Understand Better about Jewelry Production

Understand Better about Jewelry Production

Dr. Po-Hung KO BU/Global Manager

Functional Materials
Heraeus Ltd., Dr. P. H. Ko, FM, Surabaya, Apr 2011 Page 1

Metals for Jewelry Productions

Metals for Jewelry Production

Pure gold gives the unique yellow color but it is too soft (22HV) for making jewelry. Addition of other metal(s), usually in the form of master alloys can increase the strength of the gold alloys. The addition of other metals can also change the colors of the resultant karat gold. We can therefore have more color varieties in the karat gold production.

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Colors of Karat Gold Alloys

18K

Ag
Green Yellowish green Pinkish yellow Light green

Light brown
Greyish brown

Light yellow

Greenish yellow Yellow Light Pink

Pink

Zn

Cu
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How the Colors Change in Gold Alloys?

Silver gives the greenish color for the gold.

Copper enhances the reddish color of the gold.

Zn can bleach the gold color and reduce the reddih tint of the gold color.

The presence of nickel or palladium can whiten the gold alloy.

Fancy color such as purple gold can also be made with the addition of aluminum. The color is due to the formation of intermetallic compound.
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Basic Metallurgy

Nature of Metals & Alloys

Malleability is a unique character of metals. Pure metals are usually soft. Alloying the metals can increase the mechanical properties of the alloys. Besides, it can change the color of the metals. Not all metals can be miscible. It depends on metals crystal structures. Totally miscible: Au/Ag Partially miscible: Ag/Cu

Immiscible: Ag/Ni

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Phase Diagrams
Phase diagram is like a road map for the behaviours of the alloys in different temperature and metal ratio. It gives very useful information to tell the behaviour of the alloys.

Immiscible

Miscible Examples of Phase Diagrams

Partially miscible

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Phases in Alloys

A phase is a substance that is chemically & structurally homogeneous withi itself but is physically separated by definite boundary surfaces from other substances. If the metals are soluble to each other, they will form solution which is regarded as single phase. Too many phases in alloy will increase the hardness and reduce the ductility.

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Solidification of Metals
When the metals started to solidify, they will first form a nucleus. The crystal started to grow with crystalline structure. Grain refiner or just insoluble impurities can act as nuclei to stimulate the crystallization. The crystallites grow uniformly in all three directions until they meet the adjacent growing grains. The composition of crystallites may change during solidification known as coring. Fast cooling can suppress the coring and homogenize the composition.
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Why Master Alloys ?

Why Master Alloys?

Master alloy is a concentrate of various metals and additives to offer the resultant alloy special properties. Many industries have their particular master alloys.

Jewelry industry has been using silver, brass and nickel to make the alloys for decades.
Modern master alloys have been developed for various applications according to the ways how they are handled. Some alloys are designed for hand-pouring and some are for machine-casting and machining purpose. Different additives are added in these master alloys accordingly. Careful selection is a must. Otherwise, undesirable defects will appear and consequently lower the productivity. Different karatages may sometimes need different alloys.
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Common Ingredients in Master Alloys

Additives Silicon (Si) Functions Germanium (Ge) Indium (In) Tin (Sn) Iridium (Ir) Deoxidizer to remove the oxygen & increase fluidity Cause cracking problem Deoxidizer & increase tarnishing resistance Porosity problem & expensive Increase the hardness & improve the surface texture Expensive Increase the tarnishing resistance Increase the hardness As grain refiner Hardspot problem & expensive
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Master Alloys vs Raw Metals

Master Alloys 1. The alloy is already in readyuse form 2. Convenient and wide varieties 3. The property is well-studied and the quality is stable 4. Special ingredients added to modify the properties Raw Metals 1. The metals have to be weighed and mixed prior to use 2. Inconvenient 3. The quality may not be stable unless proper QC is done 4. Properties may not be studied well

5. Relatively expensive

5. Cheaper

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Jewelry Production by Loss Wax Casting

Loss Wax Casting

Widely applied for solid jewelry production Stone in place casting is possible Suitable for mass production

Flexible
Less machines involved Normally more labor intensive Alloys for this process is not necessary to be very ductile

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Major Steps in Loss Wax Casting

Making Wax Models Wax Setting

Model Design Rubber Mold

Treeing

Completion & Post-Treatment

Casting Burn-out

Investment Flask Making

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Examples of Jewelry by Loss Wax Casting

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What are the Major Factors for Casting?

