CN1373740A - 耐高温的可溶于盐水的纤维 - Google Patents

耐高温的可溶于盐水的纤维 Download PDF

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CN1373740A
CN1373740A CN00812697A CN00812697A CN1373740A CN 1373740 A CN1373740 A CN 1373740A CN 00812697 A CN00812697 A CN 00812697A CN 00812697 A CN00812697 A CN 00812697A CN 1373740 A CN1373740 A CN 1373740A
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fiber
weight
mgo
cao
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G·A·朱布
J·L·马丁
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Morgan Crucible Co PLC
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL 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
    • C03C13/00—Fibre or filament compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL 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
    • C03C2213/00—Glass fibres or filaments
    • C03C2213/02—Biodegradable glass fibres

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Abstract

本发明涉及一种最高使用温度为1200℃或更高的纤维,它包含:SiO2>64.25重量%、CaO>18重量%、MgO<17重量%,其中,MgO按摩尔%计大于按摩尔%的CaO。这类纤维具有高溶解度和低含尘率。

Description

耐高温的可溶于盐水的纤维
本发明涉及高温可溶于盐水的纤维，特别涉及钙镁硅酸盐纤维。
钙镁硅酸盐纤维例如从WO89/12032、WO93/15028和WO94/15883中是已知的。
WO89/12032首先公开了宽范围类型的耐火可溶于水的纤维。
WO93/15028表明，WO89/12032的一类纤维可以在高达1000℃或更高的温度下使用。
WO94/15883表明，部分WO93/15028的纤维仍然具有更高的使用温度，即高达1260℃或更高，并且表明这类纤维需要大于21.8摩尔％的SiO2过量(定义为在CaO、MgO和任何ZrO2以硅酸盐形式结晶后残余的SiO2量)。
WO97/16386虽然落在钙镁硅酸盐纤维的一般类型范围内，但是注意到低钙纤维表现出1260℃或更高的使用温度。
明显的是，存在CaO-MgO-SiO2和CaO-MgO-SiO2-ZrO2组成范围的区域，在该区域内可以制造高温性能的纤维，而在其它区域不能制造。
本申请人现在已经发现一种新型且窄范围的组合物，它可以在1200℃或更高的温度使用，甚至1250℃或1260℃或更高的温度使用，但是在WO94/15883和WO97/16386的范围之外。这些组合物优选的是含有少量或不含氧化锆。
因此，本发明提供一种最高使用温度为1200℃或更高的纤维，其中，用摩尔％表示的MgO量大于大于用摩尔％表示的CaO量，并且它包含：
SiO2＞64.25重量％
CaO＞18重量％
MgO＜17重量％
但是，对所说明的SiO2过量大于21.8摩尔％的纤维没有提出权利要求。
本发明的其它特征由所附权利要求是明显的。
通过把全部CaO按结合成CaO·MgO·2SiO2处理，全部ZrO2按结合成ZrO2·SiO2处理，其余的MgO按结合成MgO·SiO2处理，来计算过量的SiO2数。本申请人还假定，任何Al2O3以Al2O3·SiO2结晶。任何残余的SiO2称为过量SiO2。
本发明在下列描述中参考附图通过实施例说明，其中：
图1是表示包含下表1的纤维A4-2和A4-3的纤维毡的线收缩率随温度的变化图。
图2是表示包含下表1的纤维A4-2和A4-3的纤维毡的高度方向的收缩率的图。
图3是表示由下表1的纤维A4-1、A4-2和A4-3生产的预成形体的收缩率的图。
表1表示从WO89/12032、WO93/15028、WO94/15883和WO97/16386中摘录的组成以及A4，A4是目标组合物纤维，其组成为：
SiO2  65重量％
CaO   19.5重量％
MgO   15.5重量％
并且表示了所分析的纤维样品A4-1、A4-2和A4-3。
从WO89/12032(称为Manville纤维)、WO93/15.28、WO94/15883和WO97/16386(称为Unifrax纤维)的数据摘录的纤维是所说明的SiO2过量小于21.8摩尔％并且按摩尔％计的MgO量大于按摩尔％计的CaO量的纤维。
A4-1以散纤维形式生产，A4-2以针刺纤维毡形式生产，其密度约96kg·m-3，A4-3以针刺纤维毡形式生产，其密度约128kg·m-3。
在表1中，由所涉及的文件，或者对于A4-1、A4-2和A4-3，通过测量所涉及的纤维的真空成型预成型体的收缩率表示了收缩率。
                                                                              表1
纤维 在1260℃的收缩率                               组成wt％ 组成mol％ SiO2过量
 CaO  MgO  ZrO2 Al2O3  TiO2  SiO2 其它  CaO  MgO  ZrO2 Al2O3  TiO2  SiO2
    924  19.78  14.54  0.66  2.57  61.32  19.99  20.44  0.30  1.43  57.84   15.68
    SW-A1  20.50  15.20  1.10  63.70  20.16  20.79  0.00  0.59  58.46   16.92
    B5     6.00  19.90  15.10  0.10  0.20  64.20  0.40  19.71  20.80  0.05  0.11  59.34   18.68
    757  20.92  15.22  0.00  0.20  62.60  20.79  21.04  0.00  0.11  58.06   16.13
    A4-1     1.86  20.20  15.50  0.26  64.60  0.07  19.76  21.10  0.00  0.14  59.00   18.00
    A4-2     3.25  20.20  15.50  0.30  64.50  0.06  19.78  21.11  0.00  0.16  58.95   17.89
    A4-3     2.76  20.20  15.60  0.28  64.70  0.07  19.72  21.18  0.00  0.15  58.95   17.9
    A4目标  19.50  15.50  65.00  19.17  21.20  0.00  0.00  59.64   19.27
    SW-A2  21.40  15.40  0.80  60.80  21.40  21.42  0.00  0.44  56.74   13.49
    SW-A  20.50  15.50  3.30  59.30  20.66  21.73  0.00  1.83  55.78   11.56
    932  21.60  15.65  0.11  1.50  59.85  21.58  21.75  0.05  0.82  55.80   11.60
   Manville104  17.70  16.30  1.83  64.10  17.49  22.40  0.00  0.99  0.00  59.11   18.23
    B9     5.00  18.10  17.10  0.10  0.20  64.40  0.20  17.72  23.29  0.04  0.11  58.84   17.69
    971  23.92  17.36  0.05  0.74  56.82  23.56  23.79  0.02  0.40  52.23   4.47
    B8     6.90  18.80  17.90  0.30  0.20  63.00  0.20  18.30  24.24  0.13  0.11  57.23   14.46
    B16     4.30  15.10  18.10  0.30  0.10  0.10  66.00  0.20  14.78  24.65  0.13  0.05  0.07  60.31   20.69
    A2-12  16.55  18.00  0.05  0.33  63.56  16.37  24.76  0.02  0.18  58.67   17.34
    A2-30  16.06  18.21  0.00  0.40  63.68  15.89  25.07  0.00  0.22  58.82   17.64
                                                                                  表1
纤维 在1260℃的收缩率                             组成wt％ 组成mol％ SiO2过量
 CaO  MgO  ZrO2 Al2O3 TiO2  SiO2 其它  CaO  MgO  ZrO2 Al2O3  TiO2  SiO2
    A2-23  18.59  18.78  0.05  0.48  60.20  18.37  25.82  0.02  0.26  55.53   11.06
    71  24.04  19.66  0.00  0.20  54.68  23.44  26.67  0.00  0.11  49.77   -0.45
    A2-19  18.48  19.74  0.00  0.54  58.71  18.29  27.18  0.00  0.29  54.24   8.47
    A2-21  13.74  19.98  0.13  0.34  64.16  13.51  27.34  0.06  0.18  58.90   17.81
    Unifrax comp13     13.10  0.77  16.90  34.10  0.97  46.40  0.92  28.11  18.55  0.64  51.78   3.56
    A2-24  13.62  22.74  0.08  0.31  61.38  13.25  30.79  0.04  0.17  55.76   11.51
    Manville105  9.74  23.10  2.15  65.10  9.38  30.95  0.00  1.14   0.00  58.53   17.05
    Manville79  8.67  24.00  0.02  67.20  8.27  31.86  0.00  0.01   0.00  59.86   19.71
    A2-25  10.99  24.18  0.07  0.33  62.36  10.66  32.64  0.03  0.18  56.48   12.97
    Unifrax comp14     23.40  0.89  21.70  24.10  0.90  51.90  0.98  33.18  12.05  0.54  53.24   6.49
    A2-35  8.88  24.88  0.47  0.29  64.12  8.56  33.37  0.21  0.15  57.71   15.41
    Manville78  6.43  26.50  67.10  6.07  34.80  0.00  0.00   0.00  59.13   18.25
    A2-34  6.63  26.20  0.80  0.23  64.85  6.37  35.01  0.35  0.12  58.15   16.29
    Unifrax comp15     25.00  0.77  25.50  16.90  0.76  55.70  0.80  36.82  7.98  0.43  53.96   7.93
    Manville77  4.02  28.70  0.59  66.10  3.79  37.68  0.00  0.31   0.00  58.22   16.44
    Unifrax 42     2.00  0.30  29.75  0.58  0.62  68.63  0.28  38.92  0.25  0.32  60.23   20.47
                                                                            表1
纤维 在1260℃的收缩率                                组成wt％ 组成mol％ SiO2过量
  CaO   MgO  ZrO2  Al2O3  TiO2   SiO2 其它   CaO   MgO   ZrO2 Al2O3   TiO2   SiO2
  Manville106   2.70   29.70   1.56   65.60   2.54   38.94   0.00   0.81   0.00   57.71   15.41
  Manville80   1.60   30.10   68.40   1.49   39.02   0.00   0.00   0.00   59.49   18.98
  Manville71   3.12   30.10   1.15   65.40   2.92   39.26   0.00   0.59   0.00   57.23   14.45
  Manville76   3.12   30.10   1.15   65.40   2.92   39.26   0.00   0.59   0.00   57.23   14.45
  Unifrax 47     7.70   0.25   30.26   0.01   1.86   67.53   0.23   39.56   0.00   0.96   59.24   18.48
  Unifrax 40     9.20   0.27   30.57   0.58   0.92   67.52   0.25   39.90   0.25   0.47   59.13   18.25
  765   3.90   35.07   0.00   2.12   57.78   3.62   45.26   0.00   1.08   50.04   0.07
可以看出，除了具有根本不同的组成的纤维Unifrax 42以外，根据本发明的纤维在1260℃的收缩率比所摘录的纤维收缩率低。
在图1-3中，图形表示了纤维A4-1、A4-2和A4-3在对所示温度暴露24小时后的收缩特性。可以看出这些纤维容易在1200℃或更高的温度下使用。
下表2表示对纤维在生理盐水中的溶解度试验的结果，表明这些纤维在体液中是可溶解的。(对于测量溶解度方法的讨论，见WO94/15882)。对于每种样品的单独的试验，表示了成对的结果，以及平均总溶解度。
                                   表2
  纤维类型                      溶解度(ppm)
    CaO     MgO     SiO2     总量   平均总量
    A4-1     102     115     171     388     383
    105     110     162     377
    A4-2     105     116     172     393     395
    114     117     166     397
    A4-3     114     123     166     403     411
    114     128     177     419
本发明的纤维的典型组成范围内：
SiO2  65±0.5重量％
CaO   20±0.5重量％
MgO   15±0.5重量％
与Superwoll 607TM，公称成分(按重量计)为SiO2 65％、CaO29.5％、MgO 5.5％、Al2O3＜1％；Superwoll 612TM，公称成分(按重量计)为SiO2 64.5％、CaO 17％、MgO 13.5％、ZrO2 5％；耐火陶瓷纤维，公称成分为SiO2 56％、Al2O3 44％比较，对具有本发明组成SiO2 65％、CaO 19.5％、MgO 15.5％的纤维进行了其它试验。
第一种试验目的在于说明在处理时可能释放的粉尘量。试验包括确定在由各种纤维制造的纤维毡样品中存在的粉尘量。使纤维毡在Fritsch Analysette3010型振动筛振荡器上振动，振荡器设定为频率3000Hz、垂直振幅0.5毫米。该设备装有1.6毫米的筛网和底盘。在该试验方法中，把135毫米×135毫米的纤维毡样品放在筛网上并振动10分钟。把在底盘上收集的物料称重并表示为样品原始重量的百分数。结果如下所示：
      纤维材料               所释放的粉尘百分数
      Superwoll 607TM       0.16％
      本发明的材料           0.18％
      耐火陶瓷纤维           0.25％
      Superwoll 612TM       0.36％
从这里可以看出，本发明的纤维具有比得上Superwoll 607TM的低含尘量。
所做的第二种试验是研究由本发明的纤维和两种SuperwoolTM纤维形成的纤维毡在高温下的收缩行为。把纤维毡样品在所指明的温度下暴露24小时，并测量它们的线收缩率。结果表示在下表3中：
                          表3
                          温度
样品 1050℃  1110℃  1150℃  1200℃  1250℃  1300℃
本发明的纤维 0.8  0.6  1.0  1.0  1.5  4.2
Superwool 612TM 0.7  1.0  1.1  1.7  1.8  12.1
Superwool 607TM 0.4  0.4  0.5  0.6  4.8  7.8
这表明最高到1200℃，本发明的纤维在性能上可与两种SuperwoolTM纤维相比。在1250℃，Superwool 607TM纤维呈现4.8％的收缩率(对于大多数用途，这被认为是太高的收缩率)。在1300℃，本发明的纤维虽然表现出4.2％的高收缩率，但是，它是所试验的三种纤维中最好的。
还进行了另一个系列的试验，以便大规模生产纤维，所得的纤维组成列于下表4中。所有的纤维在1250℃表现出低收缩率(收缩率通过与表1不同的方法测量，不能直接比较)。与表1的结果结合，这表明具有可用特性的样品的组成基本由下列成分组成(用重量％表示)：
CaO   18.7-20.2
MgO   14.47-15.9
SiO2  64.5-65.1
Al2O3  0-0.56
所以，本发明的纤维具有高溶解度(允许纤维从人体迅速清除所希望的)、低含尘率(降低可能被吸入的纤维量所希望的)和良好的高温特性。
                                                                             表4
纤维 在1250℃的线收缩率(％)                                   组成wt％ 组成mol％ SiO2过量
  CaO   MgO ZrO2 Al2O3   TiO2   SiO2 其它   CaO   MgO   ZrO2 Al2O3  TiO2   SiO2
SM 0.80   20.10   15.00     0.06   65.00   19.77   20.52     0.00     0.03   59.67     19.35
TCI 0.78   18.90   15.50     0.38   65.10   18.63   21.26     0.00     0.21   59.90     19.81
TCUK 未制造预成型体   18.70   15.90     0.44   64.80   18.41   21.78     0.00     0.24   59.56     19.13
TCUK2 2.6(在1300℃测量)   19.30   14.47     0.56     0.03   64.54     0.40   19.30   20.13     0.00     0.31   60.24     20.50

Claims (13)

1.一种最高使用温度为1200℃或更高的纤维，它包含：
SiO2＞64.25重量％
CaO＞18重量％
MgO＜17重量％
其中，按摩尔％计的MgO量大于按摩尔％计的CaO量并且其中所指明的SiO2过量不大于21.8摩尔％。
2.根据权利要求1的纤维，并且包含：
CaO＜21重量％。
3.根据权利要求2的纤维，并且包含：
CaO＜20.5重量％。
4.根据权利要求1-3的任一项的纤维，并且包含：
CaO＞19重量％。
5.根据权利要求4的纤维，并且包含：
CaO＞19.5重量％。
6.根据权利要求1-4的任一项的纤维，并且包含：
MgO＞14.25重量％。
7.根据权利要求6的纤维，并且包含：
MgO＞14.75重量％。
8.根据权利要求7的纤维，并且包含：
MgO＞15.25重量％。
9.根据前面的权利要求的任一项的纤维，并且包含：
MgO＜16重量％。
10.根据前面的权利要求的任一项的纤维，并且包含：
SiO2  65±0.5重量％
CaO   20±0.5重量％
MgO   15±0.5重量％。
11.根据权利要求1-9的任一项的纤维，并且包含：
SiO2  64.5-64.7重量％
CaO   19.5-20.2重量％
MgO   15.5-15.6重量％。
12.根据前面的权利要求的任一项的纤维，并且包含：
SiO2  约65重量％
CaO   约19.5重量％
MgO   约15.5重量％。
13.根据前面的权利要求的任一项的纤维，并且基本由下列成分组成：
CaO   18.7-20.2重量％
MgO   14.47-15.9重量％。
SiO2  64.5-65.1重量％
Al2O3 0-0.56重量％。
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CN103339323A (zh) * 2011-03-30 2013-10-02 霓佳斯株式会社 无机纤维质纸及其制造方法和设备
CN108677272A (zh) * 2018-05-15 2018-10-19 华南理工大学 一种微米级无机抗菌纤维及其制备方法
CN108677272B (zh) * 2018-05-15 2020-09-22 华南理工大学 一种微米级无机抗菌纤维及其制备方法

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