WO2023221297A1 - Procédé de fabrication de céramique présentant une aptitude aux impacts multiples et plaque d'insertion pare-balles - Google Patents
Procédé de fabrication de céramique présentant une aptitude aux impacts multiples et plaque d'insertion pare-balles Download PDFInfo
- Publication number
- WO2023221297A1 WO2023221297A1 PCT/CN2022/109161 CN2022109161W WO2023221297A1 WO 2023221297 A1 WO2023221297 A1 WO 2023221297A1 CN 2022109161 W CN2022109161 W CN 2022109161W WO 2023221297 A1 WO2023221297 A1 WO 2023221297A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ceramic
- bullet
- aramid
- sintering
- insert plate
- Prior art date
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 137
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- 238000005245 sintering Methods 0.000 claims abstract description 53
- 229910052580 B4C Inorganic materials 0.000 claims abstract description 39
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000007731 hot pressing Methods 0.000 claims abstract description 13
- 230000001681 protective effect Effects 0.000 claims abstract description 12
- 238000001272 pressureless sintering Methods 0.000 claims abstract description 7
- 239000010410 layer Substances 0.000 claims description 64
- 238000013329 compounding Methods 0.000 claims description 46
- 229920003235 aromatic polyamide Polymers 0.000 claims description 45
- 239000004760 aramid Substances 0.000 claims description 40
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims description 38
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims description 38
- 239000004744 fabric Substances 0.000 claims description 33
- 239000000835 fiber Substances 0.000 claims description 26
- 239000002759 woven fabric Substances 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 17
- 238000009690 centrifugal atomisation Methods 0.000 claims description 13
- 238000005469 granulation Methods 0.000 claims description 13
- 230000003179 granulation Effects 0.000 claims description 13
- 239000012790 adhesive layer Substances 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 230000035515 penetration Effects 0.000 claims description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims description 5
- 238000005336 cracking Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000004745 nonwoven fabric Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 15
- 230000000149 penetrating effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 23
- 239000011162 core material Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 18
- 229910000831 Steel Inorganic materials 0.000 description 16
- 239000010959 steel Substances 0.000 description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 14
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 13
- 239000005011 phenolic resin Substances 0.000 description 13
- 229920001568 phenolic resin Polymers 0.000 description 13
- 239000000203 mixture Substances 0.000 description 10
- 238000003825 pressing Methods 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 239000011812 mixed powder Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 229920006231 aramid fiber Polymers 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000011094 fiberboard Substances 0.000 description 6
- 239000012634 fragment Substances 0.000 description 4
- 230000008595 infiltration Effects 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- 239000011863 silicon-based powder Substances 0.000 description 4
- -1 Al 2 O 3 ) Chemical class 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 230000009545 invasion Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
- B32B37/1284—Application of adhesive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/024—Woven fabric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
- B32B5/265—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary characterised by one fibrous or filamentary layer being a non-woven fabric layer
- B32B5/266—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary characterised by one fibrous or filamentary layer being a non-woven fabric layer next to one or more non-woven fabric layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/047—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material made of fibres or filaments
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/563—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on boron carbide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
- C04B35/645—Pressure sintering
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
- C04B35/65—Reaction sintering of free metal- or free silicon-containing compositions
-
- 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
- F41H5/0414—Layered armour containing ceramic material
- F41H5/0428—Ceramic layers in combination with additional layers made of fibres, fabrics or plastics
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0253—Polyolefin fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0261—Polyamide fibres
- B32B2262/0269—Aromatic polyamide fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2571/00—Protective equipment
- B32B2571/02—Protective equipment defensive, e.g. armour plates, anti-ballistic clothing
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3817—Carbides
- C04B2235/3826—Silicon carbides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/428—Silicon
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
- C04B2235/6581—Total pressure below 1 atmosphere, e.g. vacuum
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Definitions
- the invention relates to a bulletproof insert plate material and a preparation method thereof, specifically a preparation method of multi-bullet resistant ceramics and a bulletproof insert plate.
- Bulletproof ceramics are the core material of lightweight bulletproof inserts, which play a role in breaking bullets and dissipating energy against incoming bullets.
- rapid-fire weapons has put forward a realistic demand for protective inserts to prevent multiple rounds.
- the patent application number 201920946066.8 discloses a bulletproof insert plate structure, which is staggered and spliced by two layers of ceramic small plates to avoid the bulletproof weakness caused by the ceramic overlap seams and improve its ability to withstand multiple bullets.
- the patent application number 201220010296.1 discloses a composite structure bulletproof material plate.
- the core point is still a ceramic layer made of units composed of ceramic plates or ceramic particles.
- the present invention provides a preparation method of multi-bullet resistant ceramics and a bulletproof insert plate, which solve the problems in the prior art. It is characterized by elastic ceramics made of silicon carbide, boron carbide or a combination of the two. After ultra-high temperature sintering, it has a coarse grain structure, higher and more uniform hardness and compressive strength, and has high impact resistance. brittleness.
- the bulletproof insert plate made by combining this type of ceramics with an appropriate backing plate has low bulk density and high elastic resistance. It can be used as a human body protection insert plate to resist multiple rounds of small and medium-caliber bullets such as DBP95 type 5.8mm (steel core) bullets. Invasion.
- the present invention provides a method for preparing multi-bullet-resistant ceramics, which involves sintering silicon carbide and/or boron carbide.
- the sintering can be high-temperature sintering, reaction sintering, hot-pressing sintering or pressureless sintering.
- reaction sintering has a sintering temperature of 1750°C to 1900°C and a holding time of 4 to 6 hours;
- hot press sintering has a temperature of 2100°C to 2250°C and a pressure The temperature is 30MPa, and the holding time is 2 to 3 hours;
- the pressureless sintering has a temperature of 2050°C to 2150°C, and a holding time of 3 to 5 hours.
