CA1090238A - Process for cleaning articles after galvanic and/or chemical surface treatment - Google Patents
Process for cleaning articles after galvanic and/or chemical surface treatmentInfo
- Publication number
- CA1090238A CA1090238A CA284,532A CA284532A CA1090238A CA 1090238 A CA1090238 A CA 1090238A CA 284532 A CA284532 A CA 284532A CA 1090238 A CA1090238 A CA 1090238A
- Authority
- CA
- Canada
- Prior art keywords
- solvent
- articles
- treatment agent
- bath
- agent
- 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
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/08—Rinsing
Landscapes
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Detergent Compositions (AREA)
- Electroplating Methods And Accessories (AREA)
- Materials For Photolithography (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Chemically Coating (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
The present invention provides a process for galvanic or electrolytic chemical treatment of articles in a bath comprising an aqueous surface treatment agent including metals or metal alloys, said process comprising placing the articles to be treated in said bath to form a deposit thereon of said metals or metal alloys, removing the articles from the bath and applying to the articles by spraying, squirting or pouring a liquid, water immis-cible solvent having a density substantially different from that of water whereby residues of said treatment agent adhering to the surface of the articles from the preceding step are detached, said solvent additionally comprising a wetting agent, said applying step being carried out in a rinsing chamber, in a lower portion of which the solvent and residual aqueous treatment agent dis-charged from said article are collected, permitting the solvent and treatment agent to separate in the rinsing chamber by forming two phases; and withdrawing the phase containing the treatment agent and passing the agent back into said bath while separately recovering the solvent phase and recycling the solvent for further treatment of said articles.
The present invention provides a process for galvanic or electrolytic chemical treatment of articles in a bath comprising an aqueous surface treatment agent including metals or metal alloys, said process comprising placing the articles to be treated in said bath to form a deposit thereon of said metals or metal alloys, removing the articles from the bath and applying to the articles by spraying, squirting or pouring a liquid, water immis-cible solvent having a density substantially different from that of water whereby residues of said treatment agent adhering to the surface of the articles from the preceding step are detached, said solvent additionally comprising a wetting agent, said applying step being carried out in a rinsing chamber, in a lower portion of which the solvent and residual aqueous treatment agent dis-charged from said article are collected, permitting the solvent and treatment agent to separate in the rinsing chamber by forming two phases; and withdrawing the phase containing the treatment agent and passing the agent back into said bath while separately recovering the solvent phase and recycling the solvent for further treatment of said articles.
Description
The invention relates to a process for cleaning adher-ent aqueous surEace treatment agents from articles or objects after galvanic and/or chemical surface treatment, preferably in order to recover the valuable substances contained in these agents.
Processes for rinsing galvanically or chemically treated articles in orderto clean them for subsequent treatments are already ~nown. The sole treatment agent used for this pur-pose was water.
However, these processes have the disadvantage that they involve relatively great losses of the valuable substances, especially the metal salts, contained in the surface treatment agents.
Great efforts were therefore made to prevent, as far as possible, these losses of valuable metals and other treatment substances for economic reasons and, more recently, to preserve the environment.
Thus, the amount of water used for rinsing can be minimised by tne ~nown process of so-called spray riilsing and the use of multiple cascades. In addition, evaporation and volatilisation processes have also been used.
A technique widely used in galvanising stations and in anodising, phosp~atising and picklins plants is the recovery of the rinsing water by ion exchange means which operate in the circuit.
However, none of these processes gives satisfactory results.
Thus, according to the process first mentioned, the
Processes for rinsing galvanically or chemically treated articles in orderto clean them for subsequent treatments are already ~nown. The sole treatment agent used for this pur-pose was water.
However, these processes have the disadvantage that they involve relatively great losses of the valuable substances, especially the metal salts, contained in the surface treatment agents.
Great efforts were therefore made to prevent, as far as possible, these losses of valuable metals and other treatment substances for economic reasons and, more recently, to preserve the environment.
Thus, the amount of water used for rinsing can be minimised by tne ~nown process of so-called spray riilsing and the use of multiple cascades. In addition, evaporation and volatilisation processes have also been used.
A technique widely used in galvanising stations and in anodising, phosp~atising and picklins plants is the recovery of the rinsing water by ion exchange means which operate in the circuit.
However, none of these processes gives satisfactory results.
