobic surface of the present invention; This polymer matrix composite comprises the super-hydrophobic coat that applies on composite body and the composite body; The composite body is a carbon cloth reinforced epoxy based composites; The thickness of super-hydrophobic coat is 30 μ m, is distributed with the little flower-like structure of diameter at 10 μ m～30 μ m on this super-hydrophobic coat; The host material of super-hydrophobic coat is an epoxy resin; The main component of little flower-like structure is the mixture that burning copper nano body and the self assembly of stearic acid ethanolic solution form; The particle diameter of this cupric oxide nanometer power is 20nm～100nm, and average grain diameter is about 50nm.This super-hydrophobic coat surface is 153 ° ± 1.7 ° (see figure 4)s with the contact angle of water, and water droplet is 4 ° in the roll angle on super-hydrophobic coat surface.
The polymer matrix composite with super hydrophobic surface of above-mentioned present embodiment specifically is to adopt following method step to prepare:
1. the preparation of cupric oxide nanometer power
At first; Take by weighing 13.5g copper chloride and 8g NaOH; And be dissolved in formation copper chloride solution and sodium hydroxide solution in the 1L water respectively, and then copper chloride solution and sodium hydroxide solution are mixed, in mixed solution, drip the polyethylene glycol of 15 μ L; Again this solution is placed under 120 ℃ the condition and heat 2h; Solution after will heating then filters and washs three time, places the atrament on the filter paper 120 ℃ the dry 3h of baking oven again, obtains the cupric oxide nanometer power that average grain diameter is about 50nm.
2. the preparation of composite body (die pressing)
2.1 material is prepared: take carbon cloth, and be cut into 15cm * 15cm size, be ready to Composite Preparation and use mould, wait until subsequent use; Take by weighing 20g E51 type epoxide-resin glue and 2g diethylenetriamine, obtain basic resin system after stirring;
2.2 lay applies: mould is polished and coated releasing agent; The carbon cloth that cuts is positioned on the processing release paper; On carbon cloth, coat the basic resin system for preparing again; Then another piece carbon cloth is covered on it, eight times so repeatedly, obtain the carbon fiber/epoxy resin preform;
2.3 mold pressing: the carbon fiber/epoxy resin preform that obtains in the step 2.2 is positioned in the mould, under the pressure of 0.6MPa, 80 ℃ temperature conditions, solidifies 4h, slowly obtain tabular composite body after the cooling.
3. the preparation that has the polymer matrix composite of super hydrophobic surface
3.1 surface preparation: the tabular composite body surface to preparation in the above-mentioned steps 2 is polished with sand paper, to remove the defective on surface, blows off with the impurity such as dust of hair dryer with the surface then, and is subsequent use;
3.2 gluing: take by weighing 10g E51 epoxide-resin glue and 0.8g diethylenetriamine, after mixing the coating resin system for preparing is brushed through above-mentioned pretreated composite body surface equably, and use doctor blade;
3.3 dust: the cupric oxide nanometer power for preparing in the above-mentioned steps 1 is sprayed on equably on the glue-line of composite body surface;
3.4 self assembly: the whole composite system after will dusting is placed in the vacuum drying chamber; After solidifying 6h under 80 ℃ of temperature, take out; Self assembly 5h in 1% stearic acid ethanolic solution then obtains the polymer matrix composite with super hydrophobic surface of present embodiment.
Sem test is the result show; The polymer matrix composite super-hydrophobic coat surface that the present embodiment method prepares is made up of a large amount of " little flower " shape structures; The contact angle test result shows that this super-hydrophobic coat surface and the contact angle of water are 153 ° ± 1.7 °, and the super-hydrophobic coat surface is 4 ° with the roll angle of water.
Embodiment 4
A kind of polymer matrix composite with super hydrophobic surface of the present invention; This polymer matrix composite comprises the super-hydrophobic coat that applies on composite body and the composite body; The composite body is a glass fabric reinforced epoxy based composites; The thickness of super-hydrophobic coat is 30 μ m, is distributed with the little flower-like structure of diameter at 10 μ m～30 μ m on this super-hydrophobic coat; The host material of super-hydrophobic coat is an epoxy resin; The main component of little flower-like structure is the mixture that burning copper nano body and the self assembly of stearic acid ethanolic solution form; The particle diameter of this cupric oxide nanometer power is 20nm～100nm, and average grain diameter is about 90nm.This super-hydrophobic coat surface is 157 ° ± 1.6 ° (see figure 5)s with the contact angle of water, and water droplet is 5 ° in the roll angle on super-hydrophobic coat surface.
The polymer matrix composite with super hydrophobic surface of above-mentioned present embodiment specifically is to adopt following method step to prepare:
1. the preparation of cupric oxide nanometer power
At first; Take by weighing 13.5g copper chloride and 8g NaOH; And be dissolved in formation copper chloride solution and sodium hydroxide solution in the 1L water respectively, and then copper chloride solution and sodium hydroxide solution are mixed, in mixed solution, drip the polyethylene glycol of 20 μ L; Again this solution is placed under 100 ℃ the condition and heat 1h; Solution after will heating then filters and washs three time, places the atrament on the filter paper 120 ℃ the dry 5h of baking oven again, obtains the cupric oxide nanometer power that average grain diameter is about 90nm.
2. the preparation of composite body (die pressing)
2.1 material is prepared: take glass fabric, and be cut into 20cm * 25cm size, be ready to Composite Preparation and use mould, wait until subsequent use; Take by weighing 20g E51 type epoxide-resin glue and 2g diethylenetriamine, obtain basic resin system after stirring;
2.2 lay applies: mould is polished and coated releasing agent; The glass fabric that cuts is positioned on the processing release paper; On glass fabric, coat the basic resin system for preparing again; Then another piece glass fabric is covered on it, five times so repeatedly, obtain glass fibre/epoxy resin preform;
2.3 mold pressing: the glass fibre that obtains in the step 2.2/epoxy resin preform is positioned in the mould, under the pressure of 0.3MPa, 80 ℃ temperature conditions, solidifies 5h, slowly obtain tabular composite body after the cooling.
3. the preparation that has the polymer matrix composite of super hydrophobic surface
3.1 surface preparation: the tabular composite body surface to preparation in the above-mentioned steps 2 is polished with sand paper, to remove the defective on surface, blows off with the impurity such as dust of hair dryer with the surface then, and is subsequent use;
3.2 gluing: take by weighing 30g E51 epoxide-resin glue and 2.4g diethylenetriamine, after mixing the coating resin system for preparing is brushed through above-mentioned pretreated composite body surface equably, and use doctor blade;
3.3 dust: the cupric oxide nanometer power for preparing in the above-mentioned steps 1 is sprayed on equably on the glue-line of composite body surface;
3.4 self assembly: the whole composite system after will dusting is placed in the vacuum drying chamber; After solidifying 5h under 80 ℃ of temperature, take out; Self assembly 2h in 1% stearic acid ethanolic solution then obtains the polymer matrix composite with super hydrophobic surface of present embodiment.
Sem test is the result show; The polymer matrix composite super-hydrophobic coat surface that the present embodiment method prepares is made up of a large amount of " little flower " shape structures; The contact angle test result shows that this super-hydrophobic coat surface and the contact angle of water are 157 ° ± 1.6 °, and the super-hydrophobic coat surface is 5 ° with the roll angle of water.
Embodiment 5
A kind of polymer matrix composite with super hydrophobic surface of the present invention; This polymer matrix composite comprises the super-hydrophobic coat that applies on composite body and the composite body; The composite body is a glass fabric reinforced epoxy based composites; The thickness of super-hydrophobic coat is 60 μ m, is distributed with the little flower-like structure of diameter at 10 μ m～30 μ m on this super-hydrophobic coat; The host material of super-hydrophobic coat is an epoxy resin; The main component of little flower-like structure is the mixture that burning copper nano body and the self assembly of stearic acid ethanolic solution form; The particle diameter of this cupric oxide nanometer power is 20nm～100nm, and average grain diameter is about 65nm.This super-hydrophobic coat surface is 154 ° ± 2 ° (see figure 6)s with the contact angle of water, and water droplet is 5 ° in the roll angle on super-hydrophobic coat surface.
The polymer matrix composite with super hydrophobic surface of above-mentioned present embodiment specifically is to adopt following method step to prepare:
1. the preparation of cupric oxide nanometer power
At first; Take by weighing 27g copper chloride and 16g NaOH, and be dissolved in formation copper chloride solution and sodium hydroxide solution in the 1L water respectively, then copper chloride solution and sodium hydroxide solution are mixed; In mixed solution, drip the polyethylene glycol of 25 μ L; This solution is placed under 100 ℃ the condition again and heat 1h, the solution after will heating then filters, and washs six times; Place the atrament on the filter paper 100 ℃ the dry 5h of baking oven again, obtain the cupric oxide nanometer power that average grain diameter is about 65nm.
2. the preparation of composite body (die pressing)
2.1 material is prepared: take glass fabric, and be cut into 10cm * 10cm size, be ready to Composite Preparation and use mould, wait until subsequent use; Take by weighing 20g E51 type epoxide-resin glue and 2g diethylenetriamine, obtain basic resin system after stirring;
2.2 lay applies: mould is polished and coated releasing agent; The glass fabric that cuts is positioned on the processing release paper; On glass fabric, coat the basic resin system for preparing again; Then another piece glass fabric is covered on it, three times so repeatedly, obtain glass fibre/epoxy resin preform;
2.3 mold pressing: the glass fibre that obtains in the step 2.2/epoxy resin preform is positioned in the mould, under the pressure of 0.5MPa, 80 ℃ temperature conditions, solidifies 5h, slowly obtain tabular composite body after the cooling.
3. the preparation that has the polymer matrix composite of super hydrophobic surface
3.1 surface preparation: the tabular composite body surface to preparation in the above-mentioned steps 2 is polished with sand paper, to remove the defective on surface, blows off with the impurity such as dust of hair dryer with the surface then, and is subsequent use;
3.2 gluing: take by weighing 20g E51 epoxide-resin glue and 1.6g diethylenetriamine, after mixing the coating resin system for preparing is brushed through above-mentioned pretreated composite body surface equably, and use doctor blade;
3.3 dust: the cupric oxide nanometer power for preparing in the above-mentioned steps 1 is sprayed on equably on the glue-line of composite body surface;
3.4 self assembly: the whole composite system after will dusting is placed in the vacuum drying chamber; After solidifying 5h under 80 ℃ of temperature, take out; Self assembly 3h in 1% stearic acid ethanolic solution then obtains the polymer matrix composite with super hydrophobic surface of present embodiment.
Sem test is the result show; The polymer matrix composite super-hydrophobic coat surface that the present embodiment method prepares is made up of a large amount of " little flower " shape structures; The contact angle test result shows that this super-hydrophobic coat surface and the contact angle of water are 154 ° ± 2 °, and the super-hydrophobic coat surface is 5 ° with the roll angle of water.
Claims (5)
1. preparation method with polymer matrix composite of super hydrophobic surface; May further comprise the steps: at first; Take carbon fiber or glass fibre reinforced composion as the composite body, and polished and clean in the surface of this composite body; Take the resin system of forming by binding agent and curing agent, with surface and the strickling of this resin system brushing at said composite body; Then, take metallic oxide nano powder and it evenly is sprayed on the good resin system surface of brushing; Spraying after accomplishing is heating and curing whole material system; Semi-finished product after will being heating and curing at last place the ethanolic solution of stearic acid ethanolic solution or perfluorinated aliphatic acid or the ethanolic solution of 17 fluorine trimethoxy Ethoxysilanes to carry out self assembly, obtain having the polymer matrix composite of super hydrophobic surface after self assembly is accomplished.
2. the preparation method with polymer matrix composite of super hydrophobic surface according to claim 1; It is characterized in that; Said metallic oxide nano powder is the cupric oxide nanometer power of particle diameter at 20nm ~ 1000nm; The concrete preparation method of said cupric oxide nanometer power is: at first, get copper chloride and NaOH that mol ratio is 1:2, and be dissolved in the water the respectively copper chloride solution of formation 0.01 ~ 4mol/L and the sodium hydroxide solution of 0.01 ~ 4mol/L; Then; Said copper chloride solution and sodium hydroxide solution are mixed, in mixed solution, drip polyethylene glycol, this solution is placed under 80 ℃ ~ 120 ℃ the condition heat 1h ~ 5h again; Filter then, wash, the atrament in the filter residue is carried out obtaining cupric oxide nanometer power after the drying.
3. the preparation method with polymer matrix composite of super hydrophobic surface according to claim 1; It is characterized in that; The matrix material of said composite body is polyesters compound or epoxy resin compounds; Said matrix material is identical with the binder material of said resin system, and said composite body adopts the vacuum molding method to prepare.
4. according to claim 1 or 2 or 3 described preparation methods with polymer matrix composite of super hydrophobic surface, it is characterized in that the said temperature that is heating and curing is controlled at 80 ℃ ~ 120 ℃, the said time that is heating and curing is 3h ~ 6h.
5. according to claim 1 or 2 or 3 described preparation methods with polymer matrix composite of super hydrophobic surface; It is characterized in that the mass concentration of the ethanolic solution of the ethanolic solution of said stearic acid ethanolic solution or perfluorinated aliphatic acid or 17 fluorine trimethoxy Ethoxysilanes is 0.5% ~ 5%; The time of said self assembly is 1h ~ 5h.
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| CN102766269A (en) * | 2012-08-03 | 2012-11-07 | 上海长歌包装材料有限公司 | Epoxy resin with super-hydrophobic surface and preparation method for epoxy resin |
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| CN108372671B (en) * | 2018-02-06 | 2021-03-02 | 日丰企业（佛山）有限公司 | Hydrophobic material, inner-layer hydrophobic pipe and preparation method thereof |
| CN109822950B (en) * | 2019-01-25 | 2020-04-14 | 南京航空航天大学 | Polymer material with anti-icing function and integrated forming method thereof |
| CN110029488A (en) * | 2019-03-14 | 2019-07-19 | 新疆大学 | A kind of super-hydrophobic carbon-fiber film and preparation method thereof with nucleocapsid structure |
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