CN1739959A - A kind of interlayer composite material and preparation method thereof - Google Patents
A kind of interlayer composite material and preparation method thereof Download PDFInfo
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- CN1739959A CN1739959A CN 200510027914 CN200510027914A CN1739959A CN 1739959 A CN1739959 A CN 1739959A CN 200510027914 CN200510027914 CN 200510027914 CN 200510027914 A CN200510027914 A CN 200510027914A CN 1739959 A CN1739959 A CN 1739959A
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Abstract
The invention discloses a kind of interlayer composite material and preparation method thereof, this material be composite the layer with layer between accompany the functional material interlayer, described functional material interlayer is made of the one or more layers superfine fibre nonwoven cloth film that includes the function nano particle.Its preparation method is: earlier the function nano particle is dispersed in the polymer solution, adopts electrospinning process to prepare superfine fibre nonwoven cloth; Then be polymer solution as core matter solution, top layer perhaps with this solution, the composite ultrafine fiber nonwoven that adopts coaxial co spun technology to prepare to include the function nano particle, then, this functional nano-fiber nonwoven is inserted between the conventional composite constitute sandwich plate again.The prepared function interlayer composite material that goes out of the present invention has advantages such as thin thickness, in light weight, functional strong and structural behaviour excellence, the present invention has advantages such as preparation technology is simple, equipment cost is cheap, is particularly suitable for preparing the Aero-Space structural member.
Description
Technical field
The present invention relates to a kind of composite and preparation method thereof, specifically is a kind of incorporate composite of 26S Proteasome Structure and Function that includes functional composite ultrafine fiber nonwoven interlayer and preparation method thereof.
Background technology
Fibre reinforced composites have specific stiffness and specific strength height, and performance advantages such as light weight have been widely used in Aero-Space and other civil area.Along with increasing in carry-on application percentage, can satisfy the certain structure performance requirement except requiring fibre reinforced composites, the more important thing is also to require it to have some special function such as absorbing properties simultaneously.Conventional method generally is functional particles to be added to be prepared into the functional composite material structural member in the resin matrix again, or fortifying fibre is carried out surface modification or adopts odd-shaped cross section shape fiber etc., makes composite have specific function and bearing capacity.But, there is agglomeration usually in the functional particles that adds especially diameter tiny (as nanoscale) particle, and destroyed the adhesion strength of resin matrix and fortifying fibre to a certain extent, the mechanical property of structural member especially interlaminar shear strength there is considerable influence; Interface interaction between fiber and the matrix is carried out might influencing after function modified in the fortifying fibre surface, cause the mechanical properties decrease of composite; Though the profiled fibre mechanical property is excellent and material cost height and complicated process of preparation can be provided such as certain absorbing property.
Adopt the nanofiber of electrostatic spinning preparation to have outstanding features such as size is little, specific area is big.U.S. Pat 6265333B1 discloses a kind of application electrostatic spinning and has prepared high-performance poly benzimidazole nano-fiber film, introduces the intermediate interface of laminate again, can significantly improve the interlayer faults toughness and the whole anti-delamination ability of laminate.If in the solution of fiber Cheng Siqian, sneak into the function nano particle, perhaps use coaxial electrically spun technology (see that application number is 200310108130.9, name is called the Chinese invention patent of " coaxial compound continuous nano/micron fiber and preparation method thereof ") better, needed function nano particle is coated to polymer superfine fibre inside, again such superfine fibre is gathered into the interface layer that film is attached to composite, the structural member of making will have the structural behaviour and the functional characteristic of expection.
Summary of the invention
The object of the present invention is to provide a kind of preparation process simple, with low cost, have incorporate interlayer composite material of 26S Proteasome Structure and Function and preparation method thereof.
The function interlayer composite material that the present invention proposes is composited by superfine fibre nonwoven cloth film with specific function and conventional composite, and wherein the function of superfine fibre nonwoven cloth film is to realize by function nano particle wherein.
