阅读说明：本技术 一种利用镁铝尖晶石透明陶瓷的防弹聚氨酯复合镜片 (Bulletproof polyurethane composite lens made of magnesia-alumina spinel transparent ceramic ) 是由 金婉卿 汪山献松 陈国贵 于 2020-05-09 设计创作，主要内容包括：本发明涉及一种利用镁铝尖晶石透明陶瓷的防弹聚氨酯复合镜片的制造方法,(1)将氧化镁粉体和α-氧化铝粉体三种原料混合均匀得到原料粉体；(2)将步骤(1)制备的原料粉体放到特定模具中,得到素坯；(3)将步骤(2)制备的素坯先经素烧、无压预烧和热等静压烧结后,得到镁铝尖晶石透明陶瓷件A和B；(4)将步骤(3)制备的镁铝尖晶石透明陶瓷件A和B和胶带加工成中空的模具件；(5)在步骤(4)制备的中空的模具件间注入聚氨酯树脂,然后进行固化和镀膜；(6)镀膜后,得到最终产品镜片。本申请通过重量为16G+0.1G,直径为16mm的钢珠在氮气20KG时发射速度为220米/秒的强力冲击下,镜片不破裂,镜片具有防弹功能的要求。(The invention relates to a method for manufacturing a bulletproof polyurethane composite lens by utilizing magnesia-alumina spinel transparent ceramic, which comprises the following steps of (1) uniformly mixing three raw materials of magnesia powder and alpha-alumina powder to obtain raw material powder; (2) putting the raw material powder prepared in the step (1) into a specific mould to obtain a biscuit; (3) carrying out biscuit firing, pressureless presintering and hot isostatic pressing sintering on the biscuit prepared in the step (2) to obtain magnesium aluminate spinel transparent ceramic pieces A and B; (4) processing the magnesium aluminate spinel transparent ceramic pieces A and B prepared in the step (3) and the adhesive tape into a hollow mould piece; (5) injecting polyurethane resin between the hollow mould pieces prepared in the step (4), and then curing and coating; (6) and (5) after film coating, obtaining the final product lens. This application is through weight 16G +0.1G, and the diameter is under the powerful impact that launch velocity was 220 meters per second when nitrogen gas 20KG, and the lens does not break, and the lens has bulletproof function's requirement.)

1. A method for manufacturing a bulletproof polyurethane composite lens by utilizing magnesia alumina spinel transparent ceramics is characterized by comprising the following specific steps:

(1) magnesium oxide powder and alpha-alumina powder are mixed according to a molar ratio of 1: 3, proportioning, wherein the mass concentration of lanthanum oxide relative to the mixture of magnesium oxide powder and alpha-aluminum oxide powder is 10-50 ppm, and uniformly mixing the three raw materials to obtain raw material powder;

(2) putting the raw material powder prepared in the step (1) into a specific mould to obtain a biscuit;

(3) carrying out biscuit firing, pressureless presintering and hot isostatic pressing sintering on the biscuit prepared in the step (2) to obtain a magnesium aluminate spinel transparent ceramic piece A and a magnesium aluminate spinel transparent ceramic piece B;

(4) processing the magnesia-alumina spinel transparent ceramic piece A and the magnesia-alumina spinel transparent ceramic piece B prepared in the step (3) and an adhesive tape into a hollow mould piece, wherein the magnesia-alumina spinel transparent ceramic piece A is used as the front surface curvature of the lens; the magnesia-alumina spinel transparent ceramic piece B is used as the back surface curvature of the lens;

