CN112964132B - Special-shaped energy-consumption composite anti-explosion protective armor with flame retardant property and preparation method thereof - Google Patents
Special-shaped energy-consumption composite anti-explosion protective armor with flame retardant property and preparation method thereof Download PDFInfo
- Publication number
- CN112964132B CN112964132B CN202110194067.3A CN202110194067A CN112964132B CN 112964132 B CN112964132 B CN 112964132B CN 202110194067 A CN202110194067 A CN 202110194067A CN 112964132 B CN112964132 B CN 112964132B
- Authority
- CN
- China
- Prior art keywords
- metal
- energy
- zno
- flame retardant
- polyurea
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F41—WEAPONS
- F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
- F41H5/00—Armour; Armour plates
- F41H5/02—Plate construction
- F41H5/04—Plate construction composed of more than one layer
- F41H5/0442—Layered armour containing metal
Abstract
The invention provides a special-shaped energy-consumption composite anti-explosion protective armor with flame retardant property. The protective armor takes the energy processing layer as the center, and the polyurea coating 2 and the protective metal plate 1 are symmetrically arranged on two sides from inside to outside. The energy processing layer is composed of a metal corrugated plate 3, a viscoelastic damping layer 4 and a metal energy absorption pipe 5. The viscoelastic damping layer 4 is positioned in a sandwich formed by two corrugated metal plates 3. The corrugated metal plate 3 is an isosceles trapezoid corrugated plate. The polyurea coating 2 is sprayed on the inner side of the armor. The bulge of the corrugated metal plate 3 is directly connected with the polyurea coating 2, and the groove of the corrugated plate is connected with the polyurea coating 2 through the metal energy absorption pipe 5. The metal energy absorption pipes 5 are transversely and symmetrically arranged at two ends of the bottom of the groove of the metal corrugated plate 3. The ZnO @ MOF @ polyphosphazene flame retardant is added into the polyurea material adopted by the protective armor, so that the flame retardant property of the polyurea material is improved on the premise of not influencing the mechanical property of the polyurea material, and the flame retardant property of the protective armor is improved.
Description
Technical Field
The invention belongs to the field of materials, relates to an explosion-proof armor, and particularly relates to a special-shaped energy-consuming composite explosion-proof armor in the field of military protection, wherein the armor has good flame retardant property.
Background
In recent years, with rapid development of weaponry technology and changes in international political conditions, military forces in various countries are often attacked by terrorist car bombs, armor-breaking bombs, explosive-and-simple-explosion-equipment (IDE) and the like in anti-terrorism operations, and shock waves from the explosion of weapons can cause serious damage to vehicles and passengers inside.
The explosion-proof structure is mainly researched on two aspects, namely, on one hand, a new material is researched on the basis of the energy absorption characteristic of the material, namely, the principle that the material deforms to absorb energy or the loss factor of the material is improved. Such as protection of military transport vehicles by adding additional blast-proof armor. The method can effectively improve the safety of the vehicle, but the additional armor can greatly increase the dead weight of the transport vehicle, thereby greatly reducing the maneuverability of the vehicle and limiting the carrying capacity. On the other hand, the principle of reaction momentum is utilized to resist the incoming blast wave, and a complex structure is designed. For example, the explosion impact energy is dispersed by adopting a V-shaped vehicle bottom structure, and the explosion impact pressure at the bottom of the vehicle body is reduced, so that the ground mine prevention capability of the vehicle is improved. At present, more and more modern mine-proof vehicle all adopts similar vehicle bottom structure, however because military vehicle has higher requirement to open-air trafficability characteristic, underbody installation V-arrangement protective structure often leads to the ground clearance to reduce, thereby make vehicle centre of gravity position often higher, cause vehicle operation stability to reduce. Aiming at personnel in the carriage, the mode of optimizing seats is mostly adopted at present, and energy-consuming seats are designed to protect passengers.
The invention patent 201510211687.8 discloses an explosion wave-proof composite armor structure, which can block the shock wave in the area near the overpressure peak value in the explosion wave through the micro-structural design of the metamaterial layer; on the other hand, the energy absorption buffer layer absorbs explosion pressure waves, so that the explosion-proof capacity of the structure is improved. However, for large deformation caused by explosion, the structure can only achieve the energy absorption effect through the crushing deformation of the energy absorption buffer layer, so that the structure can only resist single explosion; once the energy absorption layer absorbs energy and is damaged, the energy absorption effect of the structure is greatly reduced. In addition, for the stress concentration action of high strain rate such as contact explosion and high-speed impact, the metamaterial layer is easy to be subjected to brittle failure, so that the protective performance of the structure is greatly reduced. The invention patent application 201911191392.3 discloses a graded energy-consumption composite anti-knock protective armor and a preparation method thereof, wherein the protective armor sequentially comprises a protective metal plate I, a polyurea coating, an energy treatment layer and a protective metal plate II. The energy processing layer is composed of a viscoelastic damping layer, a high-strength spring and a metal energy absorption pipe. The protective armor utilizes the characteristics of crushing energy absorption of the energy absorption tube and energy conversion and elastic deformation of the high-strength spring, and adopts viscoelastic damping materials to combine the energy absorption tube and the high-strength spring, so that plastic deformation, elastic deformation and damping energy consumption are fully combined, the light weight under the same protection grade is realized, the defect of one-time protection of the traditional structure is overcome, and the safety of a protected structure is improved.
However, the protective armor does not have flame retardant property, so when the structure is damaged by external concentrated load and high temperature coupling, the high temperature can soften the material and cause violent combustion, and dense smoke is generated. Once the protective structure is broken down, the combustion products of the protective material can have adverse effects on the protected object; meanwhile, due to the influence of high temperature, the mechanical property of the material is reduced, so that each protection unit is separated, and the protection performance of the armor is greatly reduced.
Disclosure of Invention
Aiming at the problems of the explosion-proof armor in the prior art, the invention provides the special-shaped energy-consumption composite explosion-proof armor with flame retardant property. The ZnO @ MOF @ polyphosphazene flame retardant is added into the polyurea material adopted by the protective armor, so that the flame retardant property of the polyurea material is improved on the premise of not influencing the mechanical property of the polyurea material, and the flame retardant property of the protective armor is improved.
The technical scheme of the invention is as follows:
the special-shaped energy-consumption composite anti-explosion protective armor with flame-retardant performance takes an energy processing layer as a center, and polyurea coatings 2 and protective metal plates 1 are symmetrically arranged on two sides from inside to outside. The energy processing layer is composed of a metal corrugated plate 3, a viscoelastic damping layer 4 and a metal energy absorption pipe 5. The viscoelastic damping layer 4 is positioned in an interlayer formed by two metal corrugated plates 3; the thickness of the viscoelastic damping layer 4 is one fourth of the thickness of the protective armor, and the thickness of the protective armor is adjusted according to the protection grade. The viscoelastic damping layer is a two-component viscoelastic damping material which is purchased from commercial sources and modified based on polyurea; wherein the component A is isocyanate, the index R value of the isocyanate is 0.8, and the component B is an amino compound. The corrugated metal plate 3 is isosceles trapezoid corrugated, the size of the corrugated is adjusted according to the protection grade, the ratio of the upper bottom to the lower bottom of the trapezoid is 1:3, the ratio of the height to the upper bottom is 7:10, and the length of the upper bottom is 10-50 mm; the corrugated metal plate 3 is made of aluminum alloy and has a thickness of 0.4-2 mm. The polyurea coating 2 is sprayed on the inner side of the armor, and the thickness is 2-5 mm; the bulge of the corrugated metal plate 3 is directly connected with the polyurea coating 2, and the groove of the corrugated plate is connected with the polyurea coating 2 through the metal energy absorption pipe 5. The metal energy absorption pipes 5 are transversely and symmetrically arranged at two ends of the bottom of the groove of the metal corrugated plate 3. The protective metal plate 1 is made of high-strength anti-explosion alloy with the thickness of 5-12 mm. The protective armor described in the application adopts a two-stage energy consumption mode, and carries out graded energy consumption on the action deformation of the protective metal plate aiming at external loads, so that the protection efficiency is greatly improved; and when the structure bears once complete deformation, the viscoelastic damping layer can slowly recover the geometric morphology of the metal corrugated plate, so that the next load effect is borne, the defect of one-time protection of the traditional structure is overcome, and the safety of the protected structure is greatly improved.
The polyurea coating 2 is a flame-retardant polyurea material and is prepared by the following method:
preparing ZnO @ MOF nanoparticles: dispersing cobalt nitrate and dimethyl imidazole in a DMF aqueous solution, and magnetically stirring until the cobalt nitrate and dimethyl imidazole are uniformly dispersed; adding ZnO powder into the mixture, and transferring the mixture into a high-pressure kettle to perform solvothermal reaction after uniform ultrasonic dispersion; and (3) after the reaction is finished, returning to the room temperature, washing, and freeze-drying to obtain the ZnO @ MOF nano particles. Wherein the mass concentration of the DMF aqueous solution is 700-850 g/L; the weight ratio of the cobalt nitrate to the dimethyl imidazole in the DMF solution is 1: 20-1: 30, the concentration of ZnO in the DMF solution is 10-20 g/L, and the magnetic stirring speed is 300-500 rpm; the temperature condition of the solvothermal reaction is 50-70 ℃, and the reaction time is 1-3 h; the temperature condition of the freeze drying is-65 to-50 ℃.
Preparing ZnO @ MOF @ polyphosphazene: firstly, dissolving hexachlorocyclotriphosphazene in a solvent to obtain a hexachlorocyclotriphosphazene solution; the ZnO @ MOF nanoparticles were dispersed in the aforementioned solvent by sonication to give a suspension. Adding diamine compound and triethylamine into the suspension respectively; then the hexachlorocyclotriphosphazene solution is dripped into the reaction system under ultrasonic treatment to obtain a reaction system. And transferring the reaction system into an oil bath, stirring for 10-30 h at 50-80 ℃ to obtain a ZnO @ MOF @ polyphosphazene solution, washing with ethanol, and drying in vacuum to obtain the ZnO @ MOF @ polyphosphazene flame retardant. All the above processes are carried out in a nitrogen atmosphere.
Wherein the solvent is acetonitrile, 1, 4-dioxane or tetrahydrofuran, and the diamine compound is 4,4 '-diaminodiphenyl ether or 4,4' -diaminodiphenyl sulfone. The concentration of the ZnO @ MOF nanoparticles in a solvent is 3-5 g/L, the weight ratio of the diamine compound to triethylamine is 1: 3-4: 3, and the concentration of the hexachlorocyclotriphosphazene solution is 10-30 g/L.
Preparing a flame-retardant polyurea material: and (3) adding the ZnO @ MOF @ polyphosphazene flame retardant obtained in the step (2) into a mixture of the amine-terminated polyether and the amine chain extender, ultrasonically dispersing uniformly, and then adding an isocyanate prepolymer into a system for reaction to obtain the flame-retardant polyurea material. The addition amount of the ZnO @ MOF @ polyphosphazene flame retardant is 0.1-5.0 wt%. The weight ratio of the amino-terminated polyether to the amine chain extender is 4: 1-2: 1; the volume ratio of the isocyanate prepolymer to the sum of the amino-terminated polyether and the chain extender is 1: 1; the isocyanate prepolymer is obtained by prepolymerization of isocyanate and hydroxyl-terminated polyether in a weight ratio of 10: 9-5: 7 in a nitrogen atmosphere.
Wherein the amino-terminated polyether is one or more of bifunctional polytetramethylene ether glycol di-p-aminobenzoate, amino-terminated polyoxypropylene ether and trifunctional amino-terminated polyoxypropylene ether; the amino chain extender is one or more of diethyl toluene diamine, dimethyl sulfur toluene diamine, N ' -dialkyl methyl diamine and 3,3' -dichloro-4, 4' -diamino diphenylmethane; the isocyanate is one or more of 4,4 '-diphenylmethane diisocyanate (4,4' -MDI), 2,4 '-diphenylmethane diisocyanate (2,4' -MDI) and isophorone diisocyanate (IPDI).
The polyurea coating 2 has excellent mechanical properties: (1) the material has certain strain rate sensitivity, and has a longer elastic stage when high strain rate is acted, and the elastic modulus can reach 117 MPa; (2) the polyurea coating has higher tensile strength and elongation at break, so that the polyurea coating has the capacity of bearing large deformation; (3) and the polyurea coating has higher tearing performance, and can resist the tearing damage brought by the high strain rate loading action so as to ensure the structural integrity. In addition, the polyurea material 2 has good adhesive force on the surface of a metal material, can tightly compound a metal energy absorption pipe and a metal corrugated pipe together, and the viscoelastic damping layer is not separated under the action of shock waves, so that the structure keeps good integrity. In addition, the polyurea coating 2 also has good flame retardant properties; the improvement of the flame retardant property is realized on the premise of ensuring the mechanical property.
The preparation method of the special-shaped energy-consumption composite anti-explosion protective armor with the flame retardant property comprises the following steps:
(a) preparing two metal corrugated plates 3 and a plurality of metal energy-absorbing pipes 5, fixedly connecting one ends of the metal corrugated plates 3 and the metal energy-absorbing pipes 5 by viscoelastic damping materials, and arranging the metal energy-absorbing pipes 5 at two ends of the bottoms of grooves of the metal corrugated plates 3 in a transverse symmetrical mode.
(b) And (3) respectively spraying a proper amount of viscoelastic damping materials on the inner sides of the two corrugated metal plates 3, spraying a layer of viscoelastic damping material after the surfaces of the viscoelastic damping materials are dried, quickly closing and fixing the two corrugated plates, and curing at normal temperature for 12 hours to obtain the energy absorption layer.
(c) Preparing two protective metal plates 1, polishing the inner sides of the protective metal plates 1, removing surface dust, spraying primer, and improving the adhesive force between the polyurea coating and the metal plates; and after the surface of the primer is dried, spraying a flame-retardant polyurea material to form a polyurea coating 2. Rapidly connecting and fixing the other end of the metal energy absorption tube 5 with the polyurea coating 2, and maintaining for 12 hours at normal temperature; the special-shaped energy-consuming composite anti-explosion protective armor with flame retardant property can be obtained.
The application of the special-shaped energy-consuming composite anti-explosion protective armor with flame retardant property is applied to the anti-explosion of vehicles or buildings; the method specifically comprises the following steps: and installing/fixing the protective armor on the outer layer of a vehicle or a building to be used as an energy-absorbing protective layer.
Energy absorption and energy consumption principle:
when an external load acts on the protective metal plate 1, the structure enters a first stage of energy consumption; energy consumes energy through the large deformation of metal sheet this moment, and the polyurea coating 2 that excels in fire-retardant converts partial mechanical energy into internal energy on the one hand because the higher loss factor of itself, and on the other hand receives the high strain rate load effect, and the coating is because strain rate effect, and material elastic modulus increases, can effectively wrap up and restrain the large deformation of meeting the face of exploding protection metal sheet 1 to the integrality of structure has been guaranteed. When the material is damaged by explosion load, the polyurea coating 2 can inhibit fragments on one hand and protect the structure and personnel safety through the flame retardant property of the polyurea coating on the other hand. When the external load continues to act after the energy consumption of the first stage is over, the protective metal plate 1 is compressed and deformed, and the load causes the compression deformation of the metal energy absorption pipe 5 and the metal corrugated plate 3. At the moment, energy is consumed in the deformation of the two energy-absorbing structures; different with traditional power consumption structure, this application consumes energy through the power consumption unit that a trapezium structure of metal energy-absorbing pipe and metal corrugated plate is constituteed at this stage, just the horizontal alternating distribution of power consumption unit has overcome the problem that can't pass through the relative displacement energy-absorbing when double-deck corrugated plate structure receives concentrated load to energy-absorbing efficiency has been improved greatly.
When the load is concentrated, the metal energy absorption pipe 5 is crushed and deformed when the load acts on the metal energy absorption pipe 5, so that energy is absorbed. The viscoelastic damping layer 4 now has two functions: on one hand, the structure is resisted by using a higher elastic modulus under a high strain rate, and on the other hand, due to the relative displacement between the upper and lower two metal corrugated plates 3, the viscoelastic damping layer 4 generates reciprocating shear deformation to convert mechanical energy into internal energy to be consumed. When load acts on the convex parts of the metal corrugated plate 3, the viscoelastic damping layer has higher elastic modulus, resists part of deformation, and transmits the other part of deformation to the metal energy absorption pipe 5 at the lower layer uniformly, thereby improving the energy absorption efficiency. Meanwhile, the bulge of the corrugated metal plate 3 is crushed, and the deformation causes the relative displacement of the whole viscoelastic damping layer, so that shearing energy absorption is realized. When concentrated load acts between the metal energy absorption pipe 5 and the convex part of the metal corrugated plate 3, the single side of the metal energy absorption pipe 5 is crushed, the bevel edge of the metal corrugated plate 3 is displaced to the maximum, and the energy absorption effect of the viscoelastic damping layer reaches the maximum at the moment, so that the impact load is fully consumed.
The flame retardant mechanism is as follows:
Firstly, PO & free radicals released by polyphosphazene are combined with hydrogen atoms in a flame region to play a role in inhibiting flame; and phosphoric acid, metaphosphoric acid and polymetaphosphoric acid generated by the combustion of polyphosphazene can promote the dehydration and carbonization of polyurea, thereby reducing the amount of combustible gas generated in the thermal decomposition process of polyurea.
Secondly, MOF employs imidazole ligands, releasing NH during polyurea combustion 3 Or N 2 And the concentration of the combustible gas generated by the oxygen and the polymer is diluted by the non-combustible gas. In addition, the MOF can be degraded in the combustion process to generate oxide particles with porous structures, so that not only can heat transmission be prevented, but also combustible/toxic gases such as CO generated by polyurea degradation can be adsorbed. Meanwhile, the oxide particles can promote carbon formation, and the formed carbon has a compact structure and is not easy to burn.
And thirdly, as the same as the oxide obtained by the degradation of the MOF, ZnO can also catalyze the pyrolysis of polyurea to form charcoal in the combustion process, so that the charcoal forming amount is obviously improved, the combustion of the internal material of the polyurea coating is avoided, and the protection effect of the polyurea coating is realized.
In addition, oxides obtained by degradation of ZnO and MOF react with phosphoric acid, metaphosphoric acid and polymetaphosphoric acid generated in the combustion process of polyphosphazene to generate cross-linked phosphorus oxynitride and a carbonized aromatic network, so that the formation of polyurea/ZnO @ MOF @ polyphosphazene carbon residue is promoted. The three have good synergistic effect in the combustion process, thereby greatly improving the flame retardant effect.
The invention has the beneficial effects that:
(1) the special-shaped energy-consumption composite anti-explosion protection armor combines the metal corrugated plate, the viscoelastic damping material and the metal thin-wall energy absorption tube together to form a hierarchical energy-consumption structure, so that the structural deformation can be effectively inhibited, and the safety of the protection structure is greatly improved; and the protective armor adopts polyurea materials with good flame retardant property, so that the normal service state of the matrix structure after detonation can be effectively protected.
(2) The application the energy absorption layer of protection armor adopt the energy-absorbing structure that metal energy-absorbing pipe, metal buckled plate and viscoelastic damping layer combined together, solved traditional protective structure problem that efficiency of protection descends by a wide margin under concentrated load effect, utilize crushing energy-absorbing, viscoelastic damping layer shear energy-absorbing and high elastic modulus to restrain the mode of warping, very big improvement the energy-absorbing efficiency of protection armor.
(3) The special-shaped energy-consumption composite anti-explosion protection armor can flexibly adjust the size and the position of the protection armor according to the requirement of a protection object, and is not limited by the protection position; and corresponding structural members can be replaced according to different protection grades.
(4) The application viscoelastic damping layer and polyurea coating in the protective armor have high elastic modulus under the action of high strain rate, and when the explosion-facing surface protective metal plate is damaged, an external fragment is broken and the penetration of an projectile occurs, the external fragment can be flicked or restrained in the coating, so that secondary damage is greatly reduced.
Drawings
FIG. 1 is a schematic cross-sectional structure diagram of the special-shaped energy-consuming composite anti-knock protective armor with flame retardant properties;
FIG. 2 is a stress-strain curve of the high-strength flame-retardant polyurea coating prepared in example 1 under the action of different speed loads;
FIG. 3 is the elastic phase of the high-strength flame-retardant polyurea coating prepared in example 1 at a stretching speed of 4 m/s;
FIG. 4 is a plot of total smoke generation versus time for the high strength flame retardant polyurea coating prepared in example 1;
FIG. 5 is a plot of CO release versus time for the high strength flame retardant polyurea coating prepared in example 1;
FIG. 6 is a graph of total heat released versus time for the high strength flame retardant polyurea coating prepared in example 1.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
the special-shaped energy-consumption composite anti-explosion protective armor with flame-retardant performance takes an energy processing layer as a center, and polyurea coatings 2 and protective metal plates 1 are symmetrically arranged on two sides from inside to outside. The protective metal plate 1 is made of high-strength anti-explosion alloy with the thickness of 5 mm. The polyurea coating 2 is a flame-retardant polyurea material. The energy processing layer is composed of a metal corrugated plate 3, a viscoelastic damping layer 4 and a metal energy absorption pipe 5. The viscoelastic damping layer 4 is positioned in an interlayer formed by two metal corrugated plates 3, and the thickness of the viscoelastic damping layer 4 is 10 mm. The viscoelastic damping layer is a two-component viscoelastic damping material which is purchased from commercial sources and modified based on polyurea; wherein the component A is isocyanate, the index R value of the isocyanate is 0.8, and the component B is an amino compound. The corrugated metal plate 3 is an isosceles trapezoid corrugated plate, the ratio of the upper bottom to the lower bottom of the trapezoid is 1:3, the ratio of the height to the upper bottom is 7:10, and the length of the upper bottom is 50 mm; the corrugated metal plate 3 is made of aluminum alloy and has a thickness of 0.4 mm. The polyurea coating 2 is sprayed on the inner side of the armor, and the thickness is 2 mm; the bulge of the corrugated metal plate 3 is directly connected with the polyurea coating 2, and the groove of the corrugated plate is connected with the polyurea coating 2 through the metal energy absorption pipe 5. The metal energy absorption pipes 5 are transversely and symmetrically arranged at two ends of the bottom of the groove of the metal corrugated plate 3.
The flame-retardant polyurea material is prepared by the following method:
preparing ZnO @ MOF nanoparticles: dispersing cobalt nitrate and dimethyl imidazole in a DMF (dimethyl formamide) aqueous solution, and magnetically stirring until the cobalt nitrate and the dimethyl imidazole are uniformly dispersed; adding ZnO powder into the mixture, and transferring the mixture into a high-pressure kettle to perform solvothermal reaction after uniform ultrasonic dispersion; and (3) after the reaction is finished, returning to the room temperature, washing, and freeze-drying to obtain the ZnO @ MOF nano particles. Wherein the mass concentration of the DMF aqueous solution is 760 g/L; the weight ratio of the cobalt nitrate to the dimethyl imidazole in the DMF solution is 1:21, the concentration of ZnO in the DMF solution is 15g/L, and the magnetic stirring speed is 300 rpm; the temperature condition of the solvothermal reaction is 60 ℃, and the reaction time is 1.8 h; the temperature condition for freeze drying was-50 ℃.
Preparing ZnO @ MOF @ polyphosphazene: firstly, dissolving hexachlorocyclotriphosphazene in a solvent to obtain a hexachlorocyclotriphosphazene solution; the ZnO @ MOF nanoparticles were dispersed in the aforementioned solvent by sonication to give a suspension. Adding diamine compound and triethylamine into the suspension respectively; then the hexachlorocyclotriphosphazene solution is dripped into the reaction system under ultrasonic treatment to obtain a reaction system. And transferring the reaction system into an oil bath, stirring for 12 hours at 55 ℃ to obtain a ZnO @ MOF @ polyphosphazene solution, washing with ethanol, and then drying in vacuum to obtain the ZnO @ MOF @ polyphosphazene flame retardant. All the above processes are carried out in a nitrogen atmosphere.
Wherein the solvent is tetrahydrofuran, and the diamine compound is 4,4' -diaminodiphenyl ether. The concentration of the ZnO @ MOF nano particles in a solvent is 3g/L, the weight ratio of the diamine compound to triethylamine is 4:3, and the concentration of the hexachlorocyclotriphosphazene solution is 18 g/L.
Preparing a flame-retardant polyurea material: and (3) adding the ZnO @ MOF @ polyphosphazene flame retardant obtained in the step (2) into a mixture of the amine-terminated polyether and the amine chain extender, ultrasonically dispersing uniformly, and then adding an isocyanate prepolymer into a system for reaction to obtain the flame-retardant polyurea material. The addition amount of the ZnO @ MOF @ polyphosphazene flame retardant is 5.0 wt%. The weight ratio of the amine-terminated polyether to the amine chain extender is 4: 1; the volume ratio of the isocyanate prepolymer to the sum of the amino-terminated polyether and the chain extender is 1: 1; the isocyanate prepolymer is obtained by prepolymerization of isocyanate and hydroxyl-terminated polyether in a weight ratio of 5:7 under a nitrogen atmosphere.
Wherein the amino-terminated polyether is polytetramethylene ether glycol bis-p-aminobenzoate with difunctional; the amino chain extender is dimethyl-sulfur-based toluene diamine; the isocyanate is 2,4 '-diphenylmethane diisocyanate (2,4' -MDI).
The preparation method of the special-shaped energy-consumption composite anti-explosion protective armor with flame retardant performance comprises the following steps:
(a) preparing two metal corrugated plates 3 and a plurality of metal energy-absorbing pipes 5, fixedly connecting one ends of the metal corrugated plates 3 and the metal energy-absorbing pipes 5 by viscoelastic damping materials, and transversely and symmetrically arranging the metal energy-absorbing pipes 5 at two ends of the bottoms of the grooves of the metal corrugated plates 3.
(b) And (3) respectively spraying a proper amount of viscoelastic damping materials on the inner sides of the two corrugated metal plates 3, spraying a layer of viscoelastic damping material after the surfaces of the viscoelastic damping materials are dried, quickly closing and fixing the two corrugated plates, and curing at normal temperature for 12 hours to obtain the energy absorption layer.
(c) Preparing two protective metal plates 1, polishing the inner sides of the protective metal plates 1 to remove surface dust, spraying primer and improving the adhesive force between the polyurea coating and the metal plates; and after the surface of the primer is dried, spraying a flame-retardant polyurea material to form a polyurea coating 2. Rapidly connecting and fixing the other end of the metal energy absorption tube 5 with the polyurea coating 2, and maintaining for 12 hours at normal temperature; the special-shaped energy-consuming composite anti-explosion protective armor with flame retardant property can be obtained.
The application of the special-shaped energy-consuming composite anti-explosion protective armor with flame retardant property is applied to the anti-explosion of vehicles or buildings; the method specifically comprises the following steps: and installing/fixing the protective armor on the outer layer of a vehicle or a building to be used as an energy-absorbing protective layer.
Example 2: in contrast to the embodiment 1, the process of the invention,
the special-shaped energy-consumption composite anti-explosion protective armor with flame-retardant performance takes an energy processing layer as a center, and polyurea coatings 2 and protective metal plates 1 are symmetrically arranged on two sides from inside to outside. The protective metal plate 1 is made of high-strength anti-explosion alloy with the thickness of 12 mm. The polyurea coating 2 is a flame-retardant polyurea material. The energy processing layer is composed of a metal corrugated plate 3, a viscoelastic damping layer 4 and a metal energy absorption pipe 5. The viscoelastic damping layer 4 is positioned in an interlayer formed by two metal corrugated plates 3; the viscoelastic damping layer 4 has a thickness of 18 mm. The corrugated metal plate 3 is an isosceles trapezoid corrugated plate, the ratio of the upper bottom to the lower bottom of the trapezoid is 1:3, the ratio of the height to the upper bottom is 7:10, and the length of the upper bottom is 10 mm; the corrugated metal plate 3 is made of aluminum alloy and has the thickness of 2 mm. The polyurea coating 2 is sprayed on the inner side of the armor, and the thickness is 5 mm; the bulge of the corrugated metal plate 3 is directly connected with the polyurea coating 2, and the groove of the corrugated plate is connected with the polyurea coating 2 through the metal energy absorption pipe 5. The metal energy absorption pipes 5 are transversely and symmetrically arranged at two ends of the bottom of the groove of the metal corrugated plate 3.
The flame-retardant polyurea material is prepared by the following method:
Preparing ZnO @ MOF nanoparticles: dispersing cobalt nitrate and dimethyl imidazole in a DMF aqueous solution, and magnetically stirring until the cobalt nitrate and dimethyl imidazole are uniformly dispersed; adding ZnO powder into the mixture, and transferring the mixture into a high-pressure kettle to perform solvothermal reaction after uniform ultrasonic dispersion; and (3) after the reaction is finished, returning to the room temperature, washing, and freeze-drying to obtain the ZnO @ MOF nano particles. Wherein the mass concentration of the DMF aqueous solution is 700 g/L; the weight ratio of the cobalt nitrate to the dimethyl imidazole in the DMF solution is 1: 23, the concentration of ZnO in DMF is 10g/L, and the speed of magnetic stirring is 500 rpm; the temperature condition of the solvothermal reaction is 50 ℃, and the reaction time is 3 hours; the temperature condition for freeze-drying was-54 ℃.
Preparing ZnO @ MOF @ polyphosphazene: firstly, dissolving hexachlorocyclotriphosphazene in a solvent to obtain a hexachlorocyclotriphosphazene solution; the ZnO @ MOF nanoparticles were dispersed in the aforementioned solvent by sonication to give a suspension. Adding diamine compound and triethylamine into the suspension respectively; then the hexachlorocyclotriphosphazene solution is dripped into the reaction system under ultrasonic treatment to obtain a reaction system. And transferring the reaction system into an oil bath, stirring for 30h at 80 ℃ to obtain a ZnO @ MOF @ polyphosphazene solution, washing with ethanol, and then drying in vacuum to obtain the ZnO @ MOF @ polyphosphazene flame retardant. All the above processes are carried out in a nitrogen atmosphere.
Wherein the solvent is 1, 4-dioxane, and the diamine compound is 4,4' -diaminodiphenyl ether. The concentration of the ZnO @ MOF nano particles in a solvent is 5g/L, the weight ratio of the diamine compound to triethylamine is 1:3, and the concentration of the hexachlorocyclotriphosphazene solution is 10 g/L.
Preparing a flame-retardant polyurea material: and (3) adding the ZnO @ MOF @ polyphosphazene flame retardant obtained in the step (2) into a mixture of the amine-terminated polyether and the amine chain extender, ultrasonically dispersing uniformly, and then adding an isocyanate prepolymer into a system for reaction to obtain the flame-retardant polyurea material. The addition amount of the ZnO @ MOF @ polyphosphazene flame retardant is 0.1 wt%. The weight ratio of the amine-terminated polyether to the amine chain extender is 7: 3; the volume ratio of the isocyanate prepolymer to the sum of the amino-terminated polyether and the chain extender is 1: 1; the isocyanate prepolymer is obtained by prepolymerization of isocyanate and hydroxyl-terminated polyether in a weight ratio of 5:6 under a nitrogen atmosphere.
Wherein the amino-terminated polyether comprises 50 parts of bifunctional polytetramethylene ether glycol di-p-aminobenzoate and 20 parts of trifunctional amino-terminated polyoxypropylene ether; the amino chain extender comprises 20 parts of N, N ' -dialkyl methyl diamine and 10 parts of 3,3' -dichloro-4, 4' -diamino diphenylmethane; the isocyanate is 4,4 '-diphenylmethane diisocyanate (4,4' -MDI), and the isocyanate and the hydroxyl-terminated polyether are mixed.
Example 3: in contrast to the embodiment 1, the process of the invention,
the special-shaped energy-consumption composite anti-explosion protective armor with flame-retardant performance takes an energy processing layer as a center, and polyurea coatings 2 and protective metal plates 1 are symmetrically arranged on two sides from inside to outside. The protective metal plate 1 is made of high-strength anti-explosion alloy with the thickness of 8 mm. The polyurea coating 2 is a flame-retardant polyurea material. The energy processing layer is composed of a metal corrugated plate 3, a viscoelastic damping layer 4 and a metal energy absorption pipe 5. The viscoelastic damping layer 4 is positioned in an interlayer formed by two metal corrugated plates 3, and the thickness of the viscoelastic damping layer 4 is 22 mm. The corrugated metal plate 3 is an isosceles trapezoid corrugated plate, the ratio of the upper bottom to the lower bottom of the trapezoid is 1:3, the ratio of the height to the upper bottom is 7:10, and the length of the upper bottom is 30 mm; the corrugated metal plate 3 is made of aluminum alloy and is 1mm thick. The polyurea coating 2 is sprayed on the inner side of the armor, and the thickness is 3 mm; the bulge of the corrugated metal plate 3 is directly connected with the polyurea coating 2, and the groove of the corrugated plate is connected with the polyurea coating 2 through the metal energy absorption pipe 5. The metal energy absorption pipes 5 are transversely and symmetrically arranged at two ends of the bottom of the groove of the metal corrugated plate 3.
The flame-retardant polyurea material is prepared by the following method:
Preparing ZnO @ MOF nanoparticles: dispersing cobalt nitrate and dimethyl imidazole in a DMF aqueous solution, and magnetically stirring until the cobalt nitrate and dimethyl imidazole are uniformly dispersed; adding ZnO powder into the mixture, and transferring the mixture into a high-pressure kettle to perform solvothermal reaction after uniform ultrasonic dispersion; and (3) after the reaction is finished, returning to the room temperature, washing, and freeze-drying to obtain the ZnO @ MOF nano particles. Wherein the mass concentration of the DMF aqueous solution is 820 g/L; the weight ratio of the cobalt nitrate to the dimethyl imidazole in the DMF solution is 1:20, the concentration of ZnO in the DMF solution is 12g/L, and the magnetic stirring speed is 360 rpm; the temperature condition of the solvothermal reaction is 70 ℃, and the reaction time is 1 h; the temperature condition for freeze-drying was-63 ℃.
Preparing ZnO @ MOF @ polyphosphazene: firstly, dissolving hexachlorocyclotriphosphazene in a solvent to obtain a hexachlorocyclotriphosphazene solution; the ZnO @ MOF nanoparticles were dispersed in the aforementioned solvent by sonication to give a suspension. Adding diamine compound and triethylamine into the suspension respectively; then the hexachlorocyclotriphosphazene solution is dripped into the reaction system under ultrasonic treatment to obtain a reaction system. And transferring the reaction system into an oil bath, stirring for 10 hours at 72 ℃ to obtain a ZnO @ MOF @ polyphosphazene solution, washing with ethanol, and then drying in vacuum to obtain the ZnO @ MOF @ polyphosphazene flame retardant. All the above processes are carried out in a nitrogen atmosphere.
Wherein the solvent is 1, 4-dioxane, and the diamine compound is 4,4' -diaminodiphenyl ether. The concentration of the ZnO @ MOF nanoparticles in a solvent is 4.6g/L, the weight ratio of the diamine compound to triethylamine is 1:2, and the concentration of the hexachlorocyclotriphosphazene solution is 30 g/L.
Preparing a flame-retardant polyurea material: and (3) adding the ZnO @ MOF @ polyphosphazene flame retardant obtained in the step (2) into a mixture of the amine-terminated polyether and the amine chain extender, ultrasonically dispersing uniformly, and then adding an isocyanate prepolymer into a system for reaction to obtain the flame-retardant polyurea material. The addition amount of the ZnO @ MOF @ polyphosphazene flame retardant is 2.3 wt%. The weight ratio of the amine-terminated polyether to the amine chain extender is 3: 1; the volume ratio of the isocyanate prepolymer to the sum of the amino-terminated polyether and the chain extender is 1: 1; the isocyanate prepolymer is obtained by prepolymerization of isocyanate and hydroxyl-terminated polyether in a weight ratio of 10:13 under a nitrogen atmosphere.
Wherein the amino-terminated polyether comprises 45 parts of bifunctional polytetramethylene ether glycol bis-p-aminobenzoate, 20 parts of bifunctional amino-terminated polyoxypropylene ether and 10 parts of trifunctional amino-terminated polyoxypropylene ether; the amino chain extender comprises 15 parts of N, N' -dialkyl methyl diamine and 10 parts of diethyl toluene diamine; the isocyanate is isophorone diisocyanate (IPDI).
Example 4: in contrast to the embodiment 1, the process,
the special-shaped energy-consumption composite anti-explosion protective armor with flame-retardant performance takes an energy processing layer as a center, and polyurea coatings 2 and protective metal plates 1 are symmetrically arranged on two sides from inside to outside. The protective metal plate 1 is made of high-strength anti-explosion alloy with the thickness of 10 mm. The polyurea coating 2 is a flame-retardant polyurea material. The energy processing layer is composed of a metal corrugated plate 3, a viscoelastic damping layer 4 and a metal energy absorption pipe 5. The viscoelastic damping layer 4 is positioned in an interlayer formed by two metal corrugated plates 3, and the thickness of the viscoelastic damping layer 4 is 18.4 mm. The corrugated metal plate 3 is an isosceles trapezoid corrugated plate, the ratio of the upper bottom to the lower bottom of the trapezoid is 1:3, the ratio of the height to the upper bottom is 7:10, and the length of the upper bottom is 40 mm; the corrugated metal plate 3 is made of aluminum alloy and has the thickness of 0.6 mm. The polyurea coating 2 is sprayed on the inner side of the armor, and the thickness is 4 mm; the bulge of the corrugated metal plate 3 is directly connected with the polyurea coating 2, and the groove of the corrugated plate is connected with the polyurea coating 2 through the metal energy absorption pipe 5. The metal energy absorption pipes 5 are transversely and symmetrically arranged at two ends of the bottom of the groove of the metal corrugated plate 3.
The flame-retardant polyurea material is prepared by the following method:
Preparing ZnO @ MOF nanoparticles: dispersing cobalt nitrate and dimethyl imidazole in a DMF aqueous solution, and magnetically stirring until the cobalt nitrate and dimethyl imidazole are uniformly dispersed; adding ZnO powder into the mixture, and transferring the mixture into a high-pressure kettle to perform solvothermal reaction after uniform ultrasonic dispersion; and (3) after the reaction is finished, returning to the room temperature, washing, and freeze-drying to obtain the ZnO @ MOF nano particles. Wherein the mass concentration of the DMF aqueous solution is 850 g/L; the weight ratio of the cobalt nitrate to the dimethyl imidazole in the DMF solution is 1:30, the concentration of ZnO in the DMF solution is 20g/L, and the magnetic stirring speed is 500 rpm; the temperature condition of the solvothermal reaction is 65 ℃, and the reaction time is 1.5 h; the temperature condition for freeze-drying was-58 ℃.
Preparing ZnO @ MOF @ polyphosphazene: firstly, dissolving hexachlorocyclotriphosphazene in a solvent to obtain a hexachlorocyclotriphosphazene solution; the ZnO @ MOF nanoparticles were dispersed in the aforementioned solvent by sonication to give a suspension. Adding diamine compound and triethylamine into the suspension respectively; then the hexachlorocyclotriphosphazene solution is dripped into the reaction system under ultrasonic treatment to obtain a reaction system. And transferring the reaction system into an oil bath, stirring for 21h at 80 ℃ to obtain a ZnO @ MOF @ polyphosphazene solution, washing with ethanol, and then drying in vacuum to obtain the ZnO @ MOF @ polyphosphazene flame retardant. All the above processes are carried out in a nitrogen atmosphere.
Wherein the solvent is tetrahydrofuran, and the diamine compound is 4,4' -diaminodiphenyl ether. The concentration of the ZnO @ MOF nanoparticles in a solvent is 4.7g/L, the weight ratio of the diamine compound to triethylamine is 2:3, and the concentration of the hexachlorocyclotriphosphazene solution is 22 g/L.
Preparing a flame-retardant polyurea material: and (3) adding the ZnO @ MOF @ polyphosphazene flame retardant obtained in the step (2) into a mixture of the amine-terminated polyether and the amine chain extender, ultrasonically dispersing uniformly, and then adding an isocyanate prepolymer into a system for reaction to obtain the flame-retardant polyurea material. The addition amount of the ZnO @ MOF @ polyphosphazene flame retardant is 1 wt%. The weight ratio of the amine-terminated polyether to the amine chain extender is 3: 1; the volume ratio of the isocyanate prepolymer to the sum of the amino-terminated polyether and the chain extender is 1: 1; the isocyanate prepolymer is obtained by prepolymerization of isocyanate and hydroxyl-terminated polyether in a weight ratio of 1:1 under a nitrogen atmosphere.
Wherein the amino-terminated polyether comprises 60 parts of bifunctional polytetramethylene ether glycol di-p-aminobenzoate and 15 parts of trifunctional amino-terminated polyoxypropylene ether; the amino chain extender is 8 parts of diethyl toluene diamine and 17 parts of dimethyl sulfur toluene diamine; the isocyanate is a mixture of 60 parts of 4,4 '-diphenylmethane diisocyanate (4,4' -MDI) and 40 parts of 2,4 '-diphenylmethane diisocyanate (2,4' -MDI).
Example 5: in contrast to the embodiment 1, the process of the invention,
the special-shaped energy-consumption composite anti-explosion protective armor with flame-retardant performance takes an energy processing layer as a center, and polyurea coatings 2 and protective metal plates 1 are symmetrically arranged on two sides from inside to outside. The protective metal plate 1 is made of high-strength anti-explosion alloy with the thickness of 6 mm. The polyurea coating 2 is a flame-retardant polyurea material. The energy processing layer is composed of a metal corrugated plate 3, a viscoelastic damping layer 4 and a metal energy absorption pipe 5. The viscoelastic damping layer 4 is positioned in an interlayer formed by two metal corrugated plates 3, and the thickness of the viscoelastic damping layer 4 is 15 mm. The corrugated metal plate 3 is an isosceles trapezoid corrugated plate, the ratio of the upper bottom to the lower bottom of the trapezoid is 1:3, the ratio of the height to the upper bottom is 7:10, and the length of the upper bottom is 18 mm; the corrugated metal plate 3 is made of aluminum alloy and is 1.5mm thick. The polyurea coating 2 is sprayed on the inner side of the armor, and the thickness is 2.5 mm; the bulge of the corrugated metal plate 3 is directly connected with the polyurea coating 2, and the groove of the corrugated plate is connected with the polyurea coating 2 through the metal energy absorption pipe 5. The metal energy absorption pipes 5 are transversely and symmetrically arranged at two ends of the bottom of the groove of the metal corrugated plate 3.
The flame-retardant polyurea material is prepared by the following method:
Preparing ZnO @ MOF nanoparticles: dispersing cobalt nitrate and dimethyl imidazole in a DMF aqueous solution, and magnetically stirring until the cobalt nitrate and dimethyl imidazole are uniformly dispersed; adding ZnO powder into the mixture, and transferring the mixture into a high-pressure kettle to perform solvothermal reaction after uniform ultrasonic dispersion; and (3) after the reaction is finished, returning to the room temperature, washing, and freeze-drying to obtain the ZnO @ MOF nano particles. Wherein the mass concentration of the DMF aqueous solution is 750 g/L; the weight ratio of the cobalt nitrate to the dimethyl imidazole in the DMF solution is 1:27, the concentration of ZnO in the DMF solution is 14g/L, and the magnetic stirring speed is 500 rpm; the temperature condition of the solvothermal reaction is 56 ℃, and the reaction time is 1.2 h; the temperature condition for freeze drying was-65 ℃.
Preparing ZnO @ MOF @ polyphosphazene: firstly, dissolving hexachlorocyclotriphosphazene in a solvent to obtain a hexachlorocyclotriphosphazene solution; the ZnO @ MOF nanoparticles were dispersed in the aforementioned solvent by sonication to give a suspension. Adding diamine compound and triethylamine into the suspension respectively; then the hexachlorocyclotriphosphazene solution is dripped into the reaction system under ultrasonic treatment to obtain a reaction system. And transferring the reaction system into an oil bath, stirring for 22h at 63 ℃ to obtain a ZnO @ MOF @ polyphosphazene solution, washing with ethanol, and then drying in vacuum to obtain the ZnO @ MOF @ polyphosphazene flame retardant. All the above processes are carried out in a nitrogen atmosphere.
Wherein the solvent is 1, 4-dioxane, and the diamine compound is 4,4' -diaminodiphenyl sulfone. The concentration of the ZnO @ MOF nanoparticles in a solvent is 3g/L, the weight ratio of the diamine compound to triethylamine is 1:1, and the concentration of the hexachlorocyclotriphosphazene solution is 19 g/L.
Preparing a flame-retardant polyurea material: and (3) adding the ZnO @ MOF @ polyphosphazene flame retardant obtained in the step (2) into a mixture of the amine-terminated polyether and the amine chain extender, ultrasonically dispersing uniformly, and then adding an isocyanate prepolymer into a system for reaction to obtain the flame-retardant polyurea material. The addition amount of the ZnO @ MOF @ polyphosphazene flame retardant is 5.0 wt%. The weight ratio of the amine-terminated polyether to the amine chain extender is 2: 1; the volume ratio of the isocyanate prepolymer to the sum of the amino-terminated polyether and the chain extender is 1: 1; the isocyanate prepolymer is obtained by prepolymerization of isocyanate and hydroxyl-terminated polyether in a weight ratio of 10:9 under a nitrogen atmosphere.
Wherein the amino-terminated polyether comprises 30 parts of bifunctional polytetramethylene ether glycol bis-p-aminobenzoate and 37 parts of bifunctional amino-terminated polyoxypropylene ether; the amino chain extender comprises 20 parts of 3,3 '-dichloro-4, 4' -diaminodiphenylmethane and 13 parts of diethyltoluenediamine; the isocyanate is a mixture of 75 parts of 4,4 '-diphenylmethane diisocyanate (4,4' -MDI) and 25 parts of 2,4 '-diphenylmethane diisocyanate (2,4' -MDI).
Example 6: high speed tensile testing of the polyurea materials prepared in examples 1-5
High speed tensile testing of the burst-resistant polyurea materials prepared in examples 1-5 was performed using an Instron VHS 160-100/20 high speed hydraulic servo Material testing machine. The specific method comprises the following steps: uniformly coating a release agent on the surface of the sampling plate, pouring the anti-fragmentation polyurea material on the sampling plate by using a PHX-40 spraying machine after the release agent is dried, and carrying out a high-speed tensile test after curing for 7 days at 25 ℃ to obtain the tensile strength, the elongation at break and the stress strain curve of the material under a specific strain rate. And intercepting the elastic stage of the stress-strain curve, and fitting the elastic stage to obtain the elastic modulus of the material. The tensile strength, elongation at break and elastic modulus are shown in Table 1. Further, the stress-strain curves of the rupture-proof polyurea materials prepared in examples 1 to 5 were substantially uniform, and the stress-strain curve of example 1 (fig. 2) is described as an example.
TABLE 1 mechanical Properties test results of the high-strength flame-retardant polyurea coatings prepared in examples 1 to 5
From fig. 2, it can be seen that in the initial region, the stress and strain of the high-strength flame-retardant polyurea coating are in a direct proportional function relationship, and this section is the elastic region. After reaching the yield point, the material enters the transition zone; in this transition zone, the material begins to yield and then enters the strain hardening phase until the material is completely destroyed and the stress still increases linearly with strain but the slope decreases.
As can be seen from Table 1, the high-strength flame-retardant polyurea coating prepared in example 1 has tensile strengths of 13.19MPa and 16.59MPa at the stretching speeds of 0.1m/s and 4m/s, respectively, and has high tensile strength; the tensile strength is increased along with the increase of the strain rate, when the strain rate is increased to 3m/s, the tensile strength of the material is increased by 25.78 percent, and the material has obvious strain rate sensitivity; the relationship between stress and strain is approximately bi-linear as strain develops; when the strain rate of the material is 0.1m/s and 4m/s, the elongation at break of the material is 333.78% and 281.90%, respectively, and the elongation at break of the material is extremely high, so that the material can meet the requirement of large deformation generated by explosive load. And intercepting the elastic stage of the stress-strain curve of the high-strength flame-retardant polyurea coating under the action of high-speed load, and fitting the elastic stage to obtain the elastic modulus of the material, wherein the elastic modulus of the high-strength flame-retardant polyurea coating is 117.70MPa respectively. The tensile strength of the high-strength flame-retardant polyurea coatings prepared in examples 2-4 is improved along with the increase of the strain rate, and the coatings also have obvious strain rate sensitivity. In addition, the elongation at break can satisfy large deformation caused by explosion load at strain rates of 0.1m/s and 4 m/s.
In conclusion, the rupture-proof polyurea material prepared in the embodiments 1 to 5 of the present application still has excellent mechanical properties including elongation at break under the action of high strain rate, and can effectively restrain deformation of a protective structure and inhibit large deformation under the action of explosive load.
Example 7: flame retardancy testing of the polyurea materials prepared in examples 1-5
To verify that the polyurea materials prepared in examples 1-5 have excellent flame retardant properties, the flame retardant properties were tested using a cone calorimeter made by FTT, UK. The specific method comprises the following steps: adding ZnO @ MOF @ polyphosphazene into amino-terminated polyether and amine chain extender, uniformly mixing, mixing with isocyanate prepolymer in a mold, and preparing a sample of 100mm x 3 mm. Weighing the sample mass, setting the radiation power of a cone calorimeter to 35KW, inputting the sample mass and the sample thickness, wrapping the sample with aluminum foil paper, placing the wrapped sample on a lining layer of a combustion box, flatly and uniformly pressing the wrapped sample with a box cover, and then placing the wrapped sample on a bracket of a weighing sensor again for experiment to obtain the total smoke generation amount, the CO release amount curve and the total release heat curve of the material. The applicant found through the above tests that the polyurea materials prepared in examples 1 to 5 had the same tendency of change in the total smoke generation amount, the CO release amount curve, and the total heat release curve. The total smoke generation (FIG. 4), CO release profile (FIG. 5) and total heat release profile (FIG. 6) of the polyurea material prepared in example 1 are described in detail below.
As can be seen from FIG. 4, the total smoke generation after adding 0.5% of ZnO @ MOF @ polyphosphazene is 1950m 2 Down to 353m 2 The decrease is 81.8%. The MOF is heated and decomposed to generate metal oxide in the combustion process, the metal oxide has a large specific surface area and can adsorb smoke dust, and meanwhile, the metal oxide can catalyze the polymer to be crosslinked into carbon to form a carbon layer, so that the smoke suppression effect is achieved. As can be seen from FIG. 5, the peak value of the CO release rate of the polyurea without the flame retardant is 0.092%, and after 0.5% of ZnO @ MOF @ polyphosphazene is added, the peak value of the CO release rate is 0.036%, which is 60.8% lower than that of the polyurea without the flame retardant. This indicates that the CO production of the flame retardant-free polyurea is significantly suppressed and reduced by the addition of ZnO @ MOF @ polyphosphazene, due to the ZnO @ MOF catalysis and the polyphosphazeneFree radical trapping of (1).
FIG. 6 is a graph of the total heat release curve for a high strength flame retardant polyurea coating, the slope of which can be considered as representative of flame spread. As can be seen from the figure, the total heat release value of the polyurea sample without flame retardant is 155MJ/m 2 The slope of the curve is larger. Compared with polyurea without flame retardant, the total heat release value of the sample is reduced to 122MJ/m after 0.5 percent of ZnO @ MOF @ polyphosphazene is added 2 And the slope of the curve decreases. The phenomenon is caused by ZnO and Co generated in the combustion process of ZnO @ MOF @ polyphosphazene 3 O 4 Can effectively promote the carbon formation of the decomposition product of the polymer, form a better carbon layer, insulate heat and transfer oxygen, prevent the further combustion of the polymer matrix and effectively improve the flame retardant property of the high-strength flame-retardant polyurea coating.
Through the test of the cone calorimeter of the high-strength flame-retardant polyurea coating, the total smoke generation amount, the CO release amount and the total release heat are analyzed and verified to obtain: the high-strength flame-retardant polyurea coating can effectively reduce the release of smoke and toxic gas of polyurea in the combustion process, and the material has good flame-retardant performance. Thereby even guarantee protective structure even because of the explosion produces the burning phenomenon, high strength fire-retardant polyurea coating can also utilize self excellent fire resistance ability to protect the structure.
In conclusion, the polyurea material prepared in the embodiments 1 to 5 of the present application has excellent mechanical properties including elongation at break, can effectively restrain deformation of a protective structure, and inhibits large deformation under the action of an explosive load; the flame-retardant fire-retardant coating has good flame-retardant property, effectively reduces the release of smoke and toxic gas in the combustion process, overcomes the technical problem of the lack of flame-retardant property of the protective armor in the prior art, and has important application value.
Claims (10)
1. Possess compound antiknock protection armor of special-shaped power consumption of fire retardant property to the layer is handled as the center to the energy, and both sides set up polyurea coating (2) and protection metal sheet (1), its characterized in that by inside to outside symmetry: the energy treatment layer consists of a metal corrugated plate (3), a viscoelastic damping layer (4) and a metal energy absorption pipe (5); the viscoelastic damping layer (4) is positioned in an interlayer formed by two metal corrugated plates (3); the corrugated metal plate (3) is isosceles trapezoid corrugated, the convex part of the corrugated metal plate (3) is directly connected with the polyurea coating (2), and the grooves of the corrugated plate are connected with the polyurea coating (2) through metal energy absorption pipes (5); the polyurea coating (2) is a flame-retardant polyurea material and is prepared by the following method:
preparing ZnO @ MOF nanoparticles: dispersing cobalt nitrate and dimethyl imidazole in a DMF aqueous solution, and magnetically stirring until the cobalt nitrate and dimethyl imidazole are uniformly dispersed; adding ZnO powder into the mixture, and transferring the mixture into a high-pressure kettle to perform solvothermal reaction after uniform ultrasonic dispersion; after the reaction is finished, the temperature is restored to the room temperature, and the ZnO @ MOF nano particles are obtained by freeze drying after washing;
preparing ZnO @ MOF @ polyphosphazene: firstly, dissolving hexachlorocyclotriphosphazene in a solvent to obtain a hexachlorocyclotriphosphazene solution; dispersing ZnO @ MOF nanoparticles in the solvent by ultrasound to obtain a suspension; adding diamine compound and triethylamine into the suspension respectively; then under ultrasonic treatment, dropwise adding the hexachlorocyclotriphosphazene solution into the reaction system to obtain a reaction system; transferring the reaction system into an oil bath, stirring for 10-30 h at 50-80 ℃ to obtain a ZnO @ MOF @ polyphosphazene solution, washing with ethanol, and drying in vacuum to obtain the ZnO @ MOF @ polyphosphazene flame retardant; the processes are all carried out in a nitrogen atmosphere;
Preparing a flame-retardant polyurea material: adding the ZnO @ MOF @ polyphosphazene flame retardant obtained in the step (2) into a mixture of amine-terminated polyether and amine chain extender, ultrasonically dispersing uniformly, and then adding isocyanate prepolymer into the system for reaction to obtain a flame-retardant polyurea material; the addition amount of the ZnO @ MOF @ polyphosphazene flame retardant is 0.1-5.0 wt%.
2. The special-shaped energy-consuming composite anti-explosion protective armor with flame retardant property according to claim 1, characterized in that: in the step (II), the concentration of the ZnO @ MOF nanoparticles in a solvent is 3-5 g/L, the weight ratio of the diamine compound to triethylamine is 1: 3-4: 3, and the concentration of the hexachlorocyclotriphosphazene solution is 10-30 g/L.
3. The special-shaped energy-consuming composite anti-explosion protective armor with flame retardant property according to claim 2, wherein: the solvent in the step (II) is acetonitrile, 1, 4-dioxane or tetrahydrofuran, and the diamine compound is 4,4 '-diaminodiphenyl ether or 4,4' -diaminodiphenyl sulfone.
4. The special-shaped energy-consuming composite anti-explosion protective armor with flame retardant property according to claim 2, wherein: the mass concentration of the DMF aqueous solution in the step I is 700-850 g/L; the weight ratio of the cobalt nitrate to the dimethyl imidazole in the DMF aqueous solution is 1: 20-1: 30, and the concentration of ZnO in the DMF aqueous solution is 10-20 g/L.
5. The special-shaped energy-consuming composite anti-explosion protective armor with flame retardant property according to claim 2, wherein: the speed of magnetic stirring in the first step is 300-500 rpm; the temperature condition of the solvothermal reaction is 50-70 ℃, and the reaction time is 1-3 h; the temperature condition of the freeze drying is-65 to-50 ℃.
6. The special-shaped energy-consuming composite anti-knock protective armor with flame retardant property according to any one of claims 2-5, wherein: the weight ratio of the amino-terminated polyether to the amine chain extender is 4: 1-2: 1; the volume ratio of the isocyanate prepolymer to the sum of the amino-terminated polyether and the chain extender is 1: 1; the isocyanate prepolymer is obtained by prepolymerization of isocyanate and hydroxyl-terminated polyether in a weight ratio of 10: 9-5: 7 in a nitrogen atmosphere.
7. The special-shaped energy-consuming composite anti-explosion protective armor with flame retardant property according to claim 6, wherein: the amino-terminated polyether is one or more of poly (tetramethylene ether) glycol bis-p-aminobenzoate with two functionality degrees, amino-terminated polyoxypropylene ether and amino-terminated polyoxypropylene ether with three functionality degrees; the amino chain extender is one or more of diethyl toluene diamine, dimethyl sulfur toluene diamine, N ' -dialkyl methyl diamine and 3,3' -dichloro-4, 4' -diamino diphenylmethane; the isocyanate is one or more of 4,4 '-diphenylmethane diisocyanate (4,4' -MDI), 2,4 '-diphenylmethane diisocyanate (2,4' -MDI) and isophorone diisocyanate (IPDI).
8. The special-shaped energy-consuming composite anti-explosion protective armor with flame retardant property according to claim 6, wherein: the metal energy absorption pipes (5) are transversely and symmetrically arranged at two ends of the bottom of the groove of the corrugated metal plate (3); the thickness of the viscoelastic damping layer (4) is one fourth of that of the protective armor, and the corrugated metal plate (3) is made of aluminum alloy and has a thickness of 0.4-2 mm; the thickness of the polyurea coating (2) is 2-5 mm; the protective metal plate (1) is made of high-strength anti-explosion alloy with the thickness of 5-12 mm.
9. The method for preparing the special-shaped energy-consuming composite anti-explosion protective armor with flame retardant property according to claims 1-8, wherein the method comprises the following steps: the method comprises the following steps:
(a) preparing two metal corrugated plates (3) and a plurality of metal energy absorption pipes (5), fixedly connecting one ends of the metal corrugated plates (3) and the metal energy absorption pipes (5) by adopting viscoelastic damping materials, and transversely and symmetrically arranging the metal energy absorption pipes (5) at two ends of the bottoms of grooves of the metal corrugated plates (3);
(b) spraying a proper amount of viscoelastic damping material on the inner sides of the two corrugated metal plates (3), spraying a layer of viscoelastic damping material after the surfaces of the viscoelastic damping material are dried, quickly closing and fixing the two corrugated plates, and curing at normal temperature for 12 hours to prepare an energy absorption layer;
(c) Preparing two protective metal plates, polishing the inner sides of the protective metal plates, removing surface dust, and spraying primer; after the surface of the primer is dried, spraying a flame-retardant polyurea material to form a polyurea coating (2); quickly connecting and fixing the other end of the metal energy-absorbing pipe (5) with the polyurea coating (2), and maintaining for 12 hours at normal temperature; the special-shaped energy-consuming composite anti-explosion protective armor with flame retardant property can be obtained.
10. The use of the profiled energy dissipating composite blast resistant armor with fire retardant properties of claims 1-8 wherein: the anti-explosion brick bed is applied to the anti-explosion of vehicles or buildings; the method specifically comprises the following steps: and installing/fixing the protective armor on the outer layer of a vehicle or a building to be used as an energy-absorbing protective layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110194067.3A CN112964132B (en) | 2021-02-20 | 2021-02-20 | Special-shaped energy-consumption composite anti-explosion protective armor with flame retardant property and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110194067.3A CN112964132B (en) | 2021-02-20 | 2021-02-20 | Special-shaped energy-consumption composite anti-explosion protective armor with flame retardant property and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112964132A CN112964132A (en) | 2021-06-15 |
| CN112964132B true CN112964132B (en) | 2022-07-29 |
Family
ID=76285300
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110194067.3A Active CN112964132B (en) | 2021-02-20 | 2021-02-20 | Special-shaped energy-consumption composite anti-explosion protective armor with flame retardant property and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112964132B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114562531B (en) * | 2022-03-04 | 2023-09-12 | 南京理工大学 | Collapsible type vehicle bottom explosion protection unidirectional damper |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103234390A (en) * | 2013-04-02 | 2013-08-07 | 西安交通大学 | Double-layer composite structure armor filled with active concrete and method for preparing armor |
| CN206722277U (en) * | 2017-05-23 | 2017-12-08 | 浙江恒鼎涂料有限公司 | A kind of water-and fire-proof coating |
| CN110823000A (en) * | 2019-11-28 | 2020-02-21 | 青岛理工大学 | Multilayer composite energy-absorbing material and preparation thereof |
| CN110823001A (en) * | 2019-11-28 | 2020-02-21 | 青岛理工大学 | Graded energy-consumption composite anti-explosion protective armor and preparation thereof |
| CN111486049A (en) * | 2020-04-29 | 2020-08-04 | 中材科技风电叶片股份有限公司 | Composite structure and blade |
| CN212534791U (en) * | 2020-05-23 | 2021-02-12 | 广东省杰熙科技有限公司 | Novel light environment-friendly waterproof fireproof moistureproof wallboard |
-
2021
- 2021-02-20 CN CN202110194067.3A patent/CN112964132B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103234390A (en) * | 2013-04-02 | 2013-08-07 | 西安交通大学 | Double-layer composite structure armor filled with active concrete and method for preparing armor |
| CN206722277U (en) * | 2017-05-23 | 2017-12-08 | 浙江恒鼎涂料有限公司 | A kind of water-and fire-proof coating |
| CN110823000A (en) * | 2019-11-28 | 2020-02-21 | 青岛理工大学 | Multilayer composite energy-absorbing material and preparation thereof |
| CN110823001A (en) * | 2019-11-28 | 2020-02-21 | 青岛理工大学 | Graded energy-consumption composite anti-explosion protective armor and preparation thereof |
| CN111486049A (en) * | 2020-04-29 | 2020-08-04 | 中材科技风电叶片股份有限公司 | Composite structure and blade |
| CN212534791U (en) * | 2020-05-23 | 2021-02-12 | 广东省杰熙科技有限公司 | Novel light environment-friendly waterproof fireproof moistureproof wallboard |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112964132A (en) | 2021-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103803028B (en) | The platform bulkhead structure of a kind of antiknock, fire prevention, insulation, noise reduction | |
| CN112964132B (en) | Special-shaped energy-consumption composite anti-explosion protective armor with flame retardant property and preparation method thereof | |
| US8276497B2 (en) | Blast attenuator and method of making same | |
| CN109880423A (en) | A kind of heat-insulated protective coating of novel flame-retardant and preparation method thereof | |
| CN113211819B (en) | Composite explosion-proof barrel and fiber composite curved surface member forming method | |
| CN110806146B (en) | Honeycomb damping unit multilayer composite energy-absorbing material and preparation thereof | |
| CN203714155U (en) | Blast-resistant fireproof insulated noise-reducing ocean platform bulkhead structure | |
| CN110823001A (en) | Graded energy-consumption composite anti-explosion protective armor and preparation thereof | |
| CN111141185A (en) | Multifunctional ammunition packing box | |
| CN113639604B (en) | Composite core sandwich cylinder explosion-proof structure | |
| CN211373355U (en) | Multilayer composite energy-absorbing material | |
| CN107842125A (en) | High strength anti-explosion wall with shock-absorbing capacity | |
| CN211373356U (en) | Graded energy-consumption composite anti-explosion protective armor | |
| CN113108646B (en) | Novel lightweight armor component module | |
| CN211373354U (en) | Honeycomb damping unit multilayer composite energy-absorbing material | |
| CN110823000A (en) | Multilayer composite energy-absorbing material and preparation thereof | |
| CN216917096U (en) | Explosion-proof box for battery | |
| CN207672792U (en) | High strength anti-explosion wall with cushion performance | |
| CN211363766U (en) | Bionic ball multilayer composite energy-absorbing material | |
| CN211601755U (en) | Multipurpose ammunition packing box | |
| CN115127398A (en) | Light bulletproof and antiknock multiphase composite armor material based on high-toughness heterogeneous interface layer | |
| CN113739660A (en) | Design and manufacturing method of folding type explosion-proof fence and product thereof | |
| CN207113719U (en) | High strength bulletproof profiling fabric is armoring | |
| CN207567983U (en) | A kind of high-performance fiber cloth package monolithic corrugated steel-porous metals Protective armor | |
| CN109837927A (en) | A kind of shock resistance composite protection structure for building of paddling |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |