CN101535214B - 用于铸造活性合金的模具系统 - Google Patents
用于铸造活性合金的模具系统 Download PDFInfo
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- CN101535214B CN101535214B CN2007800416585A CN200780041658A CN101535214B CN 101535214 B CN101535214 B CN 101535214B CN 2007800416585 A CN2007800416585 A CN 2007800416585A CN 200780041658 A CN200780041658 A CN 200780041658A CN 101535214 B CN101535214 B CN 101535214B
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- paste compound
- organic polymer
- slurry
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- melts
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- 238000005266 casting Methods 0.000 title abstract description 17
- 229910045601 alloy Inorganic materials 0.000 title description 10
- 239000000956 alloy Substances 0.000 title description 10
- 239000002002 slurry Substances 0.000 claims abstract description 83
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 38
- 239000003795 chemical substances by application Substances 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 30
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 28
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 24
- 239000000155 melt Substances 0.000 claims description 22
- 229920000620 organic polymer Polymers 0.000 claims description 22
- 238000005245 sintering Methods 0.000 claims description 22
- 230000007935 neutral effect Effects 0.000 claims description 15
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 229910052727 yttrium Inorganic materials 0.000 claims description 12
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 11
- 238000002844 melting Methods 0.000 claims description 11
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
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- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000005495 investment casting Methods 0.000 claims description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- DJOYTAUERRJRAT-UHFFFAOYSA-N 2-(n-methyl-4-nitroanilino)acetonitrile Chemical compound N#CCN(C)C1=CC=C([N+]([O-])=O)C=C1 DJOYTAUERRJRAT-UHFFFAOYSA-N 0.000 claims description 3
- 229910001092 metal group alloy Inorganic materials 0.000 abstract description 3
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- 238000000034 method Methods 0.000 description 19
- 239000000853 adhesive Substances 0.000 description 14
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- 229910052751 metal Inorganic materials 0.000 description 8
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- 239000000126 substance Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- BNUDRLITYNMTPD-UHFFFAOYSA-N acetic acid;zirconium Chemical compound [Zr].CC(O)=O BNUDRLITYNMTPD-UHFFFAOYSA-N 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
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- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
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- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 241000024287 Areas Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000002245 Penicillium camembertii Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229920006387 Vinylite Polymers 0.000 description 1
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- 230000032683 aging Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
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- 238000004364 calculation method Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
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- 238000011049 filling Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
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- 239000005350 fused silica glass Substances 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 230000009897 systematic effect Effects 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22C1/18—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of inorganic agents
- B22C1/183—Sols, colloids or hydroxide gels
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- B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
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- B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
- B22C1/2206—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained by reactions only involving carbon-to-carbon unsaturated bonds
- B22C1/222—Polyacrylates
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- B22C9/00—Moulds or cores; Moulding processes
- B22C9/02—Sand moulds or like moulds for shaped castings
- B22C9/04—Use of lost patterns
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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
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- C04B35/484—Refractories by fusion casting
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Abstract
本发明涉及形成浇铸金属合金,更尤其是活性金属合金的模具所用的新型粘合剂和浆料配方。与其它目前可用的壳模系统相比,本发明壳模产生表现出有限α-case的更均匀铸件。
Description
技术领域
本发明涉及一种浆料组合物和由其制备的、用于浇铸金属合金尤其是活性金属合金的模具。
背景技术
已知由于活性合金,如钛、锆等由于其强烈的反应特性,而非常难以获得用于熔模铸造这类合金的合适耐熔系统。这些合金将在浇铸过程中还原其所接触的大多数氧化物,产生大量气化缺陷并导致氧溶解在铸件表面层中,从而需要大量化学机械加工来除去这种表面层,因为它的脆性而使其不适合大多数应用领域,例如,若将其用于航空领域便是非常严重的问题。目前已开发出氧化钇体系并在商业上使用,但这些体系由于短寿命的底涂层浆料,使其必须被小心控制并只能仅仅使用一周或更短时间。然后,这类浆料便趋于严重的性能下降。
在市场上目前使用的氧化钇底浆料中,克服因氧化钇在较低pH条件下相对溶解快而释放离子的趋势所用的两种常用方法为下述之一:一种是添加大量有机碱,如氢氧化四乙铵到氧化钇浆料中,在保持浆料稳定所需的高pH水平下以阻止二氧化硅溶解。另一种方法是在熔化过程中用其它非活性氧化物“合金化”氧化钇,这可减少氧化钇颗粒上溶解位点的数目,或用大的吸附性有机分子涂覆氧化钇以达到相同结果,两种方法都有助于体系的整体稳定性。尽管这些方法都在一定程度上起作用,但仍需要一种只需有限量(即使有的话)这类添加剂的活性合金模具系统,并利用可市购的耐融材料,如纯熔融氧化钇或烧结氧化钇材料,来生产较长寿的稳定浆料。本发明正是提供这类系统。
发明内容
本发明的浆料和最终由其制造的熔模铸造模具包含:耐融材料;含有机聚合物的低二氧化硅含量的溶胶粘合剂;以及根据具体情况,视需要选择加入的以下一种或多种添加剂:交联剂,烧结剂,表面活性剂,消泡剂和促稳定性酸。这些将在下面更详细地讨论,视应用的不同,低二氧化硅含量溶胶可带正电荷、负电荷或为中性。
通过利用本发明的新型浆料形成模具或本技术领域中另一称呼“壳”,来浇铸活性金属部件,可容易地形成铸件质量提高并较少表现出alpha case的部件。
具体实施方式
尽管本文描述的浆料组合物通常被用作底涂层浆料,此为本技术领域中普遍被理解的术语,但本文描述的组合物还可在某些情况下稍加改变而用作中间浆料,这将在下文中解释。
在用于模制金属物体的铸造壳的制备中,至少将一种底浆料涂覆物涂到蜡模上,从模中排去过量浆料,然后一般用任何合适的耐融粒料,包括但不限于熔融氧化钇、熔融氧化铝和熔融氧化锆等来粉刷该部件。然后,再粉刷或不粉刷本领域中已知的底涂料和/或背层涂料的附加层到由底浆料形成的、未经处理过的壳上,直到壳具有所需厚度。
如上所述,本发明的浆料包括适合形成壳模的耐融材料,其中所述壳模可用于浇铸例如钛和锆之类的活性金属制成的航空、医疗、船舶和运动优良产品以及由活性较小合金如718、738和792、Rene80和Mar M302形成的产品,这些都作为非限制性例子。因而,耐融材料优选为不仅产生坚固壳模而且能在与被浇铸的熔融金属接触时限制氧化物还原的那些材料。有用的耐融材料的例子包括氧化钇、氧化锆和稀土金属氧化物。优选的耐融材料包括熔融氧化钇、烧结氧化钇、熔融氧化锆、熔融锆酸钙、Er2O3、Sc2O3、Pr2O3、SrO、La2O3和它们的混合物。优选地,耐融材料具有约-200至-325之间的平均目径,这种目径在本领域中被称为“粉”。该浆料中一般存在约70.0-90.0wt%的耐融材料。
根据壳的预定用途,低二氧化硅含量溶胶粘合剂可带正电荷、负电荷或不带电,例如中性,这取决于应用。当使用带正电荷的二氧化硅溶胶时,该二氧化硅颗粒将在几乎所有pH水平下保持稳定,因为耐融材料的溶出离子本身带正电荷,不会附着到该溶胶颗粒上导致它们的电中和并因此造成凝聚而失去它们的粘合能力。以添加蒸馏水而形成溶胶的市售带正电荷的胶态二氧化硅的例子,包括可从Wesbond购得的Bluonic PB9430和同样可从Wesbond购得的WesolP。浆料中通常存在0.5-约20.0wt%,优选2.0-10.0wt%的正电二氧化硅溶胶。
通常还使用有机聚合物。有机聚合物优选为可溶性聚合物如聚乙烯醇。非常优选的聚乙烯醇具有约85至100%之间的水解度。完全水解级聚乙烯醇(PVA)是优选的,因为它在壳建造过程中该涂层后续润湿时不太易于溶解。用于本发明浆料中的市售聚乙烯醇组合物的一个例子是可从Celenese Corp得到的Celvol08-125。有机聚合物通常最多占浆料的约2.0wt%(以干重为基础计算)。
除了上述外,使用正电溶胶的浆料还通常包括促稳定性酸,作为非限制性例子,优选羟基乙酸或羟丙基纤维素。促稳定性酸通常最多占浆料的约2.9wt%,优选约0.1和1.0wt%之间的。
另外,可使用交联剂限制浆料在干燥后的再溶解。当使用交联剂时,其量不超过约1.0wt%。可用的交联剂为例如乙二醛、二醛、聚酰胺-表氯醇树脂或碳酸锆铵。产自BASF公司的Curesan200为可商购的例子。
可使用足够量的表面活性剂和/或消泡剂润湿蜡模和从浆料中除去空气。本领域技术人员熟知,每100g浆料中,通常只需大约10滴或更少的表面活性剂和消泡剂。优选地,表面活性剂为非离子型表面活性剂,优选的消泡剂为以聚硅氧烷为基础(silicone based)的消泡剂。
浆料的液体部分即二氧化硅溶胶、有机聚合物、促稳定性酸(如果有的话)、交联剂和水,可为含有约25-32%总固体量的预混合粘合剂组合物的形式。这种预混合液体粘合剂的配制简化了浆料的制备,尤其在生产条件下。
还可使用少量充分细磨的耐融烧结助剂,作为非限制性例子,例如氧化锆或氧化铝。“充分细磨”意味着烧结助剂具有小于约2.0微米的平均粒径。通常含有约0.10和3.0wt%之间的烧结助剂。可以添加耐融烧结助剂到浆料中,或者也可使其与耐融材料预混合,从而这些干的预混合耐融材料混合物可在单一步骤中被加入到液体粘合剂成分中形成浆料。这些预混合物的使用简化了浆料制备,同时允许其他用户随alpha case而进行控制,如当预混合氧化锆、氧化钇和烧结助剂降低了成本时,同时也仍保持了可接受的低alpha case水平。
在下面提供的实施例1-6中阐述了使用带正电荷的溶胶的浆料配方。
在本发明的其它实施方案中,可使用带负电荷或中性的二氧化硅溶胶形成用于制造活性金属铸件壳的稳定浆料。发现这种浆料在8-9的pH范围内保持稳定而没有明显老化趋向。以添加蒸馏水而形成溶胶的市售带负电荷胶体二氧化硅的例子,包括从Eka Chemical可得到的Bindzil830。另外,市售中性二氧化硅为Bindzil DP-5110,其也可从Eka Chemical得到。
除了主要如上所述的耐融材料外,使用带负电荷或中性的二氧化硅溶胶的浆料还包括有机聚合物。而在这里,有机聚合物可包括乳胶、聚乙烯醇、羟丙基纤维素和基于苯乙烯、丁二烯、丙烯酸和乙烯基树脂,连同其它聚合物和共聚物的聚合物乳液。对于带负电荷或中性电荷的溶胶/浆料,有机聚合物含量可高于带正电荷的溶胶的有机聚合物含量,在这种情况下,有机聚合物组分以干重为基础计不超过约3.0%。
为了使浆料更耐再溶解,可将若干市售有机交联剂之一加入到带负电荷或中性溶胶基的浆料中与聚合物和粘合剂反应。随着上述浆料添加剂的加入,通常再需要表面活性剂来增强过程中所用蜡模的“润湿”,并且如果需要,可使用少量消泡剂。应注意到,尽管通常利用弱有机酸添加物增强正电溶胶浆料的稳定性,但对于带负电荷或中性的体系,不使用这类酸添加剂,因为这会导致粘合剂胶凝或加速老化。
同样,可添加少量极细的耐融氧化物例如氧化锆等以增加涂覆层的烧结强度和避免浇铸过程中任何可能的表面磨蚀。还可使用这类其它氧化物例如氧化铝。这些氧化物在浇铸以前进行的模具烧结过程中与耐融组分反应,尤其是包含氧化钇的耐融组分。
下面提供的实施例9-14中描述了使用带负电荷或中性溶胶的浆料配方。
在干燥底层几小时后,施加第二或中间浆料。可使用能在公开文献中找到的任何合适的高温稳定耐融浆料。第二或中间浆料的粘合剂体系可为醇基的,例如硅酸乙酯,或水基的,如胶态二氧化硅或其它无机粘合剂。如果使用胶态二氧化硅中间体系,则可使用上述交联剂之一的添加物进一步防止底涂层浆料的任何溶解作用。在这种情况下,还可使用无机交联剂如碳酸锆铵限制底涂层在浸渍过程中的软化。这类交联剂或阻溶剂的优选量在0.1-0.5wt%之间。可根据需要施加一个或多个中间层,并用类似于初始氧化钇层所用耐融颗粒物的合适稳定耐融颗粒来粉刷。
实施例15和16中描述了与本文描述的浆料一起使用的合适中间浆料配方。
然后施加几个背层浆料层。这些层由熔模铸造工业中常见的任何合适体系组成,并用于主要构建材工业模具厚度和有助于承受模具脱蜡时的严酷性所需的强度。通常用与初始层和中间层相比具有更大尺寸的耐融颗粒粉刷这些层。用于粉刷上述浆料组合物的耐融颗粒可具有例如20-70之间的粒度。作为非限制性例子,合适的耐融粉刷物包括氧化钇、氧化铝、氧化锆、莫来石、铝硅酸盐、稀土金属氧化物和它们的混合物。
在完成模具构造过程后,一般利用最终干燥循环确保在除去蜡模前达到模具的完全设计强度。然后使用工业上常用方法中的任何一种对模具脱蜡,优选高压釜或闪火脱蜡。这些方法是常规知识,并在整个工业界使用多年。然后检查脱蜡的模具,并在必要时加以修补。用合适的耐融水泥覆盖可见的任何裂纹,并涂覆密封浸渍浆料到修补区域上。然后烧制模具到约1600和2200°F之间的温度,并保持2-4小时以使模具达到能承受铸造应力的烧结强度。烧制还有助于通过二氧化硅、烧结助剂和氧化钇粉的烧结使新的底层氧化钇涂层充分达到强度,在浇铸工艺期间和之后产生与活性金属仅仅最少反应的光滑不起尘的表面。
使用常规的活性金属浇铸工艺中的任何一种在真空条件下完成模具的填充。可在不超过2200°F的任意温度或更低温度下,甚至在室温下预热如上所述的模具,这取决于模具和部件构形以及所用合金。能够预料到,模具预热温度越低,产生的金属/模具反应越少,在钛合金铸件的情况下,较少产生alpha case,即富氧的脆层,其在铸件投入使用前必须要被除去。
然后在冷却时通过任何常规方法从模具中取出铸件,并按照需要清洗和机械加工以满足最终用户的技术要求。
提供下面的实施例进一步描述本发明,但并不打算以此为限。
实施例1:氧化钇底涂层浆料
按上面所示顺序添加并混合各成分。优选使用高剪切混合器恰当分散成分以获得所需结果。在最初的配制后,浆液维持缓慢搅拌直到观察到粘度开始稳定为止。用户可少量添加蒸馏水和羟基乙酸调整粘度到所需的值。在最终调整后,如果封闭下持续搅拌,可发现浆液能稳定几周。如果保持在敞开容器中,则由于蒸发而必须定期添加蒸馏水到浆料中以保持所需的粘度。
实施例2:氧化钇底涂层浆料
按所示顺序添加和混合各成分。在这种情况下不使用交联剂,建议这种浆料只供与有机(即硅酸乙酯)中间浆料一起使用。
实施例3:氧化钇底涂层浆料
按实施例1和2的方式混合浆料。这种浆料利用正电二氧化硅溶胶(WesbondP)和阻溶剂Berset2040、乙二醛基材料使浆料在干燥后不溶。
实施例4:预混合粘合剂
强烈混合这些成分直到均匀,然后在室温下储存在带盖容器中直到使用。
实施例5:氧化钇底涂层浆料(用预混合粘合剂制备)
这种浆料与前面实施例中的那些类似,但是使用实施例4的预混合粘合剂制备的。
实施例6:氧化锆底涂层浆料(利用预混合粘合剂制备)
使用实施例4的预混合粘合剂制备这种浆料,并用于制备浇铸较小钛铸件的模具,其中不会有太强的热输入,产生的alpha case在可接受范围内。值得注意的是,许多目前使用的氧化锆模具系统采用有异议的氨基粘合剂,它们的气味不合要求。
尽管氧化钇底涂层通常被认为是活性最小和最优选的底涂层体系,尤其对于浇铸钛合金,但利用本发明中教导的相同粘合剂技术的其它底涂层体系也是可以的。实施例6显示了使用熔融钙(石灰)稳定化的氧化锆粉的底涂层体系。使用氧化锆的底涂层有时用于浇铸钛,尤其当需要较低成本系统时,通常用于较小或不太关键的部件如高尔夫球棍。现有技术的氧化锆底涂层通常利用醋酸锆或碳酸锆铵作为基础粘合剂。醋酸锆粘合剂存在不足,因为这些涂层通常有些溶于水,或对水接触充分敏感从而需要利用额外的步骤使涂层不溶或者完全避免高压釜脱蜡。通过使用碳酸锆铵作为基础粘合剂可有利于高压釜脱蜡,但由于强烈的氨味和使用碳酸锆铵相关的固有毒性,因而出于健康和安全原因不能被接受。本发明中教导的粘合剂技术克服了这两种缺陷,因为几乎没有出现因使用正电溶胶(Bluonic PB-9430),如实施例4中所示的正电溶胶相关的气味或毒性。大量其它耐融材料,如熔融或片状氧化铝、莫来石、各种铝硅酸盐、锆石、熔融二氧化硅和各种其它市售耐融材料也与这种粘合剂相容,并可按照需要用在底涂层或背层浆料中,这取决于正被浇铸的合金类型和/或经济因素。
实施例7:中间交联含水浆料
包含也可用作无机粘合剂与本发明的氧化钇浆料一起使用的交联阻溶剂。
材料 重量百分比
碳酸锆铵 18.0
片状氧化铝(-325目) 82.0
这种浆料不会引起氧化钇底涂层浆料的任何软化,因为碳酸锆铵(AZC)对于上面实施例1、2和3中的任何一个,都起双重作用,既作为无机粘合剂,又作为交联阻溶剂。
实施例8:中间不溶含水浆料
这种浆料包含有机交联的阻溶剂以消除实施例1、2和3的氧化钇浆料在浸涂过程中重新溶解的任何趋势。
这种浆料利用更常规的带负电荷的胶态二氧化硅溶胶作为主要粘合剂。
实施例9:氧化钇底涂层浆料(负电溶胶)
按所示顺序添加并混合各成分。
实施例10:预混合粘合剂(负电溶胶)
强烈混合这些成分直到均匀,然后在室温下储存在带盖容器中直到使用。
实施例11:氧化钇底涂层浆料(具有实施例10的预混合粘合剂)
这种浆料类似于前面实施例中的其它浆料,但是使用实施例10的预混合粘合剂制备的。
实施例12:氧化锆底涂层浆料(具有实施例10的预混合粘合剂)
这种浆料类似于前面实施例中的其它浆料,但是使用实施例10的预混合粘合剂制备的。
实施例13:氧化锆+氧化钇底涂层浆料(具有实施例10的预混合粘合剂)
这种浆料类似于前面实施例中的其它浆料,但是使用实施例10的预混合粘合剂制备的。
实施例14:氧化钇底涂层浆料(中性电荷溶胶)
按所示顺序添加并混合各成分。这种浆料使用具有中性电荷的胶态二氧化硅粘合剂。当不使用时,应储存在封闭容器中。
本发明浆料经浸渍、粉刷和干燥后,随之进行形成壳层的工艺,首先涂一个或多个中间涂层,然后涂典型的任何背层壳体系。供这些和类似的底涂层使用的中间浆料,其配制要求是要使干燥底涂层在浸渍过程中的再溶解达最小。中间浆料包含负电溶胶胶态二氧化硅粘合剂、为增进湿强度的一定百分比的可溶聚合物以及进一步硬化底涂层和防止有机聚合物还未烧结的结合物溶解的交联剂(如在底涂层中一样)。
下面列举氧化铝基中间浆料的两个例子。
实施例15:中间交联含水浆料
包含也可用作无机粘合剂与本发明的氧化钇浆料一起使用的交联阻溶剂。
材料 重量百分比
碳酸锆铵 18.0
片状氧化铝(-325目) 82.0
这种浆料不会引起氧化钇底涂层浆料的任何软化,因为碳酸锆铵(AZC)对于上面实施例1、2和3中的任何一个,都起双重作用,既作为无机粘合剂,又作为交联阻溶剂。
