Electroless copper deposition
Louis Hom
silver without too much difficulty, but is there a method for copper
deposition that's accessible? The recipes I've seen so far all involve
palladium, which isn't really available to me (unless it's hiding in my
garage somewhere in a form unrecognized by me). TIA.
--
______________________________________________________________________________
Lou Hom >K'93
lh...@ocf.berkeley.edu
http://www.ocf.berkeley.edu/~lhom/
Uncle Al
Louis Hom wrote:
>
> I'd like to turn some labware into Christmas ornaments and I know I can do
> silver without too much difficulty, but is there a method for copper
> deposition that's accessible? The recipes I've seen so far all involve
> palladium, which isn't really available to me (unless it's hiding in my
> garage somewhere in a form unrecognized by me). TIA.
Electroless deposition onto dielectric surfaces (notable exception of
silvering) requires bound low valent Pd or Sn catalytic species to
initiate. Electroless plating onto metals is spontaneous. Surfaces
are typically wet with dilute palladous or stannous whatever, dried to
fix the catalyst, then electrolessly plated with chromium, copper, or
nickel.
Do a pilot study where you give your glassware a very thin silver
mirror, a quick wash, and then immediately plate your main metal atop
that. The result should be quite attractive as the buried silver
cannot tarnish, and side of the glassware viewed through the glass
should be spectacular.
For making silvered bottles, we would slosh aluminum paint inside the
bottle and then allow to drain and dry. KISS. A variety of metallic
solvent-based paints are available.
--
Uncle Al
http://www.mazepath.com/uncleal/
http://www.ultra.net.au/~wisby/uncleal/
(Toxic URLs! Unsafe for children and most mammals)
"Quis custodiet ipsos custodes?" The Net!
donald haarmann
"Louis Hom" lh...@OCF.Berkeley.EDU
--------
"When solutions of cupric oxide are reduced by means
of aromatic hydrazine in clear glass vessels, copper is
deposited upon the glass in the form of a brilliant coherent
film. The mirrors obtained have the lustrous red colour of
burnished copper, and are as perfect in reflecting surface
and uniformity as the similar mirrors obtained by the
deposition of silver.
FD Chattaway
Copper Mirrors
Chem. News, 1907, 96, 85.
Abstracted in:
The Journal of the Society of Chemical Industry
1907, 26(17)970
I do not have a copy of Chem. News.
More:
Bruno Schweig
Mirrors:A Guide to the Manufacture of Mirrors and
Reflecting Surfaces
Pelham Books London 1973
Devotes several pages to copper mirrors. Time permitting
I'll scan them. Not today however.
--
donald j haarmann - independently dubious
Uncle Al
donald haarmann wrote:
[snip]
> "When solutions of cupric oxide
It's not that easy! What is a solvent for cuprous oxide that leaves
it as Cu(I)? 15M aqueous ammonia less oxygen, perhaps. MeCN perhaps,
though I expect an auxilliary ligand is probably necessary. Modern
electroless deposition generally employs a hypophosphite or borane
reducing agent, thus incorporating metal phosphide or boride. Thermal
annealing can give you a very hard coating (especially with nickel).
The recipies and conditions are high art.
> are reduced by means
> of aromatic hydrazine
Whoa! Hydrazine H2NNH2? That isn't aromatic! Phenylhydrazine?
> in clear glass vessels, copper is
> deposited upon the glass in the form of a brilliant coherent
> film. The mirrors obtained have the lustrous red colour of
> burnished copper, and are as perfect in reflecting surface
> and uniformity as the similar mirrors obtained by the
> deposition of silver.
>
> FD Chattaway
> Copper Mirrors
> Chem. News, 1907, 96, 85.
>
> Abstracted in:
> The Journal of the Society of Chemical Industry
> 1907, 26(17)970
There are some lovely old manipulations. Consider growing willemite
in ceramic glazes - beautiful! Reproducing "common" knowledge with
modern pure chemicals can be unexpectedly adventuresome. It's a
shame jackbooted State compassion has made garage experimentation a
capital (as in $) offense.
donald haarmann
> I'd like to turn some labware into Christmas ornaments and I know I can do
> silver without too much difficulty, but is there a method for copper
> deposition that's accessible? The recipes I've seen so far all involve
> palladium, which isn't really available to me (unless it's hiding in my
> garage somewhere in a form unrecognized by me). TIA.
> --
>
-------
Bruno Schweig
Mirrors
Pelham Books London 1973
[scaned and you know what that means!]
COLOURED MIRRORS
Copper Mirrors
Dr. Weiskopf of Morchenstern, Bohemia, appears to be the first who succeeded
in depositing brilliant copper directly on glass. In 1900 he obtained the German
Patent 124 710, his but for glass pearls.
The basic composition of his solution starts from Fehling's solution. Fehling's
solution, in turn, is composed from two solutions. The first contains 69 g. of
copper sulphate crystals [CuSO4-5H20] in 1000 mi. of distilled water, the second
350 g. of Rochelle salt (sodium potassium tartrate crystals [NaKC406-4H20]),
and 104 g. of sodium hydroxide [NaOH] in 1000 ml. of distilled water. It had long
been known that a mixture of equal parts of these two solutions when boiled with
a solution of glucose yields bright red cuprous oxide powder [CU20] and this
reaction was also used to detect glucose in the urine of diabetics. Yet no copper
mirror was formed.
Weiskopf's invention consisted in the use of the stronger reducing agent
formaldehyde and the addition of platinum chloride. Formaldehyde alone
produces a dull, non-reflecting layer, which hardly settles on the glass, but the
addition of platinum chloride makes the coat bright and reflecting, and well
adherent.
His formula, the mother of all the following ones, may be given in full:
Copper Formula A (Weiskopf)
Solution 1
(1) 100 parts of a solution of copper chloride in distilled water at the ratio 1:5.
(2) 2 parts solution of platinum chloride 1:10.
(3) 2 parts solution of zinc chloride 1:5.
(4) 50 parts solution of ammonium nitrate 3:100.
(5) 100 parts solution of Rochelle salts 1:2.
(6) 200 parts of sodium hydroxide 1:10.
Solution 2
(1) 2 parts solution of ordinary sugar 1:20
(2) 1 part solution of glycerine.
(3) 1 part of formaldehyde (40%).
454 parts of solution I are to be mixed with one part of solution 2.
Joseph Karfunkel of Berlin started from this formula in about 1930, and he
succeeded in simplifying it to some extent, so as to be able to make fairly good
mirrors. He substituted gold chloride for platinum chloride to improve the colour
of the copper film.
In 1934 Karfunkel joined forces with the present writer. The formula was further
simplified and at that time sold by Karfunkel to various firms in Germany and on
the European continent, and, through his son Adolf Karfunkel, in America, while
the present writer introduced it to firms in England. As far as could be
ascertained, no one else sold processes for copper mirrors at that time.
After Adolf Karfunkel's death, the writer continued the work. And, after literally
more than 1000 experiments, he came in 1945 to the composition, which, with
only minor alterations made since, is as follows:
Copper Formula B (Schweig)
Solution A (made up from solutions 1-3 into solution 4)
(1) Hydrochloric acid 35 ml.
Distilled water 1000 ml
(2) Palladium chloride [PdCl2] 1.5g.
Solution 1 30 ml.
Distilled water 570 ml.
Total 600 ml.
(3) Copper bichloride crystals [CuCl2-2H20] 100 g.
Zinc sulphate crystals [ZnS04-7H20] 30 g.
Solution 1 60 ml.
Distilled water 1240 ml.
Total 1300 mi.
(4) Complete Solution A
Solution 2 400 ml.
Solution 3 1300 ml.
Total 1700 mi.
Solution B
Rochelle salt (sodium potassium tartrate) 400 g.
Ordinary sugar (sucrose) 165 g
Glycerine 120 ml.
Distilled water 1580 m.
Total 1700 ml.
Solution C
Sodium hydroxide 270 g.
Distilled water 1700 ml.
Solution D
Formaldehyde (40 %) 850 ml.
Distilled water 850 ml.
Total 1700 ml.
Solution E 'Flood'
Solution A (2) (Palladium Chloride) 30 ml.
Distilled water 1000 ml.
The formula will be more easily understood if a few instructions are followed.
Solution A (1) is a diluted hydrochloric solution of about 3 1/3% strength. It keeps
well.
Solution A (2) must be shaken from time to time and allowed to stand for several
hours, or gently warmed until the palladium chloride is completely dissolved and
the solution looks a manifestly cloudless, clear light brown. It keeps well.
GOLD CHLORIDE, WHICH DISSOLVES VERY EASILY, CAN BE
SUBSTITUTED FOR PALLADIUM CHLORIDE. [emphasis added] The colour of
the mirror is slightly better when gold chloride is used, but the process appears
to work more surely with palladium chloride. Platinum chloride can also be used,
but it offers no advantages.
Solution A (3). Chloride of copper is chosen instead of copper sulphate solely
because it dissolves more readily. Similarly, zinc sulphate is preferred to zinc
chloride, which is difficult to manipulate. The solution keeps for about a month,
but must not be stored too long.
Solution A (4) keeps fairly well, and can be used even after a month.
Solution B. Rochelle salt, sugar and glycerine solution does not keep well, only
for about one week. The addition of mould killers, such as Nipagin M or Nipasept
of Nipa Laboratories, Pontypridd, Glamorgan, in the amount of 0.1 %, makes it
stable for about a year, without interfering with its action.
Solution C. Caustic soda keeps for several weeks, but appears to become less
active when it becomes older. It is perhaps inhibited by the slight attack on the
glass, also by the carbonate formed form the carbon dioxide in the air.
It has been found that solutions B and C lose strength when combined for some
time. No explanation for this behaviour can be advanced. For this reason the two
solutions are kept separate, but can be united before use, even in bulk. Also,
solution C can be added to either solution B or D, or to B united with D, so that
eventually only two solutions have to be combined.
Solution D. Diluted formaldehyde keeps better than the concentrated form, and
does not become cloudy.
Solution E 'Flood'. This diluted solution of palladium chloride keeps for a few
days, but gradually looses its strength.
It may be of interest for the in the way that most formulae for the sake of
comparison to write the formula in the way that most formulae have been
presented.
Formula B (Schweig)
Copper chloride [CuCl2-2H2O] 15 g.
Zinc sulphate [ZnS04-7H20] 4.5 g.
Palladium chloride [PdCI2] Rochelle salt 60 g .
Sugar 24 g.
Glycerine 18 ml.
Sodium hydroxide 40 g.
Formaldehyde 125 ml.
Distilled water 1000 ml.
'Flood'
Palladium chloride 0.075 g.
Hydrochloric acid 0.05 ml.
Distilled water 1000 ml.
Some explanatory and even of this chapter on Formula B, but first the exact
procedure of coppering will be given. This is done to enable the reader to obtain
the desired results, but also because the method of application is typical for
other formulae for coppering and for depositing nickel and cobalt solutions, in
fact for practically all electroless plating solutions.
Procedure for Coppering Glass
(1) The glass is prepared as for ordinary silvering. That is to say, the well
cleaned glass is sensitised with stannous chloride solution, usually using a little
greater strength of 1 g. of stannous chloride in 1000 ml. of distilled water, and
rinsed with distilled water.
(2) The glass is now super sensitised by covering it completely with solution E
'Flood' for a few seconds. An invisible coat of palladium (or gold) is formed. The
glass is rinsed again with distilled water and tilted.
(3) The coppering solution is mixed. Firstly, equal parts of solutions A, B and C
have been mixed and stirred. A clear dark blue solution is obtained. Finally, an
equal part of solution D, that is equal to the amount of A (or B or C, which are all
equal) is added, and the final mixture is very well stirred.
(4) A little of the solution is poured on the glass and tilted off to remove the wash
water. This is the same operation as recommended for the gold process.
(5) The bulk of the coppering solution is now poured on to the glass plate, and
the glass should be well covered.
(6) If scum or bubbles form they are moved and scattered by blowing air on it
with bellows, or by gentle use of clean compressed air. Alternatively, the glass is
rocked in a bath of the solution.
(7) The deposition is finished when the solution has lost its colour and a coat of
copper is down.
(8) The glass is rinsed well with distilled water and the scum removed; it is dried
well, and protected with shellac and paint, or with a good paint only.
The room temperature should be about 21oC., or 70oF. The time of deposition
must not exceed 20 minutes, and the coat should be opaque, or almost opaque
when looked through at a distance of 3-4 metres against an electric light bulb. If
necessary, a second coat can be applied. Its time of deposition is much shorter
than needed for the first coat.
As said before, the solution should be fairly freshly mixed, preferably within the
last six days. All the utensils, particularly the coppering jug, should be swilled
with distilled water after each operation.
Remarks
Good results are obtained with this method, but it remains intricate. It is much
easier to deposit copper on a thin film of silver. Several methods are based on
such a procedure and some formulae will be mentioned later on, also for
producing lighter shades. The replacement of palladium by gold has already
been mentioned.
It is possible to simplify the formula greatly by omitting several chemicals except
copper salt, a complexing agent, sodium hydroxide and a reducer. The present
author has made well over a thousand experiments - varying, omitting and
replacing the additional chemicals. With out contending that all the findings are
correct, it appears that the following was observed:
Copper chloride works slightly better than copper sulphate. The sulphate tends
to dull the reflectance of the copper.
The presence of zinc sulphate facilitates the deposition, and Rochelle salt,
glycerine and sugar each form complexes with copper salt and sodium
hydroxide.
Mirrors can, of course, be obtained by using Rochelle salt alone, also by using
either glycerine or sugar only, by using a combination of the two, or by using one
or the other with Rochelle salt. Yet the combination of all appeared to be best.
Ammonia can also be used alone or in combination, but it makes the reduction to
copper more difficult. Other complexing materials such as
ethylenediaminetetra-acetic acid have also been tried out, but none was as good
as the proved combination.
One drawback of the formula is the high content of formaldehyde, which, if not
exhausted, affects the silverer, in particular his eyes. It is most likely that it can
be drastically reduced by increasing the amount of palladium chloride, or by
replacing it by an increased proportion of gold chloride. It should be possible to
reduce the formaldehyde content to one-tenth of the amount hitherto used in
Formula B, or even to one-twentieth.
Another difficulty is the danger of blistering. If the amount of sodium is higth, the
copper shows a desirable colour. But hardly is the film deposited than it begins to
come off, to blister, sometimes with an astonishing speed. The cause of this is
not clear. The addition of nickel chloride is supposed to eliminate this blistering
as will be reported later, but it also influences the colour.
Perhaps an undue space was given to Formula B and its discussion. It is,
however, felt that copper mirrors can play a great role in the future. Not only is
the process already very important for the manufacture of printed circuits, but
many mirrors will be made in copper for heat absorption and for the beauty of the
mirrors when the process has become easy, reliable and quick.
Coppering Vacuum Flasks, Printed Circuits and Other Uses
Becky and Glenn Drew
donald haarmann <donald-...@worldnet.att.net> wrote in message
news:auuZ5.14028$2P3.1...@bgtnsc06-news.ops.worldnet.att.net...
donald haarmann
> These sound interesting, anybody have procedure for Gold Mirror?????
> > Bruno Schweig
> > Mirrors
> > Pelham Books London 1973
-----
Devotes 11 pages to gold mirrors.
--
donald j haarmann
-----------------------------
Do you believe that the sciences would ever had
arisen and became great if there had not beforehand
been magicians, alchemists, astrologers and WiZards,
who thirsted and hungered after abscondite and
forbidden powers?
Friedrich Nietzsche
Die fröhliche Wissenschaft, IV, 1886
Uncle Al
donald haarmann wrote:
> Do you believe that the sciences would ever had
> arisen and became great if there had not beforehand
> been magicians, alchemists, astrologers and WiZards,
> who thirsted and hungered after abscondite and
> forbidden powers?
NSF grants would have been just as good.
Nick Hoffman
--
Nick Hoffman - Geophysicist Extraordinaire
Uncle Al <Uncl...@hate.spam.net> wrote in article
<3A3D1238...@hate.spam.net>...
>
>
> donald haarmann wrote:
>
> > Do you believe that the sciences would ever had
> > arisen and became great if there had not beforehand
> > been magicians, alchemists, astrologers and WiZards,
> > who thirsted and hungered after abscondite and
> > forbidden powers?
>
> NSF grants would have been just as good.
>
And just as illusory?
--
Nick Hoffman - Geophysicist Extraordinaire
Oscar Lanzi III
in water through the addition of thiourea, a water-soluble soft base.
I think I've posted this before.
--OL
kres...@my-deja.com
Uncle Al <Uncl...@hate.spam.net> wrote:
>
>
> donald haarmann wrote:
> [snip]
>
> > "When solutions of cupric oxide
>
> It's not that easy! What is a solvent for cuprous oxide that leaves
> it as Cu(I)? 15M aqueous ammonia less oxygen, perhaps. MeCN perhaps,
> though I expect an auxilliary ligand is probably necessary. Modern
MeCN is, indeed. A suspension of Cu2O in MeCN dissolves on slow
addition of concentrated H2SO4. You don't even need to try that hard,
though. Concentrated HCl, or even concentrated NaCl
with gentle acidification. Palmer's old recipe for
Cu2O advocates reducing Cu++ with sulphite in high
[Cl-], and it works fine.
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