Metal Injection Moulding (MIM)

Technology With 18ct Gold,

Feasability Study
By Klaus Wiesner, Production Manager, C. Hafner
Gold and Silver Refining Company

©2011 The Bell Group, Inc. All rights reserved.

800.545.6566 riogrande.com
 Metal Injection Moulding (MIM)
Technology with 18ct Gold, a
Feasability Study
Klaus Wiesner
Production Manager
C. Hafner Gold and Silver Refining Company
Pforzheim, Germany

1. Introduction
Precious metal powder applications are not new; they can be found in different
areas of the precious metal industry, for example:
• Electric contact materials (AgCdO, AgSnO2)
• Brazing alloys, soldering alloys and solder pastes
• Conducting varnish/conducting binder/burn-in materials
• Dental alloys (Degusint), amalgams
• Decorative parts, for example: precious metals clay, gold flash, ring
blanks, watch cases and bracelet parts
• Extraction of PGMs from powdered scrap
• Many other applications
MIM technolgy for gold alloys requires that inital tests be conducted prior to
producing parts. The goal is to produce what may be referred to as net-shape, or
near net-shape pieces. This approach results in production of items that need
little, or no, additional steps to achieve the final form desired. The MIM
technology process provides optimized material usage and low scrap percentage.
The greatest advantages of MIM technology are:
1. Complex parts can be produced economically.
2. Drilling, undercuts, toothing, pockets, sharp edges and threads are easily
accomplished.
3. Large production runs (20,000–200,000 p.A.) are achieved economically.
4. It eliminates need for costly finishing work.
5. Alloys normally difficult to work can be processed using this technology.
6. It results in excellent mechanical properties and good corrosion resistance.

May 2003 443

 MIM
produ
are re
The C
inject
appro
metal
indus
in-de
Figure 1 Typical complex MIM part binde
indus
in mi
answe
in Br
Germa

2. M
2.1 M
The m
the b
The p
powd

444 The Santa Fe Symposium on Jewelry Manufacturing Technology May 20

 Figure 2 When MIM can be economical

MIM technology is not confined to producing parts in precious metal. Parts

produced from stainless steel, iron-nickel, cobalt alloys, hard metals and titanium
are readily manufactured utilizing MIM technology.
The C. Hafner Company realized that developing the technology for metal
injection moulding would be very expensive, and that such a project must be
approached very carefully. It was very important to learn whether the powder
metallurgical process from gold alloys for the precious metal manufacturing
industry was feasible. As a metal supplier, the C.Hafner Company conducted
in-depth research to determine exactly which powder specifications and MIM
binders would bring the desired results. We understood that for the jewelry
industry, it was vital that density and homogenious mix be such that it resulted
in minimum porosity for ease of finishing. In order to have all the questions
answered, the C. Hafner Company enlisted the cooperation of Fraunhofer Institut
in Bremen, one of the leading institutions for powder metallurgy research in
Germany, and possibly in the world.

2. MIM for gold alloys

2.1 MIM principle
The metal injection moulding process normally begins by mixing the powder and
the binder.
The process for the precious metal industry is different because there is no
powder source. The powder must be produced by atomizing the gold alloys and

nology May 2003 445

then classifying the powder by utilizing a sieving process. The next step is to
mix the powder with a binder. This is accomplished by using a blade kneader or
other mixing equipment. The mixture is then converted into grains in a grinding
mill granulator. Then, the homegenious granulate is molded into a die at
elevated temperatures. The resulting “green part” is then ejected from the die.
You could compare this process to the wax injection process in rubber moulds,
part of accepted jewelry casting processes. The “green part” then has to be
de-bindered, normally by thermal cracking in a furnace, by solvent extraction or
a catalytic process. This procedure provides what we call a “brown” part. As a
final procedure, the part is conventionally sintered, with the result that we have
100% of the metal input transferred into the product (see Figure 3).

Figure 3 MIM principle

2.2 P
There
meth
utiliz
meta

446 The Santa Fe Symposium on Jewelry Manufacturing Technology May 20

 is to
der or
nding
ie at
e die.
oulds,
to be
on or
As a
have

Figure 4 Powder characteristics

2.2 Powder producing techniques

There are various techniques used to produce metal powders. In the chemical
method, the precipitation technique from solutions, or fusion technology, is
utilized. An atomizing machine is used in this process. In this procedure, the
metal is induction melted under protective atmosphere in a highly purified

nology May 2003 447

graphite crucible. The liquidous metal is poured from the bottom of the crucible. 2.3 I
The stream is blasted under high pressure. The atomized plume (see Figure 5) is
2.3.1
quenched with a spray of de-ionized water.
For th
The most common techniques are: alloy,
• Water atomizing Comp
• Gas atomizing
Densi
Vicke
Age h
Melti
Grain

The t
Alloy
zinc,
effect
prese
eleme
is no
check
Figure 5 Gas and water atomization 2.3.2
The m
Trials were conducted using six different powders from four different supply
the s
sources. Production method was by gas or water atomization. All powder
The in
suppliers used as a source are manufacturers of atomization equipment and/or
sinter
trade atomizers.
togra
Atomizing parameters from different sources: (only
Melt temperature: 1000–1490°C form.

