CN101045639B - 熔凝硅质耐火材料的制造方法 - Google Patents
熔凝硅质耐火材料的制造方法 Download PDFInfo
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- CN101045639B CN101045639B CN2007100875643A CN200710087564A CN101045639B CN 101045639 B CN101045639 B CN 101045639B CN 2007100875643 A CN2007100875643 A CN 2007100875643A CN 200710087564 A CN200710087564 A CN 200710087564A CN 101045639 B CN101045639 B CN 101045639B
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000005350 fused silica glass Substances 0.000 claims abstract description 69
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims description 73
- 239000000463 material Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 17
- 238000001354 calcination Methods 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 7
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 7
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- -1 sodium aluminum fluoride Chemical compound 0.000 claims description 5
- 150000002222 fluorine compounds Chemical class 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 20
- 239000000047 product Substances 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 229910000861 Mg alloy Inorganic materials 0.000 description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 10
- 229910052749 magnesium Inorganic materials 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 8
- 238000005266 casting Methods 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 4
- 239000011819 refractory material Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011133 lead Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- 238000001704 evaporation Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000013001 point bending Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- 229910016036 BaF 2 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940070337 ammonium silicofluoride Drugs 0.000 description 1
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001506 inorganic fluoride Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000005360 phosphosilicate glass Substances 0.000 description 1
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229940105963 yttrium fluoride Drugs 0.000 description 1
- RBORBHYCVONNJH-UHFFFAOYSA-K yttrium(iii) fluoride Chemical compound F[Y](F)F RBORBHYCVONNJH-UHFFFAOYSA-K 0.000 description 1
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Abstract
本发明提供一种熔凝硅质耐火材料,其含有熔凝二氧化硅和氟化物。此外,本发明还公开了该熔凝硅质耐火材料的制造方法。
Description
技术领域
本发明涉及熔凝硅质耐火材料,更具体地说,本发明涉及这样一种熔凝硅质耐火材料,该熔凝硅质耐火材料适合作为耐热材料而被用在熔点相对较低的金属(例如为铝、镁、锌、锡、铅或它们的合金)所用铸造设备中的与这类低熔点金属形成的金属液接触的位置处,其中所述低熔点金属的熔点通常为800℃或更低。
背景技术
熔凝硅质耐火材料是一种通过烧结熔凝二氧化硅而得到的耐火材料,其热膨胀系数低并且其耐热震性优异。因此,在用于铸造(例如)铝、镁、锌、锡、铅或它们的合金的设备中,熔凝硅质耐火材料已经用在输送、供应和保持金属液的位置处。具体而言,熔凝硅质耐火材料被用作(例如)浇铸箱、流槽和保持炉所用衬里材料的构成材料,或者被用作诸如浮子、流出槽和热顶环之类的附件的构成材料。
就所述熔凝硅质耐火材料的制造方法而言,已知有(例如)这样一种制造方法:用熔凝二氧化硅粗粒粉和熔凝二氧化硅超细粉制备滑料(slip material)或捏合料,并且在模制和干燥之后于特定温度下进行煅烧(参见专利文献1)。根据该方法,会得到只含有熔凝二氧化硅作为其成分的熔凝硅质耐火材料。此外,还已知有这样一种制造方法:对含有熔凝二氧化硅粉以及含硼化合物或含磷化合物的模制用混合物进行模制,并且在特定条件下进行煅烧(参见专利文献2)。根据该方法,通过使用硼酸或磷酸作为上述化合物,会得到在熔凝二氧化硅中形成有硼硅酸盐玻璃相或磷硅酸盐玻璃相的熔凝硅质耐火材料。
专利文献1:JP-B-52-43849(第2页,第4栏)
专利文献2:JP-A-11-60330(第2页,第1栏;第4页,第5栏;以及第4页,第6栏)
另一方面,为了减轻重量,便携设备(例如数码照相机、数码摄像机、手机和个人笔记本电脑)或载重物体(例如汽车、框架和箱体)也趋向于由镁合金制成。然而,镁或含镁合金的活性极高,因此,常规的熔凝硅质耐火材料存在着只能使用几次、或者在某些情况下只能使用一次的问题,由此,使得人们要更换这些熔凝硅质耐火材料。
发明内容
由此,本发明的目的是提供一种对由高活性的金属液所产生的腐蚀作用具有优异的耐受性的熔凝硅质耐火材料。
通过以下说明,本发明的其它目的和效果将显而易见。
在这样一种实际情况下,本发明人进行了广泛的研究。结果发现,通过将氟化物引入熔凝二氧化硅中,会得到耐腐蚀性优异的熔凝硅质耐火材料,由此完成了本发明。也就是说,本发明提供了下述的熔凝硅质耐火材料及其制造方法:
(1)一种熔凝硅质耐火材料,其含有熔凝二氧化硅和氟化物;
(2)上述(1)中所述的熔凝硅质耐火材料,其中以氟计,所述氟化物的含量为0.01重量%到10重量%;
(3)上述(1)或(2)中所述的熔凝硅质耐火材料,其中所述氟化物含有选自氟化钙(CaF2)、氟化镁(MgF2)和冰晶石(Na3AlF6)中的至少一种;
(4)上述(1)到(3)中任意一项所述的熔凝硅质耐火材料,其体密度为1.3g/cm3到2.2g/cm3;
(5)上述(1)到(4)中任意一项所述的熔凝硅质耐火材料,其弯曲强度为5MPa或更高;
(6)上述(1)到(5)中任意一项所述的熔凝硅质耐火材料,其热膨胀系数为2.5×10-6℃-1或更低;
(7)上述(1)到(6)中任意一项所述的熔凝硅质耐火材料,其中该耐火材料被用在与镁的金属液或含镁合金的金属液接触的位置处;
(8)一种熔凝硅质耐火材料的制造方法,该方法包括:
浆料制备步骤,在该步骤中制备含有固态原料物质的浆料,该固态原料物质含有熔凝二氧化硅粉和氟化物粉;
模制步骤,在该步骤中由所述浆料得到模制制品;以及
煅烧步骤,在该步骤中在1050℃到1250℃下煅烧所述的模制制品;
(9)上述(8)中所述的熔凝硅质耐火材料的制造方法,其中以氟计,所述固态原料物质中的所述氟化物的含量为0.01重量%到10重量%;
(10)上述(8)或(9)中所述的熔凝硅质耐火材料的制造方法,其中所述的熔凝二氧化硅粉含有由50重量%到90重量%的第一熔凝二氧化硅粉和10重量%到50重量%的第二熔凝二氧化硅粉形成的混合物,所述第一熔凝二氧化硅粉的平均粒径为1μm到10μm,所述第二熔凝二氧化硅粉的平均粒径为50μm到500μm;
(11)上述(8)到(10)中任意一项所述的熔凝硅质耐火材料的制造方法,其中所述氟化物粉含有选自氟化钙(CaF2)、氟化镁(MgF2)和冰晶石(Na3AlF6)中的至少一种氟化物,并且该氟化物粉的平均粒径为1μm到10μm;以及
(12)上述(8)到(11)中任意一项所述的熔凝硅质耐火材料的制造方法,其中所述浆料含有100重量份的所述固态原料物质和10重量份到40重量份的水。
本发明中的术语“含镁合金”通常是指镁与除镁之外的其它低熔点金属(例如铝、锌、锡或铅)构成的合金。尽管镁可以为任意含量,但是,切合实际的是,镁的含量占合金总量的0.1重量%到99.9重量%。
根据本发明的熔凝硅质耐火材料含有氟化物,因此与传统材料相比,本发明的耐火材料对由强腐蚀性金属液(例如镁的金属液或含镁合金的金属液)产生的腐蚀作用具有非常优异的耐受性。此外,根据本发明的熔凝硅质耐火材料的制造方法,可以容易而有效地得到这种耐腐蚀性优异的熔凝硅质耐火材料。
附图说明
图1是用于说明各例子中腐蚀试验的试验方法的示意图。
具体实施方式
以下详细说明本发明。
本发明的熔凝硅质耐火材料是一种含有熔凝二氧化硅和氟化物的模制制品。为了制造这种熔凝硅质耐火材料,首先要制备含有固态原料物质的浆料,其中所述固态原料物质含有熔凝二氧化硅粉和氟化物粉。
熔凝二氧化硅粉通常是平均粒径为1μm到500μm的混合物,并且可直接用作固态原料物质。然而,优选的是,使用由相对细粒状的第一熔凝二氧化硅粉和相对粗粒状的第二熔凝二氧化硅粉形成的混合物。这样,第一熔凝二氧化硅粉便进入在第二熔凝二氧化硅粉的颗粒之间所形成的空隙中,当这种混合后的熔凝二氧化硅粉被制成模制制品时,该制品的填充性能会得到提高,从而使得熔凝硅质耐火材料的结构在煅烧后变得致密化,由此使耐热性提高。因此这种方式是优选的。此外,当把熔凝硅质耐火材料用作衬里材料等时,这种耐热性的改善使得有可能降低该材料的厚度,并由此减轻其质量,从而提高其工作性能并进一步减小其比热(热容)。因此这种方式是优选的。
当使用由第一熔凝二氧化硅粉和第二熔凝二氧化硅粉形成的混合物时,该第一熔凝二氧化硅粉的平均粒径优选为1μm到10μm、更优选为2μm到6μm。另一方面,该第二熔凝二氧化硅粉的平均粒径优选为50μm到500μm、更优选为100μm到300μm。此外,关于在这种混合后的熔凝二氧化硅粉中第一熔凝二氧化硅粉和第二熔凝二氧化硅粉的混合比,该比例优选为:10重量%到50重量%的第二熔凝二氧化硅粉比50重量%到90重量%的第一熔凝二氧化硅粉,更优选为20重量%到40重量%的第二熔凝二氧化硅粉比60重量%到80重量%的第一熔凝二氧化硅粉。当第一熔凝二氧化硅粉和第二熔凝二氧化硅粉各自的平均粒径以及它们的混合比选自上述范围时,模制制品中熔凝二氧化硅粉的填充性能会得到更好的改善。
对氟化物没有特别限定,但是其包括无机氟化物,例如氟化钙(CaF2)、氟化镁(MgF2)、冰晶石(Na3AlF6)、氟化锂(LiF)、氟化钡(BaF2)、氟化铝(AlF3)、氟化锶(SrF2)、氟化铈(CeF3)、氟化钇(YF3)、氟化钠(NaF)、氟化钾(KF)、氟硅酸钠(Na2SiF6)和氟硅酸铵((NH4)2SiF6)。在本发明中,优选使用选自氟化钙(CaF2)、氟化镁(MgF2)和冰晶石(Na3AlF6)中的至少一种,这是因为这几种化合物的成本较低。
氟化物的平均粒径优选为1到10μm、更优选为2到6μm。当氟化物粉的粒径选自上述范围时,氟化物粉可以容易地均匀分散在熔凝二氧化硅粉中。因此,这种方式是优选的。特别是,当熔凝二氧化硅粉是由第一熔凝二氧化硅粉和第二熔凝二氧化硅粉形成的混合物时,通过使用其粒径与第一熔凝二氧化硅粉的粒径相似的氟化物粉,就会使氟化物粉易于进入在第二熔凝二氧化硅粉的颗粒之间所形成的空隙中,因此易于形成更均匀的分散。因此,这种方式是更优选的。
对固态原料物质中熔凝二氧化硅粉和氟化物粉的混合比没有特别限定,只要在最后得到的熔凝硅质耐火材料中,氟的含量在优选为0.01重量%到10重量%、更优选为0.1重量%到3.0重量%的范围内即可。例如,将0.01重量%到10重量%的氟化物粉和90重量%到99.99重量%的熔凝二氧化硅粉混合。更优选的是,将1重量%到5重量%的氟化物粉和95重量%到99重量%的熔凝二氧化硅粉混合。当混合比选自上述范围时,熔凝硅质耐火材料的强度、耐热震性(热膨胀系数)和耐腐蚀性都是令人满意的,因此这种方式是优选的。
通过将上述固态原料物质与水混合来制备浆料。可以使用已知的方法作为混合方法。浆料中固态原料物质和水的混合比优选被调配为:相对于100重量份的固态原料物质,水为10重量份到40重量份,更优选的是,水为20重量份到30重量份。
此外,可按需向浆料中加入成型助剂、粘结剂等。本发明使用的成型助剂包括(例如)PVA(聚乙烯醇)和CMC(羧甲基纤维素)。此外,本发明使用的粘结剂包括(例如)硅酸盐玻璃和苛性钠。优选使用成型助剂,因为这样会改善成型性,并且优选使用粘结剂,因为 这样会改善模制制品的形状保持性。
然后,实施模制步骤,从而由上述浆料得到具有所需形状的模制制品。对用于得到模制制品的方法没有特别限定,可以使用(例如)浇铸成型法、压机模压成型法或挤出成型法。在这些方法中,优选浇铸成型法,因为这种方法可以使浆料被致密地填充在模具中,从而可以容易地使所得到的模制制品的密度很大。
可直接使所得到的模制制品进入煅烧步骤,然后进行煅烧。然而,当模制制品中残留有大量的水时,或者当煅烧步骤中模制制品被快速升温时,为了防止由于模制制品中的水分被快速蒸发而在煅烧后的制品中形成裂纹等,可以按需在实施煅烧步骤之前先采取干燥步骤。可以在模制制品中的水分被逐渐蒸发的条件下实施干燥步骤,并且可采用已知的方法来实施干燥步骤。
然后,实施煅烧步骤,从而由上述模制制品得到熔凝硅质耐火材料。对煅烧温度没有限定,只要在该温度下可以将熔凝二氧化硅粉颗粒烧结在一起即可。然而,1050℃到1250℃是合适的,并且优选为1100℃到1200℃。如果煅烧温度低于1050℃,则不利的是,熔凝二氧化硅粉颗粒难以被烧结在一起。另一方面,如果煅烧温度超过1250℃,则不利的是,有方晶石形成,从而导致熔凝硅质耐火材料的热膨胀系数增大。对煅烧时间没有限定,只要完成了上述模制制品的煅烧操作即可。然而,0.5到20小时是合适的,并且优选为1到5小时。如果煅烧时间少于0.5小时,则不能得到足够的烧结强度。因此,这种方式是不利的。此外,即使煅烧时间超过20小时,烧结效果也几乎不会发生改变。
如此得到的本发明的熔凝硅质耐火材料含有无定型熔凝二氧化硅相、以及几乎均匀地分散于该熔凝二氧化硅相中的氟化物,其中所述的无定型熔凝二氧化硅相是通过使熔凝二氧化硅粉熔融并对其进行烧结而得到的。当把由第一熔凝二氧化硅粉和第二熔凝二氧化硅粉形成的混合物用作熔凝二氧化硅粉时,第一熔凝二氧化硅粉和氟化物便进入在第二熔凝二氧化硅粉的颗粒之间所形成的空隙中。熔凝硅质耐火材料中的熔凝二氧化硅和氟化物的含量比仍保持为固态原料物 质中的二者的混合比。
本发明的熔凝硅质耐火材料的体密度优选为1.3g/cm3到2.2g/cm3、更优选为1.4g/cm3到1.8g/cm3。如果体密度低于1.3g/cm3,则不利的是,其强度降低。另一方面,如果体密度超过2.2g/cm3,则不利的是,会导致质量增加。
此外,考虑到加工性能和强度,本发明的熔凝硅质耐火材料的弯曲强度优选为5MPa或更高,更优选为6MPa或更高。
此外,本发明的熔凝硅质耐火材料在使用位置处与由其它材料构成的基材相连接。因此,为了防止熔凝硅质耐火材料从基材上脱离,熔凝硅质耐火材料的热膨胀系数优选为2.50×10-6℃-1或更低、更优选为2.0×10-6℃-1或更低、还更优选为1.5×10-6℃-1或更低、特别优选为1.0×10-6℃-1或更低。
通过调节固态原料物质的组成、模制条件和煅烧条件可得到上文所述的体密度、弯曲强度和热膨胀系数。
由于氟化物赋予本发明的熔凝硅质耐火材料以优异的耐腐蚀性,因此该熔凝硅质耐火材料最适合使用在特别是与镁的金属液或含镁合金的金属液接触的位置处。因此,本发明的熔凝硅质耐火材料适于作为铸造镁或含镁合金的设备中的浇铸箱、流槽和保持炉所用的衬里材料;或者作为诸如浮子、流出槽、热顶环和过渡板之类的附件。
例子
参照以下实施例和对比例将更加详细地说明本发明,但是本发明不应被解释成受限于这些例子。
实施例1到13及对比例1
如表1和表2所示,将熔凝二氧化硅粉A、熔凝二氧化硅粉B和氟化钙粉(或氟化镁)混合以制备固态原料物质,并且向100重量份的这种固态原料物质中加入20重量份的水,然后进行捏合操作,从而得到实施例和对比例中的各种浆料。各成分的详细情况如下所示。将得到的浆料倒入石膏模具中,并浇铸成型。在氮气气氛中在 1150℃下对所得到的模制制品煅烧3小时,从而得到150mm长、30mm宽和15mm厚的片状试验样品。
熔凝二氧化硅粉A | 平均粒径:5μm |
熔凝二氧化硅粉B | 平均粒径:200μm |
氟化钙粉 | 试剂级(氟含量:48重量%),由Wako Pure Chemical Industries株式会社制造 |
氟化镁粉 | 试剂级(氟含量:60重量%),由Wako Pure Chemical Industries株式会社制造 |
水 | 蒸馏水 |
测量各个试验样品的体密度、三点弯曲强度和热膨胀系数,并进行腐蚀试验。其结果共同示于表1和表2中。
热膨胀系数是在1,000℃下根据JIS-R1618方法所得到的测量值。
此外,从试验样品上切下150mm长、20mm宽、7mm厚的试验片,使用由Shimadzu公司制造的Autograph“AG-50kNG”,在加载速率为2mm/分钟、支点间距为100mm的条件下测量三点弯曲强度。
在腐蚀试验中,从试验样品上切下其中一条边长为约70mm、厚为25mm的长方形试验片。如图1示意性示出的那样,将直径为8mm、高为10mm的镁合金(AZ31)圆柱体放置在基本为试验片中心部分的位置处,其中该试验片被布置在定位器上,然后将0.2MPa的负荷施加到所述圆柱体的上表面上。在该状态下,在氩气气氛中经2小时将温度由室温升至800℃,从而使镁合金熔化。然后,在氩气气氛中,在相同的负荷被施加到镁合金熔体的液面上的状态下,将试验片于800℃保持1小时,由此维持试验片与镁合金熔体接触的状态。经过1小时之后,解除压力,并从试验片表面上回收镁合金熔体。在试验片被冷却至室温后,观察该试验片的横截面,并测量因与镁合金熔体接触而被腐蚀的那一部分的面积。没有实际性地造成任何问题的区域 被评为“A”,稍微造成一点问题、但没有实际性地造成问题的区域被评为“B”,而实际性地造成问题的区域被评为“C”。试验结果示于表1和表2中。
与不含氟化物的对比例1的试验样品相比较,实施例1到8的各个试验样品的耐腐蚀性都得到显著的改善。此外,实施例1到8的各个试验样品的弯曲强度也降低得较少,并且其热膨胀系数也被抑制在较低的水平。实施例4和8的试验样品的耐腐蚀性略差,但是因为它们的热膨胀系数低,所以其适合于用在需要具有高的抗剥落性的工件中。
尽管参照本发明的具体实施方式对本发明进行了详细地说明,但是在不脱离本发明实质和范围的情况下对本发明做各种改变和修改对于本领域的技术人员来说是显而易见的。
本申请基于2006年3月31日提交的日本专利申请No.2006-100492,该专利申请的内容以引用方式并入本文。
Claims (3)
1.一种熔凝硅质耐火材料的制造方法,该方法包括:
浆料制备步骤,在该步骤中制备含有固态原料物质的浆料,该固态原料物质含有熔凝二氧化硅粉和氟化物粉,其中以氟计,所述固态原料物质中的所述氟化物的含量为0.01重量%到10重量%,并且所述熔凝二氧化硅粉的含量为90-99.9重量%,其中所述的熔凝二氧化硅粉含有由50重量%到90重量%的第一熔凝二氧化硅粉和10重量%到50重量%的第二熔凝二氧化硅粉形成的混合物,所述第一熔凝二氧化硅粉的平均粒径为1μm到10μm,所述第二熔凝二氧化硅粉的平均粒径为50μm到500μm;
模制步骤,在该步骤中由所述浆料得到模制制品;以及
煅烧步骤,在该步骤中在1050℃到1250℃下煅烧所述的模制制品。
2.根据权利要求1所述的熔凝硅质耐火材料的制造方法,其中所述氟化物粉含有选自氟化钙(CaF2)、氟化镁(MgF2)和冰晶石(Na3AlF6)中的至少一种氟化物,并且该氟化物粉的平均粒径为1μm到10μm。
3.根据权利要求1或2所述的熔凝硅质耐火材料的制造方法,其中所述浆料含有100重量份的所述固态原料物质和10重量份到40重量份的水。
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JP2006100492A JP2007269605A (ja) | 2006-03-31 | 2006-03-31 | 溶融シリカ質耐火物及びその製造方法 |
JP2006-100492 | 2006-03-31 | ||
JP2006100492 | 2006-03-31 |
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CN101045639A CN101045639A (zh) | 2007-10-03 |
CN101045639B true CN101045639B (zh) | 2012-07-18 |
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EP (1) | EP1840101B1 (zh) |
JP (1) | JP2007269605A (zh) |
CN (1) | CN101045639B (zh) |
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CA2619307C (en) | 2007-02-14 | 2013-04-30 | Nec Corporation | Optical transmitting apparatus and temperature controlling method used therefor |
PL2349490T3 (pl) | 2008-11-25 | 2015-01-30 | Procter & Gamble | Kompozycja wybielająca z topioną krzemionką |
US20110129784A1 (en) * | 2009-11-30 | 2011-06-02 | James Crawford Bange | Low thermal expansion doped fused silica crucibles |
JP5606152B2 (ja) * | 2010-05-24 | 2014-10-15 | 株式会社神戸製鋼所 | 取鍋の地金除去方法 |
RU2466965C1 (ru) * | 2011-03-29 | 2012-11-20 | Открытое акционерное общество "Обнинское научно-производственное предприятие "Технология" | Способ получения изделий из кварцевой керамики |
JP6964787B2 (ja) * | 2019-04-17 | 2021-11-10 | 黒崎播磨株式会社 | コークス炉用プレキャストブロック及びこれを使用したコークス炉 |
US11561338B2 (en) | 2019-09-30 | 2023-01-24 | Nichia Corporation | Light-emitting module |
US11112555B2 (en) | 2019-09-30 | 2021-09-07 | Nichia Corporation | Light-emitting module with a plurality of light guide plates and a gap therein |
CN113717530B (zh) * | 2021-08-31 | 2023-05-26 | 广东爱沃硅胶科技有限公司 | 一种加成型阻燃硅橡胶及其制备方法 |
CN116332662A (zh) * | 2023-04-23 | 2023-06-27 | 中钢集团洛阳耐火材料研究院有限公司 | 一种无硼硅质干式料 |
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JPS5243849B1 (zh) | 1969-05-28 | 1977-11-02 | ||
DE2308100C3 (de) * | 1973-02-19 | 1975-10-02 | Jenaer Glaswerk Schott & Gen., 6500 Mainz | Hochtemperaturbeständiger, verschleißfester Gleitwerkstoff niedriger Wärmedehnung |
DE3419199A1 (de) | 1984-05-23 | 1985-12-19 | Didier-Werke Ag, 6200 Wiesbaden | Feuerfeste koerper oder massen, insbesondere zum auskleiden von oefen oder gefaessen fuer geschmolzene metalle |
US4998710A (en) * | 1987-05-22 | 1991-03-12 | Union Carbide Industrial Gases Technology Corporation | Apparatus for holding and refining of molten aluminum |
JP2760541B2 (ja) * | 1988-03-02 | 1998-06-04 | 新光電気工業株式会社 | セラミック組成物 |
US4929579A (en) * | 1988-06-29 | 1990-05-29 | Premier Refractories & Chemicals Inc. | Method of manufacturing cast fused silica articles |
JP2825888B2 (ja) * | 1989-12-12 | 1998-11-18 | 黒崎窯業株式会社 | 低融点金属用耐火組成物 |
US5096865A (en) * | 1990-02-13 | 1992-03-17 | Ferro Corporation | High density fused silica process and product |
JPH1160330A (ja) | 1997-08-20 | 1999-03-02 | Toshiba Ceramics Co Ltd | 溶融シリカ質耐火物の製造方法 |
US5900381A (en) * | 1997-08-26 | 1999-05-04 | General Electric Company | Opaque silica composition |
US6458732B1 (en) | 1999-06-07 | 2002-10-01 | Allied Mineral Products, Inc. | Lightweight dry refractory |
US6193926B1 (en) * | 1999-09-03 | 2001-02-27 | Heraeus Amersil, Inc. | Process for making molded glass and ceramic articles |
JP2002274959A (ja) * | 2001-03-14 | 2002-09-25 | Nippon Crucible Co Ltd | アルミニウムおよびアルミニウム合金用耐火物 |
US6864199B2 (en) | 2003-02-07 | 2005-03-08 | Allied Mineral Products, Inc. | Crack-resistant dry refractory |
JP4292016B2 (ja) * | 2003-03-20 | 2009-07-08 | ニチアス株式会社 | 溶融シリカ質耐火物の製造方法 |
JP2006100492A (ja) | 2004-09-29 | 2006-04-13 | Sanken Electric Co Ltd | 支持板上への電子部品の固着法 |
JP5420815B2 (ja) * | 2006-03-27 | 2014-02-19 | ニチアス株式会社 | 低融点金属鋳造装置用耐熱材料 |
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- 2007-03-27 US US11/727,555 patent/US20070243994A1/en not_active Abandoned
- 2007-03-30 CN CN2007100875643A patent/CN101045639B/zh not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
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EP1840101A2 (en) | 2007-10-03 |
CN101045639A (zh) | 2007-10-03 |
JP2007269605A (ja) | 2007-10-18 |
EP1840101A3 (en) | 2010-09-22 |
US20070243994A1 (en) | 2007-10-18 |
EP1840101B1 (en) | 2013-01-09 |
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