US20230372995A1 - Compositions and methods for refractory coatings with ester carriers - Google Patents
Compositions and methods for refractory coatings with ester carriers Download PDFInfo
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- US20230372995A1 US20230372995A1 US18/222,244 US202318222244A US2023372995A1 US 20230372995 A1 US20230372995 A1 US 20230372995A1 US 202318222244 A US202318222244 A US 202318222244A US 2023372995 A1 US2023372995 A1 US 2023372995A1
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- 239000000203 mixture Substances 0.000 title claims description 51
- 150000002148 esters Chemical class 0.000 title claims description 38
- 238000000576 coating method Methods 0.000 title abstract description 105
- 238000000034 method Methods 0.000 title abstract description 14
- 239000000969 carrier Substances 0.000 title description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008199 coating composition Substances 0.000 claims description 33
- 239000011230 binding agent Substances 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000375 suspending agent Substances 0.000 claims description 10
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical group CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000011819 refractory material Substances 0.000 claims description 8
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- -1 carbonate ester Chemical class 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229910052845 zircon Inorganic materials 0.000 claims description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000006254 rheological additive Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000000080 wetting agent Substances 0.000 claims description 2
- 239000013032 Hydrocarbon resin Substances 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 239000013530 defoamer Substances 0.000 claims 1
- 235000013312 flour Nutrition 0.000 claims 1
- 229920006270 hydrocarbon resin Polymers 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 40
- 238000001035 drying Methods 0.000 abstract description 27
- 239000012855 volatile organic compound Substances 0.000 abstract description 25
- 238000005266 casting Methods 0.000 abstract description 18
- 230000009467 reduction Effects 0.000 abstract description 10
- 238000005058 metal casting Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000003759 ester based solvent Substances 0.000 abstract description 2
- 231100001261 hazardous Toxicity 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 64
- 230000004580 weight loss Effects 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000004576 sand Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000945 filler Substances 0.000 description 8
- 238000009472 formulation Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 101000662809 Homo sapiens Trafficking protein particle complex subunit 4 Proteins 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 102100037496 Trafficking protein particle complex subunit 4 Human genes 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000005336 cracking Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- RXGUIWHIADMCFC-UHFFFAOYSA-N 2-Methylpropyl 2-methylpropionate Chemical compound CC(C)COC(=O)C(C)C RXGUIWHIADMCFC-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000004927 clay Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 235000019439 ethyl acetate Nutrition 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052625 palygorskite Inorganic materials 0.000 description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 2
- WOYWLLHHWAMFCB-UHFFFAOYSA-N 2-ethylhexyl acetate Chemical compound CCCCC(CC)COC(C)=O WOYWLLHHWAMFCB-UHFFFAOYSA-N 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- PPXUHEORWJQRHJ-UHFFFAOYSA-N ethyl isovalerate Chemical compound CCOC(=O)CC(C)C PPXUHEORWJQRHJ-UHFFFAOYSA-N 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 239000012802 nanoclay Substances 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- RCSBILYQLVXLJG-UHFFFAOYSA-N 2-Propenyl hexanoate Chemical compound CCCCCC(=O)OCC=C RCSBILYQLVXLJG-UHFFFAOYSA-N 0.000 description 1
- XEYIWOWYMLEPSD-UHFFFAOYSA-N 2-ethylhexyl decanoate Chemical compound CCCCCCCCCC(=O)OCC(CC)CCCC XEYIWOWYMLEPSD-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- HIQIXEFWDLTDED-UHFFFAOYSA-N 4-hydroxy-1-piperidin-4-ylpyrrolidin-2-one Chemical compound O=C1CC(O)CN1C1CCNCC1 HIQIXEFWDLTDED-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000870659 Crassula perfoliata var. minor Species 0.000 description 1
- 229910001141 Ductile iron Inorganic materials 0.000 description 1
- 229910001060 Gray iron Inorganic materials 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 229940007550 benzyl acetate Drugs 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 1
- 238000004710 electron pair approximation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 231100001244 hazardous air pollutant Toxicity 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- 229940117955 isoamyl acetate Drugs 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 235000012243 magnesium silicates Nutrition 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 1
- 229940073769 methyl oleate Drugs 0.000 description 1
- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C3/00—Selection of compositions for coating the surfaces of moulds, cores, or patterns
-
- 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
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/481—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing silicon, e.g. zircon
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5042—Zirconium oxides or zirconates; Hafnium oxides or hafnates
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
-
- 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
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
Definitions
- This technology relates to refractory coatings used in metal casting by the foundry industry.
- refractory coatings are like special paints used in metal casting. Unlike conventional paints, however, refractory coatings can withstand the high temperatures of molten metal and also act as a barrier between the molten metal and a mold into which the metal is poured for casting.
- Refractory coatings are generally comprised of a high temperature mineral, or other substance that is resistant to heat, suspended in a liquid (solvent) carrier.
- the coating is applied to, for example, a sand mold or core surface prior to casting.
- the liquid carrier is removed by evaporation, while the layer of mineral is left behind to coat the mold surface. This layer can help prevent penetration of molten metal into the sand, prevent erosion of the sand, and otherwise improve the quality of a casting surface.
- Solvent based coatings can be air dried in a reduced amount of time or ignited for very short dry times.
- Current solvent based foundry refractory coatings comprise of isopropyl alcohol (“IPA”), ethanol, methanol, naphtha, etc.
- IPA isopropyl alcohol
- HAPs hazardous air pollutants
- VOCs volatile organic compounds
- IPA and ethanol are the most commonly used solvent carriers in refractory coatings of the foundry industry. Such pollutants and volatile compounds are subject to intense regulation, and many foundries that use conventional solvent based coatings spend considerable time and resources permitting for the VOCs.
- VOC-exempt solvents such as acetone have been used in the past.
- acetone's high evaporation rate increases usage, and the low flash point introduces serious explosion and fire risks to the foundry.
- the present invention provides a partial or full replacement of refractory coating solvents with ester carriers, such as dimethyl carbonate (“DMC”) or t-butyl acetate, to form a solvent based refractory coating with reduced or no reportable HAPs or VOCs.
- ester carriers such as dimethyl carbonate (“DMC”) or t-butyl acetate
- a refractory coating also known as mold wash, paint, or dressing
- a liquid ester carrier such as 100% DMC
- a suspending agent such as 100% DMC
- a binding agent such as water
- an additive such as additive
- a particulate refractory filler blend such as water, an additive, and a particulate refractory filler blend.
- refractory coatings formed in accordance with a preferred embodiment of the present invention comprising DMC achieved an approximately 50%-97% reduction in reportable VOC's as compared to conventional refractory coatings.
- 100% VOC exempt coatings are achievable in accordance with preferred embodiments of the present invention, although some coatings formed as described herein may include trace VOCs that are introduced to the composition by the binding agent.
- carrier solvent may comprise one or more ester carriers or a combination of one or more ester carriers with non-ester solvents.
- additives are surface active agents, such as, wetting agents, defoamers, dispersants, and rheology modifiers.
- FIG. 1 is a graphic representation of weight loss % over time in minutes (drying time) data produced from a refractory coating comprising an approximately 25/75 DMC/IPA (1:3 ratio DMC:IPA) ester carrier formulation. As shown, the data was collected at room temperature (“RT”), 35 degrees Celsius, and 49 degrees Celsius.
- RT room temperature
- FIG. 2 is a graphic representation of weight loss % over time in minutes (drying time) data produced from a refractory coating comprising an approximately 50/50 DMC/IPA ester carrier formulation. As shown, the data was collected at RT, 35 degrees Celsius, and 49 degrees Celsius.
- FIG. 3 is a graphic representation of weight loss % over time in minutes (drying time) data produced from a refractory coating comprising an approximately 75/25 DMC/IPA ester carrier formulation. As shown, the data was collected at RT, 35 degrees Celsius, and 49 degrees Celsius.
- FIG. 4 is a graphic representation of weight loss % over time in minutes (drying time) data produced from a refractory coating comprising an approximately 100% DMC ester carrier formulation. As shown, the data was collected at RT, 35 degrees Celsius, and 49 degrees Celsius.
- FIG. 5 is a graphic representation of weight loss % over time in minutes (drying time) data produced from a refractory coating comprising an approximately 100° A IPA carrier formulation. As shown, the data was collected at RT, 35 degrees Celsius, and 49 degrees Celsius.
- FIG. 6 is a graphic representation of weight loss % over time in minutes (drying time) data produced from a refractory coating comprising an SBDN 1087 base formula and various carrier solvents comprising DMC and IPA. As shown, the data was collected at RT.
- FIG. 7 is a graphic representation of weight loss % over time in minutes (drying time) data produced from a refractory coating comprising an SBDN 1087 base formula and various carrier solvents comprising DMC and IPA. As shown, the data was collected at 35 degrees Celsius.
- FIG. 8 is a graphic representation of weight loss % over time in minutes (drying time) data produced from a refractory coating comprising an SBDN 1087 base formula and various carrier solvents comprising DMC and IPA. As shown, the data was collected at 49 degrees Celsius.
- FIG. 9 is a graphic representation of weight loss % over time in minutes (drying time) data produced from a refractory coating comprising an SBDN 1086 or 1087 base formula and a carrier solvent comprising approximately 75/25 DMC/IPA. As shown, the data was collected at 49 degrees Celsius.
- FIG. 10 is a graphic representation of weight loss % over time in minutes (drying time) data produced from a refractory coating comprising an SBDN 1086 base formula and a carrier solvents comprising approximately 75/25 DMC/IPA. As shown, the data was collected at 35 degrees Celsius and 49 degrees Celsius.
- FIG. 11 is a graphic representation of weight loss % over time in minutes (drying time) data produced from a refractory coating comprising an SBDN 1086 or 1087 base formula and a carrier solvent comprising approximately 75/25 DMC/IPA. As shown, the data was collected at 35 degrees Celsius.
- FIG. 12 is a graphic representation of weight loss % over time in minutes (drying time) data produced from a refractory coating comprising a carrier solvent comprising approximately 75/25 DMC/IPA and various % wt binder.
- FIG. 13 is a graphic representation of weight loss % over time in minutes (drying time) data produced from a refractory coating comprising a carrier solvent comprising approximately 50/50 DMC/IPA and various % wt binder.
- FIG. 14 is a graphic representation of weight loss % over time in minutes (drying time) data produced from refractory coatings comprising a carrier solvent comprising either approximately 75/25 or approximately 50/50 DMC/IPA and approximately 3% binder.
- FIG. 15 is a graphic representation of weight loss % over time in minutes (drying time) data produced from refractory coatings comprising a carrier solvent comprising either approximately 75/25 or approximately 50/50 DMC/IPA and approximately 2.5% binder.
- FIG. 16 is a graphic representation of weight loss % over time in minutes (drying time) data produced from refractory coatings comprising a carrier solvent comprising either approximately 75/25 or approximately 50/50 DMC/IPA and approximately 2% binder.
- FIG. 17 is a graphic representation of weight loss % over time in minutes (drying time) data produced from refractory coatings comprising a carrier solvent comprising either approximately 75/25 or approximately 50/50 DMC/IPA and approximately 1.5% binder.
- FIG. 18 is a graphic representation of weight loss % over time in minutes (drying time) data produced from refractory coatings comprising a carrier solvent comprising approximately 100% DMC and approximately 2% binder.
- FIG. 19 is a graphic representation of weight loss (drying time) data produced from refractory coatings comprising a carrier solvent comprising either approximately 75/25 DMC/IPA or approximately 100% DMC and approximately 2% binder.
- a preferred embodiment of the present invention comprises a low to absent VOC refractory coating having performance characteristics that are comparable to conventional solvent-based coatings and a safety profile that is highly advantageous over known refractory coatings.
- the preferred embodiment comprises an ester carrier, such as dimethyl carbonate or t-butyl acetate, to form a solvent based refractory coating composition.
- ester solvent based refractory coating composition is formed as follows:
- a refractory coating (also known as mold wash, paint, or dressing) composition provided in accordance with the present invention preferably comprises a liquid ester carrier, a suspending agent, a binding agent, water, and a particulate refractory filler blend.
- the liquid ester carrier is preferably primarily an organic compound that is colorless, flammable, and exempt from the restrictions placed on most VOCs in the United States.
- the liquid ester carrier is preferably classified as a carbonate ester, with or without the presence of a secondary solvent.
- the suspending agent is preferably a fine-grained natural rock or soil material that comprises one or more clay minerals with traces of metal oxides and organic matter.
- the suspending agent examples include palygorskite, montmorillonite, and sepiolite.
- the binding agent is preferably a copolymer having a chemical affinity to the liquid ester carrier in the presence or not of a secondary binding agent such as a natural rosin.
- the particulate refractory filler blend preferably comprises a fine to medium size fraction, the blend preferably having an average particle size of approximately d ⁇ 30 microns, wherein no more than approximately 10% by weight or volume of the total particulate refractory filler blend has a particle size of approximately d ⁇ 2 microns.
- the filler blend include zirconium silicate (also known as zircon) and/or aluminum silicate, graphite, silica, magnesium silicates, and the like, including combinations or blends of refractories.
- the liquid ester carrier is dimethyl carbonate (“DMC”).
- DMC has a similar flash point to IPA, and as such the light-off/burn properties of DMC are similar to IPA. Additionally, the evaporation rate of DMC is much higher than IPA or ethanol. Therefore, the drying times of refractory coatings comprising DMC are substantially less than traditional coatings comprising IPA or ethanol. This represents a significant advantage over traditional air dry applications.
- Exemplary refractory coating compositions preferably comprise: (i) a carrier DMC at approximately 25-100% wt of the carrier and IPA at approximately 0-75% wt of the carrier, wherein the carrier comprises approximately 20-80% wt of the coating composition; (ii) clays at approximately 2% wt maximum of the coating composition; (iii) a binder (i.e., a vinyl acetate and vinyl laurate copolymer in ethyl acetate, the copolymer provided at approximately 50% by weight of the binder), at approximately 1.5-3.0% wt of the coating composition; (iv) water at approximately 0-2% wt of the coating composition; (v) additives at approximately 0-2% wt of the coating composition; and (vi) a particulate refractory blend at approximately 13-78.5% wt of the coating composition.
- a carrier DMC at approximately 25-100% wt of the carrier and IPA at approximately 0-75% wt of the carrier, where
- liquid ester carriers may be used in refractory coating compositions provided in accordance with the present invention, including: t-butyl acetate, ethyl acetate, n-butyl acetate, allyl hexanoate, benzyl acetate, butyl butyrate, ethyl butyrate, ethyl benzoate, ethyl hexanoate, ethyl isovalerate, ethyl lactate, isobutyl acetate, isoamyl acetate, ethyl ethanoate, n-butyl oleate, 2-ethylhexyl caprate/caprylate, isopropyl myristate, methyl oleate, n-propyl acetate, 2-ethylhexyl acetate, pentyl acetate, ethylene glycol diacetate (EGDA), 2-ethyl
- ester carriers may also be used as VOC-exempt solvents for dilution of refractory coating compositions prior to application of the composition to a foundry article.
- the liquid ester carrier is t-butyl acetate.
- an alternative refractory coating composition preferably comprises: (i) a carrier t-butyl acetate at approximately 52% wt of the carrier and IPA/Methanol/VM&P Naphtha at approximately 7.5% wt of the carrier; (ii) clays at approximately 1.7% wt maximum; (iii) a phenolic resin at approximately 0.4% wt; (iv) water at approximately 0.9% wt; and (vi) a zircon refractory blend at approximately 66% wt.
- this formulation Prior to application to a mold or core during production, this formulation is preferably diluted with t-butyl acetate to approximately 37% solids.
- DMC dimethyl methacrylate
- IPA adiol
- water adiol
- attapulgite clay also known as palygorskite
- shear is increased to approximately 700 rpm for a blade diameter of 22 inches.
- the mixed materials form a gel after approximately 10 minutes of mixing.
- Refractory powders such as a zircon blend, binder, additives, and remaining liquids if available are then added to the vessel and mixed together for approximately another 10 minutes. Blade action is ceased and the product is inspected for conformity with suitable refractory coating parameters.
- a method of using a refractory coating as described herein and provided in accordance with the present invention is as follows.
- a refractory coating provided in accordance with the present invention may be applied to a foundry article, such as molds and cores, in variable ways due to variable substrates with which the coating is used, and also variable requirements of the user.
- the refractory coating of the present invention may be provided in a concentrated form. In all cases, the coating is applied to provide a protective barrier between a liquid metal and the mold or core.
- the refractory coating Before application to the mold or core, the refractory coating is preferably diluted with an appropriate VOC-exempt solvent until the required application viscosity for the coating is achieved. Coatings of the present invention may also be applied absent any dilution, such as in a concentrated form, depending on the application and intended use of the coating.
- the solvent is a liquid ester carrier comprising DMC.
- the coating can be applied to the mold or core by several methods, including dip, spray, flood (flow coat), brush, swab, and mitt application methods. Dip application includes an immersing of the mold or core into the coating. This application allows full contact of the coating to all areas.
- Spray application is a blowing of the coating through the air in the form of tiny drops to form a coating layer on the surface of the mold or core.
- Flood application is a pumping of the coating through a hose to splash or flood onto the mold or core. The excess coating is collected and run again through the pump.
- Brush, swab, and mitt applications all use a tool (such as a paint brush, horse hair swab, or cotton mitt) soaked in the coating and contacted with the mold or core to apply the coating. Although these are the primary methods of applying a coating to a mold or core in the foundry industry, the invention is not limited to these applications, as will be appreciated by one of ordinary skill in the art.
- the wet refractory coating provided in accordance with the present invention is allowed to dry or ignited to remove the ester carrier. It is important to fully remove the ester carrier from the coating layer. If residual ester carrier remains, the ester carrier can be a source of gas which can cause defects in the metal casting.
- refractory coatings formed in accordance with a preferred embodiment of the present invention comprising DMC achieved an approximately 50% -97% reduction in reportable VOC's as compared to conventional refractory coatings.
- a first production test includes a pouring of high alloy iron and high alloy steel castings with pouring weights of approximately 2,000-11,800 lb. Castings were poured using a vacuum process where a baseline refractory coating is sprayed onto a vacuum process mold film.
- a baseline coating comprising an IPA carrier was compared to two experimental refractory coating formulations provided in accordance with the present invention.
- the experiment coatings, Formula A and Formula B both comprised an ester carrier and employed an approximately 1:1 ratio of DMC:IPA.
- the difference between Formula A and Formula B was the choice of binder employed therein.
- Formula A used a natural Binder A, such as gum rosin
- Formula B used a synthetic Binder B, such as vinyl acetate copolymer.
- Spray application of the Formula A and Formula B coatings was satisfactory as required thicknesses were developed. Dry times for the Formula A and Formula B coatings averaged 2 minutes while the baseline IPA coating dried in an average of 3 minutes and 30 seconds.
- Formula A Approximately a 50% reduction in reportable VOCs and reduced drying time as compared to conventional refractory coatings.
- Formula B Approximately a 50% reduction in reportable VOCs, reduced drying time, and improved resistance to coating layer cracking as compared to conventional refractory coatings.
- Formula C exhibited sufficient sand erosion resistance. Once the mold was stripped from the pattern, it was observed that Formula C showed improved resistance to cracking of the refractory coating layer.
- metal was poured, the molds were allowed to cool, and castings were shot blasted before review.
- Formula C displayed acceptable casting performance. Moreover, Formula C displayed acceptable properties to produce a commercially viable casting.
- Formula C An approximately 97+% reduction in reportable VOCs, reduced drying time, and improved resistance to coating layer cracking as compared to conventional refractory coatings.
- a refractory coating was once again produced with a liquid ester carrier, a suspending agent, a binding agent, a dispersant, and a particulate refractory filler blend.
- the liquid ester carrier in this embodiment is dimethyl carbonate.
- the suspending agent is preferably a nanoclay, and more specifically an organo-modified clay.
- the nanoclay component is preferably montmorillonite, a 2-to-1 layered smectite clay mineral with a platey structure, and a surface modified to become organophilic with increased compatibility with the solvent of choice.
- the binding agent is preferably a copolymer having a chemical affinity to the liquid ester carrier.
- the dispersant agent is preferably an aromatic-free solution of a high molecular weight block copolymer with pigment affinic groups.
- the particulate refractory filler blend preferably comprises a fine to medium size fraction, the blend preferably having a medium particle size of approximately d ⁇ 30 microns, wherein no more than approximately 10% by weight or volume of the total particulate refractory filler blend has a particle size of approximately d ⁇ 2 microns.
- Another exemplary refractory coating compositions provided in accordance with the present invention preferably comprise: (i) a carrier DMC at approximately 100% wt of the carrier, wherein the carrier comprises approximately 28.5-32.5% wt of the coating composition; (ii) organoclay at approximately 2% wt maximum; (iii) a binding agent, such as vinyl acetate copolymer, at approximately 1.5-3.0% wt; (iv) a block copolymer dispersant with pigment affinic groups at approximately 0-0.5% wt; and (v) a zircon refractory blend at approximately 66% wt.
- a carrier DMC at approximately 100% wt of the carrier, wherein the carrier comprises approximately 28.5-32.5% wt of the coating composition
- organoclay at approximately 2% wt maximum
- a binding agent such as vinyl acetate copolymer, at approximately 1.5-3.0% wt
- a block copolymer dispersant with pigment affinic groups
- DMC refractory coating
- the clay is added and shear is increased to approximately 700 rpm for a blade diameter of 22 inches.
- the mixed materials form a gel after approximately 10 minutes of mixing.
- Refractory powder(s), binder, and dispersant are then added to the vessel and mixed together for approximately another 10 minutes. Blade action is ceased and the product is inspected for conformity with suitable refractory coating parameters.
- Formula D was made comprising an approximately 100% DMC carrier and zircon refractory.
- the carrier is preferably 36.2 wt of the composition.
- This coating was tested under EPA Method 24 and found to have zero measurable VOCs with a ⁇ 0.05% by weight detection limit.
- Formula D was used to spray green sand molds in a high production foundry. The green sand molds are produced and require assembly within approximately 15 minutes to meet production needs.
- the Formula D coating is preferably completely dry before assembly to avoid gas related casting defects.
- Formula D is preferred in this application because foundries typically cannot permit for additional VOCs on such lines, so traditional solvent based options are disadvantageous because they result in emission of VOCs.
- VOC-exempt ester based coatings such as Formula D
- Formula D is therefore preferred and meets all VOC-exempt emission requirements.
- the DMC based Formula D met all requirements.
- Formula D was produced and diluted to spray application Baume with DMC. Mixing properties were acceptable for this application. Spray application properties were suitable for an even coat on the molds. Several large gray and ductile iron castings (500-5,000 lb.) were poured. Casting results were substantially better than uncoated molds which resulted in significantly lower cleaning times.
- a conventional solvent based paste coating may also be diluted with t-butyl acetate to achieve a reduction in VOC emission from the coating.
- the coating was diluted to typical flood coating or dipping viscosity (properties below at Table 1) and applied to a core.
- Application properties were acceptable for flood coating. Ignition properties were sufficient for drying without excessive heat to the core.
- VOC emissions were reduced as a result of the dilution with t-butyl acetate. It is contemplated that other esters have a similar reduction of VOC emission.
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Abstract
This technology relates to refractory coatings used in metal casting by the foundry industry. Refractory coatings are often used to coat foundry cores and molds for the purpose of improving the quality of castings formed in connection with the cores or molds, particularly at the surface of the casting. Whereas traditional coatings comprise water based solvents that require excessive drying times or HAPs that emit hazardous VOCs, preferred embodiments of the present invention comprise refractory coatings having VOC-exempt ester based solvents, such as a dimethyl carbonate (DMC). Other preferred embodiments of the present invention comprise methods for reduction of VOC content in a foundry article.
Description
- This continuation application claims priority to, and the benefit of, U.S. patent application Ser. No. 17/127,340 filed Dec. 18, 2020, U.S. patent application Ser. No. 16/039,200 filed on Jul. 18, 2018, now U.S. Pat. No. 11,484,935, U.S. Provisional Patent Application Ser. No. 62/557,291 filed on Sep. 12, 2017, and U.S. Provisional Patent Application Ser. No. 62/534,082 filed on Jul. 18, 2017.
- This technology relates to refractory coatings used in metal casting by the foundry industry.
- In many respects, refractory coatings are like special paints used in metal casting. Unlike conventional paints, however, refractory coatings can withstand the high temperatures of molten metal and also act as a barrier between the molten metal and a mold into which the metal is poured for casting.
- Refractory coatings are generally comprised of a high temperature mineral, or other substance that is resistant to heat, suspended in a liquid (solvent) carrier. The coating is applied to, for example, a sand mold or core surface prior to casting. The liquid carrier is removed by evaporation, while the layer of mineral is left behind to coat the mold surface. This layer can help prevent penetration of molten metal into the sand, prevent erosion of the sand, and otherwise improve the quality of a casting surface.
- Foundries typically employ either a water based or solvent based coating. Water requires energy and equipment intensive drying, but it is environmentally friendly. Solvent based coatings can be air dried in a reduced amount of time or ignited for very short dry times. Current solvent based foundry refractory coatings comprise of isopropyl alcohol (“IPA”), ethanol, methanol, naphtha, etc. However, some of these solvent based systems comprise hazardous air pollutants (“HAPs”) and all of them comprise volatile organic compounds (“VOCs”). IPA and ethanol are the most commonly used solvent carriers in refractory coatings of the foundry industry. Such pollutants and volatile compounds are subject to intense regulation, and many foundries that use conventional solvent based coatings spend considerable time and resources permitting for the VOCs.
- Some VOC-exempt solvents such as acetone have been used in the past. However, acetone's high evaporation rate increases usage, and the low flash point introduces serious explosion and fire risks to the foundry.
- Therefore, there is an unmet need in the prior art for a solvent based refractory coating for use in the foundry industry, wherein the coating provides suitable performance characteristics, but is much safer to use and does not require additional permitting or include restrictions that accompany traditional solvent based coatings.
- To meet the needs described above, the present invention provides a partial or full replacement of refractory coating solvents with ester carriers, such as dimethyl carbonate (“DMC”) or t-butyl acetate, to form a solvent based refractory coating with reduced or no reportable HAPs or VOCs.
- In one preferred embodiment of the present invention, a refractory coating (also known as mold wash, paint, or dressing) composition is provided preferably comprising a liquid ester carrier, such as 100% DMC, a suspending agent, a binding agent, water, an additive, and a particulate refractory filler blend.
- In operation, it has been found that refractory coatings formed in accordance with a preferred embodiment of the present invention comprising DMC achieved an approximately 50%-97% reduction in reportable VOC's as compared to conventional refractory coatings. Notably, 100% VOC exempt coatings are achievable in accordance with preferred embodiments of the present invention, although some coatings formed as described herein may include trace VOCs that are introduced to the composition by the binding agent.
- As described herein, the term “carrier solvent” may comprise one or more ester carriers or a combination of one or more ester carriers with non-ester solvents.
- Examples of additives are surface active agents, such as, wetting agents, defoamers, dispersants, and rheology modifiers.
- A preferred embodiment of the present invention is:
-
- a refractory coating composition for foundry use comprising:
- a liquid carrier comprising an ester carrier, the ester carrier being provided at approximately 25% to 100% by weight of the liquid carrier and 20% to 80% by weight of the composition;
- a suspending agent provided at 2% or less by weight of the composition;
- a binder provided at approximately 1.5% to 3% by weight of the composition;
- water provided at up to approximately 2% by weight of the composition;
- one or more additives provided at approximately 2% or less by weight of the composition;
- and a particulate refractory material provided at approximately 13 to 78.5% by weight of the composition.
- An alternative preferred embodiment of the present invention is:
-
- a method for reduction of the VOC content in a foundry article, the method comprising the steps of:
- forming a foundry article;
- forming a refractory coating composition comprising a liquid carrier having an ester carrier;
- diluting the composition with a VOC-exempt solvent;
- applying the composition to the foundry article;
- drying the composition to remove the ester carrier;
- wherein the composition comprises: the ester carrier being provided at approximately 25% to 100% by weight of the liquid carrier and approximately 20% to 80% by weight of the composition; a suspending agent provided at up to approximately 2% by weight of the composition; a binder provided at approximately 1.5% to 3% by weight of the composition; water provided at up to approximately 2% by weight of the composition; one or more additives provided at up to approximately 2% by weight of the composition; and a particulate refractory material provided at approximately 13 to 78.5% by weight of the composition.
- a method for reduction of the VOC content in a foundry article, the method comprising the steps of:
- Another alternative preferred embodiment of the present invention is:
-
- A method for reduction of VOC content in a foundry article, the method comprising the steps of:
- providing a refractory coating composition having a solvent carrier that comprises VOCs; and
- diluting the composition with a VOC-exempt solvent.
-
FIG. 1 is a graphic representation of weight loss % over time in minutes (drying time) data produced from a refractory coating comprising an approximately 25/75 DMC/IPA (1:3 ratio DMC:IPA) ester carrier formulation. As shown, the data was collected at room temperature (“RT”), 35 degrees Celsius, and 49 degrees Celsius. -
FIG. 2 is a graphic representation of weight loss % over time in minutes (drying time) data produced from a refractory coating comprising an approximately 50/50 DMC/IPA ester carrier formulation. As shown, the data was collected at RT, 35 degrees Celsius, and 49 degrees Celsius. -
FIG. 3 is a graphic representation of weight loss % over time in minutes (drying time) data produced from a refractory coating comprising an approximately 75/25 DMC/IPA ester carrier formulation. As shown, the data was collected at RT, 35 degrees Celsius, and 49 degrees Celsius. -
FIG. 4 is a graphic representation of weight loss % over time in minutes (drying time) data produced from a refractory coating comprising an approximately 100% DMC ester carrier formulation. As shown, the data was collected at RT, 35 degrees Celsius, and 49 degrees Celsius. -
FIG. 5 is a graphic representation of weight loss % over time in minutes (drying time) data produced from a refractory coating comprising an approximately 100° A IPA carrier formulation. As shown, the data was collected at RT, 35 degrees Celsius, and 49 degrees Celsius. -
FIG. 6 is a graphic representation of weight loss % over time in minutes (drying time) data produced from a refractory coating comprising anSBDN 1087 base formula and various carrier solvents comprising DMC and IPA. As shown, the data was collected at RT. -
FIG. 7 is a graphic representation of weight loss % over time in minutes (drying time) data produced from a refractory coating comprising anSBDN 1087 base formula and various carrier solvents comprising DMC and IPA. As shown, the data was collected at 35 degrees Celsius. -
FIG. 8 is a graphic representation of weight loss % over time in minutes (drying time) data produced from a refractory coating comprising anSBDN 1087 base formula and various carrier solvents comprising DMC and IPA. As shown, the data was collected at 49 degrees Celsius. -
FIG. 9 is a graphic representation of weight loss % over time in minutes (drying time) data produced from a refractory coating comprising anSBDN -
FIG. 10 is a graphic representation of weight loss % over time in minutes (drying time) data produced from a refractory coating comprising anSBDN 1086 base formula and a carrier solvents comprising approximately 75/25 DMC/IPA. As shown, the data was collected at 35 degrees Celsius and 49 degrees Celsius. -
FIG. 11 is a graphic representation of weight loss % over time in minutes (drying time) data produced from a refractory coating comprising anSBDN -
FIG. 12 is a graphic representation of weight loss % over time in minutes (drying time) data produced from a refractory coating comprising a carrier solvent comprising approximately 75/25 DMC/IPA and various % wt binder. -
FIG. 13 is a graphic representation of weight loss % over time in minutes (drying time) data produced from a refractory coating comprising a carrier solvent comprising approximately 50/50 DMC/IPA and various % wt binder. -
FIG. 14 is a graphic representation of weight loss % over time in minutes (drying time) data produced from refractory coatings comprising a carrier solvent comprising either approximately 75/25 or approximately 50/50 DMC/IPA and approximately 3% binder. -
FIG. 15 is a graphic representation of weight loss % over time in minutes (drying time) data produced from refractory coatings comprising a carrier solvent comprising either approximately 75/25 or approximately 50/50 DMC/IPA and approximately 2.5% binder. -
FIG. 16 is a graphic representation of weight loss % over time in minutes (drying time) data produced from refractory coatings comprising a carrier solvent comprising either approximately 75/25 or approximately 50/50 DMC/IPA and approximately 2% binder. -
FIG. 17 is a graphic representation of weight loss % over time in minutes (drying time) data produced from refractory coatings comprising a carrier solvent comprising either approximately 75/25 or approximately 50/50 DMC/IPA and approximately 1.5% binder. -
FIG. 18 is a graphic representation of weight loss % over time in minutes (drying time) data produced from refractory coatings comprising a carrier solvent comprising approximately 100% DMC and approximately 2% binder. -
FIG. 19 is a graphic representation of weight loss (drying time) data produced from refractory coatings comprising a carrier solvent comprising either approximately 75/25 DMC/IPA or approximately 100% DMC and approximately 2% binder. - While the present invention may be susceptible to embodiment in different forms, there is described herein in detail, specific preferred embodiments with the understanding that the present disclosure is to be considered an exemplification of the principles of the invention, and is not intended to limit the invention to that described herein.
