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Visit to company PNJ in Ho Chi Minh City

between 30 July and 3 August 2007


Contact person: Mr. Nguyen Chi Cuong (PNJ)

Electrolytes: Rhodium plating bath K4 (2.5 g Rh/ ltr.), Palladium plating bath
DEKOR NF, Electrolytic Anti-tarnish, Silver stripping bath H

(1) Electroplating of silver parts

Problem: Palladium-plated and rhodium-plated silver jewellery tarnishes


quickly

Situation:
1. The silver castings have particularly many pores on the surfaces.

2. The silver castings have particularly oxidation skins (bluesilver) on


the surfaces.

3. Due to insufficient rinsing and particularly very complicated


geometries of the necklaces electrolyte rests stay in surface pores
and on the surfaces.

4. Due to insufficient depositions in the pores and deepenings it is not


possible to coat these spots with Rhodium and Palladium.

5. Particularly the necklaces do not hang freely enough on the jigs.


There are no even depositions of the precious metals to the
surfaces. Pieces of jewellery are hung up too generously (for
example 4 small rings on one big jig). In such cases more precious
metals are deposited to the hooks of the jigs than on the parts
themselves resulting in insufficient layer thicknesses on the
jewellery.

6. Drying of jewellery is made by hairdryers. This is not suitable


because moisture stays inside pores and deepenings of the
jewellery which accelerates oxidation of the silver.

7. The circulation water has a conductivity amounting 300-3500 µS.

8. The rectifiers of the electroplating baths are working unexactly and


have to be checked by using voltmeters always before starting any
processes. Checking voltages by voltmeters takes too long as for
example the Rhodium plating process takes only 2 minutes.

9. The rhodium concentration in the electrolyte is repeatingly restored


to 2.5 g/ltr. by an ampere-minutes-counter.
10. The Palladium plating bath is being filtered permanently through
activated carbon.

11. The Palladium plating bath is replenished by NH2SO3NH4 and a


higher concentration of R1 and R2 in order to achieve longer
deposition times and higher deposition rates.

12. Shelf-life and the cleaning of the anodes.

Advices for solving problems with Pd and Rh processes according to the


above stated situation points

To 1: Very porous parts should be silver-plated for approximately 5-10 minutes and
be polished SMOOTHLY afterwards. Herewith pores of the surfaces are
closed. Thereafter such parts should not be cleaned ultra sonically as hard
and as long as normally because in this case pores of the surfaces may open
again. This special treatment does not work with fine and thin chains.

To 2: For removing blue-silver layers parts should be silver-plated and polished as


written above. It is NOT recommendable to etch the silver surfaces with
potassium cyanide and H2O2 (Bombing) because this process is dangerous as
it can create explosive reactions.

To 3: The rinsing process can be optimised by doing the rinsing between Palladium
plating and Rhodium plating by steaming instead of rinsing by dipping in
rinsing water (Chains MUST only be touched when wearing plastic gloves) and
doing additional ultra sonic cleaning, degreasing, acid dip treatment and final
rinsing in hot demineralised water after Rhodium plating.

To 4: In order to achieve quicker depositions and in order to improve spreadings of


depositions in deepenings of parts both electroplating baths can be heated
and the current densities can be changed as follows:

Pd-bath necklaces: 2 min, 1.8- 2.2 V, 45-50°C


Rh-bath necklaces: 2 min, 3.2-3.5 V, 45°C

To 5: When hanging-up necklaces it must be avoided that they shield themselves


from each other. Even depositions can be achieved by turning the necklaces
during electroplating by hand - provided that the person who does this wears
plastic gloves. Apart from that parts to electroplated should always be hung-up
onto jigs with suitable sizes:

A few parts => Small jig


Many parts => Big jig

To 6: Drying process must be done in a centrifugal hot-air dryer. The cotton inserts
inside the centrifugal dryer as well as parts to be dryed must be clean and
must not be covered with any rests of chemicals or any other substances.
To 7: The conductivity of the circulation water is too high. The last rinsing before the
actual electroplating must be done in demineralised/destilled water only. The
demineralised/destilled water has to be replaced by new
demineralised/destilled water every day.

To 8: The rectifiers should be repaired or replaced as soon as possible.

To 9: If possible the Rhodium concentration should be raised to 3.5-4.0 grams of


Rhodium per litre. This would improve depositions and spreadings of
depositions additionally and would effect the final colour positively.

To 10: In order to avoid too low concentrations of organic ingrediants inside the
Palladium plating bath filtering cartridges containing activated carbon should
be used MAXIMUM once every 3 weeks. In the meantime - in between this 3
weeks period - only normal filtering cartridges WITHOUT activated carbon
should be used.

To 11: We do not have any experience with special regeneration cycles which are
different to our standard regeneration instructions.

To 12: The platinised titanium anodes should be exchanged every 1-1.5 years or
when their surfaces become dark. If the electrolyte is not used for a longer
time the anodes should be taken out of the solution. Platinised titanium anodes
should be cleaned by ultra sonic cleaning only.

The following tests were made:

Test 1: 20 necklaces thin


• Palladium 40 °C / 2 min / 1.5 V
• Steaming instead of normal dip rinsing
• Rhodium 40° C / 3 min / 3.0 V
• Dried in centrifuge 4 min 100 °C

Test 2: 20 necklaces thin


• Palladium 40 °C / 2 min / 2.0 V
• Steaming instead of normal dip rinsing
• Rhodium 45 °C / 2 min / 3.0 V
• Dried in centrifuge 4 min 100 °C

Test 3: 18 necklaces thin


• Palladium 40 °C / 2 min / 2.0 V
• Steaming instead of normal dip rinsing
• Rhodium 45 °C / 2 min / 3,4 V
• Dried in centrifuge 4 min 100 °C
• During the electropling processes the necklaces should be
turned

These tests are executed in different climates. Long-term tests are executed by
wearing necklaces and laying them into shop windows for a certain period. The “Mont
Blanc” test is recommended for tests within a short period.
Results:

Due to improvement of the rinsing technique and modification of the working


parameters chains should tarnish significantly later. If this should not be the case an
alloy palladium plating bath should be used.

(2) Electropolishing of silver parts


Problem: Dull surfaces after electropolishing

In order to get representative results the anodes were cleaned first. The electrolyte
was heaten and 10 grams of potassium cyanide per litre were added. The
electropolishing tests were made at 20 V.

1. test Temperature 53 °C
+10 gr/ltr. potassium cyanide
20 V
- Bad result

2. test Temperature 53 °C
+10 gr/ltr. potassium cyanide
20 V
- Better result

3. test Temperature 55 °C
+10 gr/ltr. potassium cyanide
20 V
- Same result

4. test Temperature 60 °C
+10 gr/ltr. potassium cyanide
20 V
- Bad result; repeated electropolishing and moving of the goods during
electropolishing the results became much better

Result:
The electrolyte was too old. The shelf-life of the electropolishing solution is
amounting approximately 6-8 weeks. The solution gets also exhausted when 400-
500 grams of goods per litre electropolishing solution have been electropolished.

The electropolishing solution must be heated and used at 50-60 °C. If the solution is
older than 6-8 weeks potassium cyanide has to be added to the solution because the
free potassium cyanide inside the electropolishing solution disappears relatively
quickly. If goods to be electropolished are being moved during electropolishing
process the polishing results become much better. Electropolishing is a relatively
aggressive process which easily cracks hidden pores below surfaces resulting in
additional open pores and deepenings. This can cause problems afterwards when
electroplating such goods.

(3) Electrolytic Anti-tarnish:


Test 1: Silver parts

• Degreased
• Rinsed
• Acid dipped
• Rinsed
• Anti-tarnished (3min/3V)
• Rinsed
• Dried
• Tested in a sulphide containing silver blackening agent

Result: After 10 seconds the surface staines intensively

Test 2: Silver parts

• Degreased
• Rinsed
• Acid dipped
• Rinsed
• Anti-tarnished (5min/4V)
• Rinsed
• Dried
• Tested in a sulphide content silver black coloration

Result: After 10 seconds the surface does not stain intensively

Interpretation of the test results:


The electrolyte used during the tests was relatively old. If the electrolyte is being used
daily it should be replaced by a new Anti-tarnish bath every 4-6 weeks. After Anti-
tarnish treatment goods MUST be rinsed in cold water only and the last rinsing
should be done in demineralised/destilled water. Goods which have been tarnish-
protected by the Anti-tarnish bath and dryed should not be rubbed or polished any
more because this may remove the Anti-tarnish layer.
The Mont-Blanc-test:

1. Pre-treatment of materials to be tested


Degrease parts to be tested in solvents (for example Freon), eventually wipe
the surface with a soft cloth before degreasing - if necessary.

2. Corrosion chamber
“Novus”-exsikkator, diameter = 25 cm
Put parts to be tested on a suitable rack made of stainless steel and which is
isolated by a galvanic lacquer.

3. Corrosion atmosphere
Relative humidity = 80 %
Adjusted the humidity by filling 25 ml of nourished sodium sulfide solution into
a 50 ml beaker and put it into an exsikkator - below the hole plate inside the
exsikkator. Furthermore fill 25 ml Thioacetamid into an additional 50 ml beaker
and place it next to the beaker containing the nourished sodium sulfide
solution inside the exsikkator.

Nourished sodium sulfide solution => 25 ml in a 50 ml beaker

Thioacetamid => 25 ml in a 50 ml beaker

Temperature => 18-25 °C

4. Corrosion development
Pores on surfaces of tested parts become dark coloured and well visible due
to reactions of sulfides. This test is suitable for substrates which are reacting
sensitively to materials containing sulphuric acid (Ms, Cu, Ag).

5. Test period / interpretation

Level 1

7 cycles of 24 hours each


After each cycle the samples are judged. During this period there must not
appear any corrosion.

Level 2

21 cycles of 24 hours each


After each cycle the samples are judged. Appearing corrosions must by
judged in look and size of the corrosions.