CN1863750A - 板状凝合剂产品和其制备方法 - Google Patents

板状凝合剂产品和其制备方法 Download PDF

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CN1863750A
CN1863750A CNA2004800288225A CN200480028822A CN1863750A CN 1863750 A CN1863750 A CN 1863750A CN A2004800288225 A CNA2004800288225 A CN A2004800288225A CN 200480028822 A CN200480028822 A CN 200480028822A CN 1863750 A CN1863750 A CN 1863750A
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CN1863750B (zh
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C·法米
G·卡多勒
P·黄
V·阿帕雷西多扎姆皮里
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
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    • 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
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    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/006—Aspects relating to the mixing step of the mortar preparation involving the elimination of excess water from the mixture
    • C04B40/0064—Processes of the Magnini or Hatscheck type
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
    • E04C2/02—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials
    • E04C2/04—Building 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
    • E04C2/044—Building 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 of concrete
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    • Y10T428/249921—Web or sheet containing structurally defined element or component
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Abstract

本发明涉及一种产品，具体而言是板，能够通过Hatschek工艺同时无需高压釜处理制成，而且能够用作挡风板、包覆元件或分隔元件，所述产品由包括至少一种水硬粘结剂比如凝合剂、至少一种填料比如碳酸钙和至少合成纤维的纤维强化凝合剂质基质形成。本发明还涉及制备所述产品的工艺。

Description

板状凝合剂产品和其制备方法
本发明涉及基于凝合剂(ciment)(通常是Portland凝合剂)或其它纤维的用金属加固的(armé)或强化的水硬粘结剂的产品的制备领域。更具体涉及制备片状或板状的、可用作建筑元件，尤其是挡风板(clin)、包覆元件(élément de bardage)或者分隔元件，的产品的制备。
这些产品通常采用在混合物中采用纤维的湿造纸技术制备。该技术的要点在于通过凝合剂、纤维和水的必要混合而得到的流体含水悬浮液进行渗透，形成和纸张类似的片；然后通过抽吸和/或压力排光所述片或者需要时的叠加片的水。纤维，通常是纤维素纤维，变得附着到过滤器上，形成辅助筛子或滤网，其网格单元的尺寸适于保留凝合剂或其它粘结剂或添加剂的颗粒，甚至细颗粒，以及相当量的水，后者有助于在所述筛子上形成的厚层的内聚。
在一种特殊技术中，过滤器由安装在含有悬浮液的罐中的覆盖有滤布的桶构成；由于所述桶在罐中旋转，所以静水压力迫使一些水穿过滤布，但固体，也即尤其是纤维素纤维、凝合剂颗粒和其它添加剂颗粒，在所述桶的筛子上累积成薄层，其厚度随着桶的旋转而增加。这种技术称作Hatschek技术。
这种技术用于制备各种类型的产品，比如屋面板、挡风板、包覆元件等，这些各种类型的产品每种都必须满足具体的要求。因此，屋面产品首要必须具有好的机械强度性质，但是所述打算用钉子钉住的挡风板、包覆元件或分隔元件通常具有稍微低些的机械强度性质，却同时具有比较严格的尺寸稳定性性质(收缩率值)(尤其是为了避免在钉子处出现开裂)。
对来自Hatschek工艺的产品采用高温(高于150℃)高压(数巴量级的饱和压力)下的高压釜处理步骤，通常能够对这种收缩性质进行限制(纵向几乎不随水分含量的变化而变化)。虽然好的、在尺寸稳定性性能水平上要求较不严格的屋面产品，可以无需采用这种高压釜处理操作而获得，但是迄今为止，还不可能通过不执行高压釜处理步骤或者不采用复杂的、对维护有苛刻要求的或者昂贵的制剂的Hatschek技术来获得可以用作挡风板或者包覆元件或者分隔元件的好产品。
所以，本发明的目标是开发可以通过Hatschek工艺在较低成本并无需高压釜处理下得到的新型产品，所述产品具有令人满意的机械性质和/或尺寸稳定性性能水平，尤其是适用作挡风板、包覆元件或分隔元件的那些。
此目标通过本发明的产品得以实现，所述产品具体而言是板状、能够通过Hatschek工艺并且无需高压釜处理而获得、能用作挡风板、包覆元件或分隔元件，所述产品包括至少一种水硬粘结剂比如凝合剂、至少一种填料比如碳酸钙、和至少合成纤维比如聚乙烯醇或聚烯烃纤维。
术语“合成纤维”和天然纤维比如纤维素纤维相反，是指通过合成(涉及人为控制的化学反应)获得的纤维，尤其是有机纤维，具体而言是来自石油衍生物的纤维，这些纤维通常可以熔融并由至少一种聚合物形成，该聚合物特别是热塑性聚合物，比如聚乙烯醇或聚烯烃。优选，这些纤维是聚乙烯醇(PVA)纤维，或者有利的是聚丙烯(PP)纤维或者可能的聚乙烯(PE)纤维。
根据本发明的产品能够通过Hatschek工艺，也就是说，从片状材料获得，所述片状材料具体而言通过含水悬浮液(在本发明中，所述悬浮液包括上面限定的组分，也即至少一种水硬粘结剂、一种填料和上述定义的合成纤维)在筛子或过滤器上的过滤获得，这样得到的所述片状材料的厚度在适当时叠加起来直到获得所需的最终厚度，从而得到板。所述板可以进一步通过抽干和/或压制(具体而言是为了调整密度和/或印刷装饰性图案)，例如，通过定径辊(在其上通常叠加了由毡垫圈(feutre)带来的材料片并卷绕到该辊上)或者静态机械压床，排光水，和/或通常在低温(例如，约60℃)烘箱中和/或在开放空气中经受固化步骤。本发明的产品有利地具有所需性质同时不需要使用高压釜处理步骤。
通过这种方式得到的本发明产品，通常处于通过过滤上述含水悬浮液形成的一个或多个片形成的板型，所以由纤维的用金属加固的凝合剂质基质形成，所述基质包括在本发明定义中提到的组分，所述基质或所述产品任选能够具有其它元件，尤其是附着在根据上述工艺得到的板上的那些，比如装饰(涂料涂层、印刷物等)、附件等。
根据本发明的定义，本发明产品包括至少一种水硬粘结剂，比如凝合剂；通常是Portland凝合剂(ciment Portland)。在悬浮液中用来获得上述产品的所述粘结剂或凝合剂的用量，相对于干物质的总重量，优选是18-75wt％，有利的是18-65wt％(下面，悬浮液中的重量含量或值通常用干物质相对干物质总重量的重量比给出)。
本发明的产品还包括至少一种填料，有利的是惰性或弱反应性无机填料，比如碳酸钙。优选，这种填料在悬浮液中的存在量是18-75重量％。
本发明的产品还包括合成纤维，比如上述的那些。有利地，这些纤维在悬浮液中的量是0.5-10重量％，而且可以处于相对分散或结合的形式。优选，这些纤维选择直径为5-16μm(通常10-15μm)的短纤维(长度小于数厘米)，具体选择长度为3-15mm(例如，对于PVA纤维而言是3-8mm或者甚至4-7mm，对于PP纤维而言是5-15mm或者甚至6-12mm)。还优选地，这些纤维选择拉伸强度(或者抗拉强度)至少为400MPa(具体而言，对于PP纤维为至少500MPa，对于PVA纤维而言至少为800MPa或者甚至900MPa)、杨氏模量至少为4GPa(具体而言，对于PP纤维至少为6GPa，对于PVA纤维而言至少为20GPa)和伸长率为6-40％(具体而言，对于PVA纤维为6-12％或者甚至7-11％，对于PP纤维为15-25％或者甚至17-20％)，这些值通过DIN 53816标准测量。
一般而言，本发明的产品还包括和上述纤维组合的至少植物纤维，尤其是纤维素纤维，具体而言是漂白的或者未加工的(未漂白的)纤维，优选精炼(raffinées)到约40-70，或者甚至55-65的SR度(或Schopper)，尤其是来自松树的纤维，但也来自剑麻或者其它植物，在悬浮液中的纤维总含量(包括合成纤维和任选的纤维素纤维)优选不超过10wt％。
凝合剂部分也可以用至少一种能够和该凝合剂反应，尤其涉及硅酸钙的形成的反应性材料替换，具体而言用至少一种白榴火山灰(pouzzolane)或者白榴火山灰反应性的材料替换。该白榴火山灰(或者白榴火山灰反应性的材料)优选选自铝硅酸盐、铝硅酸钙和无定形二氧化硅，而且尤其优选为硅酸铝脱羟基(déshydroxylée)形式的偏高岭土(métakaolin)，或者来自热发电站的飞灰，所述飞灰是铝硅酸盐类型或者铝硅酸钙类型的材料(根据ASTM C618标准是类型F或C)，或者另一包括米糠灰的反应性材料，所述材料基于二氧化硅的无定形形式或者来自生铁制造的高炉炉渣，所述炉渣是铝硅酸钙类型的材料，或者天然白榴火山灰，比如火山石或灰、凝灰岩、粗面凝灰岩、化石硅石或者硅藻土。
优选的，该以粉末形式使用的白榴火山灰具有平均直径(D50)大于1μm且小于或等于50μm、有利的为约10-30μm的颗粒尺寸。该粉末通常还有约10-50m2/g的比表面积(用BET方法测量)。
有利地，凝合剂(或粘结剂)和任何白榴火山灰(或者白榴火山灰反应性的材料)在悬浮液中的总含量不超过75wt％，优选不超过65wt％，尤其优选不超过60wt％，所述凝合剂和所述白榴火山灰的重量比优选大于或等于2。将凝合剂和白榴火山灰(在本发明定义的组分中)组合的实施方案，有益于获得机械性能得到改善同时仍能够具有相对令人满意的尺寸稳定性能水平的最终产品。同样，当有限凝合剂含量(18-55％，优选20-50％)和较高碳酸钙(或填料)含量(30-70％，优选35-65％)组合时，无论白榴火山灰存在与否，都获得了在尺寸稳定性方面的好结果以及在机械性能方面的极其令人满意的结果，如下面所述。
本发明的产品还可以包括添加剂，比如高岭土和/或絮凝剂和/或含水悬浮液的其它助剂，等。
在一个特别优选的实施方案中，悬浮液包括：
——20-50wt％，有利的25-45wt％的水硬粘结剂(或凝合剂)；
——35-65wt％，有利的38-62wt％的惰性或弱反应性无机填料(或碳酸钙)；
——2-10wt％，有利的3-8wt％的纤维，其中至少一部分是合成纤维；
——0-30wt％，有利的0-25wt％的白榴火山灰(或者白榴火山灰反应性的材料)；
——0-10wt％，尤其是0-5wt％的添加剂；
所述粘结剂(或凝合剂)和白榴火山灰的含量优选小于60％，而且凝合剂/白榴火山灰比大于或等于2。
优选，合成纤维在悬浮液中的含量至少为1wt％或者相对于纤维(所述任选的其它纤维有利地是纤维素纤维)总重量至少为25wt％，特别优选地，合成纤维在悬浮液中的含量为1-5wt％，或者甚至1.5-4wt％。
本发明的产品有利地是挡风板、包覆元件或分隔元件(或者打算这样使用)的形式。
本发明的目标也是本发明产品的制备方法，特征在于片状材料通过上述含水悬浮液在筛子或过滤器上过滤而制备，所述片状材料的厚度在适当时叠加直到获得所需的最终厚度以形成板，而且任选的所述板经受抽干和/或机械压制(在定径辊和/或压床中)步骤和/或固化步骤，通常在烘箱中于数十度(例如60℃)进行数小时(例如8小时)和/或在开放空气中进行。
任选地，所述板可以经受其它处理，例如可以成型和/或印刷和/或装置，例如注模，尤其是当其仍处于有延展性形式时(例如，在压制操作过程中)，具体而言是为了获得波纹状或非平面的板、具有木材外观的板，等。
下面的实施例举例说明了本发明产品的两种制剂以及所述产品的机械和尺寸稳定性性质。
实施例1
在该实施例中，基质由下列以干物质重量表示的组合物制备：
——34.7％的标准(CEM I 52.5)Portland凝合剂；
——60％的碳酸钙；
——2.3％的PVA纤维，得自Lanzhou；和
——3％的漂白的松树纤维素纤维，精炼到60°的Shopper。
实施例2
在该实施例中，基质由下列以干物质重量表示的组合物制备：
——39.7％的标准(CEM I 52.5)Portland凝合剂；
——40％的碳酸钙；
——2.3％的PVA纤维，得自Kuraray；
——3％的漂白的松树纤维素纤维，精炼到60°的Shopper；和
——15％的飞灰，得自Pozo Fly Comercio de Cinzas Lima Ltda。
试样制备
由Hatschek工艺制备纤维凝合板。
具体而言，制备上述组合物的稀释含水悬浮液(稀释度为例如每升水约50-200g干物质，这是Hatschek技术中常见的)，相对于上述组分的干物质重量，加入了0.04％的阴离子聚丙烯酰胺絮凝剂。
所制备的板长度为约2.5-3.6m，宽度为1.2-1.5m，厚度为约8mm。它们是由多个(通常为7-9个单层)以新鲜状态叠加的单层形成，所述单层是采用上述稀释的纤维凝合剂悬浮液在上述Hatschek生产线上制备的，这些单层叠加起来以形成板，所述板用定径辊压制从而去除一定量的水并提高单层互相之间的粘合。
固化(m rissement)
压制的板在60℃、100％相对湿度的烘箱中固化8小时。然后，存储板28天以完成固化。固化结束时，将板切割并如下进行表征。
表征：
基于ISO 8336标准规定的程序，对板进行表征。
——确定抗弯强度(三点)或MOR(断裂模量)：
一方面，确定在20℃的水中浸泡了24小时的测试块的抗弯强度(饱和的MOR)，另一方面，确定在2O℃和60％相对湿度的试验室气氛中干燥的测试块的抗弯强度(干燥的MOR)。最终的抗弯强度值是10个测试决的平均值。当饱和MOR大于7MPa而干燥MOR大于10MPa时，认为该抗弯强度足以用作挡风板、包覆元件或分隔元件。
——收缩率或水分移动：
测量在水中浸泡48小时后和在105℃在环境室中干燥后的测试块的长度。当在105℃干燥的测试块的质量变化恒定在约0.1％时，测试它的长度。该最终收缩值是3个试样的平均值。当收缩率值小于或等于0.2％时，认为对于用作挡风板、包覆元件或分隔元件是特别令人满意的。
下表1给出了评价结果。
                            表1
 实施例  凝合剂(％)  CaCo3(％)  PVA(％)  纤维素(％)  飞灰(％)  干燥MOR(MPa)  饱和MOR(MPa) 收缩率(％)
 1  34.7  60  2.3   3   0  14.7  9.2  0.18
 2  39.7  40  2.3   3   15  15.4  10.3  0.20
由配方1和2制备的板的收缩率值使其可以极其令人满意地用作挡风板、包覆元件或分隔元件，而且其良好的机械性质也使其可以令人满意地用作挡风板、包覆元件或分隔元件。
根据本发明的产品可用作挡风板、包覆元件或分隔元件等，其可以是平的或波纹状的等等。

Claims (8)

1、一种产品，具体而言是板，能够通过Hatschek工艺同时无需高压釜处理制成，而且能够用作挡风板、包覆元件或分隔元件，所述产品包括至少一种水硬粘结剂比如凝合剂、至少一种填料比如碳酸钙和至少合成纤维。
2、权利要求1的产品，特征在于它还包括至少一种白榴火山灰或白榴火山灰反应性的材料，优选选自铝硅酸盐、铝硅酸钙和无定形二氧化硅。
3、权利要求1或2的产品，特征在于它还包括植物纤维，比如纤维素纤维。
4、上述权利要求之一的产品，特征在于它由悬浮液制成，所述悬浮液包括以干物质重量表示的下列物质：
●20-50wt％的凝合剂；
●35-65wt％的碳酸钙；
●2-10wt％的纤维，其中至少一部分是合成纤维；
●0-30wt％的白榴火山灰；
●0-10wt％的添加剂。
5、权利要求4的产品，特征在于所述合成纤维的含量相对于干物质总重量为至少1wt％，或者相对于纤维的总重量为至少25wt％。
6、上述权利要求任一的产品，特征在于它呈挡风板或包覆元件或分隔元件的形式。
7、制备上述权利要求任一的产品的方法，通过过滤含有至少一种水硬粘结剂、填料和纤维的含水悬浮液，并任选地通过叠加片状材料的厚度直到获得最终所需厚度，以形成板。
8、权利要求7的方法，特征在于所述板被干燥和/或压制和/或经受固化步骤。
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