CN1243194C - 50-litres hydrogen composite cylinder having carbon fiber wholly-wound, reinforced aluminum lining - Google Patents
50-litres hydrogen composite cylinder having carbon fiber wholly-wound, reinforced aluminum lining Download PDFInfo
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- CN1243194C CN1243194C CNB2004100175464A CN200410017546A CN1243194C CN 1243194 C CN1243194 C CN 1243194C CN B2004100175464 A CNB2004100175464 A CN B2004100175464A CN 200410017546 A CN200410017546 A CN 200410017546A CN 1243194 C CN1243194 C CN 1243194C
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
一种50升碳纤维全缠绕增强铝内衬储氢复合气瓶，以筒体及对称于筒体的两个含有内螺纹瓶口的椭圆曲面端部光滑无缝连接而成的铝内衬为芯模，铝内衬表面上按优化设计的铺层次序缠绕碳纤维层，其外表面上缠绕玻璃纤维抗冲击保护层，并在制造过程中采用“自紧”技术进行处理，其中铝内衬筒体部分上交替缠绕纵向螺旋缠绕纤维层和环向缠绕纤维层，纵向铺层次序与椭圆曲面端部纵向螺旋缠绕纤维层一致，并与椭圆曲面端部在筒体的连接处的纵向螺旋缠绕角连续，两个椭圆曲面端部的碳纤维层为变角度纵向螺旋缠绕纤维层。本发明可使氢燃料电动车在单次加满氢燃料的情况下的行驶里程接近或达到燃油汽车行驶里程，具有实际使用价值，具有持久的良好气密性能和安全性能。
A 50-liter carbon fiber full-winding reinforced aluminum-lined hydrogen storage composite gas cylinder, with a cylinder body and an aluminum liner formed by smooth and seamless connection of two elliptical curved surface ends with internal threaded bottle mouths symmetrical to the cylinder body. The carbon fiber layer is wound on the surface of the aluminum lining according to the optimally designed layering sequence, and the glass fiber impact protection layer is wound on the outer surface, and is processed by "self-tightening" technology in the manufacturing process, in which the aluminum lining cylinder The longitudinal helical winding fiber layer and the hoop winding fiber layer are alternately wound on the part, and the longitudinal layering sequence is consistent with the longitudinal helical winding fiber layer at the end of the elliptical surface, and is continuous with the longitudinal helical winding angle of the end of the elliptical surface at the junction of the cylinder , the carbon fiber layers at the ends of the two elliptical surfaces are longitudinal helically wound fiber layers with variable angles. The invention can make the mileage of the hydrogen fuel electric vehicle close to or reach the mileage of the fuel vehicle when the hydrogen fuel is filled up once, has practical use value, and has long-lasting good airtight performance and safety performance.
Description
Technical field
The present invention relates to a kind of 50 liters of carbon fibers and twine entirely and strengthen aluminum liner storage hydrogen composite cylinder, is the indispensable equipment that hydrogen is provided in the hydrogen fuel cell system in the hydrogen fuel electrocar, is used for storing compression hydrogen under the 35Mpa high pressure conditions.
Background technique
Proton Exchange Membrane Fuel Cells directly is converted into electric energy with the chemical energy of hydrogen, and electrolyte is a PEM.The working principle of Proton Exchange Membrane Fuel Cells is very simple: the hydrogen that acts as a fuel flows to an electrode tip of battery pack from hydrogen storage equipment, under the effect of anode catalyst, hydrogen molecule ionization is the hydrogen ion (being proton) and the electronegative electronics of positively charged; Electronics forms electric current at external circuit, can export electric energy to load in succession by suitable; PEM in the middle of hydrogen ion (proton) passes arrives negative electrode, and the oxygen (or air) that is input to negative electrode with the air pipe from the battery the other end generates water under the effect of catalyzer.Fuel cell is efficient with it, zero pollution characteristics has worldwide caused concern widely.Continuous decline along with development of technology and manufacture cost, Proton Exchange Membrane Fuel Cells is except being used in military fields such as space flight, because its operating temperature is low and it is fast to start, be a kind of zero environment protection type energy that pollutes that has, thereby become the traffic tool, particularly the optimal power of automobile obtains the favor of each big car manufactures of the world.
The hydrogen fuel electric motor car is filled it up with at single under the situation of fuel and the fuel-engined vehicle same distance of travelling, and under the requirement of limited space and weight, the storage of the hydrogen that acts as a fuel also is to be badly in need of the big technical barrier that solves.At present, the hydrogen storage cylinder that uses on the sample car of the hydrogen fuel electrocar of domestic development is to utilize the existing rock gas supporting compressed natural gas gas cylinder of fuel automobile that is used as power that is, the design work pressure of such compressed natural gas gas cylinder only is 20MPa.Energy conversion efficiency according to present hydrogen fuel cell, if on the hydrogen fuel electrocar, use working pressure only to be 50 liters of hydrogen storage cylinders of 20MPa, then fill it up with under the situation of hydrogen fuel at single, the distance travelled of hydrogen fuel electric motor car only is half of fuel-engined vehicle distance travelled, is difficult to reach the effect of actual use.Some big motor corporations in the world; Be 35MPa as design work pressure general and 50 liters of hydrogen storage cylinders that Volkswagen uses on the sample car of the hydrogen fuel electrocar that they develop, thereby make the hydrogen fuel electric motor car fill it up with at single under the situation of hydrogen fuel distance travelled near or reach the fuel-engined vehicle distance travelled, have the value of actual use.
At present, 50 liters of storage hydrogen composite cylinders of hydrogen fuel electrocar use have two kinds in the world.A kind of is the full winding plastic liner of carbon fiber composite cylinder, and another kind twines Thin-walled Aluminum liner composite cylinder entirely for carbon fiber.Before a kind of production procedure of storing up the hydrogen composite cylinder simpler, but leak easily the joint that in use fatigue life, short, its plastic inner lining and gas cylinder metal connect mouth.A kind of carbon fiber in back twines Thin-walled Aluminum liner composite cylinder entirely and in use has good fatigue life (fatigue life is greater than 45000 times), be difficult for to leak, Safety performance is good and deadweight also the composite cylinder than plastic inner lining is light; Guarantee that the difficult point that this kind composite cylinder has an above-mentioned good characteristic is stacking sequence and corresponding " self-tightening " pressure that how to provide rational carbon fiber structural layer in design.Though it is that the working pressure used of hydrogen fuel electrocar is that 35MPa stores up hydrogen composite cylinder main product in the world that the carbon current fiber twines Thin-walled Aluminum liner storage hydrogen composite cylinder entirely, but mainly be to utilize empirical correlation to determine stacking sequence and corresponding " self-tightening " pressure of carbon fiber structural layer in their design, be difficult to provide stacking sequence and rational " self-tightening " pressure of best carbon fiber structural layer, make the potential good characteristic of himself be difficult for playing a role.The carbon fiber of domestic present design twines entirely that to strengthen the aluminum liner composite cylinder supporting for the rock gas fuel automobile that is used as power, and its working pressure only is 20MPa, and fatigue life is less than 20000 times.The prior art also is difficult to be used for designing the composite structure stacking sequence of 35MPa high-pressure hydrogen storing composite cylinder and is to improve ' self-tightening ' technical finesse mode of taking its fatigue life.
Therefore, utilize finite element program software virtual emulation technology in design, to provide the stacking sequence of optimum carbon fiber structural layer and rational " self-tightening " pressure, guarantee that carbon fiber twines entirely and strengthen the aluminum liner composite cylinder and when bearing higher working pressure, have good fatigue life, Safety performance and less weight capacity ratio and be still an arduous challenge.The carbon fiber of making based on the stacking sequence of optimal design gained twines aluminum liner storage hydrogen composite cylinder entirely, under rational ' self-tightening ' pressure storage hydrogen composite cylinder is being carried out ' self-tightening ' in manufacture process handles, and makes the hydrogen fuel electrocar use working pressure to twine the key technical indexes that aluminum liner stores up the hydrogen composite cylinder reach advanced world standards fully (international automobile-used gas cylinder standard ISO 11439-2000) entirely as 50 liters of carbon fibers of 35MPa.
Summary of the invention
The objective of the invention is to for the hydrogen fuel electrocar provides a kind of novel, service behaviour safety, hydrogen storage ability height, working pressure is that 35MPa, 50 liters of carbon fibers twine aluminum liner storage hydrogen composite cylinder entirely, make it to have light as far as possible weight, and can satisfy the requirement of the international automobile-used gas cylinder standard ISO 11439-2000 that represents international most advanced level.
For realizing such purpose; the present invention is to twine by the stacking sequence of optimal design on core, the aluminum liner surface to twine glass fibre on carbon fiber layer, its outer surface as the shock resistance protective layer with the seamless thin wall aluminum liner, utilizes ' self-tightening ' treatment technology that storage hydrogen composite cylinder is carried out ' self-tightening ' in manufacture process and handles.
50 liters of carbon fibers that the present invention uses according to the hydrogen fuel electrocar twine the functional requirement of aluminum liner storage hydrogen composite cylinder, the requirement of the international automobile-used gas cylinder standard ISO 11439-2000 of reference entirely, adopt the composite structure finite element program that carbon fiber is twined the optimal design that aluminum liner storage hydrogen composite cylinder carries out stacking sequence entirely.The main bearing structure that carbon fiber twines aluminum liner storage hydrogen composite cylinder entirely is made up of aluminum liner and carbon fiber winding layer.Aluminum liner is to be formed by shell portion and two oval calotte end seamless links that contain internal screw finish that are symmetrical in shell portion.Carbon fiber winding layer on the aluminum liner shell portion is to twine layer of fibers (angle of fiber reinforcement direction and the vertical symmetry axis of Chu Qing composite cylinder is less than 20 °) and hoop winding layer of fibers (angle of fiber reinforcement direction and the vertical symmetry axis of Chu Qing composite cylinder equals 90 °) by longitudinal spiral alternately to be entwined by the stacking sequence of optimal design gained; the carbon fiber layer of two oval calotte ends of aluminum liner twines layer of fibers for the varied angle longitudinal spiral, twines glass fibre layer on the surface of the full winding layer of carbon fiber as the shock resistance protective layer.
50 liters of carbon fibers that hydrogen fuel electrocar of the present invention uses twine the inner lining structure that strengthens aluminum liner storage hydrogen composite cylinder entirely, are L by internal diameter as D, length
1Identical shaped, the rise of shell portion, two be L
2The oval calotte end and to contain internal thread be that M25, length are L
3The smooth seamless link of bottleneck form.Geometric parameter L wherein
2Choose and make the hoop working stress of two equal oval calotte ends of storage hydrogen composite cylinder approach zero, and D and L
1To choose be to guarantee that the volume that stores up the hydrogen composite cylinder equals 50 liters, the wall thickness t of aluminum liner choose be to guarantee its under the situation of minimum weight, carbon fiber twines the aluminum liner storage hydrogen composite cylinder maintenance of the aluminum liner under hydraulic test pressure elastic deformation after ' self-tightening ' handled entirely, scribble one deck anti-electrocorrosion coating on the aluminum liner outer surface, then T700-12KC or T700-24KC carbon fiber are wrapped in moulding on the aluminum liner entirely.
The carbon fiber winding layer of aluminum liner shell portion is to twine layer of fibers (angle of fiber reinforcement direction and the vertical symmetry axis of Chu Qing composite cylinder is less than 20 °) and hoop winding layer of fibers (angle of fiber reinforcement direction and the vertical symmetry axis of Chu Qing composite cylinder equals 90 °) by longitudinal spiral alternately to be entwined by the stacking sequence of optimal design gained; The cotton yarn tape sheet total number that vertically twines a full circulation layer is M (bar/circulation layer), at cylindrical shell L
1It is b (mm/ bar) that part adopts the winding of hoop uniform thickness, its cotton yarn tape sheet width; Only there is the layer of fibers that twines along curved surface geodesic curve longitudinal spiral two equal oval calotte ends of aluminum liner, and its stacking sequence is consistent with the longitudinal spiral winding layer of fibers of cylindrical shell; The last glass fibre layer of winding of one deck longitudinal spiral and the winding of one deck hoop that twines on the surface of the full winding layer of carbon fiber is as the shock resistance protective layer.
The material behavior of aluminum liner satisfy to wait that (the plastic yield criterion of Feng-Mi Saisi), the carbon fiber winding layer satisfies the maximum tension stress failure criterion for the linear elasticity material to sclerosis Von Mises among the present invention.Twine fatigue life, the air-tightness that aluminum liner stores up the hydrogen composite cylinder for the working pressure that the hydrogen fuel electrocar that improves the present invention's design uses entirely as 35MPa, 50 liters of carbon fibers, need to handle numerical simulation determined " self-tightening " pressure P according to " self-tightening "
zComposite cylinder after the moulding is carried out " self-tightening " to be handled, being about to carbon fiber after the moulding twines pressure that the pressurization of aluminum liner storage hydrogen composite cylinder surpasses certain hydrostatic test regulation entirely and makes the aluminum liner of storage hydrogen composite cylinder enter state of plastic deformation fully, unload and be depressed into zero then, make the aluminum liner of this storage hydrogen composite cylinder under zero pressure, present compressive stress state, and the full winding layer of carbon fiber presents tensile stress state, guarantee that under given working pressure and hydraulic test pressure the aluminum liner that carbon fiber twines aluminum liner storage hydrogen composite cylinder entirely is in elastic deformation fully.
50 liters of carbon fibers that the hydrogen fuel electrocar of the present invention design uses twine aluminum liner storage hydrogen composite cylinder entirely and can be undertaken Wrapping formed by certain stacking sequence and technology mode at an easy rate and by handling numerical simulation determined ' self-tightening ' pressure P by ' self-tightening '
zComposite cylinder after the moulding is carried out ' self-tightening ' to be handled.Storage hydrogen composite cylinder of the present invention satisfies the rational Stress Field Distribution that international automobile-used gas cylinder standard ISO 11439-2000 design code requires, guarantee that the design work pressure of storage hydrogen composite cylinder under the condition of using minimum fiber consumption is 35MPa, its safety coefficient n 〉=2.35, destruction is torn the cylindrical shell position that originates in composite cylinder, no fragment, the aluminum liner of storage hydrogen composite cylinder is in elastic deformation all the time under given working pressure, guarantees that this storage hydrogen composite cylinder has the Safety performance of lasting (fatigue life cycle N 〉=45000 time) good air-tightness and the best.
Description of drawings
Fig. 1 twines the structural drawing of aluminum liner storage hydrogen composite cylinder entirely for 50 liters of carbon fibers of the present invention.
Among Fig. 1, the shell portion of 1 expression aluminum liner, the oval calotte end of 2 expression aluminum liners, the bottleneck of 3 expression aluminum liners, 4 expression anti-electrocorrosion coatings, 5 expression aluminum liner shell portion carbon fiber winding layer [± α
1/ H
3/ ± α
2/ H
2/ ± α
3/ H
2] wherein: H
iExpression i layer hoop winding layer, α
iThe angle of (i=1,2,3) expression fiber reinforcement direction and composite cylinder symmetry axis, the longitudinal spiral of 6 expression aluminum liner oval calotte ends twines layer of fibers [± α
1/ ± α
2/ ± α
3], 7 expression glass fibre shock resistance protective layers, L
1The cylindrical shell length of expression storage hydrogen composite cylinder, L
2The rise of expression storage hydrogen composite cylinder oval calotte end, L
3Expression contains the bottleneck length of internal thread M25, and D represents to store up the internal diameter of hydrogen composite cylinder cylindrical shell, and t represents the wall thickness of aluminum liner shell portion.
Fig. 2 twines the limited element calculation model of aluminum liner storage hydrogen composite cylinder 1/8th symmetrical structures entirely for 50 liters of carbon fibers of the present invention.
Fig. 3 twines the stacking sequence of aluminum liner storage hydrogen composite cylinder Fig. 2 middle cylinder body part 1 entirely for 50 liters of carbon fibers of the present invention.Angle between layer angle, shop (θ) expression fiber reinforcement direction and gas cylinder cylindrical shell hoop.
Fig. 4 twines the stacking sequence of oval calotte end 2 among aluminum liner storage hydrogen composite cylinder Fig. 2 entirely for 50 liters of carbon fibers of the present invention.Angle between layer angle, shop (θ) expression fiber reinforcement direction and the composite cylinder cylindrical shell hoop.
Embodiment
Below in conjunction with drawings and Examples technological scheme of the present invention is further described.
50 liters of carbon fibers of the present invention twine full aluminum liner storage hydrogen composite cylinder be core with the aluminum liner, utilize fiber winding machine, the T700-12KC carbon fiber be wrapped in moulding on the aluminum liner entirely by the stacking sequence of optimal design, its structure is as shown in Figure 1.Composite cylinder aluminum liner of the present invention is made up of cylindrical shell 1 and two oval calotte end 2 smooth seamless links that contain internal screw finish 3 being symmetrical in cylindrical shell; smear one deck anti-electrocorrosion coating 4 on the outer surface of aluminum liner; the optimization stacking sequence that obtains by numerical simulation on aluminum liner twines carbon fiber layer; comprise that shell portion carbon fiber winding layer 5 and oval calotte end longitudinal spiral twine layer of fibers 6; shell portion carbon fiber winding layer 5 twines layer of fibers by longitudinal spiral and hoop winding layer of fibers alternately is entwined; vertically stacking sequence is consistent with oval calotte end 6 longitudinal spirals winding layer of fibers; and continuous with oval calotte end 6 at the longitudinal spiral winding angle of the joint of cylindrical shell, on the surface of shell portion carbon fiber winding layer 5 and oval calotte end longitudinal spiral winding layer of fibers 6, twine the glass fibre layer of winding of one deck longitudinal spiral and the winding of one deck hoop as shock resistance protective layer 7.
Embodiment is:
1) among Fig. 1, the physical dimension of shown aluminum liner is taken as respectively:
The length of cylindrical shell 1 is L
1=531mm, inside diameter D=327mm, the rise L of oval calotte end 2
2=90mm, containing internal thread is the length L of the bottleneck 3 of M25
3=50mm, wall thickness t=3.4mm, the volume that guarantees composite cylinder of the present invention is 50 liters.
2) on the outer surface of aluminum liner, smear the very thin polyurethane varnish of one deck as anti-electrocorrosion coating 4.
3) the T700-12KC carbon fiber bundle immerses behind the epoxy resin according to certain design tension force T, is wrapped on the aluminum liner by the stacking sequence of optimal design; Wherein the stacking sequence of aluminum liner shell portion carbon fiber winding layer 5 is:
[±α
1/H
3/±α
2/H
2/±α
3/H
2]，
The stacking sequence that the longitudinal spiral of oval calotte end twines layer of fibers 6 is: [± α
1/ ± α
2/ ± α
3]
Wherein: α
iThe angle of (i=1,2,3) expression fiber reinforcement direction and composite cylinder symmetry axis is respectively: α
1=12 °, α
2=16 °, α
3=14 °, H
iExpression i layer hoop winding layer.
4) carbon fiber winding layer 5 and 6 winding process parameter:
T700 (K12-Tex800) folded yarn number of share of stock is: N=5 (thigh/bar), vertically twining completely, a circuit cotton yarn tape sheet total number is: M=242 (bar/circulation layer), the cotton yarn tape sheet width that hoop twines is: b=5.7 (mm/ bar).
5), the mean tension of single-stranded fiber: T=10-15 (N/ thigh) when twining, and in winding process, suitably control epoxy resin content, guarantee that fiber volume fraction is V
f=0.63 ± 0.02.
6) adopt 5 strands of glass fiber yarns to twine on carbon fiber layer, vertical circulation layer, a cotton yarn tape sheet total number are: M
b=160 and one deck hoop winding layer strap width be: b
b=17 (mm/ bars) are shock resistance glass protective layer 8.
7) put into curing oven and be cured moulding by the temperature curve of setting.
8) 50 liters of carbon fibers behind the solidifying are twined full aluminum liner storage hydrogen composite cylinder according to numerical simulation determined ' self-tightening ' pressure P
z=54MPa carries out ' self-tightening ' to composite cylinder to be handled.
Twine the limited element calculation model of aluminum liner storage hydrogen composite cylinder and stacking sequence entirely shown in Fig. 2-4 according to 50 liters of carbon fibers, according to numerical simulation determined ' self-tightening ' pressure composite cylinder is carried out after ' self-tightening ' handle numerical simulation, the aluminum liner of composite cylinder is in elastic deformation fully under hydraulic pressure (50MPa) test effect, guarantees volume rate of residual V
δ≤ 2%, improve its fatigue life.Finite Element Numerical Simulation result of calculation shows that hydrogen fuel electrocar of the present invention twines entirely and strengthens aluminum liner storage hydrogen composite cylinder after ' self-tightening ' handled with 35MPa, 50 liters of carbon fibers, Stress Field Distribution rationally, can be that to be subjected to maximum bursting pressure be that the bursting pressure value 95Mpa of 92Mpa and actual tests is very approaching, its safety coefficient n 〉=2.58.
