CN103980663B - A kind of composite for juvenile automobile car body panel and preparation method thereof - Google Patents
A kind of composite for juvenile automobile car body panel and preparation method thereof Download PDFInfo
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- CN103980663B CN103980663B CN201410138146.2A CN201410138146A CN103980663B CN 103980663 B CN103980663 B CN 103980663B CN 201410138146 A CN201410138146 A CN 201410138146A CN 103980663 B CN103980663 B CN 103980663B
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- Compositions Of Macromolecular Compounds (AREA)
- Body Structure For Vehicles (AREA)
Abstract
The present invention relates to a kind of composite for juvenile automobile car body panel and preparation method thereof, this composite is become, by following parts by weight, the carbon fibre composite being grouped into: modified carbon fiber 40-60 part, epoxy resin 30-50 part, elastomer 5-15 part, nanometer hydroxyapatite 3-12 part, coupling agent 0.2-3 part, Nano-meter SiO_223-8 part, reinforcer 5-15 part, firming agent 0.5-4 part.Its preparation method is first the pulp layer of carbon fiber surface and impurity to be removed, wash, aoxidize after drying, after oxidation in a solvent, reacting by heating modified carbon fiber under acid binding agent, initiator and grafted monomers exist, then prepared modified carbon fiber ultrasonic disperse is weighed in proportion, add epoxy resin reaction 1-3h, being subsequently adding after other composition is sufficiently stirred for and inject in mould, curing molding, the demoulding prepare the composite for juvenile automobile car body panel that density is low, bearing capacity is strong, safety is high, cost is low.
Description
Technical field
The present invention relates to a kind of composite and preparation method thereof, particularly relate to a kind of composite for juvenile automobile car body panel and preparation method thereof.
Background technology
Juvenile automobile vehicle body is the important component part of juvenile automobile, it constitutes taking space and taking environment of child, it addition, the appearance of vehicle body illustrates plastic arts and the feature of car load.Therefore, the material of juvenile automobile vehicle body should meet the requirement of vehicle body design, production, assembling, maintenance aspect, be also satisfied the requirement of the aspects such as use, safety.
At present, juvenile automobile car body panel is mainly made up of metal material, such as steel, magnesium, aluminum and alloy thereof etc., although the car body panel that these metal materials are made can meet intensity, rigidity, corrosion-resistant, drawability with etc. aspect requirement, but the density of metal material is high, the car body panel made is heavier, and the cost of metal material is high, needing to carry out metalworking technique, processing charges is high, and the production cycle is long.
Summary of the invention
It is an object of the invention to for the above-mentioned problems in the prior art, it is proposed that the composite for juvenile automobile car body panel that a kind of density is low, bearing capacity is strong, safety is high, cost is low.
The purpose of the present invention can be realized by following technical proposal: a kind of composite for juvenile automobile car body panel, described composite is carbon fibre composite, described carbon fibre composite is become to be grouped into by following parts by weight: modified carbon fiber: 40-60 part, epoxy resin: 30-50 part, elastomer: 5-15 part, nanometer hydroxyapatite: 3-12 part, coupling agent: 0.2-3 part, Nano-meter SiO_22: 3-8 part, reinforcer: 5-15 part, firming agent: 0.5-4 part.
The present invention is carbon fibre composite for the composite of juvenile automobile car body panel, and the maximum advantage of the juvenile automobile vehicle body that makes of carbon fibre composite is exactly that light weight, intensity are big.Because carbon fiber is when weight just corresponds to the 20-30% of steel weight, hardness but reaches more than 10 times of steel.So preparing vehicle body plate with carbon fibre composite can make automotive light weight technology, reducing about 60% than the vehicle weight of common iron, but safety but shows no sign of reducing, its mechanical strength and impact resilience are high all the better.Additionally, the juvenile automobile car body panel made by common metal material, if colliding when child is at play or being hit by hard thing, vehicle body may cave in.But the vehicle body plate made with carbon fibre composite is but very firm, if colliding when child is at play or being hit by hard thing, rapidly rebounding in the place collided or the place hit by hard thing, surface is at all damaged from.
