Language selection

Search

Patent 2175065 Summary

Third-party information liability

Some of the information on this Web page has been provided by external sources. The Government of Canada is not responsible for the accuracy, reliability or currency of the information supplied by external sources. Users wishing to rely upon this information should consult directly with the source of the information. Content provided by external sources is not subject to official languages, privacy and accessibility requirements.

Claims and Abstract availability

Any discrepancies in the text and image of the Claims and Abstract are due to differing posting times. Text of the Claims and Abstract are posted:

  • At the time the application is open to public inspection;
  • At the time of issue of the patent (grant).
(12) Patent Application: (11) CA 2175065
(54) English Title: A PROCESS FOR ACTIVATING A METAL SURFACE FOR CONVERSION COATING
(54) French Title: PROCEDE D'ACTIVATION D'UNE SURFACE METALLIQUE POUR Y APPLIQUER UN REVETEMENT PAR CONVERSION
Status: Dead
Bibliographic Data
(51) International Patent Classification (IPC):
  • C23C 22/80 (2006.01)
  • B01J 19/10 (2006.01)
(72) Inventors :
  • KRAMER, LINDA S. (United States of America)
  • DUNN, ROBIN M. (United States of America)
  • GILES, TERRENCE R. (United States of America)
  • MILLER, ROBERT W. (United States of America)
(73) Owners :
  • HENKEL CORPORATION (United States of America)
(71) Applicants :
(74) Agent: FETHERSTONHAUGH & CO.
(74) Associate agent:
(45) Issued:
(86) PCT Filing Date: 1993-10-26
(87) Open to Public Inspection: 1995-05-04
Availability of licence: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): Yes
(86) PCT Filing Number: PCT/US1993/010243
(87) International Publication Number: WO1995/012011
(85) National Entry: 1996-04-25

(30) Application Priority Data: None

Abstracts

English Abstract



The invention is a process for applying a phosphate coating to a metal substrate in which the metal substrate is contacted with an
aqueous activating bath before the phosphate coating is applied. The improved process is obtained by applying ultrasonic vibration energy
to the aqueous activating bath. The ultrasonic energy can be applied to the aqueous activating bath when the aqueous activating bath is in
contact with the metal substrate or when the metal substrate is not in contact with the aqueous activating bath.


French Abstract

L'invention concerne un procédé d'application d'un revêtement à base de phosphate sur un substrat métallique, ce procédé consistant à mettre en contact le substrat métallique avec un bain aqueux d'activation avant d'appliquer le revêtement à base de phosphate. Le procédé amélioré consiste à appliquer une énergie vibratoire ultrasonique au bain aqueux d'activation. L'énergie ultrasonique peut être appliquée au bain aqueux d'activation lorsque ce dernier est en contact avec le substrat métallique ou lorsque le substrat métallique n'est pas en contact avec le bain d'activation aqueux.

Claims

Note: Claims are shown in the official language in which they were submitted.


We claim
1. An improved process for forming a phosphate conversion
coating on a metal substrate, wherein the surface of
the metal substrate is cleaned, activated by contact
with an aqueous activating composition and coated by
a conversion coating process, the improvement which
comprises: applying ultrasonic vibration energy to the
aqueous activating composition.
2. The process of claim 1 wherein the ultrasonic
vibration energy is applied to the aqueous activating
composition in the presence of the metal substrate to
be activated.
3. The process of claim 1 wherein the ultrasonic
vibration energy is applied to the aqueous activating
composition in the absence of the metal substrate.
4. The process of claim 1 wherein the surface of the
metal substrate comprises a metal selected for the
group consisting of iron, zinc, zinc alloys, aluminum
and aluminum alloys.
5. A process of claim 1 wherein the aqueous activating
composition contains water and an activating
composition comprising titanium and phosphorous.
6. A process of claim 5 wherein the aqueous activating
bath comprises a reaction product of a titanium
compound and a phosphorous compound.

49

7. A process of claim 1 which comprises: (1) cleaning the
surface of the metal substrate with an alkaline
cleaning composition; (2) contacting the clean surface
of the metal substrate with a titanium and phosphorous
containing aqueous activating composition to which
ultrasonic vibration energy is applied and (3) forming
a phosphate conversion coating on the metal surface
which has been contacted with the titanium and
phosphate containing activating composition.
8. A process of claim 7 wherein the aqueous activating
composition comprises from about 2 to about 30 parts
per million of titanium.
9. A process of claim 1 wherein the aqueous activating
composition comprises from about 2 to about 30 parts
per million of titanium.
10. A process of claim 1 wherein the aqueous activating
composition contains water, a reaction product of a
titanium compound with a phosphorus compound, and a
condensed phosphate.
11. A process of claim 5 wherein titanium and phosphorus
are provided by a composition comprising the reaction
product of a titanium compound with a phosphate
compound.
12. A process of claim 11 wherein the metal substrate is
contacted with the aqueous activating composition at
a temperature of from ambient to about 150°F.




13. A process of claim 3 wherein the metal substrate is
contacted with the aqueous activating composition in
an activating zone and the ultrasonic vibration energy
is applied to the aqueous activating composition in an
ultrasonic zone outside of the activating zone.
14. A process of claim 1 wherein an average age of the
aqueous activating composition is greater than five
days.

51

Description

Note: Descriptions are shown in the official language in which they were submitted.


~ WO95/12011 2 1 7 5 0 ~ S PCT~S93/10243




A PROCESæ FOR ACTIVATING A NETAL 8URFACE FOR CONV~:K8ION
COATING
Field of the Invention
The invention is an improved method for providing a
phosphate conversion coating on a metal substrate.
Backqround of the Invention
S A variety of compositions and processes have been used
to provide an adherent, uniform phosphate coating on a
metal surface. The phosphate coating is applied to enhance
the adhesion of subsequently applied coatings and to
provide for improved corrosion resistance of the coated
metal substrate.
Phosphate coating processes (known as phosphating or
phosphate conversion coating processes) are well known in
the art. Generally, the phosphating process comprises
contacting the metal surface with a acidic phosphate
solution. The phosphating solution generally contains ions
of metals such as zinc, nickel, manganese, copper, chromium
and other metals which are known to provide conversion

Wo95112011 ~5~G~ PCT~S93/10243
coatings on metal substrates in an acidic phosphate
solution.
The metal substrate can be contacted with the acidic
phosphate solution by immersion, spraying, roller coating,
flowing and other means known for contacting a metal with
an aqueous solution. Acidic phosphate conversion coating
solutions are well known in the art and have been found
very useful for providing a base for application of a
protective coating to the metal substrate.
As disclosed in U.S. 2,310,239 to Jernstedt, US
2,874,812 to Cavanagh and Maurer and in U.S. 4,539,OSl, to
Hacias, conversion coatings can be improved if, prior to
contacting the metal to be phosphate coated with the acidic
phosphate solution, the metal surface is first activated by
contact with an aqueous activating composition. The
aqueous activating compositions are generally mixtures
comprising water with a reaction product of a titanium
compound and a phosphate. The aqueous activating
compositions are at an alkaline pH, generally in the range
of about 7 to about ll and preferably in the range of from
about 8 to about lO. Titanium compound-phosphate compound
reaction products generally contain from about 0.005 to
about 25% by weight titanium. As is disclosed in the cited
references, a cleaned metal substrate is contacted with an
aqueous activating composition to assist in providing an
even coating with low coating weight and small crystal
morphology in the phosphate conversion coating step.
It is well known in the art that after the aqueous

W O 95/12011 2 17 5 ~ ~ ~ PCTAUS93/10243
activating composition is prepared by ~;~;ng a dry
activating composition with water, the aqueous activating
composition loses its activating ability as time passes and
the aqueous composition ages. The activating ability of
the aqueous activating composition declines with time even
if the composition has not been exhausted by contact with
metal substrates. It would be useful to be able to extend
the useful life of the aqueous activating compositions.
The time period since preparation of the aqueous activating
composition is known as the aging period or aging.
Contacting the metal substrate with the aqueous
activating composition provides for a phosphate conversion
coating which has a small crystal size, optimal coating
weight and a more even coating than substrates which have
been contacted with acidic phosphate solutions without
prior contact with the aqueous activating composition.
Before the metal substrate is contacted with the
aqueous activating composition and conversion coated, it is
important that the metal substrate be clean. Cleaning of
the metal substrate is generally accomplished by contacting
the metal substrate with an acidic or an alkaline cleaning
composition. Generally, the alkaline compositions are
preferred since the activating composition is at an
alkaline pH. However, as long as the metal substrate is
rinsed of the cleaning solution, an acidic cleaning
solution can be utilized.


WO95112011 ~ 0 6~ PCT~S93/10243
A Brief SummarY of the Invention
According to the present invention, an improved
phosphate conversion coating can be formed on a metal
substrate by the process by contacting an aqueous
activating composition used to activate the metal substrate
with ultrasonic vibration energy. Ultrasonic vibrations
(ultrasonic energy) can be applied to the aqueous
activating composition (hereinafter activating bath), in
the presence or in the absence of the metal substrate which
is to be activated. The largest increase in the quality of
the phosphate coating in the process is obtained if the
ultrasonic vibrations are applied to the activating bath in
the presence of the metal substrate.
The process of the invention comprises cleaning the
metal substrate, contacting the metal substrate with an
activating bath which has been subjected to application of
ultrasonic energy to provide an activated metal substrate
and phosphating the activated metal substrate.
Brief DescriPtion of the Drawinqs
Figure l (a), (b) and (c) are scanning electron
photomicrographs at l,000 magnification of phosphated cold
rolled steel panels prepared by the process using Bath l
before and after aging for 12 days.
Figure 2 (a), (b? and (c) are sc~nn;ng electron
photomicrographs at l,000 magnification of phosphated cold
rolled steel panels prepared by the process using Bath 2
before and after aging for 12 days.
Figure 3 (a), (b) and (c) are sc~nn;ng electron

- ~ 21 7s~,6$
WO 95/12011 PCTtUS93tlO243
photomicrographs at 1,000 magnification of phosphated cold
rolled steel panels prepared by the process using Bath 3
before and after aging for 12 days.
Figure 4 (a), (b) and (c) are scanning electron
photomicrographs at 1,000 magnification of phosphated cold
rolled steel panels prepared by the process using Bath 4
before and after aging for 12 days.
Figure 5 (a) and (b) are scanning electron
photomicrographs at 1,000 magnification of phosphated cold
rolled steel panels prepared by the process using Bath 5
before and after aging for 12 days.
Figure 6 (a), (b) and (c) are scanning electron
photomicrographs of 1,000 magnification of phosphated cold
rolled steel panels prepared by the process using a fresh
control bath each day without ultrasonic energy applied.
Figure 7 (a), (b), (c), and (d) are s~nn;ng electron
photomicrographs at 1,000 magnification of phosphated cold
rolled steel panels prepared by the process using Bath 6,
after aging for 1, 2, 5 and 6 days.
Figure 8 (a), (b), (c), and (d) are scanning electron
photomicrographs at 1,000 magnification of phosphated cold
rolled steel panels prepared by the process using Bath 7,
after aging for 1, 2, 5 and 6 days.
Figure 9 (a), (b), (c), and (d) are sc~nn;ng electron
photomicrographs at 1,000 magnification of phosphated cold
rolled steel panels prepared by the process using Bath 8,
after aging for 1, 2, 5 and 6 days.
Figure 10 (a), (b), (c), and (d) are sr~nn;ng electron



21750~5
W O 9S/12011 PCTAUS93/10243
photomicrographs at 1,000 magnification of phosphated cold
rolled steel panels prepared by the process using Bath 9,
after aging for 1, 2, 5 and 6 days.
Figure 11 (a), (b), (c),and (d) are scAnn;ng electron
photomicrographs at 1,000 magnification of phosphated cold
rolled steel panels prepared by the process using Bath 10,
after aging for 1, 2, 5 and 6 days.
Figure 12 (a), (b), (c), and (d) are scanning electron
photomicrographs at 1,000 magnification of phosphated cold
rolled steel panels prepared by the process using Bath 11
after aging for 1, 2, 5 and 6 days.
Figure 12 (a), (b), (c) and (d) are scanning electron
photomicrographs at 1,000 magnification of cold rolled
steel panels phosphated on days 1, 2, 5 and 6 by the
process using a freshly prepared FIXODINE~ brand activating
control bath each day without ultrasonic energy applied.
Figure 14 is a scanning electron photomicrograph at
1,000 magnification of a phosphated cold rolled steel
panel, prepared without contact with an activating bath in
the process.
Figure 15 (a), (b), (c), (d) and (e) are scanning
electron photomicrographs at 1,000 magnification of the
outer surface of phosphated panels of cold rolled steel
(CRS), electrogalvanized steel (EG) and aluminum alloy 6061
(6061) prepared using activating Bath 11 under various
conditions in the process.
Figure 16 (a), (b), (c), (d) and (e) are scanning
electron photomicrographs at 1,000 magnification of the

. ~ 2l7s~G~ ~
WO 95/12011 ~ PCT/US93110243
inner surface of phosphated panels of CRS, EG and 6061
prepared using activating Bath 11 under various conditions
in the process.
Figure 17 (a), (b), (c), (d) and (e) are scanning
electron photomicrographs at 1,000 magnification of the
outer surface of phosphated panels of CRS, EG and 6061
prepared using activating Bath 12 under various conditions
in the process.
Figure 18 (a), (b), (c), (d) and (e) are scanning
electron photomicrographs at 1,000 magnification of the
inner surface of phosphated panels of CRS, EG and 6061
prepared using activating Bath 12 under various conditions
in the process.
Figure 19 (a), (b), (c), (d) and (e) are scanning
electron photomicrographs at 1,000 magnification of the
outer surface of phosphated panels of CRS, EG and 6061
prepared using activating Bath 13 under various conditions
in the process.
Figure 20 (a), (b), (c), (d) and (e) are scanning
electron photomicrographs at 1,000 magnification of the
inner surface of phosphated panels of CRS, EG and 6061
prepared using activating Bath 13 under various conditions
in the process.
Figure 21 (a), (b) and (c) are scAnning electron
photomicrographs at 1,000 magnification of the outer
phosphated surface of metal panels prepared using a freshly
prepared control bath in the process.
Figure 22 (a), (b) and (c) are scanning electron

WO9S/12011 ' ' PCT~S93/10243
photomicrographs at 1,OOo magnification of the inner
phosphated surface of metal panels prepared using a freshly
prepared control bath in the process.
Figure 23 (a), (b) and (c) are scanning electron
photomicrographs at 1,000 magnification of phosphated metal
panels (a) CRS, (b) EG and (c) 6061 prepared using stirred
Bath 14 (for comparison) in the process.
Figure 24 (a), (b) and (c) are scAnn;ng electron
photomicrographs at 1,000 magnification of phosphated metal
panels (a) CRS, (b) EG and (c) 6061 prepared by the process
by applying ultrasonic energy to Bath 15 while the metal
panels were immersed in the bath.
Figure 25 (a), (b) and (c) are scAnn;ng electron
photomicrographs at 1,000 magnification of phosphated me~al
panels (a) CRS, (b) EG and (c) 6061 prepared using Bath 15
five minutes after stopping application of ultrasonic
energy to the bath in the process.
Figure 26 (a), (b) and (c) are scanning electron
photomicrographs at 1,000 magnification of phosphated metal
panels prepared using stirred Bath 16 in the process (for
comparison).
Figure 27 (a), (b) and (c) are scAn~;ng electron
photomicrographs at 1,000 magnification of phosphated metal
panels prepared by the process by applying ultrasonic
energy to Bath 17 while the metal panels were immersed in
the bath.
Figure 28 (a), (b) and (c) are sc~nn;ng electron
photomicrographs at 1,000 magnification of phosphated metal


