Summary of the invention
The purpose of the present invention is in view of the above technical problems, provide a kind of graphene modified epoxy fiber winding shellForming method, the present invention merges it sufficiently with epoxy resin, then by graphene modified epoxy by modified to grapheneResin wet winding technology fiber winding shell, it is abundant to filament wound composite using the special construction performance of grapheneEnhancing.
In order to achieve this, the forming method of graphene modified epoxy fiber winding shell designed by the present invention,It includes the following steps:
Step 1: graphene oxide being modified, surface is carried out to graphene oxide using silane coupling agent and diluentIt is modified；
Step 2: using modified graphene oxide come reinforced epoxy, obtaining reinforced epoxy resin；
Step 3: carrying out the integrally formed of rocket motor shell, the rocket motor shell includes front connector, winding mandrelAnd rear joint, and it is covered on the heat insulating construction of front connector, winding mandrel and rear joint outer surface；
Step 4: using infiltrating the carbon fiber wire of above-mentioned reinforced epoxy resin to connecing before being covered in rocket motor shellHead, winding mandrel and the heat insulating construction of rear joint outer surface carry out multilayer Wet Winding Process；
Step 5: according to the curing cycle of reinforced epoxy resin, the rocket motor shell for having wound completion being put into baking ovenIn solidified；
Step 6: the rocket motor shell after step 5 solidifies is demoulded after cooling to room temperature, and it is modified to obtain grapheneEpoxy resin fiber winds shell.
The present invention utilizes the two-dimentional special construction of graphene, is modified to epoxy resin needed for fiber winding, makes itWith fiber by the way that after Wet Winding Process, fibre strength performance rate is improved, the burst strength of fiber winding shell is further increased,Improve the mass ratio of fiber winding motor case.
The present invention enables it to fill with selected Formulaion of epoxy resin by carrying out surface modification and grafting to grapheneThe combination divided, while mechanical stirring, ultrasound, the method for vibration are used, keep modified graphene abundant in Formulaion of epoxy resinDispersion, by adjust modified graphene, Formulaion of epoxy resin ratio, so that modified epoxy resin is suitble to Wet Winding ProcessCraftsmanship requirement, and the fiber winding shell burst strength of wet winding technology is greatly improved, raising about 12%, it is heat-resistingPerformance is promoted to 145 DEG C from 120 DEG C.
A kind of forming method of graphene modified epoxy high strength fibre winding shell, work used by the present inventionProcess is simple, with short production cycle, the performance of fiber winding motor case fibre strength is effectively increased, so that molding fiberWinding shell burst strength greatly improves, while the heat resistance of shell can be improved, and is that one kind effectively improves fiber winding engineThe method of casing rigidity.
Specific embodiment
Below in conjunction with drawings and examples, the present invention is described in further detail:
A kind of forming method of graphene modified epoxy fiber winding shell of the present invention, it includes following stepIt is rapid:
Step 1: graphene oxide being modified, surface is carried out to graphene oxide using silane coupling agent and diluentIt is modified (graphene to be grafted by above-mentioned material, so that modified graphene is preferably mixed with epoxy resin, is further expiredThe high performance resin formula that sufficient craftsmanship requires)；
Step 2: using modified graphene oxide come reinforced epoxy, obtaining reinforced epoxy resin and (give full play toThe characteristic of graphene, reinforced epoxy are improved Properties of Epoxy Resin)；
Step 3: carrying out the integrally formed of rocket motor shell, the rocket motor shell includes front connector 1, winding mandrel4 and rear joint 5, and it is covered on the heat insulating construction 2 of 5 outer surface of front connector 1, winding mandrel 4 and rear joint, as shown in Figure 1；
Step 4: using infiltrating the carbon fiber wire of above-mentioned reinforced epoxy resin to connecing before being covered in rocket motor shellFirst 1, the heat insulating construction 2 of 5 outer surface of winding mandrel 4 and rear joint carries out multilayer Wet Winding Process, forms 3 (Wet Winding Process of winding layerFor one of fiber winding forming method (generally thering is Wet Winding Process, dry method to wind two kinds).Modified resin craftsmanship meets wet processWinding requires, and can be formed using this method)；
Step 5: according to the curing cycle of reinforced epoxy resin, the rocket motor shell for having wound completion being put into baking ovenIn solidified；
Step 6: the rocket motor shell after step 5 solidifies is demoulded after cooling to room temperature, and it is modified to obtain grapheneEpoxy resin high strength fibre winds shell.
In the step 2 of above-mentioned technical proposal, the diluent is certain glycidol ether.Certain described glycidol ether is second twoAlcohol glycidol ether (669 diluent).The silane coupling agent is γ-(the third oxygen of 2,3- epoxy) propyl trimethoxy silicane(KH560), the active group of graphene ribbon can be made using this method, can be further reacted with epoxy resin.
In the step 1 of above-mentioned technical proposal, it is graphene oxide and silane that graphene oxide, which carries out the modified process in surface,Coupling agent is first mixed, then graphene oxide is reacted with the mixture of silane coupling agent with glycidol ether.It is describedThe process of mixing and the reaction carries out at 65~70 DEG C, and using mechanical stirring, ultrasonic disperse and vibration mixed phase knotThe mode of conjunction can be such that graphene disperses in the epoxy more evenly using this method, and modified material property is optimal.
In the step 2 of above-mentioned technical proposal, the formula of reinforced epoxy resin presses asphalt mixtures modified by epoxy resin based on equal mass percentRouge: curing agent: diluent: tough epoxy resin: promotor: modified graphene=70:60:25:30:0.5:(1~2.5).
Front connector 1 and rear joint 5 use metal material in the step 3 of above-mentioned technical proposal, and heat insulating construction 2 is rubber materialMaterial, winding mandrel 4 are metal core die or gypsum core model or water-soluble core mould.
In the step 4 of above-mentioned technical proposal before Wet Winding Process, to reinforced epoxy resin ultrasonic disperse again, it is wrapped over40~70 DEG C of Heating Water is used in journey to reinforced epoxy resin, winding casing surroundings heat (heating temperature using light bathAbout 30~40 DEG C), such as using super bath light irradiation (using the heating means first is that process is simple, second is that can in heating processThe wetting fibre for changing resin, plays fibre strength more preferably).
Curing cycle in the step 5 of above-mentioned technical proposal is to be first heated to 80 DEG C of 2~5h of heat preservation, is then heated to120 DEG C of heat preservations 2h~5h, finally heated to 150 DEG C 6~9h of heat preservation.Above-mentioned parameter is true according to modified epoxy cure kineticsIt is fixed, epoxy resin can be made to avoid that implode occurs using the curing cycle, obtain thoroughly solidifying while reducing internal stress, make to windComposite materials property and heat resistance reach best after molding.
In the step 6 of above-mentioned technical proposal, shell demoulding obtains graphene modified epoxy high strength fibre winding shellBody refers to the winding mandrel structure disassembly in above-mentioned forming process, abjection.
In the present embodiment, the structural parameters of rocket motor shell are as follows: shell cylinder section outer diameter φ 400mm, front and back end socket shapeFor ellipsoid, front and back end socket ellipsoid ratio is 1.7, and front connector hanging wire pole bore dia is 140mm, and rear joint hanging wire pole bore dia is208mm, shell cylinder segment length are 400mm.
In the present embodiment,
Step 1 is modified graphene oxide；
Using 200ml silane coupling agent KH560 and 10g graphene oxide (lamella diameter 400nm~4 μm；Thickness 0.8~It 1.5nm) is mixed, and carries out mechanical stirring 48h at a temperature of 70 DEG C ± 5 DEG C, then again and in 150g Formulaion of epoxy resin669 diluent of diluent, that is, glycol glycidyl ethers used carries out hybrid reaction, is not less than 36h using mechanical stirring after mixingAnd handled and be not less than 1.5 hours with 800W ultrasonic power, 3 hours modes are not less than in conjunction with mechanical shock, obtain modified graphiteAlkene solution.
Step 2 uses modified graphene reinforced epoxy；
The formula of reinforced epoxy resin presses epoxy resin based on equal mass percent: curing agent: diluent: toughness ringOxygen resin: promotor: modified graphene=70:60:25:30:0.5:1.5；
Step 3: winding shell components molding；
Add to obtain front and rear connector metal parts using TC11 titanium alloy forging machine, using sand core mold forming winding mandrel, adoptHeat insulating construction is formed with ethylene propylene diene rubber manual pasting, obtains the winding mandrel with heat insulating construction.
Step 4: using wet winding technology composite material casing；
By the above-mentioned Formulaion of epoxy resin mixed, the processing of ultrasonic disperse 800W ultrasonic power is not less than again before winding0.5 hour, scattered modified epoxy solution is then poured into wrapping machine dipping system, and using 40~70 DEG C of watersReinforced epoxy resin is heated, the above-mentioned φ 400 of molding is then twined using toray T700 carbon fiber and winds shell, winding processIt is middle that heating is irradiated to winding surface of shell using 200W super bath.
Step 5: shell solidification；
Above-mentioned Wrapping formed φ 400 is wound shell to be put into baking oven, according to 80 DEG C of heat preservation 3h, then 120 DEG C of heat preservations3h, last 150 DEG C of heat preservations 7h are solidified, cool to room temperature with the furnace and come out of the stove.
Step 6: shell demoulding obtains graphene modified epoxy high strength fibre winding shell.By above-mentioned shellSand core mould is washed out with (60 DEG C~80 DEG C) of hot water, obtains graphene modified epoxy high strength fibre winding shell.
Graphene modified epoxy tree is respectively adopted in other immovable situations for above-mentioned φ 400 winding shellRouge and unmodified epoxy resin have carried out shell production, and have carried out hydraulic bursting test, obtain graphene modified epoxyThe winding shell burst strength of winding preparation reaches 17.5MPa；Unmodified winding shell hydraulic pressure demolition intensity is 15.3MPa, is adoptedIt is obtained with DMA test method, the composite material prepared using graphene modified epoxy, glass transition temperature is 145 DEG C；The composite material of unmodified epoxy resin preparation, glass transition temperature are 120 DEG C, illustrate the modified epoxy resin that improvesTemperature tolerance.
The content that this specification is not described in detail belongs to the prior art well known to professional and technical personnel in the field.