CN101151210B - 碳化钛粉末和碳化钛-陶瓷复合粉末及其制造方法,以及碳化钛粉末的烧结体和碳化钛-陶瓷复合粉末的烧结体及其制造方法 - Google Patents
碳化钛粉末和碳化钛-陶瓷复合粉末及其制造方法,以及碳化钛粉末的烧结体和碳化钛-陶瓷复合粉末的烧结体及其制造方法 Download PDFInfo
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- CN101151210B CN101151210B CN2006800106921A CN200680010692A CN101151210B CN 101151210 B CN101151210 B CN 101151210B CN 2006800106921 A CN2006800106921 A CN 2006800106921A CN 200680010692 A CN200680010692 A CN 200680010692A CN 101151210 B CN101151210 B CN 101151210B
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- 239000000843 powder Substances 0.000 title claims abstract description 178
- 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 title claims abstract description 136
- 239000010936 titanium Substances 0.000 title claims abstract description 81
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 81
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 72
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- 229910052799 carbon Inorganic materials 0.000 claims abstract description 97
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 95
- 238000000034 method Methods 0.000 claims abstract description 53
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- 239000002184 metal Substances 0.000 claims abstract description 18
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- -1 titanium alkoxide Chemical class 0.000 claims abstract description 11
- 125000000524 functional group Chemical group 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
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- 125000000896 monocarboxylic acid group Chemical group 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 238000005245 sintering Methods 0.000 claims description 24
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 22
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 claims description 17
- 229910052786 argon Inorganic materials 0.000 claims description 12
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 12
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
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- 150000007524 organic acids Chemical class 0.000 claims description 3
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- 239000011780 sodium chloride Substances 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 13
- 239000012535 impurity Substances 0.000 abstract description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 8
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 239000007791 liquid phase Substances 0.000 description 9
- 239000010409 thin film Substances 0.000 description 8
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- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
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- 238000007254 oxidation reaction Methods 0.000 description 7
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- 238000002441 X-ray diffraction Methods 0.000 description 6
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- 239000003960 organic solvent Substances 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
