A METHOD IN THE MECHANICAL WORKING OF ALUMINIUM AND ALUMINIUM ALLOYS IN THE PRESENCE OF A COOLING LUBRICANT, AND A CONCENTRATE OF THE COOLING LUBRICANT

Abstract: Mechanical working of aluminium and aluminium alloys is carried out in the presence of a water-based cooling lubricant, which has the form of a stable solution and contains as lubricating and corrosion inhibiting agents a combination of (a) a carboxyl compound having a hydrophobic group of 7-22 carbon atoms, (b) a tertiary alkylalkanol amine having a molecular weight of less than 300 and (c) a water soluble organic solubiliser having a molecular weight of less than 400 and a maximum hydrocarbon group of 6 carbon atoms. The amounts of the carboxyl compound and the tertiary alkyl­ alkanol amine are chosen so that a base/acid equivalent ratio between the alkanol amine and the carboxyl compound is less than 1.0, preferably less than 0.9. A concentrate, which after dilution with water, may be used as a cooling lubricant is also disclosed.

Description: The present invention relates to a method in the mechani­ cal working of aluminium and aluminium alloys in the presence of a water-based cooling lubricant, and to a concentrate which, after dilution with water, may be used as cooling lubricant. The invention has been developed especially for the cold rolling. Normally, kerosene-based cooling lubricants are used for cold rolling of aluminium. However, the use of kerosene-based cooling lubricants has been found to entail a number of dis­ advantages, among which may be mentioned high emission of hydrocarbons, considerable fire hazard and limited cooling effect. The poor cooling effect causes undesired restrictions in production capacity. It has therefore been proposed to replace the kerosene-­ based cooling lubricants by water-based emulsions containing specific additives which reduce corrosion and/or the friction between the metal surface and the working tool, especially at high pressures. Such water-based systems are disclosed in, inter alia, US patent specification 4.243.537 and European patent application 115.926, and they contain as lubricating and corrosion inhibiting agents a mixture of an alkanol amine, a carboxylic acid, and a polyoxyalkylene polymer. In US Patent Specification No. 3 374 171 similar lubricant compositions are disclosed for use in metal working, e.g. in the machining of iron. In spite of the obvious advantages provided by water-­ based cooling lubricant systems, they have not found wide-­ spread use in the rolling of aluminium or aluminium alloys because such systems, with low contents of lubricating and corrosion inhibiting agents, cause water stains on the metal surfaces, poor lubrication and/or insufficient corrosion protection of the working tools. Water staining, so called white rust, of the aluminium metal surfaces is primarily due to the fact that the components included in the cooling lubricant provide insufficient corrosion protection for aluminium. Although, admittedly, the lubrication and corrosion protection are improved if the content of lubricant and corrosion inhibitor is increased, there is obtained during the subsequent heat treatment a disagreeable staining which is due to the fact that the components of the cooling lubricant have been converted and burned into the metal surfaces. Another problem that is difficult to master in rolling work is that roll marks and other physical damage may occur in the rolled metal surface because metal is torn from the billet which is being rolled, and is welded to the rolls. The resulting irregularities may, upon continued rolling, cause physical damage to the rolled metal surface. It has now been found possible to effect cold or hot rolling of aluminium or aluminium alloys so that satisfactory lubrication and low corrosion are obtained without any disagreeable staining of the metal surface during subsequent heat treatment. This is achieved, according to the present invention, in that the mechanical working is effected in the presence of a water-based cooling lubricant in the form a stable solution, at least at a temperature within the range of 20-70°C, and containing (a) a carboxyl compound having the formula R₁COOH, in which R₁ is a hydrophobic group having 7-22 carbon atoms, and (b) an tertiary alkyl alkanol amine having a molecular weight of less than 300, and (c) a water-soluble, organic solubiliser having a molecular weight of less than 400 and a maximum hydrocarbon group of 6 carbon atoms, the base/acid equivalent ratio between the amine and the carboxyl compound being less than 1.0, preferably less than0.9. By stable solution is meant in the context of this invention a solution which does not within a foreseeable period of time, i.e. during at least one month, separate into two or more phases. It is of essential importance that the base/acid equiva­ lent ratio is less than 1.0, preferably less than 0.9, most preferably between 0.5-0.8 in order to obtain