CN101374780B - 用于绝热材料的可生物降解的陶瓷纤维组合物 - Google Patents
用于绝热材料的可生物降解的陶瓷纤维组合物 Download PDFInfo
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- CN101374780B CN101374780B CN2007800035333A CN200780003533A CN101374780B CN 101374780 B CN101374780 B CN 101374780B CN 2007800035333 A CN2007800035333 A CN 2007800035333A CN 200780003533 A CN200780003533 A CN 200780003533A CN 101374780 B CN101374780 B CN 101374780B
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- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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- Glass Compositions (AREA)
Abstract
本发明涉及一种在人造体液中具有好的可溶性的用于高温绝热材料的可生物降解的陶瓷纤维组合物,更具体地,涉及这样一种用于高温绝热材料的可生物降解的陶瓷纤维组合物,其按合适的比例包含作为主要组分的网络形成物氧化物(SiO2),以及网络外体氧化物(CaO,MgO,Na2O和K2O)以及中间体氧化物(ZrO2和Al2O3)。该组合物在体液中具有良好的可溶性;良好的高温性能,通过控制R2O的含量,其中R是碱金属,甚至在高SiO2含量的高粘度范围内在体液中具有良好的可溶性,以及通过控制CaO+MgO的含量而在高温下应用时具有良好的耐热性,好的压缩强度,以及好的可恢复性。利用这种组合物,可以通过采用传统的设备,以高产率方便经济地制备纤维。
Description
发明领域
本发明涉及一种用于高温绝热材料的可生物降解的陶瓷纤维组合物,更具体地,涉及这样一种用于高温绝热材料的可生物降解的陶瓷纤维组合物,其按合适的比例包含作为这种组合物的主要组分的网络形成物氧化物(SiO2),以及网络外体氧化物(CaO,MgO,Na2O和K2O)以及中间体氧化物(ZrO2和Al2O3)。该组合物具有良好的可生物降解性;通过控制在热处理过程中沉积并生长的微晶的数量而具有良好的高温性能;通过控制R2O的含量,其中R是碱金属,甚至在高SiO2含量的高粘度区内具有良好的可生物降解性,由此降低当陶瓷纤维粉体被吸入时对人体的危害;以及通过控制CaO+MgO的含量而具有足以在高温下应用的好的热性能,机械性能,比如良好的耐热性,良好的压缩强度,以及良好的可恢复性。利用这种组合物,可以通过采用传统的设备,高产率地方便经济地制备纤维。
背景技术
由于无机纤维通常具有低的热导率以及细长的形状,其通常被用于高温和低温下的绝热材料,隔音材料,吸声材料,过滤材料等。取决于它们的耐热温度,这些无机纤维被分类成玻璃纤维,矿物纤维以及陶瓷纤维。玻璃纤维和矿物纤维具有相对较低的耐热温度,而陶瓷纤维在1000℃或者更高的温度下表现出的线性收缩低到3%或者更低,而且具有良好的抗水性和化学稳定性。
作为在高温下具有良好性能的耐火陶瓷纤维(RCF),Al2O3-SiO2(RCF-AS)基纤维的安全使用温度为1100-1260℃,Al2O3-SiO2-ZrO2(RCF-ASZ)基纤维的安全使用温度为大约1430℃。
制备RCF无机纤维的方法包括:将满足所希望性能的原料组合物熔融,将熔体纤维化,然后进行热处理或者根据目的进行处理。作为纤维化的方法,有采用压缩空气或者蒸汽的喷吹法,以及将熔体滴落在高速旋转的圆筒上的纺丝法。由于在耐热温度方面呈现出良好的性能,这种RCF无机纤维被用于高温绝热材料。
依据以前的报道,在体液中具有低溶解性的纤维,当以碎裂细小的形式被吸入后,会聚集在肺里,损害人体健康。所以,为了通过提高生理可溶性来将纤维的伤害最小化并同时满足高温性能的需要,最近,已经进行了热烈的研究。
将与上述相关的技术总结如下:
美国专利No.5,332,699公开了一种CaO-MgO-SiO2(CMS)基陶瓷纤维作为RCF无机纤维,通过往传统的RCF无机纤维中加入CaO和MgO代替Al2O3来制备。这种CMS基陶瓷纤维具有的平均纤维直径为3.5μm或者更细,在人造体液中的可溶性为0.02wt%Si/天,这是良好的可溶性特性。然而,其只能在840℃下满足2小时的耐火测试,因此,与传统的RCF无机纤维相比,具有差的高温性能。
美国专利No.5,994,247;5,955,389;5,928,975和5,811,360等是对上述美国专利No.5,332,699的改进。但是,由这里所公开的方法制备的无机纤维在1000℃的线性收缩低于3.5%,因而与传统的RCF无机纤维相比呈现出差的性能。而且,在制备纤维方面,熔体的粘度低,因而纤维化产率低。
美国专利No.5,874,375以及6,025,288公开了一种SMZ基陶瓷纤维,其由SiO2,MgO和ZrO2构成,具有可生物降解性,并且,在用于1000-1260℃或者更高温度下的绝热材料时,依赖于各组分的含量,热线性收缩为4.5%或者更低。
然而,由上面的方法制备的纤维具有的平均纤维直径在6μm或者更粗,因而如果制成纤维,其高温绝热性能会变差。而且,由于提供MgO的天然原料,比如白云石,菱镁矿,苦土,方镁石,滑石或者其它类似材料中大多含有大量的CaO,为了满足上述专利的条件,相对较贵的MgO需要纯化到高纯度再使用,因此,它们从经济上不适合作为大规模生产的原料。
因而,有一种强烈的需求以发展一种新的可作为用于高温绝热材料的无机纤维的陶瓷纤维,其当被吸入人体后在体液中具有可生物降解性,具有化学稳定性,良好的热性能,机械性能,比如在高温下良好的耐热性,良好的压缩强度以及在压缩后良好的可恢复性;给出适合于大规模生产的高产率,提供具有竞争力的价格;并且容易处理,可以采用相对便宜的原料来制造。
发明简述
作为为解决上述问题而辛苦努力的结果,通过将作为用于高温绝热材料的无机纤维的主要组分的网络形成物氧化硅(SiO2),与网络外体氧化物(CaO,MgO,Na2O和K2O)以及中间体氧化物(ZrO2和Al2O3)按合适的比例混和,制成纤维组合物,本发明人可以制备出具有良好的高温性能和改善的可生物降解性的陶瓷纤维,特别地,通过控制R2O的含量,R为碱金属,可以制备出甚至在高SiO2含量的高粘度区内具有良好的可生物降解性的陶瓷纤维。而且,通过提高产率,本发明人可以经济地制备陶瓷纤维。
所以,本发明的目的是提供一种用于高温绝热材料的可生物降解的陶瓷纤维组合物,当所述陶瓷纤维被吸入后,对人体具有降低了的危害性,以及具有足以在高温下使用的良好的热性能,机械性能,比如良好的耐热性,良好的压缩强度,以及良好的可恢复性,并且,通过采用传统的设备,可以由其方便经济地制备纤维,并具有提高了的产率。
发明详述
本发明涉及一种用于高温绝热材料的可生物降解的陶瓷纤维组合物,其包含75-80wt%的SiO2,13-20wt%的CaO,1-8wt%的MgO,0.5wt%或者更低的Al2O3,0.5-3wt%的ZrO2,2.5-4wt%的R2O,其中,R是碱金属,以及1wt%或者更低的杂质,所述杂质包含Fe2O3,TiO2,B2O3以及P2O5;优选0.5-3wt%的Al2O3+ZrO2,15-26wt%的CaO+MgO以及2.5-3.5wt%的Na2O。
在采用依据本发明的陶瓷纤维组合物制备纤维中,可以采用传统的方法,比如喷吹法或者纺纱法。采用前述传统方法所需要的纤维组合物的理想粘度应该低到20-100泊,或者与传统的Al2O3-SiO2(RCF-AS)基组合物的粘度相似,或者与其没有显著不同。具体地,相同组合物的粘度依赖于温度。也就是说,如果在纤维化过程中的熔体温度高,熔体的粘度将变低,反过来,如果在纤维化过程中熔体的温度低,熔体的粘度将变高,由此影响纤维化。当纤维组合物的粘度在纤维化温度下太低时,存在的问题是,制备的纤维短而细,由于未纤维化的渣球的含量高,纤维化产率太低。相反,如果粘度太高,存在的问题是,所得到的纤维具有大的纤维直径和长度,粗的未纤维化的渣球比例高。由于玻璃熔体的粘度通常依赖于温度和玻璃的组成,为了保持合适的纤维化粘度,需要合适的组成设计。对于高粘度的组合物,纤维化应该在较高的温度下进行,因此需要在纤维化温度附近对粘度进行合理控制。而且,为了确定合适的纤维化特性,可以对所制备的纤维的性质(纤维的直径,渣球含量等)进行测量,并与传统RCF(Al2O3-SiO2体系)的性质相比较。
下面基于依据本发明的可生物降解的陶瓷纤维组合物的组分给出更加详细的描述,除非另外提到,否则这里所采用的单位,wt%,基于组合物的总重量。
首先,依据本发明的可生物降解的陶瓷纤维组合物优选包含75-80wt%的SiO2作为陶瓷纤维的主要组分。如果SiO2的含量超过80wt%,带来的缺陷是纤维组合物熔融困难,纤维化粘度提高,由此引起纤维直径和长度的增加,产生更多粗的未纤维化渣球。相反,如果SiO2的含量低于75wt%,需要增加CaO和MgO的含量以改善可生物降解性,这带来的问题是原料的成本增加,纤维的长度高度缩短,因而降低了刚性,由于增加了未纤维化渣球的含量而使纤维化困难,由于增加了热收缩而导致性能变坏。
依据本发明的可生物降解的陶瓷纤维组合物包含CaO和MgO作为网络外体氧化物以提高所制备的纤维在体液中的可溶性。
优选依据本发明的纤维组合物中包含的CaO的量在13-20wt%。如果该含量低于13wt%,可生物降解性,即在体液中的可溶性下降。相反,如果该含量超过20wt%,在纤维制备过程中沉积的微晶的量增加。因而,在所制备的纤维中SiO2的含量相对降低,由此带来的问题是在高温下的热线性收缩增加。
优选依据本发明的纤维组合物中包含1-8wt%的MgO作为提高纤维可生物降解性的另一种网络外体氧化物。如果MgO含量低于1wt%,存在的问题是在体液中的可生物降解性降低,或者在纤维制备过程中抑制纤维微晶生长的效果降低。相反,如果该含量超过8wt%,存在的问题是在透辉石和硅灰石的共晶点附近的纤维化粘度增加。
具体地,优选依据本发明的纤维组合物中包含的作为网络外体氧化物的CaO和MgO的总量为CaO+MgO占15-26wt%。如果总量低于15wt%,在体液中的可溶性下降,反过来,如果总量超过26wt%,在高温下形成的结晶相的量增加,因而耐用性变坏。
进一步,当CaO和MgO的总量为15-26wt%时,更优选的是MgO的量在2-8wt%,以在体液中具有高的溶解速率常数。
依据本发明的纤维组合物可以进一步包含2.5-4wt%,优选2.6-3.7wt%,更优选2.6-3.6wt%的R2O,其中,R是碱金属,以提高可生物降解性,并降低纤维化粘度,由此提高产率。如果R2O的含量低于2.5wt%,对熔体粘度产生的效果不明显,因而对提高产率没有帮助。相反,如果含量超过4wt%,热线性收缩(1100℃/24小时)会变到10%或者更大,在耐热性上产生问题。
对于依据本发明的纤维组合物,R优选是Na和/或K。优选在纤维组合物中含有2.5-3.5wt%,更优选2.5-3.3wt%的Na2O,以及0-0.6wt%,更优选0-0.5wt%的K2O。上述含量范围适合于通过降低熔体的粘度而提高产率,并且不显著损害热线性收缩。
实际上,在用传统的RCF无机纤维制备方法,喷吹法或者纺丝法,制备纤维时,传统的Al2O3-SiO2(RCF-AS)基陶瓷纤维具有相对低的SiO2含量,大约50%,通常给出大约80%的产率。然而,如果SiO2的含量提高,将组合物熔融会变得困难,纤维化粘度增加并因而导致未纤维化的渣球的含量增加,以及整体纤维产率降低。
如果R2O的含量超过了上述范围,保持合适的纤维化粘度将变困难,因而产率下降。而在本发明中,通过将R2O的含量维持在上述范围内,可以合适地控制具有高SiO2含量的高粘度纤维组合物的纤维化粘度,由此提高产率。
依据本发明的组合物可以包含Al2O3和ZrO2作为中间体氧化物。Al2O3在本发明中是可选择的组分,优选将其在整个纤维组合物中的含量严格控制在低于0.5wt%。如果Al2O3的含量超过0.5wt%,存在的问题是在体液中的可溶性下降,特别是增加了纤维的线性收缩。
在整个纤维组合物中的ZrO2的含量优选0.5-3wt%。如果ZrO2的含量超过3wt%,在体液中的可溶性严重下降,反过来如果ZrO2的含量低于0.5wt%,在熔融和纤维化中会有困难。ZrO2+Al2O3的总量优选0.5-3wt%,更优选0.5-2wt%。如果总量低于0.5wt%,纤维在高温下的耐用性变坏,熔融变得困难,由于熔体粘度增加而纤维化产率变低。相反,如果总量超过3wt%,纤维在体液中的可溶性下降,并由此损害可生物降解性。
另外,依据本发明的组合物可以进一步可选地包含杂质,包括Fe2O3,TiO2,B2O3,以及P2O5,其含量为1wt%或者更低。杂质可以取决于用于制备纤维组合物的原料的纯度而被引入。如果杂质的含量超过1wt%,在纤维组合物中的组分间的反应会受到阻碍,由此损害所制备的纤维的性能。
依据本发明的用上述纤维组合物制备的陶瓷纤维的特征在于具有30wt%或者更低的渣球含量,带来高的纤维化产率,6μm或者更细的纤维直径,给出良好的绝热性能,以及甚至在1100℃下热处理24小时后不超过3%的热线性收缩,给出良好的高温性能。依据本发明的陶瓷纤维除了上述优异性能外,仍然可以采用传统的纤维制备工艺来得到经济优势,带来高产率。
基于如下对其不具限制的实施例对本发明进行详细说明,
[测试方法]
1.可纤维化性能:可纤维化性能基于采用传统的纤维制备设备制备纤维的可能性确定,条件是其中未纤维化的渣球的含量为30%或者更低,平均纤维直径为6μm或者更细。
2.平均纤维直径:平均纤维直径通过用电子显微镜在放大倍数大于1000倍时进行10次以上的测量确定。
3.未纤维化渣球的含量:未纤维化渣球的含量依据ASTM C892确定。将陶瓷纤维在1260℃热处理5个小时,以0.0001g的精度称出10g重的测试样品(W0)。将测试样品用橡胶棒过70目筛。在将测试样品过70目筛完毕后,对剩余颗粒进行称重(W1),用下面的公式1计算未纤维化渣球的含量(Ws):
[公式1]
其中,Ws表示未纤维化渣球的含量,W0表示初始颗粒的重量,W1表示剩余颗粒的重量。
4.熔融粘度比率:熔融的纤维组合物的温度高到2000℃甚至更高,因而不可能在将熔体从熔炉中排出时测量纤维化粘度。因此,采用下面的公式2来理论计算相对熔融粘度比率:
[公式2]
其中,η1表示参比粘度,其是对比例1中具有良好产率的Al2O3-SiO2(RCF-AS)基陶瓷纤维组合物的粘度,设定为1,η2表示其它每个实施例和对比例的相对粘度;以及
F1,F2:每小时排出的熔体的量(kg);
R1,R2:拉丝漏孔的有效直径(mm)
[R=拉丝漏孔的半径-tan 15°×{27.99-拉丝漏孔和针(needle)之间的距离(mm)}]
5.产率:采用下面的公式3来计算给定时间内生产的纤维的量与排出的熔体的量之间的比。
[公式3]
产率(%)=[生产的纤维的量/小时]/[排出的熔体的量/小时]
6.热线性收缩:用于高温绝热材料的耐火纤维的高温性能通常靠从由所制备的纤维制成的部件在高温下的长度变化测量出的热线性收缩来确定。为了确定陶瓷纤维的热线性收缩,将用纤维制备的测试样品作成垫状。通过往0.2%的淀粉水溶液中充分分散220g的纤维,将没有均匀分散的纤维整平以减少表面偏差,然后从模具(300×200mm)底倒出来制成垫。之后,将所述垫放到烘箱中在50℃下充分干燥超过24小时,并切成150×100×25mm的尺寸制成垫状测试样品。在垫状测试样品上用足够难熔的材料比如铂,陶瓷或者其它类似的材料制作测试标记。在用游标卡尺测量测试标记之间的距离之后,将测试样品放到炉子内,在1100℃加热24小时,然后慢慢冷却。通过测量测试标记之间的距离对结果进行彼此比较,用下面的公式4计算热线性收缩。
[公式4]
其中,10表示测试标记间的初始平均距离(mm),11表示加热后的测试标记间的平均距离(mm)。
7. 在人造体液中的可溶性常数:为了评价所制备的纤维在体液中的可溶性,按如下所述获得溶解速率常数。通过在人造体液中的可溶性来评价陶瓷纤维在体内的可生物降解性。溶解速率常数(Kdis)用下面的公式5来进行计算,所得结果如表3中所示。
[公式5]
KSi=[d0 ρ(1-MSi/M0)0.5]/2t
KCa=[d0 ρ(1-MCa/M0)0.5]/2t
Kdis=[d0 ρ(1-M/M0)0.5]/2t
其中,d0表示初始平均纤维直径,ρ表示纤维的初始密度,M0表示纤维的初始质量,M表示溶解后剩余纤维的质量,t表示测试时间。
在下面的表1中,给出了在用来确定纤维溶解速率的1L人造体液(Gamble溶液,一种生理盐水溶液)中的成分的含量(g)
表1
成分 | 含量(g/L) |
NaCl | 7.120 |
MgCl2·6H2O | 0.212 |
CaCl2·2H2O | 0.029 |
Na2SO4 | 0.079 |
Na2HPO4 | 0.148 |
NaHCO3 | 1.950 |
酒石酸钠·2H2O | 0.180 |
柠檬酸钠·2H2O | 0.152 |
90%乳酸 | 0.156 |
甘氨酸 | 0.118 |
丙酮酸钠 | 0.172 |
通过将依据本发明的陶瓷纤维和商购的无机纤维放置在固定于塑料过滤器支架上的聚碳酸酯膜过滤器的0.2μm的间隙内,然后使人造体液通过过滤器过滤来测量溶解速率。在测量过程中,将人造体液保持在37℃,流速145mL/天,pH保持在7.4±0.2,使用CO2/N2(5%/95%)气体。
为了精确确定长时间产生的纤维溶解性,对纤维进行40天的浸出,在给定的间隔(5,10,20,30和40天)测量纤维的重量。用电感耦合等离子体谱(ICP)对滤过的人造体液进行分析,以确定Si,Ca,Mg,Al,等的含量。采用这些结果,从上面的公式5确定溶解速率常数(Kdis)。
关于动物实验中的溶解速率常数和毒性测试之间的关系,已有报道,Kdis值为100ng/cm2·hr或者更高的纤维在动物吸入实验中不会引起纤维化或者肿瘤(参见:Inhalation Toxicology,12:26-280,2000,Estimating invitro glass fiber dissolution rate fromcomposition.,Walter Eastes,et al.)。然而,由于在采用人造体液(生理盐水溶液)的生物降解性实验中实际确定的Kdis的值具有±30%的最大偏差,要称为可生物降解的纤维,Kdis的值需要至少为150ng/cm2·hr。在本发明中,为了开发在人造体液中具有更优异可溶性的陶瓷纤维,将阈值设定为200ng/cm2·hr。
实施例
测试实施例1:可纤维化性能
在制备了具有特定成分和含量(如表2中所示)的陶瓷纤维组合物后,用传统的RCF无机纤维制造工艺制备陶瓷纤维。
在表2中也给出了所制备的陶瓷纤维的可纤维化性能,平均纤维直径,未纤维化渣球的含量,熔融粘度比率,以及产率的结果。
表2
如上表2中所示,平均纤维直径一般倾向于随SiO2含量的增加而增加,由于组合了其它的成分,比如CaO,MgO,Al2O3,Na2O,K2O和ZrO2,在平均纤维直径,未纤维化渣球的含量,熔融粘度比率,以及产率上表现出一些差异。
具有粗纤维直径和粗糙表面的纤维一般具有低绝热效果和对接触不友好的缺点。然而,需要提到的是,用依据本发明的纤维组合物制备的纤维具有高质量的性能,因为它的平均纤维直径(3.6-4.3μm)比可商购到的陶瓷纤维的直径(6μm)小,如此小的平均纤维直径有希望给出优异的绝热效果。
而且,依据实施例1-7,用本纤维组合物制备的陶瓷纤维进一步包含少量的Na2O或者K2O,由于低于30%,在22-25%的范围内的低的渣球含量,而呈现出高的纤维化产率。
用依据对比例7的组合物制备的陶瓷纤维包含非常少量的Al2O3和ZrO2,由于熔体粘度增加,未纤维化的渣球的含量上升到了48%。相反,在依据实施例4制备的陶瓷纤维中,包含0.71wt%的Al2O3+ZrO2,未纤维化的渣球的含量降低到了25%,这表明这样的事实,中间体氧化物比如Al2O3和ZrO2的总量应为0.5wt%或者更高。
由依据对比例9的组合物制备的陶瓷纤维包含非常少量的Na2O,未纤维化的渣球的含量上升到了35%。相反,在依据实施例1制备的陶瓷纤维中,包含2.52wt%的Na2O,未纤维化的渣球的含量降低到了23%,以及在依据实施例7制备的陶瓷纤维中,包含3.24wt%的Na2O,未纤维化的渣球的含量降低到了23%,这表明这样的事实,Na2O的含量应为2.5-3.5wt%。
而且,如在对比例13-14中,在SiO2的含量比80wt%还要高的范围内,熔体粘度高,因而制备的纤维直径粗,长度长;并且未纤维化的渣球的含量高,因而呈现出低的纤维化产率,所以导致纤维化不可能进行。
为了证实用依据本发明的纤维组合物制备的陶瓷纤维的纤维化粘度和产率之间的关系,在表2中给出了所制备的陶瓷纤维的熔融粘度比率和产率。
纤维化粘度应针对熔融纤维组合物进行测量,但当将熔体从熔炉中排出时进行纤维化粘度测量是不可能的,因为熔体的温度高达2000℃或者更高。因而,理论计算相对熔融粘度比率,从计算结果可以知道,不采用碱金属的对比例一般呈现出比采用碱金属的高的熔融粘度比率。这表明这样的事实,碱金属的含量显著影响熔融粘度比率。
当将具有良好产率的传统的Al2O3-SiO2(RCF-AS)基陶瓷纤维组合物(对比例1)的粘度设为1作为参比粘度时,实施例1-7的熔融粘度比率在1.20-1.43之间的范围,对比例2-14的熔融粘度比率在1.64-5.91之间的范围。一般的,SiO2含量的增加引起纤维化粘度的增加并由此降低产率。然而,在依据本发明的纤维组合物的情况下,尽管组合物具有75wt%或者更高的SiO2含量,是高度粘稠的,熔融粘度比率与参比粘度(即1)之间的偏差小,因而提高了产率。
在对比例中,由于其熔融粘度比率与参比粘度之间偏差大,产率急剧下降。在对比例8中,由于它的熔融粘度比率与参比粘度之间的偏差小,产率提高到了71%,但是,在体液中的可溶性和热线性收缩降低。
也就是说,通过合适地调节熔融粘度比率,即使在高SiO2含量的高粘度范围内,依据本发明的纤维组合物可以提高产率,其是所制备的纤维的量与排出的熔体量之比,这与未纤维化的渣球的含量结果是一致的,其是确定纤维化产率的基准。实际上,采用依据本发明的纤维组合物的纤维的产率在66-71%之间的范围,这与对比例中的那些明显不同。
测试实施例2:可生物降解性和热线性收缩
下面的表3给出了依据前述实施例和对比例制备的每种纤维组合物在人造体液中的溶解速率常数和热线性收缩(1100℃/24小时)。
表3:在人造体液中的溶解速率常数以及热线性收缩
如上表3中所示,用依据对比例1和2的传统的RCF纤维组合物制备的纤维呈现出低于30ng/cm2·hr的溶解速率常数。相反,由依据本发明的实施例的纤维组合物制备的纤维,溶解速率常数保持在252-451ng/cm2·hr之间的范围,因而在体液中表现出好得多的提高了的可溶性。
Al2O3+ZrO2的含量超过3wt%的对比例3-6的组合物,呈现出的热线性收缩低于3%,但具有低的溶解速率常数(分别为129,182,116和85ng/cm2·hr)。因而,在提高陶瓷纤维的可生物降解性方面,结论性的是优选将已知用来提高耐用性的成分Al2O3+ZrO2的含量限制在3wt%或更低。而且,对比例7的组合物Al2O3+ZrO2的含量低于0.5wt%,呈现出明显提高的550ng/cm2·hr的溶解速率常数,但是,具有6.9%的增大了的热线性收缩。因而,从改善陶瓷纤维的耐热性方面来看,结论性的是优选将Al2O3+ZrO2的含量限制在0.5wt%或者更高。在依据本发明的纤维组合物中,正是当Al2O3+ZrO2的量不超过2wt%时,溶解速率常数(Kdis)保持在250ng/cm2·hr或者更高。
Na2O含量为4.52wt%的对比例8的组合物,呈现出490ng/cm2·hr的高溶解速率常数,但具有14.3%的热线性收缩,因而具有差的耐热性。而且,如对比例12中所示,快速提高MgO的含量带来280ng/cm2·hr的溶解速率常数和4.5%的热线性收缩,因而带来差的耐热性。
对比例9-11的组合物推测由于MgO量的降低而具有低的溶解速率常数,尽管它们的Al2O3+ZrO2的含量分别为2.19,2.14和1.60wt%。尽管提高交联网络外体比如碱土金属通常是为了提高溶解速率常数,上述结果表明,即使含有相同量的CaO+MgO,如果纤维组合物中包含相对太少量的MgO,溶解速率常数会降低。所以,为了获得高的溶解速率常数,MgO的量应该在2wt%或者更高,同时,Al2O3+ZrO2应为大约2wt%或者更少。
Na2O含量为3.24wt%的实施例7的组合物呈现出326ng/cm2·hr的溶解速率常数和2.4%的热线性收缩,这表明,本发明的无机纤维组合物应该含有3.5wt%或者更低的Na2O。
所以,可纤维化的,高度可生物降解的,以及耐热良好的陶瓷组合物的组成为75-80wt%的SiO2,13-20wt%的CaO,1-8wt%的MgO,0.5wt%或更低的Al2O3,0.5-3wt%的ZrO2以及2.5-3.5wt%的Na2O。另外,当Al2O3+ZrO2的量为0.5-3wt%时,在人造体液中的溶解速率常数变得更高。
而且,由本发明的实施例中的组合物制备的陶瓷纤维,当在1100℃热处理24小时时,呈现出低于3.0%,在1.5-2.4%范围内的低的热线性收缩。
所以,包含75-80wt%的SiO2,13-20wt%的CaO,1-8wt%的MgO,0.5wt%或者更低的Al2O3,0.5-3wt%的ZrO2以及2.5-3.5wt%的Na2O的陶瓷纤维,具有细的纤维直径,因而给出好的绝热效果,小含量的未纤维化材料,因而是可纤维化的,好的可生物降解性,以及具有相比于传统的可商购到的陶瓷纤维非常相似的性能,比如热线性收缩,压缩强度和在压缩后良好的可恢复性。优选地,当Al2O3+ZrO2的量为0.5-3wt%时,在人造体液中的溶解速率常数更高,当R2O的量为2.5-4wt%时,纤维化产率和产量提高。更优选地,当CaO+MgO的量为15-26wt%时,性能甚至可以进一步提高。
如上所述,由本发明的实施例的组合物制备的陶瓷纤维在人造体液中呈现出良好的溶解速率常数,良好的纤维化特性,具有高纤维化产率的良好的可生产性,以及甚至在1100℃热处理24小时时低的热线性收缩,因而在高温绝热材料方面具有良好的可应用性。
工业可应用性
如上所述,与传统的陶瓷纤维相比,采用本发明的组合物制备的用于高温绝热材料的可生物降解的陶瓷纤维在体液中具有优异的溶解速率,由于其在吸入到肺中时能够容易的溶解并去除,因而可以降低危害。而且,考虑到传统的可生物降解的陶瓷纤维的缺点,也就是在高温下的性能劣化,依据本发明的陶瓷纤维在1100℃下热处理24小时后,呈现出的收缩率为3%或者更低,具有基本上与传统的高温绝热材料一致的良好的热性能,机械高温性能。进一步,本发明具有经济上的优势,可以用低价格的原料比如白云石或者石灰石来代替高纯度的MgO,传统的纤维生产设备仍然可以用来得到高的产率。
Claims (6)
1.陶瓷纤维组合物,其包含75-80wt%的SiO2,13-20wt%的CaO,1-8wt%的MgO,0.5wt%或者更低的Al2O3,0.5-3wt%的ZrO2,以及2.5-4wt%的R2O,其中R是碱金属,R2O中的Na2O的量为2.5-3.5wt%。
2.依据权利要求1的陶瓷纤维组合物,其中CaO和MgO的总量为15-26wt%,MgO的量为2-8wt%。
3.依据权利要求1的陶瓷纤维组合物,其中ZrO2和Al2O3的总量为0.5-3wt%。
4.依据权利要求1的陶瓷纤维组合物,其中杂质的量为1wt%或者更低,所述杂质包括Fe2O3,TiO2,B2O3和P2O5。
5.用于绝热材料的陶瓷纤维,其包含依据权利要求1-4任一项的组合物,其中,渣球的含量为30wt%或者更低,在1100℃下暴露24小时时的热线性收缩是3%或者更低。
6.用于绝热材料的陶瓷纤维,其包含依据权利要求1-4任一项的组合物,其中,纤维的平均直径为6μm或者更细,在人造体液中的溶解速率常数是200ng/cm2·hr或者更高。
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CN1138717C (zh) * | 1997-09-10 | 2004-02-18 | 法国韦特罗特克斯有限公司 | 适用于增强有机材料和/或无机材料的玻璃纤维 |
EP1323687A2 (en) * | 2001-12-29 | 2003-07-02 | Kumkang Korea Chemical Co., Ltd. | Biosoluble ceramic fiber composition with improved solubility in a physiological saline solution for a high temperature insulation material |
Also Published As
Publication number | Publication date |
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WO2007086677A1 (en) | 2007-08-02 |
EP1979284B1 (en) | 2012-05-30 |
EP1979284A4 (en) | 2010-12-22 |
CN101374780A (zh) | 2009-02-25 |
KR100676167B1 (ko) | 2007-02-01 |
EP1979284A1 (en) | 2008-10-15 |
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