(5) injecting polyurethane resin between the hollow mould pieces prepared in the step (4), wherein the polyurethane resin is prepared from norbornane diisocyanate, pentaerythritol tetrakis (3-mercaptopropionate) and dibutyltin dichloride; the preparation method comprises the following steps of (1) putting a mould piece injected with polyurethane resin into an oven, and then curing, wherein the molar ratio of norbornane diisocyanate to pentaerythritol tetra (3-mercaptopropionate) is 1: 1-1.1: 1, and the mass fraction of dibutyltin dichloride in a mixture of norbornane diisocyanate and pentaerythritol tetra (3-mercaptopropionate) is 1.5%;

removing the adhesive tape at 80 ℃, and beautifying and cleaning the edge; then, carrying out secondary curing on the cleaned lens, wherein the temperature of the secondary curing is 100 ℃, and the time is 2-4 hours; after the secondary curing, the surface of the lens is subjected to film coating treatment after the temperature of the lens is reduced to room temperature;

(6) after film coating, the reflectivity of the bulletproof lens is less than or equal to 1 percent, and the magnesium aluminate spinel transparent ceramic and polyurethane composite lens with the bulletproof function is obtained.

2. The method for manufacturing a bulletproof polyurethane composite lens using magnesium aluminate spinel transparent ceramic as claimed in claim 1, wherein the magnesium aluminate spinel transparent ceramic piece is manufactured by using MgO powder with purity of 99.95% or more and particle size of 10-50 nm; the purity of the alpha-Al 2O3 powder is more than or equal to 99.95%, and the particle size is 10-50 nm; the purity of the sintering aid lanthanum oxide is more than or equal to 99.95%, and the particle size is 10-50 nm.

3. The method of claim 1, wherein the curvature radius of the curvature of the magnesium aluminate spinel transparent ceramic piece A and the magnesium aluminate spinel transparent ceramic piece B is 50-2000 mm, and the diameter thereof is 300-900 mm.

4. The method of claim 1, wherein the curvature radius of the curvature of the magnesium aluminate spinel transparent ceramic piece A and the magnesium aluminate spinel transparent ceramic piece B is 500-1000 mm, and the diameter thereof is 500-800 mm.

5. The method of claim 1, wherein the central thickness of the lens is in the range of 0.1 to 6.0 mm, and the radius of curvature of the lens surface curvature is in the range of 50 to 2000 mm.

6. The method of claim 1, wherein the central thickness of the lens is in the range of 0.1 to 3.0 mm, and the radius of curvature of the lens surface curvature is in the range of 500 to 1000 mm.

7. The method of claim 1, wherein the curing procedure comprises:

0.5 to 3 hours at the room temperature of-20 DEG C

20℃～40℃8h～12h

40℃～50℃2h～5h

50℃～70℃3h～4h

70℃～95℃3h～5h

95℃～120℃1h～3h

120℃～120℃2h～3h

120℃～80℃1h～2h

Preserving the heat at 80-80 ℃.

8. The method of claim 1, wherein the curing procedure comprises:

room temperature-20 deg.C for 2h

20℃～40℃9h

40℃～50℃3h

50℃～70℃3h

70℃～95℃4h

95℃～120℃2h

120℃～120℃2h

120℃～80℃2h

Preserving the heat at 80-80 ℃.

9. The method for manufacturing a bulletproof polyurethane composite lens using magnesium aluminate spinel transparent ceramic as claimed in claim 1, wherein the material used for the coating film is silicon oxide, zirconium oxide, aluminum oxide, indium tin oxide and fluoride; fluoride is coated on the outermost layer of the film layer by adopting one of two modes of an electron gun and a main evaporation.

10. The method for manufacturing a bulletproof polyurethane composite lens using magnesium aluminate spinel transparent ceramic as claimed in claim 1, wherein the fluoride is coated on the outermost layer of the film layer by a main evaporation method.

Technical Field

The invention relates to the technical field of lenses, in particular to a bulletproof polyurethane composite lens utilizing magnesia-alumina spinel transparent ceramic.

Background

Bulletproof glass is generally formed by pasting two pieces of glass at a certain temperature and pressure by a tough plastic inner layer (pc/PVB), wherein the thickness of a sandwich layer pc is generally 0.5mm-5mm. The laminated glass can be made of common glass, toughened glass and heat-strengthened glass according to different requirements, and can also be made into hollow glass. The safety glass has good safety, impact resistance and penetration resistance, and has the functions of theft prevention, bullet prevention and explosion prevention. In order to achieve the bulletproof effect, the thickness of the bulletproof glass generally needs to be more than 10 mm.