Weight flow: 0.185–4.0 kg/min

Gas pressure: 17–20 bar

448 The Santa Fe Symposium on Jewelry Manufacturing Technology May 20

cible. 2.3 Influence factor powder
5) is
2.3.1 Alloy
For the feaseability study, we concentrated on one, internationally most common
alloy, that of 18ct binary gold, with the colour 3N.
Composition (Wt.%): Au 75, Ag 13, Cu 12
Density (gr/cm3): 15.30
Vickers hardness, annealed: 150 HV 5
Age hardening: no
Melting range (°C): 900–870
Grain size: Cast 500–600 µm
Coldformed 70% and annealed 20–25 µm

The tests showed that the alloy composition influences the process significantly.
Alloy composition is very important in the sintering process. The presence of
zinc, for example, which is very often used in gold jewelry alloys, has a negative
effect in the sintering process. Even minute zinc impurities in zinc-free alloys
present problems in the sintering process. There are several other dangerous
elements that have a negative effect on sintering. The tests showed that there
is no easy transfer from one alloy to another. Each alloy composition must be
checked separately.
2.3.2 Powder shape
The method used to produce powder dictates the resulting powder shape, and
upply
the shape determines how efficiently the powder can be injected and pressed.
owder
The initial (press) step provides strength to the “green” body, and influences the
nd/or
sintering process. The shape of the powder particles is shown in the REM pho-
tographs (Figures 6 and 7). The produced, and tested, powders are gas atomized
(only one water atomized powder was checked) and have the typical spherical
form. Here and there on the surface you will note agglomerated fine particles.

nology May 2003 449

 <45 μ
were
fine p
to m
suppl
Teste
Powd
1
2
3
4
5
6*

Figures 6 and 7 Different powder sievings 2.3.4

Cross
2.3.3 Powder size and powder distribution
hollo
A very important standard to be observed in the MIM process is that of powder learne
size and powder distribution. During atomization, powder size and distribution proce
can be controlled by following different process parameters. Partical size for the reaso
MIM process is normally 10–40 micrometers. To achieve a desired powder densi- are u
ty, different powder sizes are needed, along with a quantity of very fine powder. vario
The total recovery of atomized powder is 99.3–99.8%. Then the powder is sieved The p
in different particle sizes. Some manufacturers supplied <75 μm (-200mesh), order

450 The Santa Fe Symposium on Jewelry Manufacturing Technology May 20

 <45 μm (-325mesh) and <20 μm (-635mesh). The best press and sinter results
were achieved with fraction <45 μm, which gave us the best mix of coarse and
fine particles. The usable output was 56–90%. A laser granulometer must be used
to measure particle size. The comparison of all powders tested, from all
suppliers, showed that they were able to provide powders for the MIM process.
Tested powder sources
Powder source D10/µm D50/µm D90/µm Mean/µm
1 35.29 15.31 4.49 18.37
2 40.03 15.25 4.72 19.64
3 39.46 14.42 5.28 18.87
4 28.25 11.92 4.46 15.03
5 20.30 9.65 2.35 10.93
6* 41.93 17.30 5.20 20.24

Figure 8 Typical MIM powder distribution*

2.3.4 Hollow powder particles

Cross-sections of the powder particles show that some of the particles are
hollow (see Figure 9). Based on the experience of the Fraunhofer Institute, we
owder learned that these round-shaped pores cannot be eliminated by the sinter
ution procedure. Tests designed to eliminate the pores by hip were not succesful. The
or the reasons why these hollow particles were created during the atomization process
densi- are unknown, and we did not pursue the answer. Not all powders from the
wder. various sources created this effect. Two out of four parts exhibited this problem.
ieved The process of producing and atomizing powder must be carefully controlled in
esh), order to minimize surface porosity in the finished part.

nology May 2003 451

 The b
Comm
Binde
Therm

Durop
Figure 9 Cross-section of MIM powder showing hollow particles Gel b
Freez
2.3.5 Microstructrure
All six powders tested had the same composition and came from the same metal Polym
supplier. The powders produced, however, showed different microstructures
(Figures 10 and 11). That means that the influence of the atomization process
on the microstructure of the particles is extremly important. The particle
microstructure significantly influences the sintering procedure. The origin of the 2.5 I
different microstructures was not analyzed and remains unclear.
The m
Surface oxidation of the powder is an important factor to be taken into mould
consideration. Some powders have more surface oxides (copper, for example) decid
than others. Prior to the sintering operation, we had to reduce the surface oxides to 15
by treating the particles in a diluted nitric acid solution. of th
would
We fo
follow
meta
and o
costs
anyw

Figures 10 and 11 Microstructure of particles

2.4 Binder system influence

Many different tests were conducted on various binders and we finally settled on
two binders as usable. The binders are not patented and there is no conflict with
common binder systems which are on the MIM market. Both binders are different
in composition. Our goal was to achieve different “green” body strengh of the
parts. We believe that this is an important point in jewelry applications where,
very often, there are fine filigree parts. There was no negative influence on the
different binders (such as de-bindering) during sintering trials.

452 The Santa Fe Symposium on Jewelry Manufacturing Technology May 20

 The binders are between 2.5–2.8 weight %, this is 27–30 vol. %.
Common
Binder systems Major component
Thermoplastic binder Paraffin, carnauba wax, bees wax, peanut oil,
naphthalene
Duroplastic binder Epoxy resin, furan resin, wax
Gel binder Water, methylcellulose, boric acid
Freeze dried binder Water, aniline, paraffin

metal Polymer binder Polyoxymetylene

ctures
ocess
rticle
of the 2.5 Injection/Part design
The mixed feedstock was molded to test parts on a high-pressure injection
into moulding machine. Because the test parts had to be similar to jewelry parts, we
mple) decided to produce rings. For one binder system, we warmed up the steel mold
oxides to 150°C–200°C to achieve a complete form filling. We measured the viscosity
of the feedstock. The viscosity had to be within a certain range so that there
would be no problems with segregation, and there would be smooth injection.
We followed the same basic rules in the design of injected parts as would be
followed in the design of parts that would be cast (Figure 12). The creation of
metal molds is a process that can itself present many problems. It is a complex
and often tricky procedure that requires a great deal of expertise. The tooling
costs involved in making metal molds can vary over a wide spectrum, costing
anywhere from a few thousand euros up to a hundred thousand.

ed on
t with
ferent
of the
where,
n the

nology May 2003 453

 2.7 M
Mech
Disso

Evapo

Decom

Figure 12 Rules for part design Sinte

and s
2.6 De-bindering and sintering
be va
De-bindering of parts was performed by using either a thermal or solvent process. under
The binder type was the deciding factor. The influence of different atmospheres perfo
(H2, N2, Ar and N2H2) on the de-bindering process was checked and analyzed. result
The de-bindering cycles utilized were between 4–20 hours. appro
Some
optim
the p
The s
densi
boun
succe
Typic

454 The Santa Fe Symposium on Jewelry Manufacturing Technology May 20

 2.7 Mechanisms for binder removal in MIM
Mechanism Reactions
Dissolution Solution of undestroyed binder
molecules (wax, PMMA, PEG)
Evaporation Evaporation of undestroyed binder Gaseous products, little
molecules (wax, stearic acid)
Decomposition Retropolymerisation into the
monomers (PMMA, POM)
Statistical break up of polymer
main chain (PE, PP)
Break up of polymer main chain
close to unstable bonds, e.g.,
carbon-oxygen-bonds
(EVA, PA, PE-AA)
Products
Liquid products, residue
that undergoes the other
mechanisms
or no residue
Gaseous products, little
or no residue
Gaseous and more stable
liquid or solid products
as residue
Gaseous and more stable
liquid or solid products
as residue

Sintering under different atmospheres showed a wide range of results on density

and surface quality. Regarding that, the de-bindering and sintering cycles must
be varied to arrive at the best parameters. Parts from all test runs were checked
ocess. under microscope, and the density was measured and analyzed. Sintering was
heres performed at temperatures ranging from 840°C–880°C. Lower temperatures
lyzed. resulted in lower densities. Optimum density was found by sintering at
approximately 870°C.
Some of the sintered parts were additionally hot isostatic pressed (HIP) to
optimize density. This procedure was not successful, and the measurements of
the parts before and after showed the same density.
The surface on parts after sintering should be closed, but on the other hand, the
density cannot be too great or the powder parts cannot creep along the grain
boundaries. Rings that have a density over 15 gr/cm3 after sintering cannot be
successfully hot isostatic pressed.
Typical HIP-Cycle: 10K/minute --->775°C 2 hours holding by 1500 bar