Described function nano particle can be one or more of following nano particle: 1) nano metal or alloy, 2) nano-oxide, 3) nano-carbide, 4) nano nitride, 5) nanometer conductive polymer, 6) other nano-ceramic powder etc.The function that is possessed can be one or more of following function: 1) light absorption function, 2) the INFRARED ABSORPTION function, 3) electromagnetic wave absorption function, 4) absorb or the function of shielding ultraviolet rays 5) other is as high-low temperature resistant, function such as corrosion-resistant, antibiotic, antifouling.
The preparation method of the composite ultrafine fiber nonwoven that comprises the function nano particle that the present invention proposes is, the function nano particle is dispersed in the polymer solution, adopts method of electrostatic spinning to prepare superfine fibre nonwoven cloth.Because the diameter of fiber generally can reach sub-micron (1 micron is following) even nanoscale, thereby the function nano particle will be difficult to form bigger cluster of grains in fiber.Also the function nano particle can be dispersed in the polymer solution as core matter solution, the identical or different polymer solution that does not contain nano particle adopts the coaxial electrostatic spinning method as surface solution, prepares the superfine fibre nonwoven cloth film.Because fibre diameter is very tiny, intersecting at random of numerous fibers stacks the shortage that can compensate function nano particle in the single fiber, though it is (general to make the thickness of this non-woven thin-film very thin, 100 fibers gather into folds successively also less than 0.1 millimeters thick), but the function nano particle can be evenly distributed therein.
It is inner and surperficial that function nano particle in the above-mentioned superfine fibre nonwoven cloth film is dispersed in superfine fibre; Perhaps be wrapped in superfine fibre inside, do not contact with outside other material of fiber.This non-woven thin-film can be made up of one or more layers, and different layers can comprise the nano particle of difference in functionality.The thickness of this non-woven thin-film and size all can be controlled by preparation technology.
Above-mentioned conventional composite can be fibre reinforced composites such as glass fibre, carbon fiber, ceramic fibre, metallic fiber, also can be sandwich (interlayer such as sheet metal and Fiber composite laminate are pasted) material.
Preparing the integrated composite detailed process of a kind of typical 26S Proteasome Structure and Function is described as follows.
Certain function nano particle is dispersed in the polymer liquid body medium, prepares superfine fibre nonwoven cloth by electrostatic spinning technique; Perhaps with above-mentioned solution as core matter solution, the polymer solutions different with core matter adopt coaxial co spun technology to prepare superfine fibre nonwoven cloth as surface solution.Speed by control ectonexine solution is controlled the compaction rate of nano particle at fibrous inside.The reception of superfine fibre can be: (1) directly is received on the receiver (as metal forming or net); (2), can also directly nanofiber be received on fiber cloth or the prepreg cloth for fibre reinforced composites.Take the superfine fibre nonwoven cloth film of (1) gained off the also interface layer of insert layer plywood, its thickness, size and insertion position can be regulated as required, perhaps fiber cloth or the prepreg with (2) gained stacks into laminate by design form, immerse suitable resin, the final curing moulding, as shown in Figure 1,1 is the structural wood bed of material among the figure, and 2 for containing the superfine fibre nonwoven cloth layer of function nano particle.
The present invention adopts coaxial co spun technology fully the function nano particle to be coated to superfine fibre inside, after the function nano particle is wrapping to superfine fibre inside, nano particle has had certain dispersion effect at fibrous inside, and do not contact with other medium of nanofiber outside, in stable condition, nano particle can reach the state that is evenly distributed in certain thickness film.Because the function nano particle does not contact with the component of composite, therefore do not influence the mechanical property of composite substantially.Again because polymer superfine fibre has certain intensity and toughness, and diameter is little, specific area is big, join in the composite and also may play the interface modification effect, therefore certain thickness superfine fibre film inserts the interface layer of composite, one side makes composite show excellent function, and is less to the thickness and the weight influence of composite on the other hand, and the mechanical property of composite is not influenced even certain humidification substantially.The prepared function interlayer composite material that goes out of the present invention has advantages such as thin thickness, in light weight, functional strong and structural behaviour excellence, the present invention has advantages such as preparation technology is simple, equipment cost is cheap, is particularly suitable for preparing the composite material element that Aero-Space have both with structure and function.
Description of drawings
Fig. 1 is the part-structure schematic diagram of interlayer composite material of the present invention;
Fig. 2 contains the variation relation figure that the interlaminar shear strength of the sandwich plate of the superfine fibre nonwoven cloth film of inhaling the ripple nano SiC increases with the thickness of plate;
Fig. 3 contains the superfine fibre nonwoven cloth film of inhaling the ripple nano SiC figure that influences to the impact flexibility of sandwich plate.
The number in the figure explanation
1-structural wood bed of material 2-contains the superfine fibre nonwoven cloth layer of function nano particle
3-contains the plate of epoxy clad nano SiC superfine fibre nonwoven cloth film
4-is the plate that contains nylon 6 clad nano SiC superfine fibre nonwoven cloth films
5-contains the plate of TPU (thermoplastic polyurethane) clad nano SiC superfine fibre nonwoven cloth film
The 6-blank plate
7-adds the plate of SiC/Epoxy composite Nano superfine fibre film
8-adds the plate of SiC/TPU composite Nano superfine fibre film
The specific embodiment
How further specify the present invention below by specific embodiment realizes:
Characteristics such as nano SiC has fabulous mechanics, calorifics, electricity and chemical property, has high thermoconductivity, low thermal coefficient of expansion and elevated temperature strength, and have good absorbing property.Configuration nano SiC (particle diameter is less than 50nm)/epoxy 609 solution, the concentration of nano SiC in solution is 0-20%, adds dispersant, sonic oscillation evenly disperses, as the internal layer solution of coaxial cospinning; Solids epoxy 609 is configured to the outer solution of solution as coaxial cospinning, adds curing agent.Adopt coaxial cospinning to obtain composite ultrafine fiber.Superfine fibre is gathered into non-woven thin-film.Insert then between the alkali-free glass fiber cloth, adopt hand to stick with paste technology, shop one deck fiber cloth, brush one deck epoxy resin is put into a layer superfine fibre film, makes certain thickness sandwich type laminate, and curing molding is the laminate with absorbing property then.Adopt the mechanical property of short beam shear method test clip laminate.When incorporating thickness increase that the superfine fibre film that comprises nano particle makes plate into and be no more than 18%, interlaminar shear strength is increase trend, and maximum has increased about 10%; Just obviously descend when the thickness increase surpasses 18%, until thickness increases above about 25% o'clock, the interlaminar shear strength value just is lower than the value of blank plate.(as shown in Figure 2)
Adopt above-mentioned coaxial cospinning internal layer SiC solution, the concentration of nano SiC in solution is 0-20%, and the top layer is nylon-6/formic acid solution, adopts coaxial co spun technology to prepare nylon and coats the nano SiC superfine fibre nonwoven cloth.Adopt above-mentioned method to incorporate the interface layer of laminate, curing molding into.Adopt short beam shear method test clip laminate mechanical property, in the thickness increase was no more than 11% scope, the interlaminar shear strength value was standard value substantially.(as shown in Figure 2)
Adopt above-mentioned coaxial cospinning internal layer SiC solution, the concentration of nano SiC in solution is 0-20%, the top layer is thermoplastic polyurethane (TPU)/nitrogen, nitrogen dimethyl formamide and tetrahydrofuran solution, adopts coaxial co spun technology to prepare TPU clad nano SiC superfine fibre nonwoven cloth.Adopt above-mentioned method to incorporate the interface layer of laminate, curing molding into.Adopt short beam shear method test clip laminate mechanical property, when the thickness increase surpassed 30%, the interlaminar shear strength value just descended.(as shown in Figure 2)
Adopt above-mentioned coaxial cospinning internal layer SiC solution, wherein SiC concentration is 0-20%, and the top layer is epoxy 609 solution, adds curing agent.Adopt coaxial co spun technology to prepare epoxy clad nano SiC superfine fibre nonwoven cloth.The interface layer of incorporating laminate then into, curing molding.Adopt freely-supported beam type impact ductility test method test impact property, the impact flexibility relative value that obtains blank plate is 100%, and the impact flexibility of the plate behind the insertion SiC-epoxy composite superfine fibre nonwoven cloth film is 110.7%, increases by 11% approximately.Wherein the thickness of plate increases about 3%.(as shown in Figure 3)
Adopt the coaxial cospinning internal layer SiC solution in above-mentioned, wherein SiC concentration is 0-20%, and the top layer is thermoplastic polyurethane (TPU)/nitrogen, nitrogen dimethyl formamide and tetrahydrofuran solution.Adopt coaxial co spun technology to prepare TPU clad nano SiC superfine fibre nonwoven cloth.The interface layer of incorporating laminate then into, curing molding.Adopt freely-supported beam type impact ductility test method test impact property, the impact flexibility relative value that obtains blank plate is 100%, and the impact flexibility of this routine plate is 102%, increases by 2% approximately.Wherein the thickness of plate increases about 14%.(as shown in Figure 3)
Nano TiO 2 has good stability, shielding ultraviolet rays, and absorbs advantage such as light wave wider range.Configuration TiO2/ polyurethane (TPU) solution, the mass percentage concentration of TiO2 in solution is 0-20%, with the sandwich layer of this solution as coaxial cospinning, the top layer is a polyurethane solutions.Adopt coaxial co spun technology to prepare superfine fibre nonwoven cloth, insert the interface layer of glass fibre/epoxy composite material then, prepare structure sheaf plywood with absorption and shielding ultraviolet rays function.After this nonwoven is incorporated laminate into, make the increase of laminate thickness be no more than at 15% o'clock, the bending property of laminate and interlaminar shear strength there are not influence substantially.
High temperature resistant, long acting antibiotic effect that Nano Silver has.Configuration polyacrylonitrile (PAN)/dimethylformamide solution, surface solution as coaxial cospinning, Nano Silver is distributed in the above-mentioned solution as sandwich layer solution, adopt coaxial co spun technology to prepare superfine fibre nonwoven cloth, this nonwoven has high temperature resistant and antibiotic function, incorporate certain thickness this nonwoven into glass fibre/epoxy layer plywood interface layer, common moulding has obtained having antibiotic and resistant to elevated temperatures laminate, and laminate has higher mechanical property.
Claims (6)
1, a kind of interlayer composite material, comprise composite layer and the above functional material layer of one deck that one deck is above, it is characterized in that: accompany the functional material interlayer between the layer of described composite and the layer, described functional material interlayer is made of the one or more layers superfine fibre nonwoven cloth film that includes the function nano particle.
2, a kind of interlayer composite material according to claim 1 is characterized in that: described function nano particle is one or more a mixture of nano metal or alloy, nano-oxide, nano-carbide, nano nitride, nanometer conductive polymer or nano-ceramic powder.
3, according to claim 1 or the described a kind of interlayer composite material of 2 any claims, it is characterized in that: different functional material interlayers includes different function nano particles.
4, according to the described a kind of interlayer composite material of claim 1, it is characterized in that: described composite is a kind of in fibre reinforced composites such as glass fibre, carbon fiber, ceramic fibre, metallic fiber or the sandwich material.
5, claim 1,2,3 or 4 described a kind of interlayer composite materials, its preparation method is as follows:
Any one of following two kinds of methods selected in the preparation of A, superfine fibre nonwoven cloth for use: 1) the function nano particle is dispersed in the polymer liquid body medium, prepares superfine fibre nonwoven cloth by method of electrostatic spinning; 2) the function nano particle is dispersed in solution in the polymeric liquid as core matter solution, the polymer solutions different with core matter adopt coaxial co spun technology to prepare superfine fibre nonwoven cloth as surface solution;
The receive mode of B, superfine fibre is selected any one in following two kinds of methods for use: 1) directly be received on the receiver; 2), directly nanofiber is received on fiber cloth or the prepreg cloth for fibre reinforced composites;
C, will be received in directly that superfine fibre nonwoven cloth film on the receiver is taken off and the interface layer of insert layer plywood, perhaps with B step 2) fiber cloth or the prepreg of gained stack into laminate by design form, immerses suitable resin, the final curing moulding.
6, the preparation method of a kind of interlayer composite material according to claim 5 is characterized in that: during the interface layer of the superfine fibre nonwoven cloth film insert layer plywood in the described C step, its thickness, size and insertion position can be regulated as required.
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