DE2748319A1 - PROCEDURE FOR LUBRICATING A METALLIC MATERIAL FOR THE PROCESSING ITEM AND LUBRICANT FOR CARRYING OUT THE PROCESS - Google Patents

Description

"Method of lubricating a metallic material for its processing and lubricants for carrying out the process "

The processing of metals, such as rolling, forging, hot pressing, Punching, bending, embossing, drawing, cutting, punching and pressing on the lathe generally requires a lubricant. This facilitates such operations by, for example, reducing the effort required, avoids excessive adhesion and the wear and tear of punching tools and cutting jaws reduced. In addition, the lubricant gives the metal to be machined corrosion-preventing properties Properties. In the usual way of working, the metal becomes different chemical after it has been worked Subjected to treatments, e.g. coated with solutions, therefore, a cleaning process is necessary between the machining of the metal and the chemical treatment. That's why the lubricant should also offer the possibility, in addition to the properties mentioned above, that it can be used more commonly Cleaning agent can be easily removed from the metal surface.

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So far, lubricants for the aforementioned purposes have been liquids. The devices for applying such liquids are often expensive to operate and inconvenient to use. Also is Generally a drying oven is required to remove water or solvent from the lubricant as a carrier remove, thereby creating further significant investment costs. onen and arise for the use of such lubricants. In addition, difficulties often arise in automatic Devices for loading metal parts to be processed or in other devices conveying the metal parts because the liquid lubricants that are generally applied to the metal parts make them wet and slippery and therefore complicate the handling of the metal parts.

The invention is based on the object of providing a method using a lubricant a metallic material to be processed a particularly advantageous combination of good properties, such as lubricity, Corrosion resistance, good behavior under extreme pressure and gentle behavior towards tools, gives, wherein the lubricant is relatively easily removed completely from the surface of the metal after machining can be. Another task is to provide suitable lubricants.

These objects are achieved by the invention as it is characterized in the claims.

An essential feature of the method according to the invention is that lubricants are used which have a melting point above ambient temperature. Such lubricants are preferably used according to the invention, melt the fluids into easy flowing liquids which are also easily applied to the metal surface can. One advantage of such lubricants is that metal parts coated therewith can be stored under normal storage conditions can be handled more easily than usual

Metal parts coated with lubricants. L -J

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An essential feature of the lubricants used in accordance with the invention is their ability to act on the metal surface to impart sufficient lubricity. In this context, lubricity can be defined in various ways as is known to those skilled in the art. Different test methods are used, which in different Way to simulate the machining of a metal. In the context of the present invention, a lubricant is given lubricity ascribed to a metallic material when using the method described below a deflection of at most 135 »6 Nm is reached.

A strip of cold rolled steel with the dimensions

2
5 * 08 χ 3 ^, 29 cm is pulled between two jaws in an Instron Universal Tester (Model TT-C). Before drawing, the edges of the strip are deburred and the strip is steam degreased and then wiped with a clean cloth. The cleaned strip is evenly coated with a lubricant and secured in the test device.

The jaws of the test device are tightened with a torque wrench closed up to a torque of 54.24 Nm. The strip is withdrawn between the jaws 5 »08 cm at a speed of 12.70 cm / min. That for this required force torque, given in Nm, and the deviation of a uniform moment of force are registered.

The lubricants used according to the invention are solid at ambient temperature and ambient pressure. They melt preferably in the range of 35 to 7O ⁰ C, in particular from 38 to 55 ° C. When melted, these lubricants are easily flowable liquids.

The main component of the lubricants according to the invention is at least one essentially neutral ester, i.e. that im essentially all of that present from the acid component Acid groups are esterified. The following compounds are particularly suitable as the alcohols and acids on which this ester is based: *

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The alcohol A is a polyalkylene glycol, usually a Polyethylene or polypropylene glycol, preferably a polyethylene glycol. The polyalkylene glycol contains about 20 to 50 polyalkylene units. Such polyalkylene glycols are as commercial mixtures, such as the polyethylene glycol "Carbowax" (manufacturer Union Garbide), are available.

The alcohol B is at least one saturated aliphatic alcohol with at least 10 carbon atoms. Special examples are decanol, dodecanol, tetradecanol, stearyl alcohol, eicosanol and commercially available mixtures of such alcohols, as well corresponding polyols such as diols and triols. Preference is given to carbon alcohols, in particular saturated alkanols with in each case a hydroxyl group, especially straight-chain alkanoia.

The acid C is at least one aliphatic (^^ "pc-monocarboxylic acid, such as laurine, crystal, palmitine, stearine, eicosan, Oleic or linoleic acid. Mixtures of such acids are also suitable. Stearic acid is preferred.

The acid D is at least one aliphatic C ^ ₂₀ polycarboxylic acid, such as maleic, fumaric, succinic, adipic, glutaric, pimelic, sebacic, azelaic, suberic and citric acid, and mixtures thereof. Preferred polycarboxylic acids are dicarboxylic acids, in particular adipic, azelaic and sebacic acids.

Various esters and ester mixtures can be used in the process according to the invention. For example, esters are off an alcohol A and an acid G, such as a monostearate of a polyethylene glycol with an average of 22 to 4-8 oxyethylene units per molecule. However, the preferred esters contain a plurality of alcohol and acid components. So they consist, for example, of a mixture of at least one ester of an alcohol A and an acid G and at least an ester of an alcohol B and an acid D, the latter ester being about 5 to 95 percent by weight of the Represents ester mixture.

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Mixtures of neutral esters of alcohols A and B and acids C and D are particularly preferred Reacting the alcohol mixture with the acid mixture produced, generally in the presence of a strong acid as Catalyst. Most of the time, the alcohol mixture will contain about 2 to 4 equivalents of A per equivalent of B, and the mixture of acids will contain about 2 to 4 equivalents of C per equivalent of D. Below equivalent weight In the context of this invention, of an alcohol is its molecular weight divided by the number of hydroxyl groups per molecule understood. The equivalent weight can be determined analytically, especially for polyalkylene glycols. In the context of the present invention, its molecular weight is divided under the equivalent weight of a carboxylic acid by the number of carboxyl groups per molecule,

15 stood.

According to the invention, those lubricants are preferred which, in addition to the aforementioned esters, contain at least one agent which improves the properties under very high pressure. The most suitable agents for this are phosphoric acid salts the formula given in the claims. In this

12th
Formula R and R each denote a hydrocarbon radical, which means a radical having mainly hydrocarbon character. Such residues are for example

1. Hydrocarbon radicals, such as aliphatic radicals, for example Alkyl or alkenyl radicals, alicyclic radicals, such as cycloalkyl or cycloalkenyl radicals, optionally through aliphatic or alicyclic radicals substituted aromatic radicals as well as aromatic radicals substituted ali-

30 phatic and alicyclic residues,

2. Substituted hydrocarbon radicals, such as those radicals which do not contain a hydrocarbon radical as a substituent, however, the hydrocarbon character of the whole The rest is essentially not changed, and

3. Residues with heteroatoms, the hydrocarbon character of the entire remainder is essentially not changed and the remainder other atoms than carbon atoms, such as nitrogen, Oxygen and sulfur atoms, in a chain or

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contains a ring and this chain or this ring otherwise consists of carbon atoms.

In general, there are at most 3 substituents or heteroatoms, preferably at most 1, in the hydrocarbon radical Substituent or hetero atom, per 10 carbon atoms of the residue.

The hydrocarbon radicals in the phosphoric acid salt are generally free from acetylenic and ethylenic unsaturation and have no more than 30 carbon atoms, preferably at most 12 carbon atoms _/ on. In general, they are hydrocarbon radicals, such as the methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, decyl, dodecyl, vinyl, decenyl, cyclohexyl and phenyl groups, and also the corresponding isomers come into question. Phosphoric acid salts of the formula given are particularly preferred,

1 ^

in which R and R ″ each denote a lower alkyl radical having a maximum of 7 carbon atoms.
20th

The phosphoric acids from which the salts mentioned are derived also include dialkyl phosphoric acids, dialkyl phosphinic acids and thio derivatives of these acids. Preference is given to the salts of the formula mentioned, in which J? and X each represent a sulfur atom, in particular the salts of dithiophosphoric acid, ie salts of the formula mentioned in which a and b

1 2
each the number 1 and X and X each represent an oxygen atom. If M denotes an ammonium group in the formula mentioned, this also includes substituted ammonium salts, such as amine salts, within the scope of the invention. M is preferably zinc or lead, especially zinc.