实施例16:中间不溶含水浆料
这种浆料包含有机交联阻溶剂以消除实施例1、2和3的氧化钇浆料在浸涂过程中任何重新溶解的趋势。
实施例17:中间不溶含水浆料(具有实施例10的预混合粘合剂)
这种浆料包含有机交联阻溶剂以消除实施例1、2和3的氧化钇浆料在浸涂过程中任何重新溶解的趋势。
Claims (23)
1.一种用于形成熔模铸造模具的浆料组合物,包含:
包括选自氧化钇、氧化锆和稀土金属氧化物中的一种或多种材料的耐融材料;
带负电荷或中性的胶态二氧化硅;
可溶性有机聚合物;
与该可溶性有机聚合物反应并在干燥后充分防止该浆液再溶解的交联剂;
水;和
视需要而选择的一种或多种添加剂,所述添加剂选自烧结助剂、表面活性剂和消泡剂。
2.权利要求1的浆料组合物,其中所述耐融材料选自熔融氧化钇、烧结氧化钇、熔融氧化锆、熔融锆酸钙、Er2O3、Sc2O3、Pr2O3、SrO、La2O3和它们的混合物。
3.权利要求1的浆料组合物,其中所述带负电荷或中性的胶态二氧化硅的含量为浆液的0.5wt%至20.0wt%。
4.权利要求1的浆料组合物,其中所述可溶性有机聚合物的含量以干重为基础计不超过3.0wt%。
5.权利要求1的浆料组合物,其中所述可溶性有机聚合物为聚乙烯醇。
6.权利要求5的浆料组合物,其中所述聚乙烯醇被水解至少85.0%。
7.权利要求1的浆料组合物,其中所述烧结助剂为平均粒径小于2.0微米的磨细耐融材料的形式。
8.权利要求7的浆料组合物,其中烧结助剂的含量为0.10wt%至3.0wt%。
9.权利要求7的浆料组合物,其中耐融材料和烧结助剂在加入到浆液前被预混合。
10.权利要求1的浆料组合物,其中所述带负电荷或中性的胶态二氧化硅、所述可溶性有机聚合物、所述交联剂和水在加入到所述浆液前被预混合形成粘合剂溶液。
11.权利要求1的浆料组合物,其中所述浆液组合物具有至少8.0的pH。
12.权利要求1的浆料组合物,其中,所述交联剂为乙二醛,或二醛,或聚酰胺-表氯醇树脂,或碳酸锆铵。
13.权利要求12的浆料组合物,其中,该可溶性有机聚合物是聚乙烯醇。
14.权利要求12的浆料组合物,其中,该交联剂是聚酰胺-表氯醇树脂。
15.权利要求12的浆料组合物,其中,该可溶性有机聚合物的量以干重为基础计为3.0%。
16.权利要求15的浆料组合物,其中,该可溶性有机聚合物是聚乙烯醇。
17.权利要求16的浆料组合物,其中,该聚乙烯醇被水解至少85%。
18.权利要求15的浆料组合物,包括烧结助剂,该烧结助剂为平均粒径小于2.0μ的磨细耐融材料的形式。
19.权利要求17的浆料组合物,包括按重量计0.1%到按重量计3.0%的烧结助剂。
20.权利要求12的浆料组合物,其中,该耐融材料主要包括熔融氧化钇、烧结氧化钇、熔融氧化锆、熔融锆酸钙、Er2O3、Sc2O3、Pr2O3、SrO、La2O3和它们的混合物。
21.权利要求12的浆料组合物,其中,该耐融材料包括熔融氧化钇、烧结氧化钇或熔融氧化锆。
22.权利要求1的浆料组合物,其中,该交联剂以不超过按重量计1.0%的量限制浆料在干燥后的再溶解。
23.一种用于形成熔模铸造模具的浆料组合物,包含:
包括选自氧化钇、氧化锆和稀土金属氧化物中的一种或多种材料的耐融材料;
带负电荷或中性的胶态二氧化硅;
可溶性有机聚合物;
与该可溶性有机聚合物反应的交联剂;以及
水;
其中,该可溶性有机聚合物是聚乙烯醇,交联剂选自乙二醛、聚酰胺-表氯醇树脂、碳酸锆铵。
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- 2007-11-12 CN CN2007800416585A patent/CN101535214B/zh active Active
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2008
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Also Published As
Publication number | Publication date |
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US20080119347A1 (en) | 2008-05-22 |
US8980778B2 (en) | 2015-03-17 |
EP2091888B1 (en) | 2017-03-01 |
EP2091888A4 (en) | 2011-06-29 |
CN101535214A (zh) | 2009-09-16 |
ES2626274T3 (es) | 2017-07-24 |
WO2008061051A3 (en) | 2008-08-07 |
US20090075809A1 (en) | 2009-03-19 |
US20150183024A1 (en) | 2015-07-02 |
EP2091888A2 (en) | 2009-08-26 |
WO2008061051A2 (en) | 2008-05-22 |
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