A method for preparing a composite-based impact-resistant aircraft glazing laminate

Abstract

The application discloses a kind of based on composite material's impact resistance aviation glass laminated preparation method, the present application relates to aviation glass manufacturing technical field, select aviation glass substrate after washing and make pyramid micro post array, deposition transition layer and graft coupling agent, three layers are assembled after vacuum hot pressing, by edge processing, coating and circulation processing etc., get finished product, the advantages of the present application are that: by constructing the pyramid micro post array of regular arrangement on the surface of aviation glass substrate, and after grafting silane coupling agent on the surface of post deposition metal oxide transition layer, form the cross-scale functional surface including mechanical lock structure and chemical anchoring site, multidimensional synergistic enhancement glass and interfacial bonding force of interlayer material, effectively solve the interlayer peeling problem caused by insufficient interfacial bonding force in prior art, so that aviation glass can efficiently transfer energy under impact load through interface, reduce delamination failure, while improving the structural stability under extreme environment.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of aviation glass manufacturing, in particular to a composite material-based impact-resistant aviation glass lamination preparation method. BACKGROUND

[0002] Aviation glass is a core functional material for key parts such as aircraft cockpits and windscreens, and needs to guarantee structural integrity and optical performance under severe working conditions such as high-speed flight, extreme temperature change, aerodynamic load and bird strike. The impact resistance of aviation glass is an important indicator of flight safety. With the development of the aviation industry towards high speed, light weight and high reliability, traditional single-layer glass has been gradually replaced by composite material laminated glass because of its brittleness and insufficient impact resistance. The composite material laminated aviation glass combines the high stiffness of glass and the toughness of the polymer interlayer through multi-layer material collaborative design, forming a composite structure of "stiffness and flexibility", which significantly improves the impact energy absorption capacity and crack propagation resistance.

[0003] The prior art has certain defects. First, in the existing aviation glass lamination structure, the interfacial bonding force between the glass and the interlayer material is insufficient, only relying on physical adhesion, lacking mechanical locking and chemical covalent bonds, and being prone to interlayer peeling, poor impact resistance and extreme environment stability. Secondly, the traditional laminated glass has concentrated impact energy and straight-line crack penetration, lacks multi-stage energy dissipation and crack guiding mechanism, and has poor edge stress concentration and functional coating compatibility, which is difficult to meet the reliability requirements of complex working conditions. Therefore, we propose a composite material-based impact-resistant aviation glass lamination preparation method. SUMMARY

[0004] The application aims to provide a composite material-based impact-resistant aviation glass lamination preparation method.

[0005] To achieve the above-mentioned purpose, the application provides the following technical scheme: a composite material-based impact-resistant aviation glass lamination preparation method, the preparation method comprising the following specific steps:

[0006] Step one, select an aviation glass substrate and perform surface cleaning, then prepare a regular array of pyramid-shaped micron-level bosses on the glass surface, deposit a metal oxide transition layer on the boss surface after processing, and finally graft a silane coupling agent on the surface of the transition layer to form a cross-scale functionalized surface containing chemical anchoring sites;

[0007] Step two, for the gap characteristics of the glass surface microposts, select shape memory polymer microspheres, mix bisphenol A type epoxy resin and acid anhydride curing agent, add shape memory polymer microspheres and single-walled carbon nanotubes, and prepare a conductive composite material as an interlayer material after dispersion;

[0008] Step three, the glass substrate treated in step one and the interlayer material prepared in step two are assembled in a "glass / interlayer / glass" three-layer structure, a machine vision positioning system and a pre-pressure are used to form a pre-interface;

[0009] Step four, the assembly is placed into a vacuum hot press forming machine, a three-stage temperature pulse pressure process is used for interface bonding, a three-dimensional reinforced interface containing mechanical locking, chemical covalent bond and nanoscale network is formed;

[0010] Step five, the chamfering treatment is performed on the glass edge of the laminated and formed glass, then a short fiber reinforced epoxy resin glue is uniformly coated by using an automatic glue coating machine, and a conductive film is deposited on the outer surface of the glass and an ultraviolet absorbing coating is coated on the inner surface;

[0011] Step six, the glass is placed in a high-low alternating box for cyclic treatment, then the carbon nanotube network is ordered by using a pulse magnetic field treatment, and finally the glass is ultrasonically cleaned.

[0012] As a further scheme of the present application: in step one, an aviation glass substrate with a thickness of 2mm-5mm and a light transmittance of ≥85% is selected, acetone solution is used for ultrasonic cleaning at a frequency of 40kHz-60kHz for 10min-20min to remove surface contaminants, then a regular arranged pyramid-shaped micro-level boss array is prepared on the glass surface by using an ultraviolet pulse laser processing system, and the laser processing parameters are as follows: pulse energy 50μJ-150μJ, scanning speed 10mm / s-30mm / s.

