CN1071652A - 纤维增强成型固体制品 - Google Patents
纤维增强成型固体制品 Download PDFInfo
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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
- C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
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- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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- Y—GENERAL 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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- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Artificial Filaments (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
- Reinforced Plastic Materials (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract
本发明是有关用含有水、水硬性粘结料和增强纤
维的水硬性硬化组合物制造的成型固体制品,此外,
操作纤维的含量是相对于干基混合物总量的0—10
重量%,填充料的量为相对于干基混合物总量的0—
50重量%,其中增强纤维含有相对于干基混合物总
量为0.1—5重量%的高结晶度聚丙烯纤维,其纤维
断裂强度在490N/mm2以上并具有Q<5、
97<HI<100、以及94<IPF<100,Q是重均分子量
与数均分子量之比,HI是相对于聚合物总量的沸腾
正庚烷不溶物含量(以重量%计算),IPF是用摩尔%
表示的全同立构五价物的分数。
Description
本发明涉及制备纤维增强成型固体制品的一种新型建筑材料,这种成型制品的制造方法以及用这种新建筑材料混合物制造的成型固体制品。
通常已知用各种不同方法成形的制品,例如石板,平涂层板或瓦楞屋顶板,檩条,管或其它成型制品可由含水硬性粘结料,填充料和增强纤维混合物的悬浮水溶液制造。
在常规的结构材料中间,用石棉和水泥制造的纤维增强水泥制品在十年前就已公知了。在石棉水泥工业中,以L.哈谢克的卷绕法(奥地利专利说明书5970)为基础的工艺仍然是制备结构部件最常用的工艺。这种生产过程的工艺,例如,在现有技术(由Harald Klos撰写的题为石棉水泥的书中(“Asbestos Cement”),Springer Verlag,1967.)中已经完全描述清楚了。可适用的其它工艺,例如,马格纳尼法,马查制管法,Flow-on法,挤压和喷射法
制造石棉水泥板的哈谢克法是基于使用园筒形筛网脱水机。在该方法中,把由装在桶容器里的稀释的石棉水泥悬浮液制成的薄毡输送到毡上,通过筛网料筒并用成型滚筒缠绕卷紧到所要求的厚度。为制造瓦楞板,可把在成型滚筒上形成的石棉水泥板在达到所要求厚度之后进行切割,然后把这种板加工成型并在润滑的瓦楞金属模板之间进行硬化。
石棉的增强特性与它的固有抗拉强度有关,也与在水泥的悬浮水溶液中有极好的分散性能相关的工艺质量有关。因为有良好的过滤性能和良好的水泥亲合力,所以在脱水步骤中,石棉纤维可以牵制形成的混合物悬浮液中的细颗粒。在水化的最终产品中,与高的弹性模量相结合的高抗张强度以及断裂伸长小有助于形成已知的高抗弯强度的石棉水泥制品。
但是,在过去几年中,由于与环境和健康有关的一些因素,石棉变为一种不希望有的组份,并且设法用其它物质取代它。
在最近几年中,为了寻求在基于脱水方法的现有生产工艺部分或全部取代石棉的代用纤维进行了大量的研究工作。
因此,希望用新的纤维作为增强材料以及作为供水硬性粘结料(例如增强水泥)使用的辅助材料。这些纤维必须能使含纤维的制品具有所要求的从前用石棉能得到的机械性能。
对于增强水泥和其它水硬性硬化粘结料适用的纤维所满足的要求是异常高的。
下述特性表示在脱水工艺中石棉作为增强和操作纤维(process fibre)两方面的特征:
1)关于操作特性:
-高比表面积
-良好的分散性能
-极好的抗化学性和耐久性
-高的水泥滞留能力
-好的涂层成形能力
2)关于增强特性
-高抗张强度
-高的弹性模量
-断裂伸长小
就化学方面的要求来说,特别是在提高温度的条件下在饱和的氢氧化钙溶液中的抗碱性是一种绝对的先决条件。
没有发现其它天然的或人工合成的纤维能呈现出石棉纤维的全部综合性能。目前已知石棉的替代物要求相当于石棉的两种主要功能的两种不同的纤维(例如参见DE3002484)。石棉的过滤性质可以通过添加天然的或合成的料浆(例如单独的纤维素和/或合成的纤条体)再现。精选的增强纤维用作为复合增强材料。这些可以是一般切成长度为1-15mm的有机或无机的高模量纤维。
对许多用作为水泥增强材料的合成纤维性能进行了测定,令人遗憾的是由于某些原因如抗化学性能不好,缺乏水泥亲合力,机械性能差,特别是固有的韧性和弹性模量不大以及断裂伸长过多等使大多数测定都给出了不良的或不能令人满意的结果。价格昂贵也是经常限制工业应用的重要因素。
此外,纤维的物理特性,在重要性质方面应与那些水硬性粘结料是一致的。就水泥来说,已知这种材料有一定的脆性,例如,在延伸到约0.03%就可能断裂。根据现有技术,增强纤维的原始模量必须比水硬性粘结料的弹性模量高。
除了上述纤维的物理特性之外,如果这些纤维必须通过排水法处理以形成纤维水泥制品,下述特性同样也是重要的,即纤维可容易地分散在稀释的水泥悬浮液中并且在进一步加入添加剂时应仍然保持均匀地分散。
已有大量文献公布了使用各种天然的,合成的,有机和无机纤维的有关内容。由棉花、纤维素、聚酰胺、聚酯、聚丙烯腈(PAN)、聚丙烯和聚乙烯醇制成的纤维,尤其是对增强水泥已进行了研究。使用由玻璃、钢、芳族聚酰胺(aramide)和碳制成的纤维也是已知的。迄今所有这些纤维之中没有一个能具备所要求的全部必要条件,特别是对于水泥。
例如,玻璃的化学稳定性小,钢可被腐蚀并且密度过大,碳太脆,粘合力低而且价格高,纤维素的耐久性不高,聚乙烯和标准聚丙烯的抗张强度不大。
到目前为止,主要有两种合成纤维可满足作为水泥增强材料的要求。二者都是以聚乙烯醇(或PVA)和聚丙烯腈(或PAN)聚合物单独的(GB2850298)或结合在一起为基础的高模量纤维。前者可从“日本Kuraray公司商购Duralon
(DE2850337)”得到;后者,是由德国Hoechst生产的Dolanit
。
这两种纤维的特点在于具有下述高的韧性和低的断裂伸长:
PVA | PAN | |
韧性N/mm2原始模量N/mm2断裂伸长(%) | 155037007.4 | 910170009.0 |
在纤维-水泥领域中,已知当复合材料处于潮湿状态(通常是暴露在环境中)时机械强度较低,因此国际标准通常要求在水饱和的条件下进行测定。另外,断裂能量也是很重要的性质,因为它提供了制品的冲击韧性的数据。
PVA纤维具有较好的机械性能,不仅在潮湿状态具有较高的抗弯强度而且断裂能比PAN纤维要高的多。断裂能被定义为在应力-应变曲线一直到达到最大抗弯强度的点(也就是当复合材料断裂时)下面的面积。
PVA纤维的缺点是它在高温下对水的灵敏度以及其昂贵的价格。由PVA增强的成形制品在干燥状态显示出很好的机械性能但是在潮湿状态下其抗弯曲强度降低。
鉴于在纤维数据和得到的制品性质之间的相关性,依据仅使用PVA作增强纤维对抗弯曲强度,冲击韧性和断裂能规定高标准来生产纤维-水泥制品是比较简单的。PVA纤维的确是很昂贵的(比有效力较小的PAN纤维至少高50%)。
已提出的一个取得专利的解决办法是使用PVA和PAN的选择混合,这种选择混合得到的结果比根据混合规律所期待的结果更好(EP0155520)。
虽然这种解决办法从经济的(节省的)观点考虑是有吸引力的,但是断裂能仍保持在较低水平上。
本发明的目的是提供纤维增强成型固体制品,该制品克服了现有技术中的缺点,例如,在潮湿状态断裂能低和价格昂贵。
根据纤维-基质复合材料强度的混合规则,到目前为止只是高模量和高韧性纤维被用于制造具有抗弯强度的纤维-水泥制品。
纯水泥基质具有的E模量为15000N/mm2,因此,根据纤维-水泥复合材料的混合规则,必须假定增强纤维的E模量一定高于15000N/mm2。这种理论上的假定,现已被实际经验所证实。
因而始终认定当聚丙烯纤维作为基质材料的增强水泥,在比较脆性的水泥和砂浆的基质中定向拉伸或弯曲时,聚丙烯纤维在技术上是不良的。实际上,到目前为止,要得到能与作为最好的石棉代用品的高模量聚乙烯醇(PVA)纤维相比的结果似乎是完全不可能的。
意相不到的是,已经发现了有规立构的聚丙烯纤维具有可与PAN纤维相比的韧性,特别是具有低得多的弹性模量和高得多的断裂伸长,所得结果等于或好于PVA纤维。当在恶劣条件下,也就是在被水饱和的情况下对复合材料进行测定时,这些高水平的结果是特别明显的。
本发明的主题是用含水,水硬性粘结料和增强纤维的水硬性硬化组合物制造的成型固体制品,此外操作纤维的含量是干基混合物总量的0-10重量%,填充料的量为干基混合物总量的0-50重量%,其中增强纤维含有干基混合物总重的0.1-5重量%的高度结晶状聚丙烯纤维,这种聚丙烯的纤维断裂强度在490N/mm2以上并且具有Q<5,97<HI<100,和94<IPF<100,Q是重均分子量与数均分子量之比,HI是相对于聚合物总量的沸腾正庚烷不溶含量(以重量%计算),IPF是全同立构五价物的分数(以摩尔%表示)。最好是增强纤维含有相对于干基混合物总重为0.3-4重量%的高度结晶状聚丙烯纤维。
上述纤维最初含有0.05-10重量%的亲水剂,这种亲水剂是通过与钙离子反应制造的,在纤维表面上几乎是不溶的。上述亲水剂最好是含有8-18碳原子的磷酸烷基碱金属盐。
如果磷酸烷基碱金属盐的含量小于0.05重量
,不足以分散纤维,但是如果含量超过10重量%,则效果没有改进。最好是使用钠或钾盐。
Q是重均分子量与数均分子量之比。
在本申请中Q是用凝胶渗透色谱法(GPC)测定的。
(a)测量装置:ALC/GPC TYPE 150C,Waters Laboratory Co.
(b)色谱柱:TSK-GER GMH6-HT(高温型)
(c)溶剂:邻二氯苯(ODCB)
(d)温度:135℃
(e)探测器:差热折射仪
(f)流动溶剂的体积:1ml/min
在上述条件下,高结晶度的聚丙烯给出如下结果:
聚合物 Mn Mw Q(Mw/Mn) MFR(q/10 min)
高结晶度的 40,000 140,000 3.5 1,5
聚丙烯
其中:
Mw:重均分子量
Mw=[∑NiMi2]/[∑NiMi];
Mn:数均分子量
Mn=[∑NiMi]/[∑Ni];
Q:Mw/Mn之比;
MFR:熔体流动范围
通常,重均分子量对数均分子量之比被用作测定多分散性的程度,当该值大于1(单分散性)时分子量分布曲线变的更宽。当聚合物变成更多的支链时,该值也更高。
HI即正庚烷不溶物的测定是如下进行的:将5g聚丙烯样品完全溶解于500ml沸腾的二甲苯中,将该混合物注入5升甲醇中,回收沉淀物,干燥沉淀物并按照Soxhlet法在沸腾的正庚烷中萃取6小时,以得到提取残余物。HI值是以相对于聚合物总量的重量百分数给出的。
IPF即全同立构五价物分数的测定是基于正庚烷不溶物按照在“大分子”,第6卷,第925页(1973)和第8卷,第697页(1975)中提出的方法进行的。
颗粒状的这种聚丙烯的密度约为0.905,这个值与普通聚丙烯的密度是显著不同的。
高结晶度的聚丙烯纤维最好具有740N/mm2或更高的纤维断裂强度并具有Q≤4.5,HI≥98、IPF≥96。该纤维的登尼尔(d)(测量丝的纤度单位)的范围是0.5<d<20。
纤维可以被切割成2-15mm的不等长度,纤维长度的最好范围是在5-10mm之间。纤维截面可以是园形的或者不规则的形状例如X或Y形。在拉伸过程中或是在拉伸之后,纤维可以被卷曲。卷曲纤维的技术可有下述几种:例如,假捻,喷气交缠处理(包括塔斯伦卷曲变形(TASLAN)加工处理)或压缩处理(即填塞箱)。
纤维也可含有填充料,例如这种填充料可以是例如:碳酸钙、无定形的二氧化硅,天然的和合成的硅酸钙以及其他无机物。
聚丙烯的熔体流动范围(MFR)是1<PFR<100,优先选用的是5<MFR<30,最好是10<MFR<20。熔体流动范围(MFR)是在190℃,按通过喷嘴的速度(单位:g/10min,JIS K7210,载荷2.169kg)进行测定的。
为了减少分子的缠结或折叠,纤维的熔体旋转温度应保持在相对低的温度范围,最好是在260-280℃。
为了尽可能地改进拉伸性能,拉伸温度最好是140-150℃。
聚丙烯纤维的加入量是干基混合物总量的0.1-5重量%,最好的添加量是0.3-4重量%。当纤维含量低于0.1重量%时,不能达到增强的效果,当高于5重量%时,复合材料的抗弯强度急速地下降。
下面将更详细地描述本发明。为简便起见,在描述中以水泥作为优先选用的粘结料。但是所有其它的水硬性硬化粘结料都可以代替水泥而被使用。适用的水硬性硬化粘结料应理解为包括无机水泥和/或无机粘结料或通过水化作用被硬化的粘结料在内的物质。特别适用的通过水化而被硬化的粘结料包括,例如,波特兰水泥,高铝水泥、高铁波特兰水泥、火山灰质水泥、矿渣水泥、石膏,在热压釜处理过程中生成的硅酸钙以及各种单一粘结料的组合。
多种不同性质的填充料和添加剂,例如可以对水泥块的气孔结构产生有益影响的,又如可以通过排水装置改进悬浮液的排水性能的填充料和添加剂也经常被加入到粘结料中。可供使用的这种类型的添加剂例如可以是粉煤灰、非晶质二氧化硅、石英粉、岩石粉、粘土、高炉矿渣、火山灰碳酸盐等等。
按照本发明的成形固体制品还可以包括除聚丙烯纤维以外的无机纤维或有机纤维。
当其它的合成有机纤维与聚丙烯纤维一起被使用时,增强纤维的总量应保持在0.3-5重量%(相对于干基的混合物总量计算)之间。其它的合成有机增强纤维的量与增强纤维总量之比应在0.1和0.9之间,这种纤维的例子有:聚丙烯腈、聚乙烯醇、聚酰胺、聚酯、芳族聚酰胺(aramide)、碳和聚烯烃。
另一方面,当天然的或合成的无机纤维与聚丙烯纤维一起被使用时,这种纤维组合在一起的总量可以是干基混合物总量的2-20重量%之间。在这种组合起来的纤维中使用的聚丙烯纤维的量应为干基混合物总量的0.3-5重量%,作为无机纤维的实例有:玻璃纤维,矿棉、矿渣棉、硅灰石、石棉、海沧石、陶瓷纤维等等。
本发明中使用的纤维的制造不是本专利申请的主题。例如,它是通过已知的熔体旋转法完成的。例如这些高强度纤维的制备方法如下:
聚丙烯纤维的制造
将具有熔点为165℃、Q=3.5、HI=98%、IPF=97%以及熔体流动范围为15g/10min的聚丙烯树脂颗粒在275℃旋转并且在150℃、用加热滚筒干燥法将纤维拉伸4.5倍,由表面活化剂浸渍、放置通宵并在空气中干燥。得到的纤维具有1.9登尼尔、770N/mm2的拉伸强度和25%的断裂伸长。在用做建筑材料的配料之前将纤维切断。使用的表面活性剂是具有8-18个碳原子的普通磷酸烷基金属盐,例如,十二烷基磷酸钾、癸基磷酸钾或是十三烷基磷酸钾。表面活性剂的量是纤维重量的0.5-3%。
实施例1-9
为了对高晶度聚丙烯纤维与其它纤维进行比较制作了如下的九个组合物
聚丙烯(*):本发明的聚丙烯纤维
改性的PVA(1):按照在EP363.891中定义的改性PVA纤维
在哈谢克装置上制备混合物配料
将精制到65°SR(Shopper-Riegler)的牛皮纸纤维素浆与非晶形二氧化硅、隋性填充料、水泥以及合成纤维混合制成总固体浓度为200g/l的悬浮液。
用水把这种纤维水泥悬浮液的料浆进一步稀释到30g/l的浓度,然后转送到哈谢克装置的桶容器中。
在将这种料浆转送到桶容器这前不久,为了改进水泥的保存性能,另外添加200ppm的聚丙烯酰胺类型的絮凝剂。
在装配有18转的成型轴的该装置上制做板材,然后用一组压力机在涂油的钢模板之间施加250巴的压力,将上述板材进行压制以达到6mm的平均厚度。
将板材在塑料覆盖下、在相对湿度100%、温度20℃的条件下养护28天。
在潮湿状态即在用水饱和的条件下按照ISO4150进行机械(力学)测定。
结果在下面的表Ⅱ中给出。
样品抗弯强度的测定是用英斯特良(Instron)机械检验器,通过传统的三点弯曲试验进行的。该装置记录了应力一应变曲线,根据该曲线计算出的结果如下所述
MOR是用每平方毫米的牛吨(Newton)数(N/mm2)表达的断裂模量、用公式MOR=N/W给出。
其中:M=(用牛吨为单位表示的断裂负荷×支柱之间的距离)/4
W=([样品厚度的平均值]2×与支柱平行的被测样品的尺寸)/6
-用焦耳(Joules)/平方米(J/m2)表达的在最大负荷的断裂功(IMOR)是直到断裂负荷P时应力一应变函数的积分。
-断裂功(IPL20)也是用J/m2表达的、当达到某一点(在该点的负荷[曲线的纵坐标]减少至所测得最大值p的20%)时应力-应变函数的积分。
从潮湿状态试验表(表Ⅱ)可以看到,按本发明制成的制品具有更大的可延性并且其强度是可与目前用于纤维增强水泥制品的最好增强纤维所得到的强度相比的。
实施例10-13
制备了如下的组合物并且在塑料覆盖下在相对湿度为100%、温度20℃条件下养护28天,然后按下述循环进行加速老化试验:
1、在20℃水中浸渍72小时,
2、在80℃加热室中干燥72小时。
重复上述处理8次并且在用水饱和的条件下、在相对于板材的纤维取向的二个方向上测定平均断裂能。
可以观察到,当使用本发明的纤维时,不仅初始断裂能比用一般纤维时要高得多而且在经水/加热循环处理8次之后,这种能量仍被完全保持了,反之用别的纤维时其效能要损失50%以上。下面的表Ⅲ中给出了这些结果。
(*)根据本发明的聚丙烯纤维
当然,本发明并不受上面实施方案和实施例描述的限制,而是在本发明权利要求范围内可进行很多变化和改进。
注释:
IPF是全同立构五价物分数,即由五个单体单位(五价物pentads)组成的摩尔份数,这五个单体是用链式全同立构构型连接的。
Claims (13)
1、用含水、水硬性粘结料和增强纤维的水硬性硬化组合物制造的成形固体制品,此外操作纤维的含量是相对于干基混合物总量的0-10重量%,填充料的量为相对于干基混合物总量的0-50重量%,其特征在于,增强纤维含有相对于干基混合物总量为0.1-5重量%的高结晶度聚丙烯纤维,其纤维断裂强度在490N/mm2以上,并具有Q<5、97<HI<100以及94<IPF<100,Q是重均分子量与数均分子量之比,HI是相对于聚合物总量的沸腾正庚烷不溶含量(按重量%计算),IPF是以摩尔%表示的全同立构五价物的分数。
2、按照权利要求1所述的制品,其特征在于增强纤维含有相对于干基混合物总量为0.3-4重量%的高结晶度聚丙烯纤维。
3、按照上述任一权利要求所述的制品,其特征在于聚丙烯纤维具有740N/mm2或更高的纤维断裂强度,并具有Q≤4.5,HI≥98以及IPF≥96。
4、按照上述任一权利要求所述的制品,其特征在于聚丙烯纤维的登尼尔(d)的范围是0.5<d<20。
5、按照上述任一权利要求所述的制品,其特征在于聚丙烯纤维的长度范围是2-15mm。
6、按照上述任一权利要求所述的制品,其特征在于聚丙烯纤维的长度范围是5-10mm。
7、按照上述任一权利要求所述的制品,其特征在于聚丙烯纤维的截面是园形的。
8、按照权利要求1-6之一所述的制品,其特征在于聚丙烯纤维的截面是不规则的、大体上是x形的。
9、按照权利要求1-6之一所述的制品,其特征在于聚丙烯纤维的截面是不规则的、大体上是Y形的。
10、按照上述任一权利要求所述的制品,其特征在于聚丙烯纤维是卷曲的。
11、按照上述任一权利要求所述的制品,其特征在于聚丙烯纤维含有填充料。
12、按照上述任一权利要求所述的制品,其特征在于增强纤维除聚丙烯纤维之外,还含有别的合成有机纤维。
13、按照上述任一权利要求所述的制品,其特征在于增强纤维还含有无机纤维。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP28226891 | 1991-10-01 | ||
JP282268/91 | 1991-10-01 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1071652A true CN1071652A (zh) | 1993-05-05 |
CN1050346C CN1050346C (zh) | 2000-03-15 |
Family
ID=17650242
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN92109754A Expired - Fee Related CN1050346C (zh) | 1991-10-01 | 1992-08-03 | 纤维增强成型固体制品 |
Country Status (19)
Country | Link |
---|---|
US (2) | US5338357A (zh) |
EP (2) | EP0537129B1 (zh) |
JP (2) | JP2633763B2 (zh) |
CN (1) | CN1050346C (zh) |
AT (1) | ATE129992T1 (zh) |
BR (1) | BR9203102A (zh) |
CA (1) | CA2077395C (zh) |
CZ (1) | CZ287155B6 (zh) |
DE (2) | DE69205942T2 (zh) |
DK (1) | DK0537129T3 (zh) |
ES (1) | ES2080476T3 (zh) |
FI (1) | FI105912B (zh) |
GR (1) | GR3018655T3 (zh) |
HK (1) | HK1007309A1 (zh) |
HU (1) | HU214790B (zh) |
MX (2) | MX9204566A (zh) |
PL (1) | PL170636B1 (zh) |
SK (1) | SK280257B6 (zh) |
ZA (1) | ZA925720B (zh) |
Cited By (2)
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CN1070936C (zh) * | 1995-12-14 | 2001-09-12 | 智索股份有限公司 | 聚丙烯纤维及其制造方法以及由聚丙烯纤维制成的非织造布 |
CN1116241C (zh) * | 2000-04-26 | 2003-07-30 | 中国纺织大学化纤科技开发部 | 混凝土和砂浆用改性聚丙烯短纤维及其混凝土和砂浆 |
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AR015457A1 (es) * | 1997-10-15 | 2001-05-02 | Redco Nv | Fibras de polipropileno para el refuerzo de productos de fibrocemento, proceso para el tratamiento superficial de fibras de polipropileno, y producto formado en fibrocemento |
US5993537A (en) * | 1998-03-11 | 1999-11-30 | Dalhousie University | Fiber reinforced building materials |
DK0987356T3 (da) * | 1998-03-31 | 2009-11-30 | Ube Nitto Kasei Co | Fremgangsmåde til trækning |
CA2269000C (en) * | 1998-04-13 | 2007-07-03 | Kuraray Co., Ltd. | Reinforcing material for kneaded and formed hydraulic material, and kneaded and formed article |
DK1044939T3 (da) | 1999-04-13 | 2011-12-05 | Redco Sa | Formede fibercementemner og fibre til forstærkning af samme samt fremgangsmåde til behandling af sådanne fibre |
US6258159B1 (en) * | 1999-08-30 | 2001-07-10 | Polymer Group, Inc. | Product and method for incorporating synthetic polymer fibers into cement mixtures |
CA2402886C (en) | 2000-03-14 | 2012-02-14 | James Hardie Research Pty Limited | Fiber cement building materials with low density additives |
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US7585445B2 (en) | 2002-09-26 | 2009-09-08 | Saurer Gmbh & Co., Kg | Method for producing high tenacity polypropylene fibers |
MXPA05003691A (es) | 2002-10-07 | 2005-11-17 | James Hardie Int Finance Bv | Material mixto de fibrocemento de densidad media durable. |
FR2849064B1 (fr) * | 2002-12-20 | 2006-11-03 | Saint Gobain Mat Constr Sas | Fibre de renforcement en polyolefine, utilisation et produits comprenant la fibre |
BRPI0414960B1 (pt) | 2003-10-02 | 2014-11-11 | Saint Gobain Mat Constr Sas | produto de cimento reforçado de fibras, em particular uma placa, obtida pelo processo de hatschek e sem autoclavagem, e processo para a fabricação do mesmo |
US7998571B2 (en) | 2004-07-09 | 2011-08-16 | James Hardie Technology Limited | Composite cement article incorporating a powder coating and methods of making same |
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JP4990827B2 (ja) * | 2007-09-10 | 2012-08-01 | 株式会社クラレ | 水硬性組成物および水硬化物 |
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CZ304475B6 (cs) * | 2009-11-30 | 2014-05-21 | ÄŚeskĂ© vysokĂ© uÄŤenĂ technickĂ© v Praze, Fakulta stavebnĂ | Vláknobeton pro zemní konstrukce a jiné nenáročné stavby bytové a občanské výstavby |
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-
1992
- 1992-05-15 JP JP4123959A patent/JP2633763B2/ja not_active Expired - Fee Related
- 1992-07-13 JP JP4185525A patent/JP2633772B2/ja not_active Expired - Lifetime
- 1992-07-30 ZA ZA925720A patent/ZA925720B/xx unknown
- 1992-08-03 DK DK92870115.0T patent/DK0537129T3/da active
- 1992-08-03 CZ CS19922410A patent/CZ287155B6/cs not_active IP Right Cessation
- 1992-08-03 PL PL92295506A patent/PL170636B1/pl not_active IP Right Cessation
- 1992-08-03 AT AT92870115T patent/ATE129992T1/de not_active IP Right Cessation
- 1992-08-03 ES ES92870115T patent/ES2080476T3/es not_active Expired - Lifetime
- 1992-08-03 FI FI923503A patent/FI105912B/fi active
- 1992-08-03 SK SK2410-92A patent/SK280257B6/sk unknown
- 1992-08-03 HU HU9202517A patent/HU214790B/hu not_active IP Right Cessation
- 1992-08-03 DE DE69205942T patent/DE69205942T2/de not_active Expired - Fee Related
- 1992-08-03 US US07/923,596 patent/US5338357A/en not_active Expired - Fee Related
- 1992-08-03 EP EP92870115A patent/EP0537129B1/fr not_active Expired - Lifetime
- 1992-08-03 CN CN92109754A patent/CN1050346C/zh not_active Expired - Fee Related
- 1992-08-06 MX MX9204566A patent/MX9204566A/es not_active IP Right Cessation
- 1992-08-11 BR BR929203102A patent/BR9203102A/pt not_active IP Right Cessation
- 1992-08-27 DE DE69206565T patent/DE69206565T2/de not_active Expired - Lifetime
- 1992-08-27 EP EP92114661A patent/EP0535373B1/en not_active Expired - Lifetime
- 1992-09-02 CA CA002077395A patent/CA2077395C/en not_active Expired - Lifetime
- 1992-09-30 MX MX9205584A patent/MX9205584A/es unknown
-
1994
- 1994-05-27 US US08/250,658 patent/US6010786A/en not_active Expired - Lifetime
-
1996
- 1996-01-11 GR GR960400053T patent/GR3018655T3/el unknown
-
1998
- 1998-06-24 HK HK98106532A patent/HK1007309A1/xx not_active IP Right Cessation
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1070936C (zh) * | 1995-12-14 | 2001-09-12 | 智索股份有限公司 | 聚丙烯纤维及其制造方法以及由聚丙烯纤维制成的非织造布 |
CN1116241C (zh) * | 2000-04-26 | 2003-07-30 | 中国纺织大学化纤科技开发部 | 混凝土和砂浆用改性聚丙烯短纤维及其混凝土和砂浆 |
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