WO95112011 7~ PCT~S93/10243
panels prepared by the process wherein the metal panels are
immersed in Bath 17 five minutes after the ultrasonic
vibrations were discontinued.
Figure 29 (a), (b) and (c) are scanning electron
photomicrographs at l,000 magnification of phosphated metal
panels prepared using stirred Bath 18 in the process (for
comparison).
Figure 30 (a), (b) and (c) are scanning electron
photomicrographs at l,000 magnification of phosphated metal
panels prepared by the process by immersing the panels in
Bath l9 while ultrasonic energy was applied to Bath l9.
Figure 31 (a), (b) and (c) are scanning electron
photomicrographs at l,000 magnification of phosphated metal
panels prepared by the process by immersing the panels in
Bath l9 five minutes after the application of ultrasonic
energy to the bath was stopped.
Figure 32 (a), (b), and (c) are scanning electron
photomicrographs of phosphated metal panels prepared by the
process using a freshly prepared control bath.
~escription of the Preferred Embodiments of the Invention
Metal substrates which can be advantageously treated
by the process of the present invention include iron, zinc,
zinc alloys, aluminum and aluminum alloys containing at
least about 60%-70% aluminum. The substrate to be treated
by the process of the present invention need not be made of
the metal alone. That is, zinc plated and aluminum
composite materials may be advantageously treated by the
process of the invention.

WO9~/12011 2 1 ~ 5 0 6 ~ : - PCT~S93/10243
As is well known in the art for providing phosphate
coatings on metal substrates, the metal must be clean to
permit an adherent phosphate coating to be formed. The
metal substrates are generally cleaned by contact with an
alkaline or an acid cleaning solution to remove any grease,
dirt, scale, oxidized coating and the like from the surface
of the metal substrate. Acid cleaners generally contain
sulfuric and/or phosphoric acid. In addition, if the metal
substrate is aluminum, a small amount of fluoride ion is
generally included in the cleaning composition.
Alkaline cleaners can be utilized to prepare the metal
substrate for accepting the phosphate coating. Alkaline
cleaners are generally composed of alkali materials such as
caustic, soda ash, trisodium phosphate, sodium
polyphosphate, sodium silicate, and surfactants. The metal
substrate to be cleaned is contacted with a dilute solution
of the alkaline cleaner. The metal to be cleaned is
generally contacted with the aqueous cleaning solution at
a temperature in the range of from about ambient to about
160F and preferably from about 100F to about 150F.
Metal can be cleaned by contacting the metal with the
aqueous cleaning composition by immersion, spraying,
flowing, and other means for contacting a metal with an
aqueous cleaning solution. Generally, the metal substrate
is immersed in the aqueous solution or the aqueous cleaning
solution is sprayed onto the metal substrate. The metal is
contacted with the cleaning solution for from about 30
seconds to about 10 minutes and preferably from about 1 to



WO95112011 SO ~ PCT~S93/10243
about 3 minutes.
After the metal substrate has been cleaned with the
cleaning solution, the cleaning solution is rinsed from the
surface of the metal substrate with water.
After the metal substrate has been cleaned and rinsed
with water, the metal substrate is generally contacted with
a mixture of water and an activating composition. A
preferred activating composition is a reaction product of
a titanium compound with a phosphate compound. The
activating compositions are mixed with the water to form an
aqueous activating composition (activating bath) and
contacted with the metal substrates. Preferably, the
aqueous activating composition contains from about 0.05 to
about 25 grams per liter of the activating composition.
The activating composition is generally not soluble in
water and a dispersion of the activating composition in an
aqueous phase (activating bath) is generally obtained.
The activating composition lS a reaction product of a
titanium containing composition with a phosphate. This
reaction product can be combined with an additional
phosphate material such as sodium tripolyphosphate, sodium
pyrophosphate, disodium phosphate and the like. The
activating composition is a dry material containing at
least 0.005% titanium and is mixed with water to form the
aqueous activating composition. The activating composition
may contain an alkaline material such as sodium carbonate
or caustic to help provide an aqueous activating
composition with an alkaline pH. The pH is generally

2~75~
WO95/12011 PCT~S93/10243

between about 7 and ll and preferably between about 8 and
10 .
In known processes, the cleaned metal substrate is
then contacted with the activating bath for from about 5
seconds to about lO minutes, preferably from about 20
seconds to about 5 minutes. The activating bath is
contacted with the metal substrate at a temperature of from
about ambient to about 150F, preferably from about 75 to
about llOF.
Applicants have discovered that if ultrasonic
vibrations (ultrasonic energy) are applied to the
activating bath, a phosphate conversion coating, which is
later formed on the substrate, has a smaller crystal size,
an optimum coating weight and is more uniform. That is,
the surface of the metal substrate is more uniformly coated
with a phosphate coating. The ultrasonic power can be
applied to the aqueous activating composition alone or it
can be applied to the aqueous activating composition when
in contact with a metal surface which is to be activated.
The most dramatic results are provided when the ultrasonic
power is applied to the aqueous activating composition when
in contact with the metal substrate to be activated.
Ultrasonic power can be applied to the aqueous activating
composition in the metal contacting zone in the presence or
absence of a metal substrate or can be applied to the
aqueous activating composition in a separate ultrasonic
treating zone outside of the contacting zone. The
ultrasonic power can be applied to the aqueous activating


WO95/12011 1 7S~ 6~ PCT~S93/10243
composition continuously, only when the aqueous activating
composition is being used to activate a metal substrate,
only when the aqueous activating composition is not being
- used to contact metal substrate, in a predetermined
discontinuous manner or in a discontinuous random manner.
In a preferred embodiment, the metal substrate is contacted
with the aqueous activating composition at the same time as
ultrasonic power is applied to the composition.
The metal substrate can be contacted with the aqueous
activating composition by immersion, spraying, flowing or
any other method used for contacting a metal substrate with
an aqueous composition.
Applicants have discovered that the aqueous activating
composition has a lesser improvement on the final phosphate
coating when the ultrasonic power is applied to the aqueous
activating composition in the absence of the metal
substrate or applied to the aqueous activating composition
externally to the contact zone. Excellent phosphate
coatings are formed on the metal substrate when the
ultrasonic power is applied to the aqueous activating
composition in a contacting zone during contact with the
metal substrate to be activated.
After the metal substrate has been removed from
contact with the activating bath, the metal substrate is
then passed to a phosphate conversion coating zone. In the
phosphate conversion coating zone, the activated metal
substrate is contacted with an acidic phosphate containing
conversion coating solution to provide an adherent metal


2175065 - ~
WO95/12011 PCT~S93/10243
phosphate coating on the metal substrate.
Phosphate conversion coating compositions are well
known to one skilled in the art. Phosphate conversion
coating compositions have been used for more than 40 years.
The acidic phosphate compositions are well known; however,
new additives to increase the rate at which the coating is
formed, alter the size and shape of the crystals of the
coating and the like can be included in the composition to
provide a more useful coating.
As is well known in the art, the goal of a phosphate
conversion coating process is to provide an adherent
coating with a crystal structure optimized for the intended
use, with maximum coverage for the weight of phosphate
coating. Clearly, when the phosphate coating is to be
coated with an additional organic coating material, to form
a corrosion resistant coating, the phosphate coating is
desirably as even as possible and of the lowest weight per
unit area. Uniform coatings of small crystal size and
excellent coverage can be provided by the process of the
present invention.
In the phosphating process, contact with the
activating bath is required to provide a uniform coating
having crystals with a small size. After the substrate has
received the phosphate coating, the substrate is then
rinsed to remove the acid phosphate solution.
The phosphate coating can be further improved by
contacting the phosphate coated metal with a sealing and
adhesion promoting composition. Generally, the sealing and


14

~WO 95112011 So 6~ PCT/US93/10243
adhesion promoting composition is an acidic chromate
containing solution. However, other post treatment
solutions can be utilized. The phosphated metal can be
coated by additional coating materials known in the art.
A series of experiments were conducted to determine
the effect of ultrasonic vibrations on the properties of
phosphate coatings prepared by contacting a cleaned metal
substrate, to be phosphate coated, with a titanium
compound-phosphate reaction product activating composition
in an aqueous dispersion.
Experiment 1
Metal test panels were processed using a standard
phosphating process cycle. In the tests, the metal test
panels were treated according to the following process.
The metal test panels were cleaned by contact with PARCO~
CLEANER 1500C at 2 ounces per gallon at 110F by spraying
for 2 minutes; rinsing with warm water with a 45 second
spray; contact with an aqueous activating composition of
water and FIXODINE~ ZN at 80F by immersion for 30 seconds;
contact with a BONDERITE~ 3080 phosphating solution
according to manufacturers' recommendations, by immersion
in the aqueous phosphating solution at 112F for 2 minutes.
After immersion in the phosphate coating composition, the
panels were rinsed with cold water for 30 seconds and oven
dried.
PARCO~ CLEANER 1500C is an alkali cleaner (product of
Parker+Amchem). FIXODINE~ ZN activating composition is a
composition containing a reaction product of a titanium

WO95112011 2 17 ~ ~ 6 ~ PCT~S93110243
contA;n;ng compound~with phosphates, subsequently mixed
with sodium phosphates and sodium carbonate (product of
Parker+Amchem). BONDERITE~ 3080 phosphating composition is
an aqueous acidic zinc-manganese-nickel-phosphate
conversion coating composition (product of Parker+Amchem).
The effect of ultrasonic power applied to the aqueous
activating composition on the phosphate coatings formed by
the process were determined by the following experimental
design.
Bath l Bath 2 Bath 3 Bath 4 Bath 5
Day l *X US*X US*X US*X *X
Day 2 - - - US*
Day 3 * * * US* *
Day 4 - - - US*
Day 5 * * US* US* *
Day 8 * * * US* *
Day 9 - - - US*
Day l0 * * US* US* *
Day ll - - - US*
Day 12 *X *X *X *X *X
Day 12 US*X US*X US*X US*X



* Bath conditions and particle size were checked.
US Ultrasonic vibration applied to activating bath.
X Test panel contacted with the aqueous activating bath.
- No tests or treatments to the activating bath.

WO95/12011 1 7~065 PCT~S93/10243
A st~n~Ard water solution was prepared by diluting
79 ml CaCl2 solution (lO g/l)
53 ml MgSO4 solution (l0 g/l)
- 26 ml NaHCO3 solution (lO g/l)
to 9 liters with deionized water. This solution is noted
as standard water and was utilized to prepare the FIXODINE~
ZN brand activating baths. The standard water was analyzed
and found to contain: 2l ppm Ca, lO ppm Mg, 7 ppm Na and
hardness (as CaCO3) of 120 ppm.
Activating Baths 1-4 were prepared by m;~;ng 1.5 grams
of FIXODINE~ ZN brand activating composition and 0.22 grams
of soda ash (for adjustment of pH 9.0+0.3) per liter of
stAn~Ard water.
Bath 5 was prepared by mixing l.5 grams of FIXODINE~
ZN brand activating composition and 0.22 grams of soda ash
(pH adjustment to 9.0+0.3) per liter of deionized water.
No ultrasonic vibrations were applied to activating
Baths l and 5. Ultrasonic vibrations at a frequency of 40
kilohertz were applied to activating Baths 2, 3 and 4 for
2 minutes. In addition the baths were treated with
ultrasonic vibration as shown in the experimental design.
All the baths were analyzed for total titanium,
filterable titanium, pH and total alkalinity.
Total titanium is the total amount of titanium in the
activating bath in parts per million.
Filterable titanium is the amount of titanium, in
parts per million, in the activating bath which passes
through a filter medium with 2.5 micron openings.


WO95/12011 ~ ~ PCT~S93110243
Total alkalinity is determined as the number of ml of
O.lN H2SO4 required to titrate a lO ml sample to a
bromphenol blue end point.
The test panels were prepared after ultrasonic
vibrations had been applied to the activating baths in
accordance with the experimental design. The ultrasonic
vibrations were applied to the activating baths in the
ultrasonic power zone of a BRANSONIC~ Model PC620 at 40
kilohertz in all experiments reported in this application.
Test panels were prepared by the process on day l
after ultrasonic treatment of the activating bath (if
applicable) and on day 12 before and after ultrasonic
treatment of the activating bath. The ultrasonic treatment
of the activating Baths l through 4 was in the treating
zones in the absence of the metal substrate. The results
of the test are set forth in Tables l through 5. Tables l
through 5 disclose the properties of the bath and in
addition provide coating weight, crystal size and crystal
number.
The crystal number is the number of crystals in one
square inch of the scAnning electron photomicrograph at
l,000 magnification of the surface of the coated substrate.
The maximum crystal number reported is lOO. This includes
metal substrates wherein there are more than lO0+ crystals
per square inch in the Sr~nni~g electron photomicrograph at
l,000 magnification of the coated metal surface. The
preferred coatings have an optimum coating weight, small
crystal size and a large crystal number.


18

WO95112011 1 75~ PCT~S93/10243
The data in Tables 1-5 show that ultrasonic energy
treatment of aged activating baths, when not in contact
with the metal substrate, provides a lower coating weight
with a smaller crystal size and a larger crystal number
than aged aqueous activating baths which have not been
ultrasonically treated. The best phosphate coatings after
12 days aging of the bath were obtained by using activating
baths which had been treated with ultrasonic vibrations
every day during the 12 days of aging. The coating weight
after 12 days aging was the same as the coating weight of
phosphate coating obtained by using the fresh activating
bath in the process, with the same crystal size and nearly
the same crystal number.
Activating Bath 5 was prepared with deionized water.
It is generally known that the activating effect of the
activating bath made with deionized water deteriorates
during aging. Bath 5 was included in this study to show
that the effect of the application of ultrasonic energy to
the Baths l through 4 was different than the effect seen
with deionized water. With the application of ultrasonic
energy to the activating bath, excellent coatings were
obtained, even after aging of the baths.




19

WO 95/12011 2 1~ 7 5 O ~ 5 PCT/US93/10243 *



C~ DO OIO
U) cO ~~D
~ ~ -
~ Z

, 0
OI l I
U~ E
~) .
-




r
,CI~ ~
3 cr
c~ u~
_ ~ ~ N
~C7)
~, ~
.
U)
2 c ~ u~
-- o
O

O -- ~ o ~ ~ 0
o~ 0 0 1~ r_ t~

0 0 0 0 co 0
~ ~=
m ,0, ~ O ~ 0O O 0O
_ .
-- ,.
-- E . . ~

Ul

~ CO O C C C O Oc O O O

O -- C~l N
-- N ~) 't U') 0 C~ -- _ ~ _
C O ~ C~ O C~ C~ C~




WO95/12011 $o/~ PCT/US93/10243




'0
' E n 0
0




N ~ 0

~ _

.~ C
~ cr C~ C~ N
.C ~ C~

I
V o~
m Q

t~ 0 _ ~ o U~
o o) ~ 0 0 1~
c~ Q C~- ~, 0 0 0 0 0
ll~ t=
0 ~
-- ~ ~C o U~ o o o o o
~ ~ QQ ~
.~

Q -- -- _ _ _ _ _
, - o g


'--G 0 c cO cO O cO O cO c 0

O -- C~
O O O G C~

WO 95/12011 2 17 ~ O 6 ~ PCT/US93110243




D O O
,~ E _ 'D r~
Z

~, I I I
,~5 E N --

~D E
o 1`
ol U' , U~
N N N
~ o cr
I
-
~_ o ~
~ S ~ o o o o o o o
m o




0 _ u~ a) ~~) N O
Cs~ 0 1~ 1~ 1~ 1~ 0
C~ Q 0 0 0 0 0 0 0 0
F
E

1-- .
E .4 ~D ~ ~ -- ~ _
g
o~
~ ~ Coc Co ~ C oc ,~ oc oc ~

O-- N N
-- N r~) ~ U ) 0 ~ ~
O OO O O O O O O C~ O

22

W O 95/12011 ~ ~ 6~ PCTrUS93/10243




C) D O O O
~A E ~ cs)
~) Z




C
3 ~r 't cn o
CJ) ~ C`' ) ~)
C ~ C~
~ Cr

S C ~ ~ ~ ~ ~o ~ C5, o ~ ~o

~o
~ cs) ~ 0 ~ r~ 0 ~ r~ o
I cn 0 0 0 r~ r~ r~ u~ ~D u~ r~
0 0 0 10 0 0 0 0 0 0 0
F
E ~ 1~ _ ~ _ 0 0 1~ _ 1` 0
m ~ Q
~ .
c


.~ 0 u~ 0 0
. -

o -- c`~cn _ -- -- --
o ~ o o o i~ o o o o o

WO 95tl2011 2~ SO PCT/US93/10243




U~ E c~l
Z

_~ o

E I o
~) _

Q~
3 v

o ~
'~
I_ .
~ Y ~
m ~ O r) - - ~ ~ -
~ --




~ u~ O
o~ ~ 0 0 a
111
~7
m ~ E


~o Q

,u ~
-- o O O O O o O O O o
C C ~ C C C C C C




24

~1 7S06~ . '

WO 95112011 PCT/US93/10243
Figures 1 through 6 are scanning electron
photomicrographs, at a magnification of 1,000, of phospnate
coated cold rolled steel panels. The phosphate coating was
applied to cold rolled steel panels which had been
activated with activating baths according to the
experimental design. It is clear from an examination of
the figures, and in particular, a comparison of Figures 5
and 1 with Figures 2 through 4 that the ultrasonic
treatment of the activating bath substantially improves the
phosphate coating which is formed on the metal substrate by
the process.
As shown in Tables 1 through 5 and Figures 1 through
6, as the activating bath ages, its effectiveness for
promoting the rapid formation of a high quality phosphate
coating having a small crystal size and high crystal number
decreases. Subjecting the activating bath to ultrasonic
vibrations increases the usefulness of the activating bath
for prQmoting a satisfactory phosphate conversion coating
during the phosphating step of the process.
ExPeriment 2
A series of experiments was carried out to determine
the effect of water hardness on the activating ability of
the activating baths. The series of experiments disclosed
that water hardness can have a deleterious effect on the
ability of the activating bath to promote the formation of
high quality, small crystal size phosphate coatings on
metal substrates. The characterizations of the activating
baths are shown in Table 6.


.
WO 9S/12011 PCT/US93110243
2~7~


TABI-E 6

BATH ACTIVATING CONCEN- Mg2+ Ca2+ SONICATED TOTAL
BATH TRATION PPM PPM Ti PPM
6 PARCOLFNE(~ Z 1.2 g/L 0 0 NO 17
7 PARCOT.FNE(~ Z 1.2 g/L 0 0 YES 16
8 PARCOLENE~ Z 1.2 gL 2 4 NO 18
9 PARCOLENE~ Z 1.2 glL 2 4 YES 16
PARCOLENE~ Z 1.2 g/L 6 8 NO 15
11 PARCOLENE~ Z 1.2 g/L 6 8 YES 14
CONTROL FIXODINE~9 Z8 1.5 g/L NO 16

PARCOLENE~ Z contains the same titanium compound-phosphate compound reaction product as
FIXODINE~ Z8 but does not contain condensed phosphate

The test panels were coated according to the following
procedure.

- ~ 21 7~5
WO95/12011 PCT/US93/10243

STEP NATERIAL ~Ir KA- TINE APPI.ICA-
TURE TION
II~ nO
Clean lPARCO(9 120F 120 spray
CLEANER seconds
1500C
2 oz per
gal.
Rinse water 100F 60 spray
seconds
Activation 2pARcoLENE/l9 90-100F 30 immersion
Z or seconds or spray
FIXODINE~
Z8
Conver- 3BONDERITE~I9 120-130F 120 immersion
sion 958 seconds
Coating according
to manuf.
recommend-
ations
Rinse cold 60 spray
water seconds
Rinse deionized 30 spray
water seconds
Oven Dry 225F 5 minutes
PARCO19 CLEANER 1500C Alkaline cleaner (Product of
Parker+Amchem)
2 PARCOLENEI9 Z Titanium compound--phosphate
compound reaction product with
added phosphates. Does not
contain condensed phosphate.
(Product of Parker+Amchem)
3 FIXODINE!9 Z8 Titanium compound-phosphate
compound reaction product
containing condensed phosphates.
(Product of Parker+Amchem)
BONDERITE~9 958 A commercial acidic zinc-nickel-
manganese phosphate conversion
coating composition (Product of
Parker+Amchem) used according to
manufacturers' recom~enc~Ations
Table 6 shows the parameters of the activating baths.
The content of titanium was adjusted to be approximately

217~5
W O 95/12011 PCTrUS93/10243
the same in all the baths. The amount of magnesium and
calcium in the aqueous activating bath is shown in Table 6.
In addition, application of ultrasonic energy to the
activating bath is also shown in Table 6. The ultrasonic
energy was applied to the baths in the absence of the metal
substrate. Table 7 sets forth the coating weight, the
crystal size and the coverage of the phosphate coating on
the activated metal substrate provided by the process. The
Coating Ratings 1 through 6 utilized in Table 7 and other
tables in the specification are as follows: Ratings of 1-3
were given to panels which showed a continuous coating at
1,000 times magnification. A rating of 1 indicates small
crystal size morphology, a rating of 3 indicates poor
(large) crystal size morphology. Ratings of 4-6 were given
if any discontinuinties were observed in the coating at
1,000 times magnification. A rating of 4 indicates a
coating with low coating weight and small crystal size, but
with surface areas void of phosphate coating. A rating 6
indicates poor surface coverage and large crystal size.

21 7~o~
WO95/12011 PCT~S93/10243
TABLE 7
BATH 6 DAY 1 DAY 2 DAY 5 DAY 6 DAY 13
COATING 279 275 421 457
WEIGHT
CRYSTAL 2-10 2-8 5-15 5-21
SIZE
COVERAGE
RATING
FILTERABLE 10 11 2 0
Ti
BATH 7
COATING 231 221 212 197
WEIGHT
CRYSTAL 2-5 1-5 1-3 2-4
SIZE
COVERAGE
RATING
FILTERABLE 10 12 12 12
Ti
BATH 8
COATING 557 318 362 331
WEIGHT
CRYSTAL 5-40 20-60 20-60 9-65
SIZE
COVERAGE 4 6 6 6
RATING
FILTERABLE 0 0 0 o
Ti
BATH 9
COATING 566 464 438 443
WEIGHT
CRYSTAL 5-40 3-40 5-30 2-25
SIZE
COVERAGE 4 5 5 4
RATING
FILTERABLE 0 0 0 0
Ti
BATH 10
COATING 564 343 391 487 246
WEIGHT

29

WO95112011 ~ ~ 7 ~ PCT~S93/10243

TABLE 7 ~co~t;n~

BATH 10 DAY 1 DAY 2 DAY 5 DAY 6 DAY 13
CRYSTAL 6-20 20-55 20-55 9-63 7-49
SIZE
COVERAGE 3 6 6 6 5
RATING
FILTERABLE O 5 5
Ti
BATH ll
COATING 593 488 451 487 405
WEIGHT
CRYSTAL 5-40 6-40 7-35 7-29 4-25
SIZE
COVERAGE 3 5 5 5 3
RATING
FILTERABLE 5 0 0 0
Ti
CONTROL
COATING 304 212 218 177 195
WEIGHT
CRYSTAL 2-5 1-7 1-5 1-3 1-3
SIZE
COVERAGE . 1
RATING
Coating weight - milligrams per square foot
Crystal size - microns





= ~

WO95/12011 ~ PCT~S93/10243
A study of the results of Baths 6 and 7, on days 1 and
2, as reported in Table 7 shows that a good coating with
small crystal size and optimal coating weight was obtained
with a fresh activating bath prepared from PARCOLENE~ Z
with deionized water.
Bath 7 is a sonicated bath with the same composition as
Bath 6. As shown in Table 7, use of Bath 6 as an
activating bath in the process provided a good coating when
fresh, but did not provide suitable coatings on days 5 and
6. The crystal size substantially increased with a
concurrent increase in coating weight. The coating weight,
crystal size and coverage of the phosphate coating when
prepared by the process which utilizes the sonicated
activating Bath 7 was equivalent, even after aging, to that
provided by the control, which was a fresh activating bath
prepared every day and applied by spraying onto the cold
rolled steel panel.
Table 7 also shows that the magnesium and calcium
hardness in the water used to prepare the activating bath
affected the ability of the bath to promote an optimal
coating on the cold rolled steel panel. The loss of
coating quality can be seen by the results reported as
Baths 8, 9, 10 and 11. The ultrasonically treated Baths 9
and 11 promoted slightly better phosphate coatings than
Baths 8 and 10 which were not ultrasonically treated.
After one day aging the coatings were not satisfactory.
Scanning electron photomicrographs at 1,000 times
magnification of the phosphate coatings produced by use of

WO9~/12011 ~ ¦~ S 6 ~ PCT~S93/10243
activating Baths 6 through 11 and the Control Bath are
shown in Figures 7 through 13 respectively. Figure 14 is
a scanning electron photomicrograph at 1,000 magnification
of a phosphate coating produced on a non-activated cold
rolled steel surface.
A study of Figures 7 through 14 clearly illustrates the
effect of application of ultrasonic energy to the
activating bath on the phosphate coating of the metal
substrate produced by the process.
Table 7 also shows the characteristics of phosphate
coatings produced by the process using activating Baths 10
and 11 after aging for 13 days; using the same procedure as
for the previous examples (Bath 11, sonicated in the
absence of the metal substrate). The phosphate coatings
produced by the process using the activating Baths 10 and
11 aged for 13 days were not satisfactory.
An additional experiment was carried out using Bath 11
aged 13 days, but applying ultrasonic energy to the
activating bath while it was contacting the metal panel
being activated. Unexpectedly, the phosphated conversion
coating produced on the activated panel was of excellent
quality. A similar experiment was carried out using Bath
11 after aging for 150 days. Cold rolled steel,
electrogalvanized steel and aluminum panels were processed.
When ultrasonic energy was applied to Bath 11 after 150
days aging, when the bath was in contact with the metal
panels, the phosphate coatings formed on the activated
panels were excellent on all substrates. The phosphate

WO95/12011 PCT~S93/10243
coating was comparable to the phosphate obtained by the
process by using the freshly prepared control activating
bath.
In view of the excellent phosphate coatings which are
obtained when the ultrasonic vibrations are applied to the
aqueous activating bath in contact with the metal substrate
to be activated, additional experiments were carried out to
determine the effectiveness of the treatment.
It is not completely clear whether the improvement in
the phosphate coating obtained by the process, when
ultrasonic energy is applied to the activating bath in the
presence of the metal substrate, is due solely to an
optimization of the size of the particles of the activating
bath during sonication, or whether an element of the
improvement is due to an interaction between the ultrasonic
vibrations and the metal substrate.
ExPeriment 3
In many applications where a phosphate coating is
desired, the parts to be coated are irregularly shaped with
recessed or boxed areas. These recessed areas are more
difficult to coat with a high quality phosphate coating.
A series of experiments were carried out to determine the
effect of ultrasonic energy application during the
phosphate coating process, when the surface of the
substrate is not directly exposed to the ultrasonic
vibrations. Four inch by six inch metal panels were
inserted into a plastic frame to form a box in which the
internal surfaces of the box were not directly exposed to

2~7S06~
W O 95112011 PCT~US93/10243
the ultrasonic vibrations. The two panels inserted in the
plastic frame were separated by 5/8th of an inch between
the panels. The top and bottom of the box contained holes
which allowed the activating bath to fill the box while
hindering the circulation of the activating solution in the
box. The coatings formed on the panels were rated
according to the method set forth (1-6).
Both the panel surfaces which formed the outside of the
box and the panel surfaces which formed the inside of the
box were ~x~;ned for phosphate coating characteristics and
rated. The 150 day old PARCOLENE~ Z Bath 11 was included
in the study since 150 day old Bath 11, when ultrasonic
energy was applied during activation in the contact zone,
provided a metal substrate with an excellent phosphate
coating. In addition, activating baths with reduced
amounts of titanium were prepared and tested as the
activating bath in the process.
The compositions of the baths are set forth in Table 8.

TABLE 8

2 0 BATH CONDITIONER CONCEN- Mg2~ Ca2~ SONI- TOTAL
TRA- PPM PPM CATED Ti
TION PPM
11 PARCOLENE~ Z 1.2 gL 6 8 YES 14
12 PARCOLENE~g) Z 0.37 gL 6 8 YES 5
13 PARCOLENE69 Z 0.37 gL 11 22 YES 5
CONTROL E~IXODlNE~g) Z8 1.5 gL 11 22 NO 16

21 7~P65
WO95112011 PCT~S93/10243
Figures 15 and 16 are scanning electron
photomicrographs, at a 1,O00 times magnification, of the
phosphated side of the panel which was the the outer
surface of the box and the side of the phosphated panel
S which formed the inner surface of the box which were
treated by a~ueous activiting Bath 11. The various
treatments are noted as a, b, c, d, and e in Figure 15 and
Figure 16. Figures 15 and 16 clearly show the improvement
in the phosphate coating on both the inner and outer
surfaces when ultrasonic vibrations are applied to the
activating bath when it is in contact with the metal
substrate in the process of the invention. Table 9
presents the crystal size and coverage of the phosphate
coating when applied to cold rolled steel, galvanized steel
and aluminum alloy 6061 by the process of the invention
when ultrasonic energy is applied to the activating baths,
as set forth in Table 8, when the baths are in contact with
the box formed from the metal panels.





WO 95/12011 ~ ~7 5 ~ PCT/US93/10243
TABLE 9
SONICATE CRS EG 6061
outside ¦ ioside outside ¦ ioside outside ¦ ioside
BATH 11
CRYSTAL NO 5-12 10-40 4-12 20-30
SIZE
COVERAGE NO 2 3 4 5
RATING
CRYSTAL YES 3 - 15 3 - 8 3 - 7 3 - 6 5 -20 5 - 12
SIZE
COVERAGE YES 2 4 1 1 2 4
1 0 RATING
BATH 12
CRYSTAL NO 4- 15 3-12
SIZE
COVERAGE NO 2 4
RATING
CRYSTAL YES 2 - 7 3 - 7 3 - 7 3 - 7 4 - 10 3 - 6
SIZE
COVERAGE YES I 4 1 2 1 2
RATING
2 0 BATH 13
CRYSTAL NO 5 - 20 4 - 15
SIZE
COVERAGE NO 3 5
RATING
CRYSTAL YES 2 -12 4- 6 2 - 8 2 - 8 3 - 10 4 - 10
SIZE
COVERAGE YES 2 4 1 1 1 2
RATING
CONTROL
CRYSTAL NO 2 -6 1- 3 2 - 8 2 - 5 3 - 8 2 - 7
SIZE
COVERAGE
RATING
Crystal size - loicroos

WO95112011 ~ 6~ PCT~$93/10243
The phosphate coatings formed by the process are
improved. The surfaces of the metal panels which faced the
interior of the box also showed improvement in the
phosphate conversion coating. In all cases in which
ultrasonics were applied, coating coverage and crystal size
on an electrogalvanized steel on both the inner and outer
panel surfaces was excellent. The effect of the 150 day
old activating Bath ll without application of ultrasonic
vibrations (stirred) is shown for comparison. The inner
and outer panel surfaces of aluminum phosphated after
treatment with activating Bath ll showed a significant
improvement due to application of ultrasonic vibration when
in contact with the metal substrate. The inner surface is
almost completely covered with a phosphate coating with
application of ultrasonic energy while it is almost
completely bare when treated with the activating bath
without application of ultrasonic energy. The outer
surfaces of the CRS were completely phosphate coated when
activated by the 150 day old Bath ll with application of
ultrasonic energy. The inner surfaces of the CRS showed
incomplete coating but the coating is significantly better
than the coating formed when processed with Bath lO after
only l day aging (Figure ll(b)).
Baths 12 and 13 which contained a reduced amount of the
activating composition (low titanium level) also showed
improved phosphated coating when ultrasonic energy was
applied to the activating bath when the bath was in contact
with the metal substrates.