[0013] As a further scheme of the present application: in step one, a metal oxide transition layer of titanium dioxide with a thickness of 5nm-10nm is deposited on the boss surface by using atomic layer deposition technology after processing, the deposition temperature is 120-150℃, the cycle number is 20-30 times, and finally glycidyl ether oxypropyl trimethoxysilane is grafted on the surface of the transition layer by liquid phase grafting method, and the grafting density is controlled to be 6 / nm 2 -8 / nm 2 based on the formula.

[0014] ;

[0015] Wherein: represents the grafting density per unit area, c represents the concentration of the coupling agent solution, which is in the range of 0.5mol / L-1.0mol / L, V represents the treatment volume of the coupling agent solution (L), and A represents the surface area of the glass substrate (m²). The grafting density is controlled by the formula to form high-density chemical anchoring sites.

[0016] As a further scheme of the present application: in the step two, for the glass surface micro convex post gap features, the shape memory polymer microspheres with glass transition temperature of 55-65 DEG C and particle size of 1-5 mu m are selected, the bisphenol A type epoxy resin is mixed with the anhydride curing agent at the ratio of 100:80-100, 5wt%-10wt% of the shape memory polymer microspheres and 1wt%-3wt% of the single-walled carbon nanotubes with a tube diameter of 1-5 nm and a length of 1-5 mu m are added, the high-speed shearing dispersion machine is used for dispersing at a rotating speed of 5000-8000 rpm for 20-40 min, the ultrasonic treatment with a frequency of 20-30 kHz and a power of 100-200 W is introduced for 10-20 min to break the agglomerates, the conductivity of the composite material is greater than or equal to 5*10 -4 S / cm, and the dynamic modulus of the interlayer material is regulated by the following formula:

[0017] ;

[0018] Wherein, represents the dynamic modulus at temperature T, represents the room temperature modulus, and the value is 1.2-2.5 GPa, represents the modulus above the glass transition temperature, and the value is 0.2-0.6 GPa, represents the glass transition temperature of the shape memory polymer microspheres, represents the temperature variation parameter, and the value is 8-12 DEG C.

[0019] As a further scheme of the present application: in the step three, the glass substrate treated in the step one and the interlayer material prepared in the step two are assembled in a three-layer structure of "glass / interlayer / glass", the inner layer glass is synchronously treated with a convex array and the density is 60%-90% of the outer layer to balance the weight, the machine vision positioning system with a positioning accuracy of ±0.1 mm is used, the interlayer material is placed by the mechanical arm with a precision of 0.05 mm, the distribution density deviation of the shape memory polymer microspheres in each convex area is less than or equal to 5%, the pre-interface is formed by applying a pre-pressure of 5-10 N during the assembly process, the interlayer material is preliminarily embedded in the convex gap of the glass surface, the initial filling rate is greater than or equal to 80%, and the carbon nanotube tip and the coupling agent group on the convex surface form weak chemical adsorption, and the adsorption energy is greater than or equal to 20 kJ / mol, which provides site orientation for subsequent interface bonding.

[0020] As a further scheme of the present application: in step three, the glass substrate treated in step one and the interlayer material prepared in step two are assembled in a "glass / interlayer / glass" three-layer structure, the inner layer glass is simultaneously treated with the boss array and the density is 60%-90% of the outer layer to balance the weight, a machine vision positioning system with positioning accuracy of ±0.1mm is used, the interlayer material is placed by a mechanical arm with an accuracy of 0.05mm, the distribution density deviation of the shape memory polymer microspheres in the corresponding area of each boss is ≤5%, a pre-interfacial pressure of 5N-10N is applied during the assembly process to form a preliminary interface, so that the interlayer material is preliminarily embedded in the gap between the bosses on the glass surface, the initial filling rate is ≥80%, and at the same time, the carbon nanotube tips and the coupling agent groups on the surface of the boss form weak chemical adsorption, and the adsorption energy is ≥20kJ / mol, which provides site guidance for subsequent interfacial bonding.

[0021] As a further scheme of the present application: in step five, the glass edge formed by lamination is chamfered, the chamfer radius is 2mm-3mm, an automatic glue coating machine is used to uniformly coat a short fiber reinforced epoxy resin glue with a thickness of 1mm-2mm, the content of short glass fiber is 15wt%-30wt%, and the length is 3μm-5μm, a mechanical interlocking structure is formed on the edge, and then an indium tin oxide conductive film with a thickness of 50nm-100nm is deposited on the outer surface of the glass by a magnetron sputtering technology, and an ultraviolet absorption coating with a thickness of 5μm-10μm is coated on the inner surface, so that the light transmittance of the glass is ≥80% and the ultraviolet blocking rate is ≥98%.