Sprue Design Melting/Casting Methods Operation Temperatures The Choice of Alloys and Alloy Quality

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Rule of Thumb for Sprue Design

Sprue just resembles the blood vessels in our body Main Sprue > Branch Sprue > Feed Sprue

Connect to the thickest part of the cast.

Prefer in fluted shape. Extra sprue needed for heavy parts or items with large surface area Avoid the sudden turning sprue to minimize turbulence

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Opening of the Feed Sprue

Tapered sprue needs longer time for form-filling Turbulence generates by the jet-like feeding. The slightly fluted opening allows laminar flow of metals
Normal
Tapered

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Sprue Position
5-6% shrinking in solidifcation of metals Solidified sprue will shut the opening Shrinkage porosity

The sprue attaches to the thickest part of the cast.

The thickest part has to be hollowed if no attachment of sprue is allowed
Shrinkage Porosity

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How to Check the Sprue?

Experience is critical & important Different trials can be used in early stage Different designs prefered to be separated in different trees. A tracable record for particular designs is suggested.

Trial 1

Trial 2

Trial 4

Trial 3

Best Result
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Melting and Casting Methods

Torch Melting Resistance Melting Induction Melting

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Torch Melting
Fast, convenient and cheap Use only natural gas, LPG with compressed air Never use acetylene as it gives oxidizing flame The flame must always cover the melt during melting Causes oxidation problem

Not-consistent in massproduction
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Resistance Melting
Heat generated from electric resistance Longer heating time required ( higher risk in oxidation) Max. temperature of only 1100C No stirring effect Inhomogenous

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Induction Melting
The most advanced heating method With stirring effect No protection from oxidation Fast & convenient Relatively expensive

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Vacuum Assisted Casting vs. Centrifugal Casting

Vacuum Assisted Casting
- By weight & pressure difference
- For alloys with lower melt temp. - Good for cast w large surface area - More suitable for mass production - Requires higher flask temp.

Centrifugal Casting
- By centrifugal force
- For alloys with high melt temp. - Surface texture hard to control - Good for filigree items - Requires lower flask temp.

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How Operational Temperatures Affect Casting?

Casting and flask temperatures are critical for Casting quality. The casting temperature controls the fluidity of the alloys, whilst the flask temperature affects the texture of the cast surface

Studies showed that casting result is more sensitive towards the flask temperature
- Too low flask temperature incomplete form-filling. - Too high flask temperature dendritic surface & gas porosity

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Gypsum decomposes over 730C

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Dendritic Surface Formed from High Temperature

Dendritic Surface

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Examples of Flask Temperatures

Flask Temp Items Examples

< 520 C

Heavy
Bracelets

510 550 C Mens Ring

540 600 C Womens Ring 580 630 C Filigree Items

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How Investment Burnt-Out Affects Casting?

In burnt-out cycle, the wax will be burnt off in form of CO2. The residual carbon will react with metals or oxide to form CO2 which will cause serious surface defects.

Important

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Investment After Burnt-Out

Carbon soot

Incomplete Burnt-out

Complete Burnt-out
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Jewelry Production by Machining

Machining
By applying various deformation processes (e.g. Stamping, wiring, rolling, drawing, tubing, CNC cutting), the alloy is deformed to desired shape to make the jewelry. Highly automatic, machinery dependent and relatively less labour demanding. The unit production cost is low if large volume is made. Only suitable for big quantity production.

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Examples of Jewelry by Machining or Handmaking

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Major Steps in Machining

Preparation of Metal Ingots

Wiring

Rolling

Rolling

Profiling

Stamping
Chain Knitting Stamping Etching

Tubing
Diamond Cutting

Solid Chains

Findings

Hollow Jewelry

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Major Factors affecting Machining Performance

Annealing parameters Alloy Quality Etching Oxidation

Equipment Quality

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Annealing
To restore the ductility of the alloy Achieved by annealing furnace or torch

Induced by recrystalizing the metal atoms

Over-annealing excess crystal growth peeling & cracking The alloy must be covered by protective gases (e.g. cracked ammonia)
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High-Lights of Jewelry Production

Annealing Process Technical Seminar in Iran 2007

Crystals start to grow

Highly deformed crystals

Recrystalization

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Suggestions for Annealing

Alloy Type 18-22KY 8-14KY 8-18KR 8-18KW- Ni 925Ag
Sheet

Annealing Temp (C) 550 600 650 670 650 680 650 700 550 600

Temperature Color Very Dark Red Dark Red Cherry Red Cherry Red Very Dark Red

Reduction 70 80 % 60 70 % 60 70% 50 60 % 70 80 %

CW% = Int. Thick (to) Fin. Thick(t1)

Int. Thick (to) Wire CW% = Int. Area (ro ) Fin. Area (r1 )
2 2

Int. Area (ro )

2

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Why Finer Grains Better?

Metal is polycrystalline structured The lines between grains are called grain boundary The boundary is the line of weakness and site for impurities accumulation Finer grains more boundary for impurities. The alloy is less sensitive towards contaminations Easier to polish & more lustrous Larger grains deformed differently to accomodate the shape changes rough surface & peeling effect

Large Grains

Finer Grains
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Consequences of Improper Annealing Process

Too low the annealing temperature and/or time cannot induce the recrystallization. The alloy remains hard and not ductile. Too high annealing temperature and/or time enhances the crystal growth resulting large grains. It causes more peeling problem and sometimes cracking problem. No protective coverage in annealing will cause severe oxidation to the alloys resulting discoloration, embrittlement and blistering in the alloy. Too frequent annealing is also not good. It enhances the extensive crystal growth resulting peeling problem afterwards.

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Major Criteria of the Alloys for Machining

Alloy can be produced by continuous casting and static ingot casting The alloy cannot be casted with too high temperature. It would give large pipe in ingot and cause excessive grain growth

The alloys for investment casting are not suggested for machining purpose due to the presence of silicon or the investment inclusion
White gold should not have too much nickel, otherwise it becomes brittle due to nickel segregation. Prior to recycling the alloy, the oily substance must be removed by detergent or petroleum

The heavily recycled alloy should be avoided due to the content of unknown impurities
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Major Criteria of the Alloys for Machining

Segregation of Ni

Au + Ni

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Etching
Etching is a process to remove the core The etching process depends on the cores used:

- Copper/Tombac (Cu-Zn alloy) Nitric acid

- Iron hydrochloric acid or dilute Sulfuric acid - Aluminum Caustic Soda (sodium Hydroxide)

Improper etching will dissolve the gold alloy or attack the grain boundary rendering brittleness in the items
Complete removal of core is essential in order to meet the hallmarking.

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Oxidation
Oxidation happens in casting and annealing without covering gases. The presence of oxide can cause: - reduction of ductility - Formation of blisters - Formation of porosity

- Color change
The alloy must be covered with protective gas whenever heat applies

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Equipment Quality
Machining performance highly depends on the quality of equipment - Alignment of the rolls - Surface texture of the rolls

- The proper procedure for the machine operation

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Common Defects in Jewelry Production

Why Gas Porosity?

It looks like small spherical pores on the surfaces (pin-hole) & difficult to be removed by polishing

Caused by the gaseous contaminants (e.g. O2 or SO2)

High operation temperature causes the decomposition of gypsum (i.e. CaSO4) CaSO4 CaO + O2 + SO2

Heavily recycled metals contain large amount of gaseous contaminants from gypsum or copper oxide
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Oxidative Inclusion Porosity

Crow-like porosity on the surface & the region nearby may be brittle It is more abundant in the alloy with higher Zinc content (Ni-KW or 814KY) The zinc oxide is trapped along the grain boundary and left the cavity resembling shrinkage porosity The problem is caused by severe oxidation or extensive use of recycled alloys

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How the Shrinkage Porosity Forms?

- ZnO

- Cu2O
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Why We Add Zinc in Alloys?

Zinc is added to karat gold as a deoxidizer. It can reduce the copper oxide back to metallic state with itself converted to zinc oxide. Zn + Cu2O ZnO + 2Cu Zinc is added to yellow gold to enrich the yellow tints of the low karat yellow gold alloys. Zinc is added to Ni-white gold to increase the fluidity of the molten alloys. It can reduce also the surface tension of the nickel-white gold. The Zinc is easy to be oxidized to feathery Zinc oxide and trapped in the alloys resulting oxidative shrinkage porosity. It increases the melt loss.

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Why Alloy Cracks?

Some jewelry alloys are more sensitive towards cracking. It is due to the inherent problems and the operational conditions. Examples of alloys sentive towards cracking: 1. Alloy with high silicon content 2. 18K pink gold

3. 18K yellow gold with high zinc content

4. Ni-white gold with high nickel content 5. Heavily recycled alloys

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Use of Silicon in Jewelry Alloys

The use of Silicon in jewelry casting are under debate for decades. The table listed the pro and con of silicon in casting Advantages 1. Deoxidizer to give shiny surface on the cast Disadvantages 1. Favor large grains formation 2. Its segregation causes brittleness 3. Causes hard-spot problem in Ni-white gold

2. Increase the recycling time

3. Increase alloy hardness 4. Increase alloy fluidity

The more protection from oxidation during casting is, the less the silicon.
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Jewelry Alloys with Silicon

Si not soluble in Au & Ag segregation Adundant in 18KY and sterling silver
Si-rich phase

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Cracking in 18K Pink Gold

18K pink gold cracked like biscuit upon slow cooling after heating Due to the intermetallics formation

410C Ordering

Ductile

Brittle
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Why 18KY gold cracks with 14KY alloy?

The high zinc content in 18KY makes it easier to crack. Master for 14KY gold contains more zinc for bringing the yellow color.

Many different phases between Au & Zn Brittle

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Peeling
Caused by the excessive growth of crystal grains The alloy easily peels Factors favors large crystal grains

- High annealing temperature

- Long annealing time - High casting temperature - Alloy contains silicon

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Hard Ni-white Gold = Easy to Crack?

It is true that Ni-white gold is about 40 70% harder than the normal yellow gold. The cracking problem is due to the segregation of nickel from gold alloy. Alloy with higher Cu content or lower Ni content and fast quenching can improve the brittleness.
Au + Ni

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Why Recycled Alloys Easy to Crack?

In recycling of alloys, impurities will accumulate in the alloys. The impurities segregate Cracks Impruities = oxides, investment residue, iron from tools & polishing media O (ppm) 14KY Ni-14KW

1st melt
2nd melt 3rd melt 4th melt 5th melt

20.2
13.0 20.2 26.1 90.0

16.5
46.1 72.2 119.0 178.7
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Where the Hard Spot Come From?

Hard spot is not found during filing. It is often found during the polishing in the later stage.

The hard spot has higher hardness than the bulk alloys. It resembles the stones on the muddy road.

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Hard Spots in Ni-KW Gold

Commonly found in Ni-alloy with silicon Appears only on one side of the item (Due to the different densities from gold)

Possible Cause:
- The formation of nickel Silicide - The segregation of Si in Nickel

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Why Ni & Si are present Together?

Reaction Between Ni & Si - Favored by carbon from crucible and /or incomplete burnt wax - Favored by heavily recycled alloys - High Operational Temp

Si dissolves in Ni
- Silicon has good solubility nickel - Dissolved in segregated nickel

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Hard Spot from Gold

Hard spot all over the surface Originated from pure gold Tungsten (W)

Ru, Ir, Os

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Why Fire-Scale Happens?

After polishing, colored stains appeared on sterling silver, removed by intensive polishing or acid pickling not possible Caused by the formation of copper oxides (i.e. Cu2O or CuO)
Stained Area
Normal Area Cu2O Red-stain Red-stain

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Cross-section of Red-Stain Area

The stain is not only on the surface but penetrated also to sub-surface

Red-stain

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Recycling of Scraps

What are the Common Impurities in Scraps?

From casting, the scrap usually contains investment residues and oxides. From machining, the scrap contains usually gease, steel residues and oxides. The investment residue will cause hard-spot and gas porosity problem. The impurities are usually present on the surface only unless the melting is not handled properly with serious oxidation.

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Why We Need to Add New Alloy in each Cast?

There are some additives in the alloy and they may burn off or evaporate during the melting process. The purpose of adding the new material is to replenish the additives. E.g. 30% of Additive A will evaporate during melting. Initial: 1% Final: 0.7%

I. If only 100% of old material is used, only 0.7% of the additive A in the alloy. The performance of the alloy may vary. II. If 50% of new material is added, the additive A level will be: 0.7% x 0.5 + 1% x 0.5 = 0.85% The change will be less significant and the performance and quality of the alloy can be maintained.
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How Can We Clean the Scrap?

The scrap has to cut into pieces to have visual inspection whether it is heavily contaminated. The heavily contaminated parts have to be refined. The scrap is put in tumbler to clean the surface mechanically. The oxide and investment can be removed effectively.

For machined scrap, the scrap have to be washed with detergent or petroleum to remove all the geasy impurities.
The scrap is pickled in 15 20% dilute sulfuric acid to remove the oxide. The scrap is rinsed with water and dried. The scrap is clean to be recycling.