WO95112011 ` ` PCT~$93/10243
Figures 17 and 18 are scanning electron
photomicrographs at l,OOo magnification of the outer
surface and the inner surface of the metal panels prepared
by the process of the invention utilizing Bath 12 with the
reduced content of activating composition. A comparison of
Figure 17 and 18 (a) and (b) clearly shows the improvement
when ultrasonic energy is applied to the activating bath
when the bath is in contact with the metal substrate. The
inner and outer surfaces of the panels show improved
phosphate coating. Figures 17 and 18 (c) and (d) show the
effect of application of ultrasonic energy to the
activiting bath on the coating of electrogalvanized steel
and aluminum alloy 6061.
Figures l9 and 20 are sc~n~;ng electron photomicrographs
at l,000 magnification of the outer and inner surfaces of
metal panels treated with activating Bath 13. It is clear
from a comparison of Figure l9 and Figure 20 (a) and (b)
that application of ultrasonic energy to the bath while the
metal substrate is immersed in the bath substantially
improves the crystal size and coverage obtained in the
phosphate coating formed by the process of the invention.
Figures 21 and 22 (a), (b) and (c) are scanning electron
photomicrographs at l,000 magnification of the outer and
the inner surfaces of panels formed from cold rolled steel,
galvanized steel and aluminum alloy 6061 using a freshly
prepared control bath for activation.
Figures 15, 16, 17, 18, l9 and 20 illustrate that the
application of ultrasonic energy to the aqueous activating


~17sO~5,

W O 9S/12011 PCT~US93/10243
bath in the presence of the metal substrate to be activated
comprises a significant improvement in the activation of
both the exposed and recessed surfaces. The figures also
indicate that the concentration of the activating
composition in the activating bath can be reduced if
ultrasonic energy is applied to the activating bath while
the metal substrate is in contact with the activating bath.
Experiment 4
Tests were run to determine the effect of application of
ultrasonic energy to FIXODINE~ Z8 aqueous activating baths.
Treatment Baths 14, 15, 16, 17, 18 and 19 were prepared.
Baths 14, 15, 16, and 17 utilized various concentrations of
FIXODINE~ Z8 and were prepared utilizing tap water. Baths
18 and 19 were prepared with PARCOLENE~ Z at a low
concentration utilizing tap water.
The compositions of the baths and the treatments are set
out in Table 10.


WO95/12011 ~ l 7 S ~ 6 3 PCT~S93/10243

TABLE lO

BATH CONDITIONER CONCEN- WATER SONI- TOTAL
TRATION CATED Ti
PPM
14 FIXODINE~ l.5 g/L Tap NO 16
Z8
FIXODINE~ l.5 g/L Tap YES 17
Z8
16 FIXODINE~ 0.5 g/L Tap NO 5
Z8
17 FIXODINE~ 0.5 g/L Tap YES 4
Z8
18 PARCOLENE~ 0.4 g/L Tap NO 6
l9 PARCOLENE~ 0.4 g/L Tap YES 6
z




CONTROL FIXODINE~ l.5 g/L Tap NO 16
Z8


All cold rolled steel panels treated with the fresh
FIXODINE~ Baths 14 through 17 and the control bath produced
good phosphate coatings with or without application of
ultrasonic power to the activating baths. The PARCOLENE~
Z activating bath did not provide a good coating when the
fresh solution was stirred. When ultrasonic energy was
applied to Bath l9 while in contact with the metal
substrate to activate the substrate, the phosphate coating
produced by the process was satisfactory. The
charac_eristics of the phosphate coatings are shown in
Table ll.





WO95/12011 So 6~ PCT~S93/10243
TABLE 11


BATH BATH BATH BATH BATH CONTROL
14 15 16 17 18
SONICATE NO YES NO YES NO NO
COATING 219 195 312 276 369 207
WEIGHT
CRYSTAL 1-4 1-5 3-12 2-10 20-40 1-5
SIZE
COVERAGE 1 1 1 1 6
RATING
Coating we_ght - milligrams/Ft.o
Crystal size - microns


The activating Baths 14-19 were then aged for 90 days
and used to treat cold rolled steel, electrogalvanized
steel, and aluminum alloy 6061. In all cases when
ultrasonic vibration energy was applied to the activating
baths (Bath 14-19) while the baths were in contact with the
metal substrate, the phosphated coatings were good. The
results of the tests are shown in Table 12.


TABLE 12
Sonica- Filter- CRS EG 6061
tion able Ti
BATH 14 none 9
Coating Weight 354 411 315
Crystal Size 4 - 10 3 - 11 2 -13
Coverage Rating 2 1 4
BATH 15 yes 4
Coating Weight on 222 312 282
off 246 321 279
on 2-4 2-7 2-12
Crystal Size off 2 - 4 2 - 6 2 - 14
Coverage Rating on
off
BATH 16 none 0

.
2~75~5 - --
WO 95/12011 PCT/US93110243


TABLE 12 (~
Sonica- Filter- CRS EG 6061
cation able TI
Coating weight 519 531 252
Crystal size 15 - 40 3 - 8 10 - 25
Coverage Rating 6 1 6
BATH 17 yes 0
Coating Weight on 243 378 285
off 345 423 309
Crystal Size on 1 - 4 3 - 8 2 - 13
off 3 - 10 3 - 12 4 - 20
Coverage Rating on 1 1 4
off 2 2 4
BATH 18 none 0
Coating Weight 543 519 294
Crystal Size 20 - 70 7 - 20 10 - 25
Coverage Rating 6 3 6
BATH 19 yes 0
Coating Weight on 381 411 345
off 588 456 294
Crystal Size on 3 - 8 2 - 8 3 - 20
off 10 - 50 3 - 10 15 - 30
Coverage Rating on 2 1 5
off 6 1 6
Control none
Coating Weight 222 297 255
Crystal Size 2 - 4 2 - 7 2 - 14
2 0 Coverage Rating
Coating weight- milligr~mc.~t'
Crystal size - microns
Table 12 presents the characteristics of the phosphate
coatings formed on the metal substrates according to the

25 process of the invention utilizing the activating Baths 14,
15, 16, 17, 18 and 19. The results shown in Table 12 were
obtained utilizing the baths which had been aged for 90



42

So~S
WO95/12011 PCT~S93/10243
days. It is clear that the 90 day old FIXODINE~ Z8 bath
(Bath 14) does not provide an acceptable phosphate coating
on the surface of cold rolled steel, electrogalvanized
steel or aluminum alloy 6061. However, application of
ultrasonic energy to the aged bath (Bath 15), when in
contact with the metal substrate produces excellent
phosphate coatings on cold rolled steel, electrogalvanized
steel and aluminum treated by the process of the invention.




