AU2015329756A1 - PH neutral deruster composition - Google Patents
PH neutral deruster composition Download PDFInfo
- Publication number
- AU2015329756A1 AU2015329756A1 AU2015329756A AU2015329756A AU2015329756A1 AU 2015329756 A1 AU2015329756 A1 AU 2015329756A1 AU 2015329756 A AU2015329756 A AU 2015329756A AU 2015329756 A AU2015329756 A AU 2015329756A AU 2015329756 A1 AU2015329756 A1 AU 2015329756A1
- Authority
- AU
- Australia
- Prior art keywords
- composition according
- deruster composition
- deruster
- surfactant
- chelating agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 178
- 230000007935 neutral effect Effects 0.000 title abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 69
- 239000002184 metal Substances 0.000 claims abstract description 69
- 239000002738 chelating agent Substances 0.000 claims abstract description 59
- 239000004094 surface-active agent Substances 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims abstract description 30
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims description 25
- 239000006172 buffering agent Substances 0.000 claims description 14
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical group [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 8
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 6
- 150000003973 alkyl amines Chemical class 0.000 claims description 5
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims description 5
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical group C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- WDJHALXBUFZDSR-UHFFFAOYSA-N acetoacetic acid Chemical compound CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 claims description 4
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000176 sodium gluconate Substances 0.000 claims description 4
- 235000012207 sodium gluconate Nutrition 0.000 claims description 4
- 229940005574 sodium gluconate Drugs 0.000 claims description 4
- ITRHZTGVVSWIDC-UHFFFAOYSA-N 11-methyl-1-(11-methyldodecoxy)dodecane Chemical compound CC(C)CCCCCCCCCCOCCCCCCCCCCC(C)C ITRHZTGVVSWIDC-UHFFFAOYSA-N 0.000 claims description 3
- 235000010469 Glycine max Nutrition 0.000 claims description 3
- 244000068988 Glycine max Species 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 3
- 239000008139 complexing agent Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- GNBVPFITFYNRCN-UHFFFAOYSA-M sodium thioglycolate Chemical compound [Na+].[O-]C(=O)CS GNBVPFITFYNRCN-UHFFFAOYSA-M 0.000 claims description 3
- 229940046307 sodium thioglycolate Drugs 0.000 claims description 3
- 229940061605 tetrasodium glutamate diacetate Drugs 0.000 claims description 3
- UZVUJVFQFNHRSY-OUTKXMMCSA-J tetrasodium;(2s)-2-[bis(carboxylatomethyl)amino]pentanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC[C@@H](C([O-])=O)N(CC([O-])=O)CC([O-])=O UZVUJVFQFNHRSY-OUTKXMMCSA-J 0.000 claims description 3
- ZBFZBSPHMMXVMQ-UHFFFAOYSA-L O.O.O.O.O.O.N.S(=O)(=O)([O-])[O-].[Fe+2] Chemical compound O.O.O.O.O.O.N.S(=O)(=O)([O-])[O-].[Fe+2] ZBFZBSPHMMXVMQ-UHFFFAOYSA-L 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- 230000008719 thickening Effects 0.000 claims 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical group OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims 1
- 229940080258 tetrasodium iminodisuccinate Drugs 0.000 claims 1
- GYBINGQBXROMRS-UHFFFAOYSA-J tetrasodium;2-(1,2-dicarboxylatoethylamino)butanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC(C([O-])=O)NC(C([O-])=O)CC([O-])=O GYBINGQBXROMRS-UHFFFAOYSA-J 0.000 claims 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 40
- 238000004140 cleaning Methods 0.000 abstract description 12
- 238000009472 formulation Methods 0.000 description 22
- 239000000243 solution Substances 0.000 description 22
- 238000007654 immersion Methods 0.000 description 21
- 239000000047 product Substances 0.000 description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 17
- 229910052802 copper Inorganic materials 0.000 description 17
- 239000010949 copper Substances 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 238000005260 corrosion Methods 0.000 description 16
- 230000007797 corrosion Effects 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 13
- 229910001369 Brass Inorganic materials 0.000 description 11
- 239000010951 brass Substances 0.000 description 11
- -1 ferrous metals Chemical class 0.000 description 11
- 150000002739 metals Chemical class 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 10
- 239000002736 nonionic surfactant Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 6
- 239000000872 buffer Substances 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000002280 amphoteric surfactant Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical group NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229940071127 thioglycolate Drugs 0.000 description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 4
- 239000000080 wetting agent Substances 0.000 description 4
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical class CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- 244000060011 Cocos nucifera Species 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 235000013980 iron oxide Nutrition 0.000 description 3
- 231100000053 low toxicity Toxicity 0.000 description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 2
- VKZRWSNIWNFCIQ-UHFFFAOYSA-N 2-[2-(1,2-dicarboxyethylamino)ethylamino]butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NCCNC(C(O)=O)CC(O)=O VKZRWSNIWNFCIQ-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
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- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 2
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- 238000005282 brightening Methods 0.000 description 2
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- 125000002843 carboxylic acid group Chemical group 0.000 description 2
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- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 2
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- 229930182478 glucoside Natural products 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
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- 239000000463 material Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
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- VCVKIIDXVWEWSZ-YFKPBYRVSA-N (2s)-2-[bis(carboxymethyl)amino]pentanedioic acid Chemical compound OC(=O)CC[C@@H](C(O)=O)N(CC(O)=O)CC(O)=O VCVKIIDXVWEWSZ-YFKPBYRVSA-N 0.000 description 1
- FTUXVMVEKYLKGE-WECFPGDBSA-N (z)-but-2-enedioic acid;[(2s,3s)-8-chloro-5-[2-(dimethylamino)ethyl]-2-(4-methoxyphenyl)-4-oxo-2,3-dihydro-1,5-benzothiazepin-3-yl] acetate Chemical compound OC(=O)\C=C/C(O)=O.C1=CC(OC)=CC=C1[C@H]1[C@@H](OC(C)=O)C(=O)N(CCN(C)C)C2=CC=C(Cl)C=C2S1 FTUXVMVEKYLKGE-WECFPGDBSA-N 0.000 description 1
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- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229960002989 glutamic acid Drugs 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000004224 potassium gluconate Substances 0.000 description 1
- 235000013926 potassium gluconate Nutrition 0.000 description 1
- 229960003189 potassium gluconate Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- DQINEZCYJSFZBL-UHFFFAOYSA-M sodium;3-[2-carboxyethyl(3-decoxypropyl)amino]propanoate Chemical group [Na+].CCCCCCCCCCOCCCN(CCC(O)=O)CCC([O-])=O DQINEZCYJSFZBL-UHFFFAOYSA-M 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- DTXLBRAVKYTGFE-UHFFFAOYSA-J tetrasodium;2-(1,2-dicarboxylatoethylamino)-3-hydroxybutanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)C(O)C(C([O-])=O)NC(C([O-])=O)CC([O-])=O DTXLBRAVKYTGFE-UHFFFAOYSA-J 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
- C23G1/26—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions using inhibitors
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/24—Cleaning or pickling metallic material with solutions or molten salts with neutral solutions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
- C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/08—Iron or steel
- C23G1/088—Iron or steel solutions containing organic acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/16—Metals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Molecular Biology (AREA)
- Health & Medical Sciences (AREA)
- Detergent Compositions (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The present invention relates to a deruster composition of neutral pH which is designed to remove corroded metal from metal surfaces. The deruster composition can be used to remove rust or tarnish, and can also be referred to as a metal brightener. The deruster composition has a pH in the range of 5 to 8, where the composition comprises: water; at least one surfactant and at least one chelating agent; where at least one surfactant is an alkyl polyglycoside and at least one chelating agent is an aminopolycarboxylic acid. The ability to operate within a neutral pH range reduces damage to the metal during cleaning. In addition, hazards to operating personnel are minimised.
