U.S. patent number 3,798,050 [Application Number 05/147,790] was granted by the patent office on 1974-03-19 for catalytic sensitization of substrates for metallization.
This patent grant is currently assigned to PPG Industries, Inc.. Invention is credited to Roy G. Crissman, Helmut Franz.
United States Patent |
3,798,050 |
Franz , et al. |
March 19, 1974 |
CATALYTIC SENSITIZATION OF SUBSTRATES FOR METALLIZATION
Abstract
Metal films of improved uniformity are formed on substrates
having their surfaces sensitized by the deposition of palladium on
tin by buffering the palladium salt solution in contact with the
glass at a pH from 6 to 9. Buffering is preferably accomplished by
contacting the substrate with an aqueous buffering solution and an
acidic palladium salt solution.
Inventors: |
Franz; Helmut (Oakmont, PA),
Crissman; Roy G. (Lower Burrell, PA) |
Assignee: |
PPG Industries, Inc.
(Pittsburgh, PA)
|
Family
ID: |
22522908 |
Appl.
No.: |
05/147,790 |
Filed: |
May 28, 1971 |
Current U.S.
Class: |
427/304;
106/1.11; 106/1.24; 106/1.27; 427/426 |
Current CPC
Class: |
C23C
18/30 (20130101) |
Current International
Class: |
C23C
18/20 (20060101); C23C 18/30 (20060101); B44d
001/08 (); C03c 017/10 () |
Field of
Search: |
;117/47A,16R,13E,54
;106/1 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Martin; William D.
Assistant Examiner: Trenor; William R.
Attorney, Agent or Firm: Pollock; E. Kears
Claims
We claim:
1. In the electroless deposition of metal on a non-conductive
substrate wherein a substrate is contacted successively with a
tin-salt solution, then with a palladium salt solution to activate
it, making its surface catalytic, and then is contacted with a
mixture comprising a solution of metal salt of the metal to be
deposited and a solution of a reducing agent for reducing such
metal, the improvement comprising buffering the palladium salt
solution in contact with the substrate at a pH from about 7 to
about 9.
2. In the method of coating a non-conductive substrate surface with
a metal-containing deposit comprising the steps of:
first, contacting the substrate with a solution of tin salt and
then rinsing the same;
second, contacting the substrate with a solution of palladium salt
and thereafter contacting the substrate with a solution containing
the desired metal to be deposited and reducing agent for such
metal, whereby a non-uniform metal-containing deposit is formed,
the improvement comprising the steps of:
rinsing the tin salt contacted substrate with a rinse of water
containing an alkaline buffering compound in an effective amount to
provide a pH of about 7 to about 9 in the mixture of palladium salt
solution and remaining rinse in contact with the substrate whereby
a uniform metal-containing deposit results.
3. The method of claim 2 wherein the contacting solutions are
sprayed against the substrate.
4. The method of claim 2 wherein the alkaline buffer is selected
from the group consisting of ammonium hydroxide, ammonium borate
and water-soluble ammonium, alkali metal and alkaline earth metal
carbonates, bicarbonates and phosphates and mixtures thereof.
5. The method of claim 4 wherein the rinse contains as an esential
ingredient from about 0.01 to about 7 percent by weight of the
aqueous rinse, sodium bicarbonate.
Description
CROSS-REFERENCES TO RELATED APPLICATIONS
This invention is related to electroless metal deposition and to
the processes disclosed in co-pending applications here listed:
"Transparent Metal-Boron Coated Glass Articles", Ser. No. 57,575;
"Wet Chemical Method of Producing Transparent Metal Films", Ser.
No. 57,451; "Solution for Depositing Transparent Metal Films", Ser.
No. 57,754; and "Wet Chemical Method of Producing Transparent Metal
Films", Ser. No. 57,527, all filed July 23, 1970. Application Ser.
No. 57,575 is now abandoned; application Ser. No. 57,754 is now
U.S. Pat. No. 3,674,517 issued July 4, 1972; application Ser. No.
57,451 is now U.S. Pat. No. 3,723,158 issued Mar. 27, 1972, and
application Ser. No. 57,527 is now U.S. Pat. No. 3,723,155 issued
Mar. 27, 1972.