Researches find that the magnesia-alumina spinel transparent ceramic has good optical performance, high mechanical strength and stable physical and chemical properties and is widely applied to military and civil fields such as transparent armor, intelligent display equipment windows, infrared optical windows/seeker fairing hoods, ultraviolet lithography machine lenses, high-temperature windows and the like. In 1961, the transparency of the magnesia-alumina spinel ceramic is discovered for the first time by the American general electric company, magnesia-alumina spinel powder is synthesized by adopting a solid-phase reaction method, Li2O and SiO2 are used as sintering aids, the semitransparent magnesia-alumina spinel ceramic is prepared for the first time by vacuum sintering or hydrogen atmosphere sintering, and then researchers in various countries in the world carry out a great deal of research on the preparation of the magnesia-alumina spinel transparent ceramic and the densification mechanism thereof. Krell et al use special MgAl2O4 powder with a particle size of 53nm, sinter at 1240 and 1260 ℃ under pressureless conditions, and hot isostatic press at a temperature lower than 1300 ℃ to obtain a magnesium aluminate Spinel Transparent Ceramic with an average grain size of 0.2-0.3 μm (Krell A, HutzlerT, Klimke J, et al, Fine-Grained transgenic Spinel Windows by the processing of differential Nanopowders [ J ] the visible light transmittance of the American Ceramic Society,2010,93(9):2656 and 2666.) when the sample thickness is 4-10mm, which has high requirements for the particle size of the raw material powder and high cost.

Chinese patent application No. CN200610022318.5, a method for preparing magnesium aluminate spinel nano transparent ceramics, which takes magnesium aluminate spinel nano powder with purity of more than 99 percent as raw material, and comprises the process steps of powder forming and high-pressure sintering. The powder forming is to put magnesium aluminate spinel nano powder with the purity of more than 99 percent into a mould and form a biscuit at the normal temperature and the pressure of 5-20 MPa; and the high-pressure sintering is to place the biscuit into a two-sided top press and sinter the biscuit under the pressure of 2-5 GPa, wherein the sintering temperature is 500-700 ℃, and the sintering time is at least 20 minutes, so that the magnesia-alumina spinel nano transparent ceramic is prepared.

Chinese patent application No. CN200610022482.6, a preparation method of toughened magnesia-alumina spinel transparent ceramic, which takes chemically pure MgSO4 and NH4Al (SO4)2 as raw materials and comprises the following process steps: (1) preparing powder and granulating, namely preparing magnesium aluminate spinel nano powder by adopting a molten salt roasting method, adding a binder into the prepared nano powder, ball-milling for 24-48 hours, and then granulating to form particles of 40-100 mu m; (2) forming, namely filling magnesium aluminate spinel particles into a mould for primary pressing and forming, and then carrying out cold isostatic pressing to obtain a densified biscuit; (3) and sintering, namely sintering the biscuit in a vacuum and then sintering the biscuit in a hot isostatic pressing furnace. The general formula of the prepared magnesia-alumina spinel transparent ceramic is MgO. nAl2O3, wherein n is more than or equal to 1.3 and less than or equal to 1.6, the visible wave band transmittance reaches more than 80 percent, the fracture toughness is 2.7 MPa.m 1/2 when n is 1.3, and the fracture toughness is 3.2 MPa.m 1/2 when n is 1.5.

