CN100391883C - 用于可脱水料浆的添加剂 - Google Patents

用于可脱水料浆的添加剂 Download PDF

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CN100391883C
CN100391883C CNB028071360A CN02807136A CN100391883C CN 100391883 C CN100391883 C CN 100391883C CN B028071360 A CNB028071360 A CN B028071360A CN 02807136 A CN02807136 A CN 02807136A CN 100391883 C CN100391883 C CN 100391883C
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cement
flyash
aluminum oxide
alumina
weight
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CN1612847A (zh
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B·纳吉
M·奥基
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James Hardie Research Pty Ltd
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Priority claimed from AUPR3476A external-priority patent/AUPR347601A0/en
Priority claimed from AUPR3474A external-priority patent/AUPR347401A0/en
Priority claimed from AUPR3477A external-priority patent/AUPR347701A0/en
Priority claimed from AUPR3475A external-priority patent/AUPR347501A0/en
Priority claimed from AUPR3478A external-priority patent/AUPR347801A0/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B28WORKING CEMENT, CLAY, OR STONE
    • B28BSHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00Producing shaped prefabricated articles from the material
    • B28B1/52Producing shaped prefabricated articles from the material specially adapted for producing articles from mixtures containing fibres, e.g. asbestos cement
    • B28B1/522Producing shaped prefabricated articles from the material specially adapted for producing articles from mixtures containing fibres, e.g. asbestos cement for producing multi-layered articles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B13/00Layered products comprising a a layer of water-setting substance, e.g. concrete, plaster, asbestos cement, or like builders' material
    • B32B13/14Layered products comprising a a layer of water-setting substance, e.g. concrete, plaster, asbestos cement, or like builders' material next to a fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B28WORKING CEMENT, CLAY, OR STONE
    • B28BSHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B7/00Moulds; Cores; Mandrels
    • B28B7/40Moulds; Cores; Mandrels characterised by means for modifying the properties of the moulding material
    • B28B7/46Moulds; Cores; Mandrels characterised by means for modifying the properties of the moulding material for humidifying or dehumidifying
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04Waste materials; Refuse
    • C04B18/06Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
    • C04B18/08Flue dust, i.e. fly ash
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02Compositions 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 hydraulic cements other than calcium sulfates
    • EFIXED CONSTRUCTIONS
    • E04BUILDING
    • E04CSTRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C2/00Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
    • E04C2/02Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials
    • E04C2/04Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of concrete or other stone-like material; of asbestos cement; of cement and other mineral fibres
    • E04C2/06Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of concrete or other stone-like material; of asbestos cement; of cement and other mineral fibres reinforced
    • EFIXED CONSTRUCTIONS
    • E04BUILDING
    • E04FFINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F13/00Coverings or linings, e.g. for walls or ceilings
    • E04F13/02Coverings or linings, e.g. for walls or ceilings of plastic materials hardening after applying, e.g. plaster
    • EFIXED CONSTRUCTIONS
    • E04BUILDING
    • E04FFINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
    • E04F15/00Flooring
    • E04F15/12Flooring or floor layers made of masses in situ, e.g. seamless magnesite floors, terrazzo gypsum floors
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00482Coating or impregnation materials
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00612Uses not provided for elsewhere in C04B2111/00 as one or more layers of a layered structure
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/91Use of waste materials as fillers for mortars or concrete
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S106/00Compositions: coating or plastic
    • Y10S106/01Fly ash
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • Y10T428/249924Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/249932Fiber embedded in a layer derived from a water-settable material [e.g., cement, gypsum, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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    • Y10T428/249953Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249967Inorganic matrix in void-containing component
    • Y10T428/249968Of hydraulic-setting material
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/249971Preformed hollow element-containing
    • Y10T428/249972Resin or rubber element
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/249986Void-containing component contains also a solid fiber or solid particle
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

一种用于水泥料浆的添加剂,它包括主要粒度最高达10微米的粉煤灰和/或主要粒度最高达150微米的含铝材料。该添加剂充当减水剂和可替代部分或全部常规增塑剂。

Description

用于可脱水料浆的添加剂
技术领域
本申请要求下述澳大利亚临时专利申请的优先权,在此通过交叉参考引入其全部内容。
申请号    标题                     申请日
PR3474    复合产品                 2001年3月2日
PR3475    喷镀装置                 2001年3月2日
PR3476    用于可脱水料浆的添加剂   2001年3月2日
PR3477    通过喷镀形成层压片材的方 2001年3月2日
          法与装置
PR3478    建筑产品用涂料           2001年3月2日
本发明涉及料浆用混合物和特别地涉及水泥料浆组合物。
背景技术
本领域公知,以料浆形式铺设或使用大多数水泥组合物。获得用于这种水泥材料如混凝土的高质量集料的增加难度和花费迫使制造商利用低品级材料如碎石头、海底砂和甚至由拆除或旧建筑获得的回收的压碎混凝土。这导致混凝土具有诸如较高的水消耗量、渗出(当料浆沉降时,水迁移到表面上)、较低的可操作性和可泵送性之类问题。
过去,通过将某些添加剂加入到水泥组合物中来克服这些问题。对于给定量的水来说,这些增塑剂(有时称为减水剂)、分散剂或超级增塑剂起到增加可操作性和料浆的有效性作用。实例包括木质素磺酸盐、萘磺酸盐-甲醛缩合物。
典型地,取决于添加的方法,以占水泥重量的约0.3%添加减水剂,并提供8-12%的水-水泥比降低。添加最多占水泥1%的减水剂提供最多35%的水-水泥比降低。在高效混凝土领域如超高强度混凝土中,通常过量使用增塑剂/减水剂(或其结合)以获得进一步最多达50%的减水。然而,在这一剂量水平下,会产生不利效果,如凝结时间增加和水泥混合物的压缩强度降低。
本发明的目的是克服或减少现有技术的至少一个缺点,或提供有效的备用方案。
发明内容
在广义的方面,本发明提供水泥料浆用添加剂,它包括下述矿物组分中的一种或两种:
i)主要粒度最高达10微米的粉煤灰,和
ii)主要粒度最高达150微米的含铝材料。
申请人发现使用小粒度部分的粉煤灰或大粒度部分的含铝材料充当有效的水泥料浆用减水剂。申请人发现添加合适量的这种矿物添加剂确实显著降低维持预定粘度所需要的水,同时没有任何前述的由常规技术所产生的不利影响。前述添加剂不会显著增加凝结时间或引起过度充气,而这可能是一些已知混合物的主要问题所在。此外,它抑制渗出并改进可操作性。
在优选的实施方案中,前述矿物添加剂可与常规的减水剂/增塑剂结合使用,以提高这种常规添加剂的减水能力。
第二方面,本发明提供一种水泥料浆,它包括水硬粘合剂、水、增塑剂和包括下述组分中的一种或二种的矿物添加剂:
i)主要粒度最高达10微米的粉煤灰,
ii)主要粒度最高达150微米的含铝材料,和
iii)所述矿物添加剂以足以提供减水效果的用量添加。
第三方面,本发明提供一种降低水泥料浆的需水量的方法,它包括添加有效量的一种或两种下述矿物组分:i)主要粒度最高达10微米的粉煤灰,和ii)主要粒度最高达150微米的含铝材料。
第四方面,本发明提供一种改进水泥料浆性能的方法,它包括添加有效量的一种或两种下述矿物组分:i)主要粒度最高达10微米的粉煤灰,和ii)主要粒度最高达150微米的含铝材料。
谈到减水效果,它涉及矿物添加剂有效降低获得特定粘度所需的水量的能力。本领域技术人员熟知,对于某些应用来说,因流动性、可泵送性或施加因素,设计料浆具有特定的预定粘度。对料浆而言,以上所述的矿物添加剂提供优良的减水性能。正如所述的,可单独地或与常规的增塑剂/减水剂结合使用它,以提供对料浆的减水。
当与一定量的常规增塑剂/减水剂结合使用时,发现前述矿物添加剂提高料浆的减水性,正如以下所述。
在矿物添加剂中的粉煤灰是指主要粒度最高达10微米的粉煤灰。本领域技术人员熟知,粉煤灰是一种固体粉末,它的化学组成与粉化煤的燃烧过程中产生的物质组成类似或相同。组成典型地包括25-60%的二氧化硅、10-30%的Al2O3、5-25%的Fe2O3、最多约20%的CaO和最多约5%的MgO。
粉煤灰颗粒典型地为球形和直径范围为1-100微米。正是主要粒度低于10微米的较小尺寸部分的粉煤灰颗粒具有令人惊奇的减水性。
粉煤灰优选占水泥重量的30-100%。粉煤灰优选占水泥重量的40-90%,和最优选50-70wt%。
过去已知较大尺寸的粉煤灰颗粒提供减水效果。但总是认为因一些因素,较小尺寸的颗粒不适于减水。首先,本领域认为粒度越小,颗粒的反应性越大。粉煤灰是一种反应性火山灰,因此认为较小尺寸部分的粉煤灰的反应性不适于充当减水剂。
另外,由于较小尺寸部分的粉煤灰的高比表面积,所以认为该材料实际上会增加需水量。申请人令人惊奇地发现实际上情况相反。较小尺寸部分的粉煤灰显著地提高常规减水剂的减水性。
在矿物添加剂内的含铝材料优选具有小于150微米的主要粒度。术语“含铝材料”不应当照字面理解,而是指氧化铝型材料,它包括水合、部分水合和非水合的氧化铝。基于水泥的重量,含铝材料的氧化铝含量为5-30%,优选10-25%,和最优选15-20%。
若在矿物添加剂中使用水合氧化铝和粉煤灰的共混物,则水合氧化铝:粉煤灰之比为1∶1到1∶10。
此处所使用的术语“水硬或水泥粘合剂”是指所有无机材料,它们包括钙、铝、硅、氧和/或硫的化合物,这些化合物显示出“水硬活性”,也就是说,在水存在下凝固成固体并硬化。这类水泥包括普通的卜特兰水泥、快凝或超快凝的耐硫酸盐水泥、改良水泥、氧化铝水泥、高铝水泥、铝酸钙水泥和含有次级组分如粉煤灰、矿渣等的水泥。基于总的干成分,在本发明组合物中水泥的存在量的下限为10wt%,优选15wt%,更优选20wt%,水泥的上限用量为50wt%,优选40wt%,更优选30wt%。
水泥组合物可非必需地但优选包括至少一种填料材料,如分级和未分级的集料如洗过的河沙、压碎的火成岩或石灰石、轻质集料、压碎的硬烧粘土砖或空气-冷却的高炉矿渣、砂子、碳酸钙、二氧化硅粉、蛭石、珍珠岩、石膏等。
基于总的干成分,在水泥组合物中存在的填料用量的下限为5wt%,优选10wt%,更优选15wt%,上限为30wt%,优选25wt%,更优选20wt%。
水泥组合物可非必需地含有其它添加剂,这些添加剂包括:
水泥增塑剂如三聚氰胺磺酸盐-甲醛缩合物、萘磺酸盐-甲醛缩合物、萘磺酸盐、木质素磺酸钙、木质素磺酸钠、蔗糖、葡糖酸钠、磺酸、碳水化合物、氨基羧酸、多羟基羧酸、磺化三聚氰胺等。
在干燥水泥组合物中使用的常规增塑剂用量将随所选择的特定水泥增塑剂的流动能力而变化。通常,水泥增塑剂的用量优选约0.3-约3wt%,和更优选约0.5-约2wt%,基于干水泥组合物的重量。
优选的增塑剂包括Melment.F-10,三聚氰胺-甲醛-亚硫酸氢钠聚合物分散剂(由SKW-Trostberg销售,以细白色粉末形式存在)。另一合适的增塑剂是Neosyn,其为磺化萘甲醛的缩合钠盐(获自HodgsonChemicals)。
也可在水泥组合物中使用增稠剂,所述增稠剂包括一种或多种多糖流变改性剂,而多糖流变改性剂可进一步细分为纤维素基材料及其衍生物、淀粉基材料及其衍生物和其它多糖。
合适的纤维素基流变改性剂包括例如甲基羟乙基纤维素、羟甲基乙基纤维素、羧甲基纤维素、甲基纤维素、乙基纤维素、羟乙基纤维素、羟乙基丙基纤维素等。尽管合适的流变改性剂的全部范围将不在此例举,但许多其它纤维素材料仍具有与这些相同或类似的性能,并且是等价的。
合适的淀粉基材料包括例如支链淀粉、直链淀粉、海凝胶(sea-gel)、淀粉乙酸酯、淀粉羟乙基醚、离子淀粉、长链烷基淀粉、糊精、胺淀粉、磷酸淀粉和二醛淀粉。
其它天然多糖基流变改性剂包括例如藻酸、藻胶、琼脂、阿拉伯胶、瓜耳胶、welan胶、刺槐豆胶、刺梧桐树胶和龙须胶。
基于干水泥组合物的重量,在水泥组合物内增稠剂的添加量为0.0001-0.5%。
也优选添加选自丙烯酸胶乳、苯乙烯胶乳和丁二烯胶乳中的至少一种胶乳。该组分改进含它的水泥组合物的粘附、弹性、稳定性和抗渗性,且也有利于软质膜的形成。
基于干水泥组合物的重量,可使用固体含量为约0.5-约20wt%的胶乳。基于干水泥组合物的重量,它的存在量优选约1-约15wt%,和更优选约10wt%。
水泥组合物可非必需地掺入粉状乙烯基聚合物或其它等价聚合物材料作为胶乳乳液的替代物,以增加组合物的粘附、回弹性和弯曲强度以及耐磨性。
粉状乙烯基聚合物优选为聚醋酸乙烯酯或醋酸乙烯酯与另一共聚单体如乙烯的共聚物。优选的醋酸乙烯酯树脂是获自WACKER的VINNAPAS LL5044热塑性树脂粉末,它含有醋酸乙烯酯-乙烯共聚物。
基于干水泥组合物的重量,可以约0.5-约20%的用量使用粉状乙烯基聚合物。基于干水泥组合物的重量,它的存在量优选约1-约15wt%,和更优选约10wt%。
水泥组合物可非必需地含有0-40wt%其它填料/添加剂如矿物氧化物、氢氧化物和粘土、金属氧化物和氢氧化物、阻燃剂如菱镁矿、增稠剂、热解法二氧化硅或无定形二氧化硅、着色剂、颜料、水封剂、减水剂、凝固速率改性剂、硬化剂、过滤助剂、增塑剂、分散剂、发泡剂或絮凝剂、防水剂、密度改性剂或其它加工助剂。
实施本发明的方式
现通过实施例,仅参考下述实施方案,可更清楚地理解本发明。
实施例1:减水剂和小尺寸部分粉煤灰的添加对水泥:粉煤灰混合物的减水率(%)的影响
将三种混合物(各自的固体总重量=1000gm)与水混合,获得粘度为4-3秒杯排出时间的混合物。下表1示出了混合物的细节。
表1
混合物成分 混合物1的重量,gm 混合物2的重量,gm 混合物3的重量,gm
水泥 300gm 300gm 300gm
粉煤灰(大尺寸部分) 700gm 700gm 500gm
粉煤灰(小尺寸部分) - - 200gm
减水剂(磺化的萘甲醛) - 3gm 3gm
苯乙烯丙烯酸胶乳乳液(56%固体) 60ml 60ml 60ml
Welan胶(Kelconcrete) 0.1gm 0.1gm 0.1gm
550ml 350ml 325ml
混合物的减水率,% - 36% 41%
粘度(在50ml杯内的排出时间) 3秒 3秒 4秒
可看出:在水泥中添加1wt%的减水剂导致混合物中的水降低36%。根据文献,在这一高的减水剂剂量下,这一程度的减水率接近可能实现的极限。使用较高的剂量将导致水泥混合物过度延迟的凝结时间和压缩强度的降低。当在混合物3中用较小的尺寸部分(主要粒度小于10微米)替代部分大尺寸部分的粉煤灰时,获得进一步的减水率,引起总计达41%的减水率。这一结果是相当令人惊奇的,因为人们认为较细的粉煤灰由于它的高表面积导致实际上增加混合物的需水量。
尽管水泥混合物中粉煤灰的减水效果在文献中得到充分论证,但认为在已经增塑的水泥:粉煤灰混合物中较小尺寸部分的塑性增加效果是令人惊奇的,因为假设较小材料的较大表面积导致需水量增加(这是机械水涂布较小颗粒所需的)。
实施例1:证明了在增塑的混合物中使用具有特定尺寸范围的矿物添加剂(即小尺寸的粉煤灰)同时不求助于过量使用减水剂可提高减水效果的方式。结果是具有较高强度和降低收缩率的更耐用的混合物。
实施例2:在增塑的混合物中的减水,其中该混合物用小尺寸部分的粉煤灰替代较大尺寸部分的粉煤灰
将两种混合物(各自的固体总重量=1000gm)与水混合,获得粘度为6-10泊的混合物。下表2示出了混合物的细节。
表2
混合物成分 混合物1的重量,gm 混合物2的重量,gm
水泥 300gm 300gm
粉煤灰(大尺寸部分) 400gm 250gm
粉煤灰(小尺寸部分) - 150gm
煤胞 300gm 300gm
Melment15(SKW Chemicals)(磺化的三聚氰胺甲醛) 3gm 3gm
MC 1834丙烯酸树脂(Rohm & Haas) 10ml 10ml
400ml 325ml
减水率 - 19%
粘度(Rotothinner) 6.5泊 8.8泊
可看出:包括水泥、粉煤灰和煤胞(陶瓷中空球)的混合物1要求400ml水以实现所需的粘度(在1%添加的Melment F15减水剂存在下)。在这一情况下的固体%为71.4%。
但混合物2仅要求325ml水以实现类似的流动性。通过用较小尺寸部分(尺寸小于10微米,平均尺寸=4微米)的粉煤灰替代部分较大的粉煤灰颗粒能获得这种减水率(约20%)。在这一情况下的固体%增加到75.5%。
实施例3:在增塑的混合物中的减水-比较二氧化硅与粉煤灰
将两种混合物(固体总重量=1000gm)与水混合,混合物粘度达到4-3秒杯排出时间。下表3示出了混合物的细节。
表3
混合物成分 混合物1的重量,gm 混合物2的重量,gm
水泥 300gm 300gm
粉煤灰(大尺寸部分) 500gm 500gm
粉煤灰(小尺寸部分) - 200gm
二氧化硅 200gm
减水剂(磺化的萘甲醛) 3gm 3gm
苯乙烯丙烯酸胶乳乳液(56%固体) 60ml 60ml
Welan胶(Kelconcrete) 0.1gm 0.1gm
400ml 325ml
在增塑的混合物中的减水率 - 19%
粘度(在50ml杯内的排出时间) 4秒 4秒
可看出:包括水泥、粉煤灰和二氧化硅的混合物1要求400ml水以实现所需的粘度(在1%减水剂存在下)。在这一情况下的固体%为71.4%。
但混合物2仅要求325ml水以实现类似的流动性。通过用超细部分粉煤灰(尺寸小于10微米,平均尺寸=4微米)替代二氧化硅能获得这种减水(约20%)。在这一情况下的固体%增加到75.5%。
实施例4:在掺入水合氧化铝和粉煤灰的增塑混合物中的减水
在表4中,比较含有1.0%(以水泥的重量计)添加的的减水剂(即磺化的萘甲醛)的两种混合物所要求的水。
表4
混合物成分 混合物1的重量,无水合氧化铝 混合物2的重量,有水合氧化铝
水泥 10000gm 10000gm
粉煤灰(大尺寸部分) 16000gm 16000gm
粉煤灰(小尺寸部分) 8000gm 8000gm
碳酸钙(Omyacarb Grade 40) 6000gm 4000gm
水合氧化铝 - 2000gm
减水剂(萘甲醛磺酸盐) 100gm 100gm
Welan胶(Kelconcrete) 3gm 3gm
苯乙烯丙烯酸胶乳乳液(56%固体) 2000ml 2000ml
16500ml 12500ml
在增塑的混合物中的减水率,% - 25%
粘度(在50ml杯内的排出时间) 3.5秒 3秒
可看出:对于相同的粘度水平来说,在混合物2中添加2000gm水合氧化铝(替代碳酸钙)导致需水量的显著降低,即从16500降低到12500ml。
这一程度的减水率(在已经高增塑的混合物中为约25%)是完全不可预料的。也与在水泥化学文献中提出的常规减水趋势相反,这些文献认为减水量范围通常为15%-35%,和(超过某一特定剂量)进一步减水是不可能的(由Ramachandran出版的Concrete AdmixturesHandbook,第2版,447页)。
根据以上列举的实施例,可看出使用含小尺寸部分的粉煤灰和/或含铝材料的矿物添加剂在非增塑的水泥混合物中提供减水,或在含常规减水剂的增塑水泥混合物中提供额外的/增加的减水。在20%至40%间的减水率的显著增加使得能生产高性能水泥混合物(低收缩率、高强度、更耐用),同时不具有过量使用常规有机减水剂的缺点,即延迟的凝固时间、强度降低、过度充气等。
应理解可对前述实施方案作出改性或变化,而没有脱离本发明的精神和范围。特别地,应理解本发明的配方、涂料、添加剂、方法和复合产品适于或可采用它们与在各种优先权文件中所述的方法与装置结合使用。

Claims (33)

1.一种用于在水泥料浆中提供减水效果的添加剂,它包括增塑剂和下述矿物组分中的一种或二种:
i)主要粒度最高达10微米的粉煤灰,和
ii)粒度最高达150微米的含铝材料,它选自水合氧化铝、部分水合的氧化铝和未水合的氧化铝。
2.权利要求1的添加剂,其中粉煤灰包括25-60%的二氧化硅、10-30%的Al2O3、5-25%的Fe2O3、最多20%的CaO和最多5%的MgO。
3.权利要求1或2的添加剂,其中粉煤灰占30-100wt%,基于料浆中水泥的重量。
4.前述任何一项权利要求的添加剂,其中含铝材料占5-30wt%,基于料浆中水泥的重量。
5.前述任何一项权利要求的添加剂,其中水合氧化铝对粉煤灰之比为1∶1至1∶10。
6.前述任何一项权利要求的添加剂,其中增塑剂的用量为0.3-3wt%,基于干水泥的重量。
7.前述任何一项权利要求的添加剂,其中水泥料浆含有5-30wt%的填料。
8.一种水泥料浆,它包括水泥、增塑剂、水、和包括粉煤灰和下述组分中的一种或二种的矿物添加剂:
i)粒度最高达10微米的粉煤灰,所述粉煤灰的量为10-30wt%,基于浆料中水泥的量;
ii)粒度最高达150微米的含铝材料,所述含铝材料选自水合氧化铝、部分水合的氧化铝和未水合的氧化铝,其用量为5-30wt%,基于浆料中水泥的量;
其中,所述矿物添加剂以足以提供减水效果的用量添加,且粉煤灰的总重量百分比大于水泥的量。
9.权利要求8的水泥料浆,其中粉煤灰包括25-60%的二氧化硅、10-30%的Al2O3、5-25%的Fe2O3、最多20%的CaO和最多5%的MgO。
10.权利要求8或9的水泥料浆,其中水合氧化铝对粉煤灰之比为1∶1至1∶10。
11.权利要求8-10任何一项的水泥料浆,其中水泥选自普通的卜特兰水泥、快凝或超快凝水泥、耐硫酸盐水泥、改良水泥、氧化铝水泥、高铝水泥、铝酸钙水泥和含有次级组分的水泥。
12.权利要求8-11任何一项的水泥料浆,其中水泥占总的干成分的10-50wt%。
13.权利要求8-12任何一项的水泥料浆,其中增塑剂的用量为0.3-3wt%,基于干水泥的重量。
14.权利要求8-13任何一项的水泥料浆,其中水泥料浆含有5-30wt%的填料。
15.一种降低水泥料浆的需水量的方法,它包括添加增塑剂和有效量的一种或两种下述矿物组分:i)粒度最高达10微米的粉煤灰,和ii)粒度最高达150微米的含铝材料,所述含铝材料选自水合氧化铝、部分水合的氧化铝和未水合的氧化铝。
16.权利要求15的方法,其中粉煤灰包括25-60%的二氧化硅、10-30%的Al2O3、5-25%的Fe2O3、最多20%的CaO和最多5%的MgO。
17.权利要求15或16的方法,其中粉煤灰占30-100wt%,基于料浆中水泥的重量。
18.权利要求15-17任何一项的方法,其中含铝材料占5-30wt%,基于料浆中水泥的重量。
19.权利要求15-18任何一项的方法,其中水合氧化铝对粉煤灰之比为1∶1至1∶10。
20.权利要求15-19任何一项的方法,其中水泥占总的干成分的10-50wt%。
21.权利要求15-20任何一项的方法,其中增塑剂的用量为0.3-3wt%,基于干水泥的重量。
22.权利要求 5-21任何一项的方法,其中水泥料浆含有5-30wt%的填料。
23.一种改进水泥料浆性能的方法,它包括添加有效量的增塑剂和一种或两种下述矿物组分:i)粒度最高达10微米的粉煤灰,和ii)粒度最高达150微米的含铝材料,所述含铝材料选自水合氧化铝、部分水合的氧化铝和未水合的氧化铝。
24.权利要求23的方法,其中粉煤灰包括25-60%的二氧化硅、10-30%的Al2O3、5-25%的Fe2O3、最多20%的CaO和最多5%的MgO。
25.权利要求23或24的方法,其中粉煤灰占30-100wt%,基于水泥的重量。
26.权利要求23-25任何一项的方法,其中含铝材料占5-30%,基于水泥的重量。
27.权利要求23-26任何一项的方法,其中水合氧化铝对粉煤灰之比为1∶1至1∶10。
28.权利要求23-27任何一项的方法,其中水泥选自普通的卜特兰水泥、快凝或超快凝水泥、耐硫酸盐水泥、改良水泥、氧化铝水泥、高铝水泥、铝酸钙水泥和含有次级组分的水泥。
29.权利要求23-28任何一项的方法,其中水泥占总的干成分的10-50wt%。
30.权利要求23-29任何一项的方法,其中增塑剂的用量为0.3-3wt%,基于干水泥的重量。
31.权利要求23-30任何一项的方法,其中水泥料浆含有5-30wt%的填料。
32.权利要求23-31任何一项的方法,其中待改进的性能是凝结时间、可操作性、可泵送性、在沉降过程中的渗出、所得压缩强度和收缩率中的一种或多种。
33.权利要求23-32任何一项的方法,其中在水泥料浆中添加矿物组分替代部分或全部的常规增塑剂。
CNB028071360A 2001-03-02 2002-03-04 用于可脱水料浆的添加剂 Expired - Fee Related CN100391883C (zh)

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AUPR3477A AUPR347701A0 (en) 2001-03-02 2001-03-02 A method and apparatus for forming a laminated sheet material by spattering
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