Thus, according to the process first mentioned, the
- 2 -~lL09();~;38 valuable metallic substances can be recovered in a relatively pure state only by means of a separate and expensive waste water conveying arrangement and chemical precipitation of hydroxide sludges. The disadvantage of the volatilisation and evaporation processes is that they involve a particularly high degree of energy consumption; the ion exchange columns bring about the formation of neutral salks that render the waste water detrimental to the environment.
Generally, it can also be established that none of the ]~nown processes permits an even remotely quantitative recovery of the valuable substances.
The present invention thus provides a process which per-mits both the thorough cleansing of objects or articles after the completion of surface treatment of the type in question and also a quantitative and technically simple recovery of the valuable substances adhering to the objects as a result of treatment.
According to the present invention there is provided a process for galvanic or electrolytic chemical treatment of articles in a bath comprising an aqueous surface treatment agent including ~20 metals or metal alloys, said process comprising placing the articles to be treated in said bath to form a deposit thereon of said metals or metal alloys, removing the articles from the bath and applying to the articles by spraying, squirting or pour-ing a liquid, water immiscible solvent having a density substan-tially different from that of water whereby residues of said treatment agent adhering to the surface of the articles from the preceding step are detached, said solvent additionally comprising a wetting agent, said applying step being carried out in a rinsing chamber, in a lower portion of which the solvent and residual aqueous treatment agent discharged from said articles are col-lected, permitting the solvent and treatment agent to separate in the rinsing chamber by forming two phases, and withdrawing the
Generally, it can also be established that none of the ]~nown processes permits an even remotely quantitative recovery of the valuable substances.
The present invention thus provides a process which per-mits both the thorough cleansing of objects or articles after the completion of surface treatment of the type in question and also a quantitative and technically simple recovery of the valuable substances adhering to the objects as a result of treatment.
According to the present invention there is provided a process for galvanic or electrolytic chemical treatment of articles in a bath comprising an aqueous surface treatment agent including ~20 metals or metal alloys, said process comprising placing the articles to be treated in said bath to form a deposit thereon of said metals or metal alloys, removing the articles from the bath and applying to the articles by spraying, squirting or pour-ing a liquid, water immiscible solvent having a density substan-tially different from that of water whereby residues of said treatment agent adhering to the surface of the articles from the preceding step are detached, said solvent additionally comprising a wetting agent, said applying step being carried out in a rinsing chamber, in a lower portion of which the solvent and residual aqueous treatment agent discharged from said articles are col-lected, permitting the solvent and treatment agent to separate in the rinsing chamber by forming two phases, and withdrawing the
- 3 -~)9()f~38 ~hase containing the treatment agent and passing the agent back into said bath while separately recovering the solvent ~hase and recycling the solvent for further treatment of said articles.
Thus in the present invention the articles or parts are treated with a water-immiscible liquid solvent having a higher or lower specific weight than the aqueous surface treatment agent.
In the process of the invention there is advantageously used as the water-immiscible liquid solvent one having a specific weight of more than 1.25 or less than 0.75 p/cm3. Preferably the solvent is incombustible, inert to the surface treatment agents used, non~toxic, and has a boiling point above 35C.
Advantageously the solvent is a halogenated hydrocarbon, preferably a chlorofluorohydrocarbon, especially trichlorotri-fluoroethane. Preferably the solvent contains a wetting agent or a mixture of wetting agents, especially an amphoteric, non~
ionic, anion-active and/or cation-active wetting agent.
The articles are treated in a rinsing chamber, especially a rinsing chamber provided with a cooling device. The solvent collecting in the lower portion of the rinsing chamber below or above the aqueous phase of the surface treatment agent is drawn off and used again for the treatment of ob~ects, and the aqueous surface treatment agent collecting in the lower portion of the rinsing chamber below or above the solvent is drawn off and, optionally after purification, preferably by filtration by means of active carbon, is used for further surface treatment.
The process according to the invention may be applied in all galvanic and/or chemical surface treatment processes where it is necessary to purify and/or recover the aqueous surface treat-ment agents still adhering to the objects after treatment.
The process of the invention is therefore suitable in particular, for cleaning articles or ob~ects treated with chemical or galvanising baths, for example based on chromium, nickel, `~
1~)90Z38 cobalt, copper, cadmium, zinc, tin, lead, silver, gold or their alloys, in the case of which articles economic ~20~ :
:
~ ; :
. ~ ~
:
: :
.
: 30 ;~
; :
- 4a -~ ~ .