- the silicon carbide and/or boron carbide are obtained by ball milling and centrifugal atomization granulation with a molding agent or sintering aid, where the ball milling mixing time is 12-24 hours, and the inlet of centrifugal atomization granulation is The temperature is 150-210°C, and the outlet temperature is 80-110°C; the dosage of the molding agent or burning aid is 2%-15%.
- the molding agent is one or more of phenolic resin, glucose, and epoxy resin
- the burning aid is carbon (C), metal element (such as Al), metal oxide (such as Al 2 O 3 ), one or more types of borides (such as TiB 2 ), etc.
- the ceramic has an average grain size of 200-380 ⁇ m, a Vickers hardness of 23.5GPa-34GPa, and a compressive strength of 2200MPa-3100MPa.
- the invention provides an anti-multi-bullet ceramic protective insert plate based on the above-mentioned ceramic, wherein: a crack arresting layer, an anti-ballistic ceramic panel and The energy-absorbing back panel has an area density of less than 25kg/m 2 and can withstand penetration by four rounds of DBP95 5.8mm bullets. All back protrusions are less than 25mm.
- the crack-stopping layer is composed of aramid woven fabric, with an area density of 0.4-0.8kg/m 2 ;
- the areal density of the anti-ballistic ceramic panel is 10.5-13.5kg/m 2 ;
- the energy-absorbing layer is thermally cured by laminating ultra-high molecular weight polyethylene woven fabrics with an area density of 9.2 to 14.0 kg/m 2 .
- a support layer is also provided between the anti-ballistic ceramic panel and the energy-absorbing backboard.
- the support layer is thermally cured by laminating carbon fiber non-woven fabrics or aramid non-woven fabrics, with an area density of 0 to 1.8 kg/ m2 .
- the aramid woven fabric is para-aramid (aramid II) woven fabric or heterocyclic aramid (aramid III) woven fabric
- the aramid weft-free fabric is para-aramid (aramid) Aromatic II) weftless fabric or heterocyclic aramid (aromatic III) weftless fabric.
- the present invention provides a method for preparing the multi-bullet resistant ceramic protective insert plate, which includes the following steps:
- the compounding conditions are 128°C, 25MPa, and the compounding time is 25-30 minutes. After compounding, it will be used as an energy-absorbing backboard;
- the anti-cracking layer composed of aramid woven fabric, the anti-elastic ceramic panel obtained in step 1), and the energy-absorbing backing plate obtained in step 2) are laminated together through the adhesive layer in sequence, and are heated at 128°C and 1.0MPa pressure. Get compounded.
- a support layer is also provided between the anti-ballistic ceramic panel and the energy-absorbing back panel, and the support layer (4) is made of aramid UD cloth.
- the preparation step of the support layer is to press and compound aramid UD cloth.
- the compounding conditions are 128°C, 25MPa, and the compounding time is 10 minutes.
- the present invention adopts the strategy of high-strength, high-hardness and highly brittle anti-ballistic ceramics.
- the ceramic fragments produced by the impact of each bullet with ceramics greatly consume the bullet's Due to the kinetic energy, the cracks produced by the ceramic plate near the impact point are widely spaced and have little impact on the anti-elastic properties of other impact points, thus improving the ability of the bulletproof insert plate to stably withstand multiple rounds.
- the bulletproof insert plate composed of three or four layers of materials maintains the inherent advantages of light weight and high hardness of bulletproof ceramics.
- the strong support of the ceramic back plate fully exerts the bullet-breaking performance of the ceramic; the ceramic bullet-facing surface
- the anti-cracking layer effectively avoids secondary damage caused by the splashing of ceramic particles.
- FIG. 1 is a schematic structural diagram of the bulletproof inserting plate of the present invention.
- Figure 2 is a schematic diagram of the impact point position of the bulletproof insert plate
- Figure 3 is an X-ray perspective photograph (top picture) and an appearance diagram (bottom picture) of the target plate corresponding to Example 1 after being hit by four rounds of DBP95 5.8mm (steel core) bullets. The picture shows the back);
- Figure 4 is an X-ray perspective photograph (top picture) and an appearance diagram (bottom picture) of the target plate corresponding to Example 2 after being hit by four rounds of DBP95 5.8mm (steel core) bullets. The picture shows the back);
- Figure 5 is an X-ray perspective photograph (top picture) and an appearance diagram (bottom picture) of the target plate corresponding to Example 3 after four rounds of DBP95 5.8mm (steel core) bullets were hit. The picture shows the back);
- Figure 6 is an X-ray perspective photograph (top picture) and an appearance diagram (bottom picture) of the target plate corresponding to Example 4 after being hit by four rounds of DBP95 5.8mm (steel core) bullets.
- the left picture shows the front, and the right picture shows the The picture shows the back);
- Figure 7 shows the X-ray perspective photo (top photo) and the apparent morphology photo (bottom photo) of the target plate corresponding to Comparative Example 5 after being hit by four rounds of DBP95 5.8mm (steel core) bullets. The picture shows the back).
- the bulletproof insert plate is composed of three layers of materials: a crack arresting layer, a ceramic panel, and an ultra-high molecular weight polyethylene energy-absorbing layer.
- the ceramic panel material is silicon carbide and is manufactured by a reaction sintering process. Its specific preparation method is as follows:
- Step 1) Mix silicon carbide powder and phenolic resin by ball milling (time: 15h), centrifugal atomization and granulation (inlet temperature 195°C, outlet temperature 90°C), in which the mass proportion of phenolic resin is 15%, and the mixed powder is pressed and formed. Finally, a silicon cake composed of metallic silicon powder as the main body is placed on the compact. In a vacuum environment, a silicon infiltration reaction is used to obtain a dense silicon carbide ceramic.
- the reaction sintering temperature is 1800°C and the sintering holding time is 5 hours; the resulting carbonization
- the main structural and performance indicators of silicon ceramics average grain size 210 ⁇ m, Vickers hardness (GB/T 16534-2009) 23.8GPa, compressive strength (GBT 4740-1999) 2250MPa, average fracture toughness (GB/T23806-2009) 1.75 MPa ⁇ m 1/2 ;
- Step 2 Unfold and cut the ultra-high molecular weight polyethylene fiber (average molecular weight 3 million to 3.1 million) UD cloth, and place the cut ultra-high molecular weight polyethylene fiber UD cloth neatly on the mold of the heat press. Press and compound, the compounding conditions are 128°C, 25MPa, compounding time is 30 minutes, and it will be used as an energy-absorbing backing board after compounding.
- Step 3) Aramid woven fabric (area density 0.4kg/m 2 , aramid woven fabric is para-aramid (aramid II) woven fabric or heterocyclic aramid (aramid III) woven fabric)
- the crack arresting layer, the silicon carbide ceramic plate (area density 14.0kg/m 2 ) obtained in step 1), and the ultra-high molecular weight polyethylene fiber energy-absorbing backsheet (area density 10.2kg/m 2 ) obtained in step 2) are passed through EVA in sequence
- the adhesive layers were laminated together and compounded under 128°C and 1.0MPa pressure to obtain a bulletproof insert with a size of 260mm ⁇ 325mm and an area density of 24.8kg/ m2 .
- the thickness of each layer, overall thickness and specifications of the bulletproof insert are shown in Table 1. .
- the above-mentioned bulletproof insert plates were tested in accordance with the "GA141-2010 police Body Armor" standard.
- the appropriate parts of the upper left, lower right, lower left and upper right parts of the insert plates were used to defend against one DBP95 5.8mm (steel core) bullet.
- Specific test conditions The distance between the impact point of the projectile and the edge of the insert plate is not less than 50mm, the distance between the two projectile impact points is 100 ⁇ 10mm, the bullet speed is 940 ⁇ 10m/s, the incident angle is 0°, and the shooting distance is 15m.
- the bulletproof insert plate is composed of four layers of materials, including a crack arrester layer, a ceramic panel, an aramid fiber board, and an ultra-high molecular weight polyethylene energy-absorbing layer.
- the ceramic panel material is boron carbide and is manufactured by a hot-pressing sintering process. Its specific preparation method is as follows:
- Step 1) Mix boron carbide powder and phenolic resin by ball milling (time: 12h), centrifugal atomization and granulation (inlet temperature 180°C, outlet temperature 85°C). The mass proportion of phenolic resin is 2%. After the mixed powder is pressed and formed, In a vacuum environment, boron carbide ceramic panels were prepared by hot-pressing sintering. The hot-pressing sintering temperature was 2200°C, the pressure was 30MPa, and the holding time was 2 hours.
- the main structural and performance indicators of the obtained boron carbide ceramics were: average grain size 350 ⁇ m, dimension Hardness (GB/T 16534-2009) 33.8GPa, compressive strength (GBT 4740-1999) 3050MPa, average fracture toughness (GB/T23806-2009) 1.25MPa ⁇ m 1/2 .
- Step 2) Unfold and cut the aramid UD cloth and place it neatly on the mold of the hot press for pressing and compounding.
- the compounding conditions are 128°C, 25MPa, and the compounding time is 10 minutes.
- Step 3 Unfold and cut the ultra-high molecular weight polyethylene fiber (average molecular weight 3 million to 3.1 million) UD cloth, and place the cut ultra-high molecular weight polyethylene fiber UD cloth neatly on the mold of the heat press. Pressing and compounding, the compounding conditions are 128°C, 25MPa, and the compounding time is 25min.
- Step 4) Combine the crack arresting layer composed of aramid woven fabric (area density 0.8kg/m 2 ), the boron carbide ceramic plate obtained in step 1) (area density 12.2kg/m 2 ), and the aramid fiber obtained in step 2)
- the support layer (area density 1.8kg/m 2 ) and the energy-absorbing backboard (area density 9.8kg/m 2 ) composed of the ultra-high molecular weight polyethylene fiberboard obtained in step 3) are laminated together in sequence through an adhesive layer and heated at 128°C , compounded under a pressure of 1.0MPa to obtain a bulletproof insert plate with a size of 260mm ⁇ 325mm and an area density of 25kg/ m2 .
- the above-mentioned bulletproof insert plates were tested in accordance with the "GA141-2010 police Body Armor" standard.
- the appropriate parts of the upper left, lower right, lower left and upper right parts of the insert plates were used to defend against one DBP95 5.8mm (steel core) bullet.
- Specific test conditions The distance between the impact point of the projectile and the edge of the insert plate is not less than 50mm, the distance between the two projectile impact points is 100 ⁇ 10mm, the bullet speed is 940 ⁇ 10m/s, the incident angle is 0°, and the shooting distance is 15m.
- the bulletproof insert plate is composed of three layers of materials: a crack arresting layer, a ceramic panel, and an ultra-high molecular weight polyethylene energy-absorbing layer.
- the ceramic panel material is boron carbide and is manufactured by a pressureless sintering process. Its specific preparation method is as follows:
- the main structural performance indicators of the obtained boron carbide ceramic are: average grain size 300 ⁇ m, Vickers hardness (GB /T 16534-2009) 31.8GPa, compressive strength (GBT 4740-1999) 2950MPa, average fracture toughness (GB/T23806-2009) 1.75MPa ⁇ m 1/2 .
- Step 2 Unfold and cut the ultra-high molecular weight polyethylene fiber (average molecular weight 3 million to 3.1 million) UD cloth, and place the cut ultra-high molecular weight polyethylene fiber UD cloth neatly on the mold of the heat press. Pressing and compounding, the compounding conditions are 128°C, 25MPa, and the compounding time is 25min.
- Step 3) Combine the crack arresting layer composed of aramid woven fabric (area density 0.4kg/m 2 ), the boron carbide ceramic plate obtained in step 1) (area density 11.5kg/m 2 ), and the ultra-high Molecular weight polyethylene fiber energy-absorbing backsheets (area density 12.8kg/m 2 ) are laminated together through adhesive layers in sequence, and compounded under 128°C and 1.0MPa pressure to obtain a size of 260mm ⁇ 325mm and an area density of 24.9kg/m 2 bulletproof inserts.
- the above-mentioned bulletproof insert plates were tested in accordance with the "GA141-2010 police Body Armor" standard.
- the appropriate parts of the upper left, lower right, lower left and upper right parts of the insert plates were used to defend against one DBP95 5.8mm (steel core) bullet.
- Specific test conditions The distance between the impact point of the projectile and the edge of the insert plate is not less than 50mm, the distance between the two projectile impact points is 100 ⁇ 10mm, the bullet speed is 940 ⁇ 10m/s, the incident angle is 0°, and the shooting distance is 15m.
- the bulletproof insert plate is composed of three layers of materials: a crack arrester layer, a ceramic panel, and an ultra-high molecular weight polyethylene energy-absorbing layer.
- the ceramic panel material is a complex ceramic composed of silicon carbide and boron carbide, which is made by reaction sintering. Craft manufacturing. Its specific preparation method is as follows:
- Step 1) Mix boron carbide, silicon carbide powder and phenolic resin by ball milling (time: 20h), centrifugal atomization and granulation (inlet temperature 185°C, outlet temperature 90°C), where the mass ratio of boron carbide, silicon carbide, and phenolic resin is The ratio is 75:10:15.
- a silicon cake composed of metallic silicon powder as the main body is placed on the compact. In a vacuum environment, the silicon infiltration reaction is used to obtain dense silicon carbide ceramics.
- the reaction sintering temperature is 1820 °C, the sintering holding time is 5 hours; the main structural performance indicators of the obtained multi-phase ceramic: average grain size 250 ⁇ m, Vickers hardness (GB/T 16534-2009) 26.5GPa, compressive strength (GBT 4740-1999) 2710MPa, The average fracture toughness (GB/T23806-2009) is 1.85MPa ⁇ m 1/2 .
- Step 2 Unfold and cut the ultra-high molecular weight polyethylene fiber (average molecular weight 3 million to 3.1 million) UD cloth, and place the cut ultra-high molecular weight polyethylene fiber UD cloth neatly on the mold of the heat press. Pressing and compounding, the compounding conditions are 128°C, 25MPa, and the compounding time is 25min.
- Step 3) Combine the crack arresting layer composed of aramid woven fabric (area density 0.4kg/m 2 ), the composite ceramic panel obtained in step 1) (area density 14.2kg/m 2 ), and the ultra-high ceramic panel obtained in step 2) Molecular weight polyethylene fiber energy-absorbing backsheets (area density 10.2kg/m 2 ) are laminated together through adhesive layers in sequence, and compounded at 128°C and 1.0MPa pressure to obtain a size of 250mm ⁇ 300mm and an area density of 25.0kg/m 2 bulletproof inserts.
- the above-mentioned bulletproof insert plates were tested in accordance with the "GA141-2010 police Body Armor" standard.
- the appropriate parts of the upper left, lower right, lower left and upper right parts of the insert plates were used to defend against one DBP95 5.8mm (steel core) bullet.
- Specific test conditions The distance between the impact point of the projectile and the edge of the insert plate is not less than 50mm, the distance between the two projectile impact points is 100 ⁇ 10mm, the bullet speed is 940 ⁇ 10m/s, the incident angle is 0°, and the shooting distance is 15m.
- the bulletproof insert plate is composed of three layers of materials: a crack arresting layer, a ceramic panel, and an ultra-high molecular weight polyethylene energy-absorbing layer.
- the ceramic panel material is silicon carbide and is manufactured by a reaction sintering process. Its specific preparation method is as follows:
- Step 1) Mix silicon carbide powder and phenolic resin by ball milling (time: 15h), centrifugal atomization and granulation (inlet temperature 195°C, outlet temperature 90°C), in which the mass proportion of phenolic resin is 15%, and the mixed powder is pressed and formed. Finally, a silicon cake composed of metallic silicon powder as the main body is placed on the compact. In a vacuum environment, a silicon infiltration reaction is used to obtain a dense silicon carbide ceramic.
- the reaction sintering temperature is 1630°C and the sintering holding time is 2 hours; the resulting carbonization
- the main structural and performance indicators of silicon ceramics average grain size 54 ⁇ m, average Vickers hardness (GB/T 16534-2009) 22.0GPa, average compressive strength (GBT 4740-1999) 2110MPa, average fracture toughness (GB/T23806-2009 )2.75MPa ⁇ m 1/2 ;
- Step 2 Unfold and cut the ultra-high molecular weight polyethylene fiber (average molecular weight 3 million to 3.1 million) UD cloth, and place the cut ultra-high molecular weight polyethylene fiber UD cloth neatly on the mold of the heat press. Press and compound, the compounding conditions are 128°C, 25MPa, and the compounding time is 30 minutes.
- Step 3) Combine the crack arresting layer composed of aramid woven fabric (area density 0.4kg/m 2 ), the silicon carbide ceramic plate obtained in step 1) (area density 14.0kg/m 2 ), and the ultra-high Molecular weight polyethylene fiber energy-absorbing backsheets (area density 10.2kg/m 2 ) are laminated together through adhesive layers in sequence, and compounded at 128°C and 1.0MPa pressure to obtain a size of 260mm ⁇ 325mm and an area density of 24.8kg/m 2 bulletproof inserts.
- aramid woven fabric area density 0.4kg/m 2
- the silicon carbide ceramic plate obtained in step 1) area density 14.0kg/m 2
- the ultra-high Molecular weight polyethylene fiber energy-absorbing backsheets area density 10.2kg/m 2
- the above-mentioned bulletproof insert plates (six pieces) were tested in accordance with the "GA141-2010 Police Body Armor" standard.
- the appropriate parts of the upper left, lower right, lower left and upper right parts of each insert plate were used to defend against one DBP95 type 5.8mm (steel core) ) bullet, specific test conditions: the distance between the impact point of the bullet and the edge of the insert plate is not less than 50mm, the distance between the two impact points is 100 ⁇ 10mm, the bullet speed is 940 ⁇ 10m/s, the incident angle is 0°, and the shooting distance is 15m.
- the above-mentioned target test two of each of the six plates were penetrated by one shot.
- the back convexity value of the unpenetrated impact point was 24.2 to 33.1mm, with an average of 27.9mm.
- the bulletproof insert plate is composed of four layers of materials, including a crack arrester layer, a ceramic panel, an aramid fiber board, and an ultra-high molecular weight polyethylene energy-absorbing layer.
- the ceramic panel material is boron carbide and is manufactured by a hot-pressing sintering process. Its specific preparation method is as follows:
- Step 1) Mix boron carbide powder and molding agent by ball milling (time: 12h), centrifugal atomization and granulation (inlet temperature 185°C, outlet temperature 80°C). The mass proportion of molding agent is 2%. After the mixed powder is pressed and formed, In a vacuum environment, boron carbide ceramic panels were prepared by hot-pressing sintering. The hot-pressing sintering temperature was 1980°C, the pressure was 30MPa, and the holding time was 1 hour.
- the main structural and performance indicators of the obtained boron carbide ceramics were: average grain size 50 ⁇ m, average Vickers hardness (GB/T 16534-2009) 32.0GPa, average compressive strength (GBT 4740-1999) 3010MPa, average fracture toughness (GB/T23806-2009) 3.25MPa ⁇ m 1/2 ;
- Step 2) Unfold and cut the aramid UD cloth and place it neatly on the mold of the hot press for pressing and compounding.
- the compounding conditions are 128°C, 25MPa, and the compounding time is 10 minutes.
- Step 3 Unfold and cut the ultra-high molecular weight polyethylene fiber (average molecular weight 3 million to 3.1 million) UD cloth, and place the cut ultra-high molecular weight polyethylene fiber UD cloth neatly on the mold of the heat press. Pressing and compounding, the compounding conditions are 128°C, 25MPa, and the compounding time is 25min.
- Step 4) Combine the crack arresting layer composed of aramid woven fabric (area density 0.8kg/m 2 ), the boron carbide ceramic plate obtained in step 1) (area density 12.2kg/m 2 ), and the aramid fiber obtained in step 2)
- the support layer (area density 1.8kg/m 2 ) and the energy-absorbing backboard (area density 9.8kg/m 2 ) composed of the ultra-high molecular weight polyethylene fiberboard obtained in step 3) are laminated together in sequence through an adhesive layer and heated at 128°C , compounded under a pressure of 1.0MPa to obtain a bulletproof insert plate with a size of 260mm ⁇ 325mm and an area density of 25kg/ m2 .
- the above-mentioned bulletproof insert plates (six pieces) were tested in accordance with the "GA141-2010 Police Body Armor" standard.
- the appropriate parts of the upper left, lower right, lower left and upper right parts of each insert plate were used to defend against one DBP95 type 5.8mm (steel core) ) bullet, specific test conditions: the distance between the impact point of the bullet and the edge of the insert plate is not less than 50mm, the distance between the two impact points is 100 ⁇ 10mm, the bullet speed is 940 ⁇ 10m/s, the incident angle is 0°, and the shooting distance is 15m.
- the distance between the impact point of the bullet and the edge of the insert plate is not less than 50mm
- the distance between the two impact points is 100 ⁇ 10mm
- the bullet speed is 940 ⁇ 10m/s
- the incident angle is 0°
- the shooting distance is 15m.
- one of the six boards was penetrated by two shots, and one board was penetrated by one shot; the back convexity value of the unpenet
- the bulletproof insert plate is composed of three layers of materials: a crack arresting layer, a ceramic panel, and an ultra-high molecular weight polyethylene energy-absorbing layer.
- the ceramic panel material is boron carbide and is manufactured by a pressureless sintering process. Its specific preparation method is as follows:
- Step 1) Ball mill and mix boron carbide powder and sintering aid powder (time: 16h), centrifugal atomization and granulation (inlet temperature 190°C, outlet temperature 95°C), where the sintering aid is a mixture of carbon and silicon carbide (1 : 2), the mass proportion of sintering aid is 12%, after the mixed powder is pressed and formed, it is sintered and kept at 1980°C for 2 hours;
- the main structural performance indicators of the obtained boron carbide ceramic are: average grain size 35 ⁇ m, average Vickers hardness (GB /T 16534-2009) 29.5GPa, average compressive strength (GBT 4740-1999) 2900MPa, average fracture toughness (GB/T23806-2009) 3.05MPa ⁇ m 1/2 ;
- Step 2 Unfold and cut the ultra-high molecular weight polyethylene fiber (average molecular weight 3 million to 3.1 million) UD cloth, and place the cut ultra-high molecular weight polyethylene fiber UD cloth neatly on the mold of the heat press. Pressing and compounding, the compounding conditions are 128°C, 25MPa, and the compounding time is 25min.
- Step 3) Combine the crack arresting layer composed of aramid woven fabric (area density 0.4kg/m 2 ), the boron carbide ceramic plate obtained in step 1) (area density 11.5kg/m 2 ), and the ultra-high Molecular weight polyethylene fiber energy-absorbing backsheets (area density 12.8kg/m 2 ) are laminated together through adhesive layers in sequence, and compounded under 128°C and 1.0MPa pressure to obtain a size of 260mm ⁇ 325mm and an area density of 24.9kg/m 2 bulletproof inserts.
- the above-mentioned bulletproof insert plates (six pieces) were tested in accordance with the "GA141-2010 Police Body Armor" standard. Each insert plate was used to defend against one DBP95 type 5.8mm (steel core) at the appropriate parts of the upper left, lower right, lower left and upper right parts of each insert plate. ) bullet, specific test conditions: the distance between the impact point of the bullet and the edge of the insert plate is not less than 50mm, the distance between the two impact points is 100 ⁇ 10mm, the bullet speed is 940 ⁇ 10m/s, the incident angle is 0°, and the shooting distance is 15m. In the above-mentioned target test, two of the six plates were penetrated by one shot each. The back convexity value of the unpenetrated impact point was 24.2 to 30.1mm, with an average of 27.0mm.
- the bulletproof insert plate is composed of three layers of materials: a crack arrester layer, a ceramic panel, and an ultra-high molecular weight polyethylene energy-absorbing layer.
- the ceramic panel material is a complex ceramic composed of silicon carbide and boron carbide, which is made by reaction sintering. Craft manufacturing. Its specific preparation method is as follows:
- Step 1) Mix boron carbide, silicon carbide powder and phenolic resin by ball milling (time: 20h), centrifugal atomization and granulation (inlet temperature 185°C, outlet temperature 90°C), where the mass ratio of boron carbide, silicon carbide, and phenolic resin is The ratio is 75:10:15.
- a silicon cake composed of metallic silicon powder as the main body is placed on the compact. In a vacuum environment, the silicon infiltration reaction is used to obtain dense silicon carbide ceramics.
- the reaction sintering temperature is 1580 °C, the sintering holding time is 2 hours; the main structural performance indicators of the obtained multiphase ceramics: average grain size 45 ⁇ m, average Vickers hardness (GB/T16534-2009) 25.2GPa, average compressive strength (GBT 4740-1999) 2600MPa , average fracture toughness (GB/T23806-2009) 3.25MPa ⁇ m 1/2 .
- Step 2 Unfold and cut the ultra-high molecular weight polyethylene fiber (average molecular weight 3 million to 3.1 million) UD cloth, and place the cut ultra-high molecular weight polyethylene fiber UD cloth neatly on the mold of the heat press. Pressing and compounding, the compounding conditions are 128°C, 25MPa, and the compounding time is 25min.
- Step 3) Combine the crack arresting layer composed of aramid woven fabric (area density 0.4kg/m 2 ), the composite ceramic panel obtained in step 1) (area density 14.2kg/m 2 ), and the ultra-high ceramic panel obtained in step 2) Molecular weight polyethylene fiber energy-absorbing backsheets (area density 10.2kg/m 2 ) are laminated together through adhesive layers in sequence, and compounded at 128°C and 1.0MPa pressure to obtain a size of 250mm ⁇ 300mm and an area density of 25.0kg/m 2 bulletproof inserts.
- the above-mentioned bulletproof insert plates (six pieces) were tested in accordance with the "GA141-2010 Police Body Armor" standard. Each insert plate was used to defend against one DBP95 type 5.8mm (steel core) at the appropriate parts of the upper left, lower right, lower left and upper right parts of each insert plate. ) bullet, specific test conditions: the distance between the impact point of the bullet and the edge of the insert plate is not less than 50mm, the distance between the two impact points is 100 ⁇ 10mm, the bullet speed is 940 ⁇ 10m/s, the incident angle is 0°, and the shooting distance is 15m. In the above-mentioned target test, three of the six boards were penetrated by one shot each. The back convexity value of the unpenetrated impact point was 24.2 to 29.1mm, with an average of 26.9mm.
- the bulletproof insert plate is composed of four layers of materials, including a crack arrester layer, a ceramic panel, an aramid fiber board, and an ultra-high molecular weight polyethylene energy-absorbing layer.
- the ceramic panel material is boron carbide and is manufactured by a hot-pressing sintering process. Its specific preparation method is as follows:
- Step 1) Mix boron carbide powder and phenolic resin by ball milling (time: 12h), centrifugal atomization and granulation (inlet temperature 185°C, outlet temperature 80°C). The mass proportion of phenolic resin is 2%.
- boron carbide ceramic panels were prepared by hot-pressing sintering. The hot-pressing sintering temperature was 2050°C, the pressure was 30MPa, and the holding time was 2 hours.
- the main structural and performance indicators of the obtained boron carbide ceramics were: average grain size 63 ⁇ m, dimension Hardness (GB/T 16534-2009) 29.5GPa, compressive strength (GBT 4740-1999) 2600MPa;
- Step 2) Unfold and cut the aramid UD cloth and place it neatly on the mold of the hot press for pressing and compounding.
- the compounding conditions are 128°C, 25MPa, and the compounding time is 10 minutes.
- Step 3 Unfold and cut the ultra-high molecular weight polyethylene fiber (average molecular weight 3 million to 3.1 million) UD cloth, and place the cut ultra-high molecular weight polyethylene fiber UD cloth neatly on the mold of the heat press. Pressing and compounding, the compounding conditions are 128°C, 25MPa, and the compounding time is 25min.
- Step 4) Combine the crack arresting layer composed of aramid woven fabric (area density 0.8kg/m 2 ), the boron carbide ceramic plate obtained in step 1) (area density 12.2kg/m 2 ), and the aramid fiber obtained in step 2)
- the support layer (area density 1.8kg/m 2 ) and the energy-absorbing backboard (area density 9.8kg/m 2 ) composed of the ultra-high molecular weight polyethylene fiberboard obtained in step 3) are laminated together in sequence through an adhesive layer and heated at 128°C , compounded under a pressure of 1.0MPa to obtain a bulletproof insert plate with a size of 260mm ⁇ 325mm and an area density of 25kg/ m2 .
- the above-mentioned bulletproof insert plates were tested in accordance with the "GA141-2010 police Body Armor" standard.
- the appropriate parts of the upper left, lower right, lower left and upper right parts of the insert plates were used to defend against one DBP95 5.8mm (steel core) bullet.
- Specific test conditions The distance between the impact point of the projectile and the edge of the insert plate is not less than 50mm, the distance between the two projectile impact points is 100 ⁇ 10mm, the bullet speed is 940 ⁇ 10m/s, the incident angle is 0°, and the shooting distance is 15m.
- Two identical target plates obtained by the above process were subjected to a target test.
- the invention discloses a method for preparing a multi-bullet-resistant ceramic, especially a bullet-resistant ceramic composed of silicon carbide, boron carbide or a composite of the two. It is characterized in that the ceramic has a coarse grain structure after being sintered at ultra-high temperature. It has high and more uniform hardness and compressive strength, and has high impact brittleness. It is a ceramic with specific metallographic structure and mechanical properties.
- the main mechanism of composite armor to resist bullet penetration is: the bullet-resistant ceramic panel uses its high hardness and high strength characteristics to exert bullet-breaking effect to fragment the invading bullet. In the process of continued penetration, the bullet interacts with the fragments generated by the ceramic fragmentation.
- the counter-grinding further consumes the mass and kinetic energy of the bullet; the bullet after penetrating the ceramic panel causes the fiber material of the back plate to shear and elongate, thereby consuming the remaining kinetic energy of the bullet and trapping the bullet fragments in the back plate, thereby preventing the bullet from Penetrate armor.
- the support material in the bulletproof back plate of the present invention has relatively high stiffness, which prevents the ceramic panel from excessive bending during bullet penetration and gives full play to the bullet-breaking effectiveness of the ceramic panel.
- increasing the grain size of the ceramic microstructure can improve the hardness and compressive strength of the ceramic.
- brittleness properties can also fully break the ceramic around the impact point, thereby increasing the consumption of the bullet's kinetic energy and mass, and also causing it to produce
- the angle (spacing) between multiple cracks is larger, so that the subsequent impact point has a greater probability of being in a complete ceramic position, thus improving its ability to resist penetration.
- the bulletproof insert plate made by combining this type of ceramics with an appropriate backing plate has low bulk density and high elastic resistance. It can be used as a human body protection insert plate to resist multiple rounds of small and medium-caliber bullets such as DBP95 type 5.8mm (steel core) bullets. Invasion.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- General Engineering & Computer Science (AREA)
- Aiming, Guidance, Guns With A Light Source, Armor, Camouflage, And Targets (AREA)
- Laminated Bodies (AREA)
- Ceramic Products (AREA)
Abstract
La présente invention concerne un procédé de fabrication d'une céramique présentant une aptitude aux impacts multiples et une plaque d'insertion pare-balles. La céramique est obtenue par frittage de carbure de silicium et/ou de carbure de bore, le procédé de frittage étant constitué par un ou plusieurs procédés parmi un frittage à haute température, un frittage par réaction, un frittage par pressage à chaud ou un frittage sans pression. La céramique présente une grosseur moyenne de grain de 200 à 380 µm, une dureté Vickers de 23,5 à 34 GPa et une résistance à la compression de 2200 à 3100 MPa. La plaque d'insertion pare-balles est obtenue par collage d'une couche d'arrêt de fissures (1), d'un panneau céramique pare-balles (2) et d'une plaque arrière d'absorption d'énergie (3), à partir de la surface vers l'intérieur. La plaque d'insertion pare-balles présente une densité de surface inférieure à 25 kg/m2, peut résister à l'impact de quatre balles DBP95 de 5,8 mm et toutes les déformations de face arrière sont inférieures à 25 mm. Sous l'hypothèse que la plaque d'insertion pare-balles n'est pas percée par une balle, la déformation de face arrière provoquée par la balle pénétrante est efficacement atténuée, ce qui permet de répondre aux diverses exigences pare-balles de plaques d'insertion de protection de nouvelle génération.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210554078.2 | 2022-05-19 | ||
CN202210554078.2A CN114933479B (zh) | 2022-05-19 | 2022-05-19 | 一种抗多发弹陶瓷的制备方法及防弹插板 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2023221297A1 true WO2023221297A1 (fr) | 2023-11-23 |
Family
ID=82864411
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2022/109161 WO2023221297A1 (fr) | 2022-05-19 | 2022-07-29 | Procédé de fabrication de céramique présentant une aptitude aux impacts multiples et plaque d'insertion pare-balles |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN114933479B (fr) |
WO (1) | WO2023221297A1 (fr) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115420146B (zh) * | 2022-09-16 | 2024-06-11 | 北京航天凯恩新材料有限公司 | 一种新型轻量化防弹插板防护结构及制备方法 |
CN117326871B (zh) * | 2023-12-01 | 2024-02-09 | 浙江吉成新材股份有限公司 | 一种碳化硼喷嘴及其制备方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106380199A (zh) * | 2016-08-31 | 2017-02-08 | 浙江立泰复合材料股份有限公司 | 纤维增加碳化硅陶瓷防弹板的制作方法 |
CN112592184A (zh) * | 2020-12-23 | 2021-04-02 | 宁波伏尔肯科技股份有限公司 | 一种超轻质碳化硼防弹陶瓷及其制备方法和应用 |
CN113277863A (zh) * | 2021-06-18 | 2021-08-20 | 衡阳凯新特种材料科技有限公司 | 陶瓷复合材料及其制备方法、防弹板及装甲防护装备 |
CN113587728A (zh) * | 2021-07-30 | 2021-11-02 | 浙江吉成新材股份有限公司 | 一种抗多弹多曲面碳化硼防弹插板及其制备方法 |
CN114656277A (zh) * | 2022-03-17 | 2022-06-24 | 南通三责精密陶瓷有限公司 | 一种环保型无压烧结碳化硼陶瓷材料的制造方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105541336A (zh) * | 2015-12-28 | 2016-05-04 | 中国人民解放军总后勤部军需装备研究所 | 一种碳化硼/碳化硅陶瓷整板及其制备方法与应用 |
CN105503192A (zh) * | 2015-12-30 | 2016-04-20 | 山东大学 | 一种注射成型反应烧结B4C/SiC复合陶瓷材料及其制备方法 |
CN105601280A (zh) * | 2016-01-19 | 2016-05-25 | 山东宝纳新材料有限公司 | 一种低成本轻质高防弹性能B4C/SiC复合陶瓷防弹板及制备方法 |
CN206269673U (zh) * | 2016-11-14 | 2017-06-20 | 江苏中益特种纤维有限公司 | 防弹插板 |
CN108467272A (zh) * | 2018-03-21 | 2018-08-31 | 浙江立泰复合材料股份有限公司 | 一种碳化硼/碳化硅层状复合陶瓷材料的制备方法 |
CN109180192A (zh) * | 2018-10-29 | 2019-01-11 | 山东宝纳新材料有限公司 | 碳化硅复合陶瓷的制备方法、其制得的碳化硅复合陶瓷和应用以及陶瓷制品 |
KR102255465B1 (ko) * | 2019-03-20 | 2021-05-24 | 국방과학연구소 | 붕소화지르코늄이 포함된 탄화규소 방탄 세라믹 및 이의 제조방법 |
CN113698215B (zh) * | 2020-05-20 | 2022-10-11 | 中国科学院金属研究所 | 一种致密的层状碳化硅陶瓷及其制备方法 |
CN215064067U (zh) * | 2021-04-02 | 2021-12-07 | 中航装甲科技有限公司 | 一种多曲面复合陶瓷防弹插板 |
-
2022
- 2022-05-19 CN CN202210554078.2A patent/CN114933479B/zh active Active
- 2022-07-29 WO PCT/CN2022/109161 patent/WO2023221297A1/fr unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106380199A (zh) * | 2016-08-31 | 2017-02-08 | 浙江立泰复合材料股份有限公司 | 纤维增加碳化硅陶瓷防弹板的制作方法 |
CN112592184A (zh) * | 2020-12-23 | 2021-04-02 | 宁波伏尔肯科技股份有限公司 | 一种超轻质碳化硼防弹陶瓷及其制备方法和应用 |
CN113277863A (zh) * | 2021-06-18 | 2021-08-20 | 衡阳凯新特种材料科技有限公司 | 陶瓷复合材料及其制备方法、防弹板及装甲防护装备 |
CN113587728A (zh) * | 2021-07-30 | 2021-11-02 | 浙江吉成新材股份有限公司 | 一种抗多弹多曲面碳化硼防弹插板及其制备方法 |
CN114656277A (zh) * | 2022-03-17 | 2022-06-24 | 南通三责精密陶瓷有限公司 | 一种环保型无压烧结碳化硼陶瓷材料的制造方法 |
Also Published As
Publication number | Publication date |
---|---|
CN114933479A (zh) | 2022-08-23 |
CN114933479B (zh) | 2023-10-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2023221297A1 (fr) | Procédé de fabrication de céramique présentant une aptitude aux impacts multiples et plaque d'insertion pare-balles | |
US6389594B1 (en) | Anti-ballistic ceramic articles | |
CN111319318B (zh) | 防弹复合装甲及其制备方法 | |
WO2020107674A1 (fr) | Élément pare-balles multicouche, procédé de préparation associé et application associée | |
US11441876B2 (en) | Multilayered bullet resistant member, preparation method and application thereof | |
CN210180282U (zh) | 一种强约束碳化硼陶瓷复合装甲 | |
CN205138327U (zh) | 一种复合结构防弹板 | |
CN113587728B (zh) | 一种抗多弹多曲面碳化硼防弹插板及其制备方法 | |
CN105444622A (zh) | 一种复合结构防弹板及其制造方法 | |
Medvedovski | Lightweight ceramic composite armour system | |
CN111805983A (zh) | 一种防弹单元及其制造工艺 | |
CN115406307A (zh) | 一种基于氧化物长丝增强陶瓷复合材料的防弹插板及制备方法 | |
CN111272016A (zh) | 防弹复合装甲及其制备方法 | |
CN115388711B (zh) | 一种轻质复合材料防弹板及其制备方法 | |
CN111006547B (zh) | 一种含透明气凝胶的轻质防弹装甲复合结构 | |
CN110006291A (zh) | 高抗冲击玄武岩复合防弹板 | |
CN210533184U (zh) | 一种基于抗弹陶瓷片的防弹插板结构 | |
CN115127398A (zh) | 基于高韧性异质界面层的轻质防弹抗爆多相复合装甲材料 | |
CN110542350B (zh) | 一种防弹衣甲片及其制备方法 | |
CN108395251B (zh) | 一种整体式碳化硅木质陶瓷防弹面板的制备方法 | |
EP1288607A1 (fr) | Articles céramiques anti-ballistiques | |
CN208887480U (zh) | 玄武岩复合防弹板 | |
CN217210577U (zh) | 防弹装甲结构 | |
CN115233066B (zh) | 一种陶瓷材料及其制备方法和应用 | |
CN114963874B (zh) | 一种复合防弹插板及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22942328 Country of ref document: EP Kind code of ref document: A1 |