US3085918A - Cleaning process - Google Patents

Cleaning process Download PDF

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Publication number
US3085918A
US3085918A US29336A US2933660A US3085918A US 3085918 A US3085918 A US 3085918A US 29336 A US29336 A US 29336A US 2933660 A US2933660 A US 2933660A US 3085918 A US3085918 A US 3085918A
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United States
Prior art keywords
metal
water
solvent
cleaning
surface active
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Expired - Lifetime
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US29336A
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English (en)
Inventor
Sherliker Francis Raymond
Ellis Kenneth Charles Henry
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
    • C23G5/028—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons
    • C23G5/02806—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing halogenated hydrocarbons containing only chlorine as halogen atom
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • C23G5/06—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using emulsions

Definitions

  • This invention relates to an improved cleaning process adapted for removing from non-absorbent articles such as metal, porcelain, glass or plastics, contaminants consisting mainly of metal or metallic oxides suspended in aqueous, fatty, waxy or soapy media.
  • lubricants used which are not readily removed by the conventional metal degreasing solvents.
  • the lubricant itself may be adequately removed by simple solvent cleaning but particles of metal dust or swarf and/or metal oxide are left behind and these can only be removed by hand cleaning.
  • polishing compositions which are based on metal oxides, for instance rouges, suspended in fatty, waxy or soapy materials and which are not effectively removed by the metal degreasing solvents.
  • Typical difiicultly removable contaminants are, for instance, those which include metal soaps such as aluminium stearate or zinc naphthenate.
  • metal soaps such as aluminium stearate or zinc naphthenate.
  • it has been customary to remove such tenaciously adherent contaminants by treatment with an aqueous alkali the mechanism of the procedure being, as is believed, that the alkali saponifies at least a portion of the metal soap, whereupon the alkali metal soap so formed exerts its usual and Well-known detergent action to remove and suspend the other constituents of the contaminant.
  • such treatments With aqueous alkali must be followed by repeated water rinses to remove residual alkali and saponification products and then by drying treatments; these can be time-consuming and expensive and they can, moreover, themselves produce
  • the process is preferably, but not necessarily, carried out at elevated temperature.
  • Some form of agitation is desirable and in most cases this is conveniently provided by the thermal currents set up by the use of a heated, preferably refluxing, solution in which the articles to be cleaned are immersed.
  • a heated, preferably refluxing, solution in which the articles to be cleaned are immersed.
  • one very convenient way of carrying out the procedure is to treat the articles with the specified cleaning solution contained in a simple conventional metal degreasing plant which requires only Slight modification in a manner more particularly described hereinafter.
  • the two-phase cleaning liquid will be referred to as the cleaning solution, notwithstanding that since it is a two-phase system it is not strictly correct to call it a solution.
  • the solution to be used in the cleaning bath contains 0.001% to 1% by weight, preferably 0.05% to 0.5% of the surface active agent and a proportion of water up to 5%, preferably 1% to 2%, by weight.
  • the condensate is first passed to a water separator and the solvent, so separated from the water is returned to the rinsing bath, whence it steadily overflows into the main cleaning bath. If the specified proportions of water and cationic surface active agent are used, a simple brief dip in the rinsing bath, which is sufficiently agitated by being kept boiling, provides an adequate and expeditious final rinsing treatment which will remove any traces of the cationic surface active agent from the cleaned workpieces.
  • the emulsifying agents contemplated for use in this process were all surface active agents of an anionic character and the whole tenor of the teaching was that stable aqueous emulsions should be used, it being suggested that various phenols and aliphatic or aromatic amines be added for the specific purpose of stabilising the emulsions.
  • the teaching was to use emulsions containing large proportions of or even consisting predominantly of water, a composition specifically illustrated containing 25% to 30% of the volatile fat solvent, 1% to 2% of the emulsifying agent, 0.5% to 1% of a stabiliser and about 70% of water.