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- 241000270666 Testudines Species 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
- VQYHBXLHGKQYOY-UHFFFAOYSA-N aluminum oxygen(2-) titanium(4+) Chemical compound [O-2].[Al+3].[Ti+4] VQYHBXLHGKQYOY-UHFFFAOYSA-N 0.000 description 1
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- 238000007723 die pressing method Methods 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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Abstract
得到了对于提高与陶瓷的复合烧结体的特性有效地、不含氧化钛或金属等无机系杂质而且游离碳量少的具有纳米单位的粒径的微细的碳化钛粉末。一种高纯度微细的碳化钛粉末,最大粒径是100nm以下,钛以外的金属含有量是0.05wt%以下,游离碳含量在0.5wt%以下,通过下述工序得到,把含有1个以上能与烷氧基钛的钛配位的官能团OH基或者COOH基而且不含有C、H、N、O以外的元素的有机物溶解在作为碳源的溶剂中形成液体,在该液体中,当把碳源与烷氧基钛的摩尔比(碳源/烷氧基钛)定为α时,混合烷氧基钛使得α成为0.7≤α≤1.0,得到前体溶液,把得到的前体溶液中的生成物在非氧化气氛或真空气氛中,在1050~1500℃下进行热处理。
Description
技术领域
本发明涉及具有纳米单位的粒径的微细的碳化钛粉末和碳化钛-陶瓷复合粉末及其制造方法。另外,涉及该碳化钛粉末的烧结体和碳化钛-陶瓷复合粉末的烧结体及其制造方法。
背景技术
碳化钛多用作与陶瓷的复合烧结体,特别是与氧化铝的复合烧结体产生高温强度性、耐热性、耐磨损性、耐药性等优良的特性,被用在切削工具或耐磨损性构件、薄膜磁头基板等多种用途上。
但是,碳化钛烧结性低,即使作为复合材料的一部分来制作烧结体,也有容易残留空隙的缺点,为此,必需添加用于提高烧结性的烧结助剂,这又存在与烧结体的强度变差相关联的问题。
作为解决该问题的手段,通过微细化碳化钛粉末来提高烧结性是有效的。由于碳化钛粉末越微细化烧结性越高,可以低温烧结,因此在制作与陶瓷粉末的复合烧结体时,有抑制陶瓷的晶粒生长的效果。该效果在粒径为100nm以下时非常高,除此而外,在烧结体中显示出优良的分散强化效果。
另外,通过添加碳化钛粉末来改善WC/Co系超硬切削工具的高温强度和耐磨损特性,或者通过与Ni等金属粉末形成复合体,碳化钛粉末被广泛地用在金属陶瓷工具、轧辊和金型材料用的初期原料粉末。
最近,由于通过碳化钛的微粒化使工具的硬度变高、抗弯力变高,工具的耐磨损性增加,因此,碳化钛粉末的微粒化技术成为重要的课题。
以前,作为碳化钛粉末的制造方法,使用在非氧化性气氛中在大约1500℃的高温下热处理二氧化钛(TiO2)和碳的混合粉末的还原/碳化方法,或Ti和TiH2的直接碳化法。
但是,由于所制造的TiC的粉末尺寸大到1~10μm,虽然由球磨机粉碎进行微细化,但是把最大粒径做到0.5μm以下也是困难的,除此而外,由于粉碎介质的混入,粉末的低品位化也不能避免。
为了解决这些问题,专利文献1公开了如下方法:在惰性气氛下,把四氯化钛(TiCl4)和氯化碳的混合溶液投入容纳了镁(Mg)熔融金属的密闭容器内,在该密闭容器内,真空分离镁还原反应后残存的剩余的液状Mg和氯化镁(MgCl2),从真空分离了液状的Mg和MgCl2的密闭容器中回收TiC合成物。
但是,在这样得到的碳化钛粉末中,存在问题是含有0.3~0.8wt%的Mg、0.1~0.3wt%的Cl、0.1~0.6wt%的Fe和大量的杂质。
另外,专利文献2中,公开了如下方法:将含钛的水溶性盐、偏钛酸TiO(OH)2浆料或者超微粒钛氧化物粉末中的一种、和含有过渡性金属的水溶性金属盐溶解在水中制备混合原料,在喷雾干燥该混合原料得到前体粉末后,热处理该前体粉末制作超微粒Ti-过渡性金属复合氧化物粉末,然后,在该超微粒Ti-过渡性金属复合氧化物粉末中混合纳米尺寸的碳粒子,之后,在非氧化性气氛中还原干燥了的复合氧化物粉末,在1200~1350℃下进行碳化热处理,制造碳化钛粒径为35~81nm的TiC-Co复合粉末。
在该专利文献2公开的方法中,由于把过渡性金属的含有量定为1wt%以上,虽然可以在1350℃以下进行还原/碳化热处理,可以得到超微细粉末,但是难以制造高纯度且微细的碳化钛粉末的单体。
另一方面,通过碳化钛的液相的合成法,具有能稳定地得到微细的碳化物,而且可以简单地进行与其它成分的混合的优点。
另外,当作为钛源使用烷氧基钛时,具有比较廉价地得到其它的金属成分的混入量非常少的碳化钛粉末的优点。
但是,到目前为止,由液相法得到的碳化钛粉末,由于作为杂质含有数wt%以上的游离碳量,在作为烧结原料使用时,烧结时该游离碳阻碍烧结,存在不能得到致密的烧结体的问题。
例如,在非专利文献1中,混合对异丙氧基钛的螯合倾向不同的数种二元羧酸,在随后的干燥后,在含有0~10%氢的氩气氛中进行热处理,得到碳化钛粉末。但是,得到的碳化钛粉末含有4.2重量%以上的游离碳。
这样的话,没有建立一种批量的制造方法,该方法合成最大粒径100nm以下、游离碳量0.5wt%以下、且钛以外的金属含有量少的碳化钛粉末。
另外,在制作复合了碳化钛和以氧化铝为代表的另外的陶瓷的烧结体时,由于作为其原料的碳化钛粉末越微细化,碳化钛粉末形成凝聚体,因此,得到碳化钛均匀分散的烧结体是困难的。
作为解决该问题的方法,将碳化钛粉末覆盖陶瓷粉末表面的具有所谓核壳型的结构的粉末,在制作碳化钛分散陶瓷烧结体上,对于防止碳化钛粉末的凝聚,得到均匀组织的烧结体是有效果的,再有,对抑制烧结时陶瓷的晶粒长大也是有效的。
专利文献3公开了这种复合粉末的制造。该专利文献3中公开的方法是,合成在氧化铝粉末表面上由CVD法(化学气相沉积)形成TiC薄膜的核壳型的结构的粉末,由此,得到碳化钛均匀分散的烧结体。但是,由于CVD法只能在真空装置内间歇式生产,存在不适合大批量生产和高成本的缺点。
专利文献1:P2005-47739
专利文献2:JP2004-323968
专利文献3:JP5-270820
非专利文献1:Tom Gallo,Carl Greco,Claude Peterson,FrankCambira and Johst Burk, Azko Chemicals Inc.,Mat.Res.Soc.Symp.Vol.271,1992,p887-892.
发明内容
本发明要解决在制造具有纳米单位的粒径的微细的碳化钛粉末及使用该粉末的烧结体时的缺点,第1课题在于得到微细的碳化钛粉末,该碳化钛粉末对于提高与陶瓷的复合烧结体的特性有效,且不含氧化钛或金属等无机杂质且游离碳含有量少。
另外,另一个课题在于,使不含氧化钛或金属等无机杂质且游离碳含量少的微细的碳化钛粉末和陶瓷粉末混合,能比较容易地得到碳化钛-陶瓷复合材料,而得到碳化钛-陶瓷复合粉末。
再有,另一个课题在于,对于这种碳化钛-陶瓷复合粉末,得到具有碳化钛粉末覆盖陶瓷粉末表面的核壳型的结构的粉末。
还有,另一个课题在于,使用这种碳化钛-陶瓷复合粉末或者具有碳化钛粉末覆盖陶瓷粉末表面的核壳型的结构的粉末,得到微细的碳化钛分散在基质的陶瓷中的烧结体。
还有,另一个课题在于,提供具有纳米单位的粒径的微细的碳化钛的批量生产性优良的制造方法。
还有,另一个课题在于,确立使用液相法批量生产这种碳化钛粉末时的最合适条件。
还有,另一个课题在于,在制造这种碳化钛-陶瓷复合粉末时,提供应用液相法的批量生产性优良的制造方法。
还有,另一个课题在于,提供具有这种碳化钛粉末覆盖陶瓷粉末表面的核壳型的结构的碳化钛-陶瓷复合粉末的批量生产性优良的制造方法。
还有,另一个课题在于,确立应用液相法批量生产具有这种碳化钛粉末覆盖陶瓷粉末表面的核壳型的结构的粉末时的最合适条件。
还有,另一个课题在于,提供使用这种微细的碳化钛-陶瓷复合粉末或者使用具有碳化钛粉末覆盖陶瓷粉末表面的核壳型的结构的粉末,制造碳化钛均匀地分散在陶瓷中的烧结体的制造方法。
附图说明
图1是由本发明制造的碳化钛粉末的X射线衍射图形。
图2是由本发明制造的碳化钛粉末的透射电子显微镜照片。
图3是由本发明制造的碳化钛覆盖氧化铝粉末的X射线衍射图形。
图4是由本发明制造的碳化钛覆盖氧化铝粉末的透射电子显微镜照片。
图5是由本发明制造的碳化钛-氧化铝复合烧结体的镜面加工面的扫描电子显微镜照片。
具体实施方式
本发明的高纯度微细的碳化钛粉末,最大粒径是100nm以下,且钛以外的金属含有量是0.05wt%以下,且游离碳量是0.5wt%以下。
当碳化钛的最大粒径为100nm以上时,不能充分发挥抑制陶瓷的晶粒生长的分散强化效果,另外,因为陶瓷中残留空隙使烧结体的强度变差,因此不理想。
作为杂质相含有的金属成分,当为0.05wt%以上时,由于在烧结时形成液相而成为脆弱的地方,使烧结体的强度显著地降低,因此不理想。
另外,当碳化钛粉末中含有游离碳时,在烧结碳化钛粉末时,该游离碳阻碍烧结,不能得到致密的烧结体。另外,游离碳成为气孔产生的原因,特别是当游离碳超过0.5wt时,烧结体的相对密度不到99%,机械强度大大地降低,因此不理想。
再有,碳化钛粉末中的游离碳含有量越少越好,通过在由本发明得到的碳化钛粉末中添加/混合二氧化钛(TiO2)粉末,在非氧化气氛中进行热处理,可以使二氧化钛和游离碳反应而降低游离碳含有量。这时,游离碳通过固溶在二氧化钛中或者进行CO气化而被去除。
另外,本发明的碳化钛粉末为NaCl型的结晶结构,组成是TiCxOyNz(0.5≤X≤1.0、0≤Y≤0.3、0≤Z≤0.2、0.5≤X+Y+Z≤1,0)。不满足0.5≤X≤1.0的碳化钛粉末,由于不能维持NaCl型的结晶结构,因此不理想。超过Y=0.3的碳化钛粉末,由于不能充分发挥上述的晶粒生长的抑制效果,而对得到的烧结体的热传导性和加工性产生不好的影响,因此不理想。超过Z=0.2的碳化钛粉末,由于对烧结体的加工性产生的不好的影响在氧以上,因此不理想。
另外,具有这种微细且高纯度的碳化钛覆盖陶瓷的核壳型的结构的粉末,可以抑制烧结时的陶瓷的晶粒生长,可以容易地得到微细的碳化钛均匀地分散在微细陶瓷组织中的复合陶瓷。另外,由于微细分散效果,该复合陶瓷能实现用原来的制法难以实现的微细组织,能提高强度和破坏韧性、硬度等。
当碳化钛粉末对陶瓷粉末的配合比率高时,全部的碳化钛粉末不能都覆盖陶瓷粉末,由于其一部分覆盖陶瓷粉末,剩余的碳化钛粉末分散在基质的陶瓷粉末中,因此与具有核壳型的结构的粉末一样,能发挥微细分散效果。
另外,在该碳化钛和陶瓷的复合材料之中,陶瓷是氧化铝的碳化钛覆盖氧化铝粉末作为切削工具或耐磨损性构件、薄膜磁头基板等用途,在很大范围上是理想的。
本发明的最大粒径是100nm以下、且钛以外的金属含有量是0.05wt%以下、且游离碳量是0.5wt%以下的高纯度微细的碳化钛粉末,通过下述工序可以得到,将含有1个以上作为能与烷氧基钛的钛配位的官能团的OH基或COOH基,而且不含C、H、N、O以外的元素的有机物作为碳源溶解在溶剂中制成液体,当把碳源和烷氧基钛的摩尔比(碳源/烷氧基钛)定为α时,在该液体中混合烷氧基钛使α为0.7≤α≤1.0而得到的溶液即前体溶液,在根据需要干燥得到的前体溶液中的生成物之后,在非氧化气氛或真空气氛中在1050~1500℃下进行热处理。
通过使用具有能与烷氧基钛的钛配位的配位体的有机物作为碳源,在溶液中置换在烷氧基钛上存在的配位体和碳源的官能团,能得到碳源和钛源的分子水平上的均匀组合物。该均匀组合物可以极显著的使其后的碳化反应温度低温化,其结果,可以抑制碳化钛的晶粒生长,可以得到最大粒径100nm以下的微细的粒子。
在该液相反应中,由于不使用含金属的催化剂,另外,作为钛源使用高纯度的烷氧基钛,因此,可以把金属杂质抑制到0.05wt%以下。
上述前体溶液中的碳源和钛源的分子水平上的均匀组合物,由于没有碳源的过剩,也没有碳源量相对钛源的不足,因此不生成氧化钛等碳化钛以外的物质。
在将上述有机物作为碳源溶解在溶剂中的液体中,将烷氧基钛的混合量按如上所述那样最佳化,能得到游离碳量0.5wt%以下的碳化钛物质。例如,当碳源相对于钛源的配合比率高时,生成游离碳,不理想。另一方面,当碳源相对于钛源的配合比率过低时,生成碳化钛基以外的物质,也不理想。
作为碳源的官能团,可以举出容易形成配位结合的OH基或COOH基,作为碳源的例子,可以举苯酚或邻苯二酚等的酚类、线型酚醛清漆型酚醛树脂、水杨酸、邻苯二甲酸、邻苯二酚、无水柠檬酸等有机酸、EDTA等。这些有机化合物,可以单独使用1种,也可以并用2种以上。但是,含有C、H、N、O以外的元素的碳源不理想,因为往往把这些元素作为杂质残留下来。
为了把最大粒径抑制到100nm以下,碳化温度最好是1050℃以上1500℃以下。在1050℃以下,碳化花费的时间成为长时间,生产性变差,在1500℃以上,碳化钛的晶粒生长显著,粒径成为100nm以上。
作为碳源,最好使用具有2个以上配位体且具有环状化合物的有机物,在配位体为2个以上的多啮配位体的情况下,在与钛形成鳌合时,与单啮配位体化合物相比,与钛之间可以更牢固地配位结合。由于能得到与钛源的非常均匀的混合状态,因此不存在碳源的过剩,抑制游离碳量是有效的。环状化合物碳残留率高,可以抑制使用的碳源的量,在削减成本上是有效的。
与钛能非常高的配位结合的碳源,即使在加热干燥前体溶液的阶段也能保持配位状态,能得到与钛源的非常均匀的混合状态,因此不存在向碳源的过剩,抑制游离碳量是有效的。
另外,作为钛源的烷氧基钛,可以举出甲氧基钛(IV)、乙氧基钛(IV)、异丙氧基钛(IV)、丁氧基钛(IV)。从价格及处理上考虑,异丙氧基钛(IV)特别好。
再有,本发明的微细的碳化物粉末的制造法,也可以用于与氧化铝、其他的氧化物、氮化物、硼化物等的陶瓷粉末的混合粉末的制造。
在这种情况下,混合作为碳源和钛源的分子水平上的均匀组合物的前体溶液和陶瓷粉末并浆料化,然后,从浆料中去除有机溶剂,得到前体溶液干燥物覆盖在陶瓷粉末的表面上的核壳型或者分散型的粉末。然后,将该覆盖粉末在非氧化气氛中或者真空气氛中进行热处理。
在这种情况下,如果把碳源和烷氧基钛的摩尔比(碳源/烷氧基钛)定为α,通过将α定为0.75≤α≤1.1,因此,能得到游离碳量0.5wt%以下的碳化钛-陶瓷复合粉末。这时的碳源和烷氧基钛的摩尔比,需要比碳化钛单体的情况下高。这是由于陶瓷粉末对碳源和钛源的均匀组合物的碳化反应存在一些阻碍。
当把具有该核壳型或者分散型的结构的粉末在真空气氛或者氮气氛中或者氩气氛中,在1400~1850℃的温度和10~50MPa的压力下进行热压来烧结时,可以得到晶粒生长被抑制的微细的碳化钛分散陶瓷烧结体。
但是,当在不到1400℃的温度下进行热压时,因为烧结不充分,残存气孔,因此不理想。当在1850℃以上进行时,由于不能发挥晶粒生长抑制效果,引起陶瓷的晶粒生长,因此不理想。
另外,当在不到10MPa的压力下进行加压状态时,由于烧结不充分而残存气孔,因此不理想。当在50MPa以上进行时,必须提高模具和压杆的强度,因此不理想。
另外,当成型具有该核壳型或者分散型的结构的粉末,在真空气氛或者氮气氛或者氩气氛中,在1500~1900℃下烧结时,可以得到晶粒生长被抑制的微细的碳化钛分散陶瓷烧结体。
当在不到1500℃进行烧结时,因为烧结不充分而残存气孔,因此不理想。当在1900℃以上进行时,因为不能发挥晶粒生长抑制效果,引起陶瓷的晶粒生长,因此不理想。
另外,以使相对密度为95%以上的方式,热压或者成型具有该核壳型或者均匀分散型的结构的粉末,并烧结而得到碳化钛和陶瓷的复合烧结体,通过在氮气氛或者氩气氛中,在1400~1600℃的温度和50~200MPa的压力下热等静压(HIP)烧结的碳化钛陶瓷的复合烧结体,可以得到微细的不残存气孔的碳化分散陶瓷烧结体。
当在不到1400℃的温度下进行HIP时,因为不能充分发挥HIP效果而残存气孔,因此不理想。当在1600℃以上进行时,因为不能发挥抑制晶粒生长效果,引起陶瓷的晶粒生长,因此不理想。
另外,当在不到50MPa进行HIP时,由于HIP效果不能充分发挥并残存气孔,因此不理想。当在200MPa以上进行时,必须提高HIP装置的强度等,因此不理想。
另外,为了得到微细的碳化钛分散陶瓷烧结体,在作为混合了碳源和有机溶剂及烷氧基钛的溶液的前体溶液中混合陶瓷粉末而得到浆料,不必使该浆料干燥,可以使其凝胶化后成为固体,进行碳化处理及烧结。
本发明是作为具有纳米单位的粒径的微细的碳化钛粉末的合成方法,采用比气相法在批量生产性上优良的液相法,通过在液相中置换存在于烷氧基钛上的配位体和碳源的官能团并使其稳定地存在,可以抑制钛的氧化物的生成和成为杂质的其他的金属成分的混入。
另外,通过控制碳源的官能团的结构和官能团的量以及与钛源的配位体的置换反应,可以显著地降低不与钛结合的游离碳量。
再有,由于在分子水平上结合了钛和碳,因此可以非常显著的将碳化反应低温化,可以抑制碳化钛粒子的晶粒生长,其结果能得到微细的高品质的碳化钛粉末。
通过在与陶瓷的混合粉末的制造中使用该微细的高纯度的碳化钛粉末的制造法,可以得到核壳型的粉末,通过烧结该粉末,可以抑制陶瓷的晶粒生长,对于作为分散了碳化钛的切削工具,耐磨损性构件、薄膜磁头用基板等,可以得到最合适的高密度的烧结体。
特别是,在分散了本发明的100nm以下的碳化钛的氧化铝系复合材料中,由于碳化钛的氧化铝结晶的抑制晶粒生长的效果,与原来相比能使氧化铝的结晶粒子微细化,即使在碳化钛粒子的接触点处也容易进行烧结并能抑制微孔的产生。
有这种微细组织的烧结体,具有优良的镜面加工性并可以容易地得到光学的镜面(Rtm是5nm以下),由于研磨速度快,所以也可以有效的生产。另外,该烧结体即使在离子加工(反应性离子蚀刻、离子束加工)中,也能得到优良的表面粗糙度。
另外,本发明的烧结体是在强度和破坏韧性(耐裂纹产生和传播性)上优良,没有加工时的裂纹产生和颗粒脱落(拔出)。另外,从纯度的观点来看也是优良的,最适合于做为薄膜磁头基板材料的用途。使用本烧结体的薄膜磁头,通过在其制造工序中进行加工条件的最佳化,可以抑制薄膜磁头滑动体端部的开裂或脱粒的产生,确保薄膜磁头的高可靠性。
再有,本发明的烧结体,因为碳化钛微细,即使用比含有30重量%~40重量%的碳化钛的基板材料少的10重量%~30重量%的碳化钛含有量,也能得到与原有基板同等以上的机械特性和加工特性,因此,可以使薄膜磁头滑动体轻量化和高热传导率化。
下面根据实施例说明本发明的实施的形态。
实施例1
作为前体的原料,把成为碳源的分子量138.1的水杨酸20g加入作为溶剂的60ml的2-甲氧基乙醇中进行搅拌,溶解后得到无色透明的液体。
在该溶液中加入钛含有量约7.8g的常温下液状的分子量284.2的异丙氧基钛46.4g,搅拌得到水杨酸配位置换异丙氧基钛的一部分的呈现均匀的赤褐色的透明性高的组合物。连续2小时搅拌后,边搅拌边在油浴器中加热后得到干燥体。该干燥体是橙色,作为钛源的异丙氧基钛和作为碳源的水杨酸的摩尔比(碳源/烷氧基钛)α为α=0.9。
接着,把得到的干燥体在内径200mm、高度80mm的石墨制的坩埚内,在13.33Pa(0.1Torr)的真空环境下,升温到最高处理温度1050~1500℃后,然后在该最高处理温度下保持4小时,然后自然冷却,由这样的热处理得到组合物。
图1表示在处理温度1350℃下得到组合物的粉末的X射线衍射测量结果。
其结果表明,得到的组合物是碳化钛单相,不含有氧化钛等结晶质的杂质。另外,合成的碳化钛的晶格常数是4.327。
图2表示用透射电子显微镜(TEM)观察得到的碳化钛粉末的照片。由该照片可知,碳化钛粉末的最大粒径是100nm以下。由碳沉淀分离燃烧红外线吸收法研究得到碳化钛粉末中的游离碳量,结果是0.07wt%。
用荧光X射线分析的标准曲线法测量得到的碳化钛粉末,结果是钛以外的金属量是0.02wt%。
实施例2
作为前体的原料,把成为碳源的水杨酸62g加入作为溶剂的2-甲氧基乙醇170ml中进行搅拌,溶解后得到无色透明的液体。
在该溶液中,加入钛含有量约22g的常温下液状的异丙氧基钛130g,搅拌得到水杨酸配位置换异丙氧基钛的一部分的呈现均匀的赤褐色透明性高的组合物。连续搅拌2小时后,加入氧化铝粉末46g,用搅拌棒搅拌3小时后,边搅拌边在油浴器中加热得到干燥体,该干燥体是橙色的,作为钛源的异丙氧基钛和作为碳源的水杨酸的摩尔比(碳源/烷氧基钛)α是α=1.0。
接着,把得到的干燥体放在内径200mm、高度80mm的石墨制的坩埚内,在13.33Pa(0.1Torr)的真空气氛下,升温到最高处理温度1050~1500℃后,在该最高处理温度下保持4小时,然后自然冷却,这样热处理后得到组合物。
图3表示在处理温度1350℃下得到的组合物的粉末的X射线衍射测量结果。
另外,图4表示用透射电子显微镜(TEM)观察得到的碳化钛粉末的照片。由该照片可知,碳化钛粉末覆盖了氧化铝粒子、碳化钛粉末的最大粒径是100nm以下。另外,由碳沉淀分离燃烧红外线吸收法研究了相对于该组合物中的碳化钛的游离碳量的比例,结果是0.03wt%。
实施例3
把在实施例2得到的碳化钛覆盖氧化铝粉末填充在碳模具内,在压力25MPa、温度1800℃、氩气氛下热压90分钟,得到□50mm、厚度4mm的烧结体。烧结体的密度用阿基米德法测量,其结果,密度是4.27×103kg/m3、相对密度是99.5%。
接着,研磨烧结体表面后,由使用锡板的抛光法进行镜面加工,进行SEM观察。
图5表示SEM观察得到的氧化铝-碳化钛复合烧结体的镜面加工面的照片。由该照片可知,碳化钛粒子在氧化铝烧结体内部均匀分布。另外,几乎不能确认由游离碳等产生的孔隙。
下面,表1表示各个实施例和比较例中的状态。在比较例1和3中,由于碳源和钛源的摩尔比α没有最优化,结果游离碳量非常多。在比较例2和4中,由于碳源和钛源的摩尔比α没有最优化,因此不能见到TiC相。
[表1]
碳源 | 前体溶液的颜色 | 干燥粉末的颜色 | 碳源/钛源(摩尔比)α | 有无TiC相 | 有无添加氧化铝粉末 | TiC晶格常数 | 由TEM观察的TiC最大粒径(nm) | 游离碳量(wt%) | |
实施例1 | 水杨酸 | 赤褐色 | 橙色 | 0.9 | 有 | 无 | 4.327 | 40 | 0.07 |
实施例2 | 水杨酸 | 赤褐色 | 橙色 | 1.0 | 有 | 有 | 4.329 | 40 | 0.03 |
实施例4 | 水杨酸 | 赤褐色 | 橙色 | 1.0 | 有 | 无 | 4.327 | 60 | 0.1 |
实施例5 | 水杨酸 | 橙色 | 橙~黄色 | 0.70 | 有 | 无 | 4.310 | 50 | 0.06 |
实施例6 | 水杨酸 | 赤褐色 | 橙色 | 1.1 | 有 | 有 | 4.329 | 55 | 0.05 |
实施例7 | 水杨酸 | 橙色 | 橙~黄色 | 0.75 | 有 | 有 | 4.325 | 50 | 0.03 |
比较例1 | 水杨酸 | 赤褐色 | 橙色 | 1.1 | 有 | 无 | 4.327 | 65 | 0.96 |
比较例2 | 水杨酸 | 黄色 | 黄色 | 0.55 | 无 | 无 | - | - | - |
比较例3 | 水杨酸 | 赤褐色 | 橙色 | 1.2 | 有 | 有 | 4.325 | 60 | 0.92 |
比较例4 | 水杨酸 | 黄色 | 黄色 | 0.55 | 无 | 有 | - | - | - |
另外,在表2中表示的是,分别把本发明的碳化钛覆盖氧化铝粉末中游离碳含有量不同的粉末在压力30MPa、温度1800℃、氩气氛下热压90分钟得到的烧结体的相对密度的一例,供参考。
[表2]
游离碳量[wt%] | 相对密度(%) |
0.1 | 99.4 |
0.3 | 99.3 |
0.5 | 99.0 |
0.7 | 98.1 |
1.0 | 97.3 |
另外,在表3中表示的是,本发明的碳化钛覆盖氧化铝粉末中的碳化钛TixOyNz的X、Y、Z值各不相同的粉末的粒径和热压得到的烧结体的热传导率的一例。
[表3]
X值 | Y值 | 粒径(nm) | 热传导率W/m·K |
0.9 | 0.1 | 20 | 24.0 |
0.8 | 0.2 | 30 | 23.6 |
0.7 | 0.3 | 70 | 22.1 |
0.6 | 0.4 | 110 | 20.1 |
0.5 | 0.5 | 130 | 18.4 |
注:如上表那样取X、Y值,但Z=0。X、Y、Z值由C分析(红外线吸收)、N及O分析及X射线衍射进行。
另外,在表4中表示的是热压本发明的碳化钛覆盖氧化铝粉末中的碳化钛TixOyNz的X、Y、Z值各不相同的粉末得到的烧结体的断裂载荷的一例。作为断裂载荷,是指用金刚石刀断裂加工时得到的烧结体时的载荷。
[表4]
X值 | Z值 | 断裂载荷(W) |
1 | 0 | 200 |
0.9 | 0.1 | 230 |
0.8 | 0.2 | 270 |
0.7 | 0.3 | 350 |
0.5 | 0.5 | 450 |