Additionally, the present invention also adds epoxy resin and elastomer, the carbon fibre composite that the composition performance such as intensity, corrosion-resistant, endurance is more excellent in the carbon fibers.Wherein, epoxy resin is a kind of very important thermosetting resin, containing active epoxide group in the strand of its molecular structure, this make it can with the firming agent generation cross-linking reaction of number of different types and form the high polymer with tridimensional network insoluble, not molten.Additionally, resin itself has advantages such as mechanical property is high, adhesive force is strong, cure shrinkage is little, but also has the outstanding advantages such as good manufacturability, excellent electrical insulating property, good stability, thermostability be good and become one of most widely used matrix in carbon fibre composite.But undressed carbon fiber surface presents chemical inertness, poor with epoxy resin-base wellability, thus causing composite bad adhesion, have a strong impact on the performance of carbon fibre composite excellent properties.Therefore, in order to improve the wellability of carbon fiber and epoxy resin-base, the present invention adopts chemical graft process that carbon fiber surface is modified, and to carbon fiber surface, ethylenediamine or the ethylene glycol with active group is carried out finishing as grafted monomers.
Before carbon fiber is carried out chemical modification, carbon fiber surface constituent content has been analyzed by the present invention, result shows, the content of inoxidized carbon fiber surface carbon is about 70%, and the content of oxygen element only has about 20%, inoxidized carbon fiber surface is mainly graphite-structure, oxygen-containing functional group isopolarity group content is less, it is unfavorable for that chemical graft process utilizes the interaction of functional group at carbon fiber surface grafted monomers, so, carbon fiber to be aoxidized by the present invention before carbon fiber is carried out chemical modification.Carbon fiber of the present invention is after acid solution aoxidizes, and the oxygen element relative amount of carbon fiber surface adds 6% after measured, and carbon have dropped 8%, and nitrogen element content change is little.The increase of carbon fiber surface oxygen element content is conducive to the carrying out of graft reaction.The carbon fibre composite section processed through peroxidating, graft reaction is more smooth, spike protein gene phenomenon is inconspicuous, there is no the phenomenon of single fiber pull-out test, illustrate that carbon fiber is after oxidative grafting reacts, the caking property of carbon fibre composite significantly improves, and improves the interface performance of carbon fiber and epoxy resin.
The present invention is also added into nanometer hydroxyapatite in carbon fibre composite, and nanometer hydroxyapatite with epoxy resin-base interface cohesion, can significantly improve the mechanical property of carbon fibre composite.And nanometer hydroxyapatite is combined the performance directly affecting composite mutually with epoxy resin interface, without good interface cohesion, composite is easily formed partial relaxation, causes stress to concentrate, and the strength of materials declines.Therefore, the present invention draws by after kinds of experiments scheme, by adding coupling agent lecithin modification nanometer hydroxyapatite, the surface-active functional group making nanometer hydroxyapatite increases, make nanometer hydroxyapatite likely with epoxy resin generation chemical bonds, thus being effectively improved the interfacial bonding property of nanometer hydroxyapatite and epoxy resin, improve the mechanical property of carbon fibre composite.
It addition, the present invention also adds Nano-meter SiO_2 in carbon fibre composite2, Nano-meter SiO_22Addition can the bond strength of enhanced carbon fiber and epoxy resin, but also be conducive to composite to form uniform transfer membrane at dual face, thus improving the wear-resisting of carbon fibre composite and antifriction performance, its wear rate and friction factor ratio respectively does not add Nano-meter SiO_22Carbon fibre composite reduce 35% and about 20%.Therefore, in use no matter there is friction or collision in the juvenile automobile vehicle body being eventually fabricated, the damaged condition of vehicle body is obtained for great reduction, also the staleness rate of body of a motor car is greatly reduced, both decrease the subsequent maintenance expense of juvenile automobile vehicle body, also extend the service life of juvenile automobile vehicle body.
As preferably, described coupling agent is lecithin.
