A kind of sandwich glass with shell-like structure and its preparation method

Abstract

The application provides a kind of interlayer glass with shell-imitating structure and its preparation method, interlayer glass includes inner shell-imitating layer, shear hardening sandwich layer and outer shell-imitating layer;The shear hardening sandwich layer is prepared by hydroxyl silicone oil and boride with mass ratio of 18-22:1.The interlayer glass of the application introduces the sandwich layer formed by hydroxyl silicone oil and boride and the shell-imitating layer with shell-imitating structure characteristics, through the joint action of shear hardening sandwich layer and shell-imitating layer, the heat insulation performance and impact resistance under different impact speed of interlayer glass are improved.

Description

TECHNICAL FIELD

[0001] The present application belongs to laminated glass, and particularly relates to a laminated glass with a shell-imitating structure and a preparation method thereof. BACKGROUND

[0002] Laminated glass is generally composed of two glass panels and an intermediate layer of polymer. Compared with ordinary single-layer glass, the intermediate layer of polymer can bond glass fragments when laminated glass is impacted by external force, maintain structural integrity and improve the impact resistance of the overall material. Due to good optical transparency, hardness, durability and significantly improved impact resistance, laminated glass has been widely used in the fields of vehicles, buildings and electronic devices. However, in accidents such as hurricanes, explosions and vehicle impacts, laminated glass will be subjected to the impact of flying objects and debris. Pure laminated glass material cannot meet the safety protection requirements in actual applications, and in order to improve the safety of human body and structures, researchers have gradually carried out related technical research to improve the impact resistance of laminated glass.

[0003] The impact resistance of laminated glass has an important influence on the safety of buildings, vehicles and the like, thereby relating to the safety of users' lives and property. At present, some researchers improve the protection performance of laminated glass by attaching a film or replacing a glass panel. A safety glass that does not produce flying objects in breaking is disclosed in Chinese Patent Publication No. CN104553207A, which increases a splash-proof safety film on the inner side of the safety glass to prevent the fragments of the broken structural bearing material from harming the human body. A bulletproof glass with replaceable glass layers is disclosed in Chinese Patent Publication No. CN207044838U, and the composite glass can replace various other functional glasses to achieve the purpose of multiple combinations of a glass.

[0004] In addition, the heat insulation performance of laminated glass is also an important factor for determining the temperature in a building or structure and affecting the comfort of human body and the normal operation of components. SUMMARY

[0005] Therefore, the purpose of the present application is to provide a laminated glass with a shell-imitating structure and a preparation method thereof, which has excellent shear hardening performance, and also has excellent impact resistance and heat insulation performance.

[0006] The present application provides a laminated glass with a shell-imitating structure, which comprises an inner shell-imitating layer, a shear hardening core layer and an outer shell-imitating layer.

[0007] The shear hardening core layer is prepared from hydroxyl silicone oil and borides with a mass ratio of 18-22:1.

[0008] Preferably, the borides are selected from one or more of boron oxide, boric acid, borate and halogenated boron.

[0009] Preferably, the imitation shell layer is composed of at least two layers of bionic transparent material plates and at least one layer of thermoplastic polymer film arranged alternately.

[0010] The bionic transparent material plate is a transparent material plate engraved with a tessellation pattern of a tessellation polygon, and the engraving depth is 50-100% of the thickness of the transparent material plate.

[0011] Preferably, the overlapping area of the tessellation pattern of the tessellation polygon of the adjacent bionic transparent material plates accounts for 10-99% of the total area of the tessellation pattern.

[0012] Preferably, the thickness of a single layer of thermoplastic polymer film is less than the thickness of a single layer of bionic transparent material plate.

[0013] Preferably, the thermoplastic polymer film is selected from polyvinyl butyral film, thermoplastic polyurethane, or ethylene-vinyl acetate copolymer film.

[0014] The transparent material plate is selected from one or more of tempered inorganic glass, semi-tempered inorganic glass, organic glass, soda-lime glass, and borosilicate glass.

[0015] Preferably, the thickness of the shear-hardening sandwich layer accounts for 50-400% of the total thickness of the outer imitation shell layer and the inner imitation shell layer.