Description
pH Neutral Deruster Composition
The present invention relates to a deruster composition of neutral pH which is designed to remove corroded metal, including rust or tarnish, from metal surfaces.
Metals and metallic materials can react with chemicals in the surrounding environment, altering the surface of the material in a process known as corrosion. Oxygen can be obtained from air or water, both of which are often present in the environment surrounding metallic materials. Oxygen readily reacts with ferrous metals to form oxides such as iron oxide, commonly known as rust. Iron oxides such as rust and magnetite are well known, however, sulphides, chlorides, phosphates, chromate films and many other contaminants can also be formed by corrosion.
Surface rust is flaky and friable and provides no protection to the underlying metal. Eventually, over time, an entire metal object can be converted to rust. Rust has less mechanical strength and an object which has converted to rust can easily disintegrate. This can have a serious detrimental impact on mechanical structures, unless they are treated to remove or prevent rust.
Another form of corrosion, which is usually caused by oxidation of the metal, is commonly known as tarnish. Tarnish changes the appearance of the metal, such that the surface of the metal appears dull and blackened. Although formed in a similar manner to rust, tarnish is self-limiting and only affects the top few layers of the metal. Tarnish can occur on non-ferrous metals, such as copper, brass, silver and other similar metals. Tarnish is generally not flaky or friable, and does not compromise the strength of the metal article. However, the appearance and reflective qualities of the metal are impeded by the layer of tarnish.
Products are available which are used to remove the deposits formed by corrosion, such as rust or tarnish, once the rust or corrosion has occurred. The corroded metal parts can be soaked in a rust removal solution, or the solution can be sprayed or otherwise applied to the part. These rust removal solutions or products are generally liquid formulations and are commonly known in the industry as "deruster" compositions or formulations. Several deruster products require elevated temperatures in order to dissolve the deposits from the metals. One of the problems with existing rust removal products is that the solutions which are capable of dissolving the rust are so corrosive that they tend to damage the surface which is being cleaned.
Existing rust removal products currently on the market rely predominantly on one of two methods. The first method involves acidic products based generally, but not exclusively, on hydrochloric acid and phosphoric acid. The acid reacts with the metal oxide and solubilises it. Unfortunately, the acid also attacks the base metal generating or evolving hydrogen gas. The acid used for the treatment is corrosive to the skin and eyes. The acid produces corrosive gases or fumes which attack the surrounding equipment. The second method involves the use of highly alkaline products, which are generally caustic based. Most alkaline deruster formulations have lower levels of gas evolution.
Typically, after the application of a derusting product the cleaned metal surface will rapidly react with oxygen to form a new layer of oxidised material in a process known as "flash rusting". Flash rusting is a common occurrence after cleaning with an acidic deruster formulation due to the sudden availability of metal surface in a reactive state. In some cases, it is encouraged after cleaning, as a thin layer of oxidised metal can protect the underlying metal from further oxidation. However, the occurrence of flash rusting can make it difficult to apply products (such as paint or rust prevention products) to the metal after cleaning.
There are several challenges to be faced when formulating a deruster composition. As well as preventing excessive stripping of the metal beyond the rust deposit, once the metallic ions from the rust have been dissolved into a solution, the ions need to be kept in solution and washed away. The metal parts which are being cleaned may also be contaminated with grease, oil or other dirt and these contaminants will also need to be kept in suspension or dissolved into the solution.
One of the main components of a deruster composition is the chelating agent which is used to dissolve the rust. Chelating agents are also known as complexing agents, or sequestrants, and are used to bind metal ions in solution. Chelating agents can be water soluble and can therefore be used in aqueous solutions. Chelation describes a particular way that ions and molecules are bound to metal ions. Chelating agents are chemicals which react with metals to improve their general stability and likelihood of bonding with other metals or chemicals. The metal that remains is known as a "chelate". Most metals have chemical structures that closely resemble chains, but chelating agents join the ends in order to form a ring, known as a ligand. This ring structure makes the ions more stable and helps them move with greater ease through a range of different environments. The chelate effect describes the enhanced affinity of chelating ligands for a metal ion compared to the affinity of a collection of similar non-chelating ligands for the same metal. Traditionally, many chelants are phosphonate based.
Chelating agents can form soluble complexes with metal ions in the rinse water thus preventing the formation of metal precipitates. By forming water soluble metal complexes, the metal from the corroded or rusted parts can be easily removed and rinsed away.
Surfactants can have multiple uses in a deruster composition. The purpose of surfactants in general can include the following; to act as a dispersing agent, to reduce surface tension, to boost foam formation, to aid emulsion formation and stabilisation, and to act as a wetting agent. In a deruster composition one or more surfactants can be added to improve surface wetting of the metal oxide, to assist with the lifting of contamination from the surface of the metal to be cleaned, to assist in the degreasing of metal parts, and/or to assist with maintaining oil and particulates of dirt in suspension. Improving the surface wetting of the metal oxide increases the penetration of the deruster composition into any metal oxide deposits. This reduces the time taken to dissolve the iron oxides, which can be particularly important for any larger encrustations on the metal surface.
Surfactants are broadly divided into the following categories: cationic, anionic, non-ionic, and amphoteric. There are a number of different types of non-ionic surfactants which are suitable for use in deruster compositions.
Non-ionic surfactants, particularly nitrogenated non-ionic surfactants, are capable of providing anti-corrosion effects as they have a partially cationic character. These surfactants exhibit good foaming properties, which can be useful for flotation of debris. Non-ionic surfactants do not dissociate in aqueous solutions, and are not affected by water pH or water hardness. Examples of non-ionic surfactants include ethyoxylated linear alcohols, ethoxylated alkyl phenols, fatty acid esters, amine and amide derivatives, alkylpolyglucosides, ethyleneoxide copolymers, propyleneoxide copolymers, polyalcohols, ethoxylated polyalcohols, thiols (mercaptans) and derivatives and nitrogenated non-ionic surfactants. This group further includes imidazoles and imides, sorbitan esters (such as SPAN®) and ethoxylated sorbitan (TWEEN® and equivalents).
The present invention provides a deruster composition with improved biodegradability whilst enabling operation within a neutral pH range. This reduces the damage caused to the metal parts being cleaned whilst also limiting the operational hazards. The deruster composition can also act as a corrosion removal agent for other forms of corrosion such as tarnish.
The deruster composition of the present invention can comprise water, one or more chelating agents, one or more surfactants, optionally one or more buffering agents, optionally one or more solvents and optionally a salt containing ferrous ions. The components are balanced in such a way as to form a pH neutral composition.
Detailed Description
According to the present invention there is provided a deruster composition with a pH in the range of 5 to 8, comprising at least one surfactant, and at least one chelating agent; where at least one surfactant is an alkyl polyglycoside and where at least one chelating agent is an aminopolycarboxylic acid; and water. Preferably, a second chelating agent may be provided. The second chelating agent can be another aminopolycarboxylic acid, a phosphonate based chelating agent, or an alternative chelating agent such as glycolic acid.
The deruster composition can be used for the removal of corrosion, including the removal of rust or tarnish from a metallic surface. When the deruster composition is used to remove tarnish, it can also be referred to as a metal brightener or tarnish remover. The tarnish remover is particularly suitable for removing tarnish from transition metals and their alloys. The tarnish remover has been found to be very effective for the removal of tarnish from copper and its alloys, including brass and bronze. The deruster composition can also act as a corrosion inhibitor for metals.
The results of using example deruster compositions prepared in accordance with the present invention are illustrated with reference to the accompanying photographs, in which:
Figure 1 comprises a set of photographs of a panel before (left-hand side) and after (right-hand side) partial immersion in a deruster composition according to this invention,
Figure 2 is a photograph of a chain before immersion in a deruster composition according to this invention,
Figure 3 is a photograph of a chain after immersion in a deruster composition according to this invention,
Figure 4 is a photograph of a strip of copper, the end of which has been partially immersed in a deruster composition according to this invention.
Figure 5 is a photograph of a strip of copper, the end of which has been partially immersed in a deruster composition according to this invention.
Figure 6 is a photograph of copper tubing, the majority of which has been immersed in a deruster composition according to this invention.
Figure 7 is a photograph of a brass object, which has been partially immersed in a deruster composition according to this invention.
Figure 8 is a photograph of a number of iron pipe and iron bar sections which have been partially immersed in different deruster compositions according to this invention.
Chelating agents
In a deruster composition of the present invention, at least one of the chelating agents is an aminopolycarboxylic acid. Aminopolycarboxylic acids are biodegradable chelating agents. The biodegradable ligands contain a basic nitrogen atom or two atoms with an electron pair capable of interacting with metal ions and acidic carboxylic acid groups capable of coordinating metal ions through the oxygen. The biodegradable quality of these chelating agents represents a huge step forward over conventional chelating agents, as they are more resistant to wastewater treatment and purification through conventional physicochemical and biological treatment methods. As environmental protection issues have become more prominent, legislation on chelating agents has become more rigorous.
Aminopolycarboxylic acids are phosphate-free and examples from this group of chelating agents include tetrasodium 3-hydroxy-2,2'-iminodisuccinate (HIDS), ethylenediamine-N,N'-disuccinic acid (EDDS), N-(l,2-dicarboxyetyhl)-D,L-aspartic acid (IDS) (also known as iminodisuccinic acid), N,N-bis(carboxymethyl)glutamic acid (GLDA, also known as tetrasodium glutamate diacetate), and methylglycin diacetic acid (MGDA).
Tetrasodium glutamate diacetate (GLDA) is a readily biodegradable chelate based on L-glutamic acid. The manufacturers of GLDA claim that it performs better than conventional chelating agents such as EDTA and NTA for hard surface cleaning, and is more effective as a chelating agent than phosphonate-based chelating agents. GLDA is marketed as Dissolvine ® GL by Akzo Nobel N.V. It has high solubility over a wide pH range. It is made from a natural and renewable raw material, a waste product from sugar refining. It therefore has a small ecological footprint.
Tests have shown that iminodisuccinic acid (IDS) and complexes formed from IDS are also very biodegradable. IDS has demonstrated good stability over a wide range of pH values and is able to form complexes with heavy metal ions.
Methylglycin diacetic acid (MGDA) is also known as glycine-N,N-diacetic acid. The developers of methylglycin diacetic acid have conducted long-term aquatic toxicology studies which have provided improved results over conventional biodegradable chelating agents (such as nitrilotriacetic acid (NTA)). The complexes formed by MGDA have been shown to have a high stability over a wide range of pH and temperatures. MGDA is currently manufactured by BASF The Chemical Company under the brand name Trilon®, and is available as an aqueous solution of 40wt%.
Another example of a suitable chelating agent for use in a deruster composition is a carboxylic acid. Examples of carboxylic acids include glycolic acid, thioglycolate, thioglycolic acid (TGA), also known as mecaptoacetic acid. Glycolic acid is a type of carboxylic acid and is the first member of the series of alpa-hydroxy carboxylic acids. It has both acid and alcohol functionality. It is also readily biodegradable and has low toxicity.
Another suitable chelating agent may be sodium thioglycolate. Experimental results have shown that thioglycolate can boost the longevity of the deruster composition. A solution containing thioglycolate is self-indicating; undergoing a colour change in the presence of the ions of iron, molybdenum, silver and tin in particular.
Another chelating agent that can be used in the deruster composition is sodium gluconate. This is formed from the sodium salt of gluconic acid. It is non-toxic and biodegradable (98% after 2 days). It forms stable chelates with calcium, iron, copper, aluminium and other heavy metals. Gluconates such as potassium and sodium gluconate can act as dual purpose chelating agents and wetting agents.
Conventionally, phosphonate based compounds have been used as the chelating agents for rust cleaning applications. A phosphonate metal chelant includes any compound that contains a phosphonate functional group and a second functional group capable of coordinating to a metal ion, e.g. a second phosphonate group, a carboxylic acid group, or an alcoholic group. Examples of phosphonate chelants include polyphosphonic acid, or the alkali metal or amine salt or the ammonium salt of this acid.
Specific examples of phosphonate chelants include l-hydroxyethylidene-l,l-diphosphonic acid (HEDP) and the salts thereof, which include an alkali metal salt, an amine salt, an ammonium salt or combinations thereof. Examples include, but are not limited to; amino tri(methylene-phosphonic acid), hexamethylenediamine tetra(methylene-phosphonic acid), 2-phosphonobutane-l,2,4-tricarboxylic acid, ethylenediamine tetra(methylene-phosphonic acid), ethylenediamine tetra(methylene-phosphonic acid), diethylenetriamine penta(methylene-phosphonic acid), hydroxymethlphosphonic acid, amino (methylenephosphonic acid), iminobis (methylenephosphonic acid), nitrilotris (methylenephosphonic acid), ethylenedintrilotetrakis (methylenephosphonic acid), diethylenetrinitrilopentakis (methylene-phosphonic acid), or salts thereof. Phosphonate chelants are often supplied as aqueous solutions.
Surfactants
To improve the surface cleaning properties of the deruster composition, the composition further includes an alkyl polyglygoside. Alkyl polyglycosides (APGs) and alkyl polyglucosides (derived from glucose) are a class of non-ionic surfactants which are commonly used in household and industrial applications. A commercially available example of alkyl glucoside is Glucopon® 215, which is supplied in aqueous solution. Alkyl glucoside is stable in caustic and saline solutions. It has good wetting and dispersing properties which makes it ideal for hard surface cleaning. It demonstrates excellent solubilising properties in highly concentrated surfactant solutions. It can be used as a coupling agent in concentrated surfactant systems and in the presence of salt and alkalis as it is compatible with other surfactants. Alkyl polyglycoside has no phase inversion temperature and so can be used over a wide temperature range.
Amine-based solvents can also act as surfactants in a deruster composition. Including an alkylamine (particularly soya alkylamines) in the deruster composition has resulted in improved cleaning and has helped to prevent flash rusting after the rinse step. Ethoxylated aliphatic amine surfactants such as diethoxylated cocoamines or diethoxylated soyamines, for example, have been found to be useful for rust inhibition. Soya alkylamines such as Bis(2-hydroxylethyl)soyaalkylamine (or Ethomeen® S12; or Ethomeen® SV/12) are useful wetting agents.
Sodium laureth sulphate (or sodium lauryl ether sulphate) can be added to the deruster composition to increase the amount of foam generated. When mixed with other surfactants it can be used to increase the viscosity of the deruster composition. This is both an anionic surfactant and a detergent, and is readily biodegradable. Studies have shown that it has very low toxicity when ingested orally. Sodium laureth sulphate has a pH of 7.5 when present at 10% in an aqueous solution.
Polyethylene glycol monoisotridecyl ether (also known as PEG monoisotridecyl ether, Berol 048, a-lsotridecyl-(jo-hydroxypoly(oxy-l,2-ethanediyl); Arlypon IT 10; Dehscoxid 732; Ethox 2400; Ethox TDA 9; Ethoxylated isotridecanol; Ethoxylated Isotridecyl Alcohol; Eusapon S; Exxal F 5716; Genapol V 4739; Genapol X; Gezetol 138; Imbentin T 050; Isotridecanol Ethoxylate; Isotrideceth 15; Leocol TD 120; Leocol TD 150; Leocol TD 50; Leocol TD 90; Leocol TDA 400-75; Lutensol TO 10; Marlipal 013/40; Marlosol TA 3050; Marlosol TA 3090; or Nissan Dispanol TOC) is a non-ionic surfactant based on tridecyl alcohol. It has a hydrophilic (water soluble) character. It is a good dispersing agent and is useful for reducing the surface tension. This surfactant is also a useful foam booster, emulsifier and wetting agent. Berol 048 has a pH of 5-7 when present at 1% in an aqueous solution.
An example of a suitable amphoteric surfactant is β-Alanine, N-(2-carboxyethyl), N-(2-ethylhexyl) monosodium salt, supplied commercially by Lakeland Laboratories Limited as AMA LF at various concentrations (for instance AMA LF40 is a 40wt% of surfactant in aqueous solution). The same salt is also available as AMA LF70. This type of surfactant exhibits good detergency with excellent dirt lifting properties. Amphoteric surfactants are good cleaning agents for hard surfaces such as metals. These types of surfactant produce little foam, resulting in good rinse properties. AMA LF has exhibited low toxicity in studies. Amphoteric surfactants can be used to restore stability in formulation used in hard water areas (where other surfactants have become unstable).
Another similar surfactant is β-Alanine, N-(2-carboxyethyl)-N-(n-octyl) mono salt, which is available commercially as LF 60 (60wt% aqueous solution).
Another example of a commercially available amphoteric surfactant is β-Alanine, N-(2-carboxyethyl)-N-[3-(decyloxy)propyl]-, monosodium salt, or Tomamine®. Tomamine® is available in a biodegradable, high foaming, hydrotroping surfactant form (Tomamine Amphoteric 16).
The viscosity of the deruster composition can be increased by creating a mixture of coconut diethanolamide and sodium laureth sulphate, and including this mixture within the deruster composition. Coconut diethanolamide (also known as Surfac CDE) is a non-ionic surfactant. Preferably, the mixture comprises coconut diethanolamide and sodium laureth sulphate at a ratio of between 1:30 to 1:9. A ratio of 1:9 is preferred.
Where more than one surfactant is used in the deruster composition, the surfactants can be of the same type, for example, non-ionic, or they can be of different types, for example, at least one surfactant could be non-ionic and at least one surfactant could be an amphoteric surfactant.
Solvents
Solvents may be added to the deruster formulation. Solvents are used to dissolve any oils, grease, lubricants and other contaminants which may be present on the surface of the metal parts. The solvent is used in addition to water, and is preferably an organic solvent.
Ammonium hydroxide is a powerful cleaning agent and solvent and can be used in the deruster composition as a solvent for this purpose. Ammonium hydroxide has a low upper limit of solubility in water. The maximum concentration at which ammonium hydroxide can be supplied is 0.88g/mol (or about 35wt% ammonia in water) at 15°C.
Other cleaning agents or solvents which are suitable for use in the composition include primary and tertiary amines. Amines such as triethanolamine (TEA or TEOA) are multifunctional, acting as a solvent, a surfactant and/or a buffer. Triethanolamine can be used in the deruster composition to dissolve oils or grease in water. 2-amino-2-methyl-l-propanol is another amine based solvent that could be used as a solvent in the deruster composition.
Buffering and Neutralising agents and ferrous ions
In addition to chelating agents, solvents and surfactants, other components such as buffering agents can be included in the deruster composition. Buffering agents are essentially neutralising agents and are used to maintain the pH of a solution such that it is neutral, or as close to neutral as possible.
Buffering agents can either be weak acids or weak alkalis and are usually added to water to form a buffer solution. The buffer solution only slightly changes its pH in response to the addition of other acids or alkali (regardless of the strength of the acid or alkali).
Examples of buffering agents include potassium hydroxide and sodium hydroxide. The use of one or more buffering agents helps to maintain the deruster composition at a neutral pH despite the use of strong acidic or alkaline components in the formulation. Potassium hydroxide and sodium hydroxide are soluble in water at room temperature and are usually supplied as aqueous solutions, for example, in the range of 40wt% to 60wt%.
Examples of buffering agents that can also act as emulsifiers and dispersing agents include tetra potassium pyrophosphate (TKPP, diphosphoric acid), triethanolamine and monoethanolamine. Tetra potassium pyrophosphate (TKPP) is often supplied as a solution of 50-60wt% in water. Triethanolamine (TEA or TEOA) is used to neutralise fatty acids, and to adjust and buffer the pH of an aqueous solution. An example of an alkali solvent which can also act as a buffer is 2-amino-2-methyl-l-propanol (also known as AMP™). It is soluble in water, with a pH of 11.3 in 0.1M aqueous solution.
Sources of ferrous ions, or salts, can optionally be added as a catalyst to accelerate the removal of metal oxides by the metal chelants in solution. Any water soluble ferrous salt can be used for this purpose, such as any salt from the group of ferrous sulphates. A specific example of a suitable source of a ferrous ion for use in the composition is ammonium iron (II) sulphate hexahydrate.
Formulation A skilled person will recognise that it is possible to adapt the composition of the deruster composition according to the desired requirements. For instance, two chelating agents can be combined with a surfactant, a buffering agent, a salt (to provide a source of ferrous ions) and solvent. Alternatively, it might be desirable to combine three chelating agents, balanced by two buffering agents, combined with one surfactant and one solvent.
Another formulation may comprise two chelating agents, three surfactants, a buffering agent, a solvent and a salt. The formulation may be combination of three chelating agents with a buffer, a solvent and a surfactant. The cleaning power of three solvents might be desired, with one chelating agent, one surfactant and one buffer. The formulation may comprise three chelating agents in combination with a surfactant only (without the use of an additional solvent). The formulation could comprise two chelating agents with a buffer and one or more surfactants.
Preferably, water is present from about 20wt% to about 98wt%, more preferably between 20wt% and 80wt% of the liquid deruster composition. The deruster composition is usually supplied in concentrated form for further dilution before use.
The following examples of quantities are provided for the concentrated form of the deruster product, where the water concentration is preferably less than 50wt%.
At least one chelating agent is an aminopolycarboxylic acid and is present in concentrations from about 0.2wt% to about 60wt%, more preferably between 0.2wt% and 40wt%, more preferably between 0.4wt% and 25wt%, most preferably between 0.4wt% and 20wt%.
Where a second chelating agent is used, it can be present in quantities of between 0.5wt% to 60wt%, more preferably between lwt% and 30wt%, most preferably between lwt% and 20wt%.
Where a third chelating agent is used, it can be present in quantities of between 0.5wt% and 15wt%, more preferably between 0.5wt% and 10wt%.
At least one surfactant is an alkyl polyglycoside. The surfactant can be present in quantities of between 0.05wt% to 5wt%, more preferably between 0.05wt% and 2.5wt%, most preferably between 0.1wt% and 2wt%.
Optionally, more than one surfactant may be present. Where a second surfactant is a soya-alkylamine, it can be present in amounts from about 0.2wt% to about 5wt%, more preferably between 0.5wt% and 2.5wt%.
At least one solvent may be present in the deruster composition, preferably in concentrations of between 0.1wt% and 15wt%, more preferably between 0.5wt% and 10wt%, most preferably between 0.5wt% and 8wt%. A buffering agent may be present in quantities between 0.5wt% and 40wt%, more preferably between lwt% and 30wt%, most preferably between lwt% and 20wt%. All of these buffering agents are usually supplied at concentrations of about 50wt%-60wt% in water and the quantities discussed are for the aqueous solution.
Optionally, a source of ferrous ions may be added, and may be present in quantities of between 0.01wt% and 5wt%, but preferably between 0.1wt% and 2wt%.
Optionally, a gluconate, such as sodium gluconate, may be added, and may be present in quantities of between 0.1wt% and 5wt%, preferably between 0.1wt% and 2wt%, more preferably between 0.1wt% and 1.5wt%.
Optionally, a thioglycolate, such as sodium thioglycolate can be added, which may be present in quantities from about lwt% to about 20wt%, more preferably between 5wt% and 10wt%.
Further examples of suitable formulations for deruster compositions are provided in Table 1, by way of illustration only. It will be recognised by a person skilled in the art that numerous formulations can be produced according to the invention.
The components of the deruster composition are slowly added to one another and mixed well until dissolved or homogenously mixed (as appropriate). Preferably, the pH is adjusted to a range of 5 to 9. More preferably, the pH is adjusted to a range of 5 to 8. Most preferably, the pH is adjusted to fall in the range from 6 to 7.5.
Typically the deruster composition product for application onto the metal surface is further diluted from 1 to 4, up to 1 to 20, preferably 1 to 10 (10%) before use. Any clean source of water free from particulates would be suitable for use. Water does not necessarily have to be purified; however, filtered, distilled or de-ionised water can be used. For tarnish removal, the deruster composition product is diluted further, up to a dilution of 1 part deruster composition to 25 parts water, before use.
Deruster Application
The deruster composition is designed to be applied after the metal objects have been initially cleaned to remove any loose soils, oil and grease.
Ideally, the deruster composition is designed to be used at a temperature of between 10°C and 60°C, more preferably between 20°C and 40°C. There is no need to heat the composition in order for the deruster composition to dissolve the rust, and the composition can be applied at room temperature.
The step of contacting the contaminated metal with the deruster composition can be carried out by any conventional method. These methods include, but are not limited to contacting by immersion and spray methods. Alternatively, the product can be painted or sponged onto the object. Metals which have been contacted with the deruster composition for a sufficient length of time can be referred to as 'treated metals'.
For immersion, simple immersion equipment, such as dip tanks, can be used. The deruster composition can be applied to the metal to be cleaned by a combination of spray and immersion processes. Alternating steps of separate spray processes or separate immersion processes can be used in order to achieve the desired result. The contacting step is performed for a length of time sufficient to result in the contaminants or rust being at least partially dissolved. Application of the deruster composition by a spray process requires optimisation of nozzle selection and arrangement as well as consideration of the spray. Immersion cleaning can be aided by the use of agitation methods to reduce immersion time.
The contacting times required for rust removal depends on the severity of the deposition or contamination. For large, severely rusted components, the contacting step is preferably performed for less than 36 hours, more preferably, for less than 24 hours, most preferably for less than 12 hours. For moderately rusted components, the contacting step is preferably performed for less than 10 hours, more preferably about 7.5 hours, most preferably about 6 hours. For products affected by light surface rust, the contacting step is preferably performed for less than 2 hours, more preferably less than 1 hour. For lightly rusted metal, 30 minutes contact time with the diluted deruster composition can be sufficient to remove all the rust from the surface of the metal, even when applied at room temperature.
In general, shorter contacting times are required when the deruster composition is used for tarnish removal or metal brightening purposes. The contacting step is then preferably performed for less than 6 hours, more preferably less than 5 hours. Most preferably, the contacting step is less than 4 hours. For brightening yellow metals, such as copper or brass, a contacting time of less than 2 hours can be sufficient to remove a thin to moderate layer of tarnish. For a thick layer of tarnish, where the article has blackened significantly, a contacting time of up to 5 hours may be required, preferably up to 4 hours.
The required contacting times are provided at room temperature. By increasing the temperature, the required contacting times can be reduced, however, this increases the energy requirements (and therefore the cost) of the process.
After the application of the deruster composition, particularly by immersion, the metal may undergo a rinsing stage to remove any particulates from the surface of the metal. The rinse step can be performed using additional "fresh" deruster composition. The deruster composition can leave behind a temporary protective coating that helps to prevent flash rusting.
An example of a formulation supplied in a "ready to use" form is Formulation 6, as shown in Table 1. Formulation 6 is a composition which does not require further dilution prior to use, and is designed to be sprayed onto or painted onto vertical surfaces where prolonged contact is required (although the composition can also be applied by equivalent methods such as sponging or dipping). Formulation 6 has improved degreasing and soil cleaning properties.
The following quantities are examples provided for the dilute form of the deruster product, where the water concentration is preferably more than 50wt%. The water concentration of the dilute deruster composition may be between 50wt% and 80wt%.
At least one chelating agent in the dilute deruster composition is an aminopolycarboxylic acid and is present in concentrations from about 0.1wt% to about 20wt%. More preferably, it can be present in quantities of between 0.2wt% and 15wt%, most preferably between 0.2wt% and 10wt%.
Where a second chelating agent is a phosphonate chelating agent it can be present in the dilute deruster composition in quantities of between 0.1wt% to 20wt%, more preferably between 0.2wt% and 15wt%, most preferably between 0.2wt% and 10wt%.
At least one surfactant in the dilute deruster composition is an alkyl polyglycoside. Alkyl polyglycoside can be present in quantities of between 0.05wt% to 5wt%, more preferably between 0.05wt% and lwt%.
Optionally, a solvent can be present in the dilute deruster composition, preferably in concentrations of between 0.1wt% and 10wt%, more preferably between 0.1wt% and 5wt%, most preferably at concentrations between 0.1wt% and 2wt%.
The deruster composition can be designed to provide protection as well as to remove the corrosion from the metal. Compositions can be formulated to be applied to the metal for prolonged contact such that they can be left on the surface of the metal to prevent corrosion, or to reduce the rate at which corrosion occurs. These compositions act as corrosion inhibitors.
Metal surfaces which have been cleaned with a deruster composition prepared according to the present invention (such as the examples compositions provided in Table 1) have demonstrated improved resistance to flash rusting compared with existing deruster products.
Table 1
Example Formulations
Formulations 1 to 5 and 7 to 12 are further diluted prior to use.
The formulations listed in Table 1 are provided as illustrative examples only and are non-limiting.
Experiment 1 A cleaned and degreased steel panel Q was placed outside in a vertical position for a period of approximately one month in order to allow it to become rusted.
Once the panel Q had rusted sufficiently, it was partially dipped into a 10% by weight dilution of a solution of deruster composition (which included MGDA and HEDP as chelating agents) prepared according to the present invention and then left for 4 hours until all the rust had been removed.
Once the rust had been removed the panel Q was removed from the de-ruster and carefully rinsed with water. The previous day, a further panel R had been cleaned and then degreased overnight. The two panels were then tethered to a fence (i.e. outdoors) in a vertical position. The panels were inspected at regular intervals noting the amount of re-rusting, this continued until a difference could be seen between the two panels.
Figure 1 is a photograph demonstrating the results of this experiment. It can be seen that after treatment with a deruster composition in accordance with the present invention, the metal surface on the lower portion of panel Q showed improved resistance to repeated rusting after 12 days of exposure. These results demonstrate that the deruster composition can be used as a rust inhibitor.
Experiment 2 A chain which was heavily incrusted with rust was immersed in a solution of deruster composition prepared in accordance with the present invention. The deruster composition was diluted to 10% by weight with water and included MGDA and HEDP as chelating agents. The chain was left in the solution for 24 hours. A chain comprises many crevices and is time consuming to manually scrub or clean. In order to manually inspect a chain for damage and cracks, the rust needs to be removed. Only then can the structural integrity of the chain be properly assessed. Removal of rust also allows the parts to be painted.
Figure 2 is a photograph of a chain before immersion in a deruster composition according to this invention and Figure 3 is a photograph of the same chain after immersion in a deruster composition according to this invention. Figure 3 demonstrates that the rust has been completely removed after immersion in the deruster formulation. The chain is much easier to inspect for structural integrity after immersion in the deruster composition.
Experiment 3
In Experiment 3, a strip of copper was used which had accumulated a thick layer of tarnish and blackened considerably over time. The tarnished copper strip was partially dipped into a solution of deruster composition prepared in accordance with the present invention, which comprised MGDA as one of the chelating agents. The deruster composition used was similar to Formulation 1 of Table 1, diluted at a ratio of up to 1 part deruster to 25 parts water.
One end of the copper strip was immersed into the deruster composition for approximately 4 hours. Figures 4 and 5 are photographs of the copper strip after partial immersion in the deruster composition. After removal from the deruster composition, the portion of the copper which had been immersed appeared to be fully restored to its original state, and was no longer tarnished, as can be seen in Figures 4 and 5. The treated metal was considerably brighter and had regained its light reflective properties. Other compositions prepared in accordance with the present invention produce a similar result.
Experiment 4 A tarnished section of copper tube was almost fully immersed into a solution of deruster composition prepared in accordance with the present invention. The deruster composition contained MGDA as a chelating agent. Before immersion, the copper tube was coated in a moderate layer of tarnish, and had a dull appearance.
One end of the copper tube was immersed into the deruster composition for 4 hours. Figure 6 is a photograph of the copper tube after partial immersion in the deruster composition. After removal from the deruster composition, the tarnish had been removed and the portion of the copper which had been immersed appeared to be restored to its original state, as can be seen in Figure 6. The treated metal was considerably brighter and more reflective.
Experiment 5 A tarnished section of brass piping was partially contacted with a solution of deruster composition prepared in accordance with the present invention. The deruster composition comprised MGDA as a chelating agent, although other compositions prepared in accordance with the present invention produce a similar result. Before immersion, the brass piping was coated in a thick layer of tarnish, and the brass had a dark, dull appearance.
Figure 7 is a photograph of the brass piping after partial contact with the deruster composition. One end of the brass piping was exposed to the deruster composition for 4 hours. After removal of the deruster composition, the tarnish had been removed from the brass piping and the portion of the brass which had been contacted with the deruster composition appeared to be restored to its original state. This can be seen in Figure 7. The treated metal was considerably brighter and lighter in colour.
Experiment 6
Tarnished sections of iron piping and iron bars were partially immersed in a 10% solution of the deruster composition at room temperature. The partially immersed sections were left in the deruster composition overnight. The following morning, the pieces were removed from the deruster solutions. The iron bars (smaller diameter) were rinsed with cold water and allowed to air dry, whilst the pipes were air dried without rinsing the deruster composition from the surface. The pipes and bars were subsequently left outside for 24 hours. The photograph shown as Figure 8 was then taken. The table below (Table 2) provides a key for use with Figure 8.
The pipe and bar labelled 26 and 27, respectively, were very heavily rusted prior to immersion in the deruster composition.
All of the proposed deruster compositions were effective at removing rust deposits from the iron, however, if the deruster composition remained on the surface of the metal after use, it was more effective as a rust preventative. Some of the deruster compositions required a longer immersion time (than 12 hours) in order to remove all of the deposited rust.
Table 2
Summary
The use of a biodegradable chelating agent improves the biodegradability of the deruster composition and any waste generated and therefore reduces the ecological impact of the deruster composition.
The deruster composition can be used to remove rust or tarnish from corroded metal objects, or can be used as a corrosion inhibitor in order to prevent or reduce further corrosion.
Claims (29)
- Claims 1) A deruster composition with a pH in the range of 5 to 8, comprising: at least one surfactant and at least one chelating agent; where at least one surfactant is an alkyl polyglycoside; and where at least one chelating agent is an aminopolycarboxylic acid; and water.
- 2) A deruster composition according to Claim 1, where the aminopolycarboxylic acid is methylglycin diacetic acid (trisodium salt).
- 3) A deruster composition according to Claim 1, where the aminopolycarboxylic acid is tetra sodium glutamate diacetate.
- 4) A deruster composition according to Claim 1, where the aminopolycarboxylic acid is tetra sodium iminodisuccinate.
- 5) A deruster composition according to any preceding claim, where the concentration of the aminopolycarboxylic acid is in the range of about 0.5wt% to about 40wt%.
- 6) A deruster composition according to any preceding claim, where the concentration of the alkyl polyglycoside is between 0.05wt% and 5wt%.
- 7) A deruster composition according to any preceding claim, where the concentration of the water is between 20wt% and 70wt%.
- 8) A deruster composition according to any preceding claim, where the composition further comprises at least one additional chelating agent.
- 9) A deruster composition according to Claim 8, where an additional chelating agent is a second aminopolycarboxylic acid.
- 10) A deruster composition according to Claim 8 or 9, where an additional chelating agent is a carboxylic acid.
- 11) A deruster composition according to any one of Claims 8-10, where an additional chelating agent is sodium gluconate.
- 12) A deruster composition according to any one of Claims 8-11, where an additional chelating agent is a phosphonate metal complexing agent.
- 13) A deruster composition according to Claim 12, where the phosphonate metal complexing agent is 1-hydroxyethylidene diphosphonic acid.
- 14) A deruster composition according to any one of Claims 8 to 13, comprising between 5wt% and 40wt% of an additional chelating agent.
- 15) A deruster composition according to any preceding claim, further comprising at least one solvent.
- 16) A deruster composition according to Claim 15, where at least one solvent is selected from ammonia, ammonia hydroxide, or a primary or tertiary amine.
- 17) A deruster composition according to Claim 15 or 16, where at least one solvent is triethanolamine.
- 18) A deruster composition according to any preceding claim, further comprising at least one additional surfactant.
- 19) A deruster composition according to Claim 18, further comprising an alkylamine or a soya alkylamine.
- 20) A deruster composition according to Claim 18 or 19, further comprising polyethylene glycol monoisotridecyl ether.
- 21) A deruster composition according to any preceding claim, further comprising at least one buffering agent.
- 22) A deruster composition according to Claim 21 where the buffering agent may be one or more of potassium hydroxide or sodium hydroxide.
- 23) A deruster composition according to any preceding claim, further comprising tetra potassium pyrophosphate.
- 24) A deruster composition according to any preceding claim, further comprising at least one source of ferrous ions.
- 25) A deruster composition according to Claim 24, where the source of the ferrous ions is ammonium iron (II) sulphate hexhydrate.
- 26) A deruster composition according to any preceding claim, further comprising a surfactant thickening system formed from a combination of a cocoamide diethanolamine salt and an alcohol ether sulphate.
- 27) A deruster composition according to any one of Claims 1-25, further comprising a surfactant thickening system formed from a combination of PPG-2 hydroxyethyl coco-isostearamide and an alcohol ether sulphate.
- 28) A deruster composition according to any preceding claim, further comprising sodium thioglycolate.
- 29) A deruster composition according to any preceding claim, comprising between 50wt% and 80wt% water, between 0.5wt% and 10wt% aminopolycarboxylic acid, between 0.05wt% and 5wt% alkyl polyglycoside surfactant, and at least one additional surfactant.
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| GB1417633.3A GB2535131B (en) | 2014-10-06 | 2014-10-06 | pH neutral deruster composition |
| GB1417633.3 | 2014-10-06 | ||
| PCT/GB2015/051869 WO2016055758A1 (en) | 2014-10-06 | 2015-06-26 | Ph neutral deruster composition |
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| US10443135B1 (en) * | 2018-05-11 | 2019-10-15 | Macdermid Enthone Inc. | Near neutral pH pickle on multi-metals |
| US11008536B2 (en) * | 2019-03-13 | 2021-05-18 | American Sterilizer Company | Liquid product for stainless-steel corrosion remediation |
| CN110257843A (en) * | 2019-07-15 | 2019-09-20 | 江苏方成生物科技有限公司 | A kind of new neutral rust remover |
| RU2715204C1 (en) * | 2019-10-17 | 2020-02-25 | ГОДЗОЕВ Олег Александрович | Composition for dissolution / removal of corrosive deposits |
| CN111254447B (en) * | 2020-03-24 | 2022-05-20 | 太仓市宝马环境工程有限公司 | Neutral rust removal passivation cleaning agent and use method thereof |
| CN111647895A (en) * | 2020-05-21 | 2020-09-11 | 上海毅诺生物科技有限公司 | non-VOC water-based soft metal cleaning agent |
| CN111790094A (en) * | 2020-07-31 | 2020-10-20 | 南通乐尔环保科技有限公司 | Fly ash chelating agent and preparation method and application thereof |
| CN112176355B (en) * | 2020-10-23 | 2022-05-17 | 山东大学 | Environment-friendly neutral rust remover and preparation method thereof |
| JP7066155B1 (en) | 2021-01-22 | 2022-05-13 | 株式会社トクヤマデンタル | Rust preventive for hypochlorous acid aqueous solution, sterilizing / cleaning agent with rust preventive effect, and its preparation method |
| CN114807950A (en) * | 2021-01-28 | 2022-07-29 | 江苏悦锌达新材料有限公司 | Aluminum alloy cleaning agent and preparation method thereof |
| KR102312863B1 (en) * | 2021-06-02 | 2021-10-14 | 주식회사 그린켐텍 | Spontaneous combustion agent of wet type eco-friendly and its manufacturing method |
| WO2023031328A1 (en) * | 2021-09-01 | 2023-03-09 | Unilever Ip Holdings B.V. | Bleach catalysts, bleach systems and cleaning compositions |
| CN115595595A (en) * | 2022-10-24 | 2023-01-13 | 浙江康星科技有限公司（Cn） | Neutral rust remover and preparation method and application thereof |
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| JP2557506B2 (en) * | 1988-11-24 | 1996-11-27 | 株式会社 オブジェ科学研究所 | Iron salt compound and its aqueous solution |
| WO1998021304A1 (en) * | 1996-11-13 | 1998-05-22 | Ashland Inc. | Liquid metal cleaner for an aqueous system |
| JP4051580B2 (en) * | 1997-02-21 | 2008-02-27 | 水道機工株式会社 | Cleaning solution for manganese dioxide scale |
| AU774805B2 (en) * | 1999-03-26 | 2004-07-08 | Calgon Corporation | Rust and scale removal composition and process |
| US8110537B2 (en) * | 2003-01-14 | 2012-02-07 | Ecolab Usa Inc. | Liquid detergent composition and methods for using |
| EP1670972A1 (en) * | 2003-09-30 | 2006-06-21 | BASF Aktiengesellschaft | Method for pickling metallic surfaces by using alkoxylated alkynols |
| EP1652969A1 (en) * | 2004-10-28 | 2006-05-03 | Henkel Kommanditgesellschaft auf Aktien | Deruster composition and method |
| EP2152843A2 (en) * | 2007-04-27 | 2010-02-17 | Bernd Schwegmann Gmbh&co. Kg | Mixture comprising an alkyl polyglucoside, a cosurfactant and a polymer additive |
| US7597766B2 (en) * | 2007-08-03 | 2009-10-06 | American Sterilizer Company | Biodegradable detergent concentrate for medical instruments and equipment |
| US7902137B2 (en) * | 2008-05-30 | 2011-03-08 | American Sterilizer Company | Biodegradable scale control composition for use in highly concentrated alkaline hard surface detergents |
| US8921295B2 (en) * | 2010-07-23 | 2014-12-30 | American Sterilizer Company | Biodegradable concentrated neutral detergent composition |
| BR112013026490B1 (en) * | 2011-04-14 | 2020-11-17 | Basf Se | METHOD OF DISSOLVING AND / OR INHIBITING THE CRUST DEPOSITION ON A SURFACE OF A SYSTEM |
| JP5824319B2 (en) * | 2011-10-21 | 2015-11-25 | 朝日化学工業株式会社 | Rust removal / rust prevention agent and removal / rust prevention method |
| JP6009320B2 (en) * | 2012-11-06 | 2016-10-19 | 花王株式会社 | Cleaning composition |
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| EP3204532A1 (en) | 2017-08-16 |
| GB201417633D0 (en) | 2014-11-19 |
| AU2015329756B2 (en) | 2020-09-10 |
| ES2716074T3 (en) | 2019-06-10 |
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| GB2535131A (en) | 2016-08-17 |
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| NB | Applications allowed - extensions of time section 223(2) |
Free format text: THE TIME IN WHICH TO PAY A RENEWAL FEE HAS BEEN EXTENDED TO 26 FEB 2022 |