As preferably, described reinforcer is one or more in chromium oxide, copper powder, aluminium oxide, carborundum, boron nitride, glass microballoon.Based on the reasonable compatibility of above-mentioned carbon fibre composite, add the reinforcing material mechanical property with reinforced article, it is also possible to play the effect saving cost.But the enhancement effect of reinforcing material depends on and the compatibility being enhanced material, therefore, the composition of the above-mentioned reinforcing material of the present invention is by passing through Data Summary careful selection out after great many of experiments.
As preferably, described nanometer hydroxyapatite, Nano-meter SiO_22, reinforcer particle diameter be 3-80nm.In carbon fibre composite, the difference of size can affect the distribution of composition, and particle diameter is more little, and the modulus of goods, tensile strength, yield strength and percentage elongation all can increase to some extent.
As preferably, described elastomer is one or more in natural rubber, epoxy natural rubber, butadiene-styrene rubber, nitrile rubber, neoprene.Elastomer has good shock resistance and anti-fatigue performance; adding elastomer in carbon fibre composite is conducive to end product juvenile automobile vehicle body can quick rebound in the region collided or the place hit by hard thing, and protection body of a motor car surface is damaged from.
As preferably, described firming agent is the one in methyl ethyl ketone peroxide, methyl tetrahydrophthalic anhydride, MDA.Firming agent is one of carbon fibre composite necessary raw material preparing juvenile automobile vehicle body, and without firming agent, the epoxy resin in carbon fibre composite is difficult to solidify.In numerous firming agent, three kinds of firming agent in use effects selected by the present invention are relatively better.
Another object of the present invention is in that the preparation method providing above-mentioned a kind of composite for juvenile automobile car body panel, and described preparation method comprises the following steps:
S1, carbon fiber is removed with acetone extraction 35-45h the pulp layer on surface and impurity, then with distilled water wash, put heated oxide 1-4h in an acidic solution after drying, then with distilled water wash, standby；
S2, putting in a solvent by the carbon fiber after above-mentioned oxidation, reacting by heating 1-5h under acid binding agent, initiator and grafted monomers exist, after reaction terminates, washing, sample preparation obtain modified carbon fiber；
S3, weigh the above-mentioned prepared modified carbon fiber ultrasonic disperse 20-50min of 40-60 part, it is subsequently adding 30-50 part epoxy resin at 60-120 DEG C, reacts 1-3h, be subsequently adding 3-12 part nanometer hydroxyapatite, 0.2-3 part coupling agent, 5-15 part elastomer, 3-8 part Nano-meter SiO_22, 5-15 part reinforcer and 0.5-4 part firming agent be sufficiently stirred for；
S4, being injected in mould by above-mentioned mixed solution, at 60-100 DEG C, curing molding under 8-15MPa, the demoulding prepares the composite for juvenile automobile car body panel.
As preferably, acid solution described in step S1 is the one in concentrated nitric acid, concentrated sulphuric acid, and heating-up temperature is 60-120 DEG C.
As preferably, solvent described in step S2 is thionyl chloride, and acid binding agent is DMF, and initiator is DMAP, grafted monomers is the one in ethylenediamine or ethylene glycol, and reaction temperature is 60-100 DEG C.
As preferably, the mol ratio of carbon fiber described in step S2 and solvent is 1:(1-8), the mol ratio of acid binding agent, initiator and grafted monomers is (0.5-5): (1-5): 1.
Compared with prior art, the method have the advantages that
1. the present invention is carbon fibre composite for the composite of juvenile automobile car body panel, carbon fiber quality is equivalent to the 20-30% of steel weight, but hardness but reaches more than 10 times of steel, so the juvenile automobile vehicle body made with carbon fibre composite can make automotive light weight technology, about 60% can be reduced than the body of a motor car weight of common iron, but safety but shows no sign of reducing, and its mechanical strength and impact resilience are high all the better.
2. the present invention is in the composite of juvenile automobile car body panel, and carbon fiber carries out surface treatment through peroxidating and chemical graft, makes carbon fiber better to combine with epoxy resin, improves the mechanical property of carbon fibre composite.