The lubricants according to the invention optionally contain up to 2% of one of the phosphorus salts mentioned. The lubricants can also contain other additives in smaller amounts, for example in an amount of about 0.01 to 5.0 percent by weight. Particularly preferred other additives

are antioxidants, for example phenol derivatives. L _J

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'If

Further possible additives, which can be contained in the lubricant in the aforementioned amount, are given below :

Surfactants, generally nonionic, such as oxyalkylated phenols;

Aids for use under very high pressure, such as chlorinated waxes, sulphated hydrocarbons and sulphated Ester;

Anti-corrosive agents and agents for reducing abrasion;

Means for adjusting the friction, for example alkyl or alkenyl phosphates or phosphites in which the alkyl or alkenyl radical contains 10 to 40 carbon atoms, and their metal salts, especially zinc salts; C ^ Q ^ o- ^ acid amides; C | o_20-alkylamines, in particular tallow amines, and their ethoxylated derivatives; Salts of such amines with acids, such as boric acid or phosphoric acid, which are partially esterified as indicated above; C> | o_2O ~ ^{allcy- Lsu} * ^{> s} * ^ituted imidazoline derivatives and similar nitrogen-containing heterocycles; sulphurized derivatives of sperm oil and other fatty oils; basic barium or calcium salts of such oils or of amine-formaldehyde condensates, in particular those which are derived from the aforementioned TaIg amines; gels derived from basic alkaline earth metal sulfonates.

Melting point adjustment agents, generally relatively low melting esters such as dioctyl phthalate.

The lubricants according to the invention can also waxes and Contain waxy polymers. Examples are crystalline (including microcrystalline) and non-crystalline hydrocarbon waxes, hydroxylated hydrocarbons waxes, petrolatum and low molecular weight olefin poly-

merisate, such as the polyethylene "Bareco Polywaxes" (Petrolite L · -I

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Corporation). Such waxes or polymers are generally in amounts of about 0.25 "to 1.0 parts by weight per
Part by weight of ester present in the lubricant.

The lubricants according to the invention can by intimately mixing the ingredients, preferably in the liquid state,
mixed if more than one ingredient is used
will. In some cases it is preferred to use a substantially inert liquid diluent in order to obtain an intimate mixture of the ingredients. The expression
"Substantially inert" means the diluent
no appreciable reaction under the mixing conditions
the constituents of the lubricant. Liquids which are preferred as diluents are those which are solvents for the constituents to be mixed. Preferred solvents are non-polar liquids such as benzene,
Toluene, xylene and chlorobenzene. After mixing is complete, the diluent is preferably separated, generally by evaporation.

The lubricants of the invention may also contain pigment-like solid particles with a small particle size to the
Lubricity increases at temperatures above the melting point
to enhance. Pigments such as titanium dioxide are suitable for this

as rutile and as anatase, zinc oxide, lead zinc oxide, zinc sulfide, lead titanate, antimony oxide, zirconium oxide, white lead, basic
Lead silicate, lithopone, titanium-containing lithopone, titanium-barium pigment, titanium-calcium pigment, titanium-magnesium pigment,
Calcium carbonate, white talc, barite, magnesium silicate, aluminum silicate, diatomaceous earth, china clay, asbestine, silicon dioxide and chalk. Calcium carbonate is preferred. The amount of such pigments will generally range from about 0.1 to 0.2 parts by weight per part by weight of ester.

Preferred compositions are shown in the table below indicated by lubricants that are used in the invention Process are used.

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Γ CO U Ό Ό - τ * —1

αί O cn O (η ο cn— ¹

Component parts by weight

A B C D

Neutral adipic acid esters from commercially available
Mixture of mainly straight-chain C ^^ gl-

Alkanols * 10 -

Neutral azelaic acid esters from commercially available
Mixture of mainly straight-chain C ^ g_yjg-1-

Oo alkanols * - 8.5

oo stearic acid esters of "Carbowax 154-0", a

j £ Polyethylene glycol with an average of 22-48 '

^ * Oxyethylene units per molecule 90 76.5 - «\ \

O ζ / ζ I

° Ester blend made from 0.75 equivalent

"Carbowax 1540", 0.25 equivalent of a commercial blend of mainly straight chain
^ 14> iQ ~ l ~ alkanols *, 0.75 equivalent of stearic acid
'and 0.25 equivalent of adipic acid - - 100 90

Zinc salt of a mixture of dithiophosphoric acid _ro

isobutyl and primary amyl esters - 15-10 "-J

oo * Manufacturer: Procter & Gamble co

co L J

Any metal to be worked can be treated according to the method according to the invention. Examples of corresponding metals are ferrous metals, aluminum, copper, magnesium, titanium, zinc and manganese as well as their alloys and alloys that

5 contain other elements such as silicon.

The method according to the invention includes all corresponding methods, in which a metallic material with a lubricant that melts at a higher temperature before or during the machining is coated. For example, a cutting knife or a drawing tool can be coated with the lubricant which is then transferred to the workpiece to be machined through contact. The inventive, at Higher temperature melting lubricants generally form a continuous film over the entire surface of the workpiece. However, this film can only be partially are present on the surface.

The physical state of the lubricant during application on the metal surface is not critical. When the invention Process the lubricant as a solid, e.g., by rubbing, or as a liquid, e.g., by Brushing, spraying, dipping, pouring, rolling or counter-rolling, can be applied. Preferably, the lubricant is im liquid state, after which it is solidified by cooling. The lubricant can also be used during machining of the workpiece are fed directly to it.

An essential advantage of the method according to the invention and the lubricants according to the invention is that the lubricants applied in liquid form solidify to form a solid, non-blocking and non-slippery film on the metal surface, making the workpieces easy to handle and saving costs.
35

The surface temperature of the lubricant to be applied Metal at the time of application of the lubricant can be different and for example in the range of L -I

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Ambient temperature close to the decomposition temperature of the lubricant. This temperature depends on the type of treatment of the metal workpiece before or after the application of the lubricant, the melting point of the lubricant and its temperature at the time of application. Surface temperatures of the metal of about 20 to 125 ° C. are particularly suitable. At the time of applying the lubricant, the temperature of the lubricant should be higher than its melting point, preferably by at least 10 ⁰ C, particularly about 20 to 4O ⁰ C, so that this flows easily and uniformly distributed on the metal surface.

The molten lubricant can be applied to the metal surface with a minimum of space required, existing devices, such as winding devices used in steelworks, can be used. Since that Liquid applied lubricants solidify rapidly at ambient temperature and are dry, non-blocking and non-blocking If it becomes slippery, other conventional devices for handling the workpieces, such as transport wheels, can also be used will. The workpieces treated according to the invention can also be transported with forklifts. Another special one The advantage of the method according to the invention is that that, in contrast to known methods, there is no need for a drying oven, since the lubricants according to the invention do not contain any Separate water or solvent.

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Claims (1)

October 27th 1977 oc: M 247 (Hi / kä)
Case: LF-159O-WG THE LUBRIZOL CORPORATION
Cleveland, Ohio, V.St.A.
10 "Method for lubricating a metallic material for its processing and lubricants for the execution of the procedure " Priorities: October 27th, 1976. V.St.A., No. 731 060 February 8, 1977, V.St.A., No. 766 642 Claims 1. A method for laminating a metallic material for the processing thereof, characterized in that a lubricant is used which I. a content of at least one substantially neutral ester on the basis a) a polyalkylene glycol with about 20 to 50 polyoxyalkylene units (A) or a mixture of such a polyalkylene glycol (A) with at least one saturated aliphatic alcohol with at least 10 carbon atoms (B) as well .. ■ '' b) at least one aliphatic "C ₁ 2 ^ 25" ^{ilonocartonsäu} ~ re (C) or a mixture of such monocarboxylic acid (C) at least one aliphatic C ^ _ ₂ q-polycarboxylic acid (D) and 809818/0908 ORIGINAL INSPECTED 1 II. Has a melting point in the range of 30 to 100 ⁰ C. 2. The method according to claim 1, characterized in that there is a lubricant with a melting point in the range from about 35 to 70 ° C begins. 3. The method according to claim 2, characterized in that a lubricant with a content of at least an ester based on an alcohol A and an acid C is used. 4. The method according to claim 2, characterized in that there is a lubricant containing at least one Esters of an alcohol A and an acid C and at least an ester of an alcohol B and an acid D is used, the latter ester constituting about 5 to 95 percent by weight of the ester mixture. 5. The method according to claim 4, characterized in that a lubricant containing esters from a polyethylene glycol A with an average of 22 to 48 oxyethylene units, a predominantly straight-chain C ^ ^ pQ-alkanol or a mixture of such alkanols, an alkanecarboxylic acid C and adipine -, azelaic and / or sebacic acid as acid D is used. 6. The method according to claim 5, characterized in that there is a lubricant containing an ester the base of stearic acid is used as acid C. 7. The method according to claim 2, characterized in that a lubricant containing an ester from a mixture of alcohols A and B and a mixture of acids C and D. 809818/0908 8. The method according to claim 7, characterized in that a lubricant containing an ester from about 2 to 4 equivalents of A per equivalent of B in the alcohol mixture and about 2 to 4 equivalents of C per equivalent of D im 5 Acid mixture begins. 9. The method according to claim 8, characterized in that a lubricant containing an ester of a polyethylene glycol A with an average of 22 to 48 oxyethylene units, a mainly straight-chain C ₁ 4_ ₂ o "" alkanol B or a mixture of such alkanols, one Alkanecarboxylic acid C and adipic, afcelainic and / or sebacic acid as acid D are used. 10. The method according to claim 9 »characterized in that there is a lubricant containing an ester the base of stearic acid is used as acid C. 11. The method according to claim 2, characterized in that a lubricant with an additional content of a phosphoric acid salt of the general formula 25 R uses, in which M is an atom of a metal from group I or II of the periodic table or an aluminum, tin, cobalt, lead, molybdenum, manganese or nickel atom or the ammonium 1 2 1 group, R and R each represent a hydrocarbon radical, X, X, X ^ and X each represent an oxygen or sulfur atom, and a and b each represent the number 0 or 1. 12. The method according to claim 11, characterized in that a SchmlermitteT with an additional content of one Phosphoric acid salt of the formula mentioned is used in which M is a 809818/0908 Zinc atom, R and R ^ each represent a lower alkyl radical, X 2 3 4 and X each represent an oxygen atom, X ^ and X each represent Sulfur atom and a and b each represent the number 1. 13. The method according to claim 1 to 12, characterized in that that one uses a lubricant with an additional content of an antioxidant. 14. Lubricant for performing the method according to claim 1 to 13, characterized by I. a content of at least one substantially neutral ester on the basis a) a polyalkylene glycol with about 20 to 50 polyoxyalkylene units (A) or a mixture of such a polyalkylene glycol (A) with at least one saturated aliphatic alcohol with at least 10 carbon atoms (B) as well b) at least one aliphatic C ^ 2-25 ~ ^ ^{onocarboxylic acid} (C) or a mixture of such a monocarboxylic acid (C) with at least one aliphatic C ^ _pQ polycarboxylic acid (D) and II. A melting point in the range from 30 to 100 ° C. 15. Agent according to claim 14, characterized by a melting point in the range from about 35 to 70 ^° C. 16. Agent according to claim 15, characterized by a content of at least one ester based on an alcohol A and an acid C. 17 · Means according to claim 14, characterized by a content of at least one ester of an alcohol A and an acid C and at least one ester of an alcohol B and an acid D, the latter ester about 5 to Represents 95 percent by weight of the ester mixture. 809818/0908 18. Agent according to claim 14, characterized by a content of an ester of a polyethylene glycol (A) with an average of 22 to 48 oxyethylene units, a predominantly straight-chain C ^^ _ 2Q "^^ ^Lano ^ ^B or a mixture of such alkanols, an alkanecarboxylic acid C and Adipic, azelaic and / or sebacic acid as acid D. 19. Agent according to claim 18, characterized by stearic acid as acid C.
10 20. Means according to claim 15 * characterized by a content on an ester from a mixture of alcohols A and B and a mixture of acids C and D. 21. Means according to claim 20, characterized by a content on an ester of about 2 to 4 equivalents of A per equivalent of B in the alcohol mixture and about 2 to 4 equivalents C per equivalent of O in the acid mixture. 22. Composition according to claim 21, characterized by a content of an ester of a polyethylene glycol A with an average 22 to 48 oxyethylene units, a mainly straight-chain Cj ^ gQ-alkanol B or a »mixture of such Alkanols «of an alkanecarboxylic acid C and adipic, ²⁵ azelaic and / or sebacic acid as acid D. 23. Composition according to claim 22, characterized by stearic acid as acid C * 24. Means according to claim 15, characterized by an additional Content of a phosphoric acid salt of the general formula " X ^{3 Ri} < ^x1 > a 35 ^ 809818/0908 in which M is an atom of a metal from group I or II of the periodic table or an aluminum, tin, cobalt, lead, Molybdenum, manganese or nickel atom or the ammonium group, 12 1 7 ~ * k R and R each represent a hydrocarbon radical, X, X, X ^ and X each represent an oxygen or sulfur atom and a and b each represent the number 0 or 1. 25 · Means according to claim 24, characterized by an additional Content of a phosphoric acid salt of the above 1 2 Formula in which M is a zinc atom, R and R each have a lower 12 3 ren alkyl radical, X and X each an oxygen atom, X and X each represent a sulfur atom and a and b each represent the number 1. 26. Means according to claim 14 to 25, characterized by an additional content of an antioxidant. 809818/0908