good lubrication properties. The EP application 115.926 and US Patent Specification 3 74 171 only discloses embodiments where the equivalent ratio is well above 10. In the US Patent Specification 3 374 171 water soluble alkanolamines, such as triethanolamine, are used in a metal working fluid as a corrosion inhibiting agent, in which the carboxylic acid is soluble and forms the corresponding salt. In addition to the function as an inhibitor the alkanolamines also have the task of forming residue upon machinery parts. This means that the alkanolamines have to be present in larger molar amounts than the carboxylic acid. According to the invention all re­ sidues on the aluminium surface have to be minimized in order to avoid the formation of annealing residues. This is achie­ ved by using the tertiary alkylalkanolamine in such an amount that the base/acid equivalent ratio is less than 1.0. The equivalent ratio of the invention results in a cooling lubri­ cant that normally has a pH-value less than 8.In air the alu­ minium surface is oxidized and obtains an isoelectric point a pH-value of about 8,5-9. Thus, the process of the invention is carried out on the acid side of the isoelectric point. The choice of amine compound is also essential. The tertiary alkylalkanolamines according to the invention contribute both to the formation of a solution and to the corrosion inhibiting properties without causing annealing residues. When the compositions disclosed in the US Patent Specification 4 243 537 is used in aluminium rolling tests, the aluminium sheets obtained exhibit physical damages as well as unacceptable annealing residues including miscolouring. It has been found that these results at least partly depends on the use of triethanolamine. Practical tests have shown that it is of great impor­ tance to the rolling characteristics that the cooling lubri­ cant is present in the form of a stable solution, and not not as an emulsion. Presumably, the kinetics in the stable solu­ tion according to the invention are promoted such that the metal surfaces quickly obtain a homogeneous and well covering protective layer of the carboxyl and the tertiary alkyl alkanol amine, whereby the formation of local deposits and excess which, during the subsequent heat treatment, may cause staining, is counteracted. A further essential advantage is that physical damage to the rolled surfaces can be avoided. A further essential advantage of the cooling lubricant according to the invention is that it is easy to filter in order to remove impurities formed during working. The cooling lubricant may then be reused without any appreciable risk of soiling, metal-catalysed oxidative degradation, or microbial degradation. In addition to the carboxyl compound (a), alkanol amine (b), and the solubiliser (c) the cooling lubricant may contain (d) a polar, predominantly hydrophobic, nonionic compound in order to further improve lubrication. The hydrophobic group R₁ of the carboxyl compound is preferably derived from straight saturated aliphatic com­ pounds, although branched unsaturated aliphatic groups are also useful. Especially preferred groups are alkyl groups containing 8-17 carbon atoms. Specific examples of suitable carboxylic acids are pelargonic acid, decanoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, and coconut fatty acids as well as mixtures thereof. The hydrophobic group R₁ may also contain hetero atoms, such as oxygen, sulphur and nitrogen which are included in such functional groups as ether, thioether, ester, hydroxyl, carboxyl, and amide groups. Examples of such carboxyl compound are wherein R₈ is an alkyl having 1-4 carbon atoms, or hydrogen, and R₇ is a hydrocarbon group, preferably an aliphatic hydrocarbon group, R₇ and R₈ being selected such that the meaning of R₁ is satisfied. The tertiary alkylalkanol amine (b) contains at least one substituent with a hydroxyl group. It will therefore be water-soluble or capable of forming micelles. Preferred tertiary alkylalkanol amines (b) are having the formula R₂R₃R₄N, wherein R₂ is a hydroxyalkyl group having 1 - 4 carbon atoms or a group of formula (A) n H, wherein A is an alkyleneoxy group having 2-4 carbon atoms, and n is an integer from 1 to 3, R₃ is an alkyl group having 1-6 carbon atoms, and R₄ represents a group having the same meaning as R₂ and R₃. Examples of suitable tertiary alkylalkanol amines are diethanol ethyl amine, diethanol propyl amine, diethanol butyl amine, diethanol pentyl amine, diethanol hexyl amine and the corresponding dipropanol amines, and ethanol diethyl amine, ethanol dipropyl amine, ethanol dibutyl amine and the corresponding propanol amines. The above mentioned compounds may also be alkoxylated with ethylene oxide, propylene oxide and/or butylene oxide. Usually, the amount of the carboxylic compound and the alkanol amine is selected in such a way that the base/acid equivalent ratio will be 0.5-.0.9, which normally results in a cooling lubricant having a pH of about 6-8. A deficiency in the alkanol amine in relation to the carboxyl compound has been shown to improve the lubricating effect. If priority is given to good lubrication, it is advisable to select a base/acid equivalent ratio between the alkanol amine and the carboxyl compound of from 0.5 up to 0.8. The solubiliser (c) is a water-soluble low-molecular compound having polar groups, such as hydroxyl groups and ether groups. Preferably, the molecular weight is below 250.Examples of such compounds are ethers of ethylene glycol, such as mono- or dibutyl ethylene glycol, mono- or dipropyl etylene glycol, mono- or diethyl ethylene glycol, or the corresponding mono- or dicompounds of diethylene glycol, triethylene glycol, and alcohols, such as pentol, butanol, propanol, and isopropanol. Of the above mentioned solubilisers, monoethers of mono- or diethylene glycol are preferred. The nonionic compound (d) which primarily contributes to the lubricating effect of the cooling lubricant must be predominantly hydrophobic in character. By this is meant that it should have a HLB value of less than 10, preferably less than 9, such nonionic compounds being preferred as are essentially insoluble in water. Suitable compounds (d) are those having the formula R₅(B) m OR₆, wherein R₅ is a hydro­ carbon or acyl group having 8-24 carbon atoms, B represents an oxyalkylene group having 2-4 carbon atoms, R₆ is hydrogen, an alkyl or acyl group having 1-4 carbon atoms, and m is an integer from 0 to 4. The nonionic compound (d) may be both aromatic and aliphatic, but the aliphatic compounds are preferred. Examples of preferred nonionic compounds are hydroxyl compounds, such as octanol, decanol, dodecanol, tetradecanol, hexadecanol, oxo alcohols having 9-17 carbon atoms, nonyl phenol, octyl phenol, and dodecyl phenol, as well as ethoxylates of the above mentioned alcohols with 1-4 moles of ethylene oxide per mole of hydroxyl compound. These hydroxyl compounds may be summarised by the general formula R₅(B) m OH wherein R₅, B, and m have the meanings indicated above. Other examples of nonionic compounds are fatty acids, alkoxylated or esterified with the compound H(B) m OR₆ wherein B, R₆, and m have the meaning indicated above. Specific examples of this type of compounds are C₁₁H₂₁COOC₂H₄OH; C₁₁H₂₃COOCH₃; C₉H₁₉CO(OC₂H₄)₂OCH₃ Preferred ester compounds are those having the general formula R₅OR₆ wherein R₅ is an acyl group having 8-24 carbon atoms, and R₆ is an alkyl group having 1-4 carbon atoms. In addition to the above mentioned components the water-based cooling lubricant according to the invention may also contain conventional additives, such as bactericidal agents, antifoam additives, viscosity controlling agents, perfumes and additional agents capable of supplementing lubrication and corrosion protection. Examples of additional agents improving the lubrication are polymers based on ethylene oxide and higher alkylene oxides. The alkylene oxides may be both random coupled and coupled in blocks. In preparing the cooling lubricant according to the invention, it is preferred first to prepare a concentrate which suitably may contain the following components. After diluting the concentrate with water, a cooling lubricant is obtained which is ready for use. A suitable composition is as follows. The solution ready for use preferably has a water content within the range 70-95% by weight. The invention is further illustrated by the following Example. Example Cold rolling of annealed aluminium sheet of grade AA3004 was carried out in a single stand with rolls having a diameter of 159 mm in the presence of any one of the cooling lubricants mentioned below. During rolling, the sheet thickness was reduced from 1.05 mm to 0.63 mm. The requisite rolling force was determined as the pressure in the hydraulic system transferring the compressive force to the rolls. After rolling, the surfaces were judged visually with respect to physical damage on a scale from 0 to 1. The value 0 designates a surface which is up to standard, i.e. a surface essentially free from physical damage, while 1 designates a surface not up to standard, i.e. a surface with visible physical damage. The rolled aluminium sheets were wiped clean and supplied with cooling lubricant in adundance, whereupon they were heated to 360°C for five hours in air. The appearance after heating was judged visually on a scale from 0 to 4 with respect to, on the one hand, the degree of blackening and, on the other hand, the proportion of stained surface. The points of the degree of colour and stained surface were summed up to a total assessment under the concept annealing residues. Points 0-1 are excellent, points 2-3 are well up to standard, points 4-5 are just up to standard, and points 6-8 are below standard. By "just up to standard" is meant that the aluminium sheets from annealing residues point of view would just be commericially acceptable. In order to determine the corrosive effect of the cooling lubricant upon iron, cast-iron ships were placed for 24 hours on a filter paper that had been soaked with a specific amount of the cooling lubricant, whereupon a grid having 126 intersections on an area of 1500 square cm was placed over the filter paper, and the occurance of corrosion was determined for each point of intersection on the grid. The iron corrosion was then expressed as the number of intersecting points with rust in relation to the total number of intersecting points. White rust was determined by coating aluminium sheets with the cooling lubricant and then stacking the sheets and cooling them for 1 hour at -20°C, whereupon they were exposed for 2 hours to humid air of room temperature. After that, the sheets were heated to 80°C for 10 hours. The white rust was then assessed in the same manner as the iron corrosion. From essentially anhydrous concentrates, the following cooling lubricants according to the invention were prepared and used for the cold rolling in this Example. All cooling lubricants were in the form of a stable solution at 20°C. For comparison, the following cooling lubricants were prepared. They all were in the form of an emulsion within the entire temperature range 20-70°C. The cooling lubricants A, B and C are in accordance with US Patent Specification 4 243 537, while the cooling lubricants D and E are formulated in accordence with EP Patent Application 115 926. As will be evident from these results, the cooling lubricants according to the invention provide, as compared with prior art technique, rolled aluminium surfaces having a far better physical appearance. Iron corrosion and white rust are maintained simultaneously at a very low level which, in general, is even essentially lower than for the cooling lubricants of the comparison compositions. In addition, the cooling lubricants according to the invention give a low level of annealing residues, which in all cases are essen­ tially lower than in the comparison test.

Claims: 1. A method in the mechanical working of aluminium and aluminium alloys, in the presence of a waterbased cooling lubricant containing lubricating and corrosion inhibiting agents, characterised in that the cooling lubricant at lest at a temperature within the range 20-70°C is present in the form of a stable solution, and that it contains, as lubricating and corrosion inhibiting agents, a combination of (a) a carboxyl compound having the formula R₁COOH, in which R₁ is hydrophobic group having 7-22 carbon atoms, (b) a tertiary alkylalkanol amine having a molecular weight of less than 300, and (c) a water soluble organic solubiliser having a molecular weight of less than 400 and a maximum hydrocarbon group of 6 carbon atoms, the base/acid equivalent ratio between the amine and the carboxyl compound being less than 1.0, preferably less than 0.9.9. 2. A method as claimed in claim 1 or 2, characterised in that the cooling lubricant further contains (c) a polar, essentially hydrophobic, nonionic compound. 3. A method as claimed in claim 3, characterised in that the compound (c) has the formula R₅(B)mOR₆, wherein R₅ is a hydrocarbon or acyl group having 8-24 carbon atoms, B represents an oxyalkylene group having 2-4 carbon atoms, R₆ is hydrogen, an alkyl or acyl group having 1-4 carbon atoms, and m is an integer from 0 to 4. 4. A method as claimed in any one of claims 1-4, characterised in that the tertiary alkylalkanol amine (b) has the formula R₂R₃R₄N, wherein R₂ is a hydroxylalkyl group having 1 - 4 carbons atoms or a group having the formula (A)nH, wherein A is an alkyleneoxy group having 2-4 carbon atoms, n is an integer from 1 to 3, R₃ is an alkyl group having 1-6 carbon atoms, and R₄ represents a group having the same meaning as R₂ or R₃. 5. A method as claimed in claims 1-5, characterised in that the hydrophobic group R₁ of the carboxyl compound (a) is an aliphatic hydrocarbon group. 6. A method as claimed in claims 1-6, characterised in that the base/acid equivalent ratio between the alkanol amine and the carboxyl compound is from 0.5 up to 0.8. 7. A method as claimed in claims 1-7, characterised in that the cooling lubricant contains the carboxyl compound (a) in a content of 0.5-25, preferably 2-15% by weight, the tertiary alkylalkanol amine (b) in a content of 0.1-20, preferably 1-15% by weight, and the solubiliser (c) in a content of 0.5 - 33, preferably 1-18% by weight. 8. A method as claimed in claims 3-8, characterised in that the cooling lubricant contains the nonionic compound (d) in a content of at most 10, preferably 0.2-10% by weight. 9. A concentrate which, after dilution with water, is suitable for use in the method as claimed in claims 1-9, characterised in that it has the following composition:

Inventors: SANDBERG, ELINA, SKOLD, ROLF, Sköld, Rolf 
Applicants: BEROL (SUISSE) S.A.
Application year: 1987
Main classification: C10M173
IPC codes: C10N40, C10N30, C10M173, C10N70