~Q~OZ3~
application and environmental demands require a recovery of the valuable substances that is as ~uantitative as possible.
These aims, which have hitherto been impossible to fulfil by any of the known processes, are now surprisingly achieved in a remarkable manner by the process according to the invention, in that this process renders possible, with a technically elegant procedure, both the thorough cleansing of objects treated in the manner described and also the straight-forward quantitative recovery of the treatment agents naturally adhering to the objects after treatment.
The solvent must fulfil theconditions on the one hand of being water--immiscible and, on the other, of havin~a specific weight sufficiently different from water, even with substances dissolved therein, that relatively rapid separation into two phases can take place.
Solvents which can be used according to the invention and which have these properties are, for example, trichlorotri-fluoroethane and trichloromonofluoromethane.
Each of these solvents may be used alone or if desired mixed with one another.
The solvents are, in particular for purposes of safe application, to be preferably incombustible and have low, or preferably no, toxicity and the most corrosive sur~ace treatment agents must be incapable of destroying them or destroy them only with great difficulty.
Advantageously the solvent should not have too low a boiling point or, if it does, it should be used in conjunction with suitable cooling devices.
Therefore, suitable solvents are those having boiling points of, if possible, more than 35C.
It has also proved advantageous that a wetting agent or a mixture of wetting agents is added to the solvent to be ~O~OZ3l~
used according to the invention, to reduce, if necessary, the surface ~ension and thereby to promote the downward migration through the solvent of the film of water on the treated objects.
For this purpose, depending on the desired aim, amphoteric, non-ionic, anion-active and cation-active wetting agents or mixtures thereof may be used, wetting agents containing fluorine or chlorine being particularly suitable.
The following may be mentioned by way of example:
Amphoteric wetting agents N-laury-~-imino-dipropionic acid (Na-salt), 2-caprylimidazolinium-1-carboxymethyl-1-sodium ethoxylate, lauroylamidopropyl-N-dimethylamino-acetic acid, lauroylamidopropyl-N-dimetnylamine oxide, and cetyl diethylamino tetraglycol ether sulphate.
Non-ionic wetting agents Nonylphenol polyglycol ether, glycol disterate, ethoxylated polypropylene glycol, perfluoroctylsulphonamido-polyglycol ether, and oleic acld amido polyglycol ether.
Anion-active wetting agents Sodium lauryl sulphate, ; perfluoroctylsulphonic acid (potassium salt), coconut oil acid sarcoside (sodium salt), dibutylnaphthalenesulphonic acid ~sodium salt), and o-phosphoric acid ester of oleyl octaglycol ether (triethanol-ammonium salt).
Cation-active wetting agents Pentoxyethylstearylammonium chloride, perfluoroctylsulphonamidopropyl-trimethyl-ammonium iodiae, a~d cetyltrimethylammonium bromide.
When cleaning articles or parts thereof treated with :~9~)Z3!3 agents or baths containing chromic acid, it is necessary to use wetting agents which are inert to such agents or baths, particu-larly fluorine-containing wetting agents.
The treatment of articles or parts according to the process of the invention is effecked in a rinsing chamber. When using solvents with low boiling points, this chamber, as mentioned above, is advantageously provided with a cooling device which is also appropriate in the case of surface treatments taking place at relatively high temperatures, for example, with hot nickel baths.
When carrying out the process of the invention, the surface treatment agent adhering to the articles after appropri-ate treatment processes is removed quantitatively by treatment with the solvent, that is, by sprinkling, spraying or pouring continuously or discontinuously, and can be collected in a container, the rinsing chamber itself being the most suited to this purpose.
Phase separation then takes place in the lower portion of the container or rinsing chamber, the solvent separating ~20 either above or below the aqueous surface treatment agent, depending on the specific weight of the solvent used.
The process of the present invention also includes, on the one hand, drawing off the solvent by means of suitable devices such, for example, as pumps and connecting systems, and using it again for cleaning and, on the other, using the separated aqueous surface treatment agent for further surface treatment, optionally after purifying, preferably by filtration.
These measures therefore permit both the thorough cleansing of objects after completed surface treatment and also a quantitative recovery by a technically simple procedure of the valuable substances used.
Further advantages result from this in individual cases, for example, the possibility of constructing smaller sur-face treatment plants, for example, galvanising plants, and the almost complete avoidance of waste water and thus the achieve-ment of ideal environmental protection.