3. the present invention is for being also added into the nanometer hydroxyapatite through coupling agent lecithin modification in the composite of juvenile automobile car body panel, make nanometer hydroxyapatite likely with epoxy resin generation chemical bonds, thus being effectively improved the interfacial bonding property of nanometer hydroxyapatite and epoxy resin, improve the mechanical property of carbon fibre composite.
4. the present invention is for, in the composite of juvenile automobile car body panel, being also added into Nano-meter SiO_22, elastomer, reinforcer and firming agent, well combine with other material, effectively improve the mechanical property of carbon fibre composite, so that the performances such as wear-resistant, the impact strength of the juvenile automobile car body panel being made up of carbon fibre composite obtain bigger improvement, reduce the follow-up upkeep cost of juvenile automobile car body panel, and extend the service life of juvenile automobile car body panel.
Detailed description of the invention
The following is specific embodiments of the invention, technical scheme is further described, but the present invention is not limited to these embodiments.
Table 1: embodiment of the present invention 1-4 is for the composite of juvenile automobile car body panel
Constituent and parts by weight
Embodiment 1:
First, carbon fiber is removed the pulp layer on surface and impurity with acetone extraction 35h, then with distilled water wash, be placed in concentrated nitric acid after drying and be heated to 80 DEG C of oxidation 2h, then use distilled water wash.Then the carbon fiber after oxidation is placed in thionyl chloride, under acid binding agent DMF, initiator DMAP and grafted monomers ethylenediamine exist, is heated to 80 DEG C of reaction 3h；Wherein, the mol ratio of carbon fiber and thionyl chloride is 1:4, and the mol ratio of acid binding agent DMF, initiator DMAP and grafted monomers ethylenediamine is 2:3:1.Reaction is washed after terminating, sample preparation obtains modified carbon fiber.
Weigh modified carbon fiber 40 parts prepared through ultrasonic disperse 30min, it is subsequently adding 30 parts of epoxy resin at 80 DEG C, reacts 2h, be subsequently adding the Nano-meter SiO_2 of the nanometer hydroxyapatite of 3 parts of 3-20nm, 0.5 part of lecithin coupling agent, 8 parts of natural rubber elastomer, 3 parts of 3-20nm2, the chromium oxide reinforcer of 8 parts of 3-20nm and 2 parts of methyl ethyl ketone peroxide firming agent are sufficiently stirred for.Injecting in mould by mixed solution after stirring, at 80 DEG C, curing molding under 10MPa, the demoulding prepares the final products composite for juvenile automobile car body panel.
Embodiment 2:
First, carbon fiber is removed the pulp layer on surface and impurity with acetone extraction 40h, then with distilled water wash, put and be heated to 80 DEG C of oxidation 2h in concentrated sulfuric acid after drying, then use distilled water wash.Then the carbon fiber after oxidation is placed in thionyl chloride, under acid binding agent DMF, initiator DMAP and grafted monomers ethylene glycol exist, is heated to 80 DEG C of reaction 3h；Wherein, the mol ratio of carbon fiber and thionyl chloride is 1:4, and the mol ratio of acid binding agent DMF, initiator DMAP and grafted monomers ethylene glycol is 2:3:1.Reaction is washed after terminating, sample preparation obtains modified carbon fiber.
Weigh modified carbon fiber 46 parts prepared through ultrasonic disperse 30min, it is subsequently adding 36 parts of epoxy resin at 80 DEG C, reacts 2h, be subsequently adding the Nano-meter SiO_2 of the nanometer hydroxyapatite of 6 parts of 20-40nm, 1 part of lecithin coupling agent, 4 parts of epoxy natural rubbers and the elastomer of 4 parts of neoprene compositions, 5 parts of 20-40nm2, the reinforcer of boron nitride composition of the aluminium oxide of 4 parts of 20-40nm and 4 parts of 20-40nm and 2 parts of methyl tetrahydrophthalic anhydride firming agent are sufficiently stirred for.Injecting in mould by mixed solution after stirring, at 80 DEG C, curing molding under 10MPa, the demoulding prepares the final products composite for juvenile automobile car body panel.
