US2789071A - Compositions and methods for treating articles - Google Patents
Compositions and methods for treating articles Download PDFInfo
- Publication number
- US2789071A US2789071A US313357A US31335752A US2789071A US 2789071 A US2789071 A US 2789071A US 313357 A US313357 A US 313357A US 31335752 A US31335752 A US 31335752A US 2789071 A US2789071 A US 2789071A
- Authority
- US
- United States
- Prior art keywords
- composition
- phosphorus
- parts
- utilized
- treatment
- 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.)
- Expired - Lifetime
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- 239000000203 mixture Substances 0.000 title claims description 62
- 238000000034 method Methods 0.000 title description 10
- VKCLPVFDVVKEKU-UHFFFAOYSA-N S=[P] Chemical compound S=[P] VKCLPVFDVVKEKU-UHFFFAOYSA-N 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 20
- 150000003973 alkyl amines Chemical class 0.000 claims description 7
- 238000005555 metalworking Methods 0.000 claims description 5
- 239000012533 medium component Substances 0.000 claims description 3
- 238000011282 treatment Methods 0.000 description 31
- 239000002609 medium Substances 0.000 description 25
- 239000003795 chemical substances by application Substances 0.000 description 23
- 239000000463 material Substances 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- 150000003460 sulfonic acids Chemical class 0.000 description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 10
- 239000000314 lubricant Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- -1 phosphorus sulfide compound Chemical class 0.000 description 9
- 229960004418 trolamine Drugs 0.000 description 9
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000001050 lubricating effect Effects 0.000 description 6
- 239000002480 mineral oil Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
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- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 5
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- 239000000126 substance Substances 0.000 description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 5
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 125000002837 carbocyclic group Chemical group 0.000 description 4
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- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000007530 organic bases Chemical class 0.000 description 4
- CGEXUOTXYSGBLV-UHFFFAOYSA-N phenyl benzenesulfonate Polymers C=1C=CC=CC=1S(=O)(=O)OC1=CC=CC=C1 CGEXUOTXYSGBLV-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 241000158728 Meliaceae Species 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000306 component Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 150000007529 inorganic bases Chemical class 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 3
- 235000013311 vegetables Nutrition 0.000 description 3
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- ILFFFKFZHRGICY-UHFFFAOYSA-N anthracene-1-sulfonic acid Chemical compound C1=CC=C2C=C3C(S(=O)(=O)O)=CC=CC3=CC2=C1 ILFFFKFZHRGICY-UHFFFAOYSA-N 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
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- 239000004615 ingredient Substances 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229940084106 spermaceti Drugs 0.000 description 2
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- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- UYBWIEGTWASWSR-UHFFFAOYSA-N 1,3-diaminopropan-2-ol Chemical compound NCC(O)CN UYBWIEGTWASWSR-UHFFFAOYSA-N 0.000 description 1
- ZMESHQOXZMOOQQ-UHFFFAOYSA-N 1-(naphthalen-1-ylmethyl)naphthalene Chemical compound C1=CC=C2C(CC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZMESHQOXZMOOQQ-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- LJJJZCPQAMJCRL-UHFFFAOYSA-N 1-chloropentane-1-sulfonic acid Chemical compound CCCCC(Cl)S(O)(=O)=O LJJJZCPQAMJCRL-UHFFFAOYSA-N 0.000 description 1
- BFSIDIWZBQSIHF-UHFFFAOYSA-N 2-oxopropane-1,3-disulfonic acid Chemical compound OS(=O)(=O)CC(=O)CS(O)(=O)=O BFSIDIWZBQSIHF-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 235000019890 Amylum Nutrition 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- UASWELLBILSTEX-UHFFFAOYSA-N S=[P]=S Chemical compound S=[P]=S UASWELLBILSTEX-UHFFFAOYSA-N 0.000 description 1
- 208000036366 Sensation of pressure Diseases 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
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- 229910045601 alloy Inorganic materials 0.000 description 1
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- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- BKUYVGOACRJHQO-UHFFFAOYSA-N benzenesulfonic acid;sulfuric acid Chemical compound OS(O)(=O)=O.OS(=O)(=O)C1=CC=CC=C1 BKUYVGOACRJHQO-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
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- 239000011248 coating agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 150000002169 ethanolamines Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- AKRQHOWXVSDJEF-UHFFFAOYSA-N heptane-1-sulfonic acid Chemical compound CCCCCCCS(O)(=O)=O AKRQHOWXVSDJEF-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- FYAQQULBLMNGAH-UHFFFAOYSA-N hexane-1-sulfonic acid Chemical compound CCCCCCS(O)(=O)=O FYAQQULBLMNGAH-UHFFFAOYSA-N 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- UAQJVNPFHGOEAH-UHFFFAOYSA-N oxido-oxo-phosphosulfanylphosphanium Chemical compound O=P(=O)SP(=O)=O UAQJVNPFHGOEAH-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
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- 239000000344 soap Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
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- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions
- C23C22/03—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions containing phosphorus compounds
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/041—Triaryl phosphates
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/12—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of organic compounds, e.g. with PxSy, PxSyHal or PxOy
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/12—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of organic compounds, e.g. with PxSy, PxSyHal or PxOy
- C10M2223/121—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of organic compounds, e.g. with PxSy, PxSyHal or PxOy of alcohols or phenols
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2225/04—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the monomers
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2225/04—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the monomers
- C10M2225/041—Hydrocarbon polymers
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/02—Groups 1 or 11
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/02—Bearings
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
- C10N2040/042—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for automatic transmissions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
- C10N2040/044—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for manual transmissions
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/04—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives
- C10N2040/046—Oil-bath; Gear-boxes; Automatic transmissions; Traction drives for traction drives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/06—Instruments or other precision apparatus, e.g. damping fluids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2080/00—Special pretreatment of the material to be lubricated, e.g. phosphatising or chromatising of a metal
Definitions
- This invention relates to the treatment of machine and seizing of such machine elements when operating underconditions of extremely high pressures and temeratures, and further relates to compositions used in uch treatments and to the articles resulting therefrom.
- Machine el ments using the term in a generic sense, .under service conditions are subject to deterioration in one'or more of many directions including scufiing, scoring, "seilzing.
- extreme pressure lubricants designed to lubricate and prevent-damage to movable machine parts are frequently entirely useless for lubrication of modern machines, especially during the breaking-in period.
- hypoid gears, pistons, piston rings, cylinder walls, cam shafts,, as well as other essential parts of the engine are severely damaged or fail completely.
- Similar considerations apply to moving parts in other combinations and especially where free lubrication is contra-indicated, as for example, in connection with hinges, particularly for automobile doors, shock absorbers, pistons, piston rod guides, aluminum pistons and rings, piston rods, etc.
- machine elements particularly those which operate under conditions where there is frictionalconta'ct of surfaces of such elements are modified in order to protect them from deterioration or development of defects under service conditions, particularly of severe character, as for example, to prevent scuffing, scoring and seizure.
- the term machine elements is used in a broad sense to cover all kinds and manner of such elements which are used under operating conditions where frictional forces come into play and include for example, gears, pistons, piston rings, cylinder Walls, cam shafts, engine parts generally, hinge shock absorbers parts, shafts, pinions, pump parts, bearings, journals, dies for drawing and stamping, etc.
- Such elements are principally of ferrous or ferrous alloy type but various features of the invention are applicable to other metals and metallic alloys besides irons and steels including copper, bronze, aluminum, etc. Exemplary effects obtained in treatment of ferrous and ferrous alloys will be utilized to illustrate the invention below.
- the surface of the metal is altered chemically and that there is formed thereon an integral thin protective lubricating film. It is further believed that there is alteration in the chemical composition of the metal sur-' face leading to the formation of complex surface coatings or metal modified at the surface which modified surfaces possess anti-welding and anti-frictional properties. But in referring to surface modification in this way whether chemical or physical or a combination of such efiects, no limitation on the invention is intended by any theoretical considerations, since the observed effects have been obtained regardless of the explanation offered to explain those results.
- the treatment is carried out by the use of a phosphorus sulfide compound either inorganic or organic with or without an organic sul-fonic derivative or combinations of such stated materials may be employed. They are utilized generally in a treating medium which carries the treating agent or combinations of treating agents. With the phosphorus sulfide materials it is believed that'there is formed on the metal surface a complex phosphosulfide and/ or sulfophosphosulfide coating or a sulfonate film or a combination of such coatings and films depending on the materials employed in the treatment. Such treated metals have the desired characteristics explained above of resisting deterioration or production of defects.
- the treatment material or agent will be dissolved or dispersed in an inert medium of liquid character such as mono or poly alcohols including ethyl or other monohydric alcohols, glycols such as ethylene glycol, glycerol, sorbitol, etc., but where the treating agent is itself liquid or liquefiable under the conditions employed in the treatment of metal therewith, it may be used by itself without any addition of inert medium.
- the treating agent may be dissolved in or dispersed in liquid treating agents produced in accordance with the present invention, the latter serving not only as a treating medium but also as a medium for carrying the first mentioned treating agent.
- the medium in which the treating agent or combinations of treating agents is employed will necessarily .vary when utilized depending on the nature ofthe treating agent or combination treating agent employed, the conditions under which it is utilized, and the metal being subjected to treatment. It should be kept in mind and emphasized that the present invention is concerned with the treatment of machine elements in their final fabricated form in condition for use Without further metal working such as rolling, drawing, stamping, etc. Itis the final fabricated element which is utilized in accordance with the present invention and which is subjected to the treatment to give it the properties set forth above so that such fabricated machines element is ready for use directly after the treatment without further metal working of any character.
- ingredients may be included for special purposes to incorporate rust-proofing, non-freezing, or active ingredients such as acids, bases, etc., lipoid materials including the animal lipoids such as fats, fatty acids, etc., and the vegetable lipoids including the vegetable fats, vegetable fatty acids, etc., or combinations of them, or the vegetable, animal, and mineral oils and their various fractions and distillates or combinations of any of these stated lipoids and mineral oil fractions, as well as organic fluids in general, both functional and non-functional, such as ((1) organic or inorganic bases'acting as solvents for phosphorus-sulfide, or to absorb gases formed, such as sulfur dioxide, hydrogen sulfide, etc.
- active ingredients such as acids, bases, etc., lipoid materials including the animal lipoids such as fats, fatty acids, etc., and the vegetable lipoids including the vegetable fats, vegetable fatty acids, etc., or combinations of them, or the vegetable, animal, and mineral oils and their various fractions and distillates or combinations of any of these
- the condi-' tions for treatment depend again on the nature of the treating composition, the metal being treated, and the degree of surface modification which is sought.
- the treatment may be carried out at elevated temperatures by immersion of the machine element in the desired treating agent or medium carrying such treating agent and after the treatment has been carried out to the degree desired, removing the treated machine element from the treating bath and subsequently if desired removing excess treating agent or bath from the element and drying it. These operations are not necessarily indicated depending on the conditions under which the operation is carried out and the treating medium itself.
- the effective film thus produced on the part in accordance with the present invention can be effected by heat and proper concentration of the active compound in a relatively short time,'or a similar surface reaction may be effected gradually over a longer period of time at lower temperatures after which the metal surface is self-sufficient in extreme pressure service.
- the active compounds of the present case may be used as additives per se in lubricants, hydrocarbon and otherwise.
- the surface phenomena which come into play as alresult of the present invention are not theoretical, a result demonstrated by the fact that the machine or other element is capable, as pointed out above, of functioning under extreme pressure conditions wlthout the necessity of maintaining an extreme pressure lubricant.
- the .treatment of the machine element is carried out with heating, but the temperatures employed should not be sutficient to cause undesirable effects either on the'treating medium or on the metal treated. Since many of the treating agents utilizable in accord- .ance with the present invention are prepared at elevated temperatures or are resistant to elevated temperatures, higher temperatures may be employed in the treating bath with such agents thanwith those which are susceptible to undesired reaction or which give undesired effects on the metal or result in too rapid action. The length of such. treatments will thus varywith different circumstances, media and'metals', and may vary from a few minutes to several hours.
- the temperatures employed need not bemore than -moderate temperatures, as for example, of the order of 50 to 200 C. or may be substantially higher than 200 C. Unless undesirable reactions take place, as a general rule, shorter treatment periods at elevated temperatures and higher concentrations of treating agent may be employed as compared with slower and longer treatments at lower temperatures, or where the treating agent is present in minor amount in a large amount of inert carrying medium.
- suitable compositions may be produced by dispersing or dissolving inorganic phosphorus sulfides in liquids, dispersions, suspensions, and emulsions, in amount of l to 18.5% by weight of the composition, and utilized in the treatment of machine elements in accordancewith the present invention.
- the liquid medium employed will be substantially inert to the particular phosphorus sulfide utilized.
- the phosphorus sulfides that may be employed 7 there may be mentioned phosphorus pentasulfide P285, phosphorus sesquisulfide P483, phosphorus P456, phosphorus heptasulfide P437, phosphorus disulfide P355, etc.
- the invention here is based on the use of alkylamines and alkylolamines. They give unique results. For some purposes other vehicles can be used but they are not the equivalents of the amines or alkyloamines.
- the inorganic phosphorus sulfide persing or dissolving the inorganic phosphorus sulfide; there may be mentioned genated and similar substitution products, materials lika alphachlornaphthalene, the caustic alkalies or of organic bases, inorganic acids such as sulfuric, hydrochloric, and nitric, or in general any diluent capable of suspending or dispersing phosphorus sulfide so as to bring it in intimate contact with the metal surface'of the machine element and thereby enable it to form the desired phosphorus sulfide protective film.
- Such added vehicle components may be used with the amines and alkylolamines.
- Gther desirable compositions that can be utilized in the treatment of metal machine elements include the reaction products of a phosphorus sulfide such as those set forth above with an organic body to produce a phosphorus-sulfur modified organic derivative.
- organic bodies may be utilized for modifica tion by the phosphorus sulfide treatment including aliphatic hydrocarbons either per se or in admixtures, fatty acids particularly hi h molecular weight fatty acids and their esters, ketones, alchohols both aliphatic and carbocyclic, dicarboxylic acids both aliphatic and aromatic, phenols and other hydroxy aromatic compounds, such as trichlordiphenyloxide, also including the hydroxy cycloaliphatics, sulfonic acids both aliphatic and carbocyclic and their derivatives, mineral oil, its fractions and distillations, olefines, olefine polymers, etc.
- the phosphorus sulfide reaction products of these organic bodies are generally produced at temperatures of elevated order usually running from about F. to 500 F.
- the reaction is conducted by heating the materials together until evolution of hydrogen sulfide ceases at which time the reaction may be considered substantially complete.
- heat treatments are carried out as With the mineral oil fractions, etc., a chemically reacted and modified product is obtained. While the mineral oil fractions, etc. may be utilized as media in which the phosphorus sulfide can be utilized in the treatment of machine elements, or with heat treatment where some phosphorus sulfide reaction product may be formed and an excess of unreacted phosphorus sulfide may also be present beyond that necessary for reaction.
- solutions of inorganic bases like Treating compositions as set forth above containing 1-20% by weight of inorganic phosphorus sulfides may be utilized with or without the organic sulfo compounds which may merely be added to the mixtures containing the phosphorus sulfides or their derivatives as set forth above to produce compositions of value.
- the presence of free organo sulfo compounds in such treating compositions appears to have a synergistic action and to activate the phosphorus sulfide materials to form a more tenacious chemical protective lubricating film on the metal surface.
- the organic sulfo compounds that may be employed include particularly the sulfonic acids and the sulfonates derived from them as well as their esters, salts, amides and chlorides, and may be both aliphatic, aromatic, carbocyclic, alicyclic and heterocyclic. Generally the organic sulfonic acids and their salts or esters may be considered primarily from the standpoint of those of the aromatic hydrocarbons and those of the aliphatic series.
- the sulfonic be those produced from individual hydrocarbons or mixtures of hydrocarbons or may be those derived in the purification or treatment of petroleum fractions and distillates such as petroleum sulfonates including the mahogany acids and the green acids.
- Exemplary sulfonic acids of which the derivatives like salts and esters may also be employed include hexane sulfonic acid, amyl sulfonic acid, monochloroamyl sulfonic acid, benzene sulfonic acid, phenol sulfonic acid, naphthalene sulfonic acid, heptane sulfonic acid, acetone disulfonic acid, dichloroamylene sulfonic acid, myristic sulfonic acid, stearic sulfonic acid, anthracene sulfonic acid, the sulfonic chlorides, disulphonic dinaphthyl methane, tristearin sulfonic acid, amylum sulfonic acid, spermaceti sulfonic acid, petroleum sulfonates such as the mahogany sulfonates and sulfonic acids, diphenyl parasulfonic acid,
- Example A The commercial benzol is sulfonated with fuming or concentrated sulfuric acid, the mixture being subjected to elevated temperatures. Starting with a definite weight of concentrated or fuming sulfuric acid, say 100 mole Weight, heated gradually, commercial benzol is added either in the liquid or vapor state to the extent of about 50 to 70 mole weight until approximately from one-half to three-fourths of sulfuric acid is reacted with the benzene to form benzene sulfonic acid and a mixture of other sulfonic acids where other materials as indicated above are present.
- a definite weight of concentrated or fuming sulfuric acid say 100 mole Weight
- commercial benzol is added either in the liquid or vapor state to the extent of about 50 to 70 mole weight until approximately from one-half to three-fourths of sulfuric acid is reacted with the benzene to form benzene sulfonic acid and a mixture of other sulfonic acids where other materials as indicated above are present.
- naphthalene sulfonic acid mixture To the sulfuric acid benzene sulfonic acid mixture, commercial naphthalene is added until about 50% of the remaining free sulfuric acid reacts with it to form naphthalene sulfonic acid.
- the crude naphthalene employed in the above mixture was approximately 50% naphthalene, 20% phenanthren-e, carbazole, and 20% anthracene. To this was added about 4 mole weight of phosphorus pentoxide to take up the water of reaction and with continued heating the resultant composition of sulfonic acids was substantially free from sulfuric acid.
- chloro benzene chloro naphthalene, stearin, spermaceti, stearic acid, and the like were used in a manner similar to that just described with extremely satisfactory results.
- any free sulfuricacid may be eliminated in a variety of ,ways as by neutralization,precipitation as an inorganic compound, etc.
- phosphorus pentoxide has been suggested as a dehydrating agent, other dehydrating agents may be employed.
- the phosphorus may serve additionally beyond its dehydrating function merely, either to catalyze the surface reaction or may form a phosphoro-metal compound with the surface, etc.
- Any neutralization which is utilized to eliminate unreacted sulfuric acid or to reduce the amount present may be carried out by utilizing inorganic bases such as the alkalis, or organic bases such as aniline and other amines alkylol-amines such as the ethanolamines, etc.
- inorganic bases such as the alkalis, or organic bases such as aniline and other amines alkylol-amines such as the ethanolamines, etc.
- Other types of amines that may be employed are illustrated below in other connections and any of them may be utilized in accordance with this invention at this stage for neutralization of any free sulfuric acid present in the sulfonic acids produced.
- organic sulfo compounds whether sulfonic acids or sulfonates or esters thereof may be utilized as indicated above with the inorganic phosphorus sulfide, or mixtures of them,-and they may be so employed either per so where the sulfonic acid or the phosphorus sulfide derivative is a liquid medium which also serves to carry the other materials, or these combinations of materials may be employed together with inert liquids or mediums of the character set forth above.
- organo sulfo derivatives referred to above have been indicated for utilization with the inorganic phosphorus sulfides.
- Any of the indicated organo sulfo compounds including the sulfonic acids, their salts and esters may be employed in this Way either individual substantially pure sulfonic acids and their derivatives, or various admixtures of such sulfonic acids with themselves and with other derivatives; and they may be so employed with Water either with or without inert liquids or diluents being present or they may be employed in inert media of the character set forth above for use in other relations and particularly in the mineral oil or petroleum oil, their fractions and distillates to produce desirable products for treating machine elements.
- a sulfonic acid may be selected that will stay in a petroleum lubricating oil fraction and utilized as such composition or a compatibilizing agent such as an alcohol may be introduced to serve as an intermediary medium in such combinations with or without the additions of other amines like Alkaterge-O, or similar materials.
- a compatibilizing agent such as an alcohol may be introduced to serve as an intermediary medium in such combinations with or without the additions of other amines like Alkaterge-O, or similar materials.
- water should be below any amount which will give the composition etching properties. Generally it will be less than 5 0% by weight of the-composition and usually will be less than- 33%.
- Amines which may be used herein include aliphatic, carbocyclic, and heterocyclic amines, and their alcoholamine derivatives such as: diethylamine, monoamylamine, diamylamine, triamylarnine, di-n-butylamine, monobutylamine, dibutylarnine, undecylamine, oleylamine, myristic amine, palmityl amine, stearylamine, mono-, diand triethanolamine, laurylolamine, palmitylolamine, stearylolamine, ethylene diamine, diamino isopropanol, cyclohexylamine, dicyclohexylamine, benzylamine, morpholine, piperidine, pyridine, quinoline, quaternary ammonium hydroxides, etc.
- amines may be added at any time either during the reaction when reaction products are being produced as set forth above, or after the reaction has been completed. They have a marked tendency to inhibit corrosion, and therefore, may desirably be included with any of the materials and compositions set forth above.
- the organic base or mixtures of them may be selected as to exhibit in addition, the property of absorbing or removing gases such as hydrogen sulfide, sulfur dioxide, and other acidic gases that maybe present in the atmosphere, or those that may form in situ. Exemplifying this feature, the triethanolamine referred to above will function in this way. It has been found that the use of alkylamines and alkylolaminesand 'ifi te i y.
- Thej alkylamines includeeither lower alkylamines such asmethyhethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl and higher long chain alkyls both straight and branched chain such as decyl, dodecyl, tetradecyl, hexadecyl,' octadecyl, in their several isomeric forms, and cycloalkyl such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc., while the alkylolamines, includethose where the alkyl is any of the alkyl groups set forth immediately above such as methylolarnines, ethylolamines, propylolamines, butylolamiues, decylolamines, tetradecyl
- compositions may be utilized per se in the treatment of machine elements in accordance with the present invention in aqueous media as explained above or may be further modified.
- sulfonic acids particul arly oil rnis proficient sulfonic acids may be incorporated with the composition.
- Diphenyl sulfonic acid may thus be employed.
- the resulting material may then be utilized either with phosphorus pentasulfide or other sulfides as illustrated above.
- Diphenyl sulfonic acid or anthracene sulfonic acid and theilike may first be plasticized, dissolved or suspended V in a suitable medium such as an alcohol, for example,
- phosphorus pentasulfide may then be added either by itself or previously dissolved in appropriate organic solvents such as an amine, for example, butyl or amyl amine
- the amine may serve a triple purpose in such connection: first, as a solvent for the phosphorus sulfide ahd lubricating medium; second, it may neutralize any acids or their gases formed when the phosphorus sulfide reacts in situ and may tend to absorb any hydrogen sulfide ⁇ , sulfur dioxide, etc., that may be formed; and third, may act by itself or enhance the rust proofing properties.
- the proportions of sulfonic acids added to such compositions will be illustrated below.
- Example 2 -50 parts of the composition of Example 1; 2 parts of diphenylsulfonic acid.
- the treating agent utilized in this example is the sulfonated commercial benzol containing toluene, etc. produced as set forth in Example A above. lt may be utilized as such in the treatment of machine elementsor with other media.
- compositions of the present invention for pretreatment of fabricated machine elements will be given below. It is not intended to suggest that each stated composition is equally as good as any other stated composition under any and; all conditions. However, good results will be obtained;
- Example .1 utilized in the pretreatment of gears, gave excellent results. This reference is to the first composition referred to at the beginning of Example 1 through addition of the triethanolamine. In the actual tests run the gears did not scuff, after 23 /2 hours operation, while operations utilizing conventional lubricants available on the market could not obtain comparative results in a test operation lasting more than 2 hours.
- Example 2 gives fair results, for example at approximately half-load, while the composition of Example 3 gives excellent results even under full maximum load.
- the compositions of Examples 4, 5,6, and 7 gave excellent results, most of them even under full load, while the compositions of Examples 8 and 9 were at least good in the results obtained under approximately to load.
- Example 6 used in the treatment of gears resulting in those machine elements which stood up 600 hours as compared with a 6 hour test for gears which had not been treated.
- the treatment with the composition of Example 6 was carried out by cooking the gears for 14 hours and 20 minutes in the'stated composition. Longer or shorter periods of treatment may be utilized and that given is merely exemplary.
- the composition of Example 4 gave most excellent results in connection with gears treated therewith. Examples 8 and 9 while satisfactory do not give as good results as those obtained with the compositions of Examples 1, 3,
- a Word should be said as to the effect of water dilution producing etching. Etching of some metal parts may be caused by dilutions with water of 50% or even 33 /3 and should be avoided as a general rule. Such effect necessarily depends on the particular composition being used and the nature of the metal part being treated, time, temperature, and other factors.
- Example I1 A mixture of 62.5 parts of sulfonic acid complex, as given in Example 10, with 6.25 parts of phosphorus pentasulfide dissolved in 6.23 parts of alcohol was used. The same parts were treated as in Example for times of to 45 minutes at a temperature 30 C. to 130 C. The pins in the Almen machine from first bath failed at 16 pounds, from the fourth bath stood up a maximum of 30 pounds, but the bath weakened sooner than that of Example 10.
- Wire drawing dies, mandrels for drawing tubes, dies for deep drawing and stamping, dies for piercing were treated with compounds of Examples 10 and 11 and functional operations carried out without aid of any additional lubricating medium and gave superior results than with the conventional lubricants.
- compositions for chemically treating fabricated machine elements in condition without further metal working for use under extreme pressure conditions normally causing wearing, scoring, and scufiing which composition consists essentially of an inorganic phosphorus sulfide in amount of from about 1 to 18.5% by weight in a liquid medium component selected from the group consisting of alkylamines and alkylolamines, and mixtures thereof.
- composition as set forth in claim 1 in which the liquid medium includes a hydrocarbon lubricating oil.
- the method of improving the load capacity of fabricated machine elements in condition without further metal working for use under extreme pressure conditions normally causing wearing, scoring and scufling comprises chemically treating said machine elements in a treating medium which consists essentially of an inorganic phosphorus sulfide in amount of from 1 to 18.5 by weight in a liquid medium component selected from the group consisting of alkylamines and alkylolamines, and mixtures thereof, at a temperature of from about F. to 400 F. to modify the Wearing pressure surfaces of the element making it capable of withstanding extreme pressures and loads.
- liquid medium includes a hydrocarbon lubricating oil.
- composition as set forth in claim 5 in which the liquid medium includes an organic sulfonate in minor amount.
- composition as set forth in claim 1 in which the liquid medium includes an organic sulfonate in minor amount.
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- Lubricants (AREA)
Description
United States Patent 6 COMPGSITIONS AND WETHGDS FOR TREATlNG ARTHILES Michael W. Freeman, Detroit, Mich.
No Drawing. Application October 6, 1952, Serial No. 313,357
ll Claims. (Cl. 1.48-6.17)
This invention relates to the treatment of machine and seizing of such machine elements when operating underconditions of extremely high pressures and temeratures, and further relates to compositions used in uch treatments and to the articles resulting therefrom.
This iapplication is a continuation-in-part of application Serial No. 737,735, filed March 27, 1947, Patent No. 2,614,943 October 21, 1952.
Machine el ments using the term in a generic sense, .under service conditions are subject to deterioration in one'or more of many directions including scufiing, scoring, "seilzing. Thus in development in structure and design of modern engines and machines, such increased power and speed has resulted that previously suitable extreme pressure lubricants designed to lubricate and prevent-damage to movable machine parts are frequently entirely useless for lubrication of modern machines, especially during the breaking-in period. Thus due to the inability of lubricating materials to withstand extreme pressures and/ or severe conditions developed in the engine or machine during operation, hypoid gears, pistons, piston rings, cylinder walls, cam shafts,, as well as other essential parts of the engine are severely damaged or fail completely. Similar considerations apply to moving parts in other combinations and especially where free lubrication is contra-indicated, as for example, in connection with hinges, particularly for automobile doors, shock absorbers, pistons, piston rod guides, aluminum pistons and rings, piston rods, etc.
In accordance with the present invention, machine elements particularly those which operate under conditions where there is frictionalconta'ct of surfaces of such elements are modified in order to protect them from deterioration or development of defects under service conditions, particularly of severe character, as for example, to prevent scuffing, scoring and seizure. The term machine elements is used in a broad sense to cover all kinds and manner of such elements which are used under operating conditions where frictional forces come into play and include for example, gears, pistons, piston rings, cylinder Walls, cam shafts, engine parts generally, hinge shock absorbers parts, shafts, pinions, pump parts, bearings, journals, dies for drawing and stamping, etc. Such elements are principally of ferrous or ferrous alloy type but various features of the invention are applicable to other metals and metallic alloys besides irons and steels including copper, bronze, aluminum, etc. Exemplary effects obtained in treatment of ferrous and ferrous alloys will be utilized to illustrate the invention below.
In accordance with the present invention, it is believed that the surface of the metal is altered chemically and that there is formed thereon an integral thin protective lubricating film. it is further believed that there is alteration in the chemical composition of the metal sur-' face leading to the formation of complex surface coatings or metal modified at the surface which modified surfaces possess anti-welding and anti-frictional properties. But in referring to surface modification in this way whether chemical or physical or a combination of such efiects, no limitation on the invention is intended by any theoretical considerations, since the observed effects have been obtained regardless of the explanation offered to explain those results.
The treatment is carried out by the use of a phosphorus sulfide compound either inorganic or organic with or without an organic sul-fonic derivative or combinations of such stated materials may be employed. They are utilized generally in a treating medium which carries the treating agent or combinations of treating agents. With the phosphorus sulfide materials it is believed that'there is formed on the metal surface a complex phosphosulfide and/ or sulfophosphosulfide coating or a sulfonate film or a combination of such coatings and films depending on the materials employed in the treatment. Such treated metals have the desired characteristics explained above of resisting deterioration or production of defects.
Ordinarily the treatment material or agent will be dissolved or dispersed in an inert medium of liquid character such as mono or poly alcohols including ethyl or other monohydric alcohols, glycols such as ethylene glycol, glycerol, sorbitol, etc., but where the treating agent is itself liquid or liquefiable under the conditions employed in the treatment of metal therewith, it may be used by itself without any addition of inert medium. Or the treating agent may be dissolved in or dispersed in liquid treating agents produced in accordance with the present invention, the latter serving not only as a treating medium but also as a medium for carrying the first mentioned treating agent.
The medium in which the treating agent or combinations of treating agents is employed will necessarily .vary when utilized depending on the nature ofthe treating agent or combination treating agent employed, the conditions under which it is utilized, and the metal being subjected to treatment. It should be kept in mind and emphasized that the present invention is concerned with the treatment of machine elements in their final fabricated form in condition for use Without further metal working such as rolling, drawing, stamping, etc. Itis the final fabricated element which is utilized in accordance with the present invention and which is subjected to the treatment to give it the properties set forth above so that such fabricated machines element is ready for use directly after the treatment without further metal working of any character. While, of course,'such machine elements may after the treatment be subjected to a simple operation such as cleaning, even this is generally 'not necessary unless there are materials in the treating agent which should be removed to prevent further action on the metal of the machine element or for any functional or non-functional reason.
Other ingredients may be included for special purposes to incorporate rust-proofing, non-freezing, or active ingredients such as acids, bases, etc., lipoid materials including the animal lipoids such as fats, fatty acids, etc., and the vegetable lipoids including the vegetable fats, vegetable fatty acids, etc., or combinations of them, or the vegetable, animal, and mineral oils and their various fractions and distillates or combinations of any of these stated lipoids and mineral oil fractions, as well as organic fluids in general, both functional and non-functional, such as ((1) organic or inorganic bases'acting as solvents for phosphorus-sulfide, or to absorb gases formed, such as sulfur dioxide, hydrogen sulfide, etc. and (b) organic fluids including aliphatic, alicyclic, carboxylic, and heteroor carrying 'medium as explained above The condi-' tions for treatment depend again on the nature of the treating composition, the metal being treated, and the degree of surface modification which is sought. The treatment may be carried out at elevated temperatures by immersion of the machine element in the desired treating agent or medium carrying such treating agent and after the treatment has been carried out to the degree desired, removing the treated machine element from the treating bath and subsequently if desired removing excess treating agent or bath from the element and drying it. These operations are not necessarily indicated depending on the conditions under which the operation is carried out and the treating medium itself.
I These treatments in the present case should be distinguished from the prior art use of extreme pressure lubricants containing additives. Such conventional prior art extreme pressure lubricants are utilized to withstand pressures as molecular ball bearings. And the extreme pressure lubricant composition must be retained and used as such. In the present invention, on the other hand, there is accomplished a surface phenomena, a definitive directed surface physico-chemical change that is an integral part of the machine or other element treated and is self-sufficient, i. e., it can function at extreme pressures in a medium ordinarily not capable of sustaining such service. The effective film thus produced on the part in accordance with the present invention can be effected by heat and proper concentration of the active compound in a relatively short time,'or a similar surface reaction may be effected gradually over a longer period of time at lower temperatures after which the metal surface is self-sufficient in extreme pressure service. Also it may be noted that because of their properties, the active compounds of the present case may be used as additives per se in lubricants, hydrocarbon and otherwise. The surface phenomena which come into play as alresult of the present invention are not theoretical, a result demonstrated by the fact that the machine or other element is capable, as pointed out above, of functioning under extreme pressure conditions wlthout the necessity of maintaining an extreme pressure lubricant.
Desirably the .treatment of the machine element is carried out with heating, but the temperatures employed should not be sutficient to cause undesirable effects either on the'treating medium or on the metal treated. Since many of the treating agents utilizable in accord- .ance with the present invention are prepared at elevated temperatures or are resistant to elevated temperatures, higher temperatures may be employed in the treating bath with such agents thanwith those which are susceptible to undesired reaction or which give undesired effects on the metal or result in too rapid action. The length of such. treatments will thus varywith different circumstances, media and'metals', and may vary from a few minutes to several hours. The temperatures employed need not bemore than -moderate temperatures, as for example, of the order of 50 to 200 C. or may be substantially higher than 200 C. Unless undesirable reactions take place, as a general rule, shorter treatment periods at elevated temperatures and higher concentrations of treating agent may be employed as compared with slower and longer treatments at lower temperatures, or where the treating agent is present in minor amount in a large amount of inert carrying medium.
Various treating agents utilizable per se and in various combinations and in a variety of treating baths utilizing different types of mediums will be illustrated below to exemplify the present invention.
As indicated, suitable compositions may be produced by dispersing or dissolving inorganic phosphorus sulfides in liquids, dispersions, suspensions, and emulsions, in amount of l to 18.5% by weight of the composition, and utilized in the treatment of machine elements in accordancewith the present invention. Generally the liquid medium employed will be substantially inert to the particular phosphorus sulfide utilized. As exem plary or". the phosphorus sulfides that may be employed 7 there may be mentioned phosphorus pentasulfide P285, phosphorus sesquisulfide P483, phosphorus P456, phosphorus heptasulfide P437, phosphorus disulfide P355, etc. As pointed out above, the invention here is based on the use of alkylamines and alkylolamines. They give unique results. For some purposes other vehicles can be used but they are not the equivalents of the amines or alkyloamines.
persing or dissolving the inorganic phosphorus sulfide; there may be mentioned genated and similar substitution products, materials lika alphachlornaphthalene, the caustic alkalies or of organic bases, inorganic acids such as sulfuric, hydrochloric, and nitric, or in general any diluent capable of suspending or dispersing phosphorus sulfide so as to bring it in intimate contact with the metal surface'of the machine element and thereby enable it to form the desired phosphorus sulfide protective film. Such added vehicle components may be used with the amines and alkylolamines.
Gther desirable compositions that can be utilized in the treatment of metal machine elements include the reaction products of a phosphorus sulfide such as those set forth above with an organic body to produce a phosphorus-sulfur modified organic derivative. A wide variety of organic bodies may be utilized for modifica tion by the phosphorus sulfide treatment including aliphatic hydrocarbons either per se or in admixtures, fatty acids particularly hi h molecular weight fatty acids and their esters, ketones, alchohols both aliphatic and carbocyclic, dicarboxylic acids both aliphatic and aromatic, phenols and other hydroxy aromatic compounds, such as trichlordiphenyloxide, also including the hydroxy cycloaliphatics, sulfonic acids both aliphatic and carbocyclic and their derivatives, mineral oil, its fractions and distillations, olefines, olefine polymers, etc.
The phosphorus sulfide reaction products of these organic bodies are generally produced at temperatures of elevated order usually running from about F. to 500 F. The reaction is conducted by heating the materials together until evolution of hydrogen sulfide ceases at which time the reaction may be considered substantially complete. Where such heat treatments are carried out as With the mineral oil fractions, etc., a chemically reacted and modified product is obtained. While the mineral oil fractions, etc. may be utilized as media in which the phosphorus sulfide can be utilized in the treatment of machine elements, or with heat treatment where some phosphorus sulfide reaction product may be formed and an excess of unreacted phosphorus sulfide may also be present beyond that necessary for reaction. The amount of phosphorus sulfide employed for chemical =reaction on the organic material will vary within sub- As exemplary of the substantially inert liquids which may be utilized for dis- 5 the lower aromatic liquid by drocarbons such as benzene and toluene, and their halo;
solutions of inorganic bases like Treating compositions as set forth above containing 1-20% by weight of inorganic phosphorus sulfides may be utilized with or without the organic sulfo compounds which may merely be added to the mixtures containing the phosphorus sulfides or their derivatives as set forth above to produce compositions of value. The presence of free organo sulfo compounds in such treating compositions appears to have a synergistic action and to activate the phosphorus sulfide materials to form a more tenacious chemical protective lubricating film on the metal surface. The organic sulfo compounds that may be employed include particularly the sulfonic acids and the sulfonates derived from them as well as their esters, salts, amides and chlorides, and may be both aliphatic, aromatic, carbocyclic, alicyclic and heterocyclic. Generally the organic sulfonic acids and their salts or esters may be considered primarily from the standpoint of those of the aromatic hydrocarbons and those of the aliphatic series. Either or both may be utilized in carrying out the present invention for purposes set forth above but the sulfonic be those produced from individual hydrocarbons or mixtures of hydrocarbons or may be those derived in the purification or treatment of petroleum fractions and distillates such as petroleum sulfonates including the mahogany acids and the green acids. Exemplary sulfonic acids of which the derivatives like salts and esters may also be employed include hexane sulfonic acid, amyl sulfonic acid, monochloroamyl sulfonic acid, benzene sulfonic acid, phenol sulfonic acid, naphthalene sulfonic acid, heptane sulfonic acid, acetone disulfonic acid, dichloroamylene sulfonic acid, myristic sulfonic acid, stearic sulfonic acid, anthracene sulfonic acid, the sulfonic chlorides, disulphonic dinaphthyl methane, tristearin sulfonic acid, amylum sulfonic acid, spermaceti sulfonic acid, petroleum sulfonates such as the mahogany sulfonates and sulfonic acids, diphenyl parasulfonic acid, polyalkylated diphenyl sulfonic acid, polyalkylated naphthalene sulfonic acids, sulfonated castor oil and similar materials, sulfo dicarboxylic acids and their esters, etc., etc. The benzene sulfonic acid is exemplary of other monocyclic aryl sulfonic acids such as toluene sulfonic acid, etc.
As an example of one method of producing a satisfactory sulfonic material, commercial benzol which may contain toluene, xylol, phenol, and other compounds, may be treated as follows:
Example A.The commercial benzol is sulfonated with fuming or concentrated sulfuric acid, the mixture being subjected to elevated temperatures. Starting with a definite weight of concentrated or fuming sulfuric acid, say 100 mole Weight, heated gradually, commercial benzol is added either in the liquid or vapor state to the extent of about 50 to 70 mole weight until approximately from one-half to three-fourths of sulfuric acid is reacted with the benzene to form benzene sulfonic acid and a mixture of other sulfonic acids where other materials as indicated above are present. To the sulfuric acid benzene sulfonic acid mixture, commercial naphthalene is added until about 50% of the remaining free sulfuric acid reacts with it to form naphthalene sulfonic acid. In production factory test runs, the crude naphthalene employed in the above mixture was approximately 50% naphthalene, 20% phenanthren-e, carbazole, and 20% anthracene. To this was added about 4 mole weight of phosphorus pentoxide to take up the water of reaction and with continued heating the resultant composition of sulfonic acids was substantially free from sulfuric acid.
In passing, it may be stated that the chloro benzene, chloro naphthalene, stearin, spermaceti, stearic acid, and the like were used in a manner similar to that just described with extremely satisfactory results. In any of these cases where sulfonic acids are present, any free sulfuricacidmay be eliminated in a variety of ,ways as by neutralization,precipitation as an inorganic compound, etc. While phosphorus pentoxide has been suggested as a dehydrating agent, other dehydrating agents may be employed. However, where the phosphorus pentoxide is utilized, the phosphorus may serve additionally beyond its dehydrating function merely, either to catalyze the surface reaction or may form a phosphoro-metal compound with the surface, etc. Any neutralization which is utilized to eliminate unreacted sulfuric acid or to reduce the amount present may be carried out by utilizing inorganic bases such as the alkalis, or organic bases such as aniline and other amines alkylol-amines such as the ethanolamines, etc. Other types of amines that may be employed are illustrated below in other connections and any of them may be utilized in accordance with this invention at this stage for neutralization of any free sulfuric acid present in the sulfonic acids produced.
These organic sulfo compounds whether sulfonic acids or sulfonates or esters thereof may be utilized as indicated above with the inorganic phosphorus sulfide, or mixtures of them,-and they may be so employed either per so where the sulfonic acid or the phosphorus sulfide derivative is a liquid medium which also serves to carry the other materials, or these combinations of materials may be employed together with inert liquids or mediums of the character set forth above.
The organo sulfo derivatives referred to above have been indicated for utilization with the inorganic phosphorus sulfides. Any of the indicated organo sulfo compounds including the sulfonic acids, their salts and esters may be employed in this Way either individual substantially pure sulfonic acids and their derivatives, or various admixtures of such sulfonic acids with themselves and with other derivatives; and they may be so employed with Water either with or without inert liquids or diluents being present or they may be employed in inert media of the character set forth above for use in other relations and particularly in the mineral oil or petroleum oil, their fractions and distillates to produce desirable products for treating machine elements. For example, a sulfonic acid may be selected that will stay in a petroleum lubricating oil fraction and utilized as such composition or a compatibilizing agent such as an alcohol may be introduced to serve as an intermediary medium in such combinations with or without the additions of other amines like Alkaterge-O, or similar materials. Where water is present in the composition it should be below any amount which will give the composition etching properties. Generally it will be less than 5 0% by weight of the-composition and usually will be less than- 33%. Amines which may be used herein include aliphatic, carbocyclic, and heterocyclic amines, and their alcoholamine derivatives such as: diethylamine, monoamylamine, diamylamine, triamylarnine, di-n-butylamine, monobutylamine, dibutylarnine, undecylamine, oleylamine, myristic amine, palmityl amine, stearylamine, mono-, diand triethanolamine, laurylolamine, palmitylolamine, stearylolamine, ethylene diamine, diamino isopropanol, cyclohexylamine, dicyclohexylamine, benzylamine, morpholine, piperidine, pyridine, quinoline, quaternary ammonium hydroxides, etc. These amines may be added at any time either during the reaction when reaction products are being produced as set forth above, or after the reaction has been completed. They have a marked tendency to inhibit corrosion, and therefore, may desirably be included with any of the materials and compositions set forth above. The organic base or mixtures of them may be selected as to exhibit in addition, the property of absorbing or removing gases such as hydrogen sulfide, sulfur dioxide, and other acidic gases that maybe present in the atmosphere, or those that may form in situ. Exemplifying this feature, the triethanolamine referred to above will function in this way. It has been found that the use of alkylamines and alkylolaminesand 'ifi te i y. pa being 'Thej alkylamines includeeither lower alkylamines such asmethyhethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl and higher long chain alkyls both straight and branched chain such as decyl, dodecyl, tetradecyl, hexadecyl,' octadecyl, in their several isomeric forms, and cycloalkyl such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc., while the alkylolamines, includethose where the alkyl is any of the alkyl groups set forth immediately above such as methylolarnines, ethylolamines, propylolamines, butylolamiues, decylolamines, tetradecylolamines, cyclohexylolamines, etc.
- Thefollowing examples. will illustrate the invention by weight unless otherwise indicated.
' Example1.-;-22O. parts of light fraction of mahogany soap wereheat ed at a temperature of 100 to 350 C. with 70 parts of phosphorus pentasulfide until the evolution of hydrogen sulfide substantially ceased, then 44 parts ofaluminum stearate were added and appeared to react with possible residual unreacted phosphorus sulfide complex; to this product 209 parts of 50 SAE oil were addcd; The whole mixture was neutralized with triethanol amine. V
; Suohcompositions may be utilized per se in the treatment of machine elements in accordance with the present invention in aqueous media as explained above or may be further modified. For example, sulfonic acids, particul arly oil rnis cible sulfonic acids may be incorporated with the composition. Diphenyl sulfonic acid may thus be employed. The resulting material may then be utilized either with phosphorus pentasulfide or other sulfides as illustrated above. In carrying out the addition of the sulfonic acids the following procedure maybe utilized. Diphenyl sulfonic acid or anthracene sulfonic acid and theilike may first be plasticized, dissolved or suspended V in a suitable medium such as an alcohol, for example,
isopropyl alcohol, butyl alcohol, etc., and the resulting material added to the composition of Example 6'above. More phosphorus pentasulfide may then be added either by itself or previously dissolved in appropriate organic solvents such as an amine, for example, butyl or amyl amine The amine may serve a triple purpose in such connection: first, as a solvent for the phosphorus sulfide ahd lubricating medium; second, it may neutralize any acids or their gases formed when the phosphorus sulfide reacts in situ and may tend to absorb any hydrogen sulfide}, sulfur dioxide, etc., that may be formed; and third, may act by itself or enhance the rust proofing properties. The proportions of sulfonic acids added to such compositions will be illustrated below.
Example 2.--50 parts of the composition of Example 1; 2 parts of diphenylsulfonic acid.
:Example 3.'5O parts of the composition of Example 1. '5 parts toluene sulfonic acid.
Example 4.50 parts of the composition of Example l, sulfonic acid dissolved in alcohol.
' i Exa 'nple 5.-.The treating agent utilized in this example is the sulfonated commercial benzol containing toluene, etc. produced as set forth in Example A above. lt may be utilized as such in the treatment of machine elementsor with other media.
Example 6.-458 parts of phosphorus pentasulfide dissolvediin 723 parts of water and in 50 parts isopropyl alcohol and then added to 2790 parts of the composition of Examplel.
, Example [+100 parts of phosphorus pentasulfide dissolved in 500'parts of triethanolamine. i V
.Exqmple.8.--5OO parts of phosphorus pentasulfide, 1000 parts of sodium bicarbonate, ll00 parts of water, 100 parts of triethanolamine,
,T Example. 9. 4 0O. parts ofphosphorus pentasulfi'de',
parts of sodium bicarbonate, 900 parts of water, 100 parts or triethanolamine.
In any of the above-entitled compositions the; materials may be mixed in any desired way unless some special method of incorporation of the ingredients has been indicated. V Machine elements pretreated according to this invention and lubricated with a good noncorrosive extreme pres sure lubricant are capable of withstanding loads far in excess of those machine elements that are untreated in accordance with the present invention. Transmission gears pretreated in accordance with the present invention, when examined after an actual test run in an automobile engine, showed no signs of any scoring, sending, or seizure, while similar gears run under the same conditions but not given any pretreatment in accordance with the present invention, showed sign of wear, scratching and scoring. 7
Other exemplary results obtained by utilizing compositions of the present invention for pretreatment of fabricated machine elements will be given below. It is not intended to suggest that each stated composition is equally as good as any other stated composition under any and; all conditions. However, good results will be obtained;
with any of these compositions under general conditions t and particular conditions may be chosen to give improved results. In some cases the results obtained were determined on an Almen testing machine designed with 30 pounds as a maximum full load. Even with full load some tested articles showed no wear at all. Some articles like gears and pinions may desirably be tested in accordance with the number of hour that they stand up under an accelerated test under actual operating conditions and. compared with the conventional lubricating mediums of even extreme pressure lubricant type, normally employed in service in that connection. I The composition of Example .1 utilized in the pretreatment of gears, gave excellent results. This reference is to the first composition referred to at the beginning of Example 1 through addition of the triethanolamine. In the actual tests run the gears did not scuff, after 23 /2 hours operation, while operations utilizing conventional lubricants available on the market could not obtain comparative results in a test operation lasting more than 2 hours.
The composition of Example 2 gives fair results, for example at approximately half-load, while the composition of Example 3 gives excellent results even under full maximum load. The compositions of Examples 4, 5,6, and 7 gave excellent results, most of them even under full load, while the compositions of Examples 8 and 9 were at least good in the results obtained under approximately to load.
The composition of Example 6 used in the treatment of gears resulting in those machine elements which stood up 600 hours as compared with a 6 hour test for gears which had not been treated. The treatment with the composition of Example 6 was carried out by cooking the gears for 14 hours and 20 minutes in the'stated composition. Longer or shorter periods of treatment may be utilized and that given is merely exemplary. The composition of Example 4 gave most excellent results in connection with gears treated therewith. Examples 8 and 9 while satisfactory do not give as good results as those obtained with the compositions of Examples 1, 3,
4and6.
were treated and tested in the Almen machine. Exemplary results are as follows. A pin from the first bath failed at 14 pounds; one from the fourth bath did not fail at 30 pounds; another from the sixth bath stood up the maximum load of 30 pounds. These results may be compared with failure at 8 pounds in the Almen machine for treatment with plain oil.
A Word should be said as to the effect of water dilution producing etching. Etching of some metal parts may be caused by dilutions with water of 50% or even 33 /3 and should be avoided as a general rule. Such effect necessarily depends on the particular composition being used and the nature of the metal part being treated, time, temperature, and other factors.
Example I1.A mixture of 62.5 parts of sulfonic acid complex, as given in Example 10, with 6.25 parts of phosphorus pentasulfide dissolved in 6.23 parts of alcohol was used. The same parts were treated as in Example for times of to 45 minutes at a temperature 30 C. to 130 C. The pins in the Almen machine from first bath failed at 16 pounds, from the fourth bath stood up a maximum of 30 pounds, but the bath weakened sooner than that of Example 10.
Wire drawing dies, mandrels for drawing tubes, dies for deep drawing and stamping, dies for piercing were treated with compounds of Examples 10 and 11 and functional operations carried out without aid of any additional lubricating medium and gave superior results than with the conventional lubricants.
Having thu set forth my invention, I claim:
1. A composition for chemically treating fabricated machine elements in condition without further metal working for use under extreme pressure conditions normally causing wearing, scoring, and scufiing, which composition consists essentially of an inorganic phosphorus sulfide in amount of from about 1 to 18.5% by weight in a liquid medium component selected from the group consisting of alkylamines and alkylolamines, and mixtures thereof.
2. A composition as set forth in claim 1 in which the liquid medium includes a hydrocarbon lubricating oil.
3. The method of improving the load capacity of fabricated machine elements in condition without further metal working for use under extreme pressure conditions normally causing wearing, scoring and scufling, which method comprises chemically treating said machine elements in a treating medium which consists essentially of an inorganic phosphorus sulfide in amount of from 1 to 18.5 by weight in a liquid medium component selected from the group consisting of alkylamines and alkylolamines, and mixtures thereof, at a temperature of from about F. to 400 F. to modify the Wearing pressure surfaces of the element making it capable of withstanding extreme pressures and loads.
4. A method as set forth in claim 3 in which the liquid medium includes a hydrocarbon lubricating oil.
5. A composition as set forth in claim 1 in which the component is triethanolamine.
6. A composition as set forth in claim 5 in which the liquid medium includes an organic sulfonate in minor amount.
7. A composition as set forth in claim 1 in which the liquid medium includes an organic sulfonate in minor amount.
8. The method as set forth in claim 3 in which the component is triethanolamine.
9. The method as set forth in claim 8 in which the liquid medium includes an organic sulfonate in minor amount.
10. The method as set forth in claim 8 in which the liquid medium includes an organic sulfonate in minor amount.
References Cited in the file of this patent UNITED STATES PATENTS 1,988,584 Dana et al Jan. 22, 1935 2,266,378 Farrington et al. Dec. 16, 1941 2,297,909 Neely et a1 Oct. 6, 1942 2,311,653 Farrington et al. Feb. 23, 1943 2,328,727 Langer Sept. 7, 1943 2,346,356 Burke Apr. 11, 1944 OTHER REFERENCES National Petroleum News, vol. 37, No. 49, pages R-lOOl, R-1002, R-1003, R-1004, R-1006, R-l00 R-lOlO.
Claims (1)
1. A COMPOSITION FOR CHEMICALLY TREATING FABRICATED MACHINE ELEMENTS IN CONDITION WITHOUT FURTHER METAL WORKING FOR USE UNDER EXTREME PRESSURE CONDITIONS NORMALLY CAUSING WEARING, SCORING, AND SCUFFING, WHICH COMPOSITION CONSISTS ESSENTIALLY OF AN INORGANIC PHOSPHORUS SULFIDE IN AMOUNT OF FROM ABOUT 1 TO 18.5% BY WEIGHT IN A LIQUID MEDIUM COMPONENT SELECTED FROM THE GROUP CONSISTING OF ALKYLAMINES AND ALKYLOLAMINES, AND MIXTURES THEREOF.
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US313357A US2789071A (en) | 1952-10-06 | 1952-10-06 | Compositions and methods for treating articles |
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US313357A US2789071A (en) | 1952-10-06 | 1952-10-06 | Compositions and methods for treating articles |
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US2789071A true US2789071A (en) | 1957-04-16 |
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US3113029A (en) * | 1959-09-03 | 1963-12-03 | Miguel A Hernandez | Beer and malt beverage concentrates and process for producing same |
US5652201A (en) * | 1991-05-29 | 1997-07-29 | Ethyl Petroleum Additives Inc. | Lubricating oil compositions and concentrates and the use thereof |
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US2297909A (en) * | 1936-04-14 | 1942-10-06 | Standard Oil Co | Method of lubrication and of treating gears |
US2311653A (en) * | 1939-08-07 | 1943-02-23 | Standard Oil Co California | Treatment of frictional surfaces to facilitate wearing-in |
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US1988584A (en) * | 1932-11-12 | 1935-01-22 | Carbide & Carbon Chem Corp | Homogeneous composition and process for making the same |
US2297909A (en) * | 1936-04-14 | 1942-10-06 | Standard Oil Co | Method of lubrication and of treating gears |
US2266378A (en) * | 1938-10-19 | 1941-12-16 | Standard Oil Co California | Treatment of metallic frictional surfaces |
US2311653A (en) * | 1939-08-07 | 1943-02-23 | Standard Oil Co California | Treatment of frictional surfaces to facilitate wearing-in |
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US3113029A (en) * | 1959-09-03 | 1963-12-03 | Miguel A Hernandez | Beer and malt beverage concentrates and process for producing same |
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