[0016] Preferably, the shear-hardening sandwich layer is prepared by stirring hydroxyl silicone oil and boride at a mass ratio of 18-22:1 at 175-185°C, and then cooling.

[0017] Preferably, the inner imitation shell layer or the outer imitation shell layer specifically comprises:

[0018] borosilicate glass plate engraved with a tessellation pattern of a tessellation polygon-ethylene-vinyl acetate copolymer film-borosilicate glass plate engraved with a tessellation pattern of a tessellation polygon-ethylene-vinyl acetate copolymer film-borosilicate glass plate engraved with a tessellation pattern of a tessellation polygon-ethylene-vinyl acetate copolymer film-borosilicate glass plate engraved with a tessellation pattern of a tessellation polygon-ethylene-vinyl acetate copolymer film-borosilicate glass plate engraved with a tessellation pattern of a tessellation polygon;

[0019] or borosilicate glass plate engraved with a tessellation pattern of a tessellation polygon-ethylene-vinyl acetate copolymer film-borosilicate glass plate engraved with a tessellation pattern of a tessellation polygon;

[0020] Or engraved sodium calcium glass plate - ethylene - vinyl acetate copolymer film - engraved sodium calcium glass plate - ethylene - vinyl acetate copolymer film - engraved sodium calcium glass plate - ethylene - vinyl acetate copolymer film - engraved sodium calcium glass plate - ethylene - vinyl acetate copolymer film - engraved sodium calcium glass plate - ethylene - vinyl acetate copolymer film - engraved sodium calcium glass plate.

[0021] The application provides a preparation method of the laminated glass with the shell-imitating structure.

[0022] The shear-hardening sandwich layer is prepared from hydroxyl silicone oil and boride with a mass ratio of 18-22:1.

[0023] The shear-hardening sandwich layer is attached between the two shell-imitating layers and tightly bonded to form the laminated glass with the shell-imitating structure.

[0024] The application provides a laminated glass with a shell-imitating structure, which comprises an inner shell-imitating layer, a shear-hardening sandwich layer and an outer shell-imitating layer. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 The laser engraving technology is used to engrave a tessellation pattern of a Tyzoon polygon on a transparent material plate for the embodiment 1 of the application;

[0026] Figure 2 The cross-sectional structure schematic diagram of the laminated glass with the shell-imitating structure is provided for the embodiment 6 of the application, wherein 1 is a borosilicate glass plate, 2 is an ethylene-vinyl acetate copolymer film and 3 is a shear-hardening material.

[0027] Figure 3 The energy consumption performance of the glass samples with different structures of the application under different impact speeds is shown in the table.

[0028] Figure 4 The light transmittance in the visible light wavelength range of the embodiment 6 of the application is shown in the table.

[0029] Figure 5 The specific energy absorption of the samples prepared in the embodiment 6 and the comparative examples 3-4 when subjected to impact loading is shown in the table.

[0030] Figure 6 The morphology diagram of the embodiment 6 of the application subjected to impact loading is shown in the table.

[0031] Figure 7 Surface temperature change curve of the laminated glass prepared for the embodiment 6 and the comparative examples 3~4 of the present application when the bottom plate temperature rises from 27℃ to 90℃;

[0032] Figure 8 Thermal conductivity data of the glass for the embodiment 6 and the comparative example 1 of the present application. DETAILED DESCRIPTION

[0033] The present application provides a laminated glass with shell-imitating structure, comprising an inner shell-imitating layer, a shear-hardening core layer and an outer shell-imitating layer.

[0034] The shear-hardening core layer is prepared from hydroxyl silicone oil and boride with a mass ratio of 18~22:1.

[0035] The laminated glass provided by the present application has good comprehensive performance such as transparency, impact-hardening performance, impact resistance and heat insulation, and can protect human body or structure from impact and high-temperature damage. The laminated glass has a mild damage process, can avoid the splashing danger of glass under impact, and has high safety.

[0036] The laminated glass with shell-imitating structure provided by the present application comprises an inner shell-imitating layer and an outer shell-imitating layer; the shell-imitating layer is composed of at least two layers of shell-imitating transparent material plates and at least one layer of thermoplastic polymer film arranged alternately; the shell-imitating transparent material plate is a transparent material plate with a carved tessellation pattern of a Thiessen polygon, and the carving depth is 50~100% of the thickness of the transparent material plate; in specific embodiments, the carving depth is 100%, 95% or 70% of the thickness of the transparent material plate. The shell-imitating transparent material plate with a carving depth of 100% has more excellent impact resistance and heat insulation performance. In the present application, the overlapping area of the tessellation patterns of the Thiessen polygons of adjacent shell-imitating transparent material plates accounts for 10~99% of the total area of the tessellation patterns; in specific embodiments, the patterns carved on the adjacent layers of transparent material plates are offset from each other by 50% of the length of the side of a square in two directions in the plane, and the overlapping area accounts for 25% of the total area of the tessellation patterns.

[0037] Specifically, the present application uses laser carving technology to carve a tessellation pattern of a Thiessen polygon on a transparent material plate to obtain a shell-imitating transparent material plate. The shell-imitating layer included in the present application has good impact resistance and heat insulation performance by simulating the microstructure in natural shells; the introduction of the shell-imitating layer not only reproduces the impact resistance mechanism in natural shells to improve the impact resistance performance, but also has a mild damage process; the anisotropic heat conduction characteristics of the shell-imitating layer make the laminated glass have good heat insulation performance, and can play a role in heat preservation and energy saving when applied to vehicles or buildings.

[0038] The transparent material plate in the present application is selected from one or more of tempered inorganic glass, semi-tempered inorganic glass, organic glass, soda-lime glass and borosilicate glass. The thickness of the transparent material plate is 0.05-20 mm, preferably 0.1-0.5 mm. The thickness of the transparent material plate used can be equal or not equal, which can be flexibly selected according to actual needs. For example, at least three transparent material plates with the same thickness (such as 0.1 mm) can be used to form a composite glass, or transparent material plates with different thicknesses (such as one transparent material plate with a thickness of 1.0 mm and multiple transparent material plates with a thickness of 0.2 mm) can be used to form a composite glass. Thus, the use requirements under different conditions can be met.

[0039] The thermoplastic polymer film is selected from polyvinyl butyral film, thermoplastic polyurethane or ethylene-vinyl acetate copolymer film. The thickness of the single-layer thermoplastic polymer film is less than the thickness of the single-layer biomimetic transparent material plate.

[0040] In a specific embodiment of the present application, the inner side shell-like layer or the outer side shell-like layer specifically comprises:

[0041] a borosilicate glass plate engraved with a tessellation pattern of a regular hexagon-a ethylene-vinyl acetate copolymer film-a borosilicate glass plate engraved with a tessellation pattern of a regular hexagon-a ethylene-vinyl acetate copolymer film-a borosilicate glass plate engraved with a tessellation pattern of a regular hexagon-a ethylene-vinyl acetate copolymer film-a borosilicate glass plate engraved with a tessellation pattern of a regular hexagon-a ethylene-vinyl acetate copolymer film-a borosilicate glass plate engraved with a tessellation pattern of a regular hexagon;

[0042] a borosilicate glass plate engraved with a tessellation pattern of a regular hexagon-a ethylene-vinyl acetate copolymer film-a borosilicate glass plate engraved with a tessellation pattern of a regular hexagon;

[0043] a soda-lime glass plate engraved with a tessellation pattern of a regular hexagon-a ethylene-vinyl acetate copolymer film-a soda-lime glass plate engraved with a tessellation pattern of a regular hexagon-a ethylene-vinyl acetate copolymer film-a soda-lime glass plate engraved with a tessellation pattern of a regular hexagon-a ethylene-vinyl acetate copolymer film-a soda-lime glass plate engraved with a tessellation pattern of a regular hexagon-a ethylene-vinyl acetate copolymer film-a soda-lime glass plate engraved with a tessellation pattern of a regular hexagon.

[0044] The invention provides a laminated glass with a shell-imitating structure, which comprises a shear-hardening interlayer arranged between the inner shell-imitating layer and the outer shell-imitating layer; the shear-hardening interlayer is prepared from hydroxyl silicone oil and boride with a mass ratio of 18-22:1. Specifically, the shear-hardening interlayer is prepared from hydroxyl silicone oil and boride with a mass ratio of 20:1. The boride is selected from one or more of boron oxide, boric acid, borate and halogenated boron. The invention introduces the shear-hardening interlayer to make the laminated glass show excellent impact resistance in a larger impact speed range; and the thermal conductivity of the shear-hardening interlayer is lower than that of traditional glass interlayer materials such as ethylene-vinyl acetate copolymer, which, together with the anisotropic thermal conduction characteristics of the shell-imitating layer, makes the laminated glass have better thermal insulation effect.

[0045] Specifically, the shear-hardening interlayer is prepared by stirring hydroxyl silicone oil and boride with a mass ratio of 18-22:1 at 175-185℃, and then cooling.

[0046] The invention provides a preparation method of the laminated glass with a shell-imitating structure, which comprises the following steps:

[0047] The shear-hardening interlayer is prepared from hydroxyl silicone oil and boride with a mass ratio of 18-22:1.

[0048] The shear-hardening interlayer is arranged between the two shell-imitating layers and tightly bonded to form the laminated glass with a shell-imitating structure.

[0049] The shear-hardening interlayer is prepared from hydroxyl silicone oil and boride with a mass ratio of 18-22:1.

[0050] The invention alternately arranges the bionic transparent material plate and the thermoplastic polymer film, and forms the shell-imitating structure layer by hot pressing in a vacuum environment. The shear-hardening interlayer is arranged between the two shell-imitating layers and tightly bonded to form the laminated glass with a shell-imitating structure.

[0051] The laminated glass with a shell-imitating structure prepared by the method of the invention has great potential in the fields of building, vehicle and electronic device.

[0052] In order to further illustrate the invention, the laminated glass with a shell-imitating structure and the preparation method thereof provided by the invention are described in detail below in combination with examples, but they should not be understood as limiting the protection scope of the invention.

[0053] The performance parameters of the laminated glass with a shell-imitating structure in the following cases provided by the invention are tested according to the following test methods:

[0054] A. The specific method for measuring the transparency of the bionic shell structure laminated glass is as follows:

[0055] The prepared bionic shell structure laminated glass is used to test the optical transmittance of the sample in the visible light spectrum by using a UV-visible spectrometer.

[0056] B. The specific method for measuring the surface temperature change curve of the bionic shell structure laminated glass when the bottom plate temperature rises from 27°C to 90°C is as follows:

[0057] First, three samples are prepared, one is a conventional laminated glass without a bionic shell structure layer and a shear hardening interlayer (Comparative Example 3); one is a laminated glass without a bionic shell structure layer but with a shear hardening interlayer (Comparative Example 4); and the last one is a laminated glass with a bionic shell structure layer and a shear hardening interlayer (Example 6). The samples are placed on a heating table, and the temperature of the heating table is gradually increased from 27°C to 90°C. During this period, the surface temperature of the three samples is measured simultaneously using a thermocouple, and the temperature change curve of the three samples during the above process is obtained.

[0058] C. The specific method for measuring the impact resistance of the bionic shell structure layer under drop hammer impact is as follows:

[0059] First, three samples are prepared, one is a bulk structure glass composed of borosilicate glass plates with a thickness of 1.4 mm (Comparative Example 1); one is a laminated structure glass composed of five complete borosilicate glass plates with a thickness of 0.2 mm and four pieces of ethylene-vinyl acetate copolymer film with a thickness of 0.1 mm (Comparative Example 2); and the last one is a bionic structure glass composed of five borosilicate glass plates with a thickness of 0.2 mm engraved with a tessellation pattern of regular hexagons and four pieces of ethylene-vinyl acetate copolymer film with a thickness of 0.1 mm (Example 6). The low-speed impact test system used includes a drop hammer impact machine, an acceleration sensor, a digital oscilloscope, and a high-speed camera. An impactor with a weight of 0.75 kg and a punch radius of 5 mm is dropped freely from a certain height. The impact velocity is calculated according to the formula , where V ini , g, and h0 are the initial velocity of the impactor hitting the sample, the acceleration of gravity, and the height of the impactor falling, respectively. An acceleration sensor is installed on the surface of the impactor and connected to a digital oscilloscope to collect the acceleration changes during the impact of the impactor on the sample. A high-speed camera is used to capture the morphological changes of the experimental sample during the impact process.

[0060] D. The specific method for measuring the impact resistance of the bionic shell structure laminated glass under drop hammer impact is as follows:

[0061] Three samples were prepared, one was a conventional laminated glass without the imitation shell structure layer and the shear hardening interlayer (see Comparative Example 3 below); one was without the imitation shell structure layer but with the shear hardening interlayer (see Comparative Example 4 below); and the last one was with the imitation shell structure layer and the shear hardening interlayer (see Example 6 below). The low-velocity impact testing system used included a drop hammer impact machine, an acceleration sensor, a digital oscilloscope and a high-speed camera. An impactor with a weight of 0.75 kg and a radius of 5 mm was dropped freely from a certain height. The impact velocity was calculated according to the formula wherein V, g and ho are the initial velocity of the impactor hitting the sample, the acceleration of gravity and the height from which the impactor was dropped, respectively. ini The acceleration sensor was mounted on the surface of the impactor and connected to the digital oscilloscope to collect the acceleration changes during the impact of the impactor on the sample. The high-speed camera was used to capture the morphological changes of the sample during the impact.

[0062] Example 1

[0063] The imitation shell structure layer was prepared as follows:

[0064] The raw materials used were five borosilicate glass plates with a thickness of 0.2 mm as the transparent material plates and four ethylene-vinyl acetate copolymer films with a thickness of 0.1 mm as the polymer films.

[0065] A laser engraving technique was used to engrave a tessellation pattern of a Figure 1 tetrahedron on the transparent material plates, as shown in FIG. 1. The patterns engraved on adjacent layers of transparent material plates were offset from each other by 50% of the length of a side of the square in both planar directions, so that the overlapping area of the tessellation patterns of adjacent imitation transparent material plates accounted for 25% of the total area of the tessellation pattern. The groove depth of the engraved pattern was 0.2 mm.

[0066] The engraved transparent material plates and the polymer films were arranged alternately, and then the stacked structure was placed in an oven at 120°C. The oven was evacuated and the sample was hot-pressed. After the polymer melted and bonded the layers of glass, the sample was removed, cooled and solidified to form the imitation shell structure layer.

[0067] Example 2:

[0068] The imitation shell structure layer was prepared as follows:

[0069] The only difference between Example 2 and Example 1 was that:

[0070] The raw materials used were two borosilicate glass plates with a thickness of 0.2 mm as the transparent material plates and one ethylene-vinyl acetate copolymer film with a thickness of 0.1 mm as the polymer film.

[0071] The rest was the same as in Example 1.

[0072] Example 3:

[0073] The method for preparing the shell-mimicking structure layer is as follows:

[0074] The difference from Example 1 is only that:

[0075] The raw materials used are five pieces of borosilicate glass plates with a thickness of 0.5 mm as the transparent material plates, and four pieces of ethylene-vinyl acetate copolymer films with a thickness of 0.2 mm as the polymer films.

[0076] The laser engraving technique is used to engrave a tessellation pattern of the Figure 1 tetrahedron on the transparent material plates, wherein the patterns engraved on the adjacent layers of transparent material plates are offset from each other by 50% of the length of the side of the square in both directions in the plane, so that the overlapping area of the tessellation patterns of the adjacent shell-mimicking transparent material plates accounts for 25% of the total area of the tessellation pattern. The groove depth of the engraved pattern is 0.35 mm.

[0077] The rest is the same as Example 1.

[0078] Example 4:

[0079] The method for preparing the shell-mimicking structure layer is as follows:

[0080] The difference from Example 1 is only that:

[0081] The raw materials used are five pieces of soda-lime glass with a thickness of 0.2 mm as the transparent material plates, and four pieces of thermoplastic polyurethane films with a thickness of 0.1 mm as the polymer films.

[0082] The rest is the same as Example 1.

[0083] Example 5:

[0084] The method for preparing the shell-mimicking structure layer is as follows:

[0085] The difference from Example 1 is only that:

[0086] The laser engraving technique is used to engrave a tessellation pattern of the Figure 1 tetrahedron on the transparent material plates, and the groove depth of the engraved pattern is 0.19 mm.

[0087] The rest is the same as Example 1.

[0088] Comparative Example 1:

[0089] The raw material used is one piece of borosilicate glass plate with a thickness of 1.4 mm as the bulk structure glass sample.

[0090] Comparative Example 2:

[0091] The raw materials used were five borosilicate glass plates with a thickness of 0.2 mm as the transparent material plates and four ethylene-vinyl acetate copolymer films with a thickness of 0.1 mm as the polymer films.

[0092] The unengraved transparent material plates and polymer films were arranged alternately, and the arranged laminated structure was placed in an oven at 120°C, the oven was vacuumized and the sample was hot-pressed, and after the polymer was melted to bond the glass layers, the sample was taken out and cooled to room temperature to form the sample.

[0093] Example 6:

[0094] The method for preparing the laminated glass with the imitation shell structure was as follows:

[0095] The imitation shell structure layer was the imitation shell structure layer sample prepared in Example 1.

[0096] Hydroxyl silicone oil and boric acid with a mass ratio of 20:1 were mixed and heated and stirred at 180°C, and a shear-thickening material was obtained after cooling.

[0097] A piece of 3.0 mm thick shear-thickening material was attached between two pieces of the imitation shell structure layer sample to form the imitation shell structure laminated glass.

[0098] Example 7:

[0099] The method for preparing the laminated glass with the imitation shell structure was as follows:

[0100] The difference from Example 6 was only that:

[0101] A piece of 2.0 mm thick shear-thickening material was attached between two pieces of the imitation shell structure layer sample to form the imitation shell structure laminated glass.

[0102] The others were the same as in Example 6.

[0103] Example 8:

[0104] The method for preparing the laminated glass with the imitation shell structure was as follows:

[0105] The difference from Example 6 was only that:

[0106] A piece of 6.0 mm thick shear-thickening material was attached between two pieces of the imitation shell structure layer sample to form the imitation shell structure laminated glass.

[0107] The others were the same as in Example 6.

[0108] Comparative Example 3:

[0109] Two 1.4mm thick borosilicate glass plates and one 3.0mm thick ethylene-vinyl acetate copolymer material were arranged alternately, and then the arranged laminated structure was placed in an oven at 150℃, the oven was vacuumized and the sample was hot-pressed, and then taken out after the polymer melted and adhered to the outer glass, and cooled and solidified to form a conventional laminated glass material.

[0110] Comparative Example 4:

[0111] Two 1.4mm thick borosilicate glass plates and hydroxy silicone oil and boric acid were used. The specific preparation process was as follows: 1) hydroxy silicone oil and boric acid with a mass ratio of 20:1 were mixed and heated and stirred at 180℃, and a shear hardening material was obtained after cooling. 2) One 3.0mm thick shear hardening material obtained in step 1) was attached between two 1.4mm thick borosilicate glass plates to form a composite glass material with no imitation shell structure layer and shear hardening sandwich layer.

[0112] Figure 3 The energy dissipation performance of different structure glass samples at different impact speeds. Comparative Example 1 showed the lowest impact energy dissipation at different impact speeds, Comparative Example 2 showed a significant increase in energy dissipation when the impact speed was greater than 3.0m / s, and Example 1 showed the best energy dissipation in the range of 0.5m / s to 3.0m / s, almost all the impact kinetic energy was dissipated, but when the impact speed was greater than 3.0m / s, the energy dissipation was lower than that of Comparative Example 2. It is shown that the imitation shell structure layer can effectively improve the impact energy dissipation of the structure in the low impact speed range, but the energy dissipation of the imitation shell structure layer cannot continue to increase with the increase of the impact speed at high speed.

[0113] Figure 4 The transmittance of Example 6 of the present application in the wavelength range of 400-750nm visible light. Compared with the 80% transmittance of Comparative Example 3 traditional laminated glass, the 86% transmittance of Comparative Example 4 composite glass material with shear hardening sandwich layer, and the transmittance of imitation shell structure laminated glass (Example 6) is about 83%, which shows that the imitation shell structure laminated glass of the present application has good transparency. Therefore, the laminated glass of the present application retains the light transmittance, and also has good impact resistance and thermal insulation performance by simulating the microstructure in natural shell.

[0114] Figure 5The specific energy absorption of the inventive example 6 under impact loading. As the initial impact speed increases from 1.0 m / s to 5.0 m / s, the specific energy absorption of the shell-imitating structure sandwich glass (example 6) increases from 11 J / kg to 160 J / kg; the specific energy absorption of the traditional sandwich glass (comparative example 3) increases from 6 J / kg to 31 J / kg; the specific energy absorption of the composite glass material without the shell-imitating structure layer and with the shear-hardening interlayer (comparative example 4) increases from 6 J / kg to 73 J / kg; the specific energy absorption of the composite glass without the shell-imitating structure layer and without the shear-hardening interlayer (comparative example 5) increases from 9 J / kg to 43 J / kg. Compared with the other two comparative examples, the shell-imitating structure sandwich glass (example 6) of the present application has greater specific energy absorption at different initial impact speeds, showing the advantages of the combination of the shell-imitating structure layer and the shear-hardening material.

[0115] Figure 6 The morphology of the inventive example 6 during impact loading. As can be clearly seen from the figure, the comparative example 4 undergoes catastrophic failure under the action of impact, generating a large amount of debris flying. The shell-imitating structure sandwich glass (example 6) of the present application has a mild damage process under the action of impact, without obvious debris flying, and has extremely high safety.

[0116] Figure 7 The surface temperature change curve of the shell-imitating structure sandwich glass when the temperature of the bottom plate increases from 27°C to 90°C. As the temperature of the heating table gradually increases from 27°C to 90°C, the maximum temperature difference of the comparative example 4 is 23.1°C, which is higher than the maximum temperature difference of the comparative example 3 of 22.6°C, indicating that the shear-hardening interlayer in the comparative example 4 has better heat insulation performance than the traditional glass interlayer in the comparative example 3. The example 6 has the largest temperature difference, with a maximum temperature difference of 30.8°C, which is significantly higher than the maximum temperature differences of the comparative examples 3 and 4, indicating that the heat insulation performance of the example 6 is significantly better than that of the comparative examples 3 and 4.

[0117] First, three samples were prepared, one being a traditional sandwich glass without a shell-imitating structure layer and a shear-hardening interlayer (comparative example 3); one being a composite glass without a shell-imitating structure layer and with a shear-hardening interlayer (comparative example 4); and the last one being a sandwich glass with a shell-imitating structure layer and a shear-hardening interlayer (example 6). The samples were placed on a heating table, and the temperature of the heating table was gradually increased from 27°C to 90°C. During this period, a thermocouple was used to measure the surface temperature of the three samples simultaneously, and the temperature change curves of the three samples during the above process were obtained.

[0118] Figure 8 The thermal conductivity data of the inventive example 6, which quantitatively compares the thermal conductivities of the bulk structure glass, the comparative example 3, the comparative example 4 and the sandwich glass with a shell-imitating structure of the example 6 of the same thickness. As can be seen from the figure, the thermal conductivity of the example 6 is 1.2 W / mK, which is lower than the thermal conductivity of the comparative example 3 of 1.3 W / mK and the thermal conductivity of the comparative example 4 of 1.3 W / mK, indicating that the shell-imitating structure sandwich glass (example 6) of the present application has better heat insulation performance than the other two comparative examples.Figure 8 It can be seen that the thermal conductivity of the shell-imitating structure sandwich glass of the present application is reduced by 44.3% compared with the bulk structure glass, reduced by 20.6% compared with Comparative Example 3, and reduced by 14.3% compared with Comparative Example 4, and has better heat insulation performance.

[0119] The specific energy absorption of the shell-imitating structure sandwich glass prepared in Examples 6-8 was tested at different initial impact speeds, and the test method was performed according to the specific method for characterizing the specific energy absorption of Example 6 when subjected to impact loading in the foregoing test method, and the test results are shown in Table 1 below:

[0120] Table 1

[0121] Example Thickness of shear-hardenable core layer (mm) Specific energy absorption at an impact initial velocity of 1.0 m / s (J / kg) Specific energy absorption at an impact initial velocity of 3.0 m / s (J / kg) Specific energy absorption at an impact initial velocity of 5.0 m / s (J / kg) Example 8 6.0 8.5 95.0 145.0 Example 6 3.0 12.0 119.4 159.9 Example 7 2.0 12.6 118.5 155.6

[0122] As can be seen from the above examples, the present application provides a sandwich glass with a shell-imitating structure, which comprises an inner shell-imitating layer, a shear hardening core layer and an outer shell-imitating layer; the shear hardening core layer is prepared by mixing hydroxyl silicone oil and boride with a mass ratio of 18-22:1. The present application introduces a core layer formed by hydroxyl silicone oil and boride and a shell-imitating layer with shell-imitating structure characteristics in the sandwich glass, and simultaneously improves the heat insulation performance and impact resistance of the sandwich glass. The shear hardening core layer and the shell-imitating layer jointly act to improve the heat insulation performance and impact resistance of the sandwich glass at different impact speeds.

[0123] The above only describes the preferred embodiments of the present application, and it should be noted that for those skilled in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A laminated glass having a shell-like structure, characterized by, The shell-like layer comprises an inner shell-like layer, a shear-hardening core layer and an outer shell-like layer. The shear-hardening core layer is prepared by stirring hydroxyl silicone oil and boride with a mass ratio of 18-22:1 at 175-185 ℃, and then cooling. The thickness of the shear-hardening core layer accounts for 50-400% of the total thickness of the outer shell-like layer and the inner shell-like layer. The shell-like layer is composed of bionic transparent material plates and thermoplastic polymer films arranged alternately. The bionic transparent material plate is a transparent material plate engraved with a tessellation pattern of a tessellation polygon, and the engraving depth is 50-100% of the thickness of the transparent material plate.

2. The laminated glass according to claim 1, characterized by The overlapping area of the tessellation patterns of the tessellation polygons of adjacent bionic transparent material plates accounts for 10-99% of the total area of the tessellation patterns.

3. The laminated glass according to claim 1, characterized by The thickness of a single layer of thermoplastic polymer film is less than the thickness of a single layer of bionic transparent material plate.

4. The laminated glass according to claim 1, characterized by The thermoplastic polymer film is selected from polyvinyl butyral film, thermoplastic polyurethane or ethylene-vinyl acetate copolymer film. The transparent material plate is selected from one or more of tempered inorganic glass, semi-tempered inorganic glass, organic glass, soda-lime glass and borosilicate glass.

5. The laminated glass according to claim 1, characterized by The inner shell-like layer or the outer shell-like layer specifically comprises: a borosilicate glass plate engraved with a tessellation pattern of a tessellation polygon-ethylene-vinyl acetate copolymer film-a borosilicate glass plate engraved with a tessellation pattern of a tessellation polygon-ethylene-vinyl acetate copolymer film-a borosilicate glass plate engraved with a tessellation pattern of a tessellation polygon-ethylene-vinyl acetate copolymer film-a borosilicate glass plate engraved with a tessellation pattern of a tessellation polygon-ethylene-vinyl acetate copolymer film-a borosilicate glass plate engraved with a tessellation pattern of a tessellation polygon; or a borosilicate glass plate engraved with a tessellation pattern of a tessellation polygon-ethylene-vinyl acetate copolymer film-a borosilicate glass plate engraved with a tessellation pattern of a tessellation polygon; or a soda-lime glass plate engraved with a tessellation pattern of a tessellation polygon-ethylene-vinyl acetate copolymer film-a soda-lime glass plate engraved with a tessellation pattern of a tessellation polygon-ethylene-vinyl acetate copolymer film-a soda-lime glass plate engraved with a tessellation pattern of a tessellation polygon-ethylene-vinyl acetate copolymer film-a soda-lime glass plate engraved with a tessellation pattern of a tessellation polygon-ethylene-vinyl acetate copolymer film-a soda-lime glass plate engraved with a tessellation pattern of a tessellation polygon-ethylene-vinyl acetate copolymer film-a soda-lime glass plate engraved with a tessellation pattern of a tessellation polygon.

6. A method for preparing the laminated glass with a shell-like structure according to any one of claims 1-5, comprising the following steps: preparing a shear-hardening core layer by stirring hydroxyl silicone oil and boride with a mass ratio of 18-22:1; attaching the shear-hardening core layer between the two shell-like layers, and tightly bonding to form the laminated glass with a shell-like structure.

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