U.S. patent number 3,847,663 [Application Number 05/273,253] was granted by the patent office on 1974-11-12 for cleaning of metals with compositions containing alkali metal silicate and chloride.
This patent grant is currently assigned to The Lubrizol Corporation. Invention is credited to Gary Allen Shumaker.
United States Patent |
3,847,663 |
Shumaker |
November 12, 1974 |
CLEANING OF METALS WITH COMPOSITIONS CONTAINING ALKALI METAL
SILICATE AND CHLORIDE
Abstract
Metal surfaces are cleaned, prior to phosphating or the like,
with compositions containing alkali metal (especially sodium)
silicates and chlorides, and preferably also containing surfactants
and chelating agents. These compositions have cleaning power
comparable to phosphate-containing cleaners and cause less water
pollution upon discharge into natural waterways.
Inventors: |
Shumaker; Gary Allen (Mentor,
OH) |
Assignee: |
The Lubrizol Corporation
(Wickliffe, OH)
|
Family
ID: |
26737336 |
Appl.
No.: |
05/273,253 |
Filed: |
July 19, 1972 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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58182 |
Jul 24, 1970 |
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Current U.S.
Class: |
134/2; 134/29;
134/42; 510/245; 510/509; 510/511; 148/254 |
Current CPC
Class: |
C23C
22/80 (20130101); C23G 1/14 (20130101) |
Current International
Class: |
C23G
1/14 (20060101); C23C 22/78 (20060101); C23C
22/80 (20060101); C23g 001/14 () |
Field of
Search: |
;252/135,527
;134/2,29,42,40 ;148/6.15R,6.15Z |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
Bennett, The Chemical Formulary, Vol. X111, 1967, page
361..
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Primary Examiner: Guynn; Herbert B.
Attorney, Agent or Firm: Adams, Jr.; J. Walter Pittman;
William H.
Parent Case Text
This application is a continuation-in-part of copending application
Ser. No. 58,182, filed July 24, 1970, now abandoned.
Claims
What is claimed is:
1. A method for cleaning the surface of metals during processing
thereof which comprises contacting said surface at a temperature of
about 50.degree.-100.degree.C. with an aqueous cleaning composition
in the liquid state wherein the active ingredients comprise
water-soluble alkali metal silicate and alkali metal chloride, the
weight ratio of said silicate to said chloride being between about
4:1 and 10:1.
2. A method according to claim 1 wherein the alkali metal is
sodium.
3. A method according to claim 2 wherein the cleaning composition
additionally contains at least one non-ionic or amphoteric
surfactant and a chelating agent, each being present in the amount
of about 3-10 parts by weight per 100 parts of active
ingredients.
4. A method according to claim 3 wherein the chelating agent is
ethylenediaminetetraacetic acid or a water-soluble salt
thereof.
5. A method according to claim 2 wherein the active ingredients in
said cleaning composition consist essentially of about 65-80 parts
by weight of sodium metasilicate, about 5-15 parts of sodium
chloride, about 5-15 parts of sodium carbonate, about 0-10 parts of
ethylenediaminetetraacetic acid or a water-soluble salt thereof,
and about 4-10 parts of at least one non-ionic or amphoteric
surfactant, said ingredients being dissolved in water to a
concentration of about 5-20 grams per liter.
6. A method according to claim 5 wherein the composition
additionally contains about 4-10 parts by weight of colloidal
titanium phosphate.
Description
This invention relates to methods for cleaning metal surfaces
during processing thereof, especially prior to phosphating. More
particularly, it relates to a method for cleaning a metal surface
which comprises contacting said surface with an aqueous cleaning
composition wherein the active ingredients comprise water-soluble
alkali metal silicate and alkali metal chloride, the weight ratio
of said silicate to said chloride being between about 4:1 and
10:1.
In the processing of metals, it is common practice to follow a
drawing operation with a phosphating treatment to produce a
phosphate coating on the metal which is resistant to corrosion and
serves as a paint base. The metal emerging from the drawing
operation almost always has foreign matter adhering to it, chiefly
drawing oils and the like. Such foreign matter is extremely
difficult to remove, but it must be removed before the metal can be
phosphated. It has been customarily removed by heavy-duty alkaline
cleaners containing various combinations of ingredients such as
phosphates, silicates and surfactants. Phosphate-containing
cleaners are particularly effective. However, the recent emphasis
on avoidance of water pollution has aroused interest in cleaners
which do not contain phosphate, since phosphates apparently promote
algae growth in natural waterways such as lakes and rivers into
which the cleaners are discharged after use.
A principal object of the present invention, therefore, is to
provide a new method for heavy-duty cleaning of metal surfaces.
A further object is to provide a metal cleaning method in which the
use of phosphates is avoided or substantially avoided, thereby
decreasing the tendency of such compositions to pollute water.
Other objects will in part be obvious and will in part appear
hereinafter.
The essential ingredients in the compositions used in the method of
this invention are a water-soluble alkali metal silicate and an
alkali metal chloride. By "alkali metal" is meant the metals in
Group IA of the Periodic Table; that is, lithium, sodium,
potassium, rubidium and cesium. Sodium and potassium are preferred,
and because of their ready availability and low cost, the sodium
salts are most often used.
Any water-soluble alkali metal silicate may be used in the method
of this invention. Thus, suitable sodium silicates include sodium
disilicate, Na.sub.2 Si.sub.2 O.sub.5 ; sodium metalsilicate,
Na.sub.2 SiO.sub.3, and its hydrates; sodium orthosilicate,
Na.sub.4 SiO.sub.4 ; and so-called "water glass," which is a liquid
mixture of various sodium silicates. Sodium metasilicate is,
however, preferred.
The alkali metal chloride may likewise be from any suitable source,
but the preferred chlorides consist of crystals with high absorbent
power. Particularly useful is a form of common salt sold by the
Morton Salt Company and identified as "North Star Fine."
The weight ratio of silicate to chloride in the compositions used
in the method of this invention should be between about 4:1 and
10:1. Weight ratios on the order of 7:1 or 8:1 are preferred.
In addition to the alkali metal silicate and chloride, the
compositions used in the method of this invention ordinarily
contain other ingredients such as surfactants, chelating agents,
fillers and pH control agents. The preferred surfactants are
non-ionic ones, chiefly polyethoxylated derivatives of phenols,
alkyl phenols and alcohols, and amphoteric ones, especially those
listed in McCutcheon's Detergents and Emulsifiers Annual as being
suitable for metal cleaning. These include but are not limited to
salts (especially alkali metal salts) of amino acids derived from
long-chain amines, of carboxylic acids derived from long-chain
alkyl-substituted imidazolines, of long-chain polycarboxylic acids,
of betaine sulfonates derived from long-chain fatty acids, and of
sulfonates of oxyethylated amines. Surfactants are particularly
desirable in the compositions used in the method of this invention
because they are ordinarily instrumental in starting the cleaning
process which is continued by the alkaline ingredients.
The presence of chelating agents is preferred partly because of the
absence of phosphates, which ordinarily serve that purpose when
they are present. Suitable chelating agents include the various
amainopolycarboxylic acids and their water-soluble salts, such as
ethylenediaminetetraacetic acid, trimethylenediaminetetraacetic
acid, nitrilotriacetic acid and the like. Particularly useful is
the tetrasodium salt of ethylenediaminetetraacetic acid, sold under
the trade name "Versene."
The proportions of surfactants and chelating agents used are
usually about 3-10 parts by weight per 100 parts of active
ingredients (excluding water).
Suitable for use as fillers and pH control agents are such
materials as sodium carbonate (soda ash) and similar alkaline
materials which are water-soluble and inexpensive.
For certain purposes, especially when the material to be removed
from the surface is very stubborn and persistent, the compositions
may also contain conditioners or activators of the type used to
prepare metal surfaces for phosphating. Exemplary of such
conditioners or activators are the titanium phosphate compositions
described in U.S. Pat. No. 2,322,349.
The preferred cleaning compositions contain about 65-80 parts by
weight of sodium metasilicate, about 5-15 parts of sodium chloride,
about 5-15 parts of sodium carbonate, about 0-10 parts of
ethylenediaminetetraacetic acid or a water-soluble salt thereof (an
optional ingredient), about 4-10 parts of at least one non-ionic or
amphoteric surfactant, and optionally about 4-10 parts of colloidal
titanium phosphate.
Exemplary concentrates for preparing the cleaning compositions used
in the method of this invention are listed in the following
table.
______________________________________ Parts by weight Ingredient
Example 1 2 3 ______________________________________ Sodium
metasilicate 75 73 67 Sodium chloride 10 10 9 Sodium carbonate 10
10 9 "Versene" -- 2 5 "Triton X-114" (octylphenoxy polyethoxy
ethanol) 2 -- -- "Triton DF-16" (modified linear alcohol
ethoxylate) 3 -- -- "Triton CF-10" (alkaryl polyether) -- -- 2.5
"Tergitol 15-S-7" (linear alcohol ethoxylate) -- 2 -- "Tergitol
Min-Foam 1X" (modified linear alcohol ethoxylate) -- 3 -- "Triton
QS-15" (sulfonate of poly- ethoxylated C.sub.12.sub.-15 tertiary
alkyl primary amine) -- -- 2.5 Colloidal titanium phosphate -- -- 5
______________________________________
For use, concentrates such as those listed in the table are
dissolved in water to a concentration of about 5-20 grams per
liter, preferably about 5-10 grams per liter. The aqueous cleaner
thus prepared is contacted with the metal surface by spraying,
dipping or the like, preferably at a temperature of about
50.degree.-100.degree.C. Contact between the metal and the cleaner
is continued for a period of time sufficient to remove drawing oils
and other foreign matters from the metal surface, usually about 30
seconds to 1 minute. The surface is then rinsed with water and a
phosphate coating is applied thereto by conventional methods.
The effectiveness of the method of this invention is shown in a
series of tests in which various drawing oils are applied by brush
to 4 inches .times. 8 inches cold-rolled steel panels which are
then sprayed with cleaning compositions prepared from the
concentrates of Examples 1-3 by dilution with water to 7.5 grams
per liter, the temperature of the cleaning composition during
spraying being 71.degree.C. The cleaning compositions are used both
pure and contaminated with 5, 10, 15 and 20 grams per liter of the
drawing oil. The cleaning operation is continued for 30 seconds,
after which the steel panels are rinsed with water, phosphated with
a phosphating solution of the type disclosed in U.S. Pat. No.
3,090,709 containing zinc, calcium and ammonium ions, and rinsed
with a conventional chromium-containing rinse solution. The
appearance of the phosphate coating is then evaluated to determine
the effectiveness of the cleaner.
When tested by this method, the cleaners of Examples 1 and 2 gave
results equal to those of comparable phosphate-containing cleaners
at all levels of contamination, when used to remove ordinary
drawing oils. Rust-preventive drawing oils were resistant to the
cleaners of Examples 1 and 2 but were removed by the cleaner of
Example 3, to a degree comparable to that of known heavy-duty
phosphate cleaners.
* * * * *