CN1325838C - High pressure gas cylinder made from carbon fiber composite material and manufacturing method thereof - Google Patents
High pressure gas cylinder made from carbon fiber composite material and manufacturing method thereof Download PDFInfo
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- CN1325838C CN1325838C CNB2005100101520A CN200510010152A CN1325838C CN 1325838 C CN1325838 C CN 1325838C CN B2005100101520 A CNB2005100101520 A CN B2005100101520A CN 200510010152 A CN200510010152 A CN 200510010152A CN 1325838 C CN1325838 C CN 1325838C
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Abstract
The present invention relates to a carbon fiber composite material high pressure gas bottle and a manufacturing method thereof, particularly to a carbon fiber winding composite material high pressure gas bottle and a manufacturing method thereof. The existing high pressure gas bottle has the defects of large weight, low strength, high cost and bad gas tightness. A metallic inner lining (1) of the carbon fiber composite material high pressure gas bottle is made from titanium alloy; the rate F<TY>/E of the tensile yield strength to the modulus of elasticity of the titanium alloy is 0.6% at least, and the elongation rate of the titanium alloy is 5% at least; a sealing head (1-1) of the carbon fiber composite material high pressure gas bottle forms a three point circular sealing head shape. The metallic inner lining (1) is formed by the steps of spinning and stretching of the sealing head (1-1), recrystallization annealing treatment, mechanical processing, welding of an end head and integral welding; the carbon fiber composite material layer (2) is a carbon fiber/epoxy winding layer. The manufacturing method of carbon fiber composite material high pressure gas bottle orderly comprises the processes of fiber baking, glue preparation, glue dipping, winding, solidifying shaping, etc. The carbon fiber composite material high pressure gas bottle which has the advantages of light weight, good gas tightness, high strength and low cost can be manufactured with the method of the present invention.
Description
Technical field:
The present invention relates to a kind of filament wound composite gas cylinder, particularly a kind of high-performance super thin metal inner lining carbon fiber wound composite gas cylinder.
Background technique:
Compare with traditional metallic material gas cylinder, that composite material high pressure gas cylinder has is in light weight, pressure is high, the plurality of advantages such as safety failure mode of leaking before the explosion.These advantages of composite material high pressure gas cylinder make it more and more be applied to each industrial department, in aerospace industry, it is the important component part of spacecraft engine system and satellite control system, its purposes is to carry the lightweight pressurized gas, with flowing of fluids such as control liquid fuel, oxygenant, freezing mixture.Along with the fast development of aerospace cause, strict more to the weight requirement of aerospace device.Lightweight, high-strength, reusable composite material high pressure gas cylinder for alleviate engine weight, improve aircraft performance, to reduce launch cost etc. significant, this also is the topmost Driving force of development composite material high pressure gas cylinder.Therefore on the raw-material basis of choose reasonable, be necessary traditional structure and manufacture method are optimized design, give full play to the potentiality of material by fair means or foul, satisfying under the prerequisite of performance requirement, reduce its inert weight as much as possible, reach the lightweight purpose.
The basic fundamental of metal lining composite material pressurized container originates from beginning of the seventies late 1960s.
High-performance carbon fibre has very high specific strength, specific stiffness, is suitable for production lightweight gas cylinder.But, have higher relatively permeability by the composite-material laminates of these fiber productions, can not long time stored high pressure liquid (gas) body or low-pressure gas.Therefore, composite material high pressure gas cylinder must have a liner to guarantee tightness, prevents the stock leakage.Because composite layer is main bearing structure, liner mainly plays the tightness effect.Therefore, gas cylinder efficient PV/W reduces along with the increase of liner weight.For high pressure or the strong stock (as helium) of gas storage thing, especially permeability, use metal inner lining usually, the structural member that these metal inner linings can be used as carrying also can be used as the non-structural part that does not carry.
For lightweight, pressurized gas stock, mainly contain two kinds of basic fundamentals at present: the metallic aluminium liner Carbon Fiber gas cylinder that (a) is in yield situation; (b) carrying liner (as stainless steel, titanium alloy etc.) Kev draws/the epoxy composite material pressurized container.Wherein, aluminum liner Carbon Fiber tank is present most popular technology, but also there is shortcoming in this technology: at first, because the deformability of carbon fiber is far longer than the elastic deformability of aluminum liner, liner all can be surrendered in each pressures cycle, therefore the cycle life of gas cylinder is limited in about 100 times, and this illustrates that also this liner is non-structure basically---and it only prevents that stock from revealing but bearing capacity is very little, increase gas cylinder weight.The maximal efficiency PV/W of this gas cylinder (P is a bursting pressure) reaches 20Km usually.What the technology of manufacturing liner end socket was commonly used has two kinds: spinning, punching press.Wherein, stamping technology only is suitable for making thick end socket, makes when approaching end socket to occur problems of crack easily, has reduced the Security of goods; Rotary pressure technology then can be used for making thin-walled vessel head, has preferable quality stability.
The employed liner of the second class composite material high pressure gas cylinder has higher limit of elasticity, thereby liner all is within the elastic range in each dust cycle.This illustrates that this gas cylinder may be more effective; But its efficient also is about 20Km, because the desired thickness of technology is big and titanium alloy density is bigger, the weight that causes the titanium liner is greater than other metal inner lining.This class carrying liner gas cylinder has higher cycle life usually, but because its selected material and desired technology, manufacture cost is more much higher than aluminum liner gas cylinder.
Summary of the invention:
At the drawback that weight is big, intensity is low, cost is high, the manufacturing cycle is long, tightness is bad that existing gas cylinder exists, the invention provides a kind of in light weight, intensity is high, cost is low, the manufacturing cycle is short, tightness is good carbon fiber composite material high pressure gas cylinder.Carbon fiber composite material high pressure gas cylinder, it comprises metal inner lining 1 and is wrapped in the carbon fiber composite layer 2 of metal inner lining 1 outside, on the end socket 1-1 at the central axis two ends of metal inner lining 1, be welded with termination 3, be wound with hoop rib 4 in carbon fiber composite layer 2 outside, described metal inner lining 1 is by the ratio F of tensile yield strength with Young's modulus
TY/ E is at least 0.6%, fracture elongation is at least 5% titanium alloy and makes, and the thickness δ of finished product metal inner lining 1 is 0.5mm～1.8mm, and the thickness δ of metal inner lining 1 is 2.8 * 10 with the ratio of diameter D
-3Below, the length L 1 of metal inner lining 1 column part is at least 1.00 with the ratio of diameter D, the end socket 1-1 of described metal inner lining 1 is 3 circular end socket shapes, and metal inner lining 1 is to be prepared from by spinning stretching end socket 1-1, recrystallization annealing processing, machining, termination welding and whole five steps of weldering system; Described carbon fiber composite layer 2 is carbon fiber/epoxy winding layers, soon epoxy resin and anhydride curing agent, benzyl dimethylamine promoter are mixed into glue according to the ratio of weight proportion 1: 0.08～0.1: 0.005～0.006, the carbon fiber behind the impregnation are twined at metal inner lining 1 outer surface to be prepared from then.A kind of manufacture method of carbon fiber composite material high pressure gas cylinder, it comprises manufacturing metal inner lining 1, twines carbon fiber composite layer 2 and solidification process in metal inner lining 1 outside, the preparation process of described metal inner lining 1 comprises following five steps successively: a. spinning stretching end socket 1-1: the spinning temperature of end socket 1-1 is 430 ℃～530 ℃, spinning speed is 200～650 commentaries on classics/min, and the depth of cut is that 0.3～0.7mm/ changes; After the end socket 1-1 moulding on 500 tons of double-acting punching stretch machines stretching stack shell 1-2 typing become metal inner lining 1 half; B. recrystallization annealing is handled: recrystallization temperature is 700 ℃～930 ℃, is incubated 20～150 minutes, is cooled to ambient temperature with the speed that is no more than 50 ℃/min then; C. machining: be machined to the oxide material that produces in the aforementioned process and removed fully; D. termination welding: end socket 1-1 and the termination 3 that processes welded together by the TIG welding method; E. weldering system is whole: by the TIG welding method with two half liners 1 by a circumferential welded seam bulk metal liner 1 that obtains welded together.
Product of the present invention can reach following target: make liner with the titanium alloy with high strength, high elastic modulus and high elongation, the composite material high pressure gas cylinder that makes manufacturing, has higher PV/W eigenvalue, the PV/W value is at least 28Km, the highlyest can reach 40Km, wherein, P refers to bursting pressure; V is the volume of gas cylinder; W is the weight of gas cylinder.Because used liner is thinner, so can also obviously improve gas cylinder efficient.
The manufacture method of composite material high pressure gas cylinder of the present invention can produce gas cylinder in light weight, that reliability is high, cost is low.This method has following innovative point: 1) end socket and stack shell are one-time formed through the spinning stretching, have reduced the longitudinal weld of shell portion and the weld seam of end socket and shell portion joint, have improved the liner performance, have increased the safety reliability of composite material high pressure gas cylinder; 2) machining end-fitting; 3) super thin metal inner lining welding method; Each the step key operation that is used for composite material high pressure gas cylinder all must be optimized, because the strain level of metal is enough to make metal to be surrendered, and this situation does not allow to take place in the full-metallic gas cylinder.To carry out concise and to the point discussion to this several Key Points below.
1. spinning stretching end socket---perhaps spinning stretching titanium alloy closing end technology once was used to make full titanium alloy cylinder, but never was used to make the metal inner lining of Carbon Fiber gas cylinder before this technology.Since before used be mostly thick-walled metal liner (more than the 2.5mm), can impact briquetting, but for this super thin metal inner lining, can't impact briquetting, select for use the spinning pultrusion method for making the metal inner lining end socket, to have novelty here.Industry standard rotary pressed head process quilt proves and can not satisfy requirement of the present invention, in order to realize the estimated performance of composite material high pressure gas cylinder, must take the process step of requirement of the present invention: as the spinning temperature, machining (as the machining after the heat treatment to remove the oxide-rich material on the end socket), heat treatment etc. can be satisfied its specific (special) requirements as liner like this.Compare with traditional stamping process, spinning process have simultaneously cost low, prepare convenient, ready-to-use advantage.
2. the welding of ultra-thin titanium alloy metal inner lining---here we select common TIG welding procedure, because this welding has lot of advantages.Can not cause losing of alloying element as it, can not produce bubble, have higher welding quality; In the arc heat quantity set, the heat affected zone is little, and the weldment distortion is little; Have " negative electrode atomizing " effect, can remove the oxide on weldment surface etc.Perhaps, this welding technique once was used to make full titanium alloy metal gas cylinder, but was not used in the manufacturing of composite material high pressure gas cylinder super thin metal inner lining before.The same with takeshapes of closure, process parameter must be optimized the super thin metal inner lining that just can be used to make composite material high pressure gas cylinder, should select different process parameters for the liner of different-thickness.
3. end socket and its end connect the assembling welding of mouth---with welding end socket and its end are connect the production that method that mouth welds together the composition liner also is not used in composite material high pressure gas cylinder before.Here we select for use TIG welding mainly to be because the TIG welding can be satisfied the requirement of high ductility that this situation butt welded seam proposes and low warpage.
The method of the invention can satisfy low cost, short period and high performance requirement simultaneously, use the method for the invention can obtain the metal inner lining of thickness as 0.5mm～1.8mm, it is thinner than existing titanium alloy liner far away, and is also thin than typical aluminium alloy lining.
Use the gas cylinder of the method for the invention manufacturing to can be used for aerospace structure, as reusable aircraft propulsion with composite material high pressure gas cylinder, satellite control system with the breathing in high pressure helium gas cylinder, the space man's life-support system with oxygen cylinder etc.
Description of drawings: Fig. 1 is the structural representation of gas cylinder of the present invention.
Embodiment:
Embodiment one: carbon fiber composite material high pressure gas cylinder, it comprises metal inner lining 1 and is wrapped in the carbon fiber composite layer 2 of metal inner lining 1 outside, on the end socket 1-1 at the central axis two ends of metal inner lining 1, be welded with termination 3, be wound with hoop rib 4 in carbon fiber composite layer 2 outside, described metal inner lining 1 is by the ratio F of tensile yield strength with Young's modulus
TY/ E is at least 0.6%, fracture elongation is at least 5% titanium alloy and makes, the thickness δ of finished product metal inner lining 1 is 0.5mm～1.8mm, this thickness is thinner than existing titanium alloy liner far away, also thin than typical aluminium alloy lining, the thickness of inner lining attenuation, the efficient of gas cylinder is increased greatly; The thickness δ of metal inner lining 1 is 2.8 * 10 with the ratio of diameter D
-3Below, can realize 2.0 * 10 through research of technique
-3, 1.5 * 10
-3, even 1.1 * 10
-3, the length L 1 of metal inner lining 1 column part is at least 1.00 with the ratio of diameter D, should be greater than 1.25 under the situation better; The end socket 1-1 of described metal inner lining 1 is 3 circular end socket shapes.We find by existing several end socket shapes being analyzed the back on the basis that tradition designs substantially: the isostension end socket is a kind of end socket shape of optimum, but be limited to the also relatively backward present situation of Chinese basic industry, can't be fully according to manufacturing and designing the isostension end socket, find 3 end socket shapes that circular end socket is a kind of present the best through a large amount of theory analysises and experiment, can be similar to and replace the isostension end socket, described end socket 1-1 shape and thickness curve and composite layer 2 near the bottle neck joint of end and the structural type of stack shell-end socket joint be the important parameter that influences container performance.Metal inner lining 1 is to be prepared from by spinning stretching end socket 1-1, recrystallization annealing processing, machining, termination welding and whole five steps of weldering system; Described carbon fiber composite layer 2 is carbon fiber/epoxy winding layers, soon epoxy resin and anhydride curing agent, benzyl dimethylamine promoter are mixed into glue according to the ratio of weight proportion 1: 0.08～0.1: 0.005～0.006, the carbon fiber behind the impregnation are twined at metal inner lining 1 outer surface to be prepared from then.The Carbon Fiber layer is the main bearing structure of gas cylinder, twines two hoop ribs 4 again at the stack shell 1-2 two ends of the gas cylinder that winds, and supplies and the fixing usefulness of total system.
The manufacture method of carbon fiber composite material high pressure gas cylinder comprises manufacturing metal inner lining 1, twines carbon fiber composite layer 2 and solidification process in metal inner lining 1 outside, and the preparation process of described metal inner lining 1 comprises following five steps successively:
A. spinning stretching end socket 1-1: the spinning temperature of end socket 1-1 is 430 ℃～530 ℃, and spinning speed is 200～650 commentaries on classics/min, and the depth of cut is that 0.3～0.7mm/ changes; After the end socket 1-1 moulding on 500 tons of double-acting punching stretch machines stretching stack shell 1-2 typing become metal inner lining 1 half;
B. recrystallization annealing is handled: recrystallization temperature is 700 ℃～930 ℃, is incubated 20～150 minutes, is cooled to ambient temperature with the speed that is no more than 50 ℃/min then; After handling like this, can remove the residual stress among the end socket 1-1, and obviously improve the ductility and the fracture toughness of liner 1.
C. machining: be machined to the oxide material that produces in the aforementioned process and removed fully;
D. termination welding: end socket 1-1 and the termination 3 that processes welded together by the TIG welding method;
E. weldering system is whole: by the TIG welding method with two half liners 1 by a circumferential welded seam bulk metal liner 1 that obtains welded together.
Embodiment two: present embodiment and embodiment one difference are that it also comprises the 6th step: clean and polishing.In preparation metal inner lining 1 process, there are embodiment one described five steps can realize obtaining the purpose of functional metal inner lining 1, if add the 6th step, promptly clean and bruting process, can guarantee metal inner lining 1 with its outside between winding layer contact good.Such as in preparation process, can be at metal inner lining 1 outer surface coated with adhesive, and then wound composite layer 2, at this moment, metal inner lining 1 outer surface through cleaning and polish can and composite layer 2 between bonding well, thereby make gas cylinder reach better performance.Described cleaning and bruting process are followed successively by: be that 0.05%～0.15% weak base cleaned liner 1 surface 5～10 minutes with mass percent concentration (a); (b) with the thin metal brush that dips in ethyl acetate solution machinery being carried out on metal inner lining 1 surface cleans; (c) smear ethyl acetate solution; (d) with the thin metal brush that dips in deionized water machinery being carried out on metal inner lining 1 surface cleans; (e) deionized water rinsing; (f) smear deionized water on metal inner lining 1 surface, form uniform coating and do not break; (g) metal inner lining 1 is put into 55 ℃～65 ℃ dry 30 minutes of vacuum drying oven, got final product after cooling.
Embodiment three: the material that the present invention requires to prepare metal inner lining 1 is a tensile yield strength and the ratio F of Young's modulus
TY/ E is at least 0.6%, specific elongation is at least 5% titanium alloy and gets final product, and can prepare gas cylinder of the presently claimed invention as long as can reach all titanium alloys of above-mentioned performance.The high-performance metal that satisfies this condition can be from including Al; Fe; Ta; Mo; Sn; Cr; Si; select for use in the titanium alloy of alloying element such as Zr and V; in practical operation; relatively the Chang Yong titanium alloy material that can reach above-mentioned performance has Ti-6V-2Sn; Ti-6Al-2Sn-4Zr-2Mo; Ti-6Al-2Cb-1Ta-0.8Mo; Ti-6Al-4V; Ti-13V-11Cr-3Al; Ti-8Al-1Mo-1V; Ti-3Al-8V-6Cr-4Mo-4Cr; Ti-11Sn-5Zr-2Al-1Mo; Ti-5Al-2Sn-2Zr-4Mo-4Cr; Ti-10V-2Fe-3Al; Ti-6Al-2Sn-4Zr-6Mo; Ti-15V-3Al-3Cr-3Sn; Ti-6Al-2Sn-2Zr-2Mo-2Cr-0.25Si or Ti-5Al-2.5Sn; above-mentioned material is that practical application is given an example; but be not limited to cited material; as long as can reach the titanium alloy of described requirement, all within protection scope of the present invention.
Embodiment four: in the described step of metal inner lining manufacture process of embodiment one desired concrete parameter for all can prepare gas cylinder of the present invention titanium alloy the number range that must abide by, as long as in its scope, can obtain the metal inner lining of performance of the present invention; When specifically selecting material, can in its scope, slightly adjust at its process parameter of different materials; Adopting the TIG welding method also is general welding method, and the rotational velocity of adjusting the electric current, wire feed rate and the weldment that are adopted according to different materials when welding also is common practise in related domain.Present embodiment has been selected for use with the Ti-6Al-4V material and has been made gas cylinder as metal inner lining 1, and its preparation process is as follows:
A. spinning stretching end socket 1-1: the spinning temperature of end socket 1-1 is 480 ℃, and spinning speed is 400 commentaries on classics/min, and the depth of cut is that 0.5mm/ changes; After the end socket 1-1 moulding on 500 tons of double-acting punching stretch machines stretching stack shell 1-2 typing become metal inner lining 1 half;
B. recrystallization annealing is handled: recrystallization temperature is 900 ℃, is incubated one hour, cools to ambient temperature then with the furnace;
C. machining: be machined to the oxide material that end socket 1-1 surface produces and removed fully;
D. termination welding: by the TIG welding method end socket 1-1 and the termination 3 that processes welded together: the electric current of welding is 80～160A, and wire feed rate is 2m/min～10m/min, and the rotational velocity of weldment is 250mm/min～320m/min.
E. weldering system is whole: by the TIG welding method with two half liners 1 by a circumferential welded seam bulk metal liner 1 that obtains welded together: the electric current of welding is 80～160A, wire feed rate is 2m/min～10m/min, and the rotational velocity of weldment is 250mm/min～320m/min.
Embodiment five: the difference of present embodiment and embodiment four is that it has been selected for use with the Ti-3Al-8V-6Cr-4Mo-4Cr material and has made gas cylinder as metal inner lining 1, and its preparation process is as follows:
A. spinning stretching end socket 1-1: the spinning temperature of end socket 1-1 is 440 ℃, and spinning speed is 230 commentaries on classics/min, and the depth of cut is that 0.4mm/ changes; After the end socket 1-1 moulding on 500 tons of double-acting punching stretch machines stretching stack shell 1-2 typing become metal inner lining 1 half;
B. recrystallization annealing is handled: recrystallization temperature is 750 ℃, is incubated 100 minutes, and the speed with 30 ℃/min is cooled to ambient temperature then;
C. machining: be machined to the oxide material that end socket 1-1 surface produces and removed fully;
D. termination welding: by the TIG welding method end socket 1-1 and the termination 3 that processes welded together: the electric current of welding is 125～130A, and wire feed rate is 4m/min～4.5m/min, and the rotational velocity of weldment is 300 ± 2mm/min.
E. weldering system is whole: by the TIG welding method with two half liners 1 by a circumferential welded seam bulk metal liner 1 that obtains welded together: the electric current of welding is 125～130A, wire feed rate is 4m/min～4.5m/min, and the rotational velocity of weldment is 300 ± 2mm/min.
Embodiment six: the difference of present embodiment and embodiment four, five is that it has been selected for use with the Ti-6Al-2Sn-2Zr-2Mo-2Cr-0.25Si material and has made gas cylinder as metal inner lining 1, and its preparation process is as follows:
A. spinning stretching end socket 1-1: the spinning temperature of end socket 1-1 is 470 ℃, and spinning speed is 600 commentaries on classics/min, and the depth of cut is that 0.6mm/ changes; After the end socket 1-1 moulding on 500 tons of double-acting punching stretch machines stretching stack shell 1-2 typing become metal inner lining 1 half;
B. recrystallization annealing is handled: recrystallization temperature is 900 ℃, is incubated 20 minutes, and the speed with 10 ℃/min is cooled to ambient temperature then;
C. machining: be machined to the oxide material that end socket 1-1 surface produces and removed fully;
D. termination welding: by the TIG welding method end socket 1-1 and the termination 3 that processes welded together: the electric current of welding is 60A, and wire feed rate is 12m/min, and the rotational velocity of weldment is 200 ± 2mm/min.
E. weldering system is whole: by the TIG welding method with two half liners 1 by a circumferential welded seam bulk metal liner 1 that obtains welded together: the electric current of welding is 125～130A, wire feed rate is 4m/min～4.5m/min, and the rotational velocity of weldment is 300 ± 2mm/min.
Embodiment seven: twining carbon fiber composite layer 2 in metal inner lining 1 outside can twine by existing winding method, twine as the winding method that is called " quadrature twine composite high pressure gas cylinder " and is provided by disclosed patent application 01113813, name, also can realize lightweight of the present invention, high-strength, purpose that tightness is good.
The present invention also provides a kind of method of twining carbon fiber composite layer 2 in metal inner lining 1 outside, composite layer 2 comprises high strength fiber peacekeeping resin system, composite layer 2 is arranged in liner 1 surface by described fiber winding technology, prove that through actual tests winding method provided by the invention is more effective with the mode that the hoop winding combines than former spiral winding technology or spiral.
This winding process is:
At first, epoxy resin and anhydride curing agent, benzyl dimethylamine promoter are mixed into glue according to the ratio of weight proportion 1: 0.08～0.1: 0.005～0.006, to twine at metal inner lining 1 outer surface immediately behind the carbon fiber impregnation then, experiment showed, that this combination can have extraordinary tensile strength and higher fracture toughness in very wide temperature range.In the fiber winding process, adopt the tension force tapering system, be decremented to 50N from 250N, and gel content be controlled at carbon fiber gross weight behind the impregnation 20～26% between, in order to prevent that liner 1 under the effect of winding tension unstability taking place, when fiber twines metal inner lining 1 is carried out pressurization, originally the interior pressure of metal inner lining 1 is 0.2Mpa, be increased to 0.3MPa at 1/3 o'clock in winding, be increased to 0.4Mpa at last, in winding process, the interior pressure of liner 1 increases gradually can be offset owing to winding tension is applied to pressure on the liner 1.
Canoe is: being that hoop twines and vertical the winding combines on stack shell 1-2, is that spiral twines or twine on the plane on end socket 1-1;
The winding rule is: the small angle stable winding and the hoop winding technology that adopt 1～10 degree.
Extraordinary small angle stable winding is another innovative point of the present invention---according to the loading characteristic of composite material high pressure gas cylinder, adopts the small angle stable winding to realize that fiber direction arranges along stressed principal direction, gives full play to the mechanical property of carbon fiber excellence.On metal inner lining 1, adopt the aforementioned stable winding technology to avoid traditional local reinforcement technology, alleviated the weight of gas cylinder greatly, improved the efficient of gas cylinder, reduced manufacture cost, twine with traditional spiral and to add the canoe that hoop twines and compare, small angle stable winding technology is more effective.
Embodiment eight: present embodiment and mode of execution seven differences are that testing employed epoxy resin is Phoenix brand high-performance epoxy resin, and carbon fiber is the T1000 carbon fiber.
Embodiment nine: the employed epoxy resin of present embodiment is Phoenix brand high-performance epoxy resin, and carbon fiber is the T700 carbon fiber.
Embodiment ten: the carbon fiber composite layer 2 that both can realize obtaining function admirable by embodiment seven described processes, for clarity sake, present embodiment has been described a kind of concrete winding pattern implementation process of carbon fiber: rib → surfacing is installed in three layers → curing → winding of two layers → vertical three layers → hoop of two layers → vertical three layers → hoop of two layers → vertical three layers → hoop of two layers → vertical three layers → hoop of vertical two layers → hoop; Do 10 winding conversion altogether, forbidden broken yarn or do yarn group more to change jobs in each winding is carried out, winding requires approaching or consistent with four yarn groups, diameter, and the assurance co-operation reduces the wave properties that yarn is rolled into a ball rotating ratio and tension force; Vertically winding angle is arranged by 1～10 degree; Vertically winding is formed by five times, and each conversion winding angle carries out secondary treatment after twining and finishing.
Embodiment 11: after twining end, gas cylinder is cured, and solidification process is to prepare the common process of gas cylinder now, both can realize the object of the invention by existing solidification method.The invention provides a kind of solidification method, this solidification method is proved to be to be used in combination with metal inner lining 1 of the present invention and carbon fiber composite has better effect.In solidification process, the pressure in the gas cylinder remains at more than the 0.4MPa; The curing system is followed successively by: (1) is elevated to 70 ± 2 ℃ with the heating rate of 0.6 ± 0.1 ℃/min, is incubated 20～25 minutes; After (2) 70 ℃ of insulations, remove unnecessary resin; (3) warming velocity with 0.5～5 ℃/min goes back up to 70 ± 2 ℃; (4) heating rate with 0.6 ± 0.1 ℃/min is elevated to 95 ± 2 ℃, and unnecessary resin is removed from composite material gas cylinder surface; (5) heating rate with 0.6 ± 0.1 ℃/min is elevated to 120 ± 2 ℃, is incubated 50～70 minutes; (6) make the gas cylinder cool to room temperature promptly finish curing with the speed that is no more than 2 ℃/min.
Embodiment 12: present embodiment is used winding method of the present invention to twine in metal inner lining 1 outside and is made gas cylinder with the metal inner lining 1 of Ti-11Sn-5Zr-2Al-1Mo material preparation gas cylinder.Its complete preparation process is as follows:
(1) preparation titanium alloy liner 1:
A. spinning stretching end socket 1-1: sheet metal should have the success that enough thickness guarantees spinning.The spinning temperature of end socket 1-1 is 500 ℃, and spinning speed is 200 commentaries on classics/min, and the depth of cut is that 0.7mm/ changes; After the end socket 1-1 moulding on 500 tons of double-acting punching stretch machines stretching stack shell 1-2 typing become metal inner lining 1 half, end socket 1-1 and stack shell 1-2 cylindrical section are spinning stretching once-throughs.Generally, the thickness of the metal inner lining 1 that obtains by this method is no more than 1.8mm, is no more than 0.8mm sometimes.
B. recrystallization annealing is handled: recrystallization temperature is 700 ℃, is incubated 60 minutes, and the speed with 40 ℃/min is cooled to ambient temperature then;
C. machining: be machined to the oxide material that metal inner lining 1 surface produces and removed fully;
D. termination welding: by the TIG welding method end socket 1-1 and the termination 3 that processes welded together: the electric current of welding is 100A, and wire feed rate is 8m/min, and the rotational velocity of weldment is 280 ± 2mm/min.
E. weldering system is whole: by the TIG welding method with two half liners 1 by a circumferential welded seam bulk metal liner 1 that obtains welded together: the electric current of welding is 100A, and wire feed rate is 8m/min, and the rotational velocity of weldment is 280 ± 2mm/min.
F. clean and polish: be that 0.1% weak base cleaned liner 1 surface 10 minutes (a) with mass percent concentration; (b) with the thin metal brush that dips in ethyl acetate solution machinery being carried out on metal inner lining 1 surface cleans; (c) smear ethyl acetate solution; (d) with the thin metal brush that dips in deionized water machinery being carried out on metal inner lining 1 surface cleans; (e) deionized water rinsing; (f) smear deionized water on metal inner lining 1 surface, form uniform coating and do not break; (g) metal inner lining 1 is put into 60 ℃ dry 30 minutes of vacuum drying oven, got final product after cooling.
(2) twine carbon fiber composite layer 2 in metal inner lining 1 outside:
After described titanium alloy liner 1 cooling of present embodiment, twine with the T1000 carbon fiber immediately.At first, epoxy resin and anhydride curing agent, benzyl dimethylamine promoter are mixed into glue according to 1: 0.09: 0.005 ratio of weight proportion, to twine at metal inner lining 1 outer surface immediately behind the carbon fiber impregnation then, in the fiber winding process, adopt the tension force tapering system, be decremented to 50N from 250N, and gel content is controlled at 20% of carbon fiber gross weight behind the impregnation, when fiber twines metal inner lining 1 is carried out pressurization, originally the interior pressure of metal inner lining 1 is 0.2Mpa, be increased to 0.3MPa at 1/3 o'clock in winding, be increased to 0.4Mpa at last;
Canoe is: being that hoop winding and vertical the winding combine on stack shell 1-2, is that vertically winding or spiral twine on end socket 1-1;
The winding rule is: the small angle stable winding and the hoop winding technology that adopt 1～10 degree.
The performance requirement that composite material high pressure gas cylinder proposes titanium alloy is higher than the requirement that typical titanium alloy is used far away, this be because: in order to guarantee that liner 1 is in the elastic range all the time in all work cycle, liner 1 is carried out the precompressed processing, relied on winding tension and cure shrinkage to make metal inner lining 1 before solidifying end, work, be in the elastic state of compression.
(3) solidify:
Curing can be adopted the normal temperature cure system, also can adopt the hot setting system, and this depends on the final Environmental Conditions of selected resin system and gas cylinder.For the generation of the liner unstability that prevents to produce owing to cure shrinkage, in solidification process, the pressure in the gas cylinder remains at more than the 0.4MPa; The curing system is followed successively by: (1) is elevated to 70 ℃ with the heating rate of 0.6 ℃/min, is incubated 25 minutes; After (2) 70 ℃ of insulations, remove unnecessary resin, temperature may reduce by 10 ℃ in this process; (3) warming velocity with 3 ℃/min goes back up to 70 ℃; (4) heating rate with 0.6 ℃/min is elevated to 95 ℃, and unnecessary resin is removed from composite material gas cylinder surface; (5) heating rate with 0.6 ℃/min is elevated to 120 ℃, is incubated 60 minutes; (6) speed with 1 ℃/min makes the gas cylinder cool to room temperature promptly finish curing.
After curing is finished, coating one deck protective coating on composite layer 2.
At last, be that 0.1%～0.2% alkali lye (as sodium bicarbonate solution) cleans to composite material high pressure gas cylinder internal surface mass concentration, satisfy following requirement until the turbidity test of internal surface.
Table 1: gas cylinder internal surface turbidity test requirement
| Particle size scope (micron) | Maximum magnitude/100ml |
| 5-10 | 140 |
| 11-25 | 20 |
| 26-50 | 5 |
| 51-100 | 1 |
| ≥100 | 0 |
After finishing above-mentioned work, gas cylinder integral body is finished the work such as cleaning, printing on surface, after can pack, transport, use for the user.
Above-mentioned mode of execution is by twining gas cylinder composite layer structure optimization design to fiber, provide best gel content, fiber winding tension, twined sequential scheduling winding rule, having prepared volume is the ultrahigh pressure metal inner lining carbon fiber composite material high pressure gas cylinder of 20L, the container performance factor (characteristic coefficient) is laid a good foundation with composite material high pressure gas cylinder for further developing the liquid engine propulsion system up to 28Km.
The described composite material high pressure gas cylinder technology of present embodiment is compared with present composite material gas cylinder technical merit commonly used has remarkable advantages: the one, and ultra-thin titanium alloy metal inner lining, the 2nd, extraordinary small angle stable winding high-performance composite materials layer.Composite material high pressure gas cylinder comprises a ultra-thin titanium alloy liner and high-performance carbon fibre wound composite layer, and the main feature of this technology is: ultra-thin titanium alloy liner and high performance composite material winding layer form the high-performance composite materials gas cylinder of a lightweight together.
Claims (2)
1. carbon fiber composite material high pressure gas cylinder, it comprises metal inner lining (1) and is wrapped in the carbon fiber composite layer (2) of metal inner lining (1) outside, on the end socket (1-1) at the central axis two ends of metal inner lining (1), be welded with termination (3), be wound with hoop rib (4) in carbon fiber composite layer (2) outside, it is characterized in that described metal inner lining (1) is by the ratio F of tensile yield strength with Young's modulus
TY/ E is at least 0.6%, fracture elongation is at least 5% titanium alloy and makes, and the thickness (δ) of finished product metal inner lining (1) is 0.5mm～1.8mm, and the thickness (δ) of metal inner lining (1) is 2.8 * 10 with the ratio of diameter (D)
-3Below, the length (L1) of metal inner lining (1) column part is at least 1.00 with the ratio of diameter (D), the end socket (1-1) of described metal inner lining (1) is 3 circular end socket shapes, and metal inner lining (1) is to be prepared from by spinning stretching end socket (1-1), recrystallization annealing processing, machining, termination welding and whole five steps of weldering system; Described carbon fiber composite layer (2) is carbon fiber/epoxy winding layer, soon epoxy resin and anhydride curing agent, benzyl dimethylamine promoter are mixed into glue according to the ratio of weight proportion 1: 0.08～0.1: 0.005～0.006, the carbon fiber behind the impregnation are twined at metal inner lining (1) outer surface to be prepared from then.
2. carbon fiber composite material high pressure gas cylinder according to claim 1, the titanium alloy material that it is characterized in that preparing metal inner lining (1) is Ti-6V-2Sn, Ti-6Al-2Sn-4Zr-2Mo, Ti-6Al-2Cb-1Ta-0.8Mo, Ti-6Al-4V, Ti-13V-11Cr-3Al, Ti-8Al-1Mo-1V, Ti-3Al-8V-6Cr-4Mo-4Cr, Ti-11Sn-5Zr-2Al-1Mo, Ti-5Al-2Sn-2Zr-4Mo-4Cr, Ti-10V-2Fe-3Al, Ti-6Al-2Sn-4Zr-6Mo, Ti-15V-3Al-3Cr-3Sn, Ti-6Al-2Sn-2Zr-2Mo-2Cr-0.25Si or Ti-5Al-2.5Sn.
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