CN102459119A - 具有增强耐水性的基于硫酸钙的产品 - Google Patents
具有增强耐水性的基于硫酸钙的产品 Download PDFInfo
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- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 title claims abstract description 59
- 235000011132 calcium sulphate Nutrition 0.000 title abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 16
- 239000001175 calcium sulphate Substances 0.000 title abstract 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 16
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 18
- 235000011007 phosphoric acid Nutrition 0.000 claims description 15
- 229940085991 phosphate ion Drugs 0.000 claims description 13
- 150000003016 phosphoric acids Chemical class 0.000 claims description 9
- -1 aluminum ion Chemical class 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 6
- 239000002562 thickening agent Substances 0.000 claims description 5
- 230000001464 adherent effect Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 159000000013 aluminium salts Chemical group 0.000 claims 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims 1
- GJYLKIZKRHDRER-UHFFFAOYSA-N calcium;sulfuric acid Chemical compound [Ca].OS(O)(=O)=O GJYLKIZKRHDRER-UHFFFAOYSA-N 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 abstract description 9
- 239000010452 phosphate Substances 0.000 abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 5
- 239000004411 aluminium Substances 0.000 abstract description 4
- 229910052925 anhydrite Inorganic materials 0.000 abstract 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 28
- 239000011505 plaster Substances 0.000 description 21
- 239000004575 stone Substances 0.000 description 20
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 8
- 238000007906 compression Methods 0.000 description 8
- 230000006835 compression Effects 0.000 description 8
- 239000011507 gypsum plaster Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 239000004568 cement Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
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- 239000000203 mixture Substances 0.000 description 3
- 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 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002512 suppressor factor Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229940001007 aluminium phosphate Drugs 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 229940031815 mycocide Drugs 0.000 description 1
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- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/025—Calcium sulfates
-
- 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
- C04B11/00—Calcium sulfate cements
- C04B11/05—Calcium sulfate cements obtaining anhydrite, e.g. Keene's cement
-
- 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
- C04B28/14—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 calcium sulfate cements
- C04B28/16—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 calcium sulfate cements containing anhydrite, e.g. Keene's cement
-
- 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
- C04B28/34—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 cold phosphate binders
- C04B28/346—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 cold phosphate binders the phosphate binder being present in the starting composition as a mixture of free acid and one or more phosphates
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- 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
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5007—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with salts or salty compositions, e.g. for salt glazing
- C04B41/5015—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with salts or salty compositions, e.g. for salt glazing containing phosphorus in the anion, e.g. phosphates
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
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Abstract
基于硫酸钙的耐水体,其包含结晶硫酸钙无水石膏基体,所述基体的晶体通过耐水磷酸盐粘合区而彼此相连,所述粘合区任选地还含有铝。所述耐水体可通过如下生产:用磷酸根离子源(任选地含有铝)浸渍多孔硫酸钙,然后煅烧。或者,对包含硫酸钙和磷酸根离子源(任选地含有铝)的糊料加热和压制以形成“生坯”,然后,煅烧以制备所述耐水体。
Description
本发明涉及具有增强耐水性的基于硫酸钙的产品及其制备方法。
生石膏(gypsum)(即,二水合硫酸钙)通常不被认为是能够用于室外环境或者用于可能有持续水接触的其它应用的材料。这是由于生石膏的溶解性以及在多晶基体中晶体之间缺乏化学粘合。
对具有改善的与水长时间接触后的抗压强度的基于硫酸钙的耐水体有持续的需求。
因此,根据本发明,提供了基于硫酸钙的耐水体,其包含硫酸钙无水石膏的多晶基体,所述基体的晶体通过耐水磷酸盐粘合区而彼此相连。所述基体和粘合区是连续的(即,基本上没有间断或孔隙),类似于陶瓷,而非不连续的(不连续的基体更类似于常规的再水合生石膏)。粘合区基本上是对水不敏感的且包含多磷酸盐形式的磷酸盐。
尤其优选的是:粘合区基本由非结晶磷酸盐组成,或者包含无水磷铝酸盐,这将在下面的说明中更详细地描述。
磷酸和磷酸盐已知用于硫酸钙配制物,例如,根据JP52114495(OnadaCement Co Ltd)、JP4016537(Dai-ichi Cement Co Ltd)和WO2006/134670,但是,磷酸和磷酸盐并不用于提供粘合区以及由此得到的耐水性。
根据本发明使用的硫酸钙无水石膏基体优选基本上不含半水合硫酸钙。
相比于常规生石膏制品,根据本发明的耐水体还可具有更高的硬度、耐火性、更低的溶解性以及更高的湿强度。
根据本发明的耐水体优选基本不含水泥,因为不需要水泥来将基体粘合在一起。如前所述,该功能通过根据本发明的耐水体中存在的磷酸盐粘合区实现。
本发明进一步包括制备硫酸钙耐水体的方法,其中,用磷酸根离子浸渍多孔硫酸钙物体并进行煅烧以制备包含由耐水磷酸盐粘合的多孔结晶硫酸钙无水石膏的耐水体。
所煅烧的多孔硫酸钙可为例如用磷酸根离子源浸渍过的基本干燥的多孔硫酸钙材料(如无水石膏或水合物)的形式。
所述基本干燥的多孔硫酸钙可例如由用磷酸根离子源浸渍过的硫酸钙的糊料形成,所述糊料在烧制前被压制形成生坯。
或者,基于生石膏的耐水体可通过这样的方法制备,在该方法中,对包含硫酸钙和磷酸根离子源的糊料加热或压制以形成“生坯”,然后,进行煅烧以制备包含由耐水磷酸盐粘合的多孔结晶硫酸钙无水石膏的耐水体。如果起始材料为硫酸钙无水石膏,则需要压制以形成生坯,因为加热不会产生相变。
用磷酸根离子浸渍过的生坯或随后将用磷酸根离子浸渍的耐水体的煅烧可在至少400℃、更优选至少500℃,但优选不超过600℃的温度下进行。煅烧应使所得耐水体基本不含硫酸钙半水合物,否则,硫酸钙半水合物将对性能产生不利影响。
根据本发明尤其优选的是:在对生坯进行压制和对经压制的耐水体进行煅烧之前,用磷酸根离子浸渍生坯,因为这可产生具有低于5重量%吸水率的耐水体,使得其适用于室外以及承重的应用。
在本发明方法的任一变型中,优选的是,基于硫酸钙的量,磷酸根离子以20-50摩尔%的量使用。
磷酸(即,式H3PO4的正磷酸)是优选的磷酸根离子源;其它这样的源包括焦磷酸(具有式H4P2O7)以及这些酸的盐,所述盐优选保留了游离酸基团。磷酸根离子源中存在的任何阳离子均应当是无害的或者(优选地)对所得耐水体的所需性能是有利的。
尤其优选的是:磷酸根离子源进一步包含含铝的离子作为这样的有利离子,在这样的情况下,粘合区包含如上所述的磷铝酸盐。含铝的离子可例如作为正磷酸铝提供。
磷铝酸盐粘结剂已经描述于例如L-Y Hong等人的“Development ofCr-free aluminium phosphate binders and their composite applications”(Composite Science and Technology,67(2007),第1195-1201页)中。该文章没有公开或者暗示磷铝酸盐粘结剂用于基于硫酸钙的耐水体。
用于根据本发明的方法的示例性的无害阳离子包括钠,典型地作为正磷酸单钠或正磷酸二钠提供。
干的多孔硫酸钙无水石膏可根据本发明用磷酸根离子源浸渍,然后干燥。或者,干的多孔硫酸钙无水石膏可通过如下制得:对通过将熟石膏(plaster)与含有磷酸根离子源的水混合而获得的湿多孔生石膏进行干燥和煅烧。
当使用干多孔生石膏时,其可通过对通过将熟石膏与水混合而获得的湿多孔生石膏进行干燥而制备。
在根据本发明的方法的优选实施方案中,将要煅烧的多孔硫酸钙无水石膏可为通过如下方式制备的湿多孔“生坯”的形式:典型地在密封容器或高压釜中,加热用磷酸根离子源处理过的生石膏的预成型混合料。这样的混合料可包括已含有磷酸根离子的生石膏废料流。
当在根据本发明的方法中使用硫酸钙无水石膏时,其可例如为无水石膏II或无水石膏III。当使用无水石膏II时,其可按照附图的图7中所示的方案1和3使用,而当使用无水石膏III时,其可按照附图的图7中所示的方案2使用。
根据本发明的耐水体可进一步包含已知用于生石膏的通常类型的添加剂,例如填料(如二氧化硅)或催化剂。
根据本发明的耐水体优选为凝固的熟石膏体,如成型制品、块或板。当所述耐水体为成型制品时,其可例如为用于生物环境的制品(即,所述耐水体可为生物陶瓷)。当所述耐水体为块时,其可例如为砖、瓦、或适于室外使用的其它承重构件的形式。
当所述耐水体为板(例如生石膏板)时,其可具有或不具有表面增强物或衬里片;当表面增强物用于板时,所述板可例如具有纤维稀松布(如玻璃纤维)或纤维网状物。根据本发明的板可为承重的且可适于室外使用。
当需要时,本发明的生石膏物体中可存在其它的无害材料、助剂和成分。这样的无害材料的实例包括任选的进一步成分,如交联剂、疏水剂(如有机硅或反应性硅烷)、淀粉、增强纤维、促凝剂和缓凝剂、超增塑剂、形变抑制剂(如防流挂剂)、防缩添加剂、再煅烧抑制剂、泡沫稳定剂、杀细菌剂、杀真菌剂、pH调节剂、着色剂、阻燃剂和填料(如粒状的矿物材料或塑料,在一些实施方案中,其可为膨胀的形式)。
附图说明
参照附图,仅以实例的方式说明本发明的某些优点和特征,其中:
图1示出了本发明第一耐水体的切片在2500倍放大率的扫描电子显微照片;
图2a和2b示出了本发明第二耐水体的切片分别在1000倍和10000倍放大率的扫描电子显微照片;
图3-6为分别示出了本发明耐水体的性质的图,所述图分别相对于纵坐标-抗压峰值应力(单位为MPa)和横坐标-密度(单位为kg/m3)绘制;和
图7示意性地示出了本发明耐水体的三种制造方案。其中,方案1是最不优选的,这是因为(如前所述)不太优选在用磷酸根离子浸渍硫酸钙之前对硫酸钙进行煅烧。
在图3和4中,所示出的误差棒相当于1单位的标准偏差。
图1示出了根据图7的方案1、使用5M正磷酸制备的耐水体的显微照片,图2a和2b示出了根据图7的方案2、使用7.5M正磷酸制备的耐水体的显微照片。(在以下实施例1中对其进行更详细的描述)。
以下加工实施例仅为了说明的目的给出。
实施例1
用手将重100g的Saint-Gobain的α配方熟石膏与100g去离子水(水∶熟石膏之比设为1∶1)混合1分钟,然后,倒入硅橡胶模具中。在单一批次中铸造一定数量的均为12mm(D)×24mm(H)的圆柱体。使该批圆柱体进行1小时的水合,然后在40℃下干燥12-18小时。
将正磷酸分别制成浓度为2.5M、5M和7.5M,并使其在真空下浸渍到生石膏圆柱体的多孔结构中(这是附图的图7的方案2中说明的方法的实例)。
试样在40℃下再次干燥过夜,然后,在500℃的炉中以5℃/min-1的升温速率和2小时的保持时间进行煅烧。在冷却后,将它们转移到40℃的烘箱中。对于每个评价条件,测试3个圆柱体。
两个测试条件为:“干”,即,从40℃烘箱中取出;和湿,即,以去离子水充分饱和。使用Zwick万能测试机,以2毫米/分钟的导向架速度进行抗压强度测试。在相应的试样载荷从其峰值降低50%后,确定峰值载荷。
结果示于图3中且表明:湿耐水体的抗压强度没有显著不同于干耐水体的抗压强度。
使用5M磷酸的圆柱体之一的显微照片示于图1中;该显微照片示出了基体像陶瓷那样是连续的,而非像再水合生石膏那样是不连续的。(对于生石膏,晶体之间的连接是对水敏感的,然而,对于根据本发明的耐水体来说,无水石膏晶体之间的粘结剂是不溶和非晶的。)对于图2a和2b中的不同实施方案,显示出了相似的结果。
实施例2
除了以下改变外,重复实施例1:通过使水∶熟石膏之比在0.6和1之间变化,制造具有不同密度/孔隙率的生石膏圆柱体。每次浸渍的磷酸均具有2.5M的相同浓度。
结果示于图4中且表明:湿耐水体的抗压强度没有显著不同于干耐水体的抗压强度。
实施例3
使用玻璃研杵和研钵,将10g生石膏粉末(分析级二水合硫酸钙,来自Fisher Scientific)与分别具有2.5M、5M和10M浓度的5ml正磷酸混合1分钟。将所得的糊料倒入200mm(H)×10mm(D)的具有封闭底部的手动Teflon圆柱模具中,并使其水平(levelled)。将该模具置于具有20ml内径的Teflon衬里的密闭的“Parr”型密闭高压釜中。
将该模具在250℃的强制对流烘箱中加热30分钟,然后冷却。使所得的生坯脱模并在40℃下干燥过夜,然后进行如前述实施例1中所述的煅烧和测试。(这是附图的图7的方案3中所说明的方法的实例。)
结果示于图5中且表明:湿耐水体的抗压强度没有显著不同于干耐水体的抗压强度。
实施例4
除了以下改变外,重复实施例1:使用40%(以重量计)的具有0.33∶1的Al3+∶H3PO4摩尔比的磷酸铝溶液作为浸渍溶液。
前述实施例1-4的结果进一步总结于下表中。
实施例5
除了以下区别外,使用与实施例1中所述相同的方法铸造生石膏圆柱体:
实施例5.1-在以水进行凝固之前,将20重量%细氧化铝干混到熟石膏中。
实施例5.2-在以水进行凝固之前,将20重量%氢氧化铝干混到熟石膏中。
两种耐水体均以5M磷酸浸渍并且如实施例1中所述进行煅烧。
通过如下对每个试样(称重<3g)进行测试:预称重并浸在100ml去离子水中4小时。取出后,将试样置于40℃强制对流烘箱中并干燥约12小时。重新称重每个试样,并将其浸在新鲜的去离子水中。重复该过程3次浸渍循环。
实施例6
将根据实施例3制造的试样用作实施例6.1(用于对比),其中,使用5M的磷酸浓度。实施例6.2按照相同的程序,只是在添加磷酸之前,将细氧化铝干混到生石膏粉末中。计算加入的量以得到0.33的Al3+∶H3PO4摩尔比。以与实施例5中所述相同的方式进行测试。
图6中示出了由实施例5和6的每个干燥试样在各浸渍循环之间的重量差算得的质量变化。这些结果表明:铝的存在提高了硫酸钙的耐久性及其对再润湿的耐受性。
Claims (8)
1.基于硫酸钙的耐水体,其包含结晶硫酸钙无水石膏基体,所述基体的晶体通过耐水磷酸盐粘合区而彼此相连。
2.权利要求1的耐水体,其中,所述粘合区基本由非结晶磷酸盐组成。
3.权利要求1的耐水体,其中,所述粘合区包含无水磷铝酸盐。
4.制备基于硫酸钙的耐水体的方法,在该方法中:(a)用磷酸根离子源浸渍多孔硫酸钙物体,然后,(b)对所述浸渍过的物体煅烧以制备包含由耐水磷酸盐粘合的多孔结晶硫酸钙无水石膏的耐水体。
5.制备基于硫酸钙的耐水体的方法,在该方法中:(a)对包含硫酸钙和磷酸根离子源的糊料加热或压制以形成生坯;然后,(b)煅烧该生坯,由此,所得经煅烧的物体包含由耐水磷酸盐粘合的多孔结晶硫酸钙无水石膏。
6.权利要求4或5的方法,其中,所述磷酸根离子源包括正磷酸和/或焦磷酸、或者它们的盐。
7.权利要求6的方法,其中,所述盐为铝盐。
8.权利要求5或6的方法,其中,所述磷酸根离子源包含铝离子。
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