Embodiment 3:
First, carbon fiber is removed the pulp layer on surface and impurity with acetone extraction 40h, then with distilled water wash, be placed in concentrated nitric acid after drying and be heated to 90 DEG C of oxidation 3h, then use distilled water wash.Then the carbon fiber after oxidation is placed in thionyl chloride, under acid binding agent DMF, initiator DMAP and grafted monomers ethylenediamine exist, is heated to 100 DEG C of reaction 4h；Wherein, the mol ratio of carbon fiber and thionyl chloride is 1:6, and the mol ratio of acid binding agent DMF, initiator DMAP and grafted monomers ethylenediamine is 3:2:1.Reaction is washed after terminating, sample preparation obtains modified carbon fiber.
Weigh modified carbon fiber 55 parts prepared through ultrasonic disperse 40min, it is subsequently adding 45 parts of epoxy resin at 100 DEG C, reacts 3h, be subsequently adding the Nano-meter SiO_2 of the nanometer hydroxyapatite of 9 parts of 40-60nm, 2 parts of lecithin coupling agents, 10 parts of butadiene-styrene rubber elastomers, 6 parts of 40-60nm2, the glass microballoon reinforcer of 8 parts of 40-60nm and 3 parts of methyl ethyl ketone peroxide firming agent are sufficiently stirred for.Injecting in mould by mixed solution after stirring, at 90 DEG C, curing molding under 12MPa, the demoulding prepares the final products composite for juvenile automobile car body panel.
Embodiment 4:
First, carbon fiber is removed the pulp layer on surface and impurity with acetone extraction 45h, then with distilled water wash, be placed in concentrated nitric acid after drying and be heated to 120 DEG C of oxidation 4h, then use distilled water wash.Then the carbon fiber after oxidation is placed in thionyl chloride, under acid binding agent DMF, initiator DMAP and grafted monomers ethylenediamine exist, is heated to 100 DEG C of reaction 5h；Wherein, the mol ratio of carbon fiber and thionyl chloride is 1:8, and the mol ratio of acid binding agent DMF, initiator DMAP and grafted monomers ethylenediamine is 5:5:1.Reaction is washed after terminating, sample preparation obtains modified carbon fiber.
Weigh modified carbon fiber 60 parts prepared through ultrasonic disperse 50min, it is subsequently adding 50 parts of epoxy resin at 120 DEG C, reacts 3h, be subsequently adding the Nano-meter SiO_2 of the nanometer hydroxyapatite of 12 parts of 60-80nm, 3 parts of lecithin coupling agents, 5 parts of nitrile rubbers and the elastomer of 5 parts of neoprene compositions, 8 parts of 60-80nm2, the copper powder of 5 parts of 60-80nm and reinforcer and 2 parts of MDA firming agent of 5 parts of 60-80nm carborundum compositions are sufficiently stirred for.Injecting in mould by mixed solution after stirring, at 100 DEG C, curing molding under 15MPa, the demoulding prepares the final products composite for juvenile automobile car body panel.
The composite being used for juvenile automobile car body panel that embodiment of the present invention 1-4 prepares is carried out performance test, and test result is as shown in table 2.
What table 2: embodiment of the present invention 1-4 prepared is used for juvenile automobile car body panel
The performance test results of composite
From table 2 it can be seen that the composite density for juvenile automobile car body panel that embodiment of the present invention 1-4 prepares is approximately in 1.5-1.6g/cm3Between, the car body panel quality prepared with composite of the present invention to alleviate many, but the bus body strength that the present invention makes for the strength ratio steel of composite of juvenile automobile car body panel is high more than 10 times, and security performance is better than the vehicle body that steel are made.
Specific embodiment described herein is only to present invention spirit explanation for example.Described specific embodiment can be made various amendment or supplements or adopt similar mode to substitute by those skilled in the art, but without departing from the spirit of the present invention or surmount the scope that appended claims is defined.
Although the present invention has made a detailed description and has quoted as proof some specific embodiments, but to those skilled in the art, as long as it is obvious for can making various changes without departing from the spirit and scope of the present invention or revise.
