close

Вход

Забыли?

вход по аккаунту

?

Патент USA US3090719

код для вставки
United States Patent 0
l
3,696,7Q9
PHOSPHATE COATENG 0F METALS
John A. Henricks, Lakewood, Ghio, assignor, by mesne
assignments, to The Luhrizol Corporation, Wicisliife,
Ohio, a corporation of ?hio
No Drawing. Filed Aug. 10, 1953, get‘. No. 373,449
19 Claims. (Cl. 148—6.15)
3390,79
Patented May 21, 1953
2
by the presence in the composition of a nitrate selected
from the group consisting of the nitrates of lithium,
beryllium, magnesium, calcium, strontium, cadmium and
barium and assisted by traces of other metals selected
from the group consisting of the amphoteric metals that
will form the coordinating atom of a hetero-poly acid.
A further object of the invention is the provision of
This invention relates to phosphate coating of metals;
methods for employing zinc dihydrogen phosphate, or
coating formulations based thereon, to provide improved
more particularly, to improved accelerating and non
highly ionized phosphate coating compositions capable of
sludging zinc phosphate coating baths and to procedures
for preparing and using the same for the production of
improved protective and paint retaining coatings on
forming an amorphous coating on metal surfaces.
The invention also has an object thereof the provision
of a ferrous metal article covered by an integral coating
of the amorphous type which is a mixed phosphate com
metals.
An object of the invention is to provide improved com 15 posed principally of zinc and one of the metals selected
positions, and procedures for preparing and employing
the same, for the production of zinc containing mixed
phosphate coatings upon metals, which coatings are char
acterized by the substantial absence of crystalline struc
from the group consisting of lithium, beryllium, mag
nesium, calcium, strontium, cadmium and barium.
Other and further objects and advantages of the in
vention will hereinafter be apparent from the following
detailed description of the novel compositions and the
procedures for preparing and using the same.
It is now customary to provide a phosphate coating
given weight of coating, and a smoother base is produced
upon metals, especially upon ferrous metals, which are
for paint or the like thereby enhancing the gloss of the
to be painted or enamelled, this practice being almost uni
latter.
Another object of the invention is to provide improved 25 versally employed in the automotive and household ap
pliance industries.
coating solutions and methods of preparing the same such
The majority of zinc phosphate coating compositions
that the solutions are substantially non-sludging, the coat
in use for this purpose at the present time are prepared
ing rate is accelerated and the coating produced upon
by dissolving various zinc dihydrogen phosphate mixtures
metals treated therewith is of the amorphous type inte
grally bonded to the metal.
30 in water together with phosphoric acid and various
oxidizers or other additives, the solutions being then
A further object of the invention is to provide a process
diluted with water and heated to provide a dilute aqueous
for accelerating the coating rate and inhibiting the forma
solution which is nearly saturated with respect to the dis
tion of crystals in coatings produced by highly ionized
solved metallic phosphate. The solutions thus prepared
baths of the zinc phosphate type.
An additional object of the invention is to provide a 35 are then “broken in” by employing them to coat a quan
tity of ferrous metal during which time the composition
process for effecting a chromic rinse of phosphate coatings
of the bath may be adjusted, if necessary, to provide “a
which does not damage the coating and which is especially
balanced bath” the acidity of which is generally expressed
e?ective with coatings of the amorphous type.
in terms of its “ratio” of total to free acid and which may
Another object ‘of the invention is the provision of
be in the order of from 5 to 40 depending upon whether
improved coating compositions and methods of preparing
the bath is to be employed for immersion or spraying of
and using the same wherein the coating anion is the
articles. The acidity of phosphate coating baths may also
phosphate radical and the major part of the coating cat
be expressed in terms ‘of their “point” content as, for ex
ions are provided by one or more soluble salts of zinc
ample, “a 15 point bath,” which is an expression of the
and of a metal selected from the group consisting of
lithium, beryllium, magnesium, calcium, strontium, cad 45 total acid content of the bath.
Baths of the nature just mentioned are employed by
mium and barium, and wherein the rate of coating is
contacting the work to be coated therewith, either by
accelerated by a nitrate, the quantity of the salt of a metal
immersion or spraying, and the coating deposited on the
from said group being su?icient to substantially inhibit
work is generally a combination of zinc and iron phos
formation of crystals in the coatings produced by the
ture therein whereby a more uniform and complete
protective coverage of the coated metal is e?ected for a
compositions.
phates deposited by electrochemical action. The coating
thus obtained consists chie?y of rather coarse crystals of
A further object of the invention is to provide coating
compositions and methods as de?ned in the preceding
the tertiary zinc phosphate, Zn3=(PO4) 241-120 overlaying
some ferrous phosphate at the metal interface and require
paragraph and wherein the compositions contain a minor
about 30 minutes at 200° F. in an immersion bath to
quantity of ferrous iron in solution.
Another object of the invention is to provide coating 55 complete the coating. Such a crystalline coating should
have a weight of at least 6000 milligrams per square foot
compositions and methods as de?ned in the preceding
of coated area so that there will be suf?cient overlapping ‘
paragraph wherein further acceleration and limitation of
of the crystals to ensure complete coverage of the surface.
the quantity of ferrous iron in solution are obtained by
However, the usual speci?cations for coatings to be em
periodic additions of a neutralizing oxidizer selected from
the group consisting of sodium nitrite, barium nitrite and 60 ployed under paint or the like in the automotive industry
calcium hypochlorite.
An additional object of the invention is the provision
of improved zinc phosphate coating compositions ‘and
calls for a minimum of 156-200 milligrams of coating per
square foot of surface, this low Weight being due to a
desire to conserve paint, secure good paint adhesion
Without sacri?cing ?exibility of the metal, and secure high
eration is provided and coating crystallization inhibited 65 paint luster all of which features are di?icult to achieve
methods of preparing and using the same in which accel
3,090,709
3
with a heavy crystalline coating. The coatings produced
coating to be amorphous andrhave a diifraction pattern
of an apatite with the pattern slightly distorted by the
to meet such speci?cations ‘consist of islands of isolated
zinc phosphate, crystals in a sea of iron phosphate conver
presence of zinc and iron.
The exact mechanism by which the additive metal and
sion coating. Consequently, the corrosion protection ob
tained from such coating is limited to that a?orded by the
nitrate ions inhibit crystalline growth is not known, but
it is believed that the cololidal insoluble phosphate of
the modifying nitrate interferes with normal crystal
iron phosphate conversion coating between the crystals of
zinc phosphate and which is less than that provided by a
continuous coating of zinc phosphate.
' growth of the zinc phosphate in a manner equivalent to
In my prior patent application, Serial No. 271,930,
the brightening action of colloids like gelatin in an elec—
?led February 16, 1952, now abandoned, improved coat 10 troplating bath. Thus, when a high concentration of
ing baths and methods of preparing and using the same
are disclosedewherein the coating rate is accelerated and
the size of the crystals in the coating are reduced by
providing all of the constituents of the compositions in
highly soluble form and in proportions to produce a zinc
pieces placed therein as the free acid in the vicinity of
the work is used while the coating proceeds. This gela
tinous ?lm enveloping the metal surface in such a high
ortho-phosphate. These improved compositions and
methods provide coatings which are distinct improvements
phosphate.
barium nitrate is added to a zinc phosphate bath, a slimy
gelatinous film is seen to envelop the iron or steel work
barium zinc phosphating bath can be identi?ed as barium
' over those produced by the dihydrogen phosphate com
.
It has also been observed that solutions of lithium,
positions but are still primarily crystalhne in nature.
beryllium, magnesium, calcium, strontium, and barium
In accordance with this invention, the improvements 20 acid phosphates per se do not coat out these metals as
in coating compositions and procedures obtained as dis
phosphates thereof similar to the manner in which zinc
closed in the aforementioned copending application are
or manganese acid phosphate solutions coat out the latter
retained while the nature of the coating produced is
metals. Thus, when steel is treated in acid phosphate
altered by inhibiting the growth of crystals therein so
solutions of the lithium, beryllium, magnesium, calcium,
that the result is a substantially amorphous coating of a
strontium, and barium phosphates without zinc but
hard slate-like ?nish integrally bonded with the material
otherwise equivalent to the commercial zinc phosphate
on which the coating is formed. This improved coat
coating baths, the steel is covered chie?y with an iron
ing, by virtue of its smooth ?nish, resulting from lack
phosphate coating and not a phosphate containing the
of appreciable crystalline structure, permits the article
lithium, beryllium, magnesium, calcium, strontium, or
thus coated to be severely ?exed and/or distorted with 30 barium which is present in the bath. It appears there
no ?aking or loss of bond between the article and its
fore that it is only in the presence of a zinc phosphate
coating. Moreover, the smooth surface of the coating
coating composition that the lithium, beryllium, mag
provides an excellent base for paint and like ?nishes so
nesium, calcium, strontium, and barium phosphates act
that the gloss of such a ?nish is substantially enhanced.
as true coating chemicals. While cadmium may be em
Further, the protection afforded ‘for a given weight of 35 ployed as a coating, coating thereof from a phosphate
coating is increased by the amorphous nature of the
bath is facilitated by the presence of zinc in the bath.
improved coatings since a more uniform coverage is
Hence, in employing this invention, a zinc phosphate
provided with less likelihood of minute openings such as
coating bath is employed and balanced with asoluble
occur between the crystals of conventional crystalline
salt of lithium, beryllium, magnesium, calcium, stron
type coatings.
4.0 tium, cadmium or barium and a nitrate so that there is
The aforementioned coating acceleration and inhibition
of crystalline formation in the improved coatings may be
achieved by adding to coating compositions, formulated
from phosphate anion and zinc cation yielding materials,
a nitrate, and a soluble salt of a metal selected from
the group consisting of lithium, beryllium, magnesium,
calcium, strontium, cadmium, and barium. Preferably,
a co-deposit of lithium or other modifying metal phos
phate in the uniform non-crystalline coating formed on
the work. As mentioned above, the said soluble salt
of the additive metal is preferably the nitrate thereof so
it is not necessary to separately add nitrate to the com
position.
' The compositions prepared in accordance with this
the said soluble salt is the nitrate,‘ in which event, no
rnventron are preferably based upon nitrate depolarized
separate nitrate need be added. The resulting accelera
formulations prepared from phosphoric acid or highly
tion of the coating composition is such that complete 50 soluble phosphates and highly soluble salts of zinc in'
coating of a metal surface can be e?ected in from 3 to
proportions equivalent to an orthophosp'nate of zinc.
5 minutes with an immersion ‘bath at a temperature in
the order of 200° F. in contrast to the 30 minutes re—
quired for coating by a conventional zinc dihydrogen
Since the ingredients are all readily soluble, the hydrol- I
ysis and sludge forming defects of the conventional di
hydrogen phosphate compositions are avoided and, more
phosphate bath and 10 minutes when conventional coat 55 over, the ratio of zinc to phosphoric acid is not limited
ing baths are modi?ed ‘by additions of zinc or sodium
by considerations of solubility. Consequently, nearly
nitrate. Moreover, the coating produced from baths of
any degree of zinc supersaturation is possible up to 10
the dihydrogen phosphate type, or those modi?ed by the
rnols of zinc to each mol of phosphoric acid, and in low
addition of Zinc or sodium nitrate, are crystalline in
Zinc content formulations, the ratio may be as low as one
nature while‘ the coatings, produced from baths to which 60 unit of zinc salts to four units of phosphoric acid, as is
a salt of lithium, beryllium, magnesium, calcium, stron
tium, cadmium or barium has been added, in at least the
minimum quantities hereinafter speci?ed, have a smooth
application, Ser. No. 271,930, now abandoned. In the
simplest of such formulations the zinc is all provided as
texture exhibiting no visible crystal structure even when
zinc nitrate but the desired zinc saturation may be se
examined under magni?cation of 100 diameters.
disclosed and claimed in my aforementioned copending
Fur~
cured by providing at least a part of the zinc in the form
thermore, the chemical analysis of, these amorphous-type
of zinc chloride with the range of balance being from
coatings reveals that they are mixed phosphates with the
metal of the recited group occurring therein in the ratio
of about 1/2 mol thereof to each mol of zinc; the com
position of the coating when calcium is used, for ex
high nitrate formulation, to 1 unit of zinc nitrate to 3'
units of zinc chloride, in low nitrate formulations. The
chloride acts to improve the non-sludging characteristics
ample, being Zn2Ca(PO4)2. Electronic diffraction anal
lyses of the coatings indicates they are apatitic in nature.
Thus, such analysis of a coating produced on low carbon
steel by a bath prepared in accordance with this inven
tion and containing calcium and chlorine showed the 75
10 units of zinc nitrate to 1 unit of zinc chloride, in a
of the bath and also effects coating at a faster rate than
baths which have all of the zinc in the form of the ni
trate. Ammonium yielding substances may also be in-‘
corporated, as for example, by employing ammonium
phosphate directly in the preparation of the composition
3,090,709
6
the modi?er material than when chemically pure grades i
of the modi?ers are employed. While the above listed
threshold values have been given for baths containing
3.2 grams per liter of zinc, substantially the same values
or by utilizing other substances therein which will facili
tate the production of the ammonium radical as is fully
disclosed in the aforementioned copending application
Ser. No. 271,930.
As mentioned above, the addition of a soluble salt of
are valid for baths ranging in zinc content from 1 to 4
lithium, beryllium, magnesium, calcium, strontium, cad
grams per liter.
'
The required amount of the modifying metal salt to
mium, and bariurn to one of the nitrate depolarized
formulations of the type mentioned acts to accelerate
the coating rate and inhibit crystalline growth, the ex
tent of crystalline inhibition depending upon the amount
of the additive metal employed. By way of example a
produce the amorphous coating may be reduced by the
additional smoothing effect of minor amounts of other
materials. For example, the elements known as the
amphoteric metals and which furnish the central co
20 to 30 point bath zinc orthophosphate is prepared by
ordinating atom in the formation of heteropoly acids, as
diluting, to a 2 to 3% solution, a concentrate containing:
is discussed in “Inorganic Chemistry” by Fritz Ephraim,
4th Edition, pages 500 to 509, may be so used.
15
Chemical
Units
Percent
composi
tion
nese, chromium, iodine and germanium, those are pre
Phosphoric acid, H3PO4 __________________ __
98x0. 2
19.6
Mono-ammonium phosphate, (NH,)H2PO4
115)“). 2
23.0
Zinc chloride, ZnOlr ___________________ __
136XO.1
13.6
Zine nitrate, Z11(NO3)2_
189X0. 1
Water added to dissolve salts__
ferred which do not form an immersion deposit on iron
or do not tend to poison the bath by preventing deposit—
ing of zinc phosphate. Besides iron, the safest auxil
iary modifying agents are the soluble salts of cerium,
zirconium, vanadium and titanium, these being utilized
18. 9
24. 9
Total
Of such
elements, which include phosphorous, arsenic, antimony,
boron, thorium, silicon, tin, cerium, titanium, cobalt,
zirconium, iron, vanadium, aluminum, copper, manga
100. 0
in concentrations of less than 1 gram per liter of the
In addition, trace amounts of antimony and
25 bath.
arsenic, which form immersion coatings of the iron but
This solution is then broken in and balanced to provide
do not accelerate electrolytic corrosion of the iron, may
a 20 to 30 point bath by a trial load of ferrous articles
be employed.
thereby providing iron ions in the bath. To the balanced
Although minor amounts of the additive substances
and broken in bath there is added a nitrate of lithium, 30 mentioned may be employed for securing synergistic
beryllium, magnesium, calcium, strontium, cadmium, or
action in obtaining non-crystalline zinc phosphate coat
barium in quantities approaching equimolan'ty with the
ings, it is presently preferred to simply employ commer
cial grade nitrates of lithium, beryllium, magnesium cal
cium, strontium, cadmium or barium thereby taking ad
vantage of the trace impurities therein. Likewise, the
iron, acquired in normal operation of commercial phos~
phating baths when coating ferrous surfaces, assists in
zinc. The bath is then ready for use.
The amount of modi?er metal which should be added
to produce an amorphous coating is not exactly stoichio
metric since some of the low molecular weig t materials
like lithium and magnesium nitrates must be added in
greater quantities than the nitrates of the heavier ele
ments such as barium. However, in each case, there
the formation of the desired coating although the concen
tration of this iron should not exceed 1 gram per liter.
The iron concentration does not materially increase
appears to be a minimum amount of the modi?er which
must be added to effect substantial elemination of zinc
during normal Working of the ‘bath with ferrous articles
probably because of the oxidizing action caused by the
phosphate crystalline structure. This amount may be
de?ned as the “threshold value” of the modi?er and these
values as determined for commercial grade materials em
ployed in a broken-in, 25 point bath, compounded as ex
plained above, containing 3.2 grams per liter of zinc and
air and by the interaction of the nitrate and chloride of
the zinc salts as is explained in my aforementioned co
pending application, Ser. No. 271,930. However, in
heavily worked baths, such as spray installations for fer
rous articles where the iron concentration tends to in~
0.5 grams per liter of iron, are substantially as follows:
crease, such increase may be controlled by the periodic
Nitrate
Lithium nitrate ______________________ __
'
'
Barium nitrate_ ___
Mol.
weight
69
Concen
tratiou
addition of barium or sodium nitrite, or calcium hypo
Such
additions of neutralizing oxidizers do not throw out the
50 chlorite, in amounts of less than 1 gram per liter.
Mol.
required, percent
gr./liter
12. 3
usual voluminous ?occulant ferric phosphate precipitates
such as would occur in a zinc dihydrogen phosphate bath.
On the contrary, the bath remains clear but turns a yel
18
187
9. 3
5
256
232
25. 6
7. 8
10
3
212
14. 1
6
308
30. 8
10
261
5. 2
2
55 low to brown color which is considered indicative of the
presence of an iron nitrosyl complex. It should also be
mentioned that the aforementioned oxidization is solely
_for the purpose of acceleration and reduction of ferrous
lI‘OD. to thereby maintain a smooth armorphous coating
60 through aoviding depositing of coarse iron phosphate
The above speci?ed threshold values are based upon
technical or commercial grade nitrates which contain
traces of other metals as impurities. For example, the
calcium nitrate was found to have at least traces of stron
tium and magnesium. Lithium nitrate was found to 65
crystals.
There is no need to effect oxidization of hy
drogen in baths compounded in accordance with this in
vention since the high nitrate content thereof provides
‘adequate depolarization.
Although the addition of nitrates of lithium, ‘beryllium,
magnesium, calcium, strontium, cadmium or barium to a
have at least traces of aluminum, tin, and strontium; cad
zinc orthophosphate composition has been heretofore de—
mium nitrate contained traces of strontium, ?uorine,
scribed speci?cally with reference to a bath compounded
iron, aluminum and magnesium; and barium nitrate con
tained traces of cerium, titanium and calcium. These 70 from a concentrate containing phosphoric acid, mono~
trace impurities have also been detected in the coatings
ammonium phosphate, zinc chloride and zinc nitrate in
by spectrographic analysis and they evidently have an
the proportions stated above, it is to be unedrstood that
auxiliary or synergist action in inhibiting crystalline
baths compounded from any of the formulations set forth
growth since the threshold concentrations of the modi?er
in my aforementioned copending application, Ser. No.
is materially less when employing commercial grades of 75 271,930 may be employed in similar manner. The fol
3,090,709
3
water, and with thezinc chloride added as the. ?nal step.
Similar results can be obtained by employing nitric acid
and ammonium chloride to convert the zinc chloride, zinc
phosphate solution to the desired chemical composition
and it will ‘be obvious that other chemicals may be utilized
for this purpose. 1It will also be evident that the order
of adding and mixing the ingredients maybe altered from
lowing may be mentioned as further examples of suitable
concentrates for such formulations:
Chemical
P
t
c0i,§§,";,‘;,_
Unit's
tion
~
Phosphoric acid. HaP04'
t
o
39- 2
..
.
.
.
.
228
The ?rst example or a formulation for providing an
100 0 16 amorphous mixed phosphate coating disclosed the addi
'
Phos
those speci?cally mentioned.
38.0
grgieil?igglzgéi‘gsoittes
Tom
horic acid, HsPOt _____________________ -_
Zinc 5mm, ZN (Nom______________ __
98><0.3
190mg
'
tion of the nitrate of the modi?er metal after the other
29-4
ingredients, provided in the form of a1concentrate, had
'
3&0
TMono-arnmoniunr phlosphate, (NH4)HZPO4___ 115x01
a
'
x
‘
;
,
'
_
been diluted to substantially bath strengtn. However, the
Water added to dlsso W Salts """ ‘f """"""""""" "
'
TOM
‘
nitrate of the modi?er metal may also be included as part
100") 15 of the concentrate as, for example:
Phosphate acid, HsPO-i
Zinc chloride, 211012...
Zinc nitrate, Zn (N03)
QSXO. 3
136X0.15
189X0. 15
29. 4
20. 4
28. 4
Water added to acid to dissolve salts .................... _-
21. 8
Tom]
Chemical
Units
100' 0 20
‘ Phosphoric acid H3190; --------------------- _-
Zinc cholride, 213012“---
98><0-2
19-6
136><0.1
Z1110 mtrate, Zn(N_03)2..T __________ __
189><0. 2
Water added to acid to dissolve salts .................... ._
Percent
composition
esxoos
18
13. 6
Mono-ammonium phosphate, NH4H2P04_____
l15><0. 10
11. 5
37- 8
29-0
Zinc chloride, Z110}; .................... -Zinc nitrate, Zn (N03)2 ____ __
Phosphoric acid, H3PO4 _____________________ __
136X0. 04.
139><0_ 06
5. 5
11_ 3
Calcium nitrate, Ca(NOs)2_
TOM
23.0
109-0 25 Water to dissolve ___________________________ __
Phosphoric acid, 1131,04"...
Ammonium nitrate, NHlNO
98x0. 25
80><0. 25
Zinc cholride, Z1101? ..... ._
Water added to dissolve sal
25.0
20.0
136X0. 25
__________ __
100.0
.
..
This concentrate was diluted to a 4% by volume so
30 lution, heated to 190—200° F. and was. employed as a
.
a‘ino-
As mentioned in the above described detailed example
.
100_ 0
34.0
21.0
Tom
.
40,9
Total
.
.
'
r
-'
'
_',
'
—-.
co L ‘’ tbathbfifr 3} W116‘e V3169’ 0? uncles lrcludlmgbiel
.
.
of the preparing of a bath to provide an amorphous coat-
.
t
-
..
,.
a
rolls a“ 051G _ e W lee S ‘an Hm?’ OW Car on “Y6 “1 111-»
ing on a metal surface, any of the concentrates is pref-
Pnor t°_ rawmgr and dle'cast Z1“? hardwa?f- The bath
erably ?rst diluted to provide the desired bath strength 35 W5? ‘ma-“named ‘at a 20 to 30 P01m Strengm ‘and had a
and the bath broken in. Thereafter the nitrate of lithium,
at“) OI Lotal '50 free ‘aclfl of befweell 5-10 t0 1‘ (303t
beryllium, magnesium, calcium, strontium, cadmium or
lngs We“? P‘mdllc?d by 1111111551011 0f the Cleaned‘ Work
barium is added thereto. It is however possible to incorporate the necessary quantity of the modi?er nitrate
1n the ‘bath for'a Period of 4 to 8 minutes and the coatings
so obtained were smooth and uniform, with no crystal
in the concentrate so that it is present when the concen- 40 structure visible under magni?cation of 100 diameters.
These coatings provided an excellent undercoat for paint
trate is diluted to provide the bath and does not need to
be added as a separate step. When so added the quan
as Well as affording excellent corrosion resistance when
tities of the modi?er nitrate to produce amorphous coat
ings are such that, when the concentrate is diluted to bath
strength, the said modi?er nitrate will be present in at
least the threshold value speci?ed above.,
I
'
covered with lanolin or a Wax type rust inhibiting ?lm. '
45
It is also possible to adapt conventional zinc dihydrogen
phosphate compositions to production of amorphous
In addition, the coatings also evidenced ability to hold a
lubricant for subsequent drawing operations or for re
duction of sliding friction.
V The proportions of the ingredients in this concentrate
may be varied from the presently preferred values stated
above with the following ranges:
mixed phosphate coatings by modifying the compositions
so that they are equivalent to ionized salt-based baths of
phosphoric acid, Zinc nitrate and ammonium phosphate.
Such a modi?ed composition in the form of a concentrate
may have the following constituents:
Chemical
Chemical:
vPercent composition
Zinc dihydrogen phosphate concentrate
Phosphoric acid, H3130; ___________ __
chloride _____________ -s ___________ __
6.0
Hydrochloric acid (37%, 22° 36.) ________ __
8.0
Ammonium
nitrate _____________________ __ 13.5
Water ________________________________ __
4.5
100.0
This composition is prepared by dissolving anhydrous
zinc chloride in the zinc \dihydrogen phosphate concen
trate. The ammonium nitrate is dissolved in the Water
and hydrochloric acid and the ‘resulting solution is added
to the concentrate containing the zinc chloride.
The re
Percent
composition
98X(0.04 to 0.12) _ -_
2.6 to 8.0
' l15><(0.02 to 0.15)--.
1 5 to 11.7
Zinc chloride, Zn Ch _______________ -_ l36><(0.01 to 0.10).-Zinc nitrate, ZI1(N0s)2~‘-____ 189X(0.02 to 0.10)__.
Calcium nitrate, 024N002 ______ __'_- 164X(0_.10 to 0.50).-.
0.9 to 9.2
2.5 to 12.3
v11.0 to 55.4
Monoammonium phosphate
(12% Zn, 48% P04) _________________ __ 68.0
Zinc
Units
60
Thus such a concentrate, containing about one to about
four parts of zinc ion and at least about 1.33 parts of
calcium ion, as indicated earlier herein, will contain cal
cium and zinc in such proportions that the Weight ratio
of calcium to zinc is Within the range of 0.31 to 10.2,
and also the nitrate ion and phosphate ion in such pro
portions that the weight ratio of nitrate ion to phosphate
ion is within the range of 0.58 to 13.0.
Amorphous zinc phosphate coatings can be obtained
sulting composition is then chemically identical with the 70
by spraying as Well as by immersion, the chief difference
concentrate in the ?rst example but is more dilute. A
ing the zinc dihydrogen phosphate solution, adding the
in the baths being that the spray must have a lower free
acid and can be run at a lower strength. For example, a
hydrochloric acid thereto, and then dissolving the am
monium nitrate in the Warm solution, without additional
spray bath needs only 10 to 20 total points but should
have an acid ratio of from 15 to 50!. ‘The required low
more concentrated solution can be obtained by first Warm
3,090,709
10
.
free acid may be initially obtained by neutralizing the
centrate and the phosphate supplied separately as another
free acid with zinc dust, zinc oxide or calcium carbonate,
sodium or ammonium hydroxides or by sodium nitrite.
concentrate. Thus:
The resulting acid balance does not change rapidly since
the baths do not hydrolyze under continuous heating.
Moreover, the crystal inhibiting salts are neutral and exert
a butler action to stabilize the bath against free acid
formation. However, the low permissible free acid in
spray formulations limits the solubility of the coating
salts in the concentrate So that it is advisable to pack
age the low acid zinc phosphate separately from the nitrate
Chemical
Calcium nitrate, Ca(NO3)24.H2O _____________ __
236X0. 10
Calcium chloride, 08.012 _________ __
111X0.05
5.6
Zinc nitrate, Z1’1(N0a)z6H2Q__
297><O. 06
17.9
Zinc chloride, 211012 ________ __
___
136X0. 04
Diacetoue alcohol, 05111202 __________________ __
116><0. 10
Water to dissolve
strontium, cadmium or barium to avoid recrystallization
of the ingredients.
An effective spray bath for producing an amorphous 15
coating can be prepared from the following:
Percent
compo 20
sition
23. 6
5. 5
11. 6
35. 8
Total
100.0
Phosphate concentrate:
Mono-ammonium phosphate, NH4H1PO4____-
115><0. 20
Water to dissolve to 46% solution ________________________ __
Total
Units
Percent
compo
sition
Salt concentrate:
or other salt of lithium, beryllium, magnesium, calcium,
Chemical
Units
'
23.0
27.0
50.0
A spray bath was prepared from these ingredients by
making a 2% solution of the salt concentrate and then
A. Zinc salt concentrate:
Mono-ammonium phosphate, NH4H2PO4__ 115><0. 125
Zinc dihydrogcn phosphate, ZnHAPOQe
261><0.125
Ammonium chloride, NH4O _
W'ater to dissolve ___________ __
6. 6
46. 4
TotalB. Calcium Nitrate Ca (N03): 41520 ____________ __
236><0. 20
adding the phosphate concentrate in quantity to provide,
14. 4
32. 6
53X0. 125
a 1% solution thereof. This bath had an acid ratio of
25 35 and a total of 25 points with optimum operation being
effected with an acid ratio 30 to 50. Hence, it is desirable
100.0
to make an occasional addition of zinc oxide or zinc dust to
47.2
the operating bath. Arnophous mixed zinc and calcium
phosphate coatings were produced upon work sprayed for
Water to provide 66% calcium nitrate
solution
23. 6
less than one minute by this bath when at a temperature
in the order of 150 to 170° F. The diacetone alcohol is
used as an organic accelerator in this bath and, in ad
dition, prevents the accumulation of excess nitrate and
The bath was prepared by mixing the above ingredients
chloride anions in the bath which, when greatly in excess
together and with water in quantities such that the result
of the phosphate anion, results in excessive attack of
ing solution contains 1.5% by volume of the composition 35 the metal to be coated. This is undesirable since not
designated A above and 1% by volume of that designated
only may more weight of the base metal to be coated
B, the free acid being reduced by zinc dust in an amount
be lost than is gained from the coating formed thereon,
in the order of 0.1% by weight of the zinc concentrate,
but also the base metal will be in an active state, equiva
A. The resulting bath analyzed 20 points, with a ratio 40 lent to pickled stock, and thus have inferior corrosion re
of 25 total acid to 1 of free acid, and was maintained at
sistance. Other organic accelerators may be used in place.
a temperature in the order of 160~170° F. At this
Total_
70.8
of that mentioned above, for example, those discussed in
my aforementioned copending application Ser. No.
271,930.
As mentioned heretofore, conventional zinc phosphate
strength and temperature an amorphous mixed phos
phate coating of 200 mg. per sq. ft. was produced on fer
rous metals by spraying them for 1 minute. The bath
was found by analysis to contain 2 grams per liter of
baths can be converted to provide an amorphous coating
zinc, 6 grams per liter of phosphate and 12 grams per liter
of a mixed phosphate and an example of how this may be
of calcium nitrate, ‘and was held at this level by a constant
accomplished has been given above. In general, it has
drip addition of both the concentrates designated A
and B.
50 been found that for best results the nitrate of lithium,
beryllium, magnesium, calcium, strontium, cadmium or
The proportions of the ingredients in the concentrates
barium should be employed in an amount at least equi~
employed in compounding this bath may be varied from
molar with the zinc phosphate and that an accelerating
the presently preferred values stated above within the fol
agent be used. The preferred accelerating agents are the
lowing ranges:
55 neutralizing oxidizers such as sodium nitrite, calcium hy
pochlorite and barium nitrite which decompose in the
Ohemic?
bath to leave a neutralizing cation in solution after the
gaseous oxidant is released. In preparing such a bath the
Units
following ingredients were employed:
Mono-ammonium phosphate, NH4H2PO-l ________ _- 115X(0.05—0.20).
Zinc dihydrogen phosphate ZI1H2(PO4)2<Ammonium chloride, Nliliél ______ __
261><(0.05—0.25).
_
Calcium nitrate, Ca (NOslz H2O“-
60
53><(0.05—O.15).
236X(0.l0—0.50).
Chemical
Thus such concentrates, containing about one to about
four parts of zinc ion and at least about 1.33 parts of
calcium ion, as indicated earlier herein, will contain cal
cium and zinc in such proportions that the weight ratio
of calcuim to zinc is within the range of 0.25 to 6.1,
and will contain phosphate ion and nitrate ion in such
proportions that the weight ratio of nitrate ion to phos
Units
Percent
Com
posi
tion
A. Zinc phosphate concentrate:
Zinc dihydrogen phosphate, ZnHz(PO4)r._-
261X0. 22
Zinc nitrate, Zn(N03)26H20 _____________ __
297x002
Water to dissolve ____________________________________ __
Total.
57. 4
5. 9
36.7
100.0
B. Calcium nitrate, Ca(NOa)z4HzO _____________ __
23GXO. 48
113.0
0. Sodium nitrite, NaNOg (25% solution) _______ __
69x0. 08
5.6
phate ion is within the range of 0.3 to 6.5.
Instead of packaging the zinc salts as one concentrate
The bath is prepared in cold solution containing 1.5%
and the calcium nitrate as the second concentrate, both
the zinc and calcium salts can be put together as one con 75 by volume of the Zinc phosphate concentrate to which
3,090,709
iii
l i.
'>
tures near boiling and with a totalacid of 25 points and.
an equal weight of crystalline calcium nitrate is, added,
a free acid of 4.
after which sodium nitrite is introduced to provide in the
order of 1 gram per liter. The make-up water of the
bath may be hot rather than cold but in that event the
Chemical
calcium nitrate should be ‘added ?rst, after which the
zinc phosphate concentrate is introduced thereby prevent
inghydrolysis of the latter. The calcium nitrate may be
Calcium phosphate, CaHzPOr ___________________ -_
supplied in the form of a 65% solution but then the bath
Phosphoric acid, H; 4
should be made up to a 3% by volume concentration of
Zinc nitrate, ZI1(NO3) ___________________________ __
I
this ingredient and a 1.5% by volume concentration of 10 Water to dissolve
the zinc phosphate concentrate. Such baths have an
Total___
i
'
Units
Percent
Com
posi
tion
252x010
25. 2
98><0. 06
6.6
297X0. 05
14. 8
53. 4
7 100.0
acid ratio of 20, with 20’ points total acid, and, when op
erated at temperatures of from 130 to 160° F., produced
Mono-ammonium phosphate, NH4H2PO4 _ _ .
_ _ __
‘ 115X0. 15
17.2
amorphous mixed phosphate deposits. The initial sodium
Zinc nitrate, Z11(N0s) _________________________ __
297X0. 07
22. 2
Phosphoric acid, H3PO4 _________________________ __
Water to dissolve
~
98x0. 07
6. 9 ‘
37. 2
Calcium chloride, CaClg _________________________ _.
nitrite will normally be sufficient for several hours and 15
is augmented thereafter by additions of 0.5 gram 1 liter
whenever the coating shows a tendency towards crystal
formation or when the coating is light in weight. Calcium
hypochlorite, barium nitrite, or a mixture of sodium hy
droxide and hydrogen peroxide may be employed as ac
celerators in place of sodium nitrite with essentially
Total
100x015
' 16.5
ice. 0
The last-mentioned bath operated satisfactorily but was
improved by adding ammonium nitrate in the order of
8% of the concentrate.
The amount of the salt of the modi?er metal, namely,
lithiuzn, beryllium, magnesium, calcium, strontium, cad
of coating obtained. Baths of this nature were found,
mium or barium, which may be employed in baths formu
by analysis, to contain 3 grams per liter of zinc and 4
grams per liter of calcium and were maintained at this 25 lated in accordance with this invention is not limited to
the minimum or threshold values speci?ed but may be
level by continuous additions of the zinc phosphate con
equivalent results with respect to the quality and weight
centrate and calcium nitrate supplied through separate
feed-pumps. The calcium nitrate for such additions may
be made barely alkaline by means of ammonium hy
increased when additional buffering action vof the added
base‘and the acceleration action of high nitrate concen
tration are desirable. 'For example, in formulations for
droxide and about 3.5 grams per, liter of sodium nitrite or 30 use in spray type baths, the quantity» of modi?er salt may
be two to three times the threshold value set forth. In
calcium hydrochlorite added thereto so that the resulting
such a case and in other relatively high concentrations of
concentrate furnishes both the crystal inhibitor and the
the modi?er metal, the latter may be in greater concentra
accelerator.
tion than the Zinc in the modi?ed bath and hence ad
The proportions of the ingredients employed in com
justments must be made in the bath to maintain balance
pounding this bath may be varied from the presently pre
and avoid sludge. This may be effected by adding phos
ferred values stated above within the following ranges:
phoric acid in amounts to provide a pH of from 2 to
3. Excessive nitrate in the bath may be avoided by em- .
ploying the chlorides of zinc, lithium, beryllium, mag
40 nesium, calcium, strontium, cadmium or barium as part
Chemical
Units
Zinc dihydrogen phosphate, ZnH2(PO4)2 _______ -_ 261X(0.11 to 0.33).
Zinc nitrate, ZI1(NO3) ziiHzO __________ __
_ 297 ><(0.01 to 0.03).
Calcium nitrate, Oa(NOa)24HzO_ ___
236X(0.36 to 0.64).
Sodium nitrite, NaNOz (25 a solution
69X(0.02 to 0.12).
of the bath components rather than supplying all of these
elements in the form of the nitrate.
It will also be understood that other modi?cations of
the bath compositions can be effected to meet speci?c coat
ing problems while still employing the principles of this
invention. For example, the formulations of‘ this inven
tion may be employed to coat surfaces of metals other than
iron although the speci?c examples given above refer
primarily to formulations employed for coating ferrous
Thus such a bath, containing about one to about four
parts of zinclion and at least about 133 parts of calcium 50 articles. Where the metal coated is other than ferrous,
ion, as indicated earlier herein, will contain calcium and
zinc in such proportions that the weight ratio of calcium
to zinc is within the range of 0.61 to 3.26 and will con
the formulations may be suitably adapted to effect the. de-'
sired coating by using nickel or iron salts for galvanic
acceleration as is now well known and commonly em
pleyed in'conventional phosphating baths. However, even
tain phosphate ion and nitrate ion in such proportions
55
without the addition of such galvanic accelerators?the
that the Weight ratio of nitrate ion to phosphate ion is
baths of this invention provide a very satisfactory coating
within the range of 0.75 to 4.0.
‘
'
'
upon die cast zinc and upon commercial magnesium metal.
The above speci?c examples have employed a nitrate of
A
bath for coating magnesium, however, should be op
Vlithium, beryllium, magnesium, calcium, strontium,
erated at room'temperature and the immersion time kept
cadmium or barium as an inhibitor of crystal formation in
one minute.
zinc phosphating formulations and other ingredients have 60 below
The
amorphous type coatings provided by the formu
been included to facilitate the. coating formation. These
lations herein described are more dense and uniform
are not, however, in?exible requirements since any zinc
than crystalline coatings heretofore provided and there-v
phosphate coating bath can be made to produce an amor
phous mixed phosphate coating bath by employing a salt
of one of the above-mentioned coating crystal inhibitor
metals in the presence of a nitrate. Hence, it is not neces
sary that the nitrate of the crystal inhibitor metal be used
since a different soluble nitrate, as for example ammonium
fore provide good corrosion resistance. Nevertheless, it
65 is standard practice in certain industries to require a
chromic acid rinse of phosphated articles, especially fer
rous articles, as additional insurance against defects‘in
the coverage provided by the coating and for other con
siderations which are not-here important. The usual 2
nitrate, may be added if nitrate is not already present. 70 to 5 grams per liter chromic acid rinse shouldnot' how
‘Moreover, the nitrate may be supplied in combination
ever be employed upon the amorphous type coatings ef
with the zinc and/ or the inhibitor metal may be employed
fected as herein described since this will remove an ap
as the phosphate thereof. Thus, satisfactory amorphous
coatings were provided by immersion of ferrous articles
preciable amount of the coating. The desired passivation
and insurance of paint adhesion resulting from a chromic
in the following baths which were operated at tempera
rinse may however be secured by rinsing the coated sur
3,090,709
13
a
14
face, preferably while still wet, with ‘a hot aqueous solu
0.15 molar part of ammonium ion, said solution being
tion containing in the order 1-5 grams per liter of a di
characterized by a total acidity of about 10 to about 30.
chromate of pyridine, piccoline and quinoline, the pre
ferred concentration being less than 3 grams per liter
and preferably is in the order of 1 to 2 grams per liter.
These cyclic base chromates have unique properties as
an inhibitory rinse after phosphate coating and do not
damage an amorphous coating nor remove appreciable
amounts thereof.
The utilization of nitrates of lithium, beryllium, mag
nesium, calcium, strontium, cadmium or barium in coat
ing bath formulations not only accelerates the bath and
provides an improved coating but also results in the pro
2. An aqueous solution, for use in producing an amor
phous mixed phosphate coating on the surfaces of metals,
containing essentially from about 0.06 to about 0.27 molar
part of phosphate ion, from about 0.03 to about 0.20
molar part of zinc ion, from about 0.12 to about 0.60
molar part of nitrate ion, from about 0.10 to about 0.50
molar part of calcium ion and from about 0.02 to about
0.15 molar part of ammonium ion, said solution being
characterized by a total acidity of about 10 to about 30,
said solution being substantially free from sulfate ion.
3. A composition for forming on metallic surfaces a
duction of a non-sludging bath in which the acid ratio
protective coating exhibiting no visible crystal structure
does not rapidly change so that it is relatively easy to 15 at a magni?cation of 100 diameters, said composition
maintain the pH value of the baths substantially constant,
consisting essentially of an aqueous acidic solution con
the preferred value being 2.0—2.5 for an immersion bath
taining about 1 to about 4 parts of zinc ion, at least about
and 2.5-4.0 for a spray bath. Hence, the baths do not
1.33 parts of calcium ion, the weight ratio of calcium
require constant attention and modi?cation. Moreover,
to zinc being within the range of 0.31 to 10.2, the phos
the baths may be readily titrated by simple methods in 20 phate ion and the nitrate ion, the weight ratio of nitrate
common use and which are well understood by even semi
skilled workers so that the services of a skilled chemist
are not needed.
The selection of the modi?er salt is in part determined
by its cost, in part by its relative e?ectiveness, and also
by its possible toxic effect upon the operators. Thus,
calcium nitrate is presently preferred because of its low
cost, non~toxic nature and its relatively low threshold
value in these formulations while barium nitrate, being
ion to phosphate ion being within the range of 0.58 to
13.0.
4. The composition of claim 3 characterized ?irther
in that said aqueous acidic solution has a ratio of total
acidity to free acidity within the range of from about 5
to about 50.
5. A composition for forming on metallic surfaces a
protective coating exhibiting no visible crystal structure
at a magni?cation of 100 diameters, said composition
still more highly effective, may be used in installations 30 consisting essentially of an aqueous acidic solution con
Where its toxicity is not objectionable. Although relative
taining about 1 to about 4 parts of zinc ion, at least about
cost, effectiveness in the formulations and possible toxicity
1.33 parts of calcium ion, the weight ratio of calcium
are the more usual considerations in the selection of the
to zinc being within the range of 0.25 to 6.1, the phos
modi?er salts, it is to be understood that other considera—
phate ion and the nitrate ion, the weight ratio of nitrate
tions may also influence the choice of one or more of the 35 ion to phosphate ion being Within the range of 0.3 to 6.5.
modi?ers. In this regard, it should be noted that more
6. The composition of claim 5 characterized further
than one of the modi?er salts may be employed in a single
in that said aqueous acidic solution has a ratio of total
formulation and that, where more than one such modi
‘acidity to free acidity within the range of about 5 to
about 50.
?er is employed in a given ‘formulation, the minimum
or threshold value for each will depend upon the total 40
7. A composition for forming on metallic surfaces a
quantity of the modi?ers utilized. It will be remembered,
however, that amounts of the modi?er salts greater than
the
of threshold values may be safely employed
with corresponding modi?cation of the bath to secure and
maintain the balance therein.
It will also be understood that although the amorphous
protective coating exhibiting no visible crystal structure
at a magni?cation of 100 diameters, said composition
consisting essentially of an aqueous acidic solution con
taining about 1 to about 4 parts of zinc ion, at least about
1.33 parts of calcium ion, the weight ratio of calcium
to zinc being within the range of 0.61 to 3.26, the phos
coatings, produced by employing the modi?er metal salts
phate ion and the nitrate ion, the weight ratio of nitrate
ion to phosphate ion being within the range of 0.75 to 4.0.
in quantities equal to or greater than the threshold value,
reveal no crystalline structure under magni?cation of 100
8. A composition for forming on metallic sun-faces a
diameters, nevertheless, somewhat lesser amounts of the 50 protective coating exhibiting no visible crystal structure
modi?er metal salts will produce coatings which are
at a magni?cation of 100 diameters, said composition
consisting essentially of an aqueous acidic solution of
smooth in appearance and afford a continuous coverage
of the coated metal. Such coatings are essentially non
from 1 to 4 parts of zinc ion, phosphate ion and at least
1 metal nitrate selected from the group consisting of
orystalline in character, even though some vestiges of crys
tal ‘form may be detected under magni?cation, and there 55 lithium nitrate, beryllium nitrate, magnesium nitrate, cal
fore the use of the term “amorphous” or “amorphous
cium nitrate, strontium nitrate, cadmium nitrate and
type” in the subjoined claims is intended to include such
barium nitrate, said metal nitrate being present in at least
the following concentrations:
coatings in the absence of other limitations. It will also
be evident that modi?cations in the compositions and
Parts
12.3
methods of preparing and using the same, other than those 60 Lithium nitrate
Beryllium nitrate
9.3
speci?cally heretofore mentioned, will be apparent to
Magnesium nitrate
25.6
those skilled in the art and consequently the invention is
Calcium nitrate
7.8
not {to be considered as limited to the substances and per
centages thereof given in the speci?c examples except as
Strontium nitrate
14.1
30.8
may be required by the spirit and scope of the subjoined 65 Cadmium nitrate
claims.
Barium nitrate
5.2
Having thus described the invention, 1 claim:
9. A solution for forming a protective coating on me
1. An aqueous solution, for use in producing an amor
tallic surfaces which comprises an aqueous acidic solution
phous mixed phosphate coating on the surfaces of metals, 70 ‘consisting essentially of about 0.l—0.4% zinc ion, at least
containing essentially from about 0.06 to about 0.27 molar
0.132 calcium ion, the weight ratio of the calcium ion
part of phosphate ion, from about 0.03 to about 0.20
to the zinc ion being in the range of 0.25-4.5, the phos
molar part of zinc ion, from about 0.12 to about 0.60
phate ion and the nitrate ion, the weight ratio of nitrate
molar part of nitrate ion, from about 0.10 to about 0.50
ion to phosphate ion being in the range of 0.5-4.35.
molar part of calcium ion and from about 0.02 to about 75
10. A solution for forming a protective coating on me
3,090,709
15
tallic surfaces which comprises an aqueous acidic solution
2,364,436
consisting essentially of about 0.1—0.4% zinc ion, at least
2,499,261
2,500,915
7 0.132 calcium ion, the weight ratio of the calcium ion
to the zinc ion being in the range of 0.25—4.5, the phos
phate ion and the nitrate ion, the weight ratio of nitrate 5
ion to phosphate ion being in the range of 0.5-4.35, said
2,514,941 -
2,515,934
12,540,314
2,588,234
2,597,406
2,609,308
solution being substantially ‘free from sulfate ion. ‘
References Cited in the tile of this patent
UNITED STATES PATENTS
Re. 24,017
1,291,352
2,628,175
10
2,702,768
2,766,154
Henricks' ______________ __ June 7, 1955
Allen ________________ __ Jan. 14, 1919
1,939,421,
Tosterud ______ .._' _____ __ Dec. 12, 1933
1,957,354
2,121,574
2,312,855
Prier _________________ __ May 1, 1934
Romig _______________ __ June 21, 1938
Thompson ____________ __ Mar. 2, 1943
.
16
Frisch et al _____________ __ Dec. 5,1944 -'
Rosen-bloom __________ __ Feb. 28, 1950
Tanner ______________ .__ Mar. 14, 1950
Drysdale ______________ __ July 11, 1950
Verner et a1 ___________ __ July 18, 1950
Amundsen _____________ __ Feb. 6, 1951,
Henricks ______________ _'_ Mar. 4, 1952
Tihome-Johanessen _____ __'May 20, 1952
Gibson _______________ __ Sept. 2,
Henderson ____________ __ Feb. 10,
‘ Hyams et a1 ___________ __ Feb. 22,
Russell ____ ___ _____ __’__..__, Oct. 9,
1952
1953
1955
1956
FOREIGN PATENTS
1,5
‘
3 10,756
Germany ____~_ _________ __ July 1, 1922 ,
440,215
Great Bn'tain _________ __ Dec. 23, 1935
Документ
Категория
Без категории
Просмотров
0
Размер файла
1 347 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа