CN108463444A - 提供无机聚合物陶瓷样材料的方法 - Google Patents
提供无机聚合物陶瓷样材料的方法 Download PDFInfo
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- CN108463444A CN108463444A CN201680073304.8A CN201680073304A CN108463444A CN 108463444 A CN108463444 A CN 108463444A CN 201680073304 A CN201680073304 A CN 201680073304A CN 108463444 A CN108463444 A CN 108463444A
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- oxide ceramics
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- 239000000463 material Substances 0.000 title claims abstract description 37
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- 239000011225 non-oxide ceramic Substances 0.000 claims abstract description 12
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- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910003481 amorphous carbon Inorganic materials 0.000 claims 1
- 229920006125 amorphous polymer Polymers 0.000 claims 1
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- 239000011777 magnesium Substances 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 11
- 239000012190 activator Substances 0.000 description 10
- 239000004115 Sodium Silicate Substances 0.000 description 9
- 239000010881 fly ash Substances 0.000 description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 8
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- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 7
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 7
- 229910052911 sodium silicate Inorganic materials 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
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- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
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- 125000002091 cationic group Chemical group 0.000 description 2
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
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- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910018516 Al—O Inorganic materials 0.000 description 1
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- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229910007857 Li-Al Inorganic materials 0.000 description 1
- 229910008447 Li—Al Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
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- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- IUHFWCGCSVTMPG-UHFFFAOYSA-N [C].[C] Chemical class [C].[C] IUHFWCGCSVTMPG-UHFFFAOYSA-N 0.000 description 1
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 1
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- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
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- 239000003637 basic solution Substances 0.000 description 1
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- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
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- 238000004132 cross linking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
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- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
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- 239000004005 microsphere Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
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- 230000009972 noncorrosive effect Effects 0.000 description 1
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- 238000005453 pelletization Methods 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
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- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003797 solvolysis reaction Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
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- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
- C04B28/26—Silicates of the alkali metals
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/003—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hybrid binders other than those of the polycarboxylate type
-
- 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
-
- 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
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/14—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silica
-
- 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
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
- C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
-
- C—CHEMISTRY; METALLURGY
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Abstract
一种提供无机聚合物陶瓷样材料的方法。该方法包括：提供包含至少一种非氧化物陶瓷粉末和至少一种金属氧化物的第一材料，并且提供包含由碱性水和溶剂构成的苛性浆料的第二材料，以及用搅拌将材料结合。还提供了由上述方法提供的物质组合物，该组合物是包含金属氧化物和非氧化物陶瓷结合的化学结合的陶瓷聚合物。
Description
以下是说明书。
发明背景
硅酸钠结合的非氧化物陶瓷粉末为人所知已有超过100年。已经将通过硅酸钠结合的研磨材料以及随后的热定型铸造成坚硬、坚韧、牢固的磨轮(US 1,555,119)。
已将具有SiC、BC和TiC的涂层与包括硅酸钠、SiOx、BrOx、五氧化二磷的无机聚合物结合(EP 1,340,735)。在50和1400℃之间的温度，由硅酸钠结合的无机陶瓷粉末作为涂层也是已知的(US 3,404,031)。
与“填料”如偏高岭土反应以粘合陶瓷粉末的硅酸钠是已知的。(US 8,480,801)。借助水玻璃(其充当粘合剂)粘合陶瓷粉末来制造这种固化陶瓷体。在制造这种固化陶瓷体中，将水玻璃与填料如偏高岭土混合，并且填料中的金属离子溶解并与水玻璃反应。因此构成水玻璃的硅酸钠交联从而变成无机聚合物。然后，脱水-缩合反应与水蒸发一起进行，这导致固化的陶瓷体。
US 7,097,679教导了一种研磨材料，其包含至少一种选自氧化铝、碳化硅、立方氮化硼和金刚石的研磨晶粒。该研磨晶粒具有无机或有机粘合剂的涂层以及包含碳酸锂和硫酸锰的混合物的磨料填充材料。美国专利US 7,094,285教导了无机聚合物基质组合物、粘合剂组合物或泡沫组合物，其包含：碱金属硅酸盐的反应产物、一种或多种非硅酸盐含氧阴离子化合物或反应性酸性玻璃或其组合；水；以及包含纤维、织物或微球或其组合的强化介质；以及任选地一种或多种添加剂；以及任选地一个或多个网络改性剂。
美国专利US 6,969,422教导了一种无机基质组合物，其包含：源于碱金属氢氧化物或氧化物和氧化硅源的碱金属硅酸盐和/或碱金属硅酸盐前体的反应产物、反应性玻璃、水以及任选的粘土和/或氧化物填料。
所利用的碱金属硅酸盐可以包括宽范围的氧化硅/碱金属氧化物(SiO2/A2O)比率和固体百分比水平。这样的溶液可以从商业来源购得或者可以在使用之前由前体(如氧化硅源和碱金属氢氧化物、碱金属氧化物或碳酸盐或其组合)立即制备。碱金属硅酸盐可源于碱金属碱(如氢氧化钾或氢氧化钠)，源于苛性钾或苏打灰和氧化硅源。
其它复合材料包括金属基质复合材料(MMC)、陶瓷基质复合材料(CMC)、碳-碳复合材料以及其它无机基质复合材料。复合基质可以是100％无机的，或者它可以含有一些有机成分。无机基质网络包括陶瓷、硅酸盐、玻璃、硅酸铝、碱金属铝硅酸盐、硅酸钾、硅酸钠、碳化硅、氮化硅、氧化铝、水泥基材料、金属、金属合金或本领域技术人员已知的其它基质材料。
基质组合物可以包括本领域技术人员通常使用的多种有机和无机填料。基质可以包括填料材料如陶瓷粉末、矿物粉末、碳化硅、氮化硅、碳、碳黑、钼及其化合物、硅酸盐、硅酸铝、铝硅酸钠、铝硅酸钾或其它无机填料。
发明内容
因此，本文公开并请求保护一种提供无机聚合物陶瓷样(ceramic-like)材料的方法。该方法包括：提供第一材料，该第一材料包含至少一种非氧化物陶瓷粉末和至少一种金属氧化物；和提供第二材料，该第二材料包含由碱性水和溶剂构成的苛性浆料；以及利用搅拌将材料结合。
在另一实施方案中，存在由上述方法提供的物质组合物，所述组合物是包含金属氧化物和非氧化物陶瓷结合的化学结合陶瓷聚合物。
该陶瓷在150℃以下化学固化，极少乃至没有收缩。金属氧化物的化学结合的陶瓷如地聚合物(geopolymer)是已知的。化学结合的非氧化物陶瓷如磷酸镁是已知的。用非反应性非氧化物陶瓷填充的金属氧化物聚合物也是已知的。然而在同一聚合物骨架中具有结合的氧化物和非氧化物的聚合物的混合系统是新颖的。
发明详述
已经发现一族含有混合氧化物和非氧化物金属结合的先进无机/有机混杂复合聚合物陶瓷。可以将这些聚合物材料悦耳地描述为热固性陶瓷。该材料将技术陶瓷的强度、硬度和高温性能与聚合物的强度、延展性、抗热冲击性、密度和容易加工相结合。聚合物材料的独特化学结构提供了定制的强度性质、硬度、韧性和磨损性能。
还已经发现了一类涂覆零件的材料和方法，以形成受控的孔隙率、热传导、发射率、表面硬度、柔性、韧性、延伸率、电传导、密度、电磁性能。
由于陶瓷材料性质的高度可定制性，其与功能性添加剂的相容性，制造的容易性和高的强度与重量比，存在许多其可用于的应用。可以定制化学结合的陶瓷配制物以便提供不仅在其形状方面是应用调整的而且在其物理化学性质方面也是应用调整的系统部件。除了在由材料本身制造零件和部件方面的陶瓷多功能性(versatility)之外，该材料还具有供用于涂料工业中的一些应用。化学惰性和该材料的达3400℉的温度耐受性允许将其用于涂覆有色金属和铁系金属以及金属合金。由于其在高温下的高尺寸稳定性以及低的反应性，该材料可允许颠覆性创新，允许将钢制造为不腐蚀、低摩擦、低的电和热传导。该材料的可调整的热导率特别令人感兴趣。
该化学结合的陶瓷具有若干显而易见尺度的吸引力：
·其组合物可以由可用的精制原料构成，并且可以任选地包括各种数量的美国来源的技术等级的后工业废物流材料，从而抵消了大宗材料成本并且降低了配制物的环境影响。
·其不含甲醛、VOC或重金属，因而减轻人员安全风险。
·其潜在地适合基于3D印刷的快速原型设计和制造方法；应用包括零件和模具的快速生产。
·当用作模具时，可以将HCPC材料在凝胶状态下快速地加工，从而使机加工时间和人工费用最小化。
·如果用作模具，它的高温稳定性和热导率允许铸造金属以及进而热固性材料/塑料的快速脱模时间。
·可使用相同模具来铸造多种材料类型，包括Li-Al合金、钢、以及有机聚合物。
·公开了一种生产新类别的无机聚合物陶瓷样材料的新方法。该聚合物是金属氧化物和非氧化物陶瓷的混合物。该聚合物可用作模具加工、涂料、泡沫和具有陶瓷样性质的宽广范围的产品。该聚合物可以被喷涂、浇铸、碾磨、印刷或它们的组合。
可以用添加剂调整功能性，以便调整韧性、强度、硬度、热导率、发射率外观等。该聚合物可以是均匀的或非均匀的，具有不同的硬度、韧性、强度、磨损或传导性能。
·树脂要求至少Si-C-C。本发明具有仅一个Si-C，或者如此将其理论化。根据本发明的可固化树脂组合物可以进一步包括无机填料。无机填料例如但不限于：纳米氧化硅、纳米氧化钛、纳米氧化锆、碳纳米管、氧化硅、氧化铝、云母、合成云母、滑石、氧化钙、碳酸钙、氧化锆、氧化钛、钛酸钡、高岭土、膨润土、硅藻土、氮化硼、氮化铝、碳化硅。
·所公开的本发明在其基本物质组成和可能更显著在其合成机理方面相对于目前的现有技术是独特的。获得所公开材料的反应途径通过如下方式进行：首先将无定形硅、氧化铝、碳和碱金属(LiOH)溶解在与一种或多种极性非质子或质子溶剂共同溶剂化的碱性溶液中。由于自由不稳定阴离子网络形成元素(Al、Si、O、C)的阳离子稳定化而实现的硅醇缩合，该溶液硬化成凝胶态。该凝胶态的物理性质和在其之前紧接的状态主要是二价阳离子：一价阳离子对网络形成元素(Al、Si、O、C)的相对浓度的函数。该凝胶在数分钟到数个月之间是稳定的，其后它将经历脱水介导的收缩和破裂。然后该凝胶态在各种压力下在提高的温度和湿度下经受固化，这由各种pH水和溶剂组成。在该固化期间，随着凝胶系统的溶剂分解恢复系统的碱度，系统的反应性增加，从而较大或较小程度地再次溶解硅醇缩合产物，并且介导网络形成元素(Al、Si、O、C)的完全无定形结构形成。系统的附加热克服了妨碍网络形成反应在先发生的吸热屏障。Al和Si通过如下结合：经由水解(其消耗凝胶的碱度)产生的桥氧，以及C-Si，
·形成Si-C-Si键以及可能亚稳态的Al-C键。该反应的基本单体可以是O、Al、C和Si的任何变体，例如Al-O-Si-C-Si-O-Al-O。更多的单阳离子物质将导致更聚合且通常更弱的结构，而二价阳离子物质(优选地Li)用于产生更大程度的交联。Ca++和Mg++是较不优选的，这是由于Ca++和Mg++快速形成水合物的倾向，所述水合物通常不会再次溶解在反应的第二相中。
实施例
如图1中所示，将聚合材料加工成与环氧树脂相似的反应性两部分材料。在制造过程期间，所混合的材料可以具有500到25,000cPS的粘度。对于喷涂薄膜而言，较低粘度更好。对于将零件铸造成形而言，中等粘度是最好的，而较高粘度适合于挤出或粒化。喷涂技术可包括空气喷涂、无空气喷涂、电喷涂、旋转锥喷涂和超声波喷涂。
当“凝胶态”零件暴露于160-250℉的温度持续2-6小时的时候，发生最终的固化反应。较长的固化时间产生较强的材料。这使聚合物固化至先进的陶瓷样状态。收缩是在小于.01％的范围内，这允许非常精细的公差。分子平滑的表面允许低成本高性能、快速、复杂的零件制造，具有优异的表面质地。该质地可以是光滑和高光泽的或者可以根据需要制造亚光(matt)。该先进的混杂物是关键和策略性涂层的合适替代物。
实施例1
包括以下的固体组分：
170g飞灰
80g碳化硅
包括以下的液体组分：
8.5g甲醇
23.9氢氧化钠
0.4乙二醇
4.6g硼砂
3.3g 37％福尔马林
95.1 8g 40％硅酸钠溶液。
4.2g水
将固体组分混入液体组分中以制造充分混合的浆料。把浆料倒入模型中并允许其形成水凝胶持续2小时。移除该模型并且将固体水凝胶置于聚乙烯袋中，密封并在80℃下固化12小时。将固化的陶瓷从袋中移出。
实施例2
与在87℃(std1,std2)和107℃(std1高温，std2高温)固化而没有添加剂的相同的2批配制物相比，非氧化物添加剂的抗弯强度数据。对于这些实施例，将活化剂与干燥组分混合成浆料并浇铸成棒状。如每个实施例中所示，将该浆料在87℃或107℃固化24小时。使用ASTM C 1341生成挠曲数据。
B4C-110：135g活化剂，175g飞灰，2g聚甲基丙烯酸甲酯钠(sodium polymethylmethacrylate)，110g碳化硼
B4C-63：135g活化剂，175g飞灰，2g聚甲基丙烯酸甲酯钠，63g碳化硼
B4C-93：135g活化剂，175g飞灰，2g聚甲基丙烯酸甲酯钠，93g碳化硼
Eut：135g活化剂，175g飞灰，2g聚甲基丙烯酸甲酯钠，27g SiC，83g碳化硼
SiC-120：135g活化剂，175g飞灰，2g聚甲基丙烯酸甲酯钠，120g碳化硼
SiC-201：135g活化剂，175g飞灰，2g聚甲基丙烯酸甲酯钠，201g碳化硼
SiC-80：135g活化剂，175g飞灰，2g聚甲基丙烯酸甲酯钠，80g碳化硼
Std1或Std 2：135g活化剂，175g飞灰
活化剂溶液
7g甲醇
20g氢氧化钾
1.8g乙二醇
3.6g硼砂
3.4g福尔马林
99.2g 40％硅酸钠溶液
Claims (9)
1.一种物质组合物，包括：
a.非氧化物陶瓷
b.选自以下的聚合物：
i.无定形聚合物，以及，
ii.微晶聚合物，
每种聚合物具有基本上由铝、硅、碳和氧组成的骨架结构。
2.如权利要求1中所述的组合物，其中所述非氧化物陶瓷共价结合到聚合物骨架。
3.一种提供无机聚合物陶瓷样材料的方法，所述方法包括：
A.提供第一材料，该第一材料包含至少一种非氧化物陶瓷粉末和至少一种金属氧化物；
B.提供第二材料，该第二材料包含由碱性水和溶剂构成的苛性浆料；
C.将A和B结合，并搅拌。
4.如权利要求3中所述的方法，其中另外存在引起内部放热反应以使材料固化的材料。
5.一种产品，其由权利要求4的方法生产。
6.如权利要求4中所述的方法，其中所述至少一种非氧化物陶瓷粉末选自基本上由以下构成的组：SiC、SiN、TiN、BC、WC和BN。
7.如权利要求3中所述的方法，其中所述至少一种金属氧化物选自氧化铝、氧化硅、氧化镁、氧化锂和氧化钙。
8.如权利要求3中所述的方法，其中所述溶剂选自基本上由以下构成的组：甲醇、乙醇和反应性无定形碳。
9.如权利要求3中所述的方法，其中另外存在选自填料和纤维的其它材料。
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| US20180371119A1 (en) | 2018-12-27 |
| EP3371124A1 (en) | 2018-09-12 |
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