CN86107644A - 胶凝混合料的改进 - Google Patents
胶凝混合料的改进 Download PDFInfo
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/20—Sulfonated aromatic compounds
- C04B24/22—Condensation or polymerisation products thereof
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- C—CHEMISTRY; METALLURGY
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1055—Coating or impregnating with inorganic materials
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- 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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1018—Coating or impregnating with organic materials
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- 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
- C04B28/02—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 hydraulic cements other than calcium sulfates
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00034—Physico-chemical characteristics of the mixtures
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Abstract
在拌和步骤前,用水对水泥进行处理,使其保持重量百分比为0.1至10的水分,就能提高水泥中塑化剂和超塑化剂的流化作用及保水效果。
Description
本发明涉及到含流化剂,即含塑化剂和超塑化剂的胶凝混合料。
塑化剂和超塑化剂均是化学助剂,能有效地应用于砂浆或混凝土,以增加新拌和的而具有同样水灰比的水泥混合料的流动度,改善其施工性及便于其浇捣成型。换句话说,当水灰比降低时,上述助剂可用作减水剂,以保持混合料原有的施工性,这样就改善了硬化砂浆或混凝土的所有工艺特性。
根据美国材料试验学会(ASTM)标准,就同样的流动度而言,使用超塑化剂至少可令拌和水减少12%;使用塑化剂能够使拌和水至少减少5%。在生产新拌的混凝土或砂浆混合料时,可将上述助剂加入到拌和水中;或在水泥生产中,将这些助剂加入到水泥中去,使这些助剂在干硬性水泥中呈干态。
令人惊奇的发现是,如果水泥在拌和前经湿法处理,那么塑化剂和塑化剂的流化作用或保水效果就会增强。
因此,本发明提供了一种生产胶凝混合料的方法,包括在至少有一种选自于塑化剂或超塑化剂的助剂存在的情况下,将水硬性胶结料、集料和水进行拌和的步骤,其特征在于搅拌步骤前,用水处理水硬性胶结料,使其保持重量百分比为0.1至10的水份。
较佳的胶凝混合料为砂浆和混凝土。水硬性胶结料可以是硅酸盐水泥、矾土(高铝)水泥或混合水泥,例如火山灰质水泥、矿渣水泥,或其他类型的水泥,其中以硅酸盐水泥为佳。更佳的水硬性胶结料是一种由粉磨熟料、硫酸钙以及从烧煤发电站产生的底灰所制成的火山灰质水泥。较佳的方法是,粉磨前,将冷却于水中而含水量一般为20-30(重量百分比)的底灰,脱水成含水量小于12(重量百分比),更佳的是含水4-7(重量百分比)。底灰中最好含重量百分比大于1的未燃尽的碳,以及含重量百分比小于1的硫酸盐。
合适的塑化剂包括基于葡糖酸盐、木素磺酸盐和羟基化聚合物的产物;合适的超塑化剂包括基于萘磺酸盐或密胺磺酸盐和甲醛、聚苯乙烯磺酸盐和羟基丙烯酸盐的缩聚产物。较佳的是混合料至少含有一种超塑化剂;更佳的是,含有一种基于β-萘磺酸盐的缩聚物,尤其是以其钙盐为好。
水泥工艺中其他常用的附加剂,如促凝剂、缓凝剂、加气剂、防冻剂、及着色剂等,也可以在按本发明所制备的胶凝混合料中使用。
可将流化剂(塑化剂或超塑化剂)与拌和水一起加入到混合料中,或者在拌和前将流化剂加到湿化的水泥中。本发明进一步提供了一种水硬性胶结料,它至少含一种选自塑化剂和塑化剂的助剂,并含有重量百分化为0.1至10的吸附水份。较佳的是,以水泥重量计,水泥中的流化剂量为0.1至1(干重量百分比);流化剂量为0.2至0.5(干重量百分比)则更佳。
在加入流化剂前,可先将这种水硬性胶结料湿化;或可将已含流化剂的水硬性胶结料湿化。换言之,可用流化剂的水溶液将胶结料湿化。因此,湿化和加入流化剂可以是同时进行的。
更佳的是,在粉磨步骤后,以液态、悬浮态或汽态的形式,使水泥经过水处理,以便使水份以水泥重量的0.1-10%的一定量(其中较佳的为0.5-5%,更佳的为0.5-2%)被水泥均匀吸收,即实现对水硬性胶结料或水泥的湿化。这些重量百分比表示水泥所吸收的水份的重量,而不是其实际应用的重量。如果紧接着粉磨过程之后,或在粉磨过程结束的一段时间后,将水以细液雾态加入到水泥中,则湿化效果最好。
进行湿化处理所用的合适的装置如图1所示。水泥通过输送管2而导入锥形管3之后进入容器1。一直径比管2小的输送管4通向喷咀5。通过喷咀5吸送水或流化剂的水溶液。通过容器的筛板6吹入气流,这样就将湿化的水泥拌和,并且通过排放管7将其送出。
已知在粉磨阶段可用流化剂的水溶液喷射水泥,就可获得含流化剂的干硬性水泥,这正如美国专利2,141,571号和3,856,542号中所叙述的。然而,正如这些专利所述,当这类水泥置于一定温度时,水份便迅速蒸发,使干流化剂沉积在水泥颗粒上,而未能增加最终产品的含水量。
在粉磨过程中,可根据一定的量或在一定温度下加水湿化,使最终的产品水泥存在若干水份,即能实现本发明的方法。但是,由于很难控制吸收水份的数量,因此最好还是在粉磨之后再进行水泥湿化。
湿化后水泥中的最佳的含水量,取决于水泥的化学组分和细度。例如,细磨的水泥就较之粗磨的水泥一般需要更多的水份。
水份主要吸附于水泥颗粒的表面,以水合矿物钙矾石(3CaO·Al2O3·3CaSO4·31H2O)和/或单硫酸盐(3CaO·Al2O3·CaSO4·16H2O)形式存在;而其存在数量可用示差扫描量热法(DSC)、示差热重量法(DTG)或示差热分析法(DTA)测出。图2表示了从两批水泥试样进行示差扫描量热法测定所得出的扫描记录图。这两批水泥试样均含干重量百分比为0.4的超塑化剂,但其中一批试样未经过水处理,由虚线曲线表示;另一批试样则已经过重量百分比为1的水处理,由实线曲线表示。从经过水处理的试样扫描可清楚看到,由于钙矾石(峰值a)及单硫酸盐(峰值b)中水份的流失分别产生的峰值。峰值(c)则是由于水份从石膏中流失而产生的。
根据本发明所制备的胶凝混合料,可以将混合料的施工性和生成的硬化混凝土或砂浆(例如混凝土制成品)的强度特性很好地结合起来。由于普遍认为水泥吸水是一种不希望出现的现象,它对生成的混凝土的强度具有消极的影响[例如见S.斯普朗(Sprung)在《水泥、石灰、石膏》(“Zement-Kalk-Gips”),1974年,第5期,259-267页上发表的“粉磨环境对水泥凝固及强度的影响”(“Einfluss der Mühlenatmosphoere auf das Erstarren und die Festigkeit von Zememt”)一文,以及由威斯巴登及柏林建筑出版有限公司(Bauverlag GmbH,Wiesbaden and Berlin)出版的W.H.哈达(Hada)著的《水泥数据手册》(“Cement data-book”),第155页,注释],因此,本发明的结果是令人意想不到的。
下面的实施例(其中所有的份数、比率及百分数,均以重量计)将说明本发明。
实施例1
制备了六批砂浆,每批含1份高强度硅酸盐水泥,3份砂,水灰比为0.45。砂浆中以水泥重量计,每批含干重为0.4%(40%水溶液的1%)的超塑化剂,它是基于β-萘磺酸盐和甲醛缩聚产物的钙盐。从三种不同的商品用高强度硅酸盐水泥中的每一种各制备了两批砂浆混合料。每次,由通常供应的水泥制备了一批混合料;而由经1%的水处理的水泥制备了另一批混合料。按意大利国家标准(UNI)7044,通过流动桌试验测定每批砂浆新拌混合料的流动度。并经1天、7天和28天后,测定其抗压强度。表1表示了三种不同水泥的平均值。
表1
水泥 流动度% 抗压强度(兆帕斯卡)(MPa)
1天 7天 28天
未经处理 120 303 515 632
经用1%的水处理 160 301 536 643
按本发明,在有超塑化剂存在的情况下,由经过处理的水泥而制备的砂浆,比较由未经处理的水泥而制备的砂浆,具有更高的流动度。并且,前者的抗压强度等于或稍大于后者。
实施例2
制备了两批砂浆,其组分及比例与例1相同。但这次不是分别地加入超塑化剂,而是采用了这样一种水泥:事前在这种水泥的生产过程中已经加入30.4%的相同的超塑化剂。两批砂浆中,其中一批所使用的是通常供应的水泥;另一批砂浆则采用了经过1%的水处理的水泥。这两批砂浆的抗压强度及流动桌试验测定结果如表2所示。
表2
水泥 经水处理(1%) 流动度(%) 抗压强度(兆帕斯卡)(MPa)
(UNI7044) 1天 7天 28天
1 否 120 38.9 60.8 73.1
2 是 155 40.6 67.8 77.5
如同例1,试验结果表明流动性有了相当大的改善,并且抗压强度也有所提高。
实施例3
制备了四批砂浆,每批含1份高强度硅酸盐水泥,3份砂,水灰比为0.50。拌和前,先用0.5%的水对其中两批砂浆的水泥进行了处理。每批砂浆含以水泥重量计,干重为0.1%(50%水溶液的0.2%)的塑化助剂。这种塑化助剂可以是木素磺酸钙盐,也可以是葡糖酸钠盐。混合料的流动桌试验测定结果如表3所示。
表3
水泥处理 助剂 流动度(%)
未经处理 木素磺酸钙盐 60
用0.5的水处理 木素磺酸钙盐 80
未经处理 葡糖酸钠盐 73
用0.5%的水处理 葡糖酸钠盐 95
实施例4
制备了八批砂浆,每批含1份高强度硅酸盐水泥,3份砂和以水泥重量计干重为0.48%(40%水溶液的1.2%)的用于例1的超塑化助剂。用于其中七批砂浆中的水泥,在其制备过程中已经过0.05%至10%的水湿化。将用于拌和砂浆的水的数量调整到使水泥中存在一定水份,以便在所有的情况下总水灰比为0.45。生成的砂浆的流动度如表4所示。
表4
砂浆编号 水泥湿化(%水) 混合料水灰比 流动度(%)
1 0 0.4500 95
2 0.05 0.4495 105
3 0.10 0.4490 110
4 0.50 0.4450 125
5 1.00 0.4400 132
6 3.00 0.4200 132
7 5.00 0.4000 125
8 10.00 0.3500 100
显然,即使把湿化水视为拌和水的一部分,按本发明所制备的2-8号砂浆仍然比对照1号砂浆具有更高的流动度。可以看出,用0.5-5%的水对水泥进行湿化,产生了特别好的效果。
实施例5
制备了六批砂浆,每批含1份水泥,3份砂和用于例1的以水泥重量计干重为0.48%(40%水溶液的1.2%)的超塑化助剂,总水灰比为0.45。采用了四种不同类型的水泥:
a)火山灰质水泥(带天然火山灰)
b)矿渣水泥
c)火山灰质水泥(带粉煤灰)
d)火山灰质水泥(带底灰)
底灰原含水份为25%,将底灰脱水至含水量为5%。
对上述四种水泥,分别按通常供应的水泥和经过1%的水湿化的水泥两种形式来使用。流动度试验结果如表5所示。
表5
砂浆编号 水泥类型 水泥处理 流动度(%)
1 天然火山灰 未经处理 90
2 天然火山灰 经1%的水处理 110
3 矿渣 未经处理 107
4 矿渣 经1%的水处理 125
5 粉煤灰火山灰 未经处理 65
6 粉煤灰火山灰 经1%的水处理 85
7 底灰火山灰 未经处理 120
8 底灰火山灰 经1%的水处理 170
显然,除了硅酸盐水泥外,其他类型水泥的流动性也都有了提高。
实施例6
制备了四批砂浆,每批含1份高强度硅酸盐水泥,3份砂,总水灰比为0.45。每批含0.4%(40%水溶液的1%)如例1的超塑化剂,但分别在不同阶段将其加入,如下所述:
1)将超塑化剂加入拌和水中。水泥未经湿化。
2)在粉磨过程中加入超塑化剂。干硬性水泥+超塑化剂未经湿化。
3)用1%的40%超塑化剂溶液将粉磨后的水泥湿化。
4)用2%的溶液将粉磨后的水泥湿化。这种溶液是通过将40%超塑化剂溶液同相同体积的水混合而得到的。
由此砂浆3)和4)为按本发明方法所制备,而砂浆1)和2)为对照物。
表6表示了所生成各砂浆的流动性。
表6
砂浆编号 超塑化剂的加入方式 水处理(%) 流动度(%)
1 至拌和水 - 110
2 在粉磨过程中 - 105
3 粉磨后 0.6 120
4 粉磨后 1.6 125
实施例7
用硅酸盐水泥制备了两批混凝土。在水泥厂的粉磨过程中,已经用干重为0.4%(40%水溶液的1%)如例一所用的超塑化剂对上述硅酸盐水泥进行了处理。其中一种情况是,使用了通常供应的水泥;另一种情况是使了经1%的水湿化处理过的水泥。两批混凝土混合料均含400公斤/米3的水泥;所含集料及其数量也相同(最大粒径为20毫米)。将上述混合料同水拌和至相同的稠度[220毫米+/-10毫米坍落度(slump)]。
表7表示,为产生上述坍落度所需的含水量以及生成的混凝土的抗压强度。
表7
试验编号 按本发明 水灰比 坍落度 抗压强度
所进行的 (毫米) (兆帕斯卡)(MPa)
处理
1天 2天 28天
1 未经处理 0.45 220 37.0 62.5 72.5
2 未经处理 0.41 225 46.5 74.0 82.0
可以看出,按本发明方法对所用的水泥进行处理,就可加强超塑化剂的减水效果。
Claims (18)
1、一种生产胶凝混合料的方法,包括在至少有一种选自于塑化剂或超塑化剂的助剂存在的情况下,将水硬性胶结料、集料以及水拌和的步骤,其特征在于拌和步骤前,先用水处理水硬性胶结料,使其保持重量百分比为0.1至10的水分。
2、按权利要求1所述的方法,其中将塑化剂或超塑化剂加入到拌和水中。
3、按权利要求1所述的方法,其中在拌和前,塑化剂或超塑化剂存在于干水硬性胶结料中。
4、按权利要求1所述的方法,其中用水处理的步骤是在水硬性胶结料粉磨后进行的。
5、按权利要求1所述的方法,其中在拌和步骤前,用塑化剂或超塑化剂的水溶液处理水硬性胶结料。
6、按前述权利要求中的任一项所述的方法,其中超塑化剂是一种磺化的芳香族化合物的甲醛缩聚物。
7、按权利要求6所述的方法,其中超塑化剂是一种β-萘磺酸/甲醛缩聚物的钙盐。
8、一种水硬性胶结料,其中含有至少一种选自于塑化剂和超塑化剂的助剂,并含有重量百分比为0.1至10的水。
9、按权利要求8所述的水硬性胶结料,其中含有重量百分比为0.5至5的水。
10、按权利要求9所述的水硬性胶结料,其中含重量百分比为0.5至2的水。
11、一种水硬性胶结料,至少含有一种选自于塑化剂和超塑化剂的助剂,并且在对应的钙矾石及单硫酸盐的示差扫描量热分析扫描记录图上呈现出峰值。
12、按权利要求8至11中任一项所述的水硬性胶结料,含重量百分比为0.2至0.5的一种磺化芳香化合物的甲醛缩聚物的超塑化剂。
13、按权利要求8至12中任一项所述的水硬性胶结料,它是基于硅酸盐水泥的。
14、按权利要求8至12中任一项所述的水硬性胶结料,它是基于火山灰质水泥的,而火山灰质水泥是通过粉磨熟料、硫酸钙以及已被脱水到含水量小于12%的底灰而获得的。
15、按权利要求1所述的方法制备的胶凝混合料。
16、按权利要求15所述的胶凝混合料是一种砂浆。
17、按权利要求15所述的胶凝混合料是一种混凝土。
18、一种成型的混凝品制品,它是由按照权利要求17所述的混合料硬化后而制得。
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IT4876085A IT1200142B (it) | 1985-11-08 | 1985-11-08 | Metodo per migliorare la fluidificazione di impasti cementizi |
IT48760A/85 | 1985-11-08 |
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CN86107644A true CN86107644A (zh) | 1987-05-27 |
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CN198686107644A Pending CN86107644A (zh) | 1985-11-08 | 1986-11-07 | 胶凝混合料的改进 |
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US (1) | US4915741A (zh) |
EP (1) | EP0245326B1 (zh) |
JP (1) | JPH06104324B2 (zh) |
KR (1) | KR880700780A (zh) |
CN (1) | CN86107644A (zh) |
AU (1) | AU589229B2 (zh) |
BR (1) | BR8606964A (zh) |
CA (1) | CA1276188C (zh) |
CS (1) | CS804786A2 (zh) |
ES (1) | ES2002432A6 (zh) |
FI (1) | FI873016A0 (zh) |
IL (1) | IL80527A (zh) |
IT (1) | IT1200142B (zh) |
MX (1) | MX170232B (zh) |
PL (1) | PL262269A1 (zh) |
PT (1) | PT83691B (zh) |
TR (1) | TR26095A (zh) |
WO (1) | WO1987002978A1 (zh) |
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GB8710605D0 (en) * | 1987-05-05 | 1987-06-10 | Modern Advanced Concrete | Cementitious mixes |
DE3929223A1 (de) * | 1988-09-09 | 1990-03-22 | Sandoz Ag | Behandlung von zementpulver |
GB8904273D0 (en) * | 1989-02-24 | 1989-04-12 | Sandoz Ltd | Improvements in or relating to chemical compounds |
CH681541A5 (zh) * | 1990-03-03 | 1993-04-15 | Sandoz Ag | |
JPH069258A (ja) * | 1991-03-07 | 1994-01-18 | Nippon Cement Co Ltd | 超高流動コンクリート |
JP3215516B2 (ja) * | 1991-09-20 | 2001-10-09 | 太平洋セメント株式会社 | 水硬性組成物及び該組成物を用いてコンクリートパイルを製造する方法 |
ES2050603B1 (es) * | 1992-06-25 | 1994-12-16 | Low Water Binder Sa | Procedimiento de fabricacion de un conglomerante decorativo con baja demanda de agua. |
ES2050604B1 (es) * | 1992-06-25 | 1994-12-16 | Low Water Binder Sa | Procedimiento de fabricacion de un conglomerante con baja demanda de agua. |
TR28817A (tr) * | 1993-12-29 | 1997-04-03 | Low Water Binder Sa | Az su gerektiren bir cimentolu malzemenin imal edilme prosesi. |
US5531823A (en) * | 1995-02-06 | 1996-07-02 | Atomic Energy Of Canada Limited | Low-heat high-performance concrete |
JPH10273353A (ja) * | 1997-03-28 | 1998-10-13 | Chichibu Onoda Cement Corp | 水硬性セメント組成物、及びその製造方法 |
DE10013664A1 (de) * | 2000-03-20 | 2001-10-18 | Voest Alpine Ind Anlagen | Verfahren und Vorrichtung zum Granulieren von Schlämmen |
JP4907754B2 (ja) * | 2000-04-26 | 2012-04-04 | 太平洋セメント株式会社 | 高流動高強度コンクリート |
EP1236699A1 (en) * | 2001-03-01 | 2002-09-04 | Sika AG, vorm. Kaspar Winkler & Co. | Composite material and shaped article with thermal conductivity and specific gravity on demand |
DE10164824B4 (de) * | 2001-04-04 | 2006-03-02 | Dyckerhoff Ag | Verwendung einer Masse aus Wasser und einer Bindemittelmischung im Feuerfestbereich |
US8118927B2 (en) * | 2002-08-02 | 2012-02-21 | Price Charles E | Cementitious compositions and methods of making and using |
JP4617073B2 (ja) * | 2003-08-08 | 2011-01-19 | 太平洋マテリアル株式会社 | 急硬性材料及び急硬性セメント組成物 |
JP3678732B2 (ja) * | 2003-09-11 | 2005-08-03 | 住友大阪セメント株式会社 | 水硬性組成物の部分水和成形体、その製造方法およびその利用方法 |
US7716901B2 (en) * | 2004-05-27 | 2010-05-18 | Price Charles E | Packaging for particulate and granular materials |
JP4878752B2 (ja) * | 2004-12-24 | 2012-02-15 | 太平洋マテリアル株式会社 | 急硬材及び急硬性セメント組成物 |
DE102011051630A1 (de) * | 2011-07-07 | 2013-01-10 | Neoton Betonsysteme Gmbh | Verfahren zum Herstellen von Beton |
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DE418706C (de) * | 1920-09-18 | 1925-09-11 | Otto Simon | Verfahren zur Herstellung von wasserdichtem Zement und Moerteln |
US1762241A (en) * | 1927-10-08 | 1930-06-10 | Smidth & Co As F L | Grinding cement materials, etc. |
US1976133A (en) * | 1931-09-28 | 1934-10-09 | Harry M Larmour | Process of grinding portland cement |
DE677597C (de) * | 1932-07-20 | 1939-06-29 | Karl Halbach | Verfahren zur Herstellung hydraulischer Bindemittel, vorzugsweise fuer den Strassen- und Wegebau |
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GB8710605D0 (en) * | 1987-05-05 | 1987-06-10 | Modern Advanced Concrete | Cementitious mixes |
-
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- 1985-11-08 IT IT4876085A patent/IT1200142B/it active
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1986
- 1986-10-30 EP EP19860906327 patent/EP0245326B1/en not_active Expired - Lifetime
- 1986-10-30 KR KR870700590A patent/KR880700780A/ko not_active Application Discontinuation
- 1986-10-30 BR BR8606964A patent/BR8606964A/pt unknown
- 1986-10-30 WO PCT/EP1986/000625 patent/WO1987002978A1/en active IP Right Grant
- 1986-11-05 US US06/927,553 patent/US4915741A/en not_active Expired - Fee Related
- 1986-11-05 TR TR61586A patent/TR26095A/xx unknown
- 1986-11-06 AU AU64879/86A patent/AU589229B2/en not_active Ceased
- 1986-11-06 IL IL8052786A patent/IL80527A/xx unknown
- 1986-11-06 MX MX427786A patent/MX170232B/es unknown
- 1986-11-06 CA CA 522392 patent/CA1276188C/en not_active Expired - Lifetime
- 1986-11-06 CS CS868047A patent/CS804786A2/cs unknown
- 1986-11-06 PT PT8369186A patent/PT83691B/pt not_active IP Right Cessation
- 1986-11-07 CN CN198686107644A patent/CN86107644A/zh active Pending
- 1986-11-07 ES ES8602949A patent/ES2002432A6/es not_active Expired
- 1986-11-07 PL PL26226986A patent/PL262269A1/xx unknown
- 1986-11-07 JP JP26411086A patent/JPH06104324B2/ja not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
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FI873016A (fi) | 1987-07-07 |
AU6487986A (en) | 1987-05-14 |
PT83691B (pt) | 1989-06-30 |
CA1276188C (en) | 1990-11-13 |
ES2002432A6 (es) | 1988-08-01 |
AU589229B2 (en) | 1989-10-05 |
PL262269A1 (en) | 1988-03-31 |
IT1200142B (it) | 1989-01-05 |
IL80527A (en) | 1990-04-29 |
MX170232B (es) | 1993-08-12 |
PT83691A (en) | 1986-12-01 |
BR8606964A (pt) | 1987-11-03 |
WO1987002978A1 (en) | 1987-05-21 |
CS804786A2 (en) | 1991-03-12 |
TR26095A (tr) | 1993-12-24 |
EP0245326B1 (en) | 1991-02-06 |
JPS62162506A (ja) | 1987-07-18 |
IL80527A0 (en) | 1987-02-27 |
KR880700780A (ko) | 1988-04-12 |
US4915741A (en) | 1990-04-10 |
JPH06104324B2 (ja) | 1994-12-21 |
FI873016A0 (fi) | 1987-07-07 |
EP0245326A1 (en) | 1987-11-19 |
IT8548760A0 (it) | 1985-11-08 |
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