However, the brittleness of magnesium aluminate spinel transparent ceramics has severely limited its use in more applications. If the magnesia-alumina spinel transparent ceramic is directly processed into the bulletproof glasses, if the central thickness of the lens is processed within 3mm, the lens has the problems of being too brittle and the impact resistance not meeting the standard. The invention provides a method for manufacturing a magnesium aluminate spinel transparent ceramic composite polyurethane lens with a bulletproof function, which is characterized by comprising the following steps of: the magnesia-alumina spinel transparent ceramic part is a barrel with MgO powder with the purity of more than or equal to 99.95 percent and the grain diameter of 10-50 nm; the purity of the alpha-Al 2O3 powder is more than or equal to 99.95%, and the particle size is 10-50 nm; the purity of the sintering aid lanthanum oxide is more than or equal to 99.95%, and the particle size is 50-100 nm. Magnesium oxide powder and alpha-alumina powder are mixed according to a molar ratio of 1: 3, mixing the three raw materials uniformly to obtain raw material powder, wherein the mass concentration of lanthanum oxide is 10-50 ppm; putting the obtained raw material powder into a specific mould to obtain a biscuit; and carrying out biscuit firing, pressureless presintering and hot isostatic pressing sintering on the obtained biscuit to obtain the magnesium aluminate spinel transparent ceramic part with the specific bending degree. Processing A and B magnesium aluminate spinel transparent ceramic pieces with specific camber and an adhesive tape into a hollow mould piece, wherein the A magnesium aluminate spinel transparent ceramic piece is used as the front surface camber of the lens; the B pieces of magnesium aluminate spinel transparent ceramic pieces are used as the back surface curvature of the lens. Injecting polyurethane resin between hollow mould pieces, wherein the polyurethane resin is prepared from norbornane diisocyanate, pentaerythritol tetra (3-mercaptopropionate) and dibutyltin dichloride with the mass ratio of 1.5%; the polyurethane resin injected mold pieces are then placed in an oven and cured according to a specified curing procedure. The solidified mould component is not only a blank of the bulletproof lens, but also vacuum coating is carried out after the lens is cleaned and dried, so that the reflectivity of the bulletproof lens reaches 1 percent, and the magnesium aluminate spinel transparent ceramic and polyurethane composite lens with the bulletproof function can be obtained. The center thickness of the magnesium aluminate spinel transparent ceramic and polyurethane composite lens with the bulletproof function reaches 3.00mm, the lens can not break under the strong impact of 16G +0.1G weight and 16mm diameter steel balls with the launching speed of 220 m/s under 20KG nitrogen, and the lens has the bulletproof function requirement.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a bulletproof polyurethane composite lens by utilizing magnesia-alumina spinel transparent ceramic.

The purpose of the invention is realized by the following technical scheme:

a method for manufacturing a bulletproof polyurethane composite lens by utilizing magnesia-alumina spinel transparent ceramic comprises the following specific steps:

(1) magnesium oxide powder and alpha-alumina powder are mixed according to a molar ratio of 1: 3, proportioning, wherein the mass concentration of lanthanum oxide relative to the mixture of magnesium oxide powder and alpha-aluminum oxide powder is 10-50 ppm, and uniformly mixing the three raw materials to obtain raw material powder;

the magnesia-alumina spinel transparent ceramic part is prepared by mixing MgO powder with the purity of more than or equal to 99.95 percent and the grain diameter of 10-50 nm; the purity of the alpha-Al 2O3 powder is more than or equal to 99.95%, and the particle size is 10-50 nm; the purity of the sintering aid lanthanum oxide is more than or equal to 99.95%, and the particle size is 10-50 nm.

(2) Putting the raw material powder prepared in the step (1) into a specific mould to obtain a biscuit;

(3) carrying out biscuit firing, pressureless presintering and hot isostatic pressing sintering on the biscuit prepared in the step (2) to obtain a magnesium aluminate spinel transparent ceramic piece A and a magnesium aluminate spinel transparent ceramic piece B;

the curvature radius of the bending degree of the magnesia alumina spinel transparent ceramic piece A and the magnesia alumina spinel transparent ceramic piece B is 50-2000 mm, and the diameter of the magnesia alumina spinel transparent ceramic piece A and the diameter of the magnesia alumina spinel transparent ceramic piece B are 300-900 mm.

The curvature radius of the bending degree of the magnesium aluminate spinel transparent ceramic piece A and the magnesium aluminate spinel transparent ceramic piece B ranges from 500mm to 1000mm, and the diameter ranges from 500mm to 800 mm.

(4) Processing the magnesia-alumina spinel transparent ceramic piece A and the magnesia-alumina spinel transparent ceramic piece B prepared in the step (3) and an adhesive tape into a hollow mould piece, wherein the magnesia-alumina spinel transparent ceramic piece A is used as the front surface curvature of the lens; the magnesia-alumina spinel transparent ceramic piece B is used as the back surface curvature of the lens;

the central thickness range of the lens is 0.1-6.0 mm, and the curvature radius range of the lens surface curvature is 50-2000 mm.

Preferably, the central thickness of the lens ranges from 0.1 mm to 3.0 mm, and the curvature radius of the lens surface curve ranges from 500mm to 1000 mm.

(5) Injecting polyurethane resin between the hollow mould pieces prepared in the step (4), wherein the polyurethane resin is prepared from norbornane diisocyanate, pentaerythritol tetrakis (3-mercaptopropionate) and dibutyltin dichloride; the preparation method comprises the following steps of (1) putting a mould piece injected with polyurethane resin into an oven, and curing according to a specific curing procedure, wherein the molar ratio of norbornane diisocyanate to pentaerythritol tetra (3-mercaptopropionate) is 1: 1-1.1: 1, and the mass fraction of dibutyltin dichloride in a mixture of the norbornane diisocyanate and the pentaerythritol tetra (3-mercaptopropionate) is 1.5%; the curing procedure was:

0.5 to 3 hours at the room temperature of-20 DEG C

20℃～40℃ 8h～12h

40℃～50℃ 2h～5h

50℃～70℃ 3h～4h

70℃～95℃ 3h～5h

95℃～120℃ 1h～3h

120℃～120℃ 2h～3h

120℃～80℃ 1h～2h

Heat preservation at 80-80 deg.C

The preferred curing procedure is:

room temperature-20 deg.C for 2h

20℃～40℃ 9h

40℃～50℃ 3h

50℃～70℃ 3h

70℃～95℃ 4h

95℃～120℃ 2h

120℃～120℃ 2h

120℃～80℃ 2h

Heat preservation at 80-80 deg.C

Removing the adhesive tape at 80 ℃, and beautifying and cleaning the edge; then, carrying out secondary curing on the cleaned lens, wherein the temperature of the secondary curing is 100 ℃, and the time is 2-4 hours; after the secondary curing, the surface of the lens is subjected to film coating treatment after the temperature of the lens is reduced to room temperature;

the coating film is made of silicon oxide, zirconium oxide, aluminum oxide, indium tin oxide and fluoride; the fluoride is arranged on the outermost layer of the film layer, and the film is coated by adopting one of an electron gun and a main evaporation mode; preferably, the compound is on the outermost layer of the film layer, and the film plating is carried out by adopting a main evaporation mode;

(6) after film coating, the reflectivity of the bulletproof lens is less than or equal to 1 percent, and the magnesium aluminate spinel transparent ceramic and polyurethane composite lens with the bulletproof function is obtained.

Compared with the prior art, the invention has the following positive effects:

compared with the prior art, the transparent ceramic and polyurethane composite lens made of magnesium aluminate spinel can pass through the steel ball with the diameter of 16mm under the condition that the central thickness reaches 3.00mm and the weight is 16G +0.1G, and the lens is not broken under the strong impact with the launching velocity of 220 m/s when the nitrogen is 20KG, and has the requirement of a bulletproof function.

The application solves the brittleness problem of the magnesia-alumina spinel transparent ceramic in the prior art through the magnesia-alumina spinel transparent ceramic and polyurethane composite technology.

Detailed Description

The following provides a specific embodiment of a bulletproof polyurethane composite lens using a magnesium aluminate spinel transparent ceramic according to the present invention.