  • Such compositions are, of course, oil-in-water emulsions.
  • surface active agents of a radically different character namely, cationic surface active agents, that is agents whereof the ion possessing the surface active properties is the positive ion or cation, and thereby we secure considerable advantage in that the process is simplified and made more expeditious.
  • FIGURE represents somewhat diagrammatically a cross-section of a conventional two-compartment metal dcgreasing plant slightly modified to adapt it for the purposes of the present process.
  • the outer container 1 is divided by a bafile into two separate compartments 2 and 3, each of which is provided with heating means 4 at its base.
  • Compartment 2 is the cleaning compartment which contains the mixture of solvent, cationic surface active agent and water and 3 is the rinsing tank which contains the virtually ptu'e solvent.
  • the liquor in each compartment is kept boiling by means of the heater 4.
  • Plates 5 are provided for supporting the work to be treated.
  • vapours of solvent rising from compartment 3 and of an azeotrope of solvent and water rising from compartment 2 form a vapour zone lying above the liquor levels.
  • These vapours condense on the condensing coils 6 which, lying adjacent to the upper walls of the container, effectively contain the vapour within the system, the normal vapour level being shown by the line '7.
  • Thermostats (not shown) control the operation of the heaters 4 so as to maintain the vapour line 7 in the desired position.
  • the condensate is collected in a trough 8 which runs round the walls below the condensing coils. From the trough 8 the condensate is passed via pipe to a water separator 10 wherein it separates into two layers.
  • the upper layer of water overflows by pipe 11 and is returned at the point 12 to the base of the cleaning compartment 2.
  • the lower layer of solvent returns by the lower pipe 13 to the rinsing compartment 3 whence it overflows by the weir 14 into the cleaning compartment 2.
  • the box-like conduit 15, which may surround two or all four Walls of the plant, is an optional further safety feature. It is maintained under slight vacuum so that in case of any sudden upward surge of vapour arising, for instance, from the introduction of an unusually wet load of work into the plant, any solvent vapour that escapes beyond the condensing coils is drawn off into the ventilating system and so is prevented from contaminating the atmosphere of the factory.
  • the work to be cleaned is immersed in the cleaning compartment 2 for an appropriate short time (of the order of a few seconds to a minute or so), the thermal agitation of the boiling solvent being adequate to bring it into intimate and effective contact with all parts of even intricately shaped workpieces.
  • the work is then removed from the liquor, optionally held in the vapour zone for a few seconds (where solvent vapour condensing on the work washes it, the liquid falling back into the cleaning compartment) dipped briefly into the rinsing compartment, and then removed slowly through the vapour zone so that it emerges from the plant cleaned, dried and free from water spots or stains.
  • Example 1 The articles to be treated are impact extruded aluminium sans made with the use of a conventional extrusion lubricant based on calcium stearate which (after use) cannot be satisfactorily removed by a thorough treatment with trichloroethylene in a conventional metal degreasing plant; even after such treatment, .the insides of the cans are not fully clean, since on wiping them with tissue paper the paper is visibly soiled.
  • a number of such cans are immersed for 30 seconds in a boiling bath of trichloroethylene containing 0.25% of cetyl pyridinium bromide and 1% of water contained in the cleaning compartment of a two-compartment plant such as is described above.
  • the cans are then removed from the bath, held momentarily in the vapour zone to allow them to drain, immersed for 30 seconds in boiling clean trichloroethylene in the rinsing compartment, and then removed slowly through the vapour zone so that they emerge from the plant quite dry. They are found to be thoroughly clean and to exhibit a particularly bright lustrous finish.
  • tissue paper When the insides of the cans are wiped with tissue paper the paper is not soiled.
  • Example 2 Optical lenses just removed from a polishing head and so contaminated with specks of pitch and coated with an aqueous polishing composition based on cerium and zirconium oxides are immersed for 30 seconds in a refluxing bath of trichloroethylene containing 0.25% of cetyl pyridinium bromide and 1% of water (both percentages being by weight based on the weight of the solvent) contained in the cleaning compartment of a two-compartment plant such as is described above.