The following Examples illustrate the invention:
Example 1 Articles made of steel or iron, for example screws, were treated galvanically at 55C in an aqueous nickel electro-lyte of conventional composition in a tank, then removed from the bath and transferred to a rinsin~ chamber. The articles were then sprayed with a solution consisting of trichlorotrifluoro-ethane tb.p.: 47.6C, specific weight 1.582 kp/m3) and 5 parts by weight of a wetting agent based on perfluoroctylsulphonic acid.
The spraying was effected at intervals with a total duration of 2 to 5 minutes whereby the nickeled parts were thoroughly cleansed of adherent bath solution.
Further articles were then cleaned in processes lasting several hours with a similar effect and at the same time the mix-ture, being formed, of the aqueous nickel electrolyte rinsedoff the articles and the solvent/wetting agent solution, was collected in the lower portion of the rinsing chamber where immediate separation into two layers took place in each case.
The lower solvent/wetting agent phase was then used, by means of a pump connecting system and a pipe connecting system, to feed the spray nozzles, and the upper aqueous electrolyte solution was fed to the tank with the nickel electrolyte after undergoing active carbon filtration.
The process involved no waste water and there were no appreciable electrolyte losses.
The experiment was repeated with equal success using a wetting agent based on ethoxylated polypropylene glycol.
~Q9~'~3~
Example 2 The ~rocess described in Example 1 was carried out using trichlorotrifluoroethane as the solvent without the addi-tion of wetting agents. Although no wetting agents were involved, this experiment, too, resulted in satisfactory cleansing of the galvanised articles. The solvent and the entrained electrolyte liquor were recovered practically quantitatively.
Example 3 The process described in Example 1 was carried out using a conventional weakly acidic zinc electrolyte. Trichloro-trifluoroethane containing, as the wetting agent, 3% by weight of cetyldiethylamino polyglycol ether sulphate was used as the solvent.
There was an optimum cleansing effect. After several days' operation electrolyte losses as a result of entrainment were not detected.
Example 4 The process described in Example 1 was carried out using a conventional alkaline, cyanide-containing zinc electro-lyte. Trichlorotrifluoroethane, containing, as the wetting agent, 2% by weight of coconut oil acid sarcoside, was used as the solvent. The articles were free of any residue. It was possible to recover the solvent practically quantitatively for re-use.
Thus in the present invention the articles or parts are treated with a water-immiscible liquid solvent having a higher or lower specific weight than the aqueous surface treatment agent.
In the process of the invention there is advantageously used as the water-immiscible liquid solvent one having a specific weight of more than 1.25 or less than 0.75 p/cm3. Preferably the solvent is incombustible, inert to the surface treatment agents used, non~toxic, and has a boiling point above 35C.
Advantageously the solvent is a halogenated hydrocarbon, preferably a chlorofluorohydrocarbon, especially trichlorotri-fluoroethane. Preferably the solvent contains a wetting agent or a mixture of wetting agents, especially an amphoteric, non~
ionic, anion-active and/or cation-active wetting agent.
The articles are treated in a rinsing chamber, especially a rinsing chamber provided with a cooling device. The solvent collecting in the lower portion of the rinsing chamber below or above the aqueous phase of the surface treatment agent is drawn off and used again for the treatment of ob~ects, and the aqueous surface treatment agent collecting in the lower portion of the rinsing chamber below or above the solvent is drawn off and, optionally after purification, preferably by filtration by means of active carbon, is used for further surface treatment.
The process according to the invention may be applied in all galvanic and/or chemical surface treatment processes where it is necessary to purify and/or recover the aqueous surface treat-ment agents still adhering to the objects after treatment.
The process of the invention is therefore suitable in particular, for cleaning articles or ob~ects treated with chemical or galvanising baths, for example based on chromium, nickel, `~
1~)90Z38 cobalt, copper, cadmium, zinc, tin, lead, silver, gold or their alloys, in the case of which articles economic ~20~ :
:
~ ; :
. ~ ~
:
: :
.
: 30 ;~
; :
- 4a -~ ~ .
~Q~OZ3~
application and environmental demands require a recovery of the valuable substances that is as ~uantitative as possible.
These aims, which have hitherto been impossible to fulfil by any of the known processes, are now surprisingly achieved in a remarkable manner by the process according to the invention, in that this process renders possible, with a technically elegant procedure, both the thorough cleansing of objects treated in the manner described and also the straight-forward quantitative recovery of the treatment agents naturally adhering to the objects after treatment.
The solvent must fulfil theconditions on the one hand of being water--immiscible and, on the other, of havin~a specific weight sufficiently different from water, even with substances dissolved therein, that relatively rapid separation into two phases can take place.
Solvents which can be used according to the invention and which have these properties are, for example, trichlorotri-fluoroethane and trichloromonofluoromethane.
Each of these solvents may be used alone or if desired mixed with one another.
The solvents are, in particular for purposes of safe application, to be preferably incombustible and have low, or preferably no, toxicity and the most corrosive sur~ace treatment agents must be incapable of destroying them or destroy them only with great difficulty.
Advantageously the solvent should not have too low a boiling point or, if it does, it should be used in conjunction with suitable cooling devices.
Therefore, suitable solvents are those having boiling points of, if possible, more than 35C.
It has also proved advantageous that a wetting agent or a mixture of wetting agents is added to the solvent to be ~O~OZ3l~
used according to the invention, to reduce, if necessary, the surface ~ension and thereby to promote the downward migration through the solvent of the film of water on the treated objects.
For this purpose, depending on the desired aim, amphoteric, non-ionic, anion-active and cation-active wetting agents or mixtures thereof may be used, wetting agents containing fluorine or chlorine being particularly suitable.
The following may be mentioned by way of example:
Amphoteric wetting agents N-laury-~-imino-dipropionic acid (Na-salt), 2-caprylimidazolinium-1-carboxymethyl-1-sodium ethoxylate, lauroylamidopropyl-N-dimethylamino-acetic acid, lauroylamidopropyl-N-dimetnylamine oxide, and cetyl diethylamino tetraglycol ether sulphate.
Non-ionic wetting agents Nonylphenol polyglycol ether, glycol disterate, ethoxylated polypropylene glycol, perfluoroctylsulphonamido-polyglycol ether, and oleic acld amido polyglycol ether.
Anion-active wetting agents Sodium lauryl sulphate, ; perfluoroctylsulphonic acid (potassium salt), coconut oil acid sarcoside (sodium salt), dibutylnaphthalenesulphonic acid ~sodium salt), and o-phosphoric acid ester of oleyl octaglycol ether (triethanol-ammonium salt).
Cation-active wetting agents Pentoxyethylstearylammonium chloride, perfluoroctylsulphonamidopropyl-trimethyl-ammonium iodiae, a~d cetyltrimethylammonium bromide.
When cleaning articles or parts thereof treated with :~9~)Z3!3 agents or baths containing chromic acid, it is necessary to use wetting agents which are inert to such agents or baths, particu-larly fluorine-containing wetting agents.
The treatment of articles or parts according to the process of the invention is effecked in a rinsing chamber. When using solvents with low boiling points, this chamber, as mentioned above, is advantageously provided with a cooling device which is also appropriate in the case of surface treatments taking place at relatively high temperatures, for example, with hot nickel baths.
When carrying out the process of the invention, the surface treatment agent adhering to the articles after appropri-ate treatment processes is removed quantitatively by treatment with the solvent, that is, by sprinkling, spraying or pouring continuously or discontinuously, and can be collected in a container, the rinsing chamber itself being the most suited to this purpose.
Phase separation then takes place in the lower portion of the container or rinsing chamber, the solvent separating ~20 either above or below the aqueous surface treatment agent, depending on the specific weight of the solvent used.
The process of the present invention also includes, on the one hand, drawing off the solvent by means of suitable devices such, for example, as pumps and connecting systems, and using it again for cleaning and, on the other, using the separated aqueous surface treatment agent for further surface treatment, optionally after purifying, preferably by filtration.
These measures therefore permit both the thorough cleansing of objects after completed surface treatment and also a quantitative recovery by a technically simple procedure of the valuable substances used.
Further advantages result from this in individual cases, for example, the possibility of constructing smaller sur-face treatment plants, for example, galvanising plants, and the almost complete avoidance of waste water and thus the achieve-ment of ideal environmental protection.
The following Examples illustrate the invention:
Example 1 Articles made of steel or iron, for example screws, were treated galvanically at 55C in an aqueous nickel electro-lyte of conventional composition in a tank, then removed from the bath and transferred to a rinsin~ chamber. The articles were then sprayed with a solution consisting of trichlorotrifluoro-ethane tb.p.: 47.6C, specific weight 1.582 kp/m3) and 5 parts by weight of a wetting agent based on perfluoroctylsulphonic acid.
The spraying was effected at intervals with a total duration of 2 to 5 minutes whereby the nickeled parts were thoroughly cleansed of adherent bath solution.
Further articles were then cleaned in processes lasting several hours with a similar effect and at the same time the mix-ture, being formed, of the aqueous nickel electrolyte rinsedoff the articles and the solvent/wetting agent solution, was collected in the lower portion of the rinsing chamber where immediate separation into two layers took place in each case.
The lower solvent/wetting agent phase was then used, by means of a pump connecting system and a pipe connecting system, to feed the spray nozzles, and the upper aqueous electrolyte solution was fed to the tank with the nickel electrolyte after undergoing active carbon filtration.
The process involved no waste water and there were no appreciable electrolyte losses.
The experiment was repeated with equal success using a wetting agent based on ethoxylated polypropylene glycol.
~Q9~'~3~
Example 2 The ~rocess described in Example 1 was carried out using trichlorotrifluoroethane as the solvent without the addi-tion of wetting agents. Although no wetting agents were involved, this experiment, too, resulted in satisfactory cleansing of the galvanised articles. The solvent and the entrained electrolyte liquor were recovered practically quantitatively.
Example 3 The process described in Example 1 was carried out using a conventional weakly acidic zinc electrolyte. Trichloro-trifluoroethane containing, as the wetting agent, 3% by weight of cetyldiethylamino polyglycol ether sulphate was used as the solvent.
There was an optimum cleansing effect. After several days' operation electrolyte losses as a result of entrainment were not detected.
Example 4 The process described in Example 1 was carried out using a conventional alkaline, cyanide-containing zinc electro-lyte. Trichlorotrifluoroethane, containing, as the wetting agent, 2% by weight of coconut oil acid sarcoside, was used as the solvent. The articles were free of any residue. It was possible to recover the solvent practically quantitatively for re-use.
Claims (15)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for galvanic or electrolytic chemical treat-ment of articles in a bath comprising an aqueous surface treatment agent including metals or metal alloys, said process comprising placing the articles to be treated in said bath to form a deposit thereon of said metals or metal alloys, removing the articles from the bath and applying to the articles by spraying, squirting or pouring a liquid, water immiscible solvent having a density sub-stantially different from that of water whereby residues of said treatment agent adhering to the surface of the articles from the preceding step are detached, said solvent additionally comprising a wetting agent, said applying step being carried out in a rins-ing chamber, in a lower portion of which the solvent and residual aqueous treatment agent discharged from said article are collected, permitting the solvent and treatment agent to separate in the rinsing chamber by forming two phases, and withdrawing the phase containing the treatment agent and passing the agent back into said bath while separately recovering the solvent phase and re-cycling the solvent for further treatment of said articles.
2. A process as claimed in claim 1, wherein the water-immiscible solvent has a specific weight of more than 1.25 or less than 0.75 p/cm3.
3. A process as claimed in claim 2 wherein the solvent is incombustible.
4. A process as claimed in claim 1, 2 or 3 wherein the solvent is inert to the surface treatment agents used.
5. A process as claimed in claim 1, 2 or 3, wherein the solvent is non-toxic.
6. A process as claimed in claim 1, 2 or 3 wherein the solvent has a boiling point above 35°C.
7. A process as claimed in claim 1, wherein the solvent is halogenated hydrocarbon.
8. A process as claimed in claim 7, wherein the solvent is a chlorofluorohydrocarbon.
9. A process as claimed in claim 8, wherein the solvent is trichlorotrifluoroethane.
10. A process as claimed in claim 1, 2 or 3 wherein the wetting agent is an amphoteric, non-ionic, anion-active and/or cation-active wetting agent.
11. A process as claimed in claim 1, 2 or 3 wherein the wetting agent is N-lauryl-.beta.-imino-dipropionic acid (Na-salt), 2-caprylimidazolinium-1-carboxymethyl-1-sodium ethoxylate, lauroylamidopropyl-N-dimethylamino-acetic acid, lauroylamidopropyl-N-dimethylamine oxide, cetyl diethylamino tetraglycol ether sulphate, nonylphenol polyglycol ether, glycol distearate, ethoxylated polypropylene glycol, perfluoroctylsulphonamido-polyglycol ether, oleic acid amido polyglycol ether, sodium lauryl sulphate, perfluoroctylsulphonic acid (potassium salt), coconut oil acid sarcoside (sodium salt), dibutylnaphthalenesulpnonic acid (sodium salt), o-phosphoric acid ester of oleyl octaglycol ether (triethanolammonium salt), pentoxyethylstearylammonium chloride, perfIuoroctylsulphonamidopropyl-trimethyl-ammonium iodide, or cetyltrimethylammonium bromide, or a mixture of any two or more of such compounds.
12. A process as claimed in claim 1, 2 or 3 wherein the rinsing chamber is provided with a cooling device.
13. A process as claimed in claim 1 wherein the aqueous surface treatment agent collecting in the lower portion of the rinsing chamber below or above the solvent is drawn off and after purification, is used again for surface treatment.
14. A process as claimed in claim 13 wherein the aqueous surface treatment agent which is drawn off is purified by filtration through active carbon.
15. A process as claimed in claim 1, 2 or 3 wherein the articles undergo treatment with a chemical or galvanising bath based on chromium, nickel, cobalt, copper, cadmium, zinc, tin, lead, silver, gold or an alloy of such metals.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2636993.7 | 1976-08-13 | ||
| DE19762636993 DE2636993A1 (en) | 1976-08-13 | 1976-08-13 | METHOD FOR CLEANING OBJECTS AFTER GALVANIC AND / OR CHEMICAL SURFACE TREATMENT |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1090238A true CA1090238A (en) | 1980-11-25 |
Family
ID=5985647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA284,532A Expired CA1090238A (en) | 1976-08-13 | 1977-08-11 | Process for cleaning articles after galvanic and/or chemical surface treatment |
Country Status (19)
| Country | Link |
|---|---|
| JP (1) | JPS5322826A (en) |
| AT (1) | AT359801B (en) |
| BE (1) | BE857757A (en) |
| BR (1) | BR7705280A (en) |
| CA (1) | CA1090238A (en) |
| CH (1) | CH631745A5 (en) |
| DD (1) | DD131187A5 (en) |
| DE (1) | DE2636993A1 (en) |
| DK (1) | DK327677A (en) |
| ES (1) | ES461378A1 (en) |
| FR (1) | FR2361479A1 (en) |
| GB (1) | GB1584407A (en) |
| HU (1) | HU177756B (en) |
| IT (1) | IT1085361B (en) |
| NL (1) | NL7708481A (en) |
| NO (1) | NO772817L (en) |
| RO (1) | RO73096A (en) |
| SE (1) | SE7709052L (en) |
| YU (1) | YU178677A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5823479B2 (en) * | 1978-06-02 | 1983-05-16 | 富士プラント工業株式会社 | Method for removing and recovering plating solution from adhesion to the object to be plated |
| DE3040037A1 (en) * | 1980-10-23 | 1982-05-13 | Defo-Chemie GmbH, 8000 München | Reclaiming of aq. electroplating solns. contg. noble metals - by immersing electroplated workpieces in water displacement bath contg. petroleum spirit fraction |
| DE3205736A1 (en) * | 1982-02-18 | 1983-08-25 | Langbein-Pfanhauser Werke Ag, 4040 Neuss | METHOD FOR SOLVENT TREATMENT OF PARTICULAR METAL TREATMENT |
| CH663554A5 (en) * | 1985-09-13 | 1987-12-31 | Serge Berruex | METHOD FOR RINSING SURFACES WITHOUT USING WATER, AND INSTALLATION FOR CARRYING OUT SAID METHOD. |
| DE4415548A1 (en) * | 1994-05-03 | 1995-11-09 | Frembgen Fritz Herbert | Method for treating electrochemically machined workpieces |
| JP2012524165A (en) * | 2009-04-16 | 2012-10-11 | ビーエーエスエフ ソシエタス・ヨーロピア | Removal and recycling of metal salt-containing ionic liquids from surface treated workpieces |
| CN114277382B (en) * | 2021-12-29 | 2023-08-01 | 泰伦特生物工程股份有限公司 | Water-cutting cleaning agent for replacing rinsing and drying process and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4879133A (en) * | 1972-01-25 | 1973-10-24 |
-
1976
- 1976-08-13 DE DE19762636993 patent/DE2636993A1/en not_active Withdrawn
-
1977
- 1977-07-18 YU YU01786/77A patent/YU178677A/en unknown
- 1977-07-19 DK DK327677A patent/DK327677A/en unknown
- 1977-07-27 AT AT548477A patent/AT359801B/en not_active IP Right Cessation
- 1977-08-01 NL NL7708481A patent/NL7708481A/en not_active Application Discontinuation
- 1977-08-05 ES ES461378A patent/ES461378A1/en not_active Expired
- 1977-08-09 CH CH976877A patent/CH631745A5/en not_active IP Right Cessation
- 1977-08-09 IT IT26600/77A patent/IT1085361B/en active
- 1977-08-10 RO RO7791321A patent/RO73096A/en unknown
- 1977-08-10 SE SE7709052A patent/SE7709052L/en unknown
- 1977-08-10 BR BR7705280A patent/BR7705280A/en unknown
- 1977-08-10 DD DD7700200515A patent/DD131187A5/en unknown
- 1977-08-11 CA CA284,532A patent/CA1090238A/en not_active Expired
- 1977-08-11 GB GB33731/77A patent/GB1584407A/en not_active Expired
- 1977-08-11 NO NO772817A patent/NO772817L/en unknown
- 1977-08-12 BE BE180142A patent/BE857757A/en not_active IP Right Cessation
- 1977-08-12 JP JP9687477A patent/JPS5322826A/en active Pending
- 1977-08-12 HU HU77SCHE618A patent/HU177756B/en unknown
- 1977-08-16 FR FR7725009A patent/FR2361479A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| NO772817L (en) | 1978-02-14 |
| GB1584407A (en) | 1981-02-11 |
| RO73096A (en) | 1981-06-26 |
| NL7708481A (en) | 1978-02-15 |
| IT1085361B (en) | 1985-05-28 |
| ES461378A1 (en) | 1978-08-16 |
| BE857757A (en) | 1978-02-13 |
| CH631745A5 (en) | 1982-08-31 |
| JPS5322826A (en) | 1978-03-02 |
| ATA548477A (en) | 1980-04-15 |
| FR2361479A1 (en) | 1978-03-10 |
| DD131187A5 (en) | 1978-06-07 |
| SE7709052L (en) | 1978-02-14 |
| DK327677A (en) | 1978-02-14 |
| DE2636993A1 (en) | 1978-02-23 |
| FR2361479B1 (en) | 1983-07-18 |
| AT359801B (en) | 1980-12-10 |
| YU178677A (en) | 1982-08-31 |
| BR7705280A (en) | 1978-05-23 |
| HU177756B (en) | 1981-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH04500242A (en) | Electrolytic method for regenerating tin or tin-lead alloy stripping compositions | |
| CA1090238A (en) | Process for cleaning articles after galvanic and/or chemical surface treatment | |
| US4740280A (en) | Electrolyte for electrochemically polishing metal surfaces | |
| US4136217A (en) | Removing oil emulsion from articles prior to coating articles and recovering oil from the emulsion | |
| US2653860A (en) | Etching aluminum using saccharic acid as a modifier | |
| JPH03223481A (en) | Acid pickling of iron and steel surface | |
| JP2002526657A (en) | Electrolytic cleaning of conductive objects | |
| JPS6045274B2 (en) | Compositions and methods for chemical stripping of metal deposits | |
| US5401379A (en) | Chrome plating process | |
| US5141563A (en) | Molten salt stripping of electrode coatings | |
| US3041259A (en) | Cleaning aluminum surfaces | |
| CN1075177A (en) | Rust removing and contaminant releasing technology for metal surface by electrochemical process | |
| US6506294B1 (en) | Process for regeneration of electrolytes from pickle liquor, in particular of NA2S04 from pickle liquor for stainless steel | |
| EP0013328B1 (en) | Method for treatment of a metal surface | |
| JP3235216B2 (en) | Cleaning method for insoluble electrode and / or electroplating tank | |
| JPS6047913B2 (en) | How to apply gold plating directly to stainless steel | |
| US5755951A (en) | Regeneration of plastic diaphragm | |
| JP3598242B2 (en) | Plate washing method for plate heat exchanger | |
| JPH02107800A (en) | Method for electrolytically pickling a long piece of a special steel | |
| DE19820001C2 (en) | Process for removing metal layers on metal, glass, ceramics and plastic parts | |
| US2063529A (en) | Cleaning ferrous articles | |
| JPH0781195B2 (en) | Additive for pickling acid solution | |
| RU2058440C1 (en) | Method for electrochemical removal of sprayed-on coatings | |
| JPS5823479B2 (en) | Method for removing and recovering plating solution from adhesion to the object to be plated | |
| SU1518412A1 (en) | Method of electrolytical or chemical coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |