CN1802327A - 用于增强有机和/或无机材料的玻璃丝、含有它们的复合材料与使用的组合物 - Google Patents

用于增强有机和/或无机材料的玻璃丝、含有它们的复合材料与使用的组合物 Download PDF

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CN1802327A
CN1802327A CNA2004800159864A CN200480015986A CN1802327A CN 1802327 A CN1802327 A CN 1802327A CN A2004800159864 A CNA2004800159864 A CN A2004800159864A CN 200480015986 A CN200480015986 A CN 200480015986A CN 1802327 A CN1802327 A CN 1802327A
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E·勒孔特
S·克勒
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Saint Gobain Adfors SAS
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    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
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    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
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    • C04B14/00Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02Granular materials, e.g. microballoons
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    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/38Fibrous materials; Whiskers

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Abstract

本发明涉及增强玻璃丝,其组合物含有在下述确定范围内的以重量百分数表示的下述组分:SiO2 50-65%、Al2O3 12-20%、CaO 13-16%、MgO 6-12%、B2O3 0-3%、TiO2 0-3%、Na2O+K2O<2%、F2 0-1%、Fe2O3<1%。这些丝由具有用比杨氏模量表示的机械性能与熔化和拉制条件之间有极佳折衷的玻璃构成。

Description

用于增强有机和/或无机材料的玻 璃丝、含有它们的复合材料与使用的组合物
本发明涉及“增强”的玻璃丝(“或纤维”),即能增强有机和/或无机材料并可用作纺织纱的玻璃丝,这些丝能采用下述方法得到:从位于一般采用焦耳效应加热的拉丝模下部模孔流出的熔融玻璃束进行机械拉伸。
更具体地,本发明涉及具有高的比杨氏模量的玻璃丝,它们具有一种特别有利的SiO2-Al2O3-CaO-MgO类的四元组成。
增强玻璃丝的领域是玻璃工业中一种非常特别的领域。使用特有的玻璃组合物生产这些丝,因为根据前面指出的方法,应该能够将所用玻璃拉制成直径几微米的细丝形式,还应该能形成可起增强作用的连续丝。
尤其是在航空的某些应用中,寻求获得在动力学条件能使用的大尺寸零件,因此它们能承受大的机械应力。这些零件往往是以有机和/或无机材料和增强物为基的,其增强物例如呈玻璃丝形式,它通常占50%以上的体积。
通过改善增强物的机械性能,特别是在增强物的密度ρ不变,甚至更低的情况下的杨氏模量,达到改善这样一些零件的机械性能,提高其零件的产率,这样又提高了比杨氏模量(E/ρ)。
在用玻璃制成的增强丝的情况下,增强物的这些性能原则上是由构成它们的玻璃组合物所决定的。人们最熟知用于增强有机和/或无机材料的玻璃丝是由玻璃E和R构成的。
通常,玻璃E丝或者原样,或者以织物形式用于构成增强物。可以拉制玻璃E的条件是非常有利的:加工温度相应于玻璃粘度接近1000泊的温度,这个温度是相对低的,约1200℃,液相线温度比加工温度低约120℃,其去玻璃化速度是低的。
在电子与航空领域应用的ASTM D 578-98标准中规定的玻璃E组成如下(以重量百分数计):52-56%SiO2、12-16%Al2O3、16-25CaO%、5-10%B2O3、0-5%MgO、0-2%Na2O+K2O、0-0.8%TiO2、0.05-0.4%Fe2O3、0-1%F2
不过,玻璃E的比杨氏模量约33MPa.kg-1m3对于目标应用是不够的。
在ASTM D 578-98标准中,描述了任选地其它无硼玻璃E增强丝。这些丝的组成如下(以重量百分数计):52-62%SiO2、12-16%Al2O3、16-25CaO%、0-10%B2O3、0-5%MgO、0-2%Na2O+K2O、0-1.5%TiO2、0.05-0.8%Fe2O3、0-1%F2
无硼玻璃E的拉制条件不与有硼玻璃E的拉制条件好,但是这些条件在经济上仍是可接受的。比杨氏模量依然是在与玻璃E性能相当的水平上。
人们由US 4 199 364还知道具有改进断裂应力的无硼和无氟玻璃E。这种玻璃特别地含有氧化锂。
人们知道玻璃R具有高的机械性能,其比杨氏模量为约35.9MPa.kg-1m3。另一方面,熔化和拉制条件比提到的E类玻璃更受约束,因此其最后成本也更高。
FR-A-1 435 073给出了玻璃R的组成。其组成如下(以重量百分数计):50-65%SiO2、20-30%Al2O3、2-10CaO%、5-20%MgO、15-25%CaO+MgO;SiO2/Al2O3=2-2.8;MgO/SiO2<0.3。
曾对提高玻璃丝的机械强度进行过其它试验,但一般而言不利于拉制能力,这时加工变得更困难,或迫使人们改动现有的拉制设备。
因此,还需要有一些其成本尽可能接近于玻璃E的成本,而其机械性能水平可与玻璃R相比的增强玻璃丝。
本发明的目的是提供连续增强玻璃丝,其机械性能与玻璃R具有同一数量级,尤其涉及比杨氏模量,同时为在经济条件下获得增强丝而具有令人满意的熔化和拉制性能。
本发明的另一个目的是提供不含氧化锂的经济玻璃丝。
这些目的可借助下述玻璃丝达到,即其玻璃丝组合物基本上含有在下述确定范围内的以重量百分数表示的下述组分:
SiO2            50-65%
Al2O3         12-20%
CaO             13-16%
MgO             6-12%
B2O3          0-3%
TiO2           0-3%
Na2O+K2O     <2%
F2             0-1%
Fe2O3        <1%。
二氧化硅SiO2是构成本发明玻璃网络(réseau des verres)的其中一种氧化物,对其稳定性起到一种实质性的作用。在本发明的范围内,二氧化硅含量低于50%时,玻璃粘度变得太低,拉制时就会增加去玻璃化的危险性。超过65%时,这种玻璃变得非常粘稠,于是难以熔化。优选地,二氧化硅的含量是56-61%。
氧化铝Al2O3也是本发明玻璃网络的一种构造物,与二氧化硅结合时可对其模量起到一种实质性的作用。在本发明确定的限度范围,这种氧化物百分数降低低于12%会使液相线温度升高,而这种氧化物百分数增加太高超过20%会导致出现去玻璃化的危险性与粘度增加。优选地,选择组合物的氧化铝含量是14-18%。有利地,二氧化硅和氧化铝的含量之和高于70%,这样能够得到有意义的比杨氏模量值。
石灰CaO可以调节粘度与控制玻璃的去玻璃化。CaO含量优选地是13-16%。
氧化镁MgO完全与CaO一样,它起流化剂的作用,还对比杨氏模量起到有利的作用。MgO的含量是6-12%,优选地8-10%。优选地,CaO/MgO重量比高于或等于1.40,有利地低于或等于1.8。
还优选地,Al2O3与MgO的含量之和高于或等于24%,这样能够得到十分令人满意的比杨氏模量值和良好的拉制条件。
氧化硼B2O3起流化剂的作用。为了避免挥发和放出污染物问题,它在本发明组合物中的含量被限制到3%,优选地2%。
二氧化钛起流化剂的作用,还有助于提高比杨氏模量。它可以作为杂质存在(在这种组合物中的含量这时是0-0.6%)或可以有意添加。在后一种情况下,必需使用非常见原料,于是增加了这种组合物的成本。在本发明的范围内,只是二氧化钛含量低于3%,优选地低于2%时,添加TiO2才有利。
往本发明的组合物中可以加入Na2O和K2O,这样有助于制约去玻璃化作用,以及任选地降低玻璃粘度。然而,Na2O和K2O的含量应该仍低于2%,以便避免损害性地降低玻璃水解强度。优选地该组合物含有0.8%以下的这两种氧化物。
这种组合物可以有氟F2,它有助于玻璃熔化和拉制。不过,它的含量限于1%,因为超过这个含量可能有放出污染物,腐蚀炉子耐火材料的危险。
铁氧化物(以Fe2O3形式表示)一般作为杂质存在于本发明的组合物中。Fe2O3含量仍应该低于1%,优选地低于0.8%,以便不会严重损害丝的颜色与拉制设备的运行,特别是在炉子中的传热。
本发明的玻璃丝没有氧化锂。这种氧化物除其高成本外还对玻璃的水解强度有负影响。
优选地,这些玻璃丝基本上含有在下述确定范围内的以重量百分数表示的下述组分:
SiO2         56-61%
Al2O3      14-18%
CaO           13-16%
MgO           8-10%
B2O3       0-2%
TiO2        0-2%
Na2O+K2O  <0.8%
F2          0-1%
Fe2O3     <0.8%。
特别有利地,这些组合物的Al2O3/(Al2O3-CaO-MgO)重量比是0.4-0.44,优选地小于0.42,这样能够得到液相线温度低于或等于1250℃的玻璃。
使用前面描述组合物的玻璃,按照下述方法可以得到本发明的玻璃丝:将从一个或多个拉丝模下部多个模孔流出的多股熔融玻璃束拉伸成一个或多个连续丝层,然后将这些细丝合并成一根或多根丝,将这些丝收集在运动的支承件上。可能涉及一种旋转支承件,这时将这些丝以卷的形式进行收集,或可能涉及一种平移支承件,这时使用一种部件切断这些丝,而这种部件也用于拉伸它们,或使用一种部件喷射这些丝,而这种部件用于拉伸它们形成一种垫(mat)。
得到的这些丝任选地能进行其它的转变操作,它们因此呈不同的形式:连续丝或切断丝、饰带、带或垫,这些丝由直径约5-30微米的细丝构成。
加到拉丝模的熔融玻璃是由纯原料,或往往是天然原料(即可以含有微量状态的杂质)得到的,因此这些原料按照适当比例进行混合,再进行熔化。熔融玻璃的温度可按照传统方式进行调节,一般能够进行拉制,并且避免出现去玻璃化问题。在将它们合并呈丝形式之前,这些细丝通常涂敷一种胶料组合物,其目的在于防止它们磨损,因此有利于它们与这些增强材料最后合并。
由本发明的丝所得到的复合材料含有至少一种有机材料和/或至少一种无机材料和玻璃丝,至少一部分丝是本发明的丝。
下面的实施例能够说明而不限制本发明。
具有表1列出的以重量百分数表示的组成的熔融玻璃经拉伸得到由直径17μm玻璃细丝组成的玻璃丝。
将玻璃粘度等于103泊(分帕.秒)的温度记为T(logη=3)。
玻璃液相线温度记为T液相线,它相应于玻璃中可去玻璃化最难熔相具有零生长速度,因此相应于这个去玻璃化相的熔化温度的温度。
再转到比杨氏模量值,它相应于杨氏模量(根据标准ASTM C 1259-01测量的)与测量时所使用玻璃试样的密度的比。
作为对比实例给出了玻璃E和R的测量结果。
显然,本发明的这些实施例在熔化和拉制性能与机械性能之间有极佳的折衷。这些拉制性能是特别有利的,液相线温度至多等于1280℃(比玻璃R的低)时更如此。拉制范围是正的,特别是T(logη=3)与T液相线之差约10-50℃。
本发明组合物的比杨氏模量与玻璃R具有同样的数量级,但比玻璃E高得多。
使用本发明玻璃达到的机械性能与玻璃R具有明显同样的水平,同时显著地降低了拉制温度,接近于玻璃E所达到的值。
本发明的玻璃丝比玻璃R丝更经济,因此在某些应用中,特别是航空应用中,或增强直升飞机桨叶或光缆时,都可以用这些玻璃丝代替玻璃R丝。
                                            表1
 实施例1  实施例2  实施例3  实施例4   实施例5  实施例6  实施例7  玻璃E   玻璃R
  SiO2Al2O3CaOMgOB2O3TiO2Na2OK2O  59.515.914.88.80.10.10.5  58.817.014.68.60.10.10.5  58.017.914.48.50.20.10.6  57.716.014.88.71.80.10.10.5   57.516.014.98.82.00.10.5  58.516.913.310.00.10.10.5  59.516.213.89.50.10.10.5  54.414.521.20.37.30.6   60.025.09.06.0
  T(logη=3)(℃)T液相线(℃)  12811230  12851260  12891280  12541220   12711240  12921250  12981210  12031080   14101330
  比杨氏模量(MPa.kg-1.m3)  35.2  35.4  35.4  35.4   35.6  35.8  35.6  33.0   35.9

Claims (8)

1、增强玻璃丝,其组合物基本上含有在下述确定范围内的以重量百分数表示的下述组分:
SiO2            50-65%
Al2O3         12-20%
CaO              13-16%
MgO              6-12%
B2O3          0-3%
TiO2            0-3%
Na2O+K2O      <2%
F2              0-1%
Fe2O3         <1%。
2、根据权利要求1所述的玻璃丝,其特征在于该组合物包含MgO+Al2O3,其含量高于24%。
3、根据权利要求1或2所述的玻璃丝,其特征在于该组合物包含SiO2+Al2O3,其含量高于或等于70%。
4、根据权利要求1-3中任一项权利要求所述的玻璃丝,其特征在于该组合物的Al2O3/(Al2O3+CaO+MgO)重量比是0.40-0.44,优选地小于0.42。
5、根据权利要求1-4中任一项权利要求所述的玻璃丝,其特征在于该组合物的CaO/MgO重量比高于或等于1.40,优选地小于或等于1.8。
6、根据权利要求1-5中任一项权利要求所述的玻璃丝,其特征在于该组合物基本上含有下述组分:
SiO2            56-61%
Al2O3         14-18%
CaO              13-16%
MgO              8-10%
B2O3          0-2%
TiO2            0-2%
Na2O+K2O      <0.8%
F2              0-1%
Fe2O3         <0.8%.
7、玻璃丝与一种或多种有机和/或无机材料的复合材料,其特征在于它含有权利要求1-6中任一项权利要求所述的玻璃丝。
8、能生产增强玻璃丝的玻璃组合物,其组合物基本上含有在下述确定范围内的以重量百分数表示的下述组分:
SiO2        50-65%
Al2O3     12-20%
CaO          13-16%
MgO          6-12%
B2O3      0-3%
TiO2        0-3%
Na2O+K2O  <2%
F2          0-1%
Fe2O3     <1%.
CNB2004800159864A 2003-06-11 2004-06-09 用于增强有机和/或无机材料的玻璃丝、含有它们的复合材料与使用的组合物 Expired - Lifetime CN100564299C (zh)

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CA2528923C (fr) 2013-01-29
FR2856055B1 (fr) 2007-06-08
ES2299864T3 (es) 2008-06-01
KR101114274B1 (ko) 2012-03-05
RU2006100296A (ru) 2006-06-27
JP2006527158A (ja) 2006-11-30
CA2528923A1 (fr) 2004-12-23
US20070087139A1 (en) 2007-04-19
KR20060017862A (ko) 2006-02-27
RU2370463C2 (ru) 2009-10-20
FR2856055A1 (fr) 2004-12-17
EP1641717B1 (fr) 2008-01-09
MXPA05013323A (es) 2006-03-17
DE602004011226D1 (de) 2008-02-21
JP4945711B2 (ja) 2012-06-06
US20170066683A1 (en) 2017-03-09
NO20056224L (no) 2005-12-29
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ATE383321T1 (de) 2008-01-15
BRPI0411336B1 (pt) 2014-04-08

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