CN1612845A - 盐水可溶的无机纤维 - Google Patents

盐水可溶的无机纤维 Download PDF

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CN1612845A
CN1612845A CNA03801937XA CN03801937A CN1612845A CN 1612845 A CN1612845 A CN 1612845A CN A03801937X A CNA03801937X A CN A03801937XA CN 03801937 A CN03801937 A CN 03801937A CN 1612845 A CN1612845 A CN 1612845A
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G·A·朱布
C·J·弗雷曼
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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
    • C03C13/00—Fibre or filament compositions
    • C03C13/06—Mineral fibres, e.g. slag wool, mineral wool, rock wool
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00—Casings; Linings; Walls; Roofs
    • F27D1/0003—Linings or walls
    • F27D1/0006—Linings or walls formed from bricks or layers with a particular composition or specific characteristics
    • 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
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
    • E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only

Abstract

本发明提供了应用于需要连续耐受温度1260摄氏度而不与硅铝酸盐耐火砖反应的隔热材料，所述隔热材料包含具有以下组成的纤维(wt％)：65％<SiO2<86％，MgO<10％，14％<CaO<28％，Al2O3<2％，ZrO2<3％，B2O3<5％，P2O5<5％，72％<SiO2+ZrO2+B2O3+5＊P2O5，95％<SiO2+CaO+MgO+Al2O3+ZrO2+B2O3+P2O5。加入选自Sc，La，Ce，Pr，Nd，Sm，Eu，Gd，Tb，Dy，Ho，Er，Tm，Yb，Lu，Y或其混合物的元素提高了纤维质量和由该纤维制成的覆盖层的强度。

Description

盐水可溶的无机纤维
本发明涉及盐水可溶的、非金属的、无定形的、无机氧化物耐火纤维材料。本发明尤其涉及具有二氧化硅作为其基本成分的玻璃纤维。
无机纤维材料是熟知的和广泛用于许多场合(如以大块、垫、或覆盖层形式用作隔热或隔音层，用作真空成型物，用作真空成型板和纸，和用作绳，纱线或纺织品；用作用于建筑材料的增强纤维；用作车辆刹车块的组分)。在这些用途的大多数中，使用无机纤维材料所用的性能需要耐热，和通常耐受侵蚀性化学环境。
无机纤维材料可以是玻璃状或结晶的。石棉是一种无机纤维材料，其一种形式与呼吸疾病非常相关。
尚不清楚是何种成因机理使一些石棉与疾病有关，但一些研究人员相信该机理与机械性和尺寸有关。具有临界尺寸的石棉可刺入体内细胞，因此通过长期和重复的细胞伤害对健康产生不良影响。无论该机理是否真实，法规部门已经表现出将具有呼吸级分的任何无机纤维产物划归为危险品的愿望，而无论是否有任何证据支持这种归类。遗憾的是对于使用无机纤维的许多场合，没有现实的替代物。
因此需要无机纤维产生尽可能小(如果有的话)的危害而且有客观理由相信它们是安全的。
已经提出了研究方向，如果所制成的无机纤维足够可溶于生理流体使得其在人体内的停留时间短；那么损害不会发生或至少被最小化。因为石棉相关疾病出现的可能性似乎明显取决于暴露的时间长度，该观点几乎是合理的。石棉是非常难溶的。
因为细胞间流体性质上是盐水，纤维在盐水溶液中的溶解度的重要性早就得到认识。如果纤维可溶于生理盐水溶液，假设溶解组分不是毒性的，那么该纤维应该比没有这么可溶的纤维更安全。纤维在体内的停留时间越短，它可产生的损害越小。H.Frster在“矿物纤维在生理溶液中的性质′”(1982 WHO IARC会议的会议录，哥本哈根，第2卷，页数27-55(1988))讨论了商业所得矿物纤维在生理盐水溶液中的性质。讨论了溶解度极为不同的各种纤维。
国际专利申请No.WO87/05007公开，包含氧化镁，硅石，氧化钙和低于10wt％矾土的纤维可溶于盐水溶液。所公开的纤维的溶解度以在暴露5小时之后存在于盐水溶液中的硅(从纤维的含硅石的材料中提取)的ppm值表示。在实施例中表现出的最高值具有硅含量67ppm。作为对比，并调整至相同的测量体系，公开于Frster论文的最高含量相当于约1ppm。相反，如果将在国际专利申请中表现出的最高值转化成Frster论文中的相同的测量体系，它具有提取率901,500mg Si/kg纤维-即比Frster测试的任何纤维高大约69倍，而且在Frster试验中具有最高萃取速率的纤维是具有高碱含量和因此具有低熔点的玻璃纤维。这是明显较好的性能，即使考虑到试验溶液差异和实验持续时间之类的因素。
国际专利申请No.WO89/12032公开其它的可溶于盐水溶液的纤维和讨论可能存在于这些纤维中的一些成分。
欧洲专利申请No.0399320公开了具有高生理溶解度的玻璃纤维。
公开了根据纤维的盐水溶解度进行选择的其它专利说明书包括例如欧洲0412878和0459897，法国2662687和2662688，PCTWO86/04807，WO90/02713，WO92/09536，WO93/22251，WO94/15883，WO97/16386和US 5250488。
公开于这些各种已有技术文件的纤维的耐火性明显不同，而且对于这些碱土硅酸盐材料，性能尤其取决于组成。
WO 94/15883公开许多可在最高1260摄氏度或更高的温度下用作耐火隔热材料的纤维。这些纤维包含CaO、MgO、SiO2和视需要的ZrO2作为基本成分。这些纤维通常被称作CMS(硅酸钙镁)或CMZS((硅酸钙镁锆)纤维。WO94/15883要求仅少量存在任何矾土。
使用这些纤维所存在的缺陷在于，在温度约1300摄氏度-1350摄氏度下纤维的收缩率明显增加。通常，收缩率从约1-3％(在1200摄氏度下)增加至例如5％或更多(在1300摄氏度下)；＞20％(在1350摄氏度下)。这意味着，例如，炉的温度超限可导致对隔热材料和因此对炉自身的损害。
另一缺陷在于，硅酸钙镁纤维可与含矾土的材料反应，并由于形成低共熔组合物而粘附其上。因为硅铝酸盐材料广泛使用，这是一个主要问题。
WO97/16386公开了在最高1260摄氏度或更多的温度下可用作耐火隔热材料的纤维。这些纤维包含MgO，SiO2，和视需要的ZrO2作为基本成分。如同WO94/15883，该专利要求仅存在少量的任何矾土。
尽管这些纤维没有表现出如WO94/15883的纤维那样明显的急剧收缩率变化，它们却在正常使用温度下表现出明显较高的收缩率，通常1200摄氏度-1450摄氏度的范围内具有收缩率3-6％。这些纤维似乎不具有与含矾土的材料反应并粘附的缺陷，但它们往往难以制造。
申请人已经创造出一类在一定温度范围内收缩率低于WO97/16386纤维，同时具有较高收缩率增加的开始点，且收缩率变化比WO94/15883纤维更温和，而且还较少倾向与矾土反应并粘附的纤维。
因此，本发明提供在需要连续耐受温度1260摄氏度而不与硅铝酸盐耐火砖反应的场合中使用的隔热材料，所述隔热材料包含纤维具有以下组成，以重量％计：
65％＜SiO2＜86％
MgO＜10％
14％＜CaO＜28％
Al2O3＜2％
ZrO2＜3％
B2O3＜5％
P2O5％＜5％
72％＜SiO2+ZrO2+B2O3+5*P2O5
95％＜SiO2+CaO+MgO+Al2O3+ZrO2+B2O3+P2O5。
优选的组成范围是：
72％＜SiO2＜80％
18％＜CaO＜26％
0％＜MgO＜3％
0％＜Al2O3＜1％
0％＜ZrO2＜1.5％
98.5％＜SiO2+CaO+MgO+Al2O3+ZrO2+B2O3+P2O5。
更优选的范围具有以下组成：
72％＜SiO2＜74％
24％＜CaO＜26％
另外，申请人已经发现，少量镧系元素，尤其镧的加入提高了纤维的质量，尤其其长度和厚度，这样得到改进的强度。在稍低溶解度方面存在损失，但改进的强度是有用的，尤其在制造覆盖层之类的产品时，其中纤维被用针缝以形成咬合纤维网。
因此，本发明包括一种硅酸盐纤维，包含：
65％＜SiO2＜86％
MgO＜10％
14％＜CaO＜28％
Al2O3＜2％
ZrO2＜3％
B2O3＜5％
P2O5＜5％
72％＜SiO2+ZrO2+B2O3+5*P2O5
95％＜SiO2+CaO+MgO+Al2O3+ZrO2+B2O3+P2O5。
0.1％＜R2O3＜4％
其中R选自Sc、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y或其混合物。
优选的元素是La和Y。为了实现在纤维质量上的显著提高，R2O3的量优选大于0.25％，更优选大于0.5％，和进一步更优选大于1.0％。为了尽量减少所出现的溶解度下降，R2O3的量以重量计优选小于2.5％，进一步更优选小于1.5％。具有以下组成(wt％)的纤维获得非常良好的结果：
SiO2：73±0.5％
CaO：24±0.5％
La2O3：1.3-1.5％
剩余组分：＜2％，优选＜1.5％
本发明的其它特征根据以下的说明性的描述并参考附图1而从权利要求书中看出，其中图1是根据本发明的一些纤维与一些工业纤维相比的收缩率对温度的图。
发明人使用一种实验装置制成许多硅酸钙纤维，其中熔体由合适的组合物形成，流过8-16mm孔，并按照已知的方式吹制成纤维。(可改变流出孔的尺寸以适合熔体的粘度-这种调整必须根据所用的装置和组合物实验确定)。
纤维被测试并将主要是具有一些MgO的硅酸钙纤维的纤维的结果在表1中给出，其中：
·所示的收缩率数值在纤维的预成型品上通过方法(参见以下)而测定，
·所示的组成通过硼的x-射线荧光通过湿化学分析而测定，
·给出了主要玻璃组分在24小时静态试验之后在生理盐水溶液中的总溶解度(ppm)。
·比表面积(m2/g)，
·对纤维质量的定性评估，
·和表示是否预成型品粘附到硅铝酸盐砖(可得自ThermalCeramics Italiana和具有约70wt％矾土和30wt％硅石的近似组成的JM 28砖)上。
收缩率通过使用在500cm30.2％淀粉溶液中的75g纤维将真空铸塑预成型品制成120×65mm工具而测定。将铂针(直径约0.1-0.3mm)在4个角上相距100×45mm而放置。最长长度(LI&L2)和对角线(L3&L4)使用移测显微镜测定至精度±5μm。样品被放在炉中并在300摄氏度/小时下升温至低于试验温度50摄氏度的温度且最后50摄氏度在120摄氏度/小时下升至试验温度并放置24小时。在从炉中取出之后，将样品放置自然冷却。收缩率值以4次测量的平均值给出。
发明人发现，硅石含量低于72％重量的那些纤维往往粘附到硅铝酸盐砖上。它们还发现，高MgO含量纤维(＞12％)不粘附(例如根据WO97/16386的性质预测)。
已知的是，具有中等含量MgO(12-20％)的硅酸钙纤维粘附到硅铝酸盐砖上，而硅酸镁纤维却不。出人意料的是，对于本发明的纤维，可以容许这些中等含量的MgO。＜10％MgO，或＜5％MgO的含量得到所需的非吸附结果，但耐火性似乎优选具有最大MgO含量2.5％重量，和更优选该量应该低于1.75％重量。
表2给出了矾土和氧化锆对这些纤维的作用。矾土已知对纤维质量有害且表2的头三种组合物具有2％以上的Al2O3和粘附到硅铝酸盐砖。另外，增加矾土导致溶解度下降。因此，发明人确定2％为矾土在其本发明组成中的上限。
相反，氧化锆已知可提高耐火性并且表2表明，可以容许低于72％的硅石含量，如果ZrO2的量足以使得SiO2和ZrO2的总和大于72％重量。但增加氧化锆会降低纤维在生理盐水溶液中的溶解度和因此优选的ZrO2含量低于3％。
一些其它普通玻璃添加剂的作用由表3给出，其说明P2O5和B2O3具有作为玻璃形成添加剂的作用。可以看出，P2O5对这些组合物的粘附性能具有不成比例的作用，因为具有低至67.7％SiO2的纤维不粘附到硅铝酸盐砖上。
B2O3还对具有低至70.9％SiO2的纤维产生不粘附的作用。发明人已经确定，满足下面关系的纤维往往不发生与硅铝酸盐砖的粘附：-
72％＜SiO2+B2O3+ZrO2+5*P2O5。
发明人已经假设B2O3和P2O5的最大含量分别为5％重量。
表1-3表明，可包括少量的其它组分和本发明允许最高5％的其它成分，但优选这些其它成分的量低于2％，更优选低于1％，因为这些其它成分往往使得纤维耐火性较差。(参见以下有关特定镧系添加剂的作用)。
以上结果在实验装置上得到，必然带来许多不确定性。大多数有利地出现的纤维的生产试验在两个不同场所进行，以试验组合物的吹制和纺丝性能。表4给出了对所得结果的选择(副本省略)和表明得到一种非常有用的纤维。在生产试验中测试的纤维具有例如以下近似范围内的组成：
72％＜SiO2＜80％
18％＜CaO＜26％
0％＜MgO＜3％
0％＜Al2O3＜1％
0％＜ZrO2＜1.5％
以及98.5％＜SiO2+CaO+MgO+Al2O3+ZrO2+B2O3+P2O5。
可以看出，MgO含量大于1.75％的组合物往往在1350摄氏度下具有比较低MgO含量时更高的收缩率。
图1以图的形式显示出本发明纤维的一个重要特征并将表4的头三种纤维和第五种纤维(分别称作SW613)与商业纤维Isofrax(硅酸镁纤维，来自Unifrax公司)，RCF(标准硅铝酸盐耐火陶瓷纤维)，和SW607 MaxTM，SW607TM，和SW612TM(硅酸钙镁纤维，来自ThermalCeramics Europe Limited)进行收缩率特性比较。
可以看出，即Isofrax和RCF在1200-1450摄氏度范围内的收缩率为3-6％。SW607 MaxTM，SW607TM，和SW612TM在1200摄氏度下的收缩率是2-5％，但在1300摄氏度之后迅速增加。本发明纤维在最高1350摄氏度下的收缩率低于2％，在1400摄氏度下移向最高5-8％并在此之后加速。
本发明纤维因此具有在1300摄氏度下的收缩率低于硅酸镁，商业硅酸钙镁，或RCF纤维的优点；与商业硅酸钙镁纤维相比，在较高温度下开始其收缩率增加；与商业硅酸钙镁纤维相比，具有较浅的收缩率随温度的升高；和不象商业硅酸钙镁纤维那样粘附到硅铝酸盐砖上。
纤维可用于隔热材料和可(如与其它纤维和/或填料和/或粘结剂一起)构成隔热材料的成分或可构成整个隔热材料。纤维可成型为覆盖层形式的隔热材料。
上述普通硅酸钙纤维所存在的一个问题在于，纤维往往较短，导致覆盖层质量不好。需要一种生产较好的用于覆盖层的纤维的方法且申请人进行筛选试验以研究向组合物中加入其它元素作为添加剂对纤维质量的影响。已经发现，镧系元素，尤其是La和Y改进了纤维质量。La被确定为商业上最有意义的元素，因此在该起始筛选试验之后将注意力集中到研究La的作用。
La2O3以0-4％的量用作包含73.5％SiO2和余量CaO和少量杂质的纤维的添加剂以确定最佳量。已经确定，加入La2O3改进了纤维化而不降低耐火性。纤维不与矾土砖反应。但在最高La2O3水平下，溶解度明显下降。因此1.3-1.5％La2O3的折中含量用于对纤维组合物的进一步试验。
为了检查和确定含镧材料在耐火性和纤维化方面的最佳配方，对包含1.3％La2O3(保持恒定)、余量CaO+少量杂质MgO和Al2O3的材料从67％至78％SiO2的硅石增加情况进行了研究。
增多的硅石增加了纤维的耐火性，得到较低的收缩率，较高的熔点和减少与矾土在高温下的反应。
耐火性和纤维化之间的最佳折中存在于以下组成：
SiO2  73％
CaO  24％
La2O3  1.3-1.5％
剩余的杂质(Al2O3，MgO，其它物质)＜1.5％
该组合物在生产规模制造覆盖层上进行试验，它具有下表4所示的″有La″组成。
已经确认，该组合物生产的纤维优于无La的情况(″无La″，在表4中)。纤维仍不与矾土砖反应，并具有良好的耐火性。
较好的纤维化通过研究具有密度128kg/m3的25mm厚覆盖层的拉伸强度而观察和评估。
                                        表4
    氧化物     无La     有La
    Na2O     ＜0,05     0,18
    MgO     0,89     0,46
    Al2O3     0,64     0,66
    SiO2     72,9     73,2
    K2O     ＜0,05     0,08
    CaO     25,5     23,6
    Fe2O3     0,11     0,14
    La2O3     0     1,3
    LOI 1025℃     0,08     0,09
    合计     100,1     99,7
    拉伸强度128-25覆盖层(kPa)     25-30     35-60
可以看出，加入仅1.3％La2O3导致拉伸强度的明显提高，这意味着纤维明显改进。
申请人推测，这种提高纤维化的作用是一种一般可适用于碱土硅酸盐纤维的粘度或表面张力的改性作用，因此本发明包括这些添加剂一般以以上所给出的量用于提高碱土硅酸盐纤维的纤维化的应用。
                            表1，第1部分
Comp.                 收缩率％/24hrs1300℃ 1350℃ 1400℃ 1450℃ 1500℃ 1550℃                             组成(wt％)CaO    SiO2 P2O5  Al2O3  B2O3  ZrO2 MgO    Na2O  K2O  TiO2 Fe2O3  ZnO     总溶解度ppm   SSAm2/g    纤维质量    JM 28粘附
  CS01/CCS02/CCS01/DCS01CS10CS10consCS02CS02/DCMS02CMS02/BCS03/DCMS03CMS03/BCS15CS04/ECS04/EconsCS04CMS04CS12CS12consCS16CS17CS18CS19CMS05CMS05/BSACM01SACM02SACM03CSMg01CSMg03CSMg02CSMg07CSMg06CSMg09CSMg08CSMg10CS Fe2O3 01CS Fe2O3 05CS Fe2O3 02CS Al03        10.34  熔化   熔化8.52   熔化   熔化5.142.60   4.34   熔化4.25   19.51  熔化4.25   14.12  熔化1.92   2.58   7.83   熔化3.852.12   熔化2.35   7.02   熔化11.872.95   熔化2.75   8.08   熔化5.67   34.47  34.022.77   11.39  21.962.77   7.621.65   0.98   3.71   30.422.35   熔化2.35   9.10   31.402.35   4.80   15.379.37   35.35  34.379.05   33.70  30.647.92   32.00  30.024.84   27.36  26.412.63   熔化3.31   8.11   14.104.01   3.56   4.793.515.46   8.63   10.387.36   21.14  28.33  37.442.24   7.17   12.617.14   12.13  16.17  27.037.38   20.476.23   25.18  12.34  29.971.28   2.332.86   8.24   9.70   31.431.85   1.801.94   8.72   19.79  26.243.47   10.11  15.34  22.521.43   3.642.18   8.47   15.15  22.38   35.00  62.40          0.83                     0.56   0.30   0.15         0.2433.00  63.80          0.77                     0.51   0.40   0.14         0.2232.90  64.60          0.80                     0.48   0.26   0.15         0.1833.80  65.00          0.80                     0.51   0.21                0.2133.00  65.40          0.76                     0.52   0.24   0.15         0.2133.00  65.40          0.76                     0.52   0.24   0.15         0.2131.90  66.50          0.77                     0.49   0.31                0.2031.20  66.60          0.75                     0.46   0.25   0.14         0.2018.30  66.90          0.31                     14.40  0.17                0.1418.30  66.90          0.31                     14.40  0.17                0.1428.90  69.30          0.70                     0.44                       0.1916.80  69.40          0.30                     13.40  0.11                0.1416.80  69.40          0.30                     13.40  0.11                0.1428.00  69.70          0.61                     0.53   0.19                0.2028.20  69.80          0.61                     0.38   0.43   0.10         0.1728.20  69.80          0.61                     0.38   0.43   0.10         0.1728.20  69.80          0.61                     0.38   0.43   0.10         0.1716.50  70.00          0.38                     13.10  0.12                0.1326.90  70.70          0.66                     0.41   0.39   0.12         0.1826.90  70.70          0.66                     0.41   0.39   0.12         0.1827.20  71.00          0.61                     0.49   0.16                0.1726.60  71.40          0.62                     0.48   0.17                0.1726.20  71.60          0.75                     0.49   0.20                0.1826.40  71.60          0.73                     0.48   0.21                0.1915.10  72.00          0.97                     11.40  0.23                0.1215.10  72.00          0.97                     11.40  0.23                0.123.17   78.00          1.60                     17.00                      0.215.04   76.50          1.62                     14.80  0.12                0.207.71   75.80          1.77                     13.10                      0.6523.60  72.90          0.61                     2.61   0.11                0.1620.20  75.70          0.57                     2.61   0.20                0.1821.60  75.20          0.54                     2.59                       0.1423.00  73.80          0.49                     1.81                       0.1724.20  72.30          0.51                     1.79   0.13                0.1818.30  78.40          0.39                     1.71                       0.1420.50  76.50          0.44                     1.65                       0.1617.30  79.40          0.28                     1.61                       0.1522.60  74.40          0.57                     0.72   0.23                0.4421.10  74.70          0.58                     0.51   0.17                2.2521.90  74.80          0.56                     0.50   0.22                0.6522.30  74.60          1.03                     0.41   0.18                0.15   230.0199.0199.1235.0199.8199.8218.0208.1213.2215.0280.1241.9260.0260.0269.8211.3211.3283.1228.2248.8248.2125.2160.0206.3170.5223.6231.3210.6250.1268.1228.7257.2248.3279.9207.1285.5   0.330.450.370.470.300.300.590.420.420.540.410.500.500.440.550.550.550.710.710.630.370.330.460.660.380.630.420.530.350.430.220.490.470.300.48     下等下等下等下等下等下等下等下等下等下等下等下等下等良好的纤维许多薄片许多薄片许多薄片下等良好的纤维良好的纤维良好的纤维良好的纤维良好的纤维良好的纤维下等下等不错的纤维不错的纤维不错的纤维良好的纤维，稍短良好的纤维，稍短良好的纤维，稍短不错的纤维良好的纤维短良好的纤维下等，短不错的纤维短短良好的纤维     粘附粘附粘附粘附粘附粘附粘附粘附粘附粘附粘附粘附粘附粘附粘附粘附粘附粘附粘附粘附粘附粘附粘附粘附粘附粘附不粘附不粘附不粘附粘附不粘附粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附
                                            表1，第2部分
Comp.                收缩率0％/24hrs1300℃ 1350℃ 1400℃ 1450℃ 1500℃ 1550℃                               组成(wt％)CaO    SiO2  P2O5  Al2O3  B2O3  ZrO2  MgO    Na2O  K2O   TiO2  Fe2O3  ZnO     总溶解度ppm  SSAm2/g   纤维质量   JM 28粘附
  CS13CS Fe2O3 04CS Fe2O3 03CS05CS06/ECS06/EconsCS Al02CS07/ECS14/BCS08/ECS06/B         1.46   3.00   23.161.79   9.03   14.51  19.782.43   12.43  20.53  24.241.21   1.79   4.14   熔化1.56   6.03   21.81  30.161.56   4.02   10.54  13.75  16.961.48   2.41   13.51  18.281.50   2.14   10.00  5.19   5.812.22   6.232.03   1.34   3.10   7.722.66   熔化   12.00  24.00  74.30           0.55                      0.39   0.17                  0.1721.60  74.90           0.52                      0.39   0.16                  1.4721.90  74.70           0.52                      0.38   0.21                  1.0626.40  72.20           0.55                      0.33   0.19   0.10           0.1624.00  73.90           0.52                      0.33   0.28                  0.1524.00  73.90           0.52                      0.33   0.28                  0.1523.10  74.70           0.48                      0.33   0.19                  0.1422.20  76.50           0.53                      0.33   0.11                  0.1522.60  75.00           0.58                      0.30   0.12                  0.1719.50  78.90           0.70                      0.27                  0.16   0.1824.30  75.00           0.39                      0.26   0.15                  0.12   156.0239.7241.0262.0222.0222.0177.9137.3160.0172.0  0.560.410.470.450.340.340.590.290.550.320.55   短良好的纤维良好的纤维许多薄片许多薄片许多薄片良好的纤维不错的纤维短下等许多薄片   不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附
                                                  表2
Comp.                收缩率％/24hrs1300℃ 1350℃ 1400℃ 1450℃ 1500℃ 1550℃                       组成(wt％)CaO   SiO2 P2O5 Al2O3 B2O3 ZrO2  MgO   Na2O  K2O TiO2 Fe2O3 ZnO      总溶解度ppm    SSAm2/g   纤维质量 JM 28粘附  总SiO2+ZrO2
  CAS01CAS02CAS03CS03/CCZrS02CZrs03CS11CS11consCZrS07CZrS06CZrS04CS13consCAS07CSMg04CS08CS05/BCS05/BconsCS05/ECS05/EconsCS06CSMg05CS07/BCS07/BconsCS07        17.62  18.4510.19  24.185.42   14.63  14.566.02   熔化   熔化15.01  31.087.39   30.644.96   19.95  34.814.96   11.42  22.67-0.29熔化   7.972.561.46   3.56   12.88  16.60  28.584.59   10.221.76   2.941.24   1.30   1.74   3.370.86   1.53   5.561.53   4.52   13.462.04   7.28   33.19  44.492.04   8.19   20.34  25.44  28.001.36   1.42   2.36   5.87   熔化1.67   1.260.86   1.50   2.17   10.00  15.001.50   1.31   2.93   5.19   5.811.08   1.06   1.15   3.34 24.50 71.70         2.78            0.45    0.28  0.12               0.1222.60 73.50         2.52            0.91    0.25  0.11               0.1520.40 75.70         2.32            1.05    0.23  0.11               0.1231.50 65.60         0.83            0.14    0.47  0.36   0.14        0.2327.40 65.80         0.70            3.85    0.40  0.37   0.12        0.1925.60 68.00         0.67            3.96    0.37  0.25   0.11        0.2129.00 68.90         0.75            0.13    0.47  0.30   0.13        0.1929.00 68.90         0.75            0.13    0.47  0.30   0.13        0.1917.90 74.70         0.62            4.94    0.24  0.48               0.1719.00 74.90         0.71            4.45    0.28  0.42               0.1324.50 70.60         0.72            3.29    0.36  0.35   0.11        0.1724.30 73.30         0.57            0.73    0.31  0.26               0.2024.80 73.10         1.10            0.43    0.28  0.14               0.1416.70 79.40         0.38            0.43    2.35                     0.1819.80 78.50         0.45            0.34    0.25  0.16               0.1426.00 72.00         0.62            0.33    0.31  0.22               0.1526.00 72.00         0.62            0.33    0.31  0.22               0.1526.00 72.00         0.62            0.33    0.31  0.22               0.1526.00 72.00         0.62            0.33    0.31  0.22               0.1523.40 73.30         1.77            0.27    0.32  0.14               0.1416.40 79.80         0.35            0.14    2.46                     0.1322.20 76.60         0.52            0.12    0.26  0.11               0.1222.20 76.60         0.52            0.12    0.26  0.11               0.1222.30 76.90         0.35            0.10    0.24  0.17               0.11     30.320.147.4222.0107.264.2200.5200.524.342.569.4156.0127.8243.0201.5182.0182.0276.0276.0244.6237.2104.0104.0203.5 0.200.310.390.210.500.500.220.250.210.560.340.090.200.340.340.480.480.320.110.230.230.25   下等下等下等下等良好的纤维良好的纤维下等下等非常短下等良好的纤维短下等下等，短许多薄片许多薄片许多薄片许等薄片许多薄片许多薄片良好的纤维，稍短许多薄片许多薄片许多薄片 粘附粘附粘附粘附粘附粘附粘附粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附  72.1574.4176.7565.7469.6571.9669.0369.0379.6479.3573.8974.0373.5379.8378.8472.3372.3372.3372.3373.5779.9476.7276.7277.00
                                  表3，第4部分
Comp.               收缩率％/24hrs1300℃ 1350℃ 1400℃ 1450℃ 1500℃ 1550℃                                    组成(wt％)CaO    SiO2   P2O5  Al2O3  B2O3  ZrO2  MgO  Na2O  K2O  TiO2  Fe2O3  ZnO    总溶解度ppm  SSAm2/g 纤维质量 JM 28粘附 总SiO2+B2O3+ZrO2+5*P2O5
 CBS04CBS03CPS02/BCPS02CPS02consCPS21CBS05CPS20CPS20consCPS18/BCPS17/BCPS01/BCPS01/CCBS02CBS07CPS01CPS01consCPS17CPS19CBS01CPS15/BCPS16         3.54   6.97   7.163.47   10.32  16.434.020.66   0.91   0.700.66   0.25   -0.213.044.14   9.98   14.712.48   9.102.48   6.21   11.94  17.39  20.691.93   6.72   16.072.39   6.361.73   8.96   12.582.05   11.86  5.87   6.104.93   18.32  23.28-0.29  6.10   14.692.29   1.25   0.152.29   1.25   0.152.862.87   19.23  26.903.79   21.922.24   12.71  27.90  35.553.96   20.90  27.90  18.00  77.90            0.43      2.03    0.70    0.31 0.17                 0.2420.40  75.20            0.48      2.12    0.84    0.33 0.18                 0.1821.40  75.00   1.54     0.48                      0.32 0.13                 0.1622.40  74.60   1.61     0.29      0.26    0.90    0.27 0.21                 0.1122.40  74.60   1.61     0.29      0.26    0.90    0.27 0.21                 0.1123 00  74.10   0.42     0.61                      0.45 0.38    0.10         0.2021.20  73.90            0.54      3.11            0.32 0.16                 0.1723.80  73.80   0.38     0.66              0.29    0.35 0.18    0.11         0.1623.80  73.80   0.38     0.66              0.29    0.35 0.18    0.11         0.1623.90  73.20   0.87     0.59                      0.34 0.19                 0.1524.70  72.80   0.88     0.65                      0.36 0.17                 0.1623.50  72.70   1.58     0.58                      0.33 0.20                 0.1523.80  72.60   1.58     0.46                      0.34 0.32                 0.3222.90  72.60            0.70      2.16    0.30    0.33 0.24                 0.1524.30  72.20            0.38      1.38    0.84    0.27 0.18                 0.1323.90  71.50   1.52     0.48      0.90    0.95    0.29 0.48                 0.1023.90  71.50   1.52     0.48      0.90    0.95    0.29 0.48                 0.1025.20  71.50   0.90     0.66                      0.37 0.37    0.11         0.2825.50  71.50   0.48     0.64              0.15    0.39 0.44    0.11         0.1825.20  70.90            0.62      2.13    0.84    0.41 0.12                 0.2027.00  70.50   0.83     0.64                      0.39 0.15                 0.1726.00  70.20   0.89     0.69              0.23    0.38 0.53    0.11         0.18   64.073.0336.0349.6336.8188.0117.0229.0229.0161.0152.0275.0338.885.090.0286.3338.8241.0172.0101.2177.0181.0  0.160.270.100.100.410.350.330.330.420.580.340.500.320.130.330.490.400.450.380.54 下等下等下等不错的纤维下等不错的纤维下等良好的纤维良好的纤维短不错的纤维良好的纤维下等良好的纤维短不错的纤维下等短良好的纤维良好的纤维下等下等 不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附粘附不粘附   80.6378.1682.7083.8183.8176.2077.0175.9975.9977.5577.2080.6080.5075.0674.4280.9580.9576.0074.0573.8774.6574.88
                                    表3，第5部分
Comp.               收缩率％/24hrs1300℃ 1350℃ 1400℃ 1450℃ 1500℃ 1550℃                                 组成(wt％)CaO    SiO2  P2O5  Al2O3  B2O3   ZrO2  MgO   Na2O  K2O  TiO2  Fe2O3  ZnO      总溶解度ppm   SSAm2/g 纤维质量   JM28粘附 总SiO2+B2O3+ZrO2+5*P2O5
  CPS15CPS15consCPS14/BCS03CS03/ECS03/EconsCPS13CPS14CPS14consCPS12CPS11         2.76   13.37  28.942.76          14.74  17.674.08   28.801.36   1.55   5.03   熔化3.81   18.22  熔化   熔化3.81   13.67  28.026.92   4.00   38.521.90   13.10  熔化1.90   5.30   11.68  15.888.72   5.93   熔化15.72  10.06  熔化  26.70  70.00  0.93     0.69                       0.43  0.38   0.12          0.2026.70  70.00  0.93     0.69                       0.43  0.38   0.12          0.2029.70  67.70  0.90     0.69                       0.46  0.19   0.10          0.2230.20  67.60  0.15     0.87                       0.42  0.21   0.11          0.1830.20  67.60  0.15     0.87                       0.42  0.21   0.11          0.1830.20  67.60  0.15     0.87                       0.42  0.21   0.11          0.1830.20  65.70  0.93     0.70                       0.47  0.54   0.13          0.2030.80  64.80  0.99     0.80                       0.48  0.30   0.13          0.2130.80  64.80  0.99     0.80                       0.48  0.30   0.13          0.2132.10  63.80  0.69     0.75                       0.49  0.31   0.14          0.2034.40  62.00  0.99     0.81               0.10    0.55  0.31   0.13          0.21     166.6166.6153.9240.5260.0260.0163.8153.9153.9165.6170.5   0.610.610.320.610.470.470.440.470.470.550.53 下等下等不错的纤维下等下等下等不错的纤维不错的纤维不错的纤维许多薄片良好的纤维   不粘附不粘附不粘附粘附粘附粘附粘附粘附粘附粘附粘附   74.6574.6572.2068.3568.3568.3570.3569.7569.7568.2567.05
                                                      表4
Comp.             收缩率％/24hrs1300 1350 1400 1450°1500°1550℃                             组成(wt％)CaO  SiO2  P2O5 Al2O  B2O3  ZrO2  Mg   Na2  K2O  TiO2  Fe2O  ZnO      总溶解度ppm  SSAm2/g 纤维质量 JM 28粘附
50％YIELDSPUNBLOWN覆盖层BAG 24BAG 7BAG 41BAG 46BAG 62No.3No.4No.5第一覆盖层最后覆盖层第一覆盖层最后覆盖层大块高速       0.64 1.30 6.78  28.55  30.830.38 0.77 5.48  30.54  40.300.80 1.30 7.89  29.43  39.640.61 0.900.85 1.43 4.69  18.36  25.690.57 0.84 2.22  22.32  26.700.83 1.02 1.51  12.12  17.851.56 0.96 1.36  7.69   12.840.65 3.24 8.33  13.25  22.843.36 8.022.54 8.121.96 6.550.541.13 1.37 6.00 16.21 28.76  熔化1.28 1.79 2.56  27.17  25.111.06 1.35 1.71  21.38  31.511.52 1.81 13.71 24.15  24.56 25.50 72.70          0.59                   0.50              0.26   0.1925.40 73.10          0.67                   0.54                     0.1825.30 73.10          0.54                   0.55                     0.2223.00 74.60          0.56                   0.43 0.22   0.12         0.1723.18 75.18          0.66                   0.42                     0.1724.26 73.95          0.63                   0.45                     0.1921.62 76.65          0.79                   0.38                     0.1718.70 79.80          0.81                   0.43                     0.1419.74 76.25          0.47            0.82   2.27                     0.1519.94 75.35          0.37            1.11   2.99                     0.1620.81 75.45          0.39            1.05   2.87                     0.1620.61 75.28          0.36            0.99   2.70                     0.1623.80 74.20          0.62                   0.7725.01 72.89          0.57                   0.9223.80 74.20          0.62                   0.7725.01 72.89          0.57                   0.9224.90 72.20          0.72                   0.82     232.0254.0196.8240.7300.0117.0127.062.095.0202.8210.2229.4205.2264.4205.2264.4267.5  0.220.230.470.160.230.160.170.170.161.150.610.880.410.150.410.150.15 非常好非常好非常好非常好非常好非常好非常好非常好非常好非常好非常好非常好非常好非常好非常好非常好非常好 不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附不粘附

Claims (26)

1.用于需要连续耐受温度1260摄氏度的场合而不与硅铝酸盐耐火砖反应的隔热材料，所述隔热材料包含具有以下组成的纤维，以重量％计：
65％＜SiO2＜86％
MgO＜10％
14％＜CaO＜28％
Al2O3＜2％
ZrO2＜3％
B2O3＜5％
P2O5＜5％
72％＜SiO2+ZrO2+B2O3+5*P2O5
95％＜SiO2+CaO+MgO+Al2O3+ZrO2+B2O3+P2O5。
2.根据权利要求1所要求的隔热材料，其中存在于纤维中的MgO的量低于2.5％。
3.根据权利要求2所要求的隔热材料，其中存在于纤维中的MgO的量低于1.75％。
4.根据权利要求1-3的任何一项所要求的隔热材料，其中CaO的量是18％＜CaO＜26％。
5.根据任何权利要求1-4的任何一项所要求的隔热材料，其中
98％＜SiO2+CaO+MgO+Al2O3+ZrO2+B2O3+P2O5。
6.根据权利要求5所要求的隔热材料，其中
98.5％＜SiO2+CaO+MgO+Al2O3+ZrO2+B2O3+P2O5。
7.根据权利要求6所要求的隔热材料，其中
99％＜SiO2+CaO+MgO+Al2O3+ZrO2+B2O3+P2O5。
8.根据权利要求1-7的任何一项所要求的隔热材料，具有以下组成：
72％＜SiO2＜80％
18％＜CaO＜26％
0％＜MgO＜3％
0％＜Al2O3＜1％
0％＜ZrO2＜1.5％
98.5％＜SiO2+CaO+MgO+Al2O3+ZrO2+B2O3+P2O5。
9.根据权利要求1-8的任何一项所要求的隔热材料，具有以下组成：
72％＜SiO2＜74％
24％＜CaO＜26％。
10.一种硅酸盐纤维，包含：
65％＜SiO2＜86％
MgO＜10％
14％＜CaO＜28％
Al2O3＜2％
ZrO2＜3％
B2O3＜5％
P2O5＜5％
72％＜SiO2+ZrO2+B2O3+5*P2O5
95％＜SiO2+CaO+MgO+Al2O3+ZrO2+B2O3+P2O5
0.1％＜R2O3＜4％
其中R选自Sc、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y或其混合物。
11.根据权利要求10所要求的硅酸盐纤维，其中R是La或Y或其混合物。
12.根据权利要求11所要求的硅酸盐纤维，其中R是La。
13.根据权利要求10-12的任何一项所要求的硅酸盐纤维，其中R2O3的量大于0.25％，更优选大于0.5％，和进一步更优选大于1.0％。
14.根据权利要求10-13的任何一项所要求的硅酸盐纤维，其中R2O3的量小于2.5％，优选小于1.5％重量。
15.根据权利要求10-14的任何一项所要求的硅酸盐纤维，具有以下组成，以重量％计：
72％＜SiO2＜80％
18％＜CaO＜26％
0％＜MgO＜3％
0％＜Al2O3＜1％
0％＜ZrO2＜1.5％
1％＜R2O3＜2.5％。
16.根据权利要求15所要求的硅酸盐纤维，其中R包含La。
17.根据权利要求16所要求的硅酸盐纤维，具有以下组成，以重量％计：
SiO2：73±0.5％
CaO：24±0.5％
La2O3：1.3-1.5％
剩余组分：＜2％，优选＜1.5％
18.隔热材料，其包含权利要求10-15的任何一项的硅酸盐纤维。
19.完全包含根据权利要求1-17的任何一项所规定的纤维的隔热材料。
20.根据权利要求1-8的任何一项所要求的隔热材料，其中隔热材料是覆盖层形式的。
21.根据权利要求1-20的任何一项的隔热材料，它用于需要连续耐受温度1300摄氏度的场合而不与硅铝酸盐耐火砖反应。
22.包含权利要求1-7的任何一项中规定的纤维的物体作为隔热材料的用途，其用于需要连续耐受温度1260摄氏度的场合而不与硅铝酸盐耐火砖反应的应用。
23.根据权利要求22所要求的应用，它用于需要连续耐受温度1300摄氏度的场合而不与硅铝酸盐耐火砖。
24.一种形成碱土硅酸盐纤维的方法，包括在纤维的组分中包含1％-4％重量的R2O3，其中R选自Sc、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Y或其混合物。
25.根据权利要求24所要求的方法，其中R是La或Y或其混合物。
26.根据权利要求25所要求的方法，其中R是La。
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CN103298987A (zh) * 2010-12-28 2013-09-11 霓佳斯株式会社 生物体溶解性无机纤维
CN103298987B (zh) * 2010-12-28 2015-07-01 霓佳斯株式会社 生物体溶解性无机纤维
CN103958753A (zh) * 2011-12-01 2014-07-30 霓佳斯株式会社 生物体溶解性无机纤维及其制造方法
CN103958753B (zh) * 2011-12-01 2016-11-02 霓佳斯株式会社 生物体溶解性无机纤维及其制造方法
CN103073307A (zh) * 2012-12-12 2013-05-01 山东安勒特生态陶瓷纤维有限公司 1050度硅酸钙生态可溶性环保耐火纤维
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