U.S. patent number 3,650,861 [Application Number 05/029,769] was granted by the patent office on 1972-03-21 for surface treatment of titanium.
This patent grant is currently assigned to Imperial Metal Industries (Kynoch) Limited. Invention is credited to Clifford Hyde Angell.
United States Patent |
3,650,861 |
Angell |
March 21, 1972 |
SURFACE TREATMENT OF TITANIUM
Abstract
A matt etched surface is provided of titanium metal or titanium
alloy, suitable for the deposition of an adhesive coating thereon
by treating the surface of the metal or alloy with an aqueous
solution of oxalic acid at a temperature greater than ambient
temperature. Preferably the concentration of the oxalic acid
solution should be greater than five percent.
Inventors: |
Angell; Clifford Hyde (Sutton
Coldfield, EN) |
Assignee: |
Imperial Metal Industries (Kynoch)
Limited (Birmingham, EN)
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Family
ID: |
10267593 |
Appl.
No.: |
05/029,769 |
Filed: |
April 27, 1970 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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558243 |
Jun 17, 1966 |
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Foreign Application Priority Data
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Jul 1, 1965 [GB] |
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27,931/65 |
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Current U.S.
Class: |
427/309; 205/212;
252/79.1 |
Current CPC
Class: |
C25D
5/38 (20130101); C23C 22/46 (20130101) |
Current International
Class: |
C25D
5/38 (20060101); C23C 22/46 (20060101); C25D
5/34 (20060101); C23C 22/05 (20060101); C23f
001/00 () |
Field of
Search: |
;156/3,18
;117/49-51,106,107,119 ;252/79.1,79.4 ;204/32,143 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Timet, Titanium Metals Handbook for the Chemical Processor, printed
by Titanium Metals Corp. of America, 1961.
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Primary Examiner: Powell; William A.
Parent Case Text
This application is a continuation of application Ser. No. 558,243,
filed June 17, 1966, now abandoned.
Claims
What is claimed is:
1. In a process for depositing an adherent coating onto at least a
part of a "titanium alloy" article wherein said part is contacted
with acid to provide a matt etched surface and the coating is
thereafter applied to said matt etched surface, the improvement
which comprises using, as the acid, an aqueous solution of oxalic
acid wherein the concentration of oxalic acid is greater than five
percent weight/volume, and at a temperature of at least 70.degree.
C. and for a period of at least four hours, said temperature and
time being sufficient to give said matt etched surface for
application of said adherent coating thereon.
2. A process according to claim 1 wherein the acid concentration is
greater than five percent but not in excess of 15 percent
weight/volume and the acid solution is used for said etching
treatment for only as long as titanium removed from said surface is
soluble therein.
3. A process according to claim 1 wherein the temperature for
contacting said part with the solution is at least 70.degree. C.
and up to 100.degree. C.
4. A process according to claim 1 wherein said part is contacted
with a 10 percent weight/volume aqueous solution of oxalic acid at
between 75.degree. C. and 85.degree. C. for approximately 16
hours.
5. A process according to claim 1 wherein said part is contacted
with a 15 percent weight/volume aqueous solution of oxalic acid at
between 95.degree. C. and 100.degree. C. for approximately eight
hours.
6. A process according to claim 1 comprising degreasing said part
before contacting the same with the aqueous solution of oxalic
acid.
7. A process according to claim 1 comprising rinsing said part with
water after contact with the aqueous solution of oxalic acid.
8. A process according to claim 1 wherein the article is immersed
in said acid solution and an adherent metal coating is applied to
the matt etched surface.
9. In a process for providing a matt etched surface on at least a
part of a "titanium alloy" article by contacting said part with an
acid, the improvement which comprises using, as the acid, an
aqueous solution of oxalic acid wherein the concentration of oxalic
acid is greater than five percent weight/volume, and contacting the
article with said oxalic acid solution at a temperature of at least
70.degree. C. and for a period of at least four hours, said
temperature and time being sufficient to give said matt etched
surface.
Description
This invention relates to the surface treatment of titanium or
titanium-base alloy articles prior to the deposition of a metallic
or nonmetallic coating thereon.
Titanium or titanium-base alloys which are hereinafter referred to
as "titanium alloys" for brevity, may be employed successfully in
the manufacture of electrodes for electrochemical applications,
provided that at least part of the surface of the titanium is
coated with an adherent layer of a noble metal. However, in order
to obtain satisfactory adhesion between the noble metal and
titanium, it is necessary to pre-treat the surface of the titanium
prior to coating.
Hitherto, this has been accomplished by etching the surface of the
titanium by immersion in concentrated hydrochloric acid.
Satisfactory adhesion between deposit and substrate may be obtained
in this way, but the etching process has several attendant
difficulties.
As examples, at ambient temperatures the action of hydrochloric
acid is slow and variable, treatment times of three days or more
being required; alternatively, the acid may be used at its boiling
point, thus shortening the treatment time to 30 minutes, but
considerable difficulty is then encountered in dealing with the
copious acidic fumes evolved and in containing the extremely
corrosive acid. Furthermore, when titanium is etched in
hydrochloric acid it becomes fouled with a black smutty deposit
composed mainly of titanium hydride, which interferes with the
subsequent coating process. It is, therefore, necessary to remove
the deposit before attempting to electroplate the etched titanium,
the only practicable method being to scour the etched surface with
a mild abrasive. This is time-consuming and demands considerable
skill on the part of the operator to remove the deposit without
damaging the delicate structure of the etched titanium surface.
According to the invention, a process for treating at least part of
a "titanium alloy" article to provide a surface suitable for the
deposition of an adherent coating thereon, comprises treating said
part with an aqueous solution of oxalic acid at a temperature
greater than ambient temperatures.
Preferably the concentration of the solution should be greater than
5 percent weight/volume and its temperature should be maintained at
at least 70.degree. C, in order to produce the desired surface
condition in a conveniently short time, but the optimum
concentration and temperature will depend on the material to be
etched and the surface required. For example, treatment with a
solution containing 10 percent of oxalic acid at 80.degree. C.
(.+-. 5.degree. C.) will produce a satisfactory surface on
commercial purity titanium sheet in 16 hours, whereas a similar
surface may be produced in 8 hours by treating the metal in a 15
percent solution at 95-100.degree. C. Thus it will be appreciated
that etching conditions are not critical provided that they are
kept fairly constant during the treatment.
The process of the invention provides a matt etched surface on
titanium which acts as a suitable key for a variety of metallic or
nonmetallic coatings. For example, metals may be deposited by means
of electrolysis or thermal or chemical decomposition of metal
salts; and nonmetallic coatings may be deposited by gas phase
polymerization, vacuum decomposition or vacuum evaporation. An
example of nonmetallic coating material is polytetrafluoroethylene
which may be used to provide a low friction film on the titanium
surface.
It is desirable to degrease the surface of the titanium before
etching, but it is not necessary to remove oxide films which have
been formed at low temperatures. Indeed, titanium articles which
had been oxidized for 60 hours at 460.degree. F. for one hour at
700.degree. C. were successfully etched in an oxalic acid
solution.
On removal from the oxalic acid etching solution, the titanium
articles normally require only a simple water rinse before being
subjected to the coating operation. However, on occasions, articles
emerge from the solution with a light grey bloom on their surface,
but unlike the smutty deposit previously referred to in connection
with the hydrochloric acid treatment, this grey bloom can be
removed by light brushing during the rinsing operation. In fact its
removal is not essential for satisfactory electroplating.
Oxalic acid etching is less sensitive to variations in both
metallurgical condition of the titanium and purity of the etching
solution, compared with etching in cold hydrochloric acid. For
example, commercially pure titanium articles having grain sizes
from 0.01 (i.e., fine) to 0.08 mm. were etched satisfactorily in
oxalic acid solution, whereas the fine grained commercially pure
titanium is only etched with difficulty in hydrochloric acid.
Furthermore, titanium containing up to 0.2 percent by weight of
iron may be successfully etched, whereas even lower amounts of iron
in titanium render it quite unsuitable for etching by hydrochloric
acid. This latter difference is of economic importance, since it
allows the use of technical quality rather than "Analytical
Reagent" quality oxalic acid.
Under the preferred conditions, the metal loss of the titanium
sheet etched is approximately 0.023g. per square centimeter of
surface. Since the limit of solubility of titanium in 10 percent
oxalic acid is 7-8g. per liter and, when this is exceeded, a very
tenacious insoluble layer of crystals forms on the surface of the
titanium being treated, it is advisable to limit the concentration
of titanium salts in the solution. A practical limit of six g. per
liter is recommended, equivalent to a throughput of about 260
square centimeters of titanium surface per liter solution.
The reaction between oxalic acid and titanium produces titanous
oxalate which is, up to the limit mentioned above, freely soluble
forming a brown solution. Upon exposure of this solution to air,
the titanous titanium is readily oxidized to the colorless titanic
form, and this inhibits further attack on metallic titanium. No
difficulty arises from this effect in the 16 hour treatment, but
because of this oxidation partly used solutions rapidly lose their
potency on subsequent contact with air. This may be largely
prevented by covering the surface of the etching solution with
plastic chips or balls to exclude air. Alternatively, the titanium
oxalate may be kept in the titanous form by continuous electrolytic
reduction using a porous diaphragm, or by chemical reduction by
means of pure aluminum sheet.
Assessment of the suitability of an etching pretreatment can, with
experience, be made by visual and microscopic examination, but is
made more often by determining how successful the coating proves to
be in its subsequent application. Quantitive laboratory methods of
assessment include measurement of surface roughness, adhesion of
coatings subsequently deposited by electrodeposition, thermal
decompositon and the like. Yet another method is to assess the
durability of coatings in electrochemical applications.
Three comparative tests were used in assessing the surface quality
of etched titanium produced by the present process.
1. Surface Roughness Test
This was applied to etched samples of titanium by means of a
standard Talysurf examination, the degree of roughness being
expressed as a centerline average (CLA), which may be defined
as:
and is expressed in micro inches.
2. Adhesion Test
This was applied to etched and coated samples of titanium, by
bonding the head of a mild steel bolt to the coated surface with an
epoxy resin, and subsequently pulling the bolt from the sample with
a standard tensile testing machine, the adhesion being proportional
to the force required to remove the bolt from the sample. This
force is expressed in pounds per square inch (p.s.i.) and is
hereinafter referred to as the "Adhesion Value."
3. Stripping Test
This was applied to electroplated, etched titanium samples by
pressing a strip of pressure-sensitive adhesive tape on the coating
so as to expel all air bubbles between the tape and the coating and
then removing the tape in a single sharp movement. The comparative
results of the test were assessed by visual examination of the test
were assessed by visual examination of the tested coating.
The invention will be further illustrated by the following
examples, in which all solution concentrations are expressed as
percentage weight/volume:
Example 1
A sheet of commercially pure titanium was etched in a 10 percent
aqueous solution of technical grade oxalic acid maintained at
80.degree. C. .+-. 5.degree. C. for 16 hours. The sheet was then
removed from the solution, rinsed in water and dried.
The surface roughness (CLA) of the sheet was then measured and
found to be 150 micro inches. The CLA value before etching was 55
micro inches.
Example 2
Sheets of the same titanium stock material were heat-treated so
that half had a grain size of 0.013 mm. and the remainder had a
grain size of 0.080 mm. Sheets from each group were then etched in
10 percent oxalic acid solution using varying temperatures and
times of immersion, and equivalent sheets etched in concentrated
hydrochloric acid at room temperature for 72 hours.
The etched sheets were electroplated with platinum to a thickness
of 100 micro inches and the plated sheets subjected to the
aforementioned adhesion test. The results are tabulated below:
##SPC1##
In each case the adhesion value is the mean of three tests.
Example 3
Two stocks of commercial purity titanium were selected, one having
higher impurities than the other. Sheets were then cut from each
stock and heat-treated so that half had a grain size of 0.020 mm.
and the remainder 0.080 mm. The sheets were then etched in 10
percent oxalic acid at 80.degree. C. for 16 hours or in
concentrated hydrochloric acid at room temperature for 72
hours.
The etched sheets were coated with platinum to a thickness of 40
micro inches by thermal decomposition of a platinum-organic base
paint composition which was applied to the surface of the sheets.
The coated sheets were subjected to the adhesion test, the results
being tabulated below:
Grain Size Adhesion levels in p.s.i. of Sheet
__________________________________________________________________________
Purer grade of Less pure grade of titanium titanium Etched in
Etched Etched in Etched in Hydrochloric in Hydrochloric Oxalic Acid
Acid Oxalic Acid Acid
__________________________________________________________________________
0.020 mm. 4 480 4 445 0.080 mm. 379 526 8 546
__________________________________________________________________________
Example 4
Sheets of commercial purity titanium were etched in 10 percent
oxalic acid for varying times and at varying temperatures and
similar sheets were etched in cold concentrated hydrochloric acid
for 72 hours.
The etched sheets were then electroplated with platinum to a
thickness of 100 micro inches and each sheet was inserted as anode
in an electrolytic cell containing five liters of saturated sodium
chloride solution as electrolyte and having a titanium cathode. The
cells were operated continuously at an anode current density of
1,000 amperes per square foot for one week, at the end of which
time the electrolyte was drained and the adhesion of the platinum
coating on the anode assessed by means of the aforementioned
"Stripping Test." The electrolyte in the cell was then renewed and
the electrolysis continued for another week, this procedure was
repeated to the end of the respective test. The results of the
tests are tabulated below: ##SPC2##
It will be seen from the above examples that etching titanium in
oxalic acid solutions provides a convenient method of producing an
etched surface on the titanium which provides a satisfactory key
for coatings subsequently deposited thereon. Since no mechanical
abrasion of the etched surface is necessary, the process is ideally
suited to large scale production, particularly when applied to
articles of large nonplanar or discontinuous surface area, such as
wire, expanded mesh and the like.
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