注:如上表那样取X、Z值,但是Y=0。X、Y、Z值由C分析(红外线吸收)、N及O分析及X射线衍射进行。
Claims (25)
1.一种高纯度微细的碳化钛粉末,其最大粒径是100nm以下,且钛以外的金属含有量是0.05wt%以下,而且游离碳量是0.5wt%以下。
2.如权利要求1所述的高纯度微细的碳化钛粉末,其中,碳化钛具有NaCl型的结晶结构,而且组成是TiCxOyNz,其中,0.5≤X≤1.0、0≤Y≤0.3、0≤Z≤0.2,满足0.5≤X+Y+Z≤1.0。
3.一种碳化钛-陶瓷复合粉末,其具有权利要求1或权利要求2所述的高纯度微细的碳化钛粉末覆盖了陶瓷粉末的核壳型的结构。
4.一种碳化钛-陶瓷复合粉末,其具有权利要求1或权利要求2所述的高纯度微细的碳化钛粉末的一部分覆盖了陶瓷粉末,而且,没有覆盖陶瓷粉末的残余的碳化钛粉末分散在基质的陶瓷粉末中的结构。
5.如权利要求3或权利要求4所述的碳化钛-陶瓷复合粉末,其中,陶瓷粉末是氧化铝。
6.如权利要求1或2所述的高纯度微细的碳化钛粉末的制造方法,其中,将含有1个以上作为能与烷氧基钛的钛配位的官能团的OH基或COOH基、且不含C、H、N、O以外的元素的有机物作为碳源溶解在溶剂中形成液体,当将碳源和烷氧基钛的摩尔比,即碳源/烷氧基钛设定为α时,在该液体中混合烷氧基钛使α为0.7≤α≤1.0,得到前体溶液,使得到的前体溶液固化得到生成物,在真空气氛中在1050~1500℃下进行热处理。
7.如权利要求6所述的高纯度微细的碳化钛粉末的制造方法,其中,碳源是苯酚或邻苯二酚的酚类、线型酚醛清漆型酚醛树脂、水杨酸、邻苯二甲酸、邻苯二酚、无水柠檬酸的有机酸、EDTA之中的任何一种。
8.如权利要求6所述的高纯度微细的碳化钛粉末的制造方法,其中,碳源是具有2个以上配位体且具有环状化合物的有机物。
9.如权利要求6所述的高纯度微细的碳化钛粉末的制造方法,其中,在使前体溶液固化而得到的生成物中,碳源具有与钛配位的结构。
10.如权利要求6所述的高纯度微细的碳化钛粉末的制造方法,其中,烷氧基钛是甲氧基钛(IV)、乙氧基钛(IV)、异丙氧基钛(IV)、丁氧基钛(IV)之中的任何一种。
11.如权利要求3~5任一项所述的碳化钛-陶瓷复合粉末的制造方法,其中,在溶剂中溶解作为碳源的有机物而形成液体,当将碳源和烷氧基钛的摩尔比,即碳源/烷氧基钛设定为α时,在该液体中混合烷氧基钛使得α为0.75≤α≤1.1,得到前体溶液,在前体溶液中混合陶瓷粉末并浆料化,使浆料化的前体溶液固化得到生成物,在非氧化气氛中在1050~1500℃下进行热处理。
12.如权利要求11所述的碳化钛-陶瓷复合粉末的制造方法,其中,在真空气氛中在1050~1500℃下进行热处理。
13.如权利要求11或12所述的碳化钛-陶瓷复合粉末的制造方法,其中,碳源是苯酚或邻苯二酚的酚类、线型酚醛清漆型酚醛树脂、水杨酸、邻苯二甲酸、邻苯二酚、无水柠檬酸的有机酸、EDTA之中的任何一种。
14.如权利要求11或12所述的碳化钛-陶瓷复合粉末的制造方法,其中,碳源是具有2个以上配位体且具有环状化合物的有机物。
15.如权利要求11或12所述的碳化钛-陶瓷复合粉末的制造方法,其中,在使前体溶液固化而得到的生成物中,碳源具有与钛配位的结构。
16.如权利要求11或12所述的碳化钛-陶瓷复合粉末的制造方法,其中,烷氧基钛是甲氧基钛(IV)、乙氧基钛(IV)、异丙氧基钛(IV)、丁氧基钛(IV)之中的任何一种。
17.如权利要求11或12所述的碳化钛一陶瓷复合粉末的制造方法,其中,陶瓷粉末是氧化铝。
18.一种由权利要求1或权利要求2所述的高纯度微细的碳化钛粉末得到的碳化钛烧结体。
19.一种碳化钛烧结体的制造方法,其中,将由权利要求6~10任一项所述的高纯度微细的碳化钛粉末的制造方法得到的碳化钛粉末在真空气氛或氮气氛或氩气氛中,在1400~1850℃的温度和10~50MPa的压力下进行热压。
20.一种碳化钛烧结体的制造方法,其中,将由权利要求6~10任一项所述的高纯度微细的碳化钛粉末的制造方法得到的碳化钛粉末成型,在真空气氛或氮气氛或氩气氛中,在1500~1900℃的温度下进行烧结。
21.一种碳化钛烧结体的制造方法,其中,在氮气氛或氩气氛中,在1400~1600℃的温度和50~200MPa的压力下,热等静压制由权利要求19或20所述的碳化钛烧结体的制造方法得到的碳化钛烧结体。
22.一种碳化钛-陶瓷复合烧结体,其由权利要求3~5任一项所述的碳化钛-陶瓷复合粉末得到。
23.一种碳化钛-陶瓷复合烧结体的制造方法,其中,将由权利要求11~17任一项所述的碳化钛-陶瓷复合粉末的制造方法得到的碳化钛-陶瓷复合粉末在真空气氛或氮气氛或氩气氛中,在1400~1850℃的温度和10~50MPa的压力下进行热压。
24.一种碳化钛-陶瓷复合烧结体的制造方法,其中,将由权利要求11~17任一项所述的碳化钛-陶瓷复合粉末的制造方法得到的碳化钛-陶瓷复合粉末成型,在真空气氛或氮气氛或氩气氛中,在1500~1900℃的温度下进行烧结。
25.一种碳化钛-陶瓷复合烧结体的制造方法,其中,以使相对密度为95%以上的方式,将由权利要求11~17任一项所述的碳化钛-陶瓷复合粉末的制造方法得到的碳化钛-陶瓷复合粉末热压或成型、并烧结而得到碳化钛-陶瓷复合烧结体,在氮气氛或氩气氛中,在1400~1600℃的温度和50~200MPa的压力下热等静压制烧结得到的碳化钛-陶瓷复合烧结体。
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WO2008040222A1 (fr) * | 2006-09-22 | 2008-04-10 | Ocean University Of China | Catalyseur en poudre d'ordre de grandeur nanométrique, et son procédé de préparation |
US20100143749A1 (en) * | 2006-09-29 | 2010-06-10 | Nippon Tungsten Co., Ltd. | Substrate material for magnetic head and method for manufacturing the same |
JP2009110571A (ja) * | 2007-10-29 | 2009-05-21 | Kyocera Corp | 磁気ヘッド用基板およびこれを用いた磁気ヘッドならびに記録媒体駆動装置 |
JP5424215B2 (ja) * | 2009-01-07 | 2014-02-26 | 福岡県 | 金属炭化物微粒子の製造方法 |
CN102351179B (zh) * | 2011-10-10 | 2013-04-24 | 北京科技大学 | 一种真空气凝胶碳化工艺制备纳米wc粉的工艺 |
CN103274412A (zh) * | 2013-06-16 | 2013-09-04 | 桂林理工大学 | 以钛酸四丁酯和酚醛树脂分别为钛源和碳源制备TiC粉体的方法 |
JP6568104B2 (ja) | 2014-05-13 | 2019-08-28 | ザ ユニバーシティ オブ ユタ リサーチ ファウンデイション | 実質的に球状の金属粉末の製造 |
AU2015358534A1 (en) | 2014-12-02 | 2017-07-20 | University Of Utah Research Foundation | Molten salt de-oxygenation of metal powders |
CN104495846B (zh) * | 2014-12-17 | 2016-08-24 | 北京科技大学 | 一种生产纳米碳化钒粉末的方法 |
CN106629732B (zh) * | 2016-11-08 | 2018-10-19 | 西安科技大学 | 一种纳米ZrC-SiC复合粉体的制备方法 |
KR101890273B1 (ko) | 2017-04-05 | 2018-08-21 | 전북대학교산학협력단 | 고밀도 및 고경도 타이타늄 소결체의 제조방법 |
CN109346681A (zh) * | 2018-08-17 | 2019-02-15 | 福建翔丰华新能源材料有限公司 | 一种核壳结构纳米硅-MXene复合负极材料及其制备方法 |
CN110407206A (zh) * | 2019-09-06 | 2019-11-05 | 华北理工大学 | 一种钛修饰膨胀石墨的改性方法 |
CN112500167A (zh) * | 2020-12-30 | 2021-03-16 | 山东东大新材料研究院有限公司 | 一种致密化碳化钛复合陶瓷的制备方法 |
CN113004048A (zh) * | 2021-03-10 | 2021-06-22 | 滁州学院 | 一种碳氮氧化钛陶瓷粉体的制备方法 |
CN115231572A (zh) * | 2022-07-20 | 2022-10-25 | 郑州航空工业管理学院 | 一种纳米碳化钛粉体的制备方法 |
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