CN106696394A - Fiber and metal laminated plate and preparation method thereof - Google Patents
Fiber and metal laminated plate and preparation method thereof Download PDFInfo
- Publication number
- CN106696394A CN106696394A CN201510444674.5A CN201510444674A CN106696394A CN 106696394 A CN106696394 A CN 106696394A CN 201510444674 A CN201510444674 A CN 201510444674A CN 106696394 A CN106696394 A CN 106696394A
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- Prior art keywords
- resin
- chopped strand
- weight portions
- fiber
- fibre
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
Abstract
The invention relates to the field of fiber and metal laminated plates, and discloses a fiber and metal laminated plate and a preparation method thereof. The fiber and metal laminated plate comprises a metal layer, a resin adhesion layer and a fiber layer which are laminated in sequence, wherein chopped fiber is embedded between the resin adhesion layer and the fiber layer, and the length of the chopped fiber is 50 mu or more and less than 2 mm. According to the fiber and metal laminated plate disclosed by the invention, the bonding strength between the metal layer and the fiber layer is relatively high.
Description
Technical field
The present invention relates to a kind of fibre metal laminate and preparation method thereof.
Background technology
Aluminum alloy materials have compared with low-density and intensity and shock resistance higher, and with good
Machinability cost is also more cheap.Therefore just it is widely used in boat since earlier 1930s
Empty space industry.But aluminum alloy materials have some limitation for example relatively low fatigue life and anticorrosive
Performance limits its further application value.And the fifties of twentieth century four invention glass fibre and
Carbon fibre composite has a specific strength and specific stiffness very high, and with good fatigue properties and resistance to
Corrosivity, but transverse strength and shock resistance are poor outside this laminated composite material face, and interlayer
Faying face easily produces delamination.In order to while overcoming some that aluminum alloy materials and fibrous composite are present
Shortcoming, in later 1970s, by TU Delft, Polytechnics have developed metal material
With the fibre metal laminate material of fiber composite, i.e. fibre metal laminate.
Fibre metal laminate is the new hybrid buildup structural composite material of a class, is referred to as in the world
FML (Fiber-Metal Laminate) laminate, its Typical Representative is that aluminium alloy-aramid fiber lamination is answered
Condensation material laminate, referred to as ARALL (ARAamid-Aluminum Laminate) in the world, and
Aluminium alloy-glass fibre laminated composite materials laminate, in the world referred to as GLARE
(GLAss-Reinforce aluminum).Bibliography (Vogelesang, L., Development of a
New Hybrid Material(ARALL)for AircraftStructure,Ind.Eng.Chem.
Prod.Res.Dev., 1983, pp.492-496) and U.S. patent Nos (US5039571, US5547735
And US5219629) all have studied in detail the preparation method of FML laminated composite materials laminates, mechanics
Performance and advantage and potential application field.At present, GLARE has been applied and flown in A380 in large area
It is a significant innovative point of A380 aircraft materials technologies on the upper fuselage shell structural of machine.
Fibre metal laminate combines the advantage of metal and fibrous composite, and it is most of to overcome it
Shortcoming, be a kind of knot for having huge applications prospect in high-tech areas such as Aero-Space, military affairs, automobiles
Structure material.
Although fibre metal laminate has a series of excellent performances, its metal level and fiber cloth it
Between adhesion it is weaker.
The content of the invention
The technical problems to be solved by the invention are directed to gold in fibre metal laminate of the prior art
A kind of weak problem of adhesion between category layer and fiber cloth, there is provided the combination between metal level and fiber cloth
Stronger fibre metal laminate of power and preparation method thereof.
The invention provides a kind of fibre metal laminate, wherein, the fibre metal laminate is included successively
The metal level of stacking, resin-bonded layer and fibrage, are embedded between the resin-bonded layer and fibrage
Chopped strand, and the length of the chopped strand is more than 50 μm and be below 2mm.
Present invention also offers the preparation method of above-mentioned fibre metal laminate, the method includes：In metal
What the surface coating of layer was formed by the resin combination containing Thermocurable resin glue and chopped strand
Binding agent, pre-soaking fiber cloth and metal level are laminated, and make the surface direction with binding agent on metal level pre-
Leaching fiber cloth, then carrying out hot pressing makes pre-soaking fiber cloth and metal level be combined as a whole, wherein, it is described short
The length for cutting fiber is more than 50 μm and is below 2mm.
Fibre metal laminate of the invention, the adhesion between its metal level and fiber cloth is strong.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The fiber metal that the present invention is provided includes the metal level, resin-bonded layer and the fiber that stack gradually
Layer, is embedded with chopped strand between the resin-bonded layer and fibrage, and the chopped strand length
For more than 50 μm and be below 2mm.
It is further to improve the adhesion between metal level and fibrage according to the present invention, it is preferably described short
The length for cutting fiber is 75 μm of -1mm.
In addition, in the present invention, the diameter of the chopped strand can be in interior variation in a big way, preferably
In the case of, the diameter of section of the chopped strand is 0.5-20 μm, more preferably 1-10 μm.
In the present invention, it is preferred to the chopped strand is using in glass fibre, carbon fiber and aramid fiber
One or more.
In the present invention, it is not particularly limited for the fibrage, its material can be the various of routine,
For example, the fibrage can be one or more braiding in glass fibre, carbon fiber and aramid fiber
Fiber cloth.
In the present invention, the mass area ratio for above-mentioned fibrage is not particularly limited, specifically can be
Interior variation in a big way, under preferable case, the mass area ratio of the fibrage is 50-650g/cm2,
More preferably 150-300g/cm2。
Above-mentioned resin-bonded layer can be by the resin containing Thermocurable resin glue and chopped strand
Composition solidifies and obtains layer.
Acrylic resin, epoxy resin, polyurethane tree are preferably as the Thermocurable resin glue
It is a kind of in fat, polyester resin, Ben Bing oxazines resin, phenolic resin, urea resin and melmac
Or it is various.Preferably epoxy resin.
Preferably, the resin combination also contains reactive diluent.It is highly preferred that relative to 100 weights
Measure the curability resin glue of part, the reactive diluent containing 10-55 weight portions；It is further excellent
Selection of land, relative to the curability resin glue of 100 weight portions, the work containing 13-53 weight portions
Property diluent.
The reactive diluent is used to dissolve and disperse film forming matter, with the participation in coating film forming procedure
Film formation reaction, formation does not play the effect that component is stayed in film.It is excellent as reactive diluent described above
Elect acrylic glycidol ether, butyl glycidyl ether, ethylene glycol bisglycidyl ether, resorcinol as
Bisglycidyl ether, hexanediol diglycidyl ether, butanediol diglycidyl ether, polypropylene glycol two contract
One or more in water glycerin ether, neopentylglycol diglycidyl ether and alkyl multicondensed water glycerin ether.From
Reduce viscosity effect more excellent, the more preferable aspect of fiber prepreg effect is considered, more preferably described activity is dilute
Agent is released for butyl glycidyl ether, butanediol diglycidyl ether, neopentylglycol diglycidyl ether and alkane
One or more in the glycidol ether of Quito.Specifically, river can be used as the reactive diluent
(composition contracts the reactive diluent of the model SM678 of wooden Group Co., Ltd of Soviet Union three for neopentyl glycol two
Water glycerin ether).
In accordance with the present invention it is preferred that, the resin combination also contains curing agent.It is highly preferred that relative
In the curability resin glue of 100 weight portions, the curing agent containing 1-55 weight portions；Enter one
Walk preferably, relative to the curability resin glue of 100 weight portions, the institute containing 2-50 weight portions
State curing agent.
Can be the various curing agent for solidifying commonly used in the art as the curing agent.Preferably two
Aminodiphenylmethane, m-phenylene diamine (MPD), diamino diphenyl sulfone adipic dihydrazide, dicyandiamide, three second
Alkene diamines, triethylene tetramine, TEPA, diethylaminopropylamine, Meng's alkane diamines, isophorone two
In amine, N- aminoethyl piperazines, double (4- amino -3- methylcyclohexyls) methane and double (4- amidos cyclohexyl) methane
One or more.More preferably dicyandiamide.
In accordance with the present invention it is preferred that, the resin combination can also contain curing accelerator.More preferably
Ground, relative to the curability resin glue of 100 weight portions, the solidification containing 0-10 weight portions
Accelerator；It is further preferred that relative to the curability resin glue of 100 weight portions, containing 0.9-8.8
The curing accelerator of weight portion.
Can be with various curing accelerators commonly used in the art as the curing accelerator.For example can be have
One or more in machine guanidine compound, glyoxaline compound and carbamide compounds；Preferably imidazoles
Compound；More preferably 1- methylimidazoles.
In accordance with the present invention it is preferred that, the resin combination can also contain defoamer, levelling agent and profit
One or more in humectant.Preferably, relative to the curability resin glue of 100 weight portions, institute
State the content respectively 0-12 weight portions of infusion, levelling agent and wetting agent, more preferably 1.5-11 weight
Part.
Can be with various defoamers, levelling commonly used in the art as the defoamer, levelling agent and wetting agent
Agent and wetting agent.Preferably, the defoamer is poly acrylic acid-poly ether copolymer defoamer, organosilicon
One or more in class defoamer, organic modified polyorganosiloxane defoamer and fluorosilicone antifoamant；Institute
It is the one kind or many in acrylate, polyether siloxane copolymer and organic modified polyorganosiloxane to state levelling agent
Kind；The wetting agent is nonionic organic surfactant.Specifically, can make as the defoamer
With the defoamers of DEGO Airex 932 (fluorosilicone antifoamant)
In addition, in the present invention, under preferable case, the thickness of the resin-bonded layer is 0.02-0.5mm,
More preferably 0.02-0.2mm.
In the present invention, the specific material and structure of above-mentioned metal level can be using existing various, for example, institute
State the one kind during metal level is selected from aluminium alloy plate, titanium alloy sheet and steel plate.In the present invention, it is preferred to use often
The aluminium alloy plate of rule.For the thickness of above-mentioned metal level, it is not particularly limited in the present invention, specifically can be with
In interior variation in a big way, those skilled in the art can be adjusted according to actual conditions, under preferable case,
The thickness of the metal level is 0.1-3mm.
, according to the invention it is preferred to the chopped strand Surface coating has silane coupler.By described short
Cut fiber surface and be coated with silane coupler, with energy and the chemically combined reactive group of fiber surface, can
With the effect of the function served as bridge that gets up between fiber and pre-soaked resin such that it is able to further improve Coating combination
Power.
Can be with side well known in the art in the method for the chopped strand Surface coating silane coupler
Method, such as by silane coupler with dispersant and the mixed spray solution of solvent in the chopped strand
Dried behind surface.
Can be various silane couplers commonly used in this field as the silane coupler.Preferably,
The silane coupler be amino silane, epoxy radicals silicone hydride, sulfenyl silane, methacryloxypropyl silane,
One or more in vinyl silanes, ureido silane and isocyanato silanes.Preferably, the silicon
Alkane coupling agent is one or more in amino silane and epoxy radicals silicone hydride.Can be as the dispersant
Various dispersants commonly used in this field, preferably waterglass, sodium tripolyphosphate, calgon, Jiao
It is sodium phosphate, triethyl group hexyl phosphoric acid, lauryl sodium sulfate, methyl anyl alcohol, cellulose derivative, poly-
One or more in acrylamide, guar gum, aliphatic poly glycol ester and modified polyalkoxide.
As long as example can may be used well by the silane coupler and dispersant solvent as the solvent
Think ethanol, dimethylbenzene, n-butanol, butyl glycol ether, butyl acetate, isopropanol, cyclohexanone and first
One or more in base isobutyl ketone.
Mixing quality ratio for silane coupler, dispersant and solvent is preferably 1：0.5-5：50-200；
Particularly preferably=1：3：100.
In addition, as known to the skilled person, the number of plies of fibre metal laminate is according to different realities
Border situation can accordingly increase and decrease.For example, conventional fibre metal laminate is including described in fibrage, two
Metal level and two resin-bonded layers；Described two resin-bonded layers be located at described two metal levels it
Between, the fiber cloth is located between described two resin-bonded layers.In the present invention, when fibre metal is laminated
When plate includes fibrage, two metal levels and two resin-bonded layers, described two resins glue
The chopped strand is embedded between knot layer and fiber cloth.
The present invention also provides a kind of preparation method of fibre metal laminate, wherein, the method includes：
The surface of metal level is coated with by the resin combination shape containing Thermocurable resin glue and chopped strand
Into binding agent, pre-soaking fiber cloth and metal level are laminated, make the surface court with binding agent on metal level
To pre-soaking fiber cloth, then carrying out hot pressing makes pre-soaking fiber cloth and metal level be combined as a whole, wherein, institute
The length for stating chopped strand is more than 50 μm and is below 2mm.
The preparation method of fibre metal laminate of the invention, in order to obtain metal level and fiber cloth it
Between the excellent fibre metal laminate of adhesion, preferably with respect to the curability binding agent of 100 weight portions
Resin, the chopped strand containing 5-50 weight portions；More preferably relative to the solidification of 100 weight portions
Property resin glue, the chopped strand containing 8-38 weight portions.
For above-mentioned chopped strand, under preferable case, its length is 75 μm of -1mm.
In the preparation method of fibre metal laminate of the invention, the diameter of chopped strand can be larger
In the range of change, under preferable case, the diameter of section of the chopped strand is 0.5-20 μm, more preferably
1-10μm。
In the preparation method of fibre metal laminate of the invention, preferably described chopped strand uses glass
One or more in fiber, carbon fiber and aramid fiber.
The preparation method of fibre metal laminate of the invention, the resin combination contains the heat
Curability resin glue.The Thermocurable resin glue be preferably acrylic resin, epoxy resin,
Polyurethane resin, polyester resin, Ben Bing oxazines resin, phenolic resin, urea resin and melamine tree
One or more in fat.Preferably epoxy resin.
The preparation method of fibre metal laminate of the invention, it is preferred in the case of, the resin group
Compound also contains reactive diluent.The consumption of the reactive diluent can be the conventional amount used of this area,
Relative to the curability resin glue of 100 weight portions, the activity dilution containing 10-55 weight portions
Agent；It is highly preferred that relative to the curability resin glue of 100 weight portions, containing 13-53 weight portions
The reactive diluent.
The reactive diluent is used to dissolve and disperse film forming matter, with the participation in coating film forming procedure
Film formation reaction, formation does not play the effect that component is stayed in film.It is excellent as reactive diluent described above
Elect acrylic glycidol ether, butyl glycidyl ether, ethylene glycol bisglycidyl ether, resorcinol as
Bisglycidyl ether, hexanediol diglycidyl ether, butanediol diglycidyl ether, polypropylene glycol two contract
One or more in water glycerin ether, neopentylglycol diglycidyl ether and alkyl multicondensed water glycerin ether；From
Reduce viscosity effect more excellent, the more preferable aspect of fiber prepreg effect is considered, more preferably described activity is dilute
Agent is released for butyl glycidyl ether, butanediol diglycidyl ether, neopentylglycol diglycidyl ether and alkane
One or more in the glycidol ether of Quito.Specifically, river can be used as the reactive diluent
(composition contracts the reactive diluent of the model SM678 of wooden Group Co., Ltd of Soviet Union three for neopentyl glycol two
Water glycerin ether).
The preparation method of fibre metal laminate of the invention, it is preferred in the case of, the resin group
Compound also contains curing agent.The consumption of the curing agent can be the conventional amount used of this area, it is preferable that
Relative to the curability resin glue of 100 weight portions, the curing agent containing 1-55 weight portions；
It is further preferred that relative to the curability resin glue of 100 weight portions, containing 2-50 weight portions
The curing agent.
Can be the various curing agent for solidifying commonly used in the art as the curing agent.Preferably two
Aminodiphenylmethane, m-phenylene diamine (MPD), diamino diphenyl sulfone adipic dihydrazide, dicyandiamide, three second
Alkene diamines, triethylene tetramine, TEPA, diethylaminopropylamine, Meng's alkane diamines, isophorone two
In amine, N- aminoethyl piperazines, double (4- amino -3- methylcyclohexyls) methane and double (4- amidos cyclohexyl) methane
One or more.More preferably dicyandiamide.
The preparation method of fibre metal laminate of the invention, it is preferred in the case of, the resin group
Compound also contains curing accelerator.The consumption of the curing accelerator can be the conventional amount used of this area,
Preferably, relative to the curability resin glue of 100 weight portions, containing described in 0-10 weight portions
Curing accelerator；It is further preferred that relative to the curability resin glue of 100 weight portions, containing
The curing accelerator of 0.9-8.8 weight portions.
Can be with various curing accelerators commonly used in the art as the curing accelerator.For example can be have
One or more in machine guanidine compound, glyoxaline compound and carbamide compounds；Preferably imidazoles
Compound；More preferably 1- methylimidazoles.
The resin combination can also be containing one or more in defoamer, levelling agent and wetting agent.
Preferably, relative to the curability resin glue of 100 weight portions, the infusion, levelling agent and wetting
The content of agent is respectively 0-12 weight portions, more preferably 1.5-11 weight portions.
Can be with various defoamers, levelling commonly used in the art as the defoamer, levelling agent and wetting agent
Agent and wetting agent.Preferably, the defoamer is, for example, poly acrylic acid-poly ether copolymer defoamer, has
One kind or many in machine silicon class defoamer, organic modified polyorganosiloxane defoamer and fluorosilicone antifoamant
Kind；During the levelling agent is, for example, acrylate, polyether siloxane copolymer and organic modified polyorganosiloxane
One or more；The wetting agent is, for example, one or more in nonionic organic surfactant.
Specifically, defoamer (the fluorosilicone froth breakings of DEGO Airex 932 can be used as the defoamer
Agent).
The preparation method of fibre metal laminate of the invention, the pre-soaking fiber cloth can be obtained with commercially available
, it would however also be possible to employ the conventional method in this area is prepared.For example can by by fiber cloth with preimpregnation
Feed composition is contacted and obtained；It is dilute that the prepreg composition contains Thermocurable resin glue, activity
Release agent, curing agent, curing accelerator and defoamer.The Thermocurable that the prepreg composition contains
Resin glue, reactive diluent, curing agent, curing accelerator and defoamer are well known in the art.
In addition, the prepreg composition contain Thermocurable resin glue, reactive diluent, curing agent,
Curing accelerator and defoamer can also contain Thermocurable binding agent with above-mentioned resin combination respectively
Resin, reactive diluent, curing agent, curing accelerator are identical with defoamer.
Material for above-mentioned fiber cloth is not particularly limited, and its material can be the various of routine, for example,
It is specifically as follows one or more in glass fabric, carbon cloth and aryl fiber cloth, or
One or more blended cloth of formation in above-mentioned glass fibre, carbon fiber and aramid fiber.
In addition, be not particularly limited for the quality of the unit area of above-mentioned fiber cloth, specifically can be
Interior variation in a big way, under preferable case, the quality of the unit area of the fiber cloth is 50-650g/cm2,
More preferably 150-300g/cm2。
The preparation method of pre-soaking fiber cloth of the invention, the specific material and structure of above-mentioned metal level can
Using existing various, for example, the metal level is selected from aluminium alloy plate, titanium alloy sheet and steel plate
Kind.In the present invention, it is preferred to use conventional aluminium alloy plate.For the thickness of above-mentioned metal level, the present invention
In be not particularly limited, specifically can be according to reality in interior variation in a big way, those skilled in the art
Situation is adjusted, and under preferable case, the thickness of the metal level is 0.1-3mm.
Additionally, it is preferred that above-mentioned metal was carried out at deoiling metal before with the stacking of pre-soaking fiber cloth
Reason.The method of the deoiling is well known in the art, for example, will again be used after above-mentioned metal acid soak
Alkali soaks.Specifically, above-mentioned metal can be for example put into the aqueous solution of nitric acid of 5 weight % and is soaked
30s, then soaks 30s in the sodium hydrate aqueous solution of 10 weight % again.
The preparation method of pre-soaking fiber cloth of the invention, it is preferred in the case of, the chopped strand table
Bread is covered with silane coupler.There is silane coupler by the chopped strand Surface coating, with energy
With the chemically combined reactive group of fiber surface, can get up function served as bridge between fiber and pre-soaked resin
Effect such that it is able to further improve inter-layer bonding force.
Can be with side well known in the art in the method for the chopped strand Surface coating silane coupler
Method, such as by silane coupler with dispersant and the mixed spray solution of solvent in the chopped strand
Surface.
Can be various silane couplers commonly used in this field as the silane coupler.Preferably,
The silane coupler be amino silane, epoxy radicals silicone hydride, sulfenyl silane, methacryloxypropyl silane,
One or more in vinyl silanes, ureido silane and isocyanato silanes；Preferably, the silicon
Alkane coupling agent is amino silane and/or epoxy radicals silicone hydride.Can be commonly used in this field as the dispersant
Various dispersants, preferably waterglass, sodium tripolyphosphate, calgon, sodium pyrophosphate, three second
Base hexyl phosphoric acid, lauryl sodium sulfate, methyl anyl alcohol, cellulose derivative, polyacrylamide, Gu
One or more in your glue, aliphatic poly glycol ester and modified polyalkoxide.As the solvent
As long as can for example can be well by the silane coupler and dispersant solvent ethanol, two
In toluene, n-butanol, butyl glycol ether, butyl acetate, isopropanol, cyclohexanone and methyl iso-butyl ketone (MIBK)
One or more.
Mixing quality ratio for silane coupler, dispersant and solvent is preferably 1：0.5-5：50-200；
Particularly preferably=1：3：100.
The preparation method of fibre metal laminate of the invention, by by resin combination it is each into
Binding agent is obtained after dividing mixing dispersion.It is no for the order by merging of each composition in resin combination special
It is required that, can be arbitrary.But, from the Coating combination further improved between metal level and fiber cloth
Consider in power, preferably after being thermally cured property resin glue and reactive diluent mixing dispersion, add
Chopped strand carries out dispersion mixing, is disperseed after being subsequently adding curing agent, curing accelerator and defoamer
Mixing, so as to obtain binding agent.
The preparation method of fibre metal laminate of the invention, it is necessary to metal level surface coating by
The binding agent that resin combination containing Thermocurable resin glue and chopped strand is formed, then with advance
Leaching fiber cloth carries out hot pressing together.The coating thickness of the binding agent is preferably 0.02-0.5mm, further
Preferably 0.05-0.2mm.
As it was previously stated, laminated when the fibre metal with two metal levels and two resin-bonded layers need to be prepared
During plate, can be by metal level, pre-soaking fiber cloth, metal level being stacked gradually and hot pressing obtains the fibre
Dimension metal laminate.
According to the present invention, finally need to make fiber cloth and metal level be combined as a whole by hot pressing.
Specific hot-press method is commonly used in this field, and under preferable case, the hot-press method is：
120-140 DEG C, hot pressing 30-120min under 0.1-10MPa pressure, release after then cooling down.
Below will the present invention will be described in detail by embodiment.
In following examples and comparative example, raw material is the commercially available product of following company.
Embodiment 1
1st, the preparation of binding agent
1) according to silane coupler：Dispersant：Ethanol=1：3：100 ratio (mass ratio) is prepared
Pretreating agent；
2) in 4kg glasses chopped strand, (glass chopped strands, length is 200 μm, and diameter of section is
10 μm) surface sprinkling pretreating agent, dry and obtain pretreatment of fiber silk X；
3) epoxy resin 48kg, reactive diluent 25kg are weighed, (upper Haifa is purchased from high speed dispersor
Fu Lai limited energies company, same as below) dispersion, obtain mixture A；
4) by step 2) in during the pretreatment of fiber silk X that obtains adds mixture A, disperseed with high speed
Machine disperses, and obtains mixture B；
5) dicyandiamide 15kg (curing agent), 1- methylimidazoles 5kg (curing accelerator), froth breaking are weighed
Agent 3kg, adds in mixture B, is disperseed with high speed dispersor, obtains binding agent；
6) metal of aluminium alloy is cut into the size (2) of a width of 200mm × 100mm of length, is put
Enter and soak 30s in the aqueous solution of nitric acid of 5 weight %, it is then water-soluble in the NaOH of 10 weight % again
30s is soaked in liquid；
7) respectively in two panels metallic surface coating step 5) (coating thickness is substantially to obtain binding agent
0.2mm), then again by metal, pre-soaking fiber cloth (size：200mm × 100mm), metal successively
Stacking (surface that metal is coated with binding agent is relative with pre-soaking fiber cloth), then at 140 DEG C, with
The pressure hot pressing 30min of 0.5MPa.Then cooling, release, obtain fibre metal laminate A1.
By the cross section of the fibre metal laminate by micro- sem observation, the fibre metal laminate
It is made up of the metal level, resin-bonded layer, fibrage, resin-bonded layer and the metal level that stack gradually, and
Chopped strand is embedded between the resin-bonded layer and fiber cloth, in addition, the thickness of adhering agent layer is big
It is 0.05mm to cause.
Embodiment 2
1) according to silane coupler：Dispersant：Ethanol=1：3：100 ratio (mass ratio) is prepared
Pretreating agent；
2) 8kg chopped strands (glass chopped strands, length is that 200 μm of diameter of sections are 10 μm)
Pretreating agent is sprayed on surface, and drying obtains pretreatment of fiber silk X；
3) epoxy resin 75kg, reactive diluent 10kg are weighed, is disperseed with high speed dispersor, mixed
Compound A；
4) by step 2) in during the pretreatment of fiber silk X that obtains adds mixture A, disperseed with high speed
Machine disperses, and obtains mixture B；
5) dicyandiamide 5kg (curing agent), 1- methylimidazoles 0.7kg (curing accelerator), froth breaking are weighed
Agent 1.3kg, adds in mixture B, is disperseed with high speed dispersor, obtains binding agent；
6) metal of aluminium alloy is cut into the size (2) of a width of 200mm × 100mm of length, is put
Enter and soak 30s in the aqueous solution of nitric acid of 5 weight %, it is then water-soluble in the NaOH of 10 weight % again
30s is soaked in liquid；
7) respectively in two panels metallic surface coating step 5) (coating thickness is substantially to obtain binding agent
0.3mm), then again by metal, pre-soaking fiber cloth (size：200mm × 100mm), metal successively
Stacking (surface that metal is coated with binding agent is relative with pre-soaking fiber cloth), then at 140 DEG C, with
The pressure hot pressing 90min of 0.5MPa.Then cooling, release, obtain fibre metal laminate A2.
By the cross section of the fibre metal laminate by micro- sem observation, the fibre metal laminate
It is made up of the metal level, resin-bonded layer, fiber cloth, resin-bonded layer and the metal level that stack gradually, and
Chopped strand is embedded between the resin-bonded layer and fiber cloth, in addition, the thickness of adhering agent layer is big
It is 0.2mm to cause.
Embodiment 3
According to silane coupler：Dispersant：Ethanol=1：3：100 ratio (mass ratio) is prepared pre-
Inorganic agent；
2) 15kg chopped strands (glass chopped strands, length is 200 μm, and diameter of section is 10 μm)
Pretreating agent is sprayed on surface, and drying obtains pretreatment of fiber silk X；
3) epoxy resin 40.5kg, reactive diluent 18kg are weighed, is disperseed with high speed dispersor, obtained
Mixture A；
4) by step 2) in during the pretreatment of fiber silk X that obtains adds mixture A, disperseed with high speed
Machine disperses, and obtains mixture B；
5) dicyandiamide 20kg (curing agent), 1- methylimidazoles 3.5kg (curing accelerator), froth breaking are weighed
Agent 3kg, adds in mixture B, is disperseed with high speed dispersor, obtains binding agent；
6) metal of aluminium alloy is cut into the size (2) of a width of 200mm × 100mm of length, is put
Enter and soak 30s in the aqueous solution of nitric acid of 5 weight %, it is then water-soluble in the NaOH of 10 weight % again
30s is soaked in liquid；
7) respectively in two panels metallic surface coating step 5) (coating thickness is substantially to obtain binding agent
0.2mm), then again by metal, pre-soaking fiber cloth (size：200mm × 100mm), metal successively
Stacking (surface that metal is coated with binding agent is relative with pre-soaking fiber cloth), then at 140 DEG C, with
The pressure hot pressing 60min of 0.5MPa.Then cooling, release, obtain fibre metal laminate A3.
By the cross section of the fibre metal laminate by micro- sem observation, the fibre metal laminate
It is made up of the metal level, resin-bonded layer, fiber cloth, resin-bonded layer and the metal level that stack gradually, and
There is chopped strand between the resin-bonded layer and fiber cloth, in addition, the thickness of adhering agent layer is substantially
It is 0.15mm.
Embodiment 4
Method according to embodiment 1 is carried out, the difference is that the length of glass chopped strands is 75 μm, is cut
A diameter of 3 μm of face, obtains fibre metal laminate A4 in the same manner.
By the cross section of the fibre metal laminate by micro- sem observation, the fibre metal laminate
It is made up of the metal level, resin-bonded layer, fiber cloth, resin-bonded layer and the metal level that stack gradually, and
There is chopped strand between the resin-bonded layer and fiber cloth, in addition, the thickness of adhering agent layer is substantially
It is 0.05mm.
Embodiment 5
Method according to embodiment 1 is carried out, the difference is that the length of glass chopped strands is 500 μm, is cut
A diameter of 5 μm of face, obtains fibre metal laminate A5 in the same manner.
By the cross section of the fibre metal laminate by micro- sem observation, the fibre metal laminate
It is made up of the metal level, resin-bonded layer, fiber cloth, resin-bonded layer and the metal level that stack gradually, and
There is chopped strand between the resin-bonded layer and fiber cloth, in addition, the thickness of adhering agent layer is substantially
It is 0.05mm.
Embodiment 6
Method according to embodiment 1 is carried out, the difference is that the length of glass chopped strands is 800 μm, is cut
A diameter of 8 μm of face, obtains fibre metal laminate A6 in the same manner.
By the cross section of the fibre metal laminate by micro- sem observation, the fibre metal laminate
It is made up of the metal level, resin-bonded layer, fiber cloth, resin-bonded layer and the metal level that stack gradually, and
There is chopped strand between the resin-bonded layer and fiber cloth, in addition, the thickness of adhering agent layer is substantially
It is 0.05mm.
Embodiment 7
Method according to embodiment 1 is carried out, the difference is that the length of glass chopped strands is 1000 μm,
Diameter of section is 10 μm, and fibre metal laminate A7 is obtained in the same manner.
By the cross section of the fibre metal laminate by micro- sem observation, the fibre metal laminate
It is made up of the metal level, resin-bonded layer, fiber cloth, resin-bonded layer and the metal level that stack gradually, and
There is chopped strand between the resin-bonded layer and fiber cloth, in addition, the thickness of adhering agent layer is substantially
It is 0.05mm.
Embodiment 8
Method according to embodiment 1 is carried out, the difference is that pre- place is not sprayed on chopped strand surface in step 1
Reason agent, obtains fibre metal laminate A8.
By the cross section of the fibre metal laminate by micro- sem observation, the fibre metal laminate
It is made up of the metal level, resin-bonded layer, fiber cloth, resin-bonded layer and the metal level that stack gradually, and
There is chopped strand between the resin-bonded layer and fiber cloth, in addition, the thickness of adhering agent layer is substantially
It is 0.05mm.
Comparative example 1
Method according to embodiment 1 is carried out, the difference is that not adding chopped strand in step 1, obtains fibre
Dimension metal laminate D1.
Comparative example 2
Method according to embodiment 1 is carried out, the difference is that the length of chopped strand is 2.5mm in step 1,
Obtain fibre metal laminate D2.