43

2 ~ 6 ~-
WO95/12011 PCT~S93/10243
Figures 23 (a), (b) and (c) are scanning electron
photomicrographs at 1,000 magnification of panels
phosphated utilizing the process of the invention and
utilizing Bath 14 as the activating bath. Figure 24 is a
scAnn;ng electron photomi~LGy~aph at 1,000 magnification of
the crystal structure of the phosphate coating formed by
the process of the invention on various metal substrates
when ultrasonic energy is applied to Bath 15 while Bath 15
is in contact with the metal substrate. Figure 24 (a), (b)
and (c) shows that cold rolled steel, electrogalvanized
steel and aluminum alloy 6061 are provided with excellent
phosphate coatings by the process of the invention.
Figure 25 is a sc~nni ng electron photomicrograph at
1,000 magnification of the phosphate coating provided on
panels which were contacted with activating bath 15 five
minutes after application of ultrasonic energy to the
activating bath was discontinued. Figure 25 shows that the
phosphate coating is acceptable even when the metal
substrate is contacted with activating Bath 15 five minutes
after the application of ultrasonic energy to the bath has
been stopped.
Baths 14 and 15 produced coatings identical to the
control bath after aging for one day. After aging for 90
days, the difference in the phosphate coating produced by
the process due to application of ultrasonic energy to the
activating bath can be clearly seen. Figures 23 through 25
show the effects of application of ultrasonic energy to the
activating bath on the phosphate coating produced by the


44

21~ ~so~
WO95/12011 PCT~S93/10243
process of the invention. The coatings formed after the
ultrasonic energy application had been discontinued 5
minutes before the panels were entered in the solution were
satisfactory (see Figure 25).
Baths 16 and 17 contained a concentration of the
activating composition only 1/3 of the concentration in
Baths 11 and 12. Baths 16 and 17 showed a reduced
activating ability after aging only one day. Bath 16, with
stirring only, and contacted with the metal panel, produced
a coating with larger crystal size and higher coating
weights than Bath 14.
Figures 26, 27 and 28 show the coatings formed after
aging the baths for 90 days. Panels treated with
activating Bath 16 produced poor coatings when phosphated;
however Bath 17 produced excellent phosphate coatings on
cold rolled steel, electrogalvanized steel and aluminum
alloy 6061 when ultrasonic energy was applied to the Bath
17 while activating Bath 17 was in contact with the metal
substrate or within 5 minutes of stopping the application
of the ultrasonic energy to the bath.
Phosphate coatings produced on cold rolled steel,
aluminum alloy 6061 and electrogalvanized steel by the
process using activating Bath 17 with application of
ultrasonic energy to the activating bath when in contact
with the metal panel were identical with phosphate coatings
prepared by the process utilizing the control bath (Figure
~ 32). The aluminum panel appeared to have several small
voids in the coating where the metal surface could be seen

WO95112011 2 ~ ~ ~ Q 6 ~ PCT~S93110243
in the sc~nn; ng electron photomicrograph. After the
application of ultrasonic energy to activating Bath 17 had
been discontinued for 5 minutes, a slight loss of
activating ability can be noted. The phosphated coatings
produced by the process using activating Bath 17 with
application of ultrasonic energy to the bath when in
contact with the metal substrate were comparable to
coatings produced from the fresh control bath containing 3
times the concentration of the FIXODINE~ Z8 activating
composition.
The PARCOLENE~ Z bath which does not contain condensed
phosphates, (Bath 18), produces poor coatings when the
activating bath is prepared with tap water containing
calcium and magnesium ion. After aging for only one day,
the bath produced coatings similar to panels processed
without contact with an aqueous activating bath.
Activating Bath l9, to which ultrasonic energy was applied
while in contact with the metal substrate, when phosphated,
provided a coating comparable to the FIXODINE~ Z8 Bath 14
on cold rolled steel and electrogalvanized steel. The
coating produced by using activating Bath l9 on aluminum in
the process was slightly more porous than that produced by
using Bath 14. After the ultrasonic energy application had
been discontinued for 5 minutes, the coatings on cold
rolled steel and aluminum were similar to coatings produced
by activating Bath 18, while the coating on electro-
galvanized steel was excellent. Figures 23 through 31 and
Figure 32 (control bath) illustrate the improved coatings


46

7~S~0~6s
WO~5112011 PCT~S93/10243
provided by the process of the invention.
The experiments and the figures clearly illustrate that
application of ultrasonic energy to an aqueous activating
bath in a phosphate coating process improves the coating
weight and crystal morphology of the phosphate coating. The
application of ultrasonic energy to the activating bath
extends the useful life of the bath. Extension of the
useful life of the activating bath provides a process in
which the activating bath is discarded at more extended
intervals and therefore reduces the effect of the process
on the environment.
The examples and the figures clearly show that phosphate
coatings can be improved by the process of the present
invention if ultrasonic energy is applied to the aqueous
activating composition (activating bath) when not in
contact with a metal substrate or when the aqueous
activating bath is in contact with the metal substrate
which is subsequently to be coated with a phosphate
conversion coating.
The process of the present invention with the
improvement of applying ultrasonic energy to the aqueous
activating bath in the process, as shown by the examples
and figures, improves the phosphate coating produced by the
process and extends the life of the aqueous activating
composition. Aged baths retain their activating ability
over extended periods. In addition, the activating bath
can contain lower concentrations of the activating
composition and still be useful in activating the metal

47

WO95/12011 PCT~S93/10243
substrate in a phosphate coating processes. The lower
concentrations of the activating composition, which can be
used in the activating bath along with the longer useful
life of the activating bath, provides a less expensive and
more environmentally friendly process.




48

Representative Drawing

Sorry, the representative drawing for patent document number 2175065 was not found.

Administrative Status

For a clearer understanding of the status of the application/patent presented on this page, the site Disclaimer , as well as the definitions for Patent , Administrative Status , Maintenance Fee  and Payment History  should be consulted.

Administrative Status

Title Date
Forecasted Issue Date Unavailable
(86) PCT Filing Date 1993-10-26
(87) PCT Publication Date 1995-05-04
(85) National Entry 1996-04-25
Dead Application 2001-10-26

Abandonment History

Abandonment Date Reason Reinstatement Date
2000-10-26 FAILURE TO REQUEST EXAMINATION
2000-10-26 FAILURE TO PAY APPLICATION MAINTENANCE FEE

Payment History

Fee Type Anniversary Year Due Date Amount Paid Paid Date
Application Fee $0.00 1996-04-25
Maintenance Fee - Application - New Act 2 1995-10-26 $100.00 1996-04-25
Registration of a document - section 124 $0.00 1996-07-25
Maintenance Fee - Application - New Act 3 1996-10-28 $100.00 1996-09-18
Maintenance Fee - Application - New Act 4 1997-10-27 $100.00 1997-10-10
Maintenance Fee - Application - New Act 5 1998-10-26 $150.00 1998-10-07
Maintenance Fee - Application - New Act 6 1999-10-26 $150.00 1999-10-01
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
HENKEL CORPORATION
Past Owners on Record
DUNN, ROBIN M.
GILES, TERRENCE R.
KRAMER, LINDA S.
MILLER, ROBERT W.
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
Documents

To view selected files, please enter reCAPTCHA code :



To view images, click a link in the Document Description column. To download the documents, select one or more checkboxes in the first column and then click the "Download Selected in PDF format (Zip Archive)" or the "Download Selected as Single PDF" button.

List of published and non-published patent-specific documents on the CPD .

If you have any difficulty accessing content, you can call the Client Service Centre at 1-866-997-1936 or send them an e-mail at CIPO Client Service Centre.


Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Description 1995-05-04 48 1,618
Drawings 1995-05-04 19 4,037
Cover Page 1996-08-01 1 19
Abstract 1995-05-04 1 40
Claims 1995-05-04 3 79
International Preliminary Examination Report 1996-04-25 6 193
Fees 1996-09-18 1 62
Fees 1996-04-25 1 50