[0022] As a further scheme of the present application: in step six, the glass is placed in a high-low alternating box at-50℃ to 150℃, and the temperature is cycled at a rate of 3℃ / min-5℃ / min for 80-100 times to eliminate residual stress, and then a pulse magnetic field with a magnetic field strength of 0.1-0.3T and a pulse frequency of 5Hz-8Hz is used for treatment for 5min-10min to order the carbon nanotube network, and finally the surface cleanliness meets the aviation standard by ultrasonic cleaning with deionized water at a frequency of 30kHz-50kHz for 5min-10min.

[0023] Compared with the prior art, the beneficial effects of the present application are:

[0024] 1. The present application forms a cross-scale functional surface containing mechanical locking structure and chemical anchoring site by constructing a regular array of pyramid-shaped micron-level boss array on the surface of aviation glass substrate, and then grafting silane coupling agent after depositing metal oxide transition layer on the boss surface, while introducing shape memory polymer microspheres and single-walled carbon nanotubes into the interlayer material, and preparing conductive composite material by high-speed shearing dispersion and ultrasonic treatment, and then realizing interface bonding by three-stage temperature pulse pressure process, wherein the micron-level boss and the shape memory polymer microspheres in the interlayer material form mechanical interlocking, the silane coupling agent reacts with the hydroxyl group on the glass surface to form covalent bond, and the single-walled carbon nanotube forms a nanoscale network at the root of the boss, which multi-dimensionally cooperates to enhance the interfacial bonding force of glass and interlayer material, effectively solving the interlayer peeling problem caused by insufficient interfacial bonding force in the prior art, enabling the aviation glass to efficiently transfer energy through the interface under impact load, reducing delamination failure, while improving the structural stability in extreme environment, and significantly enhancing the impact resistance and service reliability.

[0025] 2. The present application forms a mechanical locking structure by constructing a micron-level boss array on the glass surface, and realizes covalent bonding by combining with a nanoscale chemical anchoring coating, while introducing shape memory polymer microspheres that can dynamically respond to temperature changes and electrically enhanced single-walled carbon nanotubes into the interlayer material, and cooperating with the synergistic effect of low-temperature filling, medium-temperature bonding and high-temperature curing in the three-stage temperature pulse pressure process, so that when the aviation glass is subjected to impact, the micron boss forcibly guides the crack deflection and prolongs the extension path, the shape memory polymer microspheres absorb impact energy by softening, and the carbon nanotube network quickly and uniformly transmits stress, forming a multi-level energy dissipation mechanism of "mechanical retardation-flexible energy consumption-rigid support", effectively solving the problems of impact energy concentration and straight-line crack penetration of traditional laminated glass, significantly improving the impact energy dissipation efficiency, and the integration of edge strengthening treatment and functional coating further enhances the stress concentration resistance and environmental adaptability of the glass edge, realizing the synergistic optimization of impact resistance and multifunctionality, and meeting the stringent requirements of the aviation field for high-reliability transparent structural parts. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1 The present application is an embodiment of the method steps. DETAILED DESCRIPTION

[0027] The specific embodiments of the present application will be further described below in conjunction with the drawings, and it should be noted that the description of these embodiments is used to help understand the present application, but does not constitute a limitation on the present application.

[0028] In addition, the technical features involved in each of the embodiments of the present application described below can be combined with each other as long as they do not conflict with each other.

[0029] Please refer to the drawingsFigure 1 The application discloses a preparation method of an impact-resistant aviation glass laminate based on a composite material.

[0030] Step one, select an aviation glass substrate and perform surface cleaning, then prepare a regular array of pyramid-shaped micron-level convex arrays on the glass surface, deposit a metal oxide transition layer on the convex surface after processing, and finally graft a silane coupling agent on the surface of the transition layer to form a cross-scale functional surface containing chemical anchoring sites;

[0031] Step two, select shape memory polymer microspheres for the gap characteristics of the micron convex arrays on the glass surface, mix bisphenol A type epoxy resin with anhydride curing agent, add shape memory polymer microspheres and single-walled carbon nanotubes, and after dispersion, prepare a conductive composite material as a sandwich material;

[0032] Step three, assemble the glass substrate treated in step one and the sandwich material prepared in step two according to a "glass / sandwich / glass" three-layer structure, and form a pre-interface by using a machine vision positioning system and a pre-pressure;

[0033] Step four, place the assembly into a vacuum hot press forming machine, and perform interface bonding by using a three-stage temperature pulse pressure process to form a three-dimensional reinforced interface containing mechanical locking, chemical covalent bonding and nanoscale network;

[0034] Step five, chamfer the edges of the laminated glass, then uniformly coat short fiber reinforced epoxy resin glue by using an automatic glue coating machine, and then deposit a conductive film on the outer surface of the glass and coat an ultraviolet absorbing coating on the inner surface;

[0035] Step six, place the glass in a high-low alternating box for cyclic treatment, then order the carbon nanotube network by using a pulse magnetic field, and finally perform ultrasonic cleaning on the glass.

[0036] In an embodiment of the application: in step one, an aviation glass substrate with a thickness of 2mm-5mm and a light transmittance of ≥85% is selected, the surface contaminants are removed by ultrasonic cleaning with an acetone solution at a frequency of 40kHz-60kHz for 10min-20min, then a regular array of pyramid-shaped micron-level convex arrays is prepared on the glass surface by using an ultraviolet pulse laser processing system, and the laser processing parameters are as follows: pulse energy 50μJ-150μJ, and scanning speed 10mm / s-30mm / s.

[0037] In an embodiment of the application: in step one, a 5nm-10nm-thick metal oxide transition layer titanium dioxide is deposited on the convex surface by using atomic layer deposition technology after processing, the deposition temperature is 120-150℃, the cycle number is 20-30 times, and finally a silane coupling agent is grafted on the surface of the transition layer by using a liquid phase grafting method. - Glycidyloxypropyltrimethoxysilane, the grafting density is controlled to 6 / nm based on the formula 2 -8 pieces / nm 2 , the grafting density formula is as follows:

[0038] ;

[0039] in: represents the grafting density per unit area, c represents the concentration of the coupling agent solution, ranging from 0.5 mol / L to 1.0 mol / L, V represents the volume of the coupling agent solution treated (L), and A represents the surface area of ​​the glass substrate (m²). This formula is used to regulate and form high-density chemical anchoring sites.

[0040] In one embodiment of the present invention: in step 2, according to the micron boss gap characteristics on the glass surface, shape memory polymer microspheres with a glass transition temperature of 55°C-65°C and a particle size of 1 μm-5 μm are selected, bisphenol A epoxy resin and anhydride curing agent are mixed in a ratio of 100:80-100, 5wt%-10wt% of shape memory polymer microspheres and 1wt%-3wt% of single-walled carbon nanotubes are added, and the single-walled carbon nanotubes have a diameter of 1nm-5nm and a length of 1μm-5μm. The dispersion is carried out by a high-speed shear disperser at a speed of 5000rpm-8000rpm for 20min-40min, and then ultrasonic treatment with a frequency of 20kHz-30kHz and a power of 100-200W is introduced for 10-20min to break up the agglomerates, so that the conductivity of the composite material is ≥5×10 -4 S / cm, the dynamic modulus of the sandwich material is regulated by the following formula: ;

[0041] in, represents the dynamic modulus at temperature T, Indicates the room temperature modulus, ranging from 1.2GPa to 2.5GPa, Indicates the modulus above the glass transition temperature, ranging from 0.2GPa to 0.6GPa. represents the glass transition temperature of shape memory polymer microspheres, Indicates the temperature change parameter, with a value of 8℃-12℃.

[0042] In one embodiment of the present application: in step three, the glass substrate treated in step one and the interlayer material prepared in step two are assembled in a "glass / interlayer / glass" three-layer structure, the inner layer glass is simultaneously treated with a boss array and the density is 60%-90% of the outer layer to balance the weight, a machine vision positioning system with positioning accuracy of ±0.1 mm is used, the interlayer material is placed by a mechanical arm with an accuracy of 0.05 mm, the shape memory polymer microsphere distribution density deviation of each boss corresponding area is ≤5%, a pre-interfacial pressure of 5N-10N is applied during the assembly process to form a preliminary interface, so that the interlayer material is preliminarily embedded in the boss gap of the glass surface, the initial filling rate is ≥80%, and at the same time, the carbon nanotube tip and the coupling agent group on the boss surface form weak chemical adsorption, and the adsorption energy is ≥20kJ / mol, which provides site guidance for subsequent interfacial bonding.

[0043] In one embodiment of the present application: in step four, the assembly is placed into a hot press forming machine with a vacuum degree of ≤10Pa, and a three-stage temperature pulse pressure process is used:

[0044] The first stage is a low-temperature filling stage: the temperature is 55-65℃, the pressure is 0.3MPa-0.5MPa, and the duration is 10min-20min, so that the shape memory polymer microspheres are softened and the volume expansion rate is 15%-20%, the filling rate of the boss gap is ≥90%, and a micron-level mechanical lock is formed;

[0045] The second stage is a medium-temperature bonding stage: the temperature is raised to 90-100℃, a pulse pressure with a frequency of 8Hz-10Hz and an amplitude of 0.5MPa-0.8MPa is applied, and the duration is 30min-40min, which triggers the reaction of the coupling agent with the hydroxyl groups on the glass surface to generate Si-O-Si covalent bonds with a bond energy of ≥400kJ / mol;

[0046] The third stage is a high-temperature curing stage: the temperature is raised to 140℃-160℃, the pressure is 1.0MPa-1.2MPa, and the duration is 40min-50min, so that when the epoxy resin is cured, the carbon nanotubes form a nanoscale network with a winding density of ≥5 roots / μm at the root of the boss, locking the three-dimensional reinforced interface.

[0047] In one embodiment of the present application: in step five, the glass edge of the laminated and formed glass is chamfered, the chamfer radius is 2mm-3mm, an automatic glue coating machine is used to uniformly coat a short fiber reinforced epoxy resin glue with a thickness of 1mm-2mm, the short glass fiber content is 15wt%-30wt%, and the length is 3μm-5μm, a mechanical interlocking structure is formed on the edge, and then an indium tin oxide conductive film with a thickness of 50nm-100nm is deposited on the outer surface of the glass by magnetron sputtering technology, and an ultraviolet absorbing coating with a thickness of 5μm-10μm is coated on the inner surface, so that the glass transmittance is ≥80% and the ultraviolet blocking rate is ≥98%.

[0048] In one embodiment of the present application: in step six, the glass is placed in a high-low alternating box at -50℃ to 150℃, and cycled 80-100 times at a temperature rise rate of 3℃ / min-5℃ / min to eliminate residual stress, then treated with a pulsed magnetic field with a magnetic field strength of 0.1-0.3T and a pulse frequency of 5Hz-8Hz for 5min-10min to order the carbon nanotube network, and finally cleaned with deionized water under a frequency of 30kHz-50kHz for 5min-10min to ensure that the surface cleanliness meets the aviation standards.

[0049] Example One, please refer to the attached Figure 1 Step one: preparation of a glass substrate with a cross-scale functionalized surface

[0050] Substrate selection and cleaning:

[0051] An aviation glass substrate with a thickness of 3mm and a light transmittance of 88% is selected, with a size of 500mm×500mm, and cleaned with acetone solution (concentration 99.5%) under ultrasonic cleaning at a frequency of 40kHz for 15min to remove surface oil and particulate contaminants (detection method: microscopic observation of surface cleanliness, particle size <50μm);

[0052] Preparation of micro-post array:

[0053] An ultraviolet pulsed laser processing system (model: LPKF ProLase 300) is used, with a pulse energy of 80μJ and a scanning speed of 20mm / s.

[0054] Nanocoating and coupling agent grafting:

[0055] A titanium dioxide transition layer is deposited by an atomic layer deposition (ALD) device (model: Cambridge Nanotech Savannah S200) at a thickness of 8nm, a deposition temperature of 130℃, and a cycle number of 25 times (0.32nm deposited per cycle).

[0056] Grafting process: the glass substrate is immersed in a 0.75mol / L glycidyloxypropyltrimethoxysilane ethanol solution (volume V=2L) for a reaction time of 60min, with a grafting density of 7.2 / nm² (note: actually detected by X-ray photoelectron spectroscopy (XPS) as 7.2 / nm², meeting the requirement of 6-8 / nm²).

[0057] Step two: preparation of an intelligent sandwich composite material

[0058] Raw material ratio:

[0059] ​Bisphenol A type epoxy resin (model: EPON828, epoxy value 0.51 eq / 100g) was mixed with methylhexahydrophthalic anhydride curing agent (ratio 100:90), 8wt% shape memory polymer microspheres (glass transition temperature Tg=60℃, particle size 3μm) and 2wt% single-walled carbon nanotubes (tube diameter 2nm, length 3μm) were added.

[0060] Dispersion process:

[0061] Dispersed for 30min at 6000rpm using a high-speed shearing disperser (model: IKAT25), followed by ultrasonic treatment (model: Branson Sonifier S-450D, frequency 25kHz, power 150W) for 15min, until the carbon nanotube agglomerates were <5μm (detection method: transmission electron microscope (TEM) observation).

[0062] Dynamic modulus regulation:

[0063] According to the formula When T=25℃ (room temperature), , When T>Tg, , the modulus regulation requirement is met.

[0064] Step three: assembly of laminated structure

[0065] Structure design:

[0066] A "glass / interlayer / glass" three-layer structure was adopted, with the inner layer glass boss density being 80% of the outer layer (achieved by adjusting the laser processing distance), and the interlayer material thickness being 2mm.

[0067] Positioning and pre-pressing:

[0068] The interlayer material was placed using a machine vision positioning system (accuracy ±0.08mm) and a six-axis robot (repeatability accuracy ±0.03mm), ensuring that the microsphere distribution density deviation was 4% (detection method: fluorescent microscope observation of marker microsphere distribution), and an 8N pre-pressing force was applied to embed the interlayer material into the boss gap, with an initial filling rate of 85% (observed by scanning electron microscope cross-section).

[0069] Step four: three-stage temperature pulse pressure process

[0070] Low-temperature filling stage:

[0071] The vacuum hot press forming machine (model: Leybold HERCULES600, vacuum degree 5Pa) was heated to 60℃, and a pressure of 0.4MPa was applied for 15min, after which the shape memory polymer microspheres softened and expanded by 18%, with a filling rate of 92% (detected by CT scanning).

[0072] Intermediate temperature bonding stage:

[0073] Ramp to 95°C, pulse pressure of 9Hz, amplitude 0.6MPa, for 35min, Fourier transform infrared spectroscopy (FTIR) detected Si-O-Si bond characteristic peak (1080cm -1 ), to prove the formation of covalent bond.

[0074] High temperature curing stage:

[0075] Ramp to 150°C, pressure 1.1MPa, for 45min, carbon nanotubes form a winding network at the root of the convex, winding density 6 roots / μm (TEM observation).

[0076] Step five: edge strengthening and functional coating

[0077] Edge treatment:

[0078] Edge chamfer radius 2.5mm, coated with 1.5mm thick short fiber reinforced epoxy resin glue (short glass fiber content 25wt%, length 4μm), edge bonding force 75N / cm measured by tensile test.

[0079] Coating deposition:

[0080] The outer surface is magnetron sputtered with indium tin oxide (ITO) film, thickness 80nm, square resistance 8Ω per square (measured by four-probe method); the inner surface is coated with 8μm ultraviolet absorption coating, ultraviolet barrier rate 98.5% (detected by ultraviolet visible spectrophotometer).

[0081] Step six: post-processing and detection

[0082] Multi-field treatment:

[0083] High-low temperature alternating box (model: ESPEC SH-242) cycles 90 times (-50°C→150°C, heating rate 4°C / min), residual stress is detected by laser scattering instrument as 12MPa (<0.2τ, τ is the interfacial shear strength).

[0084] Pulsed magnetic field treatment: magnetic field strength 0.2T, frequency 6Hz, treatment 8min, carbon nanotube order degree is improved to 78% detected by Raman spectroscopy.

[0085] Ultrasonic cleaning:

[0086] Deionized water, 40kHz frequency ultrasonic cleaning for 8min, surface particle contamination is detected as 3 / mm² (size <50μm).

[0087] Performance test

[0088] Interfacial shear strength: 55 MPa (GB / T7124 standard, universal material testing machine model: Instron5982);

[0089] Impact resistance: no penetration after impact at a speed of 200 m / s, crack propagation length 45 mm, light transmittance maintained at 83%;

[0090] Peeling force after high-low temperature cycle: 45 N / cm (better than the standard requirement of 40 N / cm).

[0091] Example two, please refer to the attached Figure 1 Step one: preparation of glass substrate cross-scale functionalized surface

[0092] Substrate selection and cleaning:

[0093] An aviation glass substrate with a thickness of 5 mm and a light transmittance of 85% was selected, with a size of 800 mm x 600 mm. It was cleaned with an acetone solution under ultrasonic cleaning at a frequency of 60 kHz for 10 min, and the surface cleanliness was detected by ion chromatography to be free of organic matter residues.

[0094] Micron boss array preparation:

[0095] Laser processing parameters: pulse energy 150 μJ, scanning speed 10 mm / s.

[0096] Nano coating and coupling agent grafting:

[0097] Atomic layer deposition of titanium dioxide, thickness 10 nm, temperature 150°C, number of cycles 30, grafting glycidyl ether oxypropyltrimethoxysilane, solution concentration 1.0 mol / L, grafting density 8 / nm² (XPS detection).

[0098] Step two: preparation of intelligent interlayer composite material

[0099] Raw material ratio:

[0100] Epoxy resin and curing agent ratio 100:80, adding 10 wt% shape memory polymer microspheres (Tg=55°C, particle size 5 μm) and 3 wt% carbon nanotubes (tube diameter 5 nm, length 5 μm).

[0101] Dispersion process:

[0102] High-speed shearing 8000 rpm for 20 min, ultrasonic treatment for 20 min (frequency 30 kHz, power 200 W), conductivity detection 8 x 10 -4 S / cm.

[0103] Step four: three-stage temperature rising pulse pressure process

[0104] Low-temperature filling stage:

[0105] Temperature 55°C, pressure 0.5 MPa, duration 20 min, filling rate 90%.

[0106] Medium temperature bonding stage:

[0107] Temperature 100°C, pulse pressure frequency 10 Hz, amplitude 0.8 MPa, duration 40 min, bond energy detection 420 kJ / mol (Raman spectrum).

[0108] Step five: edge strengthening and functional coating

[0109] Short fiber reinforced glue: thickness 2 mm, short glass fiber content 30 wt%, length 5 μm;

[0110] ITO film thickness 100 nm, square resistance 10 Ω per square meter, ultraviolet coating thickness 10 μm, barrier rate 98%.

[0111] Performance test

[0112] Interfacial shear strength: 60 MPa;

[0113] Impact resistance: crack propagation 50 mm after 200 m / s impact, light transmittance 80%;

[0114] Extreme low temperature (-50°C) impact toughness: 60% higher than traditional process (Charpy impact test).

[0115] Common technical details of the embodiment

[0116] Grafting density : By adjusting the coupling agent concentration c and the treatment volume V, combined with XPS detection of hydroxyl content, the chemical anchoring site density is ensured (c = 1.0 mol / L in Example 2, = 8 / nm²).

[0117] Key equipment verification:

[0118] Laser processing machine: calibrate accuracy by standard sample plate before processing (boss size deviation ≤ ± 5%);

[0119] Hot press forming machine: equipped with infrared thermometer (accuracy ± 1°C) and pressure sensor (accuracy ± 0.05 MPa) to ensure controllable process parameters.

[0120] Detection method:

[0121] Interface microstructure: observe boss integrity and carbon nanotube winding state by scanning electron microscope (SEM, resolution 10 nm);

[0122] Chemical bonding force: XPS detects the change of Si element content, which proves the formation of Si-O-Si bond (characteristic peak at 103.5 eV).

[0123] According to the above embodiment, it can be concluded that by constructing a regular array of pyramid-shaped micron-level convex array on the surface of the aviation glass substrate and grafting silane coupling agent, a sandwich material containing shape memory polymer microspheres and single-walled carbon nanotubes is prepared, and the interface bonding is realized by three-stage temperature rising pulse pressure process, edge strengthening and functional coating treatment, which effectively solves the problems of insufficient interlayer bonding force of existing aviation glass, delamination failure and crack penetration caused by impact energy concentration. In the embodiment, the micron convex and the shape memory polymer microspheres form mechanical interlocking, the nanoscale chemical anchoring coating generates covalent bond, and the carbon nanotubes construct a nanoscale network at the root of the convex. Multi-technology synergistic enhancement of interface bonding force, at the same time, three-stage temperature rising process promotes the dynamic response of the sandwich material to temperature change, forming a multi-level energy dissipation mechanism of "mechanical resistance-flexible energy consumption-rigid support". After testing, the interface shear strength, impact resistance and extreme environment stability are significantly improved, and the edge strengthening and functional coating realize the stress concentration resistance and multi-functional integration. Through the cross-scale interface design and the application of smart materials, the invention breaks through the bottleneck of traditional lamination process and provides a high-reliability technical solution for aviation glass preparation, which has significant engineering application value and industry promotion prospect.

[0124] Although the present application is disclosed in the preferred embodiments, it is not intended to limit the present application, and any person skilled in the art can make possible changes and modifications without departing from the spirit and scope of the present application. Therefore, any modification, equivalent change and modification made to the above embodiments according to the technical essence of the present application, which does not deviate from the technical solution of the present application, falls within the protection scope defined by the claims of the present application.

Claims

1. A method for the production of a composite-based impact-resistant aircraft glazing laminate, characterized in that, The preparation method comprises the following specific steps: Step one, first, the surface of the aviation glass substrate is cleaned, then a regular array of pyramid-shaped micro-level convex array is processed on the surface, then a metal oxide transition layer is uniformly covered on the convex surface by atomic layer deposition technology, and a silane coupling agent is grafted on the transition layer, and finally a multi-scale composite interface with mechanical interlocking and chemical anchoring functions is formed; In step one, a 5-10 nm thick titanium dioxide transition layer is deposited on the processed boss surface by atomic layer deposition technology, the deposition temperature is 120-150°C, the cycle number is 20-30 times, and finally a liquid phase grafting method is used to graft - glycidyl ether oxypropyl trimethoxysilane, the grafting density is controlled to be 6 / nm based on the formula 2 - 8 / nm 2 , the grafting density formula is as follows: ; wherein: represents the grafting density per unit area, c represents the coupling agent solution concentration, the value range is 0.5-1.0 mol / L, V represents the treatment volume of the coupling agent solution, and A represents the surface area of the glass substrate. The grafting density is regulated by the formula to form high-density chemical anchoring sites. Step two, for the gap characteristics of the micro convex array on the glass surface, shape memory polymer microspheres are selected, bisphenol A type epoxy resin and anhydride curing agent are mixed, shape memory polymer microspheres and single-walled carbon nanotubes are added, and after dispersion, an electrically conductive composite material is prepared as a sandwich material; In the second step, for the glass surface micron convex boss gap features, select the glass transition temperature 55-65 ℃, particle size 1-5 μm shape memory polymer microspheres, bisphenol A type epoxy resin and anhydride curing agent mixed with 100:80-100 ratio, add 5wt%-10wt% shape memory polymer microspheres and 1wt%-3wt% single-walled carbon nanotubes, single-walled carbon nanotube diameter 1-5 nm, length 1-5 μm, by high speed shearing dispersion machine at 5000-8000 rpm speed dispersion 20-40 min, then introduce frequency 20-30 kHz, power 100-200 W ultrasonic treatment 10-20 min to break the agglomerates, the dynamic modulus of the sandwich material is regulated by the following formula: ; wherein, G' represents the dynamic modulus at temperature T, G represents the modulus at room temperature, having a value of 1.2 GPa - 2.5 GPa, G represents the modulus above the glass transition temperature, having a value of 0.2 GPa - 0.6 GPa, Tg represents the glass transition temperature of the shape memory polymer microspheres, DT represents the temperature variation parameter, having a value of 8 °C - 12 °C; Step three, the glass substrate treated in step one and the sandwich material prepared in step two are assembled in a "glass / sandwich / glass" three-layer structure, a machine vision positioning system and a pre-pressure are used to form a pre-interface; Step four, the assembly is placed into a vacuum hot press forming machine, and a three-stage temperature pulse pressure process is used for interface bonding to form a three-dimensional reinforced interface containing mechanical locking, chemical covalent bond and nanoscale network; Step five, the edges of the laminated glass are chamfered, then a short fiber reinforced epoxy resin glue is uniformly coated by using an automatic glue coating machine, and then a conductive film is deposited on the outer surface of the glass and an ultraviolet absorbing coating is coated on the inner surface; Step six, the glass is placed in a high-low alternating box for cyclic treatment, then the carbon nanotube network is ordered by using a pulse magnetic field, and finally the glass is ultrasonically cleaned.

