CN100430640C - High pressure nitrogen storage bottle made of PBO fiber and carbon fiber composite material and its preparation method - Google Patents

High pressure nitrogen storage bottle made of PBO fiber and carbon fiber composite material and its preparation method Download PDF

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CN100430640C
CN100430640C CNB2006101509866A CN200610150986A CN100430640C CN 100430640 C CN100430640 C CN 100430640C CN B2006101509866 A CNB2006101509866 A CN B2006101509866A CN 200610150986 A CN200610150986 A CN 200610150986A CN 100430640 C CN100430640 C CN 100430640C
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winding
layer
thickness
hoop
screw
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CN1948816A (en
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张春华
黄玉东
孟令辉
卢晓东
黄姗
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Harbin Institute of Technology
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Harbin Institute of Technology
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Abstract

The invention relates to a nitrogen cylinder and its preparation method, in which, on the outside surface of the neoprene lining is bonded an adhesive layer and the outside surface of the adhesive layer is bonded to the inside surface of the inner structure layer of carbon fibre composite; the inside surface of the outer structure layer of PBO fibre composite is wound on the outside surface of carbon fibre composite inner structure layer and on the outside surface of the outer structure layer of PBO fibre composite is wound an outer protective covering of glass fibre composite. The method consists in: coating an adhesive layer on the outside surface of the lining; overlying a spiral and toroidal wound inner structure layer, an outer structure layer and an outer protective covering; curing and then getting the preset inventive nitrogen cylinder.

Description

The preparation method of pbo fiber and carbon fiber hybrid composite material high pressure storage nitrogen bottle
Technical field
The present invention relates to the preparation method of composite material high pressure storage nitrogen bottle.
Background technique
Fibre reinforced composites have higher specific strength and specific stiffness, and therefore, the fibrous composite gas cylinder has obtained in fields such as space flight, aviation, advanced weaponry, boats and ships, the lifesaving of speedily carrying out rescue work, environmentally friendly vehicles using widely.The working pressure of existing fibrous composite high pressure storage nitrogen bottle is generally all up to 30MPa, the times of fatigue of cycle charge discharge is about 3000 times, particularly the high pressure storage nitrogen bottle that uses for high-technology fields such as space flight, aviation, advanced weaponries also require in light weight, i.e. gas cylinder characteristic coefficient PV/W CIt is high that value is wanted.The construction layer of existing composite material high pressure storage nitrogen bottle all is to adopt single fibrous composite to make as glass fiber compound material, organic fiber composite material (as kevlar fiber, pbo fiber etc.) or carbon fiber composite, but the tensile strength and the stretch modulus of single glass fiber compound material are lower, and the compression performance of organic fiber composite material is lower; Anti-fracture strain of carbon fiber composite and impact toughness are lower.Therefore, adopt the characteristic coefficient of the high pressure storage nitrogen bottle that single fibrous composite makes low, safety reliability is relatively poor.
Summary of the invention
The present invention adopts single glass fibre, organic fiber or carbon fiber in order to solve existing high pressure storage nitrogen bottle construction layer, and the tensile strength and the stretch modulus of glass fibre are lower, and the compression performance of organic fiber (as pbo fiber) is lower; Anti-fracture strain of carbon fiber and impact toughness are lower, cause the problem of low, safety reliability difference in high pressure storage nitrogen cascade working life, provide a kind of pbo fiber and carbon fiber hybrid composite material high pressure to store up the preparation method of nitrogen bottle.
The present invention includes inside liner, adhesives layer and fibrous composite layer, it also comprises the glass fiber compound material external protection coating, the fibrous composite layer is by carbon fiber composite inner structure layer and pbo fiber composite material external structure layer, inside liner adopts the neoprene inside liner, the outer surface and the adhesives layer of neoprene inside liner are bonding, the internal surface of the outer surface of adhesives layer and carbon fiber composite inner structure layer is bonding, the internal surface of pbo fiber composite material external structure layer is wrapped on the outer surface of carbon fiber composite inner structure layer, and the outer surface of pbo fiber composite material external structure layer twines the glass fiber compound material external protection coating.
The preparation method of pbo fiber of the present invention and carbon fiber composite high pressure storage nitrogen bottle adopts the following step:
Step 1, even brushing one deck bonding interface agent layer 2 on the outer surface of the neoprene inside liner 1 that is shaped at first.
Step 2, adopt fiber wet method winding process to carry out the making of carbon fiber composite inner structure layer 3 at the outer surface of adhesives layer 2, carry out the winding of carbon fiber composite inner structure layer 3 successively according to screw and hoop over-over mode, the winding angle that spiral twines is 16 °~18 °, each winding layer thickness is 0.6mm~0.8mm, and the winding thickness of carbon fiber inner structure layer 3 is 4.2mm~8.8mm;
Step 3, in the hocket winding of pbo fiber composite material external structure layer 4 of screw and hoop on the outer surface of the carbon fiber composite inner structure layer 3 of step 2 winding shaping, the winding angle that spiral twines is 16 °~18 °, each winding layer thickness is 0.4mm~0.5mm, and the winding thickness of pbo fiber composite material external structure layer 4 is 2.0mm~4.0mm;
Step 4, twine two~three layers and hoop at the outer surface screw of the pbo fiber external structure layer 4 of completing steps three and twine two~triplex glass fibrous composite external protection coating 5, the screw winding angle is 25 °~45 °, each winding layer thickness is 0.5mm, and the winding thickness of glass fiber compound material external protection coating 5 is 2.0mm~3.0mm;
Step 5, the bottle behind the above-mentioned stack winding shaping is put into curing oven be cured, the initial solidification temperature is 60 ℃~70 ℃, insulation 2~3h, be warming up to 110 ℃~120 ℃ insulation 2h~4h, be warming up to 145 ℃~155 ℃ at last, insulation 3h~5h naturally cools to room temperature with stove and comes out of the stove, and promptly obtains pbo fiber of the present invention and carbon fiber hybrid composite material high pressure storage nitrogen bottle.
The thickness of above-mentioned elastometric lining layer 1 is that the thickness of 2mm~3mm, elastic adhesive layer 2 is 0.5mm~0.6mm.
The present invention has remedied the failure damage that the pressure cylinder made by single carbon fiber composite causes because of its low shock resistance and low strain level, remedy the failure damage that the pressure cylinder made by the composite material of single pbo fiber causes because of compression performance a little less than it and low interface shearing stress again, two kinds of materials of pbo fiber and carbon fiber are learnt from other's strong points to offset one's weaknesses, reached two kinds of purposes that fiber composite structure is optimized.Neoprene inside liner 1 can satisfy the tightness of nitrogen under the circulation high pressure.What the glass fiber compound material external protection coating can be protected pbo fiber composite material external structure layer 5 avoids mechanical deterioration and the environment aging action to it.High pressure of the present invention storage nitrogen bottle has long working life (times of fatigue of this high pressure storage nitrogen bottle cycle charge discharge is greater than 8000 times), higher safety reliability (bursting pressure reaches more than the 82MPa, and working pressure reaches 35MPa).
Description of drawings
Fig. 1 is a longitudinal profile structural representation of the present invention.
Embodiment
Embodiment one: describe present embodiment in conjunction with Fig. 1.Present embodiment is by inside liner 1, adhesives layer 2, the fibrous composite layer, glass fiber compound material external protection coating 5 is formed, the fibrous composite layer is made up of carbon fiber composite inner structure layer 3 and pbo fiber composite material external structure layer 4, inside liner 1 adopts neoprene inside liner 1, the outer surface of neoprene inside liner 1 and adhesives layer 2 are bonding, the internal surface of the outer surface of adhesives layer 2 and carbon fiber composite inner structure layer 3 is bonding, the internal surface of pbo fiber composite material external structure layer 4 is wrapped on the outer surface of carbon fiber composite inner structure layer 3, and the outer surface of pbo fiber composite material external structure layer 4 twines glass fiber compound material external protection coating 5.
The thickness of above-mentioned elastometric lining layer 1 is that the thickness of 2mm~3mm, elastic adhesive layer 2 is that the thickness of 0.5mm~0.6mm, carbon fiber inner structure layer 3 is that the thickness of 4.2mm~8.8mm, pbo fiber external structure layer 4 is that the thickness of 2.0mm~4.0mm, glass fiber compound material external protection coating 5 is 2.0mm~3.0mm.
Embodiment two: the preparation method of present embodiment adopts the following step:
Step 1, at first brushing thickness is the bonding interface agent layer 2 of 0.5mm~0.6mm on neoprene inside liner 1, should guarantee during brushing adhesives layer 2 that coating evenly and do not have a bubble; Neoprene inside liner 1 is that to adopt two layers of thickness be that the raw rubber sheet of 2mm~3mm is pasted on column bottle mould and is shaped, and the raw rubber sheet vulcanizes the tight function layer that forms integral body when being heating and curing by the fibrous composite with bottle.
Step 2, adopt fiber wet method winding process to carry out the making of carbon fiber composite inner structure layer 3 at the outer surface of adhesives layer 2, be wound in carbon fiber composite inner structure layer 3 according to the winding of one to two helical layer, two layers of hoop winding, the winding of one to two helical layer, one to two layer of hoop winding, the winding of one to two helical layer and one deck hoop successively, the winding angle that spiral twines is 16 °~18 °, each winding layer thickness is 0.6mm~0.8mm, and the winding thickness of carbon fiber inner structure layer 3 is 4.2mm~8.8mm;
Step 3, one to three helical layer twines, one deck hoop twines, two to three helical layers twine and a hoop is wound in pbo fiber composite material external structure layer 4 carrying out on the outer surface of the carbon fiber composite inner structure layer 3 of step 2 winding shaping, the winding angle that spiral twines is 16 °~18 °, each winding layer thickness is 0.4mm~0.5mm, and the winding thickness of pbo fiber composite material external structure layer 4 is 2.0mm~4.0mm;
The outer surface screw of step 4, the pbo fiber composite material external structure layer 4 that is shaped in step 3 twines two~three layers and hoop and twines two~triplex glass fibrous composite external protection coating 5, the screw winding angle is 25 °~45 °, each winding layer thickness is 0.5mm, and the winding thickness of glass fiber compound material external protection coating 5 is 2.0mm~3.0mm;
Step 5, the bottle behind the above-mentioned stack winding shaping is put into curing oven be cured, the initial solidification temperature is 60 ℃~70 ℃, insulation 2~3h, be warming up to 110 ℃~120 ℃ insulation 2h~4h, be warming up to 145 ℃~155 ℃ at last, insulation 3h~5h naturally cools to room temperature with stove and comes out of the stove, and promptly obtains pbo fiber of the present invention and carbon fiber hybrid composite material high pressure storage nitrogen bottle.
The resin matrix of carbon fiber composite and pbo fiber composite material is epoxy-resin systems.
The thickness of elastometric lining layer 1 is 2mm~3mm, and the thickness of elastic adhesive layer 2 is 0.5mm~0.6mm.
Embodiment three: the difference of present embodiment and embodiment two is that the brushing thickness of the elastic adhesive layer 2 of step 1 is 0.5mm; Carry out the winding of one deck screw, two layers of hoop winding, helical layer winding, the winding of one deck hoop, helical layer winding and the winding of one deck hoops in the step 2 successively, the winding angle that screw twines is 16 °, the thickness of each winding layer is 0.6mm, and the thickness of carbon fiber hybrid composite material inner structure layer 3 is 4.2mm; Adopt the winding of one deck screw, the winding of one deck hoop, the winding of two helical layers and one deck hoop to twine in the step 3 successively, the winding angle that screw twines is 16 °, and the thickness of each winding layer is 0.4mm, and the thickness of pbo fiber composite material external structure layer 4 is 2mm; Screw twines two layers and two layers of glass fiber compound material of hoop winding in the step 4, and the screw winding angle is 25 °, and each winding layer thickness is 0.5mm, and the thickness of glass fiber compound material external protection coating 5 is 2mm; Solidifying temperature is 60 ℃ in the step 5, and insulation 3h is warming up to 110 ℃ then, and insulation 4h is warming up to 150 ℃ at last again, insulation 5h.Other step is identical with embodiment two.
Embodiment four: the difference of present embodiment and embodiment two is that the brushing thickness of the elastic adhesive layer 2 of step 1 is 0.55mm; Carry out two helical layers in the step 2 successively to winding, two layers of hoop winding, the winding of two helical layers, the winding of one deck hoop, helical layer winding and the winding of one deck hoops, the winding angle that screw twines is 17 °, the thickness of each winding layer is 0.7mm, and the thickness of carbon fiber hybrid composite material inner structure layer 3 is 6.3mm; Adopt two helical layers to twine in the step 3 successively to winding, the winding of one deck hoop, the winding of two helical layers and one deck hoop, the winding angle that screw twines is 17 °, the thickness of each winding layer is 0.4mm, and the thickness of pbo fiber composite material external structure layer 4 is 2.4mm; Screw twines two layers and hoop winding triplex glass fibrous composite in the step 4, and the screw winding angle is 35 °, and each winding layer thickness is 0.5mm, and the thickness of glass fiber compound material external protection coating 5 is 2.5mm; Solidifying temperature is 65 ℃ in the step 5, and insulation 2.5h is warming up to 115 ℃ then, and insulation 3h is warming up to 150 ℃ at last again, insulation 4h.Other step is identical with embodiment two.
Embodiment five: the difference of present embodiment and embodiment two is that the brushing thickness of the elastic adhesive layer 2 of step 1 is 0.6mm; Carrying out two helical layers in the step 2 successively twines and the winding of one deck hoops to winding, two layers of hoop winding, the winding of two helical layers, two layers of hoop winding, two helical layer, the winding angle that screw twines is 18 °, the thickness of each winding layer is 0.8mm, and the thickness of carbon fiber hybrid composite material inner structure layer 3 is 8.8mm; Adopt three helical layers to twine in the step 3 successively to winding, the winding of one deck hoop, the winding of three helical layers and one deck hoop, the winding angle that screw twines is 18 °, the thickness of each winding layer is 0.5mm, the thickness of pbo fiber composite material external structure layer 4 is that screw twines three layers and hoop winding triplex glass fibrous composite in the 4mm step 4, the screw winding angle is 45 °, each winding layer thickness is 0.5mm, and the thickness of glass fiber compound material external protection coating 5 is 3mm; Solidifying temperature is 70 ℃ in the step 5, and insulation 2h is warming up to 120 ℃ then, and insulation 3h is warming up to 155 ℃ at last again, insulation 3h.Other step is identical with embodiment two.
Carbon fiber has excellent compression strength, modulus of compression and good and interface performance resin matrix, but fracture strain and impact toughness are lower; And the tensile strength of pbo fiber reaches 5.8GPa, and stretch modulus 280GPa, elongation at break are 2.3%, and its density only is 1.56 * 10 3Kg/m 3, promptly pbo fiber has the highest specific tensile strength and compares stretch modulus in all high performance fibre material.In addition, the impact toughness of pbo fiber is far longer than carbon fiber.But the pbo fiber compression performance is lower, and is also relatively poor with the interface performance of resin matrix.
By the composite structure pressure cylinder that the single layer fibre material of different direction constitutes, under the pressure pressure effect, outermost surface at first reaches capacity stress and lost efficacy in bearing, and the destruction that is to say gas cylinder is that ecto-entad successively lost efficacy.Studies show that, the maximum fiber axial stress of the composite pressure gas cylinder of pressing in the carrying all occurs in end socket and locates near stack shell (flex point), all hoop layer fiber axial stresses are pressure stress herein, internal surface longitudinal layer fiber axial stress is a pressure stress, outer longitudinal layer fiber axial stress is a tensile stress, and to outer surface, the longitudinal layer fiber axis increases gradually to stress value by internal surface.Gas cylinder fiber transverse stress distributes with vertically different again, and the section fibre transverse stress is pressure stress in the end socket, and pressure stress increases gradually from inside to outside; End socket distributes with vertically just in time opposite near stack shell place fiber transverse stress, and the hoop layer fiber stress is tensile stress, and longitudinal layer inner fiber transverse stress is a pressure stress, is tensile stress near the outer surface layer transverse stress, and stress value increases from inside to outside gradually.
According to the composite structural laminate stress of column high pressure storage nitrogen bottle and the mechanics feature of pbo fiber and carbon fiber, to have outstanding compression performance, the carbon fiber design of low strain and good and interface performance resin matrix is in the inner structure layer of the gas cylinder compressive load with the carrying gas cylinder, to have the impulsive load that the design of excellent tensile property and impact toughness pbo fiber presses in main carrying gas cylinder the tension load that causes and external environment condition to cause at the skin of gas cylinder, so both can remedy the failure damage that the pressure cylinder made by single carbon fiber composite causes because of its low shock resistance and low strain level, remedy the failure damage that the pressure cylinder made by the composite material of single pbo fiber causes because of compression performance a little less than it and low interface shearing stress again, two kinds of lamination coatings are learnt from other's strong points to offset one's weaknesses, reached the purpose of two kinds of fiber composite structures and performance optimization, the working life and the Security that have improved composite material high pressure gas cylinder.

Claims (4)

1, the preparation method of pbo fiber and carbon fiber hybrid composite material high pressure storage nitrogen bottle is characterized in that the step of this method is as follows:
Step 1, even brushing one deck elastic interface adhesives layer (2) on the outer surface of the neoprene inside liner (1) that is shaped at first;
Step 2, adopt fiber wet method winding process to carry out the making of carbon fiber composite inner structure layer (3) at the outer surface of elastic interface adhesives layer (2), carry out the winding of carbon fiber composite inner structure layer (3) successively according to screw and hoop over-over mode, the winding angle that spiral twines is 16 °~18 °, each winding layer thickness is 0.6mm~0.8mm, and the winding thickness of carbon fiber composite inner structure layer (3) is 4.2mm~8.8mm;
Step 3, in the hocket winding of pbo fiber composite material external structure layer (4) of screw and hoop on the outer surface of the carbon fiber composite inner structure layer (3) of step 2 winding shaping, the winding angle that spiral twines is 16 °~18 °, each winding layer thickness is 0.4mm~0.5mm, and the winding thickness of pbo fiber composite material external structure layer (4) is 2.0mm~4.0mm;
Step 4, twine two~three layers and hoop at the outer surface screw of the pbo fiber composite material external structure layer (4) of completing steps three and twine two~triplex glass fibrous composite external protection coating (5), the screw winding angle is 25 °~45 °, each winding layer thickness is 0.5mm, and the winding thickness of glass fiber compound material external protection coating (5) is 2.0mm~3.0mm;
Step 5, the bottle behind the above-mentioned stack winding shaping is put into curing oven be cured, the initial solidification temperature is 60 ℃~70 ℃, insulation 2~3h, be warming up to 110 ℃~120 ℃ insulation 2h~4h, be warming up to 145 ℃~155 ℃, insulation 3h~5h at last, naturally cool to room temperature with stove and come out of the stove, promptly obtain pbo fiber and carbon fiber hybrid composite material high pressure storage nitrogen bottle.
2, the preparation method of pbo fiber according to claim 1 and carbon fiber hybrid composite material high pressure storage nitrogen bottle is characterized in that the brushing thickness of the elastic interface adhesives layer (2) of step 1 is 0.5mm; Carry out the winding of one deck screw, two layers of hoop winding, helical layer winding, the winding of one deck hoop, helical layer winding and the winding of one deck hoops in the step 2 successively, the winding angle that screw twines is 16 °, the thickness of each winding layer is 0.6mm, and the thickness of carbon fiber composite inner structure layer (3) is 4.2mm; Adopt the winding of one deck screw, the winding of one deck hoop, the winding of two helical layers and one deck hoop to twine in the step 3 successively, the winding angle that screw twines is 16 °, the thickness of each winding layer is 0.4mm, and the thickness of pbo fiber composite material external structure layer (4) is 2mm; Screw twines two layers and two layers of glass fiber compound material of hoop winding in the step 4, and the screw winding angle is 25 °, and each winding layer thickness is 0.5mm, and the thickness of glass fiber compound material external protection coating (5) is 2mm; Solidifying temperature is 60 ℃ in the step 5, and insulation 3h is warming up to 110 ℃ then, and insulation 4h is warming up to 145 ℃ at last again, insulation 5h.
3, the preparation method of pbo fiber according to claim 1 and carbon fiber hybrid composite material high pressure storage nitrogen bottle is characterized in that the brushing thickness of the elastic interface adhesives layer (2) of step 1 is 0.55mm; Carry out two helical layers in the step 2 successively to winding, two layers of hoop winding, the winding of two helical layers, the winding of one deck hoop, helical layer winding and the winding of one deck hoops, the winding angle that screw twines is 17 °, the thickness of each winding layer is 0.7mm, and the thickness of carbon fiber composite inner structure layer (3) is 6.3mm; Adopt two helical layers to twine in the step 3 successively to winding, the winding of one deck hoop, the winding of two helical layers and one deck hoop, the winding angle that screw twines is 17 °, the thickness of each winding layer is 0.4mm, and the thickness of pbo fiber composite material external structure layer (4) is 2.4mm; Screw twines two layers and hoop winding triplex glass fibrous composite in the step 4, and the screw winding angle is 35 °, and each winding layer thickness is 0.5mm, and the thickness of glass fiber compound material external protection coating (5) is 2.5mm; Solidifying temperature is 65 ℃ in the step 5, and insulation 2.5h is warming up to 115 ℃ then, and insulation 3h is warming up to 150 ℃ at last again, insulation 4h.
4, the preparation method of pbo fiber according to claim 1 and carbon fiber hybrid composite material high pressure storage nitrogen bottle is characterized in that the brushing thickness of the elastic interface adhesives layer (2) of step 1 is 0.6mm; Carrying out two helical layers in the step 2 successively twines and the winding of one deck hoops to winding, two layers of hoop winding, the winding of two helical layers, two layers of hoop winding, two helical layer, the winding angle that screw twines is 18 °, the thickness of each winding layer is 0.8mm, and the thickness of carbon fiber composite inner structure layer (3) is 8.8mm; Adopt three helical layers to twine in the step 3 successively to winding, the winding of one deck hoop, the winding of three helical layers and one deck hoop, the winding angle that screw twines is 18 °, the thickness of each winding layer is 0.5mm, and the thickness of pbo fiber composite material external structure layer (4) is 4mm; Screw twines three layers and hoop winding triplex glass fibrous composite in the step 4, and the screw winding angle is 45 °, and each winding layer thickness is 0.5mm, and the thickness of glass fiber compound material external protection coating (5) is 3mm; Solidifying temperature is 70 ℃ in the step 5, and insulation 2h is warming up to 120 ℃ then, and insulation 3h is warming up to 155 ℃ at last again, insulation 3h.
CNB2006101509866A 2006-11-06 2006-11-06 High pressure nitrogen storage bottle made of PBO fiber and carbon fiber composite material and its preparation method Expired - Fee Related CN100430640C (en)

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