EP0218989B1 - Procédé pour suspendre du matériau solide de lubrification - Google Patents
Procédé pour suspendre du matériau solide de lubrification Download PDFInfo
- Publication number
- EP0218989B1 EP0218989B1 EP86113474A EP86113474A EP0218989B1 EP 0218989 B1 EP0218989 B1 EP 0218989B1 EP 86113474 A EP86113474 A EP 86113474A EP 86113474 A EP86113474 A EP 86113474A EP 0218989 B1 EP0218989 B1 EP 0218989B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- colloid mill
- suspension
- process according
- mixer
- 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
Links
- 239000007787 solid Substances 0.000 title claims abstract description 41
- 239000000314 lubricant Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000000725 suspension Substances 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000084 colloidal system Substances 0.000 claims abstract description 18
- 239000010439 graphite Substances 0.000 claims abstract description 18
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 238000005520 cutting process Methods 0.000 claims abstract description 4
- 150000002739 metals Chemical class 0.000 claims abstract description 3
- 239000000470 constituent Substances 0.000 claims description 6
- 230000002093 peripheral effect Effects 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims 1
- 239000000654 additive Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- -1 vinyl alcohols Chemical class 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 7
- 239000000080 wetting agent Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920000388 Polyphosphate Polymers 0.000 description 3
- 239000003899 bactericide agent Substances 0.000 description 3
- 150000001639 boron compounds Chemical class 0.000 description 3
- 239000001205 polyphosphate Substances 0.000 description 3
- 235000011176 polyphosphates Nutrition 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 229920013820 alkyl cellulose Polymers 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920002527 Glycogen Polymers 0.000 description 1
- 229920001202 Inulin Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- HDSBZMRLPLPFLQ-UHFFFAOYSA-N Propylene glycol alginate Chemical compound OC1C(O)C(OC)OC(C(O)=O)C1OC1C(O)C(O)C(C)C(C(=O)OCC(C)O)O1 HDSBZMRLPLPFLQ-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000010407 ammonium alginate Nutrition 0.000 description 1
- 239000000728 ammonium alginate Substances 0.000 description 1
- KPGABFJTMYCRHJ-YZOKENDUSA-N ammonium alginate Chemical compound [NH4+].[NH4+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O KPGABFJTMYCRHJ-YZOKENDUSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- RXSUIDMUJJAVLM-CFYXSCKTSA-N dibutyl (z)-but-2-enedioate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CCCCOC(=O)\C=C/C(=O)OCCCC RXSUIDMUJJAVLM-CFYXSCKTSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000002193 fatty amides Chemical class 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229940096919 glycogen Drugs 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 description 1
- 229940029339 inulin Drugs 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- AIHDCSAXVMAMJH-GFBKWZILSA-N levan Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@@H]1[C@@H](O)[C@H](O)[C@](CO)(CO[C@@H]2[C@H]([C@H](O)[C@@](O)(CO)O2)O)O1 AIHDCSAXVMAMJH-GFBKWZILSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 239000001814 pectin Substances 0.000 description 1
- 235000010987 pectin Nutrition 0.000 description 1
- 229920001277 pectin Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 231100000683 possible toxicity Toxicity 0.000 description 1
- 235000010408 potassium alginate Nutrition 0.000 description 1
- 239000000737 potassium alginate Substances 0.000 description 1
- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 description 1
- 235000010409 propane-1,2-diol alginate Nutrition 0.000 description 1
- 239000000770 propane-1,2-diol alginate Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- RLQWHDODQVOVKU-UHFFFAOYSA-N tetrapotassium;silicate Chemical compound [K+].[K+].[K+].[K+].[O-][Si]([O-])([O-])[O-] RLQWHDODQVOVKU-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/80—Mixing plants; Combinations of mixers
- B01F33/82—Combinations of dissimilar mixers
- B01F33/821—Combinations of dissimilar mixers with consecutive receptacles
Definitions
- the invention relates to a method for suspending solid lubricants which are used in the non-cutting hot forming of metals, containing graphite and polymers in water as the carrier liquid.
- Solid lubricants for non-cutting metal forming at high temperatures are known from CH-A-596 294 and 609 728, containing graphite, polymers, suspension aids and optionally other auxiliaries, such as bactericides, which form a suspension with water.
- auxiliaries such as bactericides, which form a suspension with water.
- the addition of the bactericides is necessary to avoid bacterial decomposition of the solid lubricant suspension during storage;
- the suspension auxiliaries serve the purpose of keeping the liquid and solid constituents in a homogeneous mixture even over long periods.
- the solid lubricant suspension is used up during processing, i.e. the water evaporates on the tool of the workpieces, the polymer component burns off.
- the bactericidal additives When processing the solid lubricants, the bactericidal additives are also subject to evaporation, which is undesirable in view of their possible toxicity and together with the suspension aids they form a not inconsiderable non-lubricating part of the solid lubricant formulation.
- the object of the present invention was to propose a process which makes it possible to produce a homogeneous and stable solid lubricant suspension containing a carrier liquid, generally water, graphite and polymers, directly at the point of use, without adding bactericides and with the lowest possible content suspension aids.
- a carrier liquid generally water, graphite and polymers
- the dry, premixed components of the solid lubricant and the water can be combined in the colloid mill.
- the mixture of graphite, the polymer and any additives, such as suspension aids, film stabilizers, and optionally also wetting agents and inorganic additives, is referred to as dry, premixed constituents.
- additives such as e.g. Wetting agents, solvents, film formers, pH stabilizers, soluble inorganic salts (e.g. phosphates) etc. should be added beforehand.
- the water optionally with the additives mentioned, such as suspension aids, wetting agents or solvents, etc.
- the polymer e.g. as a plastic dispersion, premixed and this mixture in the colloid mill with the graphite, which if necessary with e.g. Suspension aids, film stabilizers, etc. are homogeneously mixed, are supplied.
- the gap between the rotor and housing can be 0.01 to 3 mm; the peripheral speed, calculated from the rotor circumference and speed, can range from 10 to 40 m / sec. be.
- Suspensions with a solids content of 1 to 70% by weight can be prepared by the process according to the invention.
- the possibility of achieving such high solids contents in the suspension was all the more surprising since the individual components of the solid lubricant have very low bulk densities. These are 0.2 to 0.5 kg / l for graphite, 0.2 to 0.7 kg / l for the polymers and additives and, for example, 0.2 to 0.5 kg / l for a typical dry mixture .
- the volume of the solid lubricant is greater than the volume of the water required to produce the suspension.
- the residence time of the components in the mixing area of the colloid mill is expediently in the range from 0.01 to 5 seconds.
- Suitable intensive mixers are expediently mixers with at least one co-rotating impeller shaft or counter-rotating impeller shafts, agitator ball mills, guide jet mixers or screw mixers, preferably in a cascade arrangement. If the constituents, ie the solid lubricant and the water, were mixed to form the solid lubricant suspension, for example, only in an intensive mixer, lump formation and inhomogeneity in the suspension could neither be avoided nor eliminated.
- the arrangement according to the invention the sequential connection of a colloid mill and an intensive mixer make it possible to obtain a completely lump-free, homogeneous solid suspension from the carrier liquid and the solids received, the parts of which are completely wetted and, where appropriate, open-minded.
- a suspension produced in this way is lump-free and has a significantly longer service life, measured in terms of the type and amount of suspension aid, and sedimentation of the solids only occurs after considerably longer periods of time than when mixing and suspending with only one of the mixers arranged in succession according to the invention it is possible.
- Solid lubricants to be produced by the process according to the invention are known, for example, from CH-PS 596 294 and 609 728. Accordingly, the starting materials used are at least one solid lubricant, preferably graphite, in particular those graphites with high purity, for example over 90%, and an average grain size of no more than 300 microns. The best results can be achieved with the graphite of 96 to 99.5% purity and an average grain size of 100 micrometers. If appropriate, the use of molybdenum disulfide, CaF 2 or BN alone or in a mixture with graphite is conceivable in the context of the present invention.
- Polymers are understood as meaning the organic products which decompose without leaving any heat, for example alkylene homopolymers or copolymers. These include the homo- and copolymers of alkenes (monoolefins, diolefins etc.), vinyl esters, vinyl alcohols, unsaturated dibasic acids and esters (dicarboxylic acids and esters), alkyl esters and acyclic acids and esters.
- the alkylene homopolymer or copolymer can be polyethylene, polymethyl methacrylate, polystyrene, polybutadiene, polyvinyl acetate, polyvinyl propionate, a copolymer of methyl methacrylate and styrene, a copolymer of methyl methacrylate and alphamethylstyrene, polydiallyl phthalate, polypropylene, a copolymer of styrene and butadiene, and polymethyl methacrylate Dibutyl maleate, a copolymer of vinyl acetate and ethylene and polyisobutylene.
- the polymers mentioned can be used alone or in a mixture with one another dry or, if appropriate, as a dispersion.
- substances from the group polysaccharides such as starch, celluloses, inulin, glycogen agar, levan, dichinone, pectin, lignin and araban can be used as suspension auxiliaries, furthermore alkyl celluloses, such as e.g. Methyl, ethyl, propyl and butyl celluloses, or alginates such as sodium alginate, potassium alginate, propylene glycol alginate and ammonium alginate, or mixtures of the substances can be used.
- alkyl celluloses such as e.g. Methyl, ethyl, propyl and butyl celluloses
- alginates such as sodium alginate, potassium alginate, propylene glycol alginate and ammonium alginate, or mixtures of the substances can be used.
- the solid lubricant When used, the solid lubricant should be present as a 1 to 70% by weight homogeneous aqueous dispersion and have a viscosity of 100 to 30,000 cp (0.1 to 30 Ns / m 2 at 5 to 50 ° C).
- an organic stabilizer which may be present in the solid lubricant may also be sufficient.
- a thickener e.g. water-soluble polysaccharides, alkyl celluloses, polyvinyl alcohols, polyarylates, polyvinyl pyrrolidone, optionally also inorganic substances, in particular minerals, such as clays or silica.
- the boron compound can be used in soluble and preferably in poorly soluble or insoluble form.
- borax boric acid
- B 2 0 3 KB 5 0 8 .4H 2 0
- zinc borate can be used as the boron compound.
- the alkali silicate used is preferably a sodium water glass or potassium water glass with an SiO 2 content between 21 and 47%.
- wetting agent For a safe wetting of the powdery solid lubricant mixture, it can be helpful to add a wetting agent to the mixture and / or the water.
- wetting agents are alkylarylsulfonates, fatty acid amines, fatty soaps, substituted amides of the alkyl phosphates, sulfonated esters of dicarboxylic acids, sulfonated fatty amides, alkylamines, sodium alkyl sulfates, aliphatic amine esters, polyethers such as polyoxyethylene and polyoxypropylene, sulfonated high phenols or naphthalenesulfonates.
- the solid lubricant suspensions to be produced by the process according to the invention can contain, for example, 1 to 90% by weight solid lubricant, preferably graphite, 1 to 50% by weight polymer, 1 to 80% by weight inorganic additive and 0.2 to 80% by weight of an organic stabilizer as a solid component contain.
- Water is used as the carrier liquid, with any additives to the water, such as wetting agents, solvents, e.g. Alcohols, esters, ketones or aldehydes are included.
- additives in the water may be necessary, for example, to quickly bring the solid lubricant and thereby the extremely poorly wettable graphite into suspension or, for example, to quickly dissolve or swell the polymer portion.
- the solid lubricants are suitable for high-temperature applications, at temperatures from 300 to 1300 ° C, for example for the lubrication of tools, such as mandrels, mandrel bars or dies and workpieces, such as blanks or pipes, for hot forming in so-called “multiple pipe mills", contours , Pilger step rolling mills, Asselstrasse, push bench systems, bar presses or Squeezing presses, and in rolling mills for profile and sheet metal rolling.
- the preferred materials for processing are iron and steel.
- the suspension produced by the method of the invention is by brushing, brushing and preferably by spraying onto the hot workpiece or tool.
- the carrier liquid in this case the water, and any volatile additives evaporate and leave a waterproof, graphite-containing melt film from the polymer.
- the water resistance of the film is required in order to be able to cool the surface coated with the solid lubricant if necessary.
- the film-forming properties are an essential feature of the solid lubricant. However, these do not show up at the place of application, i.e. on the workpiece or tool, but already during mixing, i.e. when the solids and then especially the polymers come into contact with the water. It is therefore all the more surprising that it is now possible to use the process of the invention to produce an extremely poorly wettable substance, such as graphite, and a polymer with strong film-forming to adhesive properties, the film which then has to be waterproof, lump-free and homogeneous with water to mix. What makes the process even more difficult is that the volume of the solids can exceed the volume of the water due to their low bulk density. Finally, the suspension, measured by the amount of suspension aids added, must be extremely stable and must not show segregation or sedimentation over long periods.
- the invention further comprises the device for carrying out the method according to the invention, consisting of a colloid mill and an intensive mixer immediately downstream.
- the colloid mill can have a gap width of 0.01 to 3 mm and can run at peripheral speeds of 10 to 40 m / sec. operate.
- the entire system is suitably designed for throughputs of 25 to 1200 kg / h and preferably up to 2000 kg / h of material.
- the colloid mill 1 consists essentially of housing 2 and rotor 3, which is set in motion by drive 4. From a storage vessel 5, the graphite / polymer mixture or the graphite alone, each with the further possible additives, and through the feed 6, the water, possibly in a mixture with the polymer and other additives, is fed into the colloid mill 1.
- the premixed suspension is passed in an intensive mixer 9, shown here by way of example with a cascade-shaped blade stirrer 10.
- an intensive mixer 9 shown here by way of example with a cascade-shaped blade stirrer 10.
- a storage vessel 11 can be provided, which can be equipped with a level meter and switches the system on and off according to the level.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Lubricants (AREA)
- Forging (AREA)
- Electroplating Methods And Accessories (AREA)
- Chemically Coating (AREA)
Claims (8)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT86113474T ATE60249T1 (de) | 1985-10-02 | 1986-10-01 | Verfahren zum suspendieren von festschmierstoffen. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH4249/85 | 1985-10-02 | ||
CH4249/85A CH665847A5 (de) | 1985-10-02 | 1985-10-02 | Verfahren zum suspendieren von festschmierstoffen. |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0218989A2 EP0218989A2 (fr) | 1987-04-22 |
EP0218989A3 EP0218989A3 (en) | 1989-04-26 |
EP0218989B1 true EP0218989B1 (fr) | 1991-01-23 |
Family
ID=4272580
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86113474A Expired - Lifetime EP0218989B1 (fr) | 1985-10-02 | 1986-10-01 | Procédé pour suspendre du matériau solide de lubrification |
Country Status (14)
Country | Link |
---|---|
US (1) | US4735734A (fr) |
EP (1) | EP0218989B1 (fr) |
JP (1) | JPS6291229A (fr) |
CN (1) | CN1006400B (fr) |
AT (1) | ATE60249T1 (fr) |
CA (1) | CA1272181A (fr) |
CH (1) | CH665847A5 (fr) |
CS (1) | CS261247B2 (fr) |
DD (1) | DD249858A5 (fr) |
DE (1) | DE3677127D1 (fr) |
ES (1) | ES2020173B3 (fr) |
PL (1) | PL261617A1 (fr) |
SU (1) | SU1498378A3 (fr) |
ZA (1) | ZA867265B (fr) |
Families Citing this family (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH674164A5 (fr) * | 1987-09-29 | 1990-05-15 | Lonza Ag | |
CH674096A5 (fr) * | 1988-01-19 | 1990-04-30 | Lonza Ag | |
CA1329802C (fr) * | 1988-08-30 | 1994-05-24 | Nippon Kokan Kabushiki Kaisha | Lubrifiant pour l'obtention de tuyauterie sans couture, en acier |
DE68901909T2 (de) * | 1988-10-10 | 1993-02-04 | Rhone Poulenc Chimie | Dispersion von halogeniden der seltenen erden in waessrigem medium. |
FR2638168A1 (fr) * | 1988-10-21 | 1990-04-27 | Rhone Poulenc Chimie | Dispersions d'halogenures de terres rares en milieu huileux |
US5308516A (en) * | 1989-06-08 | 1994-05-03 | Century Oils, Inc. | Friction modifiers |
US5173204A (en) * | 1989-06-08 | 1992-12-22 | Century Oils (Canada), Inc. | Solid lubricant with high and positive friction characteristic |
US5099667A (en) * | 1989-06-16 | 1992-03-31 | Lonza Ltd. | System for suspending and applying solid lubricants to tools or work pieces |
ATE124291T1 (de) * | 1989-06-16 | 1995-07-15 | Lonza Ag | Verwendung einer vorrichtung zum suspendieren von graphithaltigen festschmierstoffen. |
ES2063987T3 (es) * | 1990-03-26 | 1995-01-16 | Lonza Ag | Procedimiento para la pulverizacion intermitente de un liquido, sobre todo de una suspension de lubricante, y dispositivo para la realizacion de este procedimiento. |
US5114589A (en) * | 1991-01-17 | 1992-05-19 | The United States Government As Represented By The Secretary Of The Department Of Health And Human Services | Type-XLL cross-axis synchronous flow-through coil planet centrifuge for separation of biopolymers |
US5503771A (en) * | 1991-05-14 | 1996-04-02 | Washington Technology Center | Process for susupension of ceramic or metal particles using biologically produced polymers |
US5366644A (en) * | 1991-06-20 | 1994-11-22 | Gold Eagle Co. | Lubricant for fuel |
US5290336A (en) * | 1992-05-04 | 1994-03-01 | Hoeganaes Corporation | Iron-based powder compositions containing novel binder/lubricants |
US5294355A (en) * | 1992-12-28 | 1994-03-15 | Desilube Technology, Inc. | Thermally and oxidatively stable solid lubricants |
US5725807A (en) * | 1993-05-17 | 1998-03-10 | Electrochemicals Inc. | Carbon containing composition for electroplating |
US5476580A (en) * | 1993-05-17 | 1995-12-19 | Electrochemicals Inc. | Processes for preparing a non-conductive substrate for electroplating |
US5690805A (en) * | 1993-05-17 | 1997-11-25 | Electrochemicals Inc. | Direct metallization process |
US6710259B2 (en) | 1993-05-17 | 2004-03-23 | Electrochemicals, Inc. | Printed wiring boards and methods for making them |
US5389270A (en) * | 1993-05-17 | 1995-02-14 | Electrochemicals, Inc. | Composition and process for preparing a non-conductive substrate for electroplating |
US6303181B1 (en) | 1993-05-17 | 2001-10-16 | Electrochemicals Inc. | Direct metallization process employing a cationic conditioner and a binder |
US6171468B1 (en) | 1993-05-17 | 2001-01-09 | Electrochemicals Inc. | Direct metallization process |
US5498276A (en) * | 1994-09-14 | 1996-03-12 | Hoeganaes Corporation | Iron-based powder compositions containing green strengh enhancing lubricants |
US6039784A (en) * | 1997-03-12 | 2000-03-21 | Hoeganaes Corporation | Iron-based powder compositions containing green strength enhancing lubricants |
US7204112B1 (en) * | 2002-12-30 | 2007-04-17 | Dana Corporation | Method of lubricating a workpiece for hydroforming |
DE102005043542A1 (de) * | 2005-09-13 | 2007-03-15 | Graphit Kropfmühl AG | Stabile wässrige Graphitdispersion mit hohem Feststoffgehalt |
CN106362606A (zh) * | 2016-10-18 | 2017-02-01 | 上海锅炉厂有限公司 | 一种生产磁悬液的装置及方法 |
Family Cites Families (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2176879A (en) * | 1937-11-20 | 1939-10-24 | Acheson Colloids Corp | Method of disintegrating, dispersing and stabilizing graphite and product |
FR870578A (fr) * | 1940-03-08 | 1942-03-16 | Eduard Keffel A G | Dispositif pour la préparation de compositions d'enduit et de mélanges analogues pour la fabrication du simili-cuir et de produits analogues |
GB818489A (en) * | 1957-01-16 | 1959-08-19 | Columbium Carbon Company | Improvements in process and apparatus for effecting particulate dispersions |
US3198735A (en) * | 1961-10-20 | 1965-08-03 | Edward R Lamson | Solid lubricant composition and method for lubricating anti-friction bearing structures |
US3242075A (en) * | 1962-04-09 | 1966-03-22 | Acheson Ind Inc | High temperature lubricant |
US3341454A (en) * | 1963-02-25 | 1967-09-12 | Hodson Corp | Lubricant composition |
DE1472745B2 (de) * | 1965-03-09 | 1973-03-15 | Agfa-Gevaert Ag, 5090 Leverkusen | Verfahren zur herstellung von dispersionen lichtempfindlicher silbersalze |
US3384580A (en) * | 1967-05-09 | 1968-05-21 | Acheson Ind Inc | Graphite dispersions |
US3495808A (en) * | 1967-08-29 | 1970-02-17 | Owens Corning Fiberglass Corp | Automatic binder mix system |
US3472770A (en) * | 1967-09-08 | 1969-10-14 | Chevron Res | Novel pinion grease |
DE1929064B2 (de) * | 1969-06-09 | 1975-07-31 | Chemische Fabrik Kalk Gmbh, 5000 Koeln | Verfahren zur Herstellung eines pastenförmigen Mittels zur Staubbindung im Kohlenbergbau |
US3833502A (en) * | 1973-04-30 | 1974-09-03 | Nalco Chemical Co | Method for improving the adherence of metalworking coolants to metal surfaces |
GB1500901A (en) * | 1973-10-25 | 1978-02-15 | Cementation Res Ltd | Forming a colloidal suspension |
DE2403053A1 (de) * | 1974-01-23 | 1975-07-31 | Supraton Auer & Zucker | Einrichtung zur herstellung einer suspension aus hochquellfaehigen stoffen |
GB1438215A (en) * | 1974-05-08 | 1976-06-03 | Lonz Ltd | High temperature lubricant |
CH596294A5 (en) * | 1974-05-08 | 1978-03-15 | Lonza Ag | High temp. lubricants for hot forming of metals |
CH609728A5 (en) * | 1974-09-06 | 1979-03-15 | Lonza Ag | High temperature lubricant for the hot-forming of metals |
US4050932A (en) * | 1975-04-07 | 1977-09-27 | General Motors Corporation | Colloidal graphite forging lubricant and method |
US4104178A (en) * | 1975-10-24 | 1978-08-01 | Wyman-Gordon Company | Water-based forging lubricant |
US3983042A (en) * | 1975-10-24 | 1976-09-28 | Wyman-Gordon Company | Water-based forging lubricant |
US4321295A (en) * | 1977-12-23 | 1982-03-23 | Ramu International | Modified graphite and process for using same |
JPS553030A (en) * | 1978-06-22 | 1980-01-10 | Hitachi Maxell | Operation informing system |
DE2828725A1 (de) * | 1978-06-30 | 1980-01-03 | Basf Ag | Verfahren zum homogenisieren zaeher fluessigkeiten |
DE2932459C2 (de) * | 1979-08-10 | 1985-10-31 | Mobil Oil Ag In Deutschland, 2000 Hamburg | Vorrichtung zum Lösen eines granulatförmigen Feststoffes in einer Flüssigkeit |
ZA84247B (en) * | 1983-02-18 | 1984-09-26 | Lonza Ag | Parting and lubricating agent in solid form |
-
1985
- 1985-10-02 CH CH4249/85A patent/CH665847A5/de not_active IP Right Cessation
-
1986
- 1986-09-23 US US06/910,724 patent/US4735734A/en not_active Expired - Fee Related
- 1986-09-24 ZA ZA867265A patent/ZA867265B/xx unknown
- 1986-09-25 CA CA000518992A patent/CA1272181A/fr not_active Expired - Fee Related
- 1986-09-29 PL PL1986261617A patent/PL261617A1/xx unknown
- 1986-09-30 CN CN86106627A patent/CN1006400B/zh not_active Expired
- 1986-09-30 DD DD86294817A patent/DD249858A5/de not_active IP Right Cessation
- 1986-10-01 AT AT86113474T patent/ATE60249T1/de not_active IP Right Cessation
- 1986-10-01 ES ES86113474T patent/ES2020173B3/es not_active Expired - Lifetime
- 1986-10-01 JP JP61234260A patent/JPS6291229A/ja active Pending
- 1986-10-01 SU SU864028344A patent/SU1498378A3/ru active
- 1986-10-01 EP EP86113474A patent/EP0218989B1/fr not_active Expired - Lifetime
- 1986-10-01 CS CS867061A patent/CS261247B2/cs unknown
- 1986-10-01 DE DE8686113474T patent/DE3677127D1/de not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
ES2020173B3 (es) | 1991-08-01 |
DE3677127D1 (de) | 1991-02-28 |
CS261247B2 (en) | 1989-01-12 |
CS706186A2 (en) | 1988-04-15 |
SU1498378A3 (ru) | 1989-07-30 |
US4735734A (en) | 1988-04-05 |
CH665847A5 (de) | 1988-06-15 |
ATE60249T1 (de) | 1991-02-15 |
CN1006400B (zh) | 1990-01-10 |
JPS6291229A (ja) | 1987-04-25 |
ZA867265B (en) | 1987-05-27 |
EP0218989A3 (en) | 1989-04-26 |
CN86106627A (zh) | 1987-04-01 |
PL261617A1 (en) | 1987-12-28 |
EP0218989A2 (fr) | 1987-04-22 |
DD249858A5 (de) | 1987-09-23 |
CA1272181A (fr) | 1990-07-31 |
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