  • the lenses are then removed from the bath, held momentarily in the vapour zone to allow them to drain, immersed for 30 seconds in boiling clean trichloroethylene in the rinsing compartment of the plant, again held in the vapour zone to drain and then removed from the plant. They are thus obtained in a much cleaner and brighter condition than following the conventional procedures adopted hitherto, namely hot solvent treatment to remove the pitch followed by an aqueous acid wash to remove the metal oxides.
  • Example 3 Copper and brass cutlery forms which prior to plating have been polished with a composition containing aluminium oxide suspended in an aqueous medium with the aid of sodium salts of mixed long chain fatty acids and which are encrusted with this material are cleaned in the manner described in Example 1.
  • the articles are thoroughly cleaned and have a particularly bright and lustrous finish; they are suitable for passing forthwith to the plating shop.
  • Example 4 Complex components fabricated some in steel and some in aluminium alloy and having internally milled and lapped portions, including sections machined at the base of deep blind holes were cleaned in the manner described in Example 1.
  • the contaminant was mainly metal dust and swarf held in the lubricant. After this cleaning the proportion of castings rejected at the inspection was less than 1%, whereas with the ultrasonic cleaning procedure previously employed the reject rate was as high as 10%.
  • cetyl pyridinium bromide used as the cationic surface active agent in the above examples
  • other members of that class may be used, for instance, other long chain quaternary ammonium salts such as cetyl trimethyl ammonium bromide, long chain dialkyl dimethyl ammonium chlorides or bromides and long chain alkyl dimethyl benzyl-ammonium chlorides, likewise other types of cationic surface active agents, such for instance, as an agent made by condensation of methyl octadecylamine with 4.6 molecular proportions of ethylene oxide.
  • cationic surface active agents which have a pronounced emulsifying action should, for obvious reasons, be avoided.
  • the time needed for the whole treatment is surprisingly short and may be anything from a matter of seconds up to 1 or 2 minutes it is rarely necessary for it to extend beyond 3 or 4 minutes.
  • An improved procedure for removing from the surfaces of non-absorbent articles tenaciously adherent contaminants which consist mainly of particles of metal and metal oxides suspended in aqueous, fatty, waxy and soapy media and which are not freely and rapidly removed by the conventional metal-degreasing solvents which comprises treating the contaminated surfaces, with an agitated, intimately commingled, two-phase liquid system consisting essentially of a chlorinated hydrocarbon containing dissolved therein 0.001% to 1% of its weight of a cationic surface active agent and also containing mixed therewith a proportion of water not exceeding 5% by weight of the chlorinated hydrocarbon.
  • chlorinated hydrocarbon is a member of the group consisting of trichloroethylene, perchloroethylene, methylene chloride and 1 1: l-trichloroethaneL 3.
  • the proportion of cationic surface active agent employed is 0.05% to 0.5% of the weight of the chlorinated hydrocarbon and the proportion of water is 1% to 2% of the weight of the chlorinated hydrocarbon.
  • a process as set forth in claim 1 including rinsing said articles with a bath of said chlorinated hydrocarbon after immersion in said two-phase liquid system.
  • a process as set forth in claim 1 including exposing said articles to vapor of said chlorinated hydrocarbon after immersion in the two-phase liquid system.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Detergent Compositions (AREA)
  • Cleaning By Liquid Or Steam (AREA)
US29336A 1959-05-22 1960-05-16 Cleaning process Expired - Lifetime US3085918A (en)

Applications Claiming Priority (1)

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GB17484/59A GB898046A (en) 1959-05-22 1959-05-22 Improved cleaning process

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US3904430A (en) * 1972-09-07 1975-09-09 Ici Ltd Cleaning process using a non-azeotrope forming contaminated cleaning mixture
US3957531A (en) * 1971-09-27 1976-05-18 Imperial Chemical Industries Limited Two tank cleaning process using a contaminated cleaning mixture capable of forming an azeotrope
FR2369858A1 (fr) * 1976-11-04 1978-06-02 Isc Chemicals Ltd Procede pour le sechage d'articles et appareil utilise dans ce procede
US4498933A (en) * 1982-05-03 1985-02-12 Hysan Corporation Diphase drain cleaner with halogenated aliphatic solvent
US4619706A (en) * 1985-02-28 1986-10-28 Texo Corporation Method for stripping organic coatings from substrates
US4695327A (en) * 1985-06-13 1987-09-22 Purusar Corporation Surface treatment to remove impurities in microrecesses
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