CN105620713A - Skin provided with surface helium gas blocking layer and preparation method of skin - Google Patents
Skin provided with surface helium gas blocking layer and preparation method of skin Download PDFInfo
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- CN105620713A CN105620713A CN201610052623.2A CN201610052623A CN105620713A CN 105620713 A CN105620713 A CN 105620713A CN 201610052623 A CN201610052623 A CN 201610052623A CN 105620713 A CN105620713 A CN 105620713A
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- pdda
- eyelid covering
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B64—AIRCRAFT; AVIATION; COSMONAUTICS
- B64C—AEROPLANES; HELICOPTERS
- B64C1/00—Fuselages; Constructional features common to fuselages, wings, stabilising surfaces or the like
- B64C1/06—Frames; Stringers; Longerons ; Fuselage sections
- B64C1/12—Construction or attachment of skin panels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B64—AIRCRAFT; AVIATION; COSMONAUTICS
- B64C—AEROPLANES; HELICOPTERS
- B64C1/00—Fuselages; Constructional features common to fuselages, wings, stabilising surfaces or the like
- B64C2001/0054—Fuselage structures substantially made from particular materials
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Aviation & Aerospace Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
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Abstract
The invention discloses skin provided with a surface helium gas blocking layer. The surface helium gas blocking layer is formed by alternately fitting PDDA (poly dimethyl diallyl ammonium chloride) layers and graphene powder layers, and the PDDA layer at the innermost layer is fit with the surface of the skin. With the adoption of a brand-new graphene powder and PDDA alternative fitting method, the improvement of the helium gas blocking performance of the skin of an aircraft is realized, and the permeability of helium gas is reduced to 1/10-1/5 of the original permeability. Furthermore, the surface helium gas blocking layer is light in mass, low in density, and good in flexibility, and can not influence the load carrying performance of the aircraft.
Description
Technical field
The present invention has the skin material of helium barrier layer design, especially for the eyelid covering of proximity space aircraft.
Background technology
Proximity space aircraft is a kind of containing propulsion plant, the multi-functional flying platform of Novel ortho near space that can control flight, dependence uplift work in sky, and working depth height above sea level is about 20Km. The flight characteristic of aircraft determines it and has broad application prospects in fields such as military surveillance, space early warning, communication relay and space explorations, thus is extensively favored by various countries scientist. But proximity space aircraft working environment is very harsh: temperature low (minimum temperature about-55 DEG C), day and night temperature are big; Atmospheric density is only the 1/14 of ground; Ultraviolet radiation, ozonization are strong. Work under this kind of environment, first require that skin material has extremely low surface density and good weatherability; Aircraft interior temperature is continually changing, and causes eyelid covering inside and outside differential pressure to increase, aircraft during for long boat, overcomes the pressure reduction that variations in temperature causes particularly important; Owing to aircraft exists pressure reduction and more service load in its military service process inside and outside eyelid covering, therefore skin material must have enough mechanical properties; Also need to skin material for maintenance aircraft profile possess excellent creep-resistant property, sewing process and be prone to the characteristic repaired simultaneously. In addition aircraft many employings helium is as buoyance lift gas, and it is leakage that the long-term operating characteristic staying sky requires that skin material must have splendid resistance helium. Needing separately to add one layer of gas-barrier layer at aircraft illiteracy material inner layer based on above reason and prevent helium seepage, this layer is wanted to be had good bonding effect and can bear the strict external environment conditions such as low temperature, ultraviolet, high temperature difference between skin material.
In recent years, grapheme material can as helium barrier material to have scholar to find, there is good barriering effect (Science27January2012:Vol.335no.6067pp.442-444), domestic also have companies using chemical vapour deposition (CVD) method growth graphene film carry out repeatedly lamination to fitting inside eyelid covering (Jin Hu. composite gas Obstruct membrane. China .201420846448.2015-07-01) to reduce the effect of helium permeability. But preparing this Obstruct membrane needs the Graphene Copper Foil prepared by CVD to perform etching, obtain single-layer graphene and carry out successively superposition and realize multilamellar and intercept. But due to the characteristic of Graphene, adhesion between layers is very weak, the more many laminatings of the number of plies can be more difficult; Owing to the higher Graphene of the flatness requirement of coating surface can only be covered in inside eyelid covering; And lamination coating cost is high, complex procedures is difficulty with large-scale application, and graphene film production at present is difficult to adopt oversize manufacturing technology, for the near space vehicle of surface area several thousand, several ten thousand square meters easily, business application substantially cannot be realized.
Summary of the invention
Present invention aims to the deficiencies in the prior art, it is provided that a kind of eyelid covering promoting aircraft skin helium barrier property, described eyelid covering is applicable to the proximity space aircraft that condition is harsh;
The preparation method that it is a further object of the present invention to provide the above-mentioned eyelid covering promoting aircraft skin helium barrier property.
The purpose of the present invention implements by the following technical programs:
A kind of eyelid covering with surface helium barrier layer, described helium barrier layer is PDDA layer and graphene powder layer alternates laminating and constitutes, and wherein the PDDA layer of innermost layer is fitted with the surface of eyelid covering.
Preferably, the surface of described eyelid covering includes the one side of eyelid covering or two-sided, in order to ensure barriering efficiency and the process optimization of Obstruct membrane, can carry out the mutual paste layer of PDDA layer and Graphene in surface inside and outside eyelid covering.
Preferably, described PDDA layer and more than totally 6 layers of graphene powder layer, such as: 6 layers, 8 layers, 28 layers, 40 layers, 50 layers, 60 layers, 70 layers, 80 layers, 90 layers, 100 layers, 110 layers, 140 layers, 150 layers, 180 layers, 200 layers, 230 layers, 270 layers, 300 layers, 400 layers, 500 layers etc., more paste layer can be selected according to demand. More preferably 10-100 layer, for instance: 10 layers, 14 layers, 18 layers, 22 layers, 30 layers, 34 layers, 36 layers, 40 layers, 42 layers, 46 layers, 48 layers, 50 layers, 54 layers, 60 layers, 66 layers, 72 layers, 78 layers, 86 layers, 90 layers, 92 layers, 94 layers, 96 layers, 100 layers etc.; Best preferably 20-30 layer, for instance: 20 layers, 22 layers, 24 layers, 26 layers, 30 layers.
Along with the increase of the number of plies, the ability intercepting helium strengthens, and after the number of plies increases to 100 layers, the lifting income of the ability of its obstruct helium is not substantially. The present invention adopts Graphene to hand over the surface paste layer of patch with PDDA, when reaching 20 layers, it is possible to reach the obstruct requirement of high-caliber helium. Though the increase of the number of plies, through the repetition test to eyelid covering, having very strong Electrostatic Absorption characteristic and barrier characteristics due to PDDA, when less than 100 layers, mechanical performance will not be subject to the impact of the number of plies. But, the increasing of the number of plies at any time, the weight of eyelid covering and thickness are increasing, the process time cost making paste layer increases, through experiment, during with 20-30 layer, it is possible to the helium meeting proximity space aircraft intercepts the demand of the mechanical performance etc. requiring and bringing in-flight, it it is the number of plies selection of cost and demand the best.
Preferably, the thickness of described PDDA layer is 1-1000nm, for instance: 1nm, 60nm, 95nm, 130nm, 155nm, 182nm, 264nm, 310nm, 381nm, 466nm, 523nm, 600nm, 645nm, 689nm, 762nm, 810nm, 912nm, 976nm, 1000nm etc.; Preferred 3nm;
Described graphene powder layer thickness is 1-1000nm, for instance: 1nm, 67nm, 95nm, 136nm, 200nm, 248nm, 286nm, 322nm, 370nm, 410nm, 473nm, 520nm, 600nm, 675nm, 740nm, 800nm, 880nm, 926nm, 1000nm etc.; Preferred 3nm.
It is further preferred that the thickness of described PDDA layer and graphene powder layer is than for 1:0.8-1.5, more preferably 1:1. Graphene layer is blocked up impact to absorption property, and the resistance effect of oozing is played influence by the blocked up meeting of PDDA layer.
Preferably, described graphene powder layer is graphene powder material, heretofore described graphene powder material is the grapheme material of broad sense, can be graphene oxide powder can also be redox graphene powder, it is possible to be single-layer graphene powder, multi-layer graphene powder or graphite microchip (number of plies Graphene more than 10 layers) etc. The graphene powder material products obtained therefrom quality that the present invention selects flakiness ratio high is higher, ink alkene powder is formed by by containing small Graphene crystal, these crystal are from monolayer multilamellar not etc., area is also in micron level, so-called flakiness ratio refers to the ratio of area and the number of plies, and in the present invention, flakiness ratio is the bigger the better.
It is further preferred that described graphene powder is graphene oxide powder. It has been investigated that, the day and night temperature of proximity space excessive and in environment, graphene oxide is more superior to the absorption property of helium.
Preferably, described eyelid covering is high-altitude vehicle eyelid covering or high-altitude aerostatics eyelid covering, and the present invention is more suitable for proximity space aircraft skin.
When covering as during for proximity space aircraft, described PDDA layer and graphene powder layer be 20-30 layer altogether, for instance: 20,22,24,26,28,30 layers, the thickness of described PDDA layer be 3nm, described graphene powder layer thickness be 3nm. Now, namely meet the helium to proximity space and intercept requirement, it is possible in difficult environment, ensure the demand of the mechanical performance stability of high-low temperature resistant (toughness) etc. of eyelid covering, it is ensured that service life, saved cost to greatest extent simultaneously.
The preparation method of the above-mentioned eyelid covering with surface helium barrier layer, comprises the steps:
1) on clean eyelid covering, adhere to one layer of PDDA solution, dry and after all evaporating to solvent, form PDDA layer;
2) eyelid covering with PDDA layer will adhere to a layer graphene powder body solution again, dry to solvent and all evaporate formation graphene powder layer;
3) step 1 is repeated) and 2) to the number of plies of formation required for skin-surface.
Preferably, described PDDA liquid quality fraction is 0.01%-10%, for instance: 0.01%, 0.08%, 0.10%, 0.15%, 0.20%, 0.23%, 0.28%, 0.30%, 0.35%, 0.40%, 0.45%, 0.5%, 0.55%, 0.58%, 0.60%, 0.64%, 0.70%, 0.76%, 0.80%, 0.85%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% etc.; Preferably 0.5%. When the solubility excessive concentrations of PDDA solution (aqueous solution) is more than 10%, PDDA layer thickeies, and the mechanical performance of gained eyelid covering and obstruct helium performance are all subjected to impact, when 0.5%, both the most mechanical performance of eyelid covering can have been ensured, meanwhile, can be firmly glued with Graphene.
And/or, graphene powder liquid quality fraction is 0.01-10%, for instance: 0.01%, 0.08%, 0.10%, 0.15%, 0.20%, 0.23%, 0.28%, 0.30%, 0.35%, 0.40%, 0.45%, 0.5%, 0.55%, 0.58%, 0.60%, 0.64%, 0.70%, 0.76%, 0.80%, 0.85%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% etc.; Preferably 0.5%.
Preferably, described step 1) and step 2) in, described adherence method, adopt and soak method of pulling up, smooth roll coating, the coating of net roller coat cloth, scraper type, atomizing coating, curtain coating or rotation.
Preferably, the method adhering to PDDA solution adopts the method soaking lift, it is preferred that soak time >=1min, it is further preferred that soak time is 10min;
And/or, the method for attachment graphene powder layer adopts the method soaking lift, it is preferred that soak time >=1min, it is further preferred that soak time is 10min.
Preferably, described step 1) in, the temperature of drying is 60-200 DEG C, the time is 8-15min, it is preferable that dry temperature be 100 DEG C, drying time be 10min;
And/or, described step 2) in, the temperature of drying is 60-200 DEG C, the time is 8-15min, it is preferable that dry temperature be 100 DEG C, drying time be 10min.
The invention has the beneficial effects as follows:
Product of the present invention adopts the method for the mutual paste layer of brand-new graphene powder and PDDA (diallyl dimethyl ammoniumchloride) to achieve the lifting of aircraft skin helium barrier property, makes the permeability reduction of helium to original 1,/10 1/5. And surface barrier layer light weight, density is little, and (density is only 1.04g/cm-3) pliability good (elongation at break > 10%) do not interfere with the load carrying behaviour of aircraft.
Present invention process overcomes CVD Graphene lamination coating problem difficult, inefficient, solve existing grapheme material not enough as the technique of helium barrier layer, can realizing Reel-to-reel type high-volume to manufacture, eyelid covering both sides all can realize barrier layer and well be coated with, and production cost is relatively low.
Figure of description
Fig. 1 is the present invention stressed-skin construction schematic diagram with surface helium barrier layer;
Fig. 2 is the process chart of present invention process.
Detailed description of the invention
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are illustrated, it will be appreciated that preferred embodiment described herein is merely to illustrate and explains the present invention, is not intended to limit the present invention
Embodiment 1:
A kind of eyelid covering with surface helium barrier layer, structure is Fig. 1 such as, and the surface of eyelid covering 3 is alternately fitted with PDDA layer 1 and graphene powder layer 2, totally 20 layers.
Referring to the technological process of Fig. 2, adopting the method mutually handing over patch that PDDA layer and Graphene bisque are attached to skin-surface, its preparation method is:
The attachment of PDDA layer: adopt the solution of method one layer of PDDA of attachment of leaching a small brass gong lift on clean eyelid covering, PDDA liquid quality fraction is 0.5%, soak time >=1min, it is preferable that soak 10min, the eyelid covering of the PDDA solution of good attachment is dried at 100 DEG C, removes moisture. Wherein, eyelid covering cleaning adopt add surfactant deionized water ultrasonic >=1min, then with deionized water (can also use ultra-pure water, distilled water to replace) flushing >=3 times, at 60 DEG C��200 DEG C drying;
Except soaking the outer PDDA adhering mode available light roller coat cloth of lift, net roller coat cloth, scraper type coating, atomizing coating, curtain coating or spin coating method, PDDA is attached to skin-surface;
The attachment of graphene powder layer: adhere to last layer graphene powder solution again by having on the eyelid covering of PDDA layer and dry, the adhering mode of graphene solution adopts soaks czochralski method, soak time >=1min, preferred 10min, graphene powder liquid quality fraction is 0.5%, and drying temperature is 100 DEG C;
Graphene powder comprises graphene oxide powder, redox graphene powder body, single-layer graphene powder body, multi-layer graphene powder body, graphite microchip etc.;
In addition Graphene is attached to PDDA surface by the mode such as graphene solution available light roller coat cloth, net roller coat cloth, scraper type coating, atomizing coating, curtain coating and rotation;
Repeating the process of attachment PDDA layer and graphene powder layer, equal number of repetition is 10 times.
Embodiment 2:
A kind of eyelid covering with surface helium barrier layer, structure is Fig. 1 such as, and the surface of eyelid covering 3 is alternately fitted with PDDA layer 1 and graphene powder layer 2, totally 30 layers.
Preparation method with embodiment 1, is different in that substantially:
1, in the attaching process of PDDA layer, PDDA liquid quality fraction is 0.01wt%, and drying temperature is 200 DEG C;
2, in the attaching process of graphene powder layer, the concentration of graphene solution is 10wt%, and drying temperature is 60 DEG C.
3, each 15 times of the operating process of attachment PDDA layer and graphene powder layer is repeated.
Embodiment 3:
A kind of eyelid covering with surface helium barrier layer, structure is Fig. 1 such as, and the surface of eyelid covering 3 is alternately fitted with PDDA layer 1 and graphene powder layer 2, totally 100 layers.
Preparation method with embodiment 1, is different in that substantially:
1, in the attaching process of PDDA layer, PDDA liquid quality fraction is 10wt%, and drying temperature is 60 DEG C;
2, in the attaching process of graphene powder layer, the concentration of graphene solution is 0.01wt%, and drying temperature is 60 DEG C.
3, each 50 times of the operating process of attachment PDDA layer and graphene powder layer is repeated.
Embodiment 4:
A kind of eyelid covering with surface helium barrier layer, structure is Fig. 1 such as, and the surface of eyelid covering 3 is alternately fitted with PDDA layer 1 and graphene powder layer 2, totally 60 layers.
Preparation method with embodiment 1, is different in that substantially:
1, in the attaching process of PDDA layer, PDDA liquid quality fraction is 0.2wt%, and drying temperature is 120 DEG C;
2, in the attaching process of graphene powder layer, the concentration of graphene solution is 3wt%, and drying temperature is 150 DEG C.
3, each 30 times of the operating process of attachment PDDA layer and graphene powder layer is repeated.
Embodiment 5:
A kind of eyelid covering with surface helium barrier layer, structure is Fig. 1 such as, and the surface of eyelid covering 3 is alternately fitted with PDDA layer 1 and graphene powder layer 2, totally 10 layers.
Preparation method with embodiment 1, is different in that substantially:
1, in the attaching process of PDDA layer, PDDA liquid quality fraction is 7wt%, and drying temperature is 120 DEG C;
2, in the attaching process of graphene powder layer, the concentration of graphene solution is 0.6wt%, and drying temperature is 150 DEG C.
3, each 5 times of the operating process of attachment PDDA layer and graphene powder layer is repeated.
Except illustrating except above example, PDDA adhering mode can also be used with smooth roll coating, the coating of net roller coat cloth, scraper type, atomizing coating, curtain coating or spin coating method and PDDA be attached to skin-surface; Graphene is attached to PDDA surface by the modes such as the coating of graphene solution available light roller coat cloth, net roller coat cloth, scraper type, atomizing coating, curtain coating and rotation. For ensureing barriering efficiency and the process optimization of Obstruct membrane, inside and outside eyelid covering, the mutual paste layer of PDDA and Graphene can be carried out in surface.
The foregoing is only the preferred embodiments of the present invention, it is not limited to the present invention, although the present invention being described in detail with reference to previous embodiment, for a person skilled in the art, technical scheme described in foregoing embodiments still can be modified by it, or wherein portion of techniques feature carries out equivalent replacement. All within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention.
Claims (10)
1. the eyelid covering with surface helium barrier layer, it is characterized in that: described helium barrier layer is PDDA layer and graphene powder layer alternates laminating and constitutes, wherein the PDDA layer of innermost layer is fitted with the surface of eyelid covering, it is preferred that the surface of described eyelid covering includes the one side of eyelid covering or two-sided.
2. the eyelid covering with surface helium barrier layer according to claim 1, it is characterised in that: described PDDA layer and more than totally 6 layers of graphene powder layer, it is preferable that 10-100 layer, more preferably 20-30 layer.
3. the eyelid covering with surface helium barrier layer according to claim 1, it is characterised in that: the thickness of described PDDA layer is 1-1000nm, it is preferable that 3nm; Described graphene powder layer thickness is 1-1000nm, it is preferable that 3nm;
It is further preferred that the thickness of described PDDA layer and graphene powder layer is than for 1:0.8-1.5, more preferably 1:1.
4. the eyelid covering with surface helium barrier layer according to claim 1, it is characterized in that: described graphene powder layer is graphene powder material, it can be graphene oxide powder, redox graphene powder, single-layer graphene powder, multi-layer graphene powder or graphite microchip etc., it is preferable that graphene oxide powder.
5. the eyelid covering with surface helium barrier layer according to any one of claim 1-4, it is characterised in that: described eyelid covering is high-altitude vehicle eyelid covering or high-altitude aerostatics eyelid covering, it is preferred to proximity space aircraft skin;
It is further preferred that when covering as during for proximity space aircraft, described PDDA layer and graphene powder layer are total to 20-30 layer, the thickness of described PDDA layer is 3nm, the thickness of described graphene powder layer is 3nm.
6. the preparation method of the eyelid covering with surface helium barrier layer according to any one of claim 1-5, it is characterised in that: comprise the steps:
1) on clean eyelid covering, adhere to one layer of PDDA solution, dry and after all evaporating to solvent, form PDDA layer;
2) eyelid covering with PDDA layer will adhere to a layer graphene powder body solution again, dry to solvent and all evaporate formation graphene powder layer;
3) step 1 is repeated) and 2) to the number of plies of formation required for skin-surface.
7. the preparation method of the eyelid covering with surface helium barrier layer according to claim 6, it is characterised in that: described PDDA aqueous solution mass fraction is 0.01%-10%, it is preferable that 0.5%;
And/or, graphene powder liquid quality fraction is 0.01-10%, it is preferable that 0.5%.
8. the preparation method of the eyelid covering with surface helium barrier layer according to claim 6, it is characterized in that: described step 1) and step 2) in, described adherence method, adopts and soaks method of pulling up, smooth roll coating, the coating of net roller coat cloth, scraper type, atomizing coating, curtain coating or rotation.
9. the preparation method of the eyelid covering with surface helium barrier layer according to claim 8, it is characterised in that: the method for attachment PDDA solution adopts the method soaking lift, it is preferred that soak time >=1min, it is further preferred that soak time is 10min;
And/or, the method for attachment graphene powder layer adopts the method soaking lift, it is preferred that soak time >=1min, it is further preferred that soak time is 10min.
10. the preparation method of the eyelid covering with surface helium barrier layer according to claim 1, it is characterized in that: described step 1) in, the temperature dried is 60-200 DEG C, the time is 8-15min, it is preferable that dry temperature be 100 DEG C, drying time be 10min;
And/or, described step 2) in, the temperature of drying is 60-200 DEG C, the time is 8-15min, it is preferable that dry temperature be 100 DEG C, drying time be 10min.
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| CN107662386A (en) * | 2016-07-27 | 2018-02-06 | 海口未来技术研究院 | High-resistant diaphragm for aerostatics and its preparation method and application |
| CN111647872A (en) * | 2020-04-01 | 2020-09-11 | 湖南二零八先进科技有限公司 | Method for preventing gas leakage of laser gyroscope based on surface CVD growth graphene |
| CN114850010A (en) * | 2022-05-17 | 2022-08-05 | 伊诺福科光学技术有限公司 | Preparation method of graphene metamaterial three-dimensional conformal coating and three-dimensional conformal coating |
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| CN105620713B (en) | 2018-10-23 |
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