Hydrogen fuel electrocar according to specific embodiment of the invention manufacturing twines enhancing aluminum liner storage hydrogen composite cylinder entirely with 50 liters of carbon fibers, has light as far as possible weight, and can satisfy the requirement of the ISO11439 standard of representing international most advanced level.Its key technical indexes is:
1) weight W of empty bottle≤24 (kg),
2) hydraulic test pressure effect lower volume rate of residual V
δ≤ 2%,
3) safety coefficient n 〉=2.35,
4) normal temperature fatigue life cycle N 〉=45000 (inferior).
Claims (2)
1, a kind of 50 liters of carbon fibers twine entirely and strengthen aluminum liner storage hydrogen composite cylinder, it is characterized in that with the internal diameter being that D=327mm, length are L
1The cylindrical shell of=531mm (1) and rise are L
2The aluminum liner that the smooth seamless link in two the oval calotte ends (2) that are symmetrical in cylindrical shell of=90mm is formed is a core, on aluminum liner, twine carbon fiber layer, comprise that shell portion carbon fiber winding layer (5) and oval calotte end longitudinal spiral twine layer of fibers (6), shell portion carbon fiber winding layer (5) twines layer of fibers by longitudinal spiral and hoop winding layer of fibers alternately is entwined, vertically stacking sequence is consistent with oval calotte end longitudinal spiral winding layer of fibers (6), and continuous with the oval calotte end at the longitudinal spiral winding angle of the joint of cylindrical shell, the glass fibre layer that twines winding of one deck longitudinal spiral and the winding of one deck hoop on the surface of shell portion carbon fiber winding layer (5) and oval calotte end longitudinal spiral winding layer of fibers (6) is as shock resistance protective layer (7); The stacking sequence of described shell portion carbon fiber winding layer (5) is [± 12 °/(90 °) 3/ ± 16 °/(90 °) 2/ ± 14 °/(90 °) 2], the stacking sequence that two oval calotte end longitudinal spirals of aluminum liner twine layer of fibers (6) is [± 12 °/± 16 °/± 14 °], T700 (K12-Tex800) the folded yarn number of share of stock that adopts is: N=5 thigh/bar, vertically twining full circuit cotton yarn tape sheet total number is: M=242 bar/circulation layer, the cotton yarn tape sheet width that the hoop uniform thickness twines is: the b=5.7mm/ bar, the mean tension of single-stranded fiber during winding: the T=10-15N/ thigh, and in winding process, control epoxy resin content, guarantee that fiber volume fraction is V
f=0.63.
2,50 liters of carbon fibers as claimed in claim 1 twine entirely and strengthen aluminum liner storage hydrogen composite cylinder, it is characterized in that the composite cylinder after the moulding carries out " self-tightening " processing through the pressure of Pz=54MPa, composite cylinder pressurization after the moulding soon, make the aluminum liner of composite cylinder enter state of plastic deformation fully, unload then and be depressed into zero, make the aluminum liner of this composite cylinder under zero pressure, present compressive stress state, and the carbon fiber winding layer presents tensile stress state, guarantee under given working pressure and hydraulic test pressure, the aluminum liner of composite cylinder is in elastic deformation fully, its volume rate of residual V
δ≤ 2%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100175464A CN1243194C (en) | 2004-04-08 | 2004-04-08 | 50-litres hydrogen composite cylinder having carbon fiber wholly-wound, reinforced aluminum lining |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100175464A CN1243194C (en) | 2004-04-08 | 2004-04-08 | 50-litres hydrogen composite cylinder having carbon fiber wholly-wound, reinforced aluminum lining |
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| Publication Number | Publication Date |
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| CN1563781A CN1563781A (en) | 2005-01-12 |
| CN1243194C true CN1243194C (en) | 2006-02-22 |
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-
2004
- 2004-04-08 CN CNB2004100175464A patent/CN1243194C/en not_active Expired - Fee Related
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