- A preferred embodiment of the present invention comprises a low to absent VOC refractory coating having performance characteristics that are comparable to conventional solvent-based coatings and a safety profile that is highly advantageous over known refractory coatings. The preferred embodiment comprises an ester carrier, such as dimethyl carbonate or t-butyl acetate, to form a solvent based refractory coating composition.
- In at least one preferred embodiment of the present invention, the ester solvent based refractory coating composition is formed as follows:
- A refractory coating (also known as mold wash, paint, or dressing) composition provided in accordance with the present invention preferably comprises a liquid ester carrier, a suspending agent, a binding agent, water, and a particulate refractory filler blend. The liquid ester carrier is preferably primarily an organic compound that is colorless, flammable, and exempt from the restrictions placed on most VOCs in the United States. The liquid ester carrier is preferably classified as a carbonate ester, with or without the presence of a secondary solvent. The suspending agent is preferably a fine-grained natural rock or soil material that comprises one or more clay minerals with traces of metal oxides and organic matter. Examples of the suspending agent include palygorskite, montmorillonite, and sepiolite. The binding agent is preferably a copolymer having a chemical affinity to the liquid ester carrier in the presence or not of a secondary binding agent such as a natural rosin. The particulate refractory filler blend preferably comprises a fine to medium size fraction, the blend preferably having an average particle size of approximately d<30 microns, wherein no more than approximately 10% by weight or volume of the total particulate refractory filler blend has a particle size of approximately d<2 microns. Examples of the filler blend include zirconium silicate (also known as zircon) and/or aluminum silicate, graphite, silica, magnesium silicates, and the like, including combinations or blends of refractories.
- In a preferred embodiment of the present invention, the liquid ester carrier is dimethyl carbonate (“DMC”). DMC has a similar flash point to IPA, and as such the light-off/burn properties of DMC are similar to IPA. Additionally, the evaporation rate of DMC is much higher than IPA or ethanol. Therefore, the drying times of refractory coatings comprising DMC are substantially less than traditional coatings comprising IPA or ethanol. This represents a significant advantage over traditional air dry applications.
- Exemplary refractory coating compositions provided in accordance with the present invention preferably comprise: (i) a carrier DMC at approximately 25-100% wt of the carrier and IPA at approximately 0-75% wt of the carrier, wherein the carrier comprises approximately 20-80% wt of the coating composition; (ii) clays at approximately 2% wt maximum of the coating composition; (iii) a binder (i.e., a vinyl acetate and vinyl laurate copolymer in ethyl acetate, the copolymer provided at approximately 50% by weight of the binder), at approximately 1.5-3.0% wt of the coating composition; (iv) water at approximately 0-2% wt of the coating composition; (v) additives at approximately 0-2% wt of the coating composition; and (vi) a particulate refractory blend at approximately 13-78.5% wt of the coating composition.
- It is contemplated that alternative liquid ester carriers may be used in refractory coating compositions provided in accordance with the present invention, including: t-butyl acetate, ethyl acetate, n-butyl acetate, allyl hexanoate, benzyl acetate, butyl butyrate, ethyl butyrate, ethyl benzoate, ethyl hexanoate, ethyl isovalerate, ethyl lactate, isobutyl acetate, isoamyl acetate, ethyl ethanoate, n-butyl oleate, 2-ethylhexyl caprate/caprylate, isopropyl myristate, methyl oleate, n-propyl acetate, 2-ethylhexyl acetate, pentyl acetate, ethylene glycol diacetate (EGDA), 2-ethylhexyl acetate, isobutyl isobutyrate (IBIB), and propyl acetate.
- The aforementioned ester carriers may also be used as VOC-exempt solvents for dilution of refractory coating compositions prior to application of the composition to a foundry article.
- In another preferred embodiment of the present invention, the liquid ester carrier is t-butyl acetate.
- For example, an alternative refractory coating composition provided in accordance with the present invention preferably comprises: (i) a carrier t-butyl acetate at approximately 52% wt of the carrier and IPA/Methanol/VM&P Naphtha at approximately 7.5% wt of the carrier; (ii) clays at approximately 1.7% wt maximum; (iii) a phenolic resin at approximately 0.4% wt; (iv) water at approximately 0.9% wt; and (vi) a zircon refractory blend at approximately 66% wt. Prior to application to a mold or core during production, this formulation is preferably diluted with t-butyl acetate to approximately 37% solids.
- To form a refractory coating provided in accordance with the present invention, DMC, IPA, and water are first added to a mixing vessel at medium shear. Then, attapulgite clay (also known as palygorskite) is added and shear is increased to approximately 700 rpm for a blade diameter of 22 inches. The mixed materials form a gel after approximately 10 minutes of mixing. Refractory powders, such as a zircon blend, binder, additives, and remaining liquids if available are then added to the vessel and mixed together for approximately another 10 minutes. Blade action is ceased and the product is inspected for conformity with suitable refractory coating parameters.
- In a preferred embodiment of the present invention, a method of using a refractory coating as described herein and provided in accordance with the present invention is as follows.
- A refractory coating provided in accordance with the present invention may be applied to a foundry article, such as molds and cores, in variable ways due to variable substrates with which the coating is used, and also variable requirements of the user. The refractory coating of the present invention may be provided in a concentrated form. In all cases, the coating is applied to provide a protective barrier between a liquid metal and the mold or core.
- Before application to the mold or core, the refractory coating is preferably diluted with an appropriate VOC-exempt solvent until the required application viscosity for the coating is achieved. Coatings of the present invention may also be applied absent any dilution, such as in a concentrated form, depending on the application and intended use of the coating. In a preferred embodiment of the present invention, the solvent is a liquid ester carrier comprising DMC. Once at the desired viscosity, the coating can be applied to the mold or core by several methods, including dip, spray, flood (flow coat), brush, swab, and mitt application methods. Dip application includes an immersing of the mold or core into the coating. This application allows full contact of the coating to all areas. Spray application is a blowing of the coating through the air in the form of tiny drops to form a coating layer on the surface of the mold or core. Flood application is a pumping of the coating through a hose to splash or flood onto the mold or core. The excess coating is collected and run again through the pump. Brush, swab, and mitt applications all use a tool (such as a paint brush, horse hair swab, or cotton mitt) soaked in the coating and contacted with the mold or core to apply the coating. Although these are the primary methods of applying a coating to a mold or core in the foundry industry, the invention is not limited to these applications, as will be appreciated by one of ordinary skill in the art.
- In all applications, the wet refractory coating provided in accordance with the present invention is allowed to dry or ignited to remove the ester carrier. It is important to fully remove the ester carrier from the coating layer. If residual ester carrier remains, the ester carrier can be a source of gas which can cause defects in the metal casting.
- In production, it has been found that refractory coatings formed in accordance with a preferred embodiment of the present invention comprising DMC achieved an approximately 50% -97% reduction in reportable VOC's as compared to conventional refractory coatings.
- For example, a first production test includes a pouring of high alloy iron and high alloy steel castings with pouring weights of approximately 2,000-11,800 lb. Castings were poured using a vacuum process where a baseline refractory coating is sprayed onto a vacuum process mold film. A baseline coating comprising an IPA carrier was compared to two experimental refractory coating formulations provided in accordance with the present invention. The experiment coatings, Formula A and Formula B, both comprised an ester carrier and employed an approximately 1:1 ratio of DMC:IPA. The difference between Formula A and Formula B was the choice of binder employed therein. Formula A used a natural Binder A, such as gum rosin, and Formula B used a synthetic Binder B, such as vinyl acetate copolymer. Spray application of the Formula A and Formula B coatings was satisfactory as required thicknesses were developed. Dry times for the Formula A and Formula B coatings averaged 2 minutes while the baseline IPA coating dried in an average of 3 minutes and 30 seconds.
- The molds were then filled with sand. The experimental formulas both exhibited sufficient sand erosion resistance. Once the mold was stripped from the pattern, it was observed that the baseline (IPA carrier coating) and Formula A exhibited similar coating cracking, while Formula B showed improved resistance to cracking of the coating layer. Per a practice appreciated by those of ordinary skill in the art, metal was then poured into the molds, the molds were allowed to cool, and castings were shot blasted before review. Both experimental Formulas A and B displayed acceptable casting performance. Moreover, both experimental coating displayed acceptable properties to produce a commercially viable casting.
- The advantages of the experimental Formula A and B coatings include, but are not limited to:
- Formula A: Approximately a 50% reduction in reportable VOCs and reduced drying time as compared to conventional refractory coatings.
- Formula B: Approximately a 50% reduction in reportable VOCs, reduced drying time, and improved resistance to coating layer cracking as compared to conventional refractory coatings.
- In a second production test, high alloy iron and high alloy steel castings were poured with pouring weights of approximately 2,000-11,800 lb. Castings were poured using the vacuum process where a refractory coating is sprayed onto the vacuum process mold film. A baseline coating comprising an IPA carrier was compared to two experimental refractory coating formulations provided in accordance with the present invention. An experimental formulation also formed in accordance with a preferred embodiment of the present invention, Formula C, was tested utilizing an ester carrier. Formula C employed an approximately 100% DMC carrier with the synthetic Binder B described above. Spray application of the Formula C coating was satisfactory as required thicknesses were developed. Dry times for Formula C averaged 1 minute and 30 seconds while the baseline IPA coating dried in an average of 3 minutes and 30 seconds.
- The molds were then filled with sand. Formula C exhibited sufficient sand erosion resistance. Once the mold was stripped from the pattern, it was observed that Formula C showed improved resistance to cracking of the refractory coating layer. Per a practice appreciated by those of ordinary skill in the art, metal was poured, the molds were allowed to cool, and castings were shot blasted before review. Formula C displayed acceptable casting performance. Moreover, Formula C displayed acceptable properties to produce a commercially viable casting.
- The advantages of the experimental Formula C coating include, but are not limited to:
- Formula C: An approximately 97+% reduction in reportable VOCs, reduced drying time, and improved resistance to coating layer cracking as compared to conventional refractory coatings.
- In another preferred embodiment of the present invention, a refractory coating was once again produced with a liquid ester carrier, a suspending agent, a binding agent, a dispersant, and a particulate refractory filler blend. The liquid ester carrier in this embodiment is dimethyl carbonate. The suspending agent is preferably a nanoclay, and more specifically an organo-modified clay. The nanoclay component is preferably montmorillonite, a 2-to-1 layered smectite clay mineral with a platey structure, and a surface modified to become organophilic with increased compatibility with the solvent of choice. The binding agent is preferably a copolymer having a chemical affinity to the liquid ester carrier. The dispersant agent is preferably an aromatic-free solution of a high molecular weight block copolymer with pigment affinic groups. The particulate refractory filler blend preferably comprises a fine to medium size fraction, the blend preferably having a medium particle size of approximately d<30 microns, wherein no more than approximately 10% by weight or volume of the total particulate refractory filler blend has a particle size of approximately d<2 microns.
- Another exemplary refractory coating compositions provided in accordance with the present invention preferably comprise: (i) a carrier DMC at approximately 100% wt of the carrier, wherein the carrier comprises approximately 28.5-32.5% wt of the coating composition; (ii) organoclay at approximately 2% wt maximum; (iii) a binding agent, such as vinyl acetate copolymer, at approximately 1.5-3.0% wt; (iv) a block copolymer dispersant with pigment affinic groups at approximately 0-0.5% wt; and (v) a zircon refractory blend at approximately 66% wt.
- To produce a refractory coating provided in accordance with the present invention, DMC, is added to a mixing vessel at medium shear. Then, the clay is added and shear is increased to approximately 700 rpm for a blade diameter of 22 inches. The mixed materials form a gel after approximately 10 minutes of mixing. Refractory powder(s), binder, and dispersant are then added to the vessel and mixed together for approximately another 10 minutes. Blade action is ceased and the product is inspected for conformity with suitable refractory coating parameters.
- In another refractory coating composition formed in accordance with the present invention, Formula D was made comprising an approximately 100% DMC carrier and zircon refractory. In this example, the carrier is preferably 36.2 wt of the composition. This coating was tested under
EPA Method 24 and found to have zero measurable VOCs with a <0.05% by weight detection limit. In production, Formula D was used to spray green sand molds in a high production foundry. The green sand molds are produced and require assembly within approximately 15 minutes to meet production needs. The Formula D coating is preferably completely dry before assembly to avoid gas related casting defects. Formula D is preferred in this application because foundries typically cannot permit for additional VOCs on such lines, so traditional solvent based options are disadvantageous because they result in emission of VOCs. Water based coatings would fit within the permitted standards for VOC emission, but these types of coatings will not dry within the required time before assembly (i.e., approximately 15 minutes or less). Although an acetone based coating would fit both dry time and permitting parameters, the low flash point deems this technology too much of a fire and explosion risk to utilize. VOC-exempt ester based coatings, such as Formula D, are therefore preferred and meets all VOC-exempt emission requirements. Specifically, the DMC based Formula D met all requirements. Formula D was produced and diluted to spray application Baume with DMC. Mixing properties were acceptable for this application. Spray application properties were suitable for an even coat on the molds. Several large gray and ductile iron castings (500-5,000 lb.) were poured. Casting results were substantially better than uncoated molds which resulted in significantly lower cleaning times. - A conventional solvent based paste coating may also be diluted with t-butyl acetate to achieve a reduction in VOC emission from the coating. The coating was diluted to typical flood coating or dipping viscosity (properties below at Table 1) and applied to a core. Application properties were acceptable for flood coating. Ignition properties were sufficient for drying without excessive heat to the core. Additionally, and importantly, VOC emissions were reduced as a result of the dilution with t-butyl acetate. It is contemplated that other esters have a similar reduction of VOC emission.
-
TABLE 1 Viscosity, cP 500 SOLIDS % 40 BAUME, deg 37
Claims (13)
1. A refractory coating composition for foundry use comprising:
a liquid carrier comprising an ester carrier, the ester carrier being provided at approximately 25% to 100% by weight of the liquid carrier and 25% to 32.5% by weight of the composition;
a binder;
water provided at up to approximately 2% by weight of the composition;
one or more additives provided at up to approximately 2% by weight of the composition; and
a particulate refractory material provided at approximately 13 to 78.5% by weight of the composition.
2. The refractory coating composition of claim 1 , wherein the binder is provided at approximately 0.4% to 3% by weight of the composition.
3. The refractory coating composition of claim 1 , wherein the ester carrier is t-butyl acetate.
4. The refractory coating composition of claim 1 , wherein the ester carrier is a carbonate ester.
5. The refractory coating composition of claim 4 , wherein the carbonate ester is dimethyl carbonate.
6. The refractory coating composition of claim 5 , further comprising a suspending agent provided at 2% or less by weight of the composition.
7. The refractory coating composition of claim 6 , wherein the suspending agent is an organoclay, the binder is a copolymer, and the particulate refractory material comprises zircon, aluminum silicate, silica, alumina, or a combination of the foregoing particulate refractory materials.
8. The refractory coating composition of claim 4 , wherein the binder is a vinyl acetate and vinyl laurate copolymer provided at approximately 50% by weight of the binder.
9. The refractory coating composition of claim 4 , wherein the additive is a wetting agent, defoamer, dispersant, or a rheology modifier.
10. The refractory coating composition of claim 4 , wherein the particulate refractory material is a zirconium silicate flour having an average particle size of approximately d<30 microns, and wherein no greater than approximately 10% by weight or volume of the particulate refractory material has a particle size of approximately d<2 microns.
11. The refractory coating composition of claim 4 , the liquid carrier further comprising a volatile organic carrier.
12. The refractory coating composition of claim 11 , wherein the volatile organic carrier is isopropyl alcohol.
13. The refractory coating composition of claim 4 , wherein the binder is a natural rosin or a hydrocarbon resin.
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US18/222,244 US20230372995A1 (en) | 2017-07-18 | 2023-07-14 | Compositions and methods for refractory coatings with ester carriers |
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US16/039,200 US11484935B2 (en) | 2017-07-18 | 2018-07-18 | Compositions and methods for refractory coatings with ester carriers |
US17/127,340 US11712736B2 (en) | 2017-07-18 | 2020-12-18 | Compositions and methods for refractory coatings with ester carriers |
US18/222,244 US20230372995A1 (en) | 2017-07-18 | 2023-07-14 | Compositions and methods for refractory coatings with ester carriers |
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US3137046A (en) | 1960-10-24 | 1964-06-16 | Int Minerals & Chem Corp | Foundry sand composition and method of preparation |
US3115414A (en) * | 1960-11-28 | 1963-12-24 | Gen Motors Corp | Foundry mold coating |
CA1122737A (en) * | 1978-02-21 | 1982-04-27 | Robert A. Laitar | Binder compositions containing phenolic resins and organic phosphate and/or carbonate solvents |
US4506041A (en) * | 1982-07-05 | 1985-03-19 | Hitachi, Ltd. | Powdered binder for mold-making and a process for preparing a mold by using the same |
DE69411203T2 (en) * | 1993-02-03 | 1998-10-29 | Asahi Glass Co Ltd | Monolithic refractory powder mix |
GB9816080D0 (en) * | 1998-07-24 | 1998-09-23 | Foseco Int | Coating compositions |
CA2428588A1 (en) | 2000-11-10 | 2002-08-22 | Albert I. Yezrielev | Environmentally preferred fluids and fluid blends |
US7759268B2 (en) * | 2006-11-27 | 2010-07-20 | Corning Incorporated | Refractory ceramic composite and method of making |
DE102007020586A1 (en) * | 2007-05-02 | 2008-11-06 | Ashland-Südchemie-Kernfest GmbH | Coating materials for casting molds and cores to avoid reaction gas defects |
US20100099806A1 (en) | 2008-10-22 | 2010-04-22 | E. I. Du Pont De Nemours And Company | Process for Producing Dimethyl Carbonate Containing Compositions |
KR100928140B1 (en) | 2009-07-09 | 2009-11-25 | (주)부영산업 | An environmental-friendly varnish composition and a method thereof |
CN102471632B (en) * | 2009-07-22 | 2014-12-03 | 巴斯夫欧洲公司 | Aqueous polymer dispersion as a binding agent for plasters and coating materials having improved fire behavior |
PT2364795E (en) * | 2010-03-08 | 2012-09-19 | Foseco Int | Foundry coating composition |
US9029475B2 (en) | 2010-04-29 | 2015-05-12 | Axalta Coating Systems Ip Co., Llc | Process for producing a low VOC coating composition and use thereof |
WO2012014154A1 (en) * | 2010-07-30 | 2012-02-02 | Basf Se | Catalyst for oxidation of o-xylene and/or naphthalene to phthalic anhydride |
CN103596896A (en) * | 2011-05-31 | 2014-02-19 | 费罗公司 | Low volatile organic component medium |
DE102011115024A1 (en) * | 2011-10-07 | 2013-04-11 | Ask Chemicals Gmbh | Coating compositions for inorganic casting molds and cores comprising formic acid esters and their use |
US8961680B2 (en) * | 2013-03-08 | 2015-02-24 | Tbf Environmental Technology Inc. | Solvent formulations |
AU2015259768B2 (en) * | 2014-05-16 | 2019-03-14 | Vesuvius Usa Corporation | Refractory binder system |
US10442899B2 (en) * | 2014-11-17 | 2019-10-15 | Silbond Corporation | Stable ethylsilicate polymers and method of making the same |
KR101588826B1 (en) | 2014-12-08 | 2016-03-07 | 김진희 | Eco-friendly inorganic type antibacterial spray compositions for galvanized iron sheets Duct with high consistency and antibacterial function |
DE102016200491A1 (en) | 2016-01-15 | 2017-07-20 | Robert Bosch Gmbh | Micromechanical spring for an inertial sensor |
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US11484935B2 (en) | 2022-11-01 |
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EP3655177A4 (en) | 2020-12-02 |
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