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Flowchart of the Cleaning Process

Scrap
Casting Scrap? No Pickle in detergent/ gasoline Yes Visually clean? Yes Tumbling for 30 mins No Refining

Pickle in 20% sulfuric acid (10mins)

Rinse with Water

Scrap clean to be used

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High-Lights of Jewelry Production

Inspect the Quality of the Scrap Visually!!

Cut scraps into pieces to inspect visually whether it is heavily contaminated. The heavily contaminated parts have to be refined. The cut edge showed significant deformation indicating the contamination is limited.

Deformed surface

Cut edge
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Clean the Scrap Prior to Re-use?

The scrap should be tumbled in tumbler to clean the surface mechanically. The oxide and investment machined scrap, For the scrap from machining, it has to be washed with detergent or petroleum to remove all the geasy impurities.

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Pickle the Scrap to Remove Oxides

The scrap should be pickled in 1520% sulfuric acid to remove the oxide on the surface. The acid can only dissolve the oxides but it will not attack the alloys.

The acid can be used repeatingly and it is non-volatile.

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Scrap Ready to Use

After pickling, the scrap should be rinsed with plenty of water to remove the excess sulfate ions. The scrap is dried in oven and it is ready to be used.

The scrap can be used directly or granulating prior to use.

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Metal Loss in Jewelry Production

Where the Metals Lost in the Production?

There are many ways to cause the metal loss during the production. - Loss from melting or casting - Loss from machining - Loss from diamond cutting or polishing - Loss from surface finishing

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Loss from Melting or Casting

Gold is stable towards oxidation and its vapor pressure is very low and it will not evaporate easily. Karat gold contains not only gold but also other metals such as silver, copper, zinc or nickel. However, these metals can easily be oxidized to their corresponding oxides. The oxides will then be etched away.

The melt loss is in fact not due to the loss of gold but the loss of master alloys. You give more gold to your customer.
Way to avoid the high melting or casting loss - Use protective gas to cover the melt to avoid the oxidation of alloys. - To avoid the high operational temperature, the evaporation of the alloys can be reduced. - To avoid using alloys with volatile elements such as Zn or Si.
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Loss from Machining

The production loss from machining should be limited. The loss usually goes to the peeling of metals The loss can be minimized by improving the annealing condition. The smaller the grain size, the less the peeling problem is.

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Loss from Diamond Cutting or Polishing

This loss is unavoidable but it can be minimized. If the surface is rough, more intensive polihing has to be made and the polishing loss will increase. If the metal is too soft, it can also increase the polishing loss.

To minimize this loss, the polishing has to be kept minimal by carefully adjust the operational temperature in casting or annealing.

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Loss from Surface Finishing

The surface will sometimes be treated before electroplating. The bombing solution (H2O2 + cyanide solution) can help to make the surface shiny. However, it can etch away the metal on the surface and increase the metal loss. To avoid using this method in cleansing process.

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New Technology in Jewelry Production

Hard Gold or Karat-Gold Electro-forming

To produce hollow jewelry, it involves many steps in metal deformation. It can only be economical in production if the production quantity is large. Electro-forming can shorten the production period and bigger variety in the design can be achieved.

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Process for Gold Electro-forming

We will first design the wax models Followed by a metal plating on the wax master or put on silver paste layer. Conduct the electroforming process Remove the wax and the base metal layer

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How Heraeus helps the Jewelry Industry?

How can Heraeus Help?

Heraeus Group was established in Hanau Germany in 1851. We have over 150 years of experience in precious metal technology Functional Materials Unit (FM), formerly known as Semi-finished Jewelry Division (SJD) has been supplying master alloys and semi-finished jewelry products for decades. Heraeus has the alloy production in Hong Kong to give the fastest and best service to jewelry manufacturers in Asia. Our R&D laboratory in HK also keeps develop newer and better products for the industry.

Heraeus Indonesia & PT. Hemas are our partners for master alloys in Indonesia. They can give you almost the instant response whenever our clients have any requests.

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R&D Laboratory in Heraeus Ltd.

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Some Popular Master Alloys from Heraeus

Master Alloy H-128I H-147A H-148A H-449 H-PAT Application 10-18K Pink 14-18KW 14-18KW Sterling silver Sterling silver Advantages It gives nice pinkish yellow color & easy to cast with high recycling rate It gives brilliant white color and good for casting It is very ductile and perfect for machining purpose It gives very white color and easy to cast with. No firescales and no plating needed It gives very white and smooth surface after casting

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Heraeus Ltd., Dr. P. H. Ko, SJD, Iran Jul 2010

Thanks for Your Attention !

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