CN103964854A - SiC ceramic thin-layer bullet-resistant material for laminated armor, and preparation method of material - Google Patents
SiC ceramic thin-layer bullet-resistant material for laminated armor, and preparation method of material Download PDFInfo
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Abstract
The invention relates to a SiC ceramic thin-layer bullet-resistant material for a laminated armor and a preparation method of the SiC ceramic thin-layer bullet-resistant material. The SiC ceramic thin-layer bullet-resistant material is a gel-casting sheet prepared from the following raw materials: silicon carbide micro powder, boron carbide micro powder, acrylamide monomer, N'N-methylene bisacrylamide, tetramethyl ammonium hydroxide, tributyl phosphate, deionized water and ammonium persulfate. The invention also provides the preparation method of the SiC ceramic thin-layer bullet-resistant material. According to the SiC ceramic thin-layer bullet-resistant material, a silicon carbide ceramic sheet which is large in size, compact and smooth can be prepared; the SiC ceramic thin-layer bullet-resistant material is adjustable in size, good in hardness and good in fracture toughness, and is high in protective capability as a bullet-resistant material for the laminated armor.
Description
Technical field
The present invention relates to a kind of layer-built armor protection SiC thin layers of ceramic bullet resistant material and preparation method thereof, belong to armor facing material technology field.
Background technology
In modern war, armour material is one of gordian technique of military weapon.High-performance armour material not only can improve the battlefield survival of fight weapon, and the maneuverability when not reducing it and attacking.Density that silicon carbide ceramics has advantages of is low, hardness is large, shock resistance good, ballisticperformances is good, become the ideal material of making high performance ballistic harness, be widely used in and make flak jackets, vehicle bulletproof armour, naval vessel bulletproof armour, vertiplane bulletproof armour etc.
Yet stupalith toughness is low, the shortcoming of poor reliability has limited the application of silicon carbide ceramics as armor facing material to a certain extent.In recent years, along with bionic fast development, the plate armour of thin layers of ceramic material and the similar shell structure of the compound preparation of macromolecule layer lamination becomes the developing direction of high-performance plate armour.At present, the forming method that thin layers of ceramic material is conventional mainly contains rolling formation, flow casting molding, gel casting forming etc.
Gel injection technique be the nineties in 20th century U.S.'s Oak Ridge National Laboratory O.O.Omatete and a kind of near-net-shape technology of the people such as M.A.Jenny invention, there is cost low, can prepare high, the complex-shaped advantages such as ceramic component of reliability.But, while preparing large size (length of side Thickness Ratio > 100) thin layer (thickness < 2mm) stupalith by gel injection technique, in dry, sintering process, easily produce the defects such as warpage, cracking.
Chinese patent document CN101948312A discloses a kind of silicon carbide bullet-proof ceramics, and the mass percent of feed composition is: silicon carbide powder accounts for 40%～50%, nanometer carbon black accounts for 8%～12%, resol accounts for 3%～10%, silicon accounts for 38%～45%.CN103508734A provides a kind of shellproof norbide/silicon carbide compound ceramic preparation, in mortar, silicon carbide powder, boron carbide powder, nanometer carbon black is mixed, and resol is dissolved with alcohol, join in mortar, ball milling mixes, and adds plastic agent to make granule the powder mixing, then compression molding, make green compact, dry again, solidify siliconising reaction sintering, the bullet resistant material of preparation, there is density little, the advantage such as ballistic performance is good.The disclosed method of foregoing invention is applicable to the preparation of block bullet-resistant ceramic material, and is silicon carbide reaction-sintered base bulletproof ceramic, and low fragility and the hardness of free silica contained in material is unfavorable for giving full play to of silicon carbide ceramics ballistic performance.And the bulletproof ability of block bullet-resistant ceramic material compares with novel laminated composite ceramic material, protective capacities is lower.
Summary of the invention
For the deficiencies in the prior art, for solve existing ceramic armor material toughness low and gel injection technique prepare in large size thin ceramic product drying, sintering process the problem that easily produces warpage, cracking, the invention provides SiC pottery large size thin layer bullet resistant material and preparation method thereof for a kind of layer-built armor protection.
Technical scheme of the present invention is as follows:
A SiC thin layers of ceramic bullet resistant material for layer-built armor protection, is that the gel injection thin slice sintering of being prepared by the feed composition of following mass parts forms, and described sheet thickness is 0.3-2.5mm:
100 parts of silicon carbide micro-powders, boron carbide micro powder 0.5-2 part, acrylamide monomer 20-35 part, N ' N methylene-bisacrylamide 1-3 part, Tetramethylammonium hydroxide 0.5-1.5 part, tributyl phosphate 0.2-0.8 part, deionized water 30-45 part, initiator ammonium persulfate solution 2-5 part.
Described silicon carbide micro-powder median size is 0.45 μ m, purity >=98.5%;
Described boron carbide micro powder median size is 1.5-3.5 μ m, purity >=93.5%;
Described ammonium persulfate solution is the ammonium persulfate aqueous solution of 2-4wt.%;
Preferred according to the present invention, feed composition mass parts is as follows: 100 parts of silicon carbide micro-powders, boron carbide micro powder 0.5-1.5 part, acrylamide monomer 15-30 part, N ' N methylene-bisacrylamide 1.5-2.5 part, Tetramethylammonium hydroxide 0.8-1.2 part, tributyl phosphate 0.4-0.6 part, deionized water 35-42 part, initiator ammonium persulfate solution 2-3 part.
Preferred according to the present invention, the thickness 0.5-2mm of described SiC thin layers of ceramic bullet resistant material; Length and width size is selected die size as required, can realize the preparation of the SiC thin layers of ceramic product of long 100～1000mm, wide 100～1000mm.Belong to large size thin ceramic product.
The present invention's silicon carbide micro-powder used, boron carbide micro powder, acrylamide monomer, N ' N methylene-bisacrylamide, Tetramethylammonium hydroxide, tributyl phosphate, ammonium persulphate are commercially available industrial pure material.
A preparation method for SiC thin layers of ceramic bullet resistant material for layer-built armor protection, comprises that step is as follows:
(1) prepare ceramic size
By proportioning, take silicon carbide micro-powder, boron carbide micro powder, acrylamide monomer, N ' N methylene-bisacrylamide, Tetramethylammonium hydroxide, tributyl phosphate, add deionized water, ball milling mixes; Vacuum stirring de-bubble; Then add ammonium persulfate solution initiator, in vacuum stirring device, be evacuated to while stirring-0.08MPa, keep 3-7 minute, slurry is evenly mixed, and remove bubble.
(2) casting
The slurry that step (1) is made injects silica glass mould, solidifies 10-18 hour at 25-35 ℃ of temperature, and the demoulding, makes regular thin layer silicon carbide green body;
(3) body drying
Thin layer silicon carbide green body that step (2) is made moves in the kiln of 40-50 ℃, is placed between the gypsum thin plate of surface smoothing, to smooth dryly, obtains injection moulding blank;
(4) sintering
A. low-temperature primary smooths sizing
The thin layer silicon carbide green body that step (3) is made packs in vacuum oven, is placed under the graphite cake of surface smoothing, with the speed of 2-5 ℃/min, is slowly warming up to 200-300 ℃, under protective atmosphere, is incubated 1-3 hour, and base substrate is smoothed to sizing;
B. high temperature secondary smooths sintering
The thin layer silicon carbide green body that smooths sizing that step a is obtained is inserted in graphite vacuum high temperature furnace, the graphite cake of upper pressure surface smoothing, and at four jiaos of advance expenditure pads of graphite cake, spacer thickness is 1.05-1.15 times of thin layer silicon carbide green body thickness; Under protective atmosphere, at 2050-2180 ℃ of temperature, be incubated 1-3 hour, make fine and close smooth silicon carbide ceramics layer material.
Gained thin layer silicon carbide ceramics layer material can be realized the large size specification of long 100～1000mm, wide 100～1000mm, and can keep smooth, not warpage, do not ftracture; Volume density is 3.02～3.12g/cm
3, vickers microhardness > 25GPa, fracture toughness property > 4.5MPam
1/2, protective capacities reaches the IV level requirement of shelter of NIJ0101.06 standard regulation.
Preferred according to the present invention, the vacuum stirring de-bubble described in step (1), is that the slurry that ball milling is mixed adds in vacuum stirring device, is evacuated to while stirring-0.08MPa, keeps 10-30 minute, removes bubble residual in slurry.
Preferred according to the present invention, the ammonium persulfate solution initiator described in step (1) is that concentration is the ammonium persulfate aqueous solution of 2-4wt%, and wherein ammonium persulfate aqueous solution add-on accounts for silicon carbide quality and compares 2.0-3.0wt%.
Preferred according to the present invention, in step (2), silica glass mould is clean, smooth silica glass mould, cuts the corner of irregularity after the demoulding, makes regular thin layer silicon carbide green body.
Preferred according to the present invention, described in step (3), gypsum sheet gauge is 3.0-6.5mm.Gypsum thin plate size used can be determined according to the size of the dry silicon carbide green body thin slice of need.Thin layer silicon carbide green body is placed in and between the gypsum thin plate of surface smoothing, smooths dryly, to solve gel injection technique, prepare warpage, the problems of crack producing in large size thin ceramic product drying process.
Preferred according to the present invention, graphite cake described in step (4) is the graphite thin plate of thickness 2.5-7.5mm, and graphite thin plate size used can be determined according to the thin layer silicon carbide green body lamina dimensions at sintering.
Preferred according to the present invention, the protective atmosphere described in step (4) a, b is argon gas or nitrogen.
Preferred according to the present invention, the pad of the four jiaos of advance expenditures of graphite cake described in step (4) b, is the injection moulding blank section of the step (3) identical with thin layer silicon carbide green body material to be sintered; The shim size of four jiaos of advance expenditures of graphite cake can, according to the quality adjustment of graphite thin plate, be preferably the square pad of length of side 5-20mm.
Beneficial effect
1, the present invention be take acrylamide monomer as the alternative direct carbon source of carbon source, both guaranteed the dispersed of carbon, improve again blank strength, be especially applicable to gel injection technique and prepare large size silicon-carbide thin layers of ceramic material, solved the problem of easy warpage, cracking in body drying, sintering process.
2, the present invention adopts graphite thin plate to smooth sintering process, and the gel injection thin slice of preparing at the same formula of four jiaos of advance expenditures of graphite thin plate and same process, the principle of utilizing its equal proportion to shrink, guarantee that graphite thin plate is adjacent to and don't is pressed in completely on gel injection thin slice all the time, can solve the base substrate buckling deformation problem producing in sintering process, can avoid again thin layer base substrate under graphite thin plate weight to move shrinking the problem of Cracking causing, simultaneously can also laminated multi-layer, improve batch.
3, the thickness of SiC thin layers of ceramic material sheet of the present invention is 0.3-2.5mm, and product length and width size is adjusted as required, can realize the preparation of the large size SiC thin layers of ceramic product of long 100～1000mm, wide 100～1000mm.
4, the hardness of SiC thin layers of ceramic material sheet of the present invention and fracture toughness property are good, are a kind of novel laminated composite ceramic materials, good by bullet resistant material protective capacities as layer-built armor.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described further, but institute of the present invention protection domain is not limited to this.
Described silicon carbide micro-powder median size is 0.45 μ m, purity >=98.5%; Described boron carbide micro powder median size is 1.5-3.5 μ m, purity >=93.5%; Commercial product.
Embodiment 1: the preparation method of SiC thin layers of ceramic bullet resistant material for a kind of layer-built armor, and step is as follows:
1) ball milling mixes
By mass parts, take respectively median size and be 100 parts of the silicon carbide micro-powders of 0.45 μ m, median size is 1 part of the boron carbide micro powder of 1.5 μ m, 20 parts of acrylamide monomers, 1.5 parts of N ' N methylene-bisacrylamides, 1 part of Tetramethylammonium hydroxide, 0.5 part of tributyl phosphate, adds in the deionized water of 38 parts, and in tumbling ball mill, ball milling obtains gel injection silicon carbide slurry for 10 hours.
2) vacuum stirring de-bubble
By through step 1) slurry after processing adds in vacuum stirring device, is evacuated to while stirring-0.08MPa, keeps 20 minutes, removes bubble residual in slurry.
3) add initiator
The ammonium persulfate aqueous solution of configuration 2.5wt.%, as initiator, takes 3 parts of described initiator solutions by mass parts and adds through step 2) in slurry after processing, in vacuum stirring device, be evacuated to while stirring-0.08MPa, keep 4 minutes.
4) casting
Will be through through step 3) slurry after processing injects clean, smooth silica glass mould, glass size is 420mm * 420mm, between glass, gap is 1mm, at 25 ℃ of temperature, solidify 12 hours, the demoulding, cut the corner of irregularity, obtain large size thin layer silicon carbide green body regular, that specification is 400mm * 400mm * 1mm.
5) smooth dry
By step 4) the large size thin layer silicon carbide green body that obtains moves in the kiln of 40 ℃, be placed between the gypsum thin plate of surface smoothing, smooth dry, plasterboard is of a size of 420mm * 420mm * 5mm, 20 hours time of drying, obtaining specification is the large size thin layer silicon carbide green body of 372mm * 372mm * 0.92mm.
6) low-temperature primary smooths sizing
By step 5) the large size thin layer silicon carbide green body that obtains packs in vacuum oven, is placed under the graphite thin plate of surface smoothing, and graphite cake is of a size of 400mm * 400mm * 5mm.Speed with 3 ℃/min is slowly warming up to 270 ℃, under argon gas atmosphere, is incubated 2 hours, and base substrate is smoothed to sizing.
7) high temperature secondary smooths sintering
By step 6) the large size thin layer silicon carbide green body that obtains inserts in graphite vacuum high temperature furnace, the level and smooth thick graphite cake that furnace bottom is load-bearing.On base substrate, press the graphite thin plate of surface smoothing, graphite thin plate is of a size of 390mm * 390mm * 4mm, and the thickness of preparing at four jiaos of same Recipes of advance expenditure of graphite thin plate is 1mm, length of side 12mm square injection molding base sheet, under argon gas atmosphere, at 2160 ℃ of temperature, be incubated 1.5 hours, obtaining specification is 298mm * 298mm * 0.75mm, fine and close smooth large size thin layer silicon carbide ceramics layer material.
After testing, the volume density of gained thin layer thyrite is 3.10g/cm
3, vickers microhardness 26.7Gpa, fracture toughness property 5.57MPam
1/2.
Embodiment 2: SiC thin layers of ceramic bullet resistant material and preparation method thereof for a kind of layer-built armor, and step is as follows:
1) ball milling mixes
By mass parts, take respectively median size and be 100 parts of the silicon carbide micro-powders of 0.45 μ m, median size is 1.5 parts of the boron carbide micro powders of 3.5 μ m, 22 parts of acrylamide monomers, 1.6 parts of N ' N methylene-bisacrylamides, 1 part of Tetramethylammonium hydroxide, 0.5 part of tributyl phosphate, adds in the deionized water of 41 parts, and in tumbling ball mill, ball milling obtains gel injection silicon carbide slurry for 12 hours.
2) vacuum stirring de-bubble
By through step 1) slurry after processing adds in vacuum stirring device, is evacuated to while stirring-0.08MPa, keeps 20 minutes, removes bubble residual in slurry.
3) add initiator
The ammonium persulfate aqueous solution of configuration 2.5wt.%, as initiator, takes 3 parts of described initiators by mass parts and adds through step 2) in slurry after processing, in vacuum stirring device, be evacuated to while stirring-0.08MPa, keep 4 minutes.
4) casting
Will be through through step 3) slurry after processing injects clean, smooth silica glass mould, glass size is 320mm * 320mm, between glass, gap is 0.8mm, at 25 ℃ of temperature, solidify 15 hours, the demoulding, cut the corner of irregularity, obtain large size thin layer silicon carbide green body regular, that specification is 300mm * 300mm * 0.8mm.
5) smooth dry
By step 4) the large size thin layer silicon carbide green body that obtains moves in the kiln of 40 ℃, be placed between the gypsum thin plate of surface smoothing, smooth dry, plasterboard is of a size of 320mm * 320mm * 5mm, 25 hours time of drying, obtaining specification is the large size thin layer silicon carbide green body of 282mm * 282mm * 0.74mm.
6) low-temperature primary smooths sizing
By step 5) the large size thin layer silicon carbide green body that obtains packs in vacuum oven, is placed under the graphite thin plate of surface smoothing, and graphite cake is of a size of 300mm * 300mm * 4mm.Speed with 2.5 ℃/min is slowly warming up to 250 ℃, under argon gas atmosphere, is incubated 2.5 hours, and base substrate is smoothed to sizing.
7) high temperature secondary smooths sintering
By step 6) the large size thin layer silicon carbide green body that obtains inserts in graphite vacuum high temperature furnace, the level and smooth thick graphite cake that furnace bottom is load-bearing.On base substrate, press the graphite thin plate of surface smoothing, graphite thin plate is of a size of 300mm * 300mm * 4mm, and in four jiaos of advance expenditures of graphite thin plate, fill a prescription equally, to prepare thickness be 0.8mm, length of side 10mm square gel injection base sheet to technique, under argon gas atmosphere, at 2140 ℃ of temperature, be incubated 2 hours, obtaining specification is the fine and close smooth large size thin layer silicon carbide ceramics layer material of 228mm * 228mm * 0.59mm.
After testing, the volume density of gained silicon carbide ceramics layer material is 3.08g/cm
3, vickers microhardness 25.9GPa, fracture toughness property 5.48MPam
1/2.
The silicon carbide ceramics layer material that embodiment 1-2 makes carries out trajectory test, uses 53 formula 7.62mm armour piercing incendiary shelies, and during bullet velocity 840m/s, its protective capacities reaches the IV level requirement of shelter of NIJ0101.06 standard regulation.
Claims (9)
1. a SiC thin layers of ceramic bullet resistant material for layer-built armor protection, is that the gel injection thin slice sintering of being prepared by the feed composition of following mass parts forms, and described sheet thickness is 0.3-2.5mm:
100 parts of silicon carbide micro-powders, boron carbide micro powder 0.5-2 part, acrylamide monomer 20-35 part, N ' N methylene-bisacrylamide 1-3 part, Tetramethylammonium hydroxide 0.5-1.5 part, tributyl phosphate 0.2-0.8 part, deionized water 30-45 part, initiator ammonium persulfate solution 2-5 part;
Described silicon carbide micro-powder median size is 0.45 μ m, purity >=98.5%;
Described boron carbide micro powder median size is 1.5-3.5 μ m, purity >=93.5%.
2. SiC thin layers of ceramic bullet resistant material according to claim 1, it is characterized in that feed composition mass parts is as follows: 100 parts of silicon carbide micro-powders, boron carbide micro powder 0.5-1.5 part, acrylamide monomer 15-30 part, N ' N methylene-bisacrylamide 1.5-2.5 part, Tetramethylammonium hydroxide 0.8-1.2 part, tributyl phosphate 0.4-0.6 part, deionized water 35-42 part, initiator ammonium persulfate solution 2-3 part.
3. layer-built armor protects the preparation method with SiC thin layers of ceramic bullet resistant material, comprises that step is as follows:
(1) prepare ceramic size
By proportioning, take silicon carbide micro-powder, boron carbide micro powder, acrylamide monomer, N ' N methylene-bisacrylamide, Tetramethylammonium hydroxide, tributyl phosphate, add deionized water, ball milling mixes; Vacuum stirring de-bubble; Then add ammonium persulfate solution initiator, in vacuum stirring device, be evacuated to while stirring-0.08MPa, keep 3-7 minute, slurry is evenly mixed, and remove bubble;
(2) casting
The slurry that step (1) is made injects silica glass mould, solidifies 10-18 hour at 25-35 ℃ of temperature, and the demoulding, makes regular thin layer silicon carbide green body;
(3) body drying
Thin layer silicon carbide green body that step (2) is made moves in the kiln of 40-50 ℃, is placed between the gypsum thin plate of surface smoothing, to smooth dryly, obtains injection moulding blank;
(4) sintering
A. low-temperature primary smooths sizing
The thin layer silicon carbide green body that step (3) is made packs in vacuum oven, is placed under the graphite cake of surface smoothing, with the speed of 2-5 ℃/min, is slowly warming up to 200-300 ℃, under protective atmosphere, is incubated 1-3 hour, and base substrate is smoothed to sizing;
B. high temperature secondary smooths sintering
The thin layer silicon carbide green body that smooths sizing that step a is obtained is inserted in graphite vacuum high temperature furnace, the graphite cake of upper pressure surface smoothing, and at four jiaos of advance expenditure pads of graphite cake, spacer thickness is 1.05-1.15 times of thin layer silicon carbide green body thickness; Under protective atmosphere, at 2050-2180 ℃ of temperature, be incubated 1-3 hour, make smooth silicon carbide ceramics layer material.
4. the preparation method of SiC thin layers of ceramic bullet resistant material according to claim 1, it is characterized in that the vacuum stirring de-bubble described in step (1), that the slurry that ball milling is mixed adds in vacuum stirring device, be evacuated to while stirring-0.08MPa, keep 10-30 minute, remove bubble residual in slurry.
5. the preparation method of SiC thin layers of ceramic bullet resistant material according to claim 1, it is characterized in that the ammonium persulfate initiator described in step (1) is that concentration is the ammonium persulfate aqueous solution of 2-4wt%, wherein ammonium persulfate aqueous solution add-on accounts for silicon carbide quality and compares 2.0-3.0wt%.
6. the preparation method of SiC thin layers of ceramic bullet resistant material according to claim 1, is characterized in that described in step (3), gypsum sheet gauge is 3.0-6.5mm.
7. the preparation method of SiC thin layers of ceramic bullet resistant material according to claim 1, is characterized in that graphite cake described in step (4) is the graphite thin plate of thickness 2.5-7.5mm.
8. the preparation method of SiC thin layers of ceramic bullet resistant material according to claim 1, is characterized in that the protective atmosphere described in step (4) a, b is argon gas or nitrogen.
9. the preparation method of SiC thin layers of ceramic bullet resistant material according to claim 1, is characterized in that the pad of the four jiaos of advance expenditures of graphite cake described in step (4) b, is the injection moulding blank section identical with thin layer silicon carbide green body material to be sintered; Preferably, the pad of four jiaos of advance expenditures of graphite cake is the square of length of side 5-20mm.
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| CN106278348A (en) * | 2016-08-02 | 2017-01-04 | 宁波东联密封件有限公司 | The preparation method of pressureless sintering carborundum gel |
| CN106380204A (en) * | 2016-08-30 | 2017-02-08 | 宁波东联密封件有限公司 | Preparation method of silicon carbide composite material |
| CN108794015A (en) * | 2018-07-12 | 2018-11-13 | 陈群 | A kind of silicon carbide, the production method of titanium diboride composite ceramic material and its application |
| CN109534827A (en) * | 2018-12-11 | 2019-03-29 | 莱芜亚赛陶瓷技术有限公司 | A kind of preset interface hot pressing bulletproof ceramic plate and preparation method thereof |
| CN110041076A (en) * | 2019-05-28 | 2019-07-23 | 山东理工大学 | A kind of big thickness lightweight layer-built armor ceramics and preparation method thereof |
| CN114349515A (en) * | 2022-01-11 | 2022-04-15 | 宁波伏尔肯科技股份有限公司 | Layered bulletproof ceramic and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104446487A (en) * | 2014-10-31 | 2015-03-25 | 青岛店集润健泽新材料科技有限公司 | Slurry and method for gelcasting pressureless sintered silicon carbide ceramics |
| CN106278348A (en) * | 2016-08-02 | 2017-01-04 | 宁波东联密封件有限公司 | The preparation method of pressureless sintering carborundum gel |
| CN106380204A (en) * | 2016-08-30 | 2017-02-08 | 宁波东联密封件有限公司 | Preparation method of silicon carbide composite material |
| CN108794015A (en) * | 2018-07-12 | 2018-11-13 | 陈群 | A kind of silicon carbide, the production method of titanium diboride composite ceramic material and its application |
| CN108794015B (en) * | 2018-07-12 | 2020-12-22 | 李哲 | Preparation method and application of silicon carbide and titanium diboride composite ceramic material |
| CN109534827A (en) * | 2018-12-11 | 2019-03-29 | 莱芜亚赛陶瓷技术有限公司 | A kind of preset interface hot pressing bulletproof ceramic plate and preparation method thereof |
| CN110041076A (en) * | 2019-05-28 | 2019-07-23 | 山东理工大学 | A kind of big thickness lightweight layer-built armor ceramics and preparation method thereof |
| CN110041076B (en) * | 2019-05-28 | 2021-08-17 | 山东理工大学 | Large-thickness light laminated armor ceramic and preparation method thereof |
| CN114349515A (en) * | 2022-01-11 | 2022-04-15 | 宁波伏尔肯科技股份有限公司 | Layered bulletproof ceramic and preparation method thereof |
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