Test case 1 (peel strength test)
Fibre metal laminate A1-A8 and the D1-D2 difference that embodiment 1-8 and comparative example 1-2 are obtained
It is cut to the batten that size is 100mm × 20mm (wherein machine direction is batten length direction)；Will
The batten for obtaining is peeled off on universal testing machine by 10mm/min of peeling rate, makes stripping
Metal from side completely falls off, and records data, and the value is peel strength.
Its result is as shown in table 1.
Table 1
| Sequence number | Peel strength (N) |
| A1 | 235 |
| A2 | 280 |
| A3 | 256 |
| A4 | 230 |
| A5 | 242 |
| A6 | 248 |
| A7 | 260 |
| A8 | 200 |
| D1 | 150 |
| D2 | 170 |
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in range of the technology design of the invention, can be to technical side of the invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means in order to avoid unnecessary
Repetition, the present invention various possible combinations are no longer separately illustrated.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as its
Without prejudice to thought of the invention, it should equally be considered as content disclosed in this invention.
Claims (20)
1. a kind of fibre metal laminate, it is characterised in that the fibre metal laminate includes layer successively
Folded metal level, resin-bonded layer and fibrage, are embedded with short between the resin-bonded layer and fibrage
Fiber is cut, and the length of the chopped strand is more than 50 μm and is below 2mm.
2. fibre metal laminate according to claim 1, wherein, the length of the chopped strand
It is 75 μm of -1mm to spend；
Preferably, the diameter of section of the chopped strand is 0.5-20 μm；
It is highly preferred that the diameter of section of the chopped strand is 1-10 μm.
3. fibre metal laminate according to claim 1, wherein, the chopped strand is selected from
One or more in glass fibre, carbon fiber and aramid fiber.
4. the fibre metal laminate according to any one in claim 1-3, wherein, it is described
Fibrage is one or more fiber cloth of braiding in glass fibre, carbon fiber and aramid fiber；
Preferably, the mass area ratio of the fibrage is 50-650g/m2。
5. the fibre metal laminate according to any one in claim 1-3, wherein, resin
Tack coat by the resin composition containing Thermocurable resin glue and chopped strand to be obtained
Layer；
Preferably, the thickness of the resin-bonded layer is 0.02-0.5mm.
6. the fibre metal laminate according to any one in claim 1-3, wherein, it is described
Metal level is selected from the one kind in aluminium alloy plate, titanium alloy sheet and steel plate；
Preferably, the thickness of the metal level is 0.1-3mm.
7. the fibre metal laminate according to any one in claim 1-3, wherein, it is described
Chopped strand Surface coating has silane coupler.
8. a kind of preparation method of fibre metal laminate, it is characterised in that the method includes：In gold
The surface coating for belonging to layer is formed by the resin combination containing Thermocurable resin glue and chopped strand
Binding agent, pre-soaking fiber cloth and metal level are laminated, make the surface direction with binding agent on metal level
Pre-soaking fiber cloth, then carrying out hot pressing makes pre-soaking fiber cloth and metal level be combined as a whole, wherein, it is described
The length of chopped strand is more than 50 μm and is below 2mm.
9. method according to claim 8, wherein, the curability relative to 100 weight portions is glued
Knot agent resin, the chopped strand containing 5-50 weight portions；
Preferably, relative to the curability resin glue of 100 weight portions, 8-38 weight portions are contained
The chopped strand.
10. method according to claim 8 or claim 9, wherein, the resin combination is also containing living
Property diluent, relative to the curability resin glue of 100 weight portions, the institute containing 10-55 weight portions
State reactive diluent；
Preferably, relative to the curability resin glue of 100 weight portions, 13-53 weight portions are contained
The reactive diluent；
It is highly preferred that the reactive diluent is acrylic glycidol ether, butyl glycidyl ether, second
Glycol bisglycidyl ether, resorcinol bisglycidyl ether, hexanediol diglycidyl ether, butanediol
Diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether and alkyl multicondensed
One or more in water glycerin ether.
11. methods according to any one of claims of claim 7-10, wherein, the resin combination
Thing also contains curing agent, relative to the curability resin glue of 100 weight portions, contains 1-55 weight
The curing agent of part；
Preferably, relative to the curability resin glue of 100 weight portions, 2-50 weight portions are contained
The curing agent；
It is highly preferred that the curing agent is diaminodiphenyl-methane, m-phenylene diamine (MPD), diamino-diphenyl
Sulfone adipic dihydrazide, dicyandiamide, triethylene diamine, triethylene tetramine, TEPA, diethylamino
Base propylamine, Meng's alkane diamines, IPD, N- aminoethyl piperazines, double (4- amino -3- methyl cyclohexanes
Base) one or more in methane and double (4- amidos cyclohexyl) methane.
12. method according to any one in claim 7-11, wherein, the resin combination
Thing also contains curing accelerator, relative to the curability resin glue of 100 weight portions, contains 0-10
The curing accelerator of weight portion；
Preferably, relative to the curability resin glue of 100 weight portions, 0.9-8.8 weight portions are contained
The curing accelerator.
13. method according to any one in claim 7-12, wherein, the resin combination
Thing also contains one or more in defoamer, levelling agent and wetting agent.
14. method according to any one in claim 7-13, wherein, the chopped strand
Length be 75 μm of -1mm；
Preferably, the diameter of section of the chopped strand is 0.5 μm -20 μm；
It is highly preferred that the diameter of section of the chopped strand is 1-10 μm.
15. method according to any one in claim 7-14, wherein, the chopped strand
Selected from one or more in glass fibre, carbon fiber and aramid fiber.
16. method according to any one in claim 7-15, wherein, the pre-soaking fiber
Fiber cloth in layer is one or more in glass fabric, carbon cloth and aryl fiber cloth；
Preferably, the quality of the unit area of the fiber cloth is 50-650g/m2。
17. method according to any one in claim 7-16, wherein, the Thermocurable
Resin glue is preferably acrylic resin, epoxy resin, polyurethane resin, polyester resin, Ben Bing Evil
One or more in piperazine resin, phenolic resin, urea resin and melmac.
18. method according to any one in claim 7-17, wherein, the chopped strand
Surface coating has silane coupler.
19. method according to claim 8 or claim 9, wherein, the metal level be selected from aluminium alloy plate,
One kind in titanium alloy sheet and steel plate；
Preferably, the thickness of the metal level is 0.1-3mm.
20. method according to claim 8 or claim 9, wherein, by by metal level, pre-soaking fiber
Cloth, metal level are stacked gradually and hot pressing obtains the fibre metal laminate.
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| CN201510444674.5A CN106696394A (en) | 2015-07-27 | 2015-07-27 | Fiber and metal laminated plate and preparation method thereof |
| PCT/CN2016/090900 WO2017016435A1 (en) | 2015-07-27 | 2016-07-21 | Fiber metal laminate and preparation method therefor |
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| CN201510444674.5A CN106696394A (en) | 2015-07-27 | 2015-07-27 | Fiber and metal laminated plate and preparation method thereof |
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| CN107187124A (en) * | 2017-06-13 | 2017-09-22 | 北京航空航天大学 | A kind of magnesium-based superhybrid composite laminate and preparation method thereof |
| CN107187130A (en) * | 2017-06-13 | 2017-09-22 | 北京航空航天大学 | A kind of titanium-based superhybrid composite laminate and preparation method thereof |
| CN107187131A (en) * | 2017-06-13 | 2017-09-22 | 北京航空航天大学 | A kind of aluminium base superhybrid composite laminate and preparation method thereof |
| CN108312684A (en) * | 2017-12-11 | 2018-07-24 | 姜文明 | A kind of aluminium alloy and carbon-fiber-reinforced coloring process |
| CN110576646A (en) * | 2019-09-24 | 2019-12-17 | 华侨大学 | Self-locking type porous structure composite board |
| CN111013982A (en) * | 2019-11-06 | 2020-04-17 | 苏州胜禹材料科技股份有限公司 | High-temperature-resistant corrosion-resistant aluminum-zinc-plated plate and production method thereof |
| CN111186146A (en) * | 2020-01-14 | 2020-05-22 | 上海交通大学 | CFRP/high-strength steel baking hardening hot stamping co-curing integrated forming method |
| CN111391421A (en) * | 2020-02-25 | 2020-07-10 | 长安大学 | Carbon fiber and metal composite structure and preparation method thereof |
| CN111559137A (en) * | 2020-05-21 | 2020-08-21 | 燕山大学 | Preparation process of silane surface modified fiber reinforced metal composite board |
| CN112848544A (en) * | 2021-01-14 | 2021-05-28 | 中车青岛四方机车车辆股份有限公司 | Fiber metal laminated plate and preparation method thereof |
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| CN107187124A (en) * | 2017-06-13 | 2017-09-22 | 北京航空航天大学 | A kind of magnesium-based superhybrid composite laminate and preparation method thereof |
| CN107187130A (en) * | 2017-06-13 | 2017-09-22 | 北京航空航天大学 | A kind of titanium-based superhybrid composite laminate and preparation method thereof |
| CN107187131A (en) * | 2017-06-13 | 2017-09-22 | 北京航空航天大学 | A kind of aluminium base superhybrid composite laminate and preparation method thereof |
| CN108312684A (en) * | 2017-12-11 | 2018-07-24 | 姜文明 | A kind of aluminium alloy and carbon-fiber-reinforced coloring process |
| CN110576646A (en) * | 2019-09-24 | 2019-12-17 | 华侨大学 | Self-locking type porous structure composite board |
| CN110576646B (en) * | 2019-09-24 | 2023-09-29 | 华侨大学 | Self-locking porous structure composite board |
| CN111013982A (en) * | 2019-11-06 | 2020-04-17 | 苏州胜禹材料科技股份有限公司 | High-temperature-resistant corrosion-resistant aluminum-zinc-plated plate and production method thereof |
| CN111186146A (en) * | 2020-01-14 | 2020-05-22 | 上海交通大学 | CFRP/high-strength steel baking hardening hot stamping co-curing integrated forming method |
| CN111391421A (en) * | 2020-02-25 | 2020-07-10 | 长安大学 | Carbon fiber and metal composite structure and preparation method thereof |
| CN111559137A (en) * | 2020-05-21 | 2020-08-21 | 燕山大学 | Preparation process of silane surface modified fiber reinforced metal composite board |
| CN112848544A (en) * | 2021-01-14 | 2021-05-28 | 中车青岛四方机车车辆股份有限公司 | Fiber metal laminated plate and preparation method thereof |
| CN112937062A (en) * | 2021-02-03 | 2021-06-11 | 沈阳中钛装备制造有限公司 | Preparation method of adhesive type titanium alloy composite protection plate |
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