Claims (9)
1. the composite for juvenile automobile car body panel, it is characterized in that, described composite is carbon fibre composite, described carbon fibre composite is become to be grouped into by following parts by weight: modified carbon fiber: 40-60 part, epoxy resin: 30-50 part, elastomer: 5-15 part, nanometer hydroxyapatite: 3-12 part, coupling agent: 0.2-3 part, Nano-meter SiO_22: 3-8 part, reinforcer: 5-15 part, firming agent: 0.5-4 part；Wherein, described coupling agent is lecithin.
2. a kind of composite for juvenile automobile car body panel according to claim 1, it is characterised in that described reinforcer is one or more in chromium oxide, copper powder, aluminium oxide, carborundum, boron nitride, glass microballoon.
3. a kind of composite for juvenile automobile car body panel according to claim 1 and 2, it is characterised in that described nanometer hydroxyapatite, Nano-meter SiO_22, reinforcer particle diameter be 3-80nm.
4. a kind of composite for juvenile automobile car body panel according to claim 1, it is characterised in that described elastomer is one or more in natural rubber, epoxy natural rubber, butadiene-styrene rubber, nitrile rubber, neoprene.
5. a kind of composite for juvenile automobile car body panel according to claim 1, it is characterised in that described firming agent is the one in methyl ethyl ketone peroxide, methyl tetrahydrophthalic anhydride, MDA.
6. the preparation method for the composite of juvenile automobile car body panel, it is characterised in that described preparation method comprises the following steps:
S1, carbon fiber is removed with acetone extraction 35-45h the pulp layer on surface and impurity, then with distilled water wash, put heated oxide 1-4h in an acidic solution after drying, then with distilled water wash, standby；
S2, putting in a solvent by the carbon fiber after above-mentioned oxidation, reacting by heating 1-5h under acid binding agent, initiator and grafted monomers exist, after reaction terminates, washing, sample preparation obtain modified carbon fiber；
S3, weigh the above-mentioned prepared modified carbon fiber ultrasonic disperse 20-50min of 40-60 part, it is subsequently adding 30-50 part epoxy resin at 60-120 DEG C, reacts 1-3h, be subsequently adding 3-12 part nanometer hydroxyapatite, 0.2-3 part coupling agent, 5-15 part elastomer, 3-8 part Nano-meter SiO_22, 5-15 part reinforcer and 0.5-4 part firming agent be sufficiently stirred for；
S4, being injected in mould by above-mentioned mixed solution, at 60-100 DEG C, curing molding under 8-15MPa, the demoulding prepares the composite for juvenile automobile car body panel.
7. the preparation method of a kind of composite for juvenile automobile car body panel according to claim 6, it is characterised in that acid solution described in step S1 is the one in concentrated nitric acid, concentrated sulphuric acid, and heating-up temperature is 60-120 DEG C.
8. the preparation method of a kind of composite for juvenile automobile car body panel according to claim 6, it is characterized in that, solvent described in step S2 is thionyl chloride, and acid binding agent is DMF, initiator is DMAP, grafted monomers is the one in ethylenediamine or ethylene glycol, and reaction temperature is 60-100 DEG C.
9. the preparation method of a kind of composite for juvenile automobile car body panel according to claim 6 or 8, it is characterized in that, the mass ratio of carbon fiber described in step S2 and solvent is 1:(1-8), the mol ratio of acid binding agent, initiator and grafted monomers is (0.5-5): (1-5): 1.
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| CN105198279A (en) * | 2015-11-04 | 2015-12-30 | 李孟平 | Preparation method of carbon-fiber-reinforced composite material |
| CN107353599A (en) * | 2017-08-23 | 2017-11-17 | 伊婕 | A kind of wear-resisting type composite and preparation method thereof |
| CN109294168A (en) * | 2018-10-12 | 2019-02-01 | 长沙小如信息科技有限公司 | New-energy automobile body material and preparation method thereof |
| CN109401335A (en) * | 2018-11-16 | 2019-03-01 | 宁波优贝车业有限公司 | A kind of light-weight environment-friendly carbon fibre composite of perambulator and preparation method thereof |
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