2. A method of manufacturing a composite based impact resistant aircraft glazing laminate according to claim 1, characterized in that: In step one, an aviation glass substrate with a thickness of 2mm-5mm and a light transmittance of ≥85% is selected, the surface is cleaned by ultrasonic cleaning with acetone solution at a frequency of 40kHz-60kHz for 10min-20min to remove surface contaminants, and a regular array of pyramid-shaped micro-level convex array is processed on the glass surface by using an ultraviolet pulse laser system, the laser processing parameters are: pulse energy 50μJ-150μJ, scanning speed 10mm / s-30mm / s.

3. A method of making a composite based impact resistant aircraft glazing laminate according to claim 1, characterized in that: In step three, the glass substrate treated in step one and the sandwich material prepared in step two are assembled in a "glass / sandwich / glass" three-layer structure, the inner layer glass is simultaneously treated with a convex array and the density is 60%-90% of the outer layer to balance the weight, a machine vision positioning system with a positioning accuracy of ±0.1mm is used, the sandwich material is placed by a mechanical arm with an accuracy of 0.05mm, the distribution density deviation of shape memory polymer microspheres in each convex area is ≤5%, and a pre-pressure of 5N-10N is applied during the assembly process to form a pre-interface.

4. A method of making a composite based impact resistant aircraft glazing laminate according to claim 1, characterized in that: In step four, the assembly is placed into a hot press forming machine with a vacuum degree of ≤10Pa, and a three-stage temperature pulse pressure process is used: First stage, low temperature filling stage: temperature 55-65℃, pressure 0.3MPa-0.5MPa, duration 10min-20min, so that the shape memory polymer microspheres are softened and the volume expansion rate is 15%-20%, the filling rate of the convex array is ≥90%, and a micro-level mechanical locking is formed; The second section of the temperature bonding stage: the temperature is raised to 90-100℃, the pulse pressure with the frequency of 8Hz-10Hz and the amplitude of 0.5MPa-0.8MPa is applied for 30min-40min, which promotes the reaction between the coupling agent and the glass surface hydroxyl group, and generates Si-O-Si covalent bond with the bond energy ≥400kJ / mol; The third section of the high temperature curing stage: the temperature is raised to 140℃-160℃, the pressure is 1.0MPa-1.2MPa, and the process lasts for 40min-50min, which makes the carbon nanotube form a nanoscale network with the winding density ≥5 roots / μm at the root of the convex, and locks the three-dimensional reinforced interface.

5. A method of making a composite based impact resistant aircraft glazing laminate according to claim 1, characterized in that: In the fifth step, the glass edge of the laminated molding is chamfered with the chamfer radius of 2mm-3mm, and an automatic glue coating machine is used to uniformly coat the short fiber reinforced epoxy resin glue with the thickness of 1mm-2mm, the short glass fiber content is 15wt%-30wt%, and the length is 3μm-5μm, so as to form the edge mechanical interlocking structure, then the indium tin oxide conductive film with the thickness of 50nm-100nm is deposited on the outer surface of the glass by the magnetron sputtering technology, and the ultraviolet absorption coating with the thickness of 5μm-10μm is coated on the inner surface, so that the glass light transmittance is ≥80%, and the ultraviolet blocking rate is ≥98%.

6. A method of making a composite based impact resistant aircraft glazing laminate according to claim 1, characterized in that: In the sixth step, the glass is placed in a high-low alternating box at-50℃ to 150℃, and the temperature is raised at the rate of 3℃ / min-5℃ / min for 80-100 times, so as to eliminate the residual stress, then the pulse magnetic field with the magnetic field strength of 0.1-0.3T and the pulse frequency of 5Hz-8Hz is used for 5min-10min, so as to order the carbon nanotube network, finally the deionized water is used for ultrasonic cleaning at the frequency of 30kHz-50kHz for 5min-10min.

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