BACKGROUND OF THE INVENTION
This invention relates to chemical plating referred to in the art
as electroless plating, and more particularly, it relates to a new
method of sensitizing a substrate surface to produce a catalytic
surface receptive to the deposition of metal-boron containing
film.
In the art of metallizing substrates, particularly non-conductive
materials such as non-metals, for example glass and plastics, it
has been found desirable to prepare the substrate surface to make
it more receptive to metal deposition.
Bergstrom in U.S. Pat. No. 2,702,253 teaches an effective method of
sensitizing a substrate surface and thereafter metallizing it
utilizing electroless plating solution. In the method taught by
Bergstrom the substrate is first treated with a tin salt (a step
now referred to in the art as "sensitization"), then treated with a
palladium salt (a step now referred to as "supersensitization") and
finally treated with the salt of the metal desired to be deposited
in a suitable electroless plating bath.
While the method of Bergstrom has been widely accepted by workers
in the art, the method has not been free of problems. When
depositing relatively thick films on substrates by immersing the
substrates in a series of baths according to the teachings of
Bergstrom, it has been possible to produce satisfactory films.
However, attempts using the method of Bergstrom to deposit
relatively thin transparent films, particularly by economical and
rapid spray techniques suited for the production of transparent
metallized articles in commercial quantities, have resulted in
imperfect films. There has been a tendency of the films to be
streaked, to have many fine pinholes through the film, to have
bands of thicker and thinner film as visually observed and to have
a thinner film along the leading edge of a moving substrate passing
under sprays for contacting the substrate with chemical filming
solutions.
SUMMARY OF THE INVENTION
It has been discovered that by buffering a palladium salt
super-sensitizing solution in contact with a substrate to be
sensitized for chemical metal film deposition to a pH between about
4 and about 9 that uniform metal films may be obtained when thin,
transparent metal films are subsequently deposited on the
sensitized surface from electroless plating baths. The presence of
a colloidal suspension of palladium hydroxide in contact with the
substrate being treated enhances the uniformity of subsequently
deposited films. A pH within the range of from 6 to 9 for the
palladium solution in contact with the substrate provides assurance
of this desired condition for palladium treatment.
A suitable process of metallizing a plurality of substrates, such
as flat glass articles, is to convey the articles in series past
several spray, drip or flood contacting stations. The process
includes: rinsing the glass, contacting the glass with a tin salt
solution, rinsing away the residue of tin salt solution, contacting
the glass with a palladium salt solution, rinsing away the residue
of the palladium salt solution and contacting the glass with one or
more sets of metal salt solutions and boron-containing reducing
solutions followed by rinsing, drying and inspection of the
metallized glass. By including a suitable buffer, such as sodium
bicarbonate, in a rinse between the tin salt solution and the
palladium salt solution, residue buffer is retained on the glass to
buffer the pH of the contacting palladium salt solution to a pH of
from 4 to 9 and preferably from about 7 to about 9.
Other buffering agents may be successfully used rather than sodium
bicarbonate. Typical, commercially available buffers which may be
used include water soluble alkali metal carbonates, alkali metal
bicarbonates, alkali metal phosphates, ammonium hydroxide, ammonium
carbonate, ammonium bicarbonate, ammonium phosphate and ammonium
borate. The dibasic phosphates are preferred as contrasted with
other phosphates. Alkali metal salts of organic acids may be
effectively employed as well; sodium acetate, for example, is
effective to control uniform supersensitization. Also, mixtures of
buffers, such as phosphates, and alkali metal hydroxides are
effective buffers in this invention.
Although other tin and palladium salts may be used, the halides are
preferred. Stannous chloride (SnCl.sub.2) is the preferred tin salt
for initial substrate surface sensitization. Palladious chloride
(PdCl.sub.2) is the preferred palladium salt for supersensitization
of the substrate surface, although palladic chloride (PdCl.sub.4)
may be suitably employed.
It is preferred that water used for preparing the aqueous
sensitizing and chemical filming solutions and the water for
rinsing the substrate be softened, deionized or otherwise purified
since in the commercial production of metallized articles film
quality may be detrimentally affected by the uncontrolled chemical
composition of process water entering a plant from public water
supplies. Throughout the present discussion, use of the words
"water", "demineralized water" or the like shall mean water
substantially free of organic and inorganic contaminants, for
example an indicated resistance of more than one megaohm/cm at
25.degree.C. would indicate pure water. Throughout words, such as
"tap water", shall mean water of unknown quality as typically
obtainable from public supplies.
It is preferred that the palladium chloride contacting solution has
a pH from about 1 to 4, preferably from about 2 to 3.9, and most
preferably from about 3.0 to 3.6.
The buffer may be included in the intermediate rinse between tin
sensitization and palladium supersensitization, or the substrate
may be rinsed with water and then contacted, as by a spray or drip,
with an aqueous buffer solution immediately prior to the palladium
salt solution contacting the substrate. In the latter embodiment
buffer solutions of 0.1 to 70.0, preferably 0.5 to 5 and most
preferably 0.5 to 1.5 grams of buffer per liter of water, when
dripped on a horizontally disposed glass sheet being conveyed under
spray contacting stations, suitably buffer the immediately
following palladium salt solution in contact with the glass.
The present discovery provides a method by which more uniform,
mottle-free, metal-containing films may be deposited on a catalyzed
non-metallic substrate than has been possible before. Bands of
non-uniform film thickness, streaks and pinholes through the
deposited metal-containing films are substantially reduced and
commonly are absent from films produced by the method of this
invention. Thinning out of the film toward the leading edge of
substrates metallized while moving past contacting stations is
substantially reduced and generally eliminated by this method. It
has also been discovered that the adhesion of the deposited film to
the glass or other substrate is improved by applying film by this
method. This results in films of improved durability when the films
are applied according to this invention.
Any metal suited for chemical filming on a catalytic sensitized
substrate may be deposited according to the method of this
invention. Chromium, manganese and the metals of Groups VIII and IB
of the Periodic Table may be applied to substrates according to
this invention. Of particular interest are the lightest elements of
Group VIII, iron, cobalt and nickel. The method of this invention
is particularly suited for the application of iron, cobalt or
nickel to substrates which require sensitization, such as
glass.
The method has particular utility for producing thin, transparent
metal-containing films on transparent substrates, for example glass
or plastics, such as polycarbonate, acrylics and the like. The
desirability of uniform films is particularly critical for
transparent viewing closures. Visible transmittance of flat, clear,
lime-soda-silica glass metallized using the present method may be
as low as 8 percent and yet be uniform. Transparency is determined
as the percent of light having a wave length from 380 to 760
nanometers which is transmitted through the coated article relative
to the transmittance through air as measured by a Beckman Model DK
2A Spectrometer.
The mechanism by which the buffering of palladium salt
sensitization solutions promotes film uniformity is not fully
understood. In fact, the mechanism by which palladium catalytically
sensitizes substrates is not understood with universal agreement
among those skilled in the art. This lack of agreement and
understanding persists despite the many years of using palladium
sensitization.
Despite a lack of full understanding as to why the present
invention is effective, the following observations may be made.
Palladium chloride solubility in water is influenced by pH. High
concentrations of palladium chloride in a sensitizing solution
improve sensitization of the surface, presumably by increasing the
density of catalytic sites at the sensitized substrate surface. The
preferred pH range of a suitably concentrated palladium chloride
solution is from 1 to 4 with higher concentrations attainable at
lower pH. At a pH of 3.9 some incipient Pd(OH).sub.2 precipitation
is noted. A colloidal suspension apparently is present upon
adjusting pH from 6 to 9 as indicated by a yellow coloration
typical of colloidal suspensions; at pH 6 to 7 the characteristics
of colloidal suspension are apparent; at pH 7 to 9 a colloidal
suspension remains with the apparent particle size of the
precipitate smaller at pH 8 than at pH 7.8. It appears that
precipitation and formation of a relatively stable colloidal
suspension of palladium hydroxide in the supersensitization
solution when contacting the substrate is at least partially
responsible for the beneficial results obtained.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A plurality of commercial soda-lime-silica glass plates (for
example, 28 inch .times. 66 inch .times. 0.25 inch) are metallized
or coated with a nickel-boron film using the apparatus illustrated
schematically in FIGS. 1 and 2. The apparatus comprises five basic
sections, designated as the glass loading and cleaning section,
100, the glass sensitizing or activating section 200, the
metallizing or film deposition section, 300, the glass drying
section, 400, and the inspection and unloading section, 500.
The apparatus comprises in section 100 a plurality of belts 1 for
carrying and advancing glass plates 3 through the section. In
sections 200-500, the apparatus comprises a plurality of rollers 2
for carrying and advancing the plates through the sections. The
belts and rollers are rotated by conventional means (not shown) to
advance the plates at about 3 to 6 feet per minute.
In operation, plates 3 are loaded onto the belts 1 and advanced
through section 100. In this section, four rotating blocks 101
comprised of brushes gently abrade the upper surface of the plates
3 with a mixture of amorphous silica and water or cerium oxide and
water to loosen and remove any dirt. The blocks are rotated on
shafts 102 at a rate of about 350 rpm and are oscillated in a
direction transverse to the motion of the advancing plates at a
frequency of about 15 cycles per minute and an amplitude of about 4
inches. Four rotary cup brushes 104 are arranged on 12-inch centers
in a line traversing the belt and roller conveyor orientation such
that the longitudinal distance between the blocks 101 and the
rotary cup brushes is about 9 inches. The rotary cup brushes are
rotated at about 350 rpm and oscillated in a transverse direction
with a frequency of about 15 cycles per minute and an amplitude of
about 4 inches. A spray of water, the purity of which is not
critical, is used to remove residual silica or cerium oxide. A
rotary cylinder brush 105 is disposed transversely across the
conveyor and is rotated to wipe away excess water and residue
silica or cerium oxide.
After cleaning, the plates are advanced into section 200 for
surface sensitization. As the plates pass through section 200, each
is first rinsed with water which is substantially pure or
demineralized. The rinse is accomplished by employing a cross-fire
spray. A mutually opposed pair of spray guns, 201 and 202, are
supported from a carriage 203 and reciprocated transversely of the
plates on a track 204 at a rate of about 40 to 60 cycles per
minute. During the reciprocation of carriage 203, rinse water is
fed to guns 201 and 202 in alternating intermittent fashion such
that water is sprayed only from gun 201 when the carriage moves in
one direction (from bottom to top of FIG. 1), and water is sprayed
only from gun 202 when the carriage is moving in the opposite
direction. The guns 201 and 202 are tilted slightly toward each
other to provide a cross-fire effect or sweeping action tending to
wash excess water from the surface of the plates.
After undergoing the initial rinse with demineralized water, each
plate is advanced beneath a spray gun 211 which is mounted on the
reciprocating carriage 203. A stannous chloride solution (a
preferred composition is given below) is fed to spray gun 211 which
directs the solution against the top surface of each advancing
plate.
Each plate then advances beneath an intermediate set of cross-fire
rinse guns 212 and 213. These guns are similar to guns 201 and 202
in structure, mounting and operation. Water containing a sufficient
buffering agent, preferably sodium bicarbonate, to buffer the later
applied palladium supersensitizing solution is fed to guns 212 and
213 and onto the top surface of each plate. Alternatively, a drip
applicator 218 comprising a pipe having a plurality of orifices
disposed along its length is positioned between guns 212 and 213
and spray gun 214 and a buffering solution is applied to each plate
through such an applicator 218 following rinsing with demineralized
water from guns 212 and 213.
In any event, buffer-containing rinse water is retained on each
plate as it advances beneath spray gun 214. Spray gun 214 is also
mounted on carriage 203 to reciprocate across each plate. A
palladium chloride solution (a preferred composition is given
below) is fed to spray gun 214 which directs the solution against
the top surface of each advancing plate. The palladium chloride
solution, as it is sprayed from the gun 214, is acidic, generally
pH 3.9 or less, in order to maintain a high concentration of
palladium chloride in solution. The solution is atomized exiting
the spray gun 214 and contacts the plate below mixing into the
residue rinse water containing an effective amount of buffer to
adjust the pH of the mixed solutions on the plate to at least 4 and
preferably to pH 6 to 9, preferably about pH 8.
Each plate then advances past cross-fire rinse spray guns 215 and
216, which are similar in construction, mounting and operation to
cross-fire spray guns 201 and 202 and 212 and 213. Demineralized
water is fed to guns 215 and 216 though the water quality is less
critical than the rinse prior to palladium supersensitization.
As illustrated, the first, second and third cross-fire rinse guns,
as well as the tin gun and the palladium gun, i.e., all of the guns
in section 200, are mounted from a single boom that reciprocates in
the transverse direction at a rate of about 54 single passes per
minute. Each of the rinse guns comprises a single UniJet-T8001 or
T8002 spray nozzle (Spraying Systems Co., Bellwood, Ill.) operated
at a pressure of about 40 psig. and an average flow rate of about
0.12 to 0.20 gallon of rinse water per minute. Each of the tin and
palladium guns comprises a single type C spray gun equipped with a
Paasche U2, F2-8 nozzle (Paasche Air Brush Co., Chicago, Ill.)
operated at an air pressure of about 30 to 70 psig. and at a flow
rate of about 800 milliliters of the solution described below per
minute. The distance between the rotary cylinder brush and the
first cross-fire rinse guns 201 and 202 is 36 inches, while the
distance from each gun or gun set in section 200 to the next
respective gun or gun set is 18 inches.
Each plate is then advanced through section 300, wherein a
metal-boron containing coating is deposited on the now
catalytically activated or sensitized surface of each plate by
simultaneously spraying and intermixing a metal-containing solution
and a boron-containing reducing solution onto the activated surface
such that the metal ions present in the contemplated metal solution
became reduced to a transparent boron-containing metal film which
tenaciously adheres to the activated surface. For the sake of
illustration, section 300 is shown to have four gun sets 301-304
each comprising a metal-containing solution gun and a mutually
opposed reducing solution gun. Section 300 also includes a mutually
opposed pair of water spray guns 305 and 306 arranged for
cross-fire rinsing. As shown, the guns 301-304 are supported for
transverse reciprocating movement in the manner described above.
However, it should be noted that the gun sets in section 300 are
generally reciprocated in the transverse direction at a rate
greater than the reciprocation rate in section 200, for example, a
rate of 74 single passes per minute. During operation, each of the
metal deposition gun sets in section 300 is maintained at a
pressure of about 40 psig. and a flow rate of about 800 milliliters
of solution per minute, while the final cross-fire rinse guns
305-306 are operated at a pressure of about 40 psig. and an average
flow rate of about 0.12 to 0.20 gallon of rinse water per
minute.
The gun sets in section 300 of the apparatus are spaced apart from
those in section 200 such that the distance between the last rinse
guns in section 200 and gun set 301 is about 54 inches. In
addition, gun set 301 is spaced apart from gun set 302 such that
the sprays generated from these sets (301-302) are overlapped, and
such that the residence time of each plate in the spray area
defined by gun sets 301 and 302 (spray area I) provides for
deposition of a controlled film thickness. The residence time in
the dwell area between gun set 302 and gun set 304 (dwell area I),
the residence time in the spray area of gun set 304 (spray area II)
and the residence time in the dwell area between gun set 304 and
rinse guns 305-306 (dwell area II) also are established to control
film thickness. Gun set 303 may optionally be used to apply
additional metal salt and reducer solution. The metal-reducer gun
sets (301-304) typically employed have Paasche U2, F2-8 nozzles,
while the rinse guns 305-306 each comprise a single UniJet-T8001 or
T8002 spray nozzle.
After undergoing a final water rinse under guns 305 and 306, each
plate advances into section 400 of the coating apparatus where it
is dried with an air knife 401 comprising an elongated metal
housing having an 0.002 inch delivery channel extending along the
length thereof. The knife 401 is disposed at a 45.degree. angle
relative to the advancing plate and has its centermost portion
spaced about 48 inches from the final rinse guns. The air knife is
operated at about 5 psig. and an air flow rate of about 4,000 to
6,000 cfm. After passing beneath the air knife, each plate passes
beneath a Gardner-Large Area Hazemeter 501 which measures and
records the luminous transmittance of the coated plates.
The ambient air temperature during film deposition is about
80.degree. Fahrenheit, while the temperature of the demineralized
and tap water used throughout these examples is generally about
65.degree. Fahrenheit. The temperature of the metal and reducer
solutions is about 80.degree. Fahrenheit. On the basis of a liter
of solution, each of the prepared aqueous solutions employed had
the following composition:
NICKEL SOLUTION PREFERRED RANGE Nickelous acetate 5 grams 4-10
grams Boric acid 2.5 grams 2-5 grams Sodium gluconate 9.0 grams
7-18 grams Hydrazine sulfate 0.5 gram 0.4-1.0 grams Water added to
1 liter Ammonium hydroxide added to pH 7.2 pH 7.0-7.6 Ethomeen
C-20* 1 drop per liter of solution 0-2 drops Acetone 0.01 gram
0-100 grams *Ethomeen C-20 (trademark of Armour and Company) is a
cocoamine having an average molecular weight of 645 and the
following generalized formula: wherein R is derived from a
cocoamine and x+y equals 10.
REDUCING SOLUTION PREFERRED RANGE Sodium borohydride 0.5 gram
0.4-1.0 grams Water added to 1 liter added to 1 liter Sodium
hydroxide added to pH 11.5 pH 11-11.6 Ethomeen C-20 one-half drop
per liter 0-2 drops
The pH of the intermixed nickel and borohydride solutions is about
7.7.
TIN SOLUTION PREFERRED RANGE Stannous chloride 0.2 gram 0.02-0.4
gram Hydrochloric acid (12N) 0.04 milliliter 0.04-0.06 milliliter
Water added to 1 liter added to 1 liter PALLADIUM SOLUTION
Palladious chloride 0.02 gram 0.02-0.04 gram Hydrochloric acid
(12N) 0.04 milliliter 0.02-0.04 milliliter Water added to 1 liter
added to 1 liter
The pH of the palladium solution is generally about 3.
BUFFERED RINSE WATER PREFERRED RANGE Water 1 liter 1 liter Sodium
bicarbonate 0.5 gram 0.1-70 grams
The amount of buffered rinse water sprayed onto each plate is
adjusted so that the pH of the mixture of the palladium solution
and buffered rinse on the plate is about pH 8.
Table I summarizes a series of metallizing runs following the
procedure described above, except as indicated.
TABLE I ______________________________________ Run No. Rinse After
Tin Solution pH After PdCl.sub.2 Spray* Luminous Transmittance**
Film Quality ______________________________________ 1 Demineralized
Water 3.7 20 percent Mottled, leading portion of plate with less
film 2 Buffered Water (1 gm/liter, NaHCO.sub.3) 7.8 20 percent
Smooth, uniform fine grain 3 Demineralized Water followed by drip
with 1 gram/liter (NH.sub.4).sub.2 CO.sub.3.sup.. H.sub.2 O in
water 8.0 20 percent Smooth, uniform fine grain 4 Buffered Water
(0.25 gm/liter NaHCO.sub.3) 20 percent Smooth, uniform fine grain,
but leading portion somewhat lighter in film
______________________________________ *Estimated by one
twenty-fifth dilution of PdCl.sub.2 spray solution. Other rinses in
the system were varied as demineralized water and buffere water
without effect. **Determined using Beckman DK 2A Spectrometer for
visible light, 380-760nm.
Sodium carbonate is substituted for the sodium bicarbonate of run 2
in an amount of 1 gram per liter of rinse solution. The resulting
pH is estimated as 11.9. The leading edge film deficiency is
eliminated as with sodium bicarbonate. However, the film texture is
more coarsely textured than when sodium bicarbonate is used.
Substitution of sodium acetate in an amount of 2 grams per liter
improves film uniformity and texture but not as markedly as does
sodium bicarbonate.
Ammonium bicarbonate, dibasic sodium phosphate, ammonium borate and
a commercially available mixed buffer of monobasic sodium phosphate
and sodium hydroxide (Fisher Scientific "pH Seven") are each used
in an amount of one gram per liter of rinse as in run 3. Each
buffer eliminates a leading edge film deficiency, each improves
texture of the film and all but the borate result in an extremely
fine grain film.
While the present invention is described with particular reference
to specific embodiments, it is not intended to be limited by
specific chemicals or means of application of buffer in the
preparation of the substrate to be coated.
* * * * *