CN1332707A - 复合材料 - Google Patents
复合材料 Download PDFInfo
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- CN1332707A CN1332707A CN99813470A CN99813470A CN1332707A CN 1332707 A CN1332707 A CN 1332707A CN 99813470 A CN99813470 A CN 99813470A CN 99813470 A CN99813470 A CN 99813470A CN 1332707 A CN1332707 A CN 1332707A
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- 239000002131 composite material Substances 0.000 title claims abstract description 4
- 239000000463 material Substances 0.000 claims abstract description 76
- 229910052582 BN Inorganic materials 0.000 claims abstract description 23
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000004767 nitrides Chemical class 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- -1 titanium nitrides Chemical class 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000004411 aluminium Substances 0.000 claims abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000010703 silicon Substances 0.000 claims abstract description 3
- 239000010936 titanium Substances 0.000 claims abstract description 3
- 150000004706 metal oxides Chemical class 0.000 claims abstract 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000011159 matrix material Substances 0.000 claims description 23
- 230000000903 blocking effect Effects 0.000 claims description 16
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 12
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 8
- 229910017083 AlN Inorganic materials 0.000 claims description 6
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 6
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- 229910001385 heavy metal Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011819 refractory material Substances 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- 229910001338 liquidmetal Inorganic materials 0.000 abstract description 11
- 229910000831 Steel Inorganic materials 0.000 abstract description 9
- 239000010959 steel Substances 0.000 abstract description 9
- 230000035939 shock Effects 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 229910052719 titanium Inorganic materials 0.000 abstract description 2
- 238000005266 casting Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 230000008646 thermal stress Effects 0.000 description 6
- 230000035882 stress Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000009749 continuous casting Methods 0.000 description 4
- 208000037656 Respiratory Sounds Diseases 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000011157 advanced composite material Substances 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001513 hot isostatic pressing Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical group [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910002795 Si–Al–O–N Inorganic materials 0.000 description 1
- 229910026551 ZrC Inorganic materials 0.000 description 1
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
- C04B35/593—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride obtained by pressure sintering
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
- B22D11/0637—Accessories therefor
- B22D11/0648—Casting surfaces
- B22D11/0657—Caterpillars
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/58007—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on refractory metal nitrides
- C04B35/58014—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on refractory metal nitrides based on titanium nitrides, e.g. TiAlON
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/58007—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on refractory metal nitrides
- C04B35/58028—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on refractory metal nitrides based on zirconium or hafnium nitrides
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Abstract
本发明提供了一种包括六角晶系氮化硼连续相和分散在其中的第二种材料的压力烧结复合材料,其中第二种材料包括:(a)选自于氮化硅,氮化铝,或氮化钛的至少一种金属氮化物,和(b)至少一种稳定金属氧化物,其中,金属氧化物数量要使第二种材料含有不多于35重量%的氧。观察到本发明材料具有非常低的热膨胀系数,因此表现出非常优良的耐热震性能。本发明材料另一个特征是其具有非常低的对熔融钢水的润湿性。这导致本发明材料具有非常优异的耐与液体金属进行化学反应的性能。最后,这种材料耐机械磨损性非常优异。
Description
本发明涉及一种新型的复合材料，更具体地说，本发明涉及一种包括六角晶系氮化硼和含至少一种金属氮化物的第二种材料的压力烧结材料。另一方面，本发明还涉及一种特别适用于生产耐火构件的复合材料，当该耐火构件用于冶金工业时，其能够承受苛刻的腐蚀和温度条件。特别是，这种材料非常适合于生产用于带坯连铸工艺的侧板。
在用于铸造厚度大约为2-10毫米带钢的称为“带坯连铸”和“双辊连铸”的连续浇铸工艺中，通过合适的设备，用紧贴辊子端平面(称为端点)的板对由辊所限制的浇铸空间内的液体金属进行侧边密封。这些板通常称为侧墙板”和“侧挡料板”。其与液体金属接触的中心部分由耐火材料制成。侧挡料板的周边由于与辊进行摩擦而会逐渐受到磨损。这些侧挡料板以尽可能密封的方式与辊接触是绝对必不可少的，因为液体金属渗入他们的接触区域中会对带坯的尺寸质量带来灾害性的恶果。随后带坯的一部分会有与带坯其他部分相分离的可能，而且残留部分会粘连辊子。如果这样的粘连在辊子旋转了一整圈后还存在，并且边缘处的碎片漏入浇铸空间中，就会对辊子的表面产生严重的损害，其结果最终是对带坯本身造成损害。最坏时，金属渗到机器外部，这样就不得不下达指令立即停止连铸。
这样的问题有多种起因，在这些起因中包括以下原因：
1.由于机械应力和热应力的作用，辊子和侧挡料板变形，因为特别是在刚刚开始连铸，强迫使辊子和侧挡料板处于热状态之下时，它们会面临机械应力和热应力的冲击；
2.辊子或侧挡料板逐渐磨损(机械磨损或化学磨损)，而且在接触表面这种磨损不总是均匀的；
3.排除固体金属渗漏物时对侧挡料板造成的瞬间磨损。
因此需要一种既具有抗机械应力和抗热应力的性能，又具有抗化学磨损或抗机械磨损的优良性能，即将二者结合起来的材料。
从USP4885264中已经知道压力烧结的多晶混合材料。该文献公开了氮化硼，氧化物和碳化物基材料，其中六角晶系氮化硼的含量大约为30-85重量％，氧化物部分选自于氧化锆和氧化镁，并且含量大约为10-50重量％，碳化物选自于碳化硅，碳化钛，碳化锆，并且含量大约为5-20重量％。材料具有高于理论密度(以氮化硼/氧化物/碳化物混合物为基准)94％的密度。按照USP4885264所述，材料具有抗液体金属，抗磨和抗热震的性能，因此其适合用作钢和有色金属水平连铸中的分离件或隔离圈。
然而，由于该材料较高的热膨胀系数，发现该材料没有表现出足够的抗热震性。抗化学性和抗液体金属的性能也有待改善。
从USP5389587中知道了另一种材料，该文献公开了一种由至少50重量％六角晶系氮化硼和1-50重量％选自于氮化铝和氮化硅和氧化铝和氧化硅的两种或多种组分组成的常规压力烧结陶瓷材料。该材料的抗机械性能仍然远不能满足钢铁工业，例如生产侧挡料板的要求。
因此需要一种既具有抗机械应力和抗热应力的性能，又具有抗化学或抗机械磨损的优良性能，即将二者结合起来的材料，特别是该材料具有优良的抗液体金属化学反应的性能。
按照本发明，一种包括六角晶系氮化硼连续相和分散在其中的第二种材料的压力烧结复合材料能够满足这些要求中的一种或多种要求。其中第二种材料包括：
(a)选自于氮化硅，氮化铝，或氮化钛的至少一种金属氮化物，
(b)至少一种稳定金属氧化物，其数量要使第二种材料含有不多于35重量％的氧。
观察到这种材料具有较低的热膨胀系数，由此表现出良好的耐热震性。该材料另一个特征是其对熔融钢水具有较低的润湿性，而这一特征又有利于改善其耐液体金属的性能，并由此减少钢水在其上面固化的发生率。最后，观察到这种材料表现出异常好的耐机械磨损性。
六角晶系氮化硼的晶体结构主要由数个平面组成，估计这些平面起阻止裂纹扩散的作用。因此复合材料必须含有六角晶系氮化硼连续相。现已确定至少为45重量％，优选至少为55重量％的六角晶系氮化硼数量可以获得氮化硼连续相。
另一方面，单独的六角晶系氮化硼材料太软，并且具有太低的机械强度，从而导致该材料具有较高的破碎和磨损趋势。因此，复合材料应该含有少于80重量％，更优选少于70重量％的六角晶系氮化硼。
因此，本发明还涉及一种包括45-80重量％六角晶系氮化硼和55-20重量％第二种材料的压力烧结复合材料，其中第二种材料包括：
(a)选自于氮化硅，氮化铝，或氮化钛的至少一种金属氮化物，
(b)至少一种稳定金属氧化物，其数量要使第二种材料含有不多于35重量％的氧。
当材料包括57.5重量％六角晶系氮化硼时获得最好的结果。
根据本发明，复合材料包括至少一种选自于氮化硅，氮化铝，或氮化钛的至少一种金属氮化物，有利地，使用氮化硅。
根据本发明一个优选的实施方案，第二种材料可以含有至少一种稳定金属氧化物，其数量要使第二种材料含有不多于35重量％的氧。
优选地，第二种材料含有至少2.5重量％的氧。
所选择的稳定金属氧化物必要时形成在所说金属氮化物中的固溶体是必不可少的。当所说稳定金属氧化物中的较重金属原子序数不高于所说金属氮化物中的较重金属原子序数时，便通常是这种情况。
合适的稳定金属氧化物包括(但不是限于)：铝，钛，硅和镁的氧化物或其混合物。其中，氧化铝是优选的。
在本发明特定的实施方案中，将赛纶(Sialon)陶瓷相作为含氧的第二种材料。赛纶是一种众所周知的材料，其是指由Si-Al-O-N组成的材料，并且可将其描述为氧化铝在氮化硅中的固溶体。赛纶相的化学通式是Si6-zAlzOzN8-z’，其中Z为0至大约4.5之间的数值。根据本发明，Z优选地为0-大约4.5之间的数值。而更优选地是2-3之间的数值。
应该知道本发明复合材料也可包括常规的添加剂，如在高温下产生液相的钇，镁，钙和/或铈的氧化物，它们比氧化硼优选。
这些添加剂的加入量较小，数量不超过六角晶系氮化硼/第二种材料混合物重量的5％。
作为生产本发明复合材料的原料，有利地使用氧含量大约为2-8重量％，比表面积大约为5-30平方米/克(用BET法测量)的六角晶系氮化硼粉末，和金属氮化物和氧化物粉末，它们的纯度至少大约为95％。
可在标准搅拌设备中用已知的方法将这些粉末混合均匀，同时可任选地使用临时胶结剂，并随后进行压力烧结直至其密度达到理论密度的至少94％。在这种方法中，混合物可在石墨模具中进行热压，此时在大约1500-1800℃，优选大约1650-1750℃的温度下实施轴向加压。模具中的压力大约为10-40兆帕，优选大约为15-35兆帕。另外，混合物也可在真空密封的情况下在大约1400-1700℃，优选大约为1500-1600℃的温度下进行热等静压，压力大约为100-300兆帕，优选大约为100-200兆帕，热等静压在将惰性气体用作压力转换介质的高压容器中进行。将如此获得的毛坯进行机加工从而获得尺寸符合要求的合适的成型部件。
发现本发明新型复合材料可主要用作带坯连铸工艺中的侧挡料板，但也可用在其中异常好的耐机械应力和热应力性能和极其优良的耐化学或机械磨损的性能是重要的其它场合中，例如用作冶金容器如中间包或铁水包中滑动水口的滑动板。
本发明的新型复合材料性能是如此优良，特别是其耐腐蚀性和耐热震动性，以至于现在可多次使用包括本发明复合材料的侧挡料板。这表示获得了带坯连铸工艺过去从未达到的重大突破，过去，这被认为是不可想象的。
随后实施本发明侧挡料板的应用，其可相同面与金属接触，也可反面与金属接触。
本发明侧挡料板可直接再次使用，然而如果已经与液体金属接触的表面再次与液体金属接触，就需要调整挡料板的所说表面。
因此，本发明也涉及一种带坯连铸工艺的改进方法，其中用紧贴辊子端平面的侧挡料板对由辊子所限制的浇铸空间中的液体金属进行侧边密封。该改进方法包括使用可再次使用的和/或已经使用过的侧挡料板。
用以下实施例更详细地解释本发明。
实施例
制备以下粉末混合物：
在本发明实施例1-5中，第二种材料是含氧的氮化硅，其中氧是以氧化铝和氧化镁的形式引入。在这些实施例中，使用Z＝2的赛纶相，它是用已知方法如氮化硅与氧化铝进行固相反应，或使氧化硅和氧化铝的混合物处于氨气氛中并用碳对其进行还原而获得的。向赛纶相中加入3％(以赛纶相为基准)氧化镁。这样导致第二种材料的氧含量为11.45重量％。
在实施例3和4中，加入1％(以赛纶相为基准)氧化钇(Y2O3)。
表1
| 实施例 | 氮化硼 第二种材料 MgO Y2O3(重量％) (重量％) (占赛纶重量％) (占赛纶重量％) |
| 12345 | 50 50 3 065 35 3 050 50 3 165 35 3 157.5 42.5 3 0 |
为了比较，同样也制备了包括50重量％六角晶系氮化硼，40重量％氧化锆(ZrO2)，和10重量％碳化硅的粉末混合物(实施例C1)。
在1650℃的温度下，通过向模具施加20兆帕的压力，对实施例1-5和Cl中的粉末混合物进行热压。
表2表示用实施例1-5和C1中的材料获得的结果。 表2
| 实施例 热膨胀系数 R因子 润湿性(10-6K-1) (引发裂纹所必需的ΔT)(℃) (对应于1550℃下的不锈钢) |
| 1 2.5 488 130-150℃2 2.55 879 -3 1.75 915 -4 2.0 529 -5 1.85 596 130-150℃C1 3.3 337 130-150℃ |
通过比较实施例1-5和C1，可明显地看出：本发明材料表现出非常低的热膨胀系数，因此具有非常优良的耐热应力性能。这也可从所测试的R因子数据中看出，(用以下公式计算耐热震性能)：
R＝σ(1-ν)/εα
其中，σ代表弯曲模量(MOR)，ν代表Poisson’s比(泊松比)，ε代表Yong’s(扬子)模量，而α代表热膨胀系数。结果显示本发明材料可抵御足以导致在现有技术的材料中出现裂纹的ΔT的2-3倍的温差。所观测到的润湿性数据表明本发明的材料对熔融钢水的润湿性非常差。这也可通过将一滴1550℃下处于氩气氛中的不锈钢钢水放在本发明材料的试样上面而观察到。在除去钢水后，观察到实施例C1的材料存在深度为250微米的相互作用区域。而观察到本发明的材料只有50微米的相互作用区域。
Claims (14)
1.一种压力烧结复合材料，包括六角晶系氮化硼连续相和分散在其中的第二种材料，其中第二种材料包括：
(a)选自于氮化硅，氮化铝，或氮化钛的至少一种金属氮化物，和(b)至少一种稳定金属氧化物，其特征在于：金属氧化物数量要使第二种材料含有不多于35重量％的氧。
2.根据权利要求1的复合材料，其特征在于：它包括45-80重量％六角晶系氮化硼和55-20重量％所说第二种材料。
3.一种压力烧结复合材料，包括45-80重量％六角晶系氮化硼和55-20重量％第二种材料，其中第二种材料包括：(a)选自于氮化硅，氮化铝，或氮化钛的至少一种金属氮化物，和(b)至少一种稳定金属氧化物，其特征在于：金属氧化物数量要使第二种材料含有不多于35重量％的氧。
4.根据权利要求1-3任何之一的复合材料，其特征在于：所说的至少一种金属氧化物可形成在所说金属氮化物中的固溶体。
5.根据权利要求4的复合材料，其特征在于：所说至少一种稳定金属氧化物中的较重金属的原子序数不大于所说至少一种金属氮化物中的较重金属的原子序数。
6.根据权利要求2-5任何之一的复合材料，其特征在于：六角晶系氮化硼含量为55-70重量％。
7.根据权利要求1-6任何之一的复合材料，其特征在于：所说的至少一种金属氮化物包括氮化硅。
8.根据权利要求7的复合材料，其特征在于：所说的第二种材料至少包括2.5重量％的氧。
9.根据权利要求1-8任何之一的复合材料，其特征在于：所说的至少一种金属氧化物选自于铝，钛，硅和镁氧化物及其混合物。
10.根据权利要求9的复合材料，其特征在于：所说至少一种金属氧化物包括氧化铝。
11.根据权利要求1-10任何之一的复合材料，其特征在于：第二种材料包括氮化硅和氧化铝。
12.根据权利要求11的复合材料，其特征在于：第二种材料主要由化学通式为Si6-zAlzOzN8-z的赛纶相组成，其中Z为1至4.5之间的数值。
13.根据权利要求12的复合材料，其特征在于Z为2-3之间的数值。
14.一种侧挡料板，它包括根据权利要求1-13任何之一的耐火材料。
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- 1999-11-16 ES ES99972613T patent/ES2308862T3/es not_active Expired - Lifetime
- 1999-11-16 DE DE69939223T patent/DE69939223D1/de not_active Expired - Lifetime
- 1999-11-16 EP EP99972613.6A patent/EP1140730B2/en not_active Expired - Lifetime
- 1999-11-16 SK SK666-2001A patent/SK286533B6/sk not_active IP Right Cessation
- 1999-11-16 KR KR1020017006178A patent/KR100605326B1/ko active IP Right Grant
- 1999-11-16 AT AT99972613T patent/ATE402913T1/de active
- 1999-11-16 BR BR9915502-8A patent/BR9915502A/pt not_active IP Right Cessation
- 1999-11-16 JP JP2000583827A patent/JP2002530263A/ja active Pending
- 1999-11-16 CA CA002351604A patent/CA2351604C/en not_active Expired - Fee Related
- 1999-11-16 AU AU13678/00A patent/AU751368B2/en not_active Ceased
- 1999-11-16 WO PCT/BE1999/000145 patent/WO2000030996A2/en active IP Right Grant
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1922119B (zh) * | 2004-02-20 | 2013-11-13 | 戴蒙得创新股份有限公司 | 烧结复合件 |
| CN100431738C (zh) * | 2006-10-19 | 2008-11-12 | 上海大学 | 钛及钛合金熔模精密铸造用氮化硼复合涂料 |
| CN101648809B (zh) * | 2009-09-25 | 2012-06-27 | 哈尔滨工业大学 | 氮化硼基复合陶瓷透波材料及其制备方法 |
| CN102093058A (zh) * | 2010-12-23 | 2011-06-15 | 大连海事大学 | 一种α-SiAlON/BN 复合陶瓷材料及其制备方法 |
| CN102093058B (zh) * | 2010-12-23 | 2013-10-23 | 大连海事大学 | 一种α-SiAlON/BN 复合陶瓷材料及其制备方法 |
| CN103857643B (zh) * | 2011-10-11 | 2015-09-09 | 日本碍子株式会社 | 陶瓷构件、半导体制造装置用构件及陶瓷构件的制造方法 |
| CN103857643A (zh) * | 2011-10-11 | 2014-06-11 | 日本碍子株式会社 | 陶瓷构件、半导体制造装置用构件及陶瓷构件的制造方法 |
| CN104284860A (zh) * | 2012-05-09 | 2015-01-14 | Esk陶瓷有限两合公司 | 氮化硼团聚体、其制备方法及其用途 |
| CN104284860B (zh) * | 2012-05-09 | 2018-02-13 | 3M创新有限公司 | 氮化硼团聚体、其制备方法及其用途 |
| CN108314456A (zh) * | 2012-05-09 | 2018-07-24 | 3M创新有限公司 | 氮化硼团聚体、其制备方法及其用途 |
| CN108314456B (zh) * | 2012-05-09 | 2021-04-30 | 3M创新有限公司 | 氮化硼团聚体、其制备方法及其用途 |
| CN108623307A (zh) * | 2018-07-06 | 2018-10-09 | 佛山陵朝新材料有限公司 | 一种陶瓷复合材料 |
| CN109369191A (zh) * | 2019-01-02 | 2019-02-22 | 淄博市新阜康特种材料有限公司 | 含钇的氮化硼-氮化铝复合粉体的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| SK286533B6 (sk) | 2008-12-05 |
| CZ300027B6 (cs) | 2009-01-14 |
| AU751368B2 (en) | 2002-08-15 |
| CA2351604C (en) | 2007-02-06 |
| ATE402913T1 (de) | 2008-08-15 |
| CN1163439C (zh) | 2004-08-25 |
| CA2351604A1 (en) | 2000-06-02 |
| WO2000030996A2 (en) | 2000-06-02 |
| KR20010086446A (ko) | 2001-09-12 |
| BR9915502A (pt) | 2001-08-07 |
| ES2308862T3 (es) | 2008-12-01 |
| KR100605326B1 (ko) | 2006-07-28 |
| CZ20011666A3 (cs) | 2002-04-17 |
| EP1140730A2 (en) | 2001-10-10 |
| HUP0104140A3 (en) | 2003-05-28 |
| AR021288A1 (es) | 2002-07-03 |
| WO2000030996A3 (en) | 2000-08-10 |
| JP2002530263A (ja) | 2002-09-17 |
| DE69939223D1 (de) | 2008-09-11 |
| EP1140730B1 (en) | 2008-07-30 |
| AU1367800A (en) | 2000-06-13 |
| EP1140730B2 (en) | 2016-11-23 |
| SK6662001A3 (en) | 2001-11-06 |
| US6667263B1 (en) | 2003-12-23 |
| HUP0104140A2 (hu) | 2002-02-28 |
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