nology May 2003 455

2.8 Finished MIM parts 2.9 T
We fi
parts
probl
re-inj
poros
show

Figur
a por

Figur
Figures 13 and 14 MIM test parts binde

456 The Santa Fe Symposium on Jewelry Manufacturing Technology May 20

 2.9 Typical MIM defects
We find it interesting that MIM technology is defined as one without rejected
parts or scrap. All of the tests conducted showed this claim to be untrue. Many
problems can be encountered that will generate reject parts, and they cannot be
re-injected. In finished parts, it is possible to find surface problems such as
porosity, as well as other problems difficult to finish. The following illustrations
show some of the possibillities.

Figure 15 The cause of this defect is a binder particle which debinds and leaves
a pore, or an air inclusion, in the green body.

Figure 16 In this pore you can see powder particles, the result of an unequal
binder distribution.

nology May 2003 457

 manu
that
three
tumb
differ
disco
about
that
chang
manu
differ
sizing
those
in les
Dens
Figure 17 A metallic impurity, which was liquid by sintering temperature. You
can see the dendritic structure.
# of
X
Max.
Min.
S
X: me

Figure 18 Particle impurity from the same alloy composition which handicapped
the sintering process. S
2.10 Results
After completing all of our tests, we selected one powder source for a production
All te
run. In total we injected 310 rings and used the runners to have a real
densi
MIM production.
negat
After sintering, we distributed the rings to three different jewelry manufacturers. poros
Each was supplied with three different types of rings. We supplied these be se
458 The Santa Fe Symposium on Jewelry Manufacturing Technology May 20
 manufacturers with rings that had been produced utilizing MIM technology, rings
that were cast, and rings that had been cut from a continous casting tube. All
three types had the same dimensions and the same surface finish resulting from
tumbler equipment. The three manufacturers knew only that they had three
different lots. They were asked to check the rings closely to see if they could
discover any difference between the three lots. We asked these manufacturers
about the surface quality after completing their polishing operation. We asked
that they look closely at the quality of the rings we provided them and, if in
changing ring sizes, they encountered any differences. Not one of the three
manufacturers found significant differences in the rings. They saw no surface
differences in the samples after polishing. What they did find was that the ring
sizing performed on the MIM parts was far better than that of the cast rings or
those cut from tubing (Figure 19). The finer grain size of the MIM parts resulted
in less orange peel.
Density of the test runs
ou
Sintering and HIP Sintering Continuous Casting Casting
# of items 50 50 50 50
X 15,1045 15,1270 15,3096 15,2931
Max. 15,1454 15,2227 15,3467 15,3256
Min. 15,0003 15,0098 15,2707 15,2288
S 0,0303 0,0506 0,0148 0,0211
X: mean of measured density Max: highest density Min: lowest density S: standard deviation

pped
Sheet 20–25 µm Casting 550 µm MIM 30–40 µm
Figure 19 Microstructure of three different manufacturing techniques
uction
All tested powders provided good density after sintering. The slightly lower
real
density we encountered, in comparison to other production methods, had no
negative surface effect in the form of porosity. We found that the very miniscule
urers. porosity visible after sintering was so small and homogenous that it could not
these be seen, especially after polishing.
nology May 2003 459
3. Economical considerations 4. A
We know that the technical side of the MIM process works, so it is important that Adva
we now look at the economical side. Everything we learned about equipment and • P
the manufacturing process was accomplished by calculation. We’ll now take a • C
look at whether the MIM process is compatible to other methods. d
• L
3.1 Financial investment
• H
There are two different buisness plans you have to think about, supplier of feed-
• F
stock or MIM manufacturer. The costs of investment are different.
• L
Disad
Powder production: Atomizer 150-500 T€
• H
Powder classification 20 T€ • H
Quality control 40 T€ • O
• T
Feedstock production: Blade kneader extruder 40 T€
• T
Granulator 8 T€
5. S
Quality control 50 T€
Injection moulding: Inj. moulding machine 40-80 T€ In co
in ge
Tools 20 T€ > throu
De-bindering 75 T€ becau
emplo
Sintering 75-200 T€ extre
The cost of investment for feedstock production was calculated with 500,000 €. long
for fe
3.2 Calculation in MI
The calculation would be done until feedstock production. to inv
Example: Alloying 10kg 18ct More
Input 10kg alloy, 7.5kg output usable powder
Loss of powder production 0.4% Ack
Working time
Many
Consumables Germ
Loss in feedstock production matio
Cost of write-off Eddie
Rate of utilization and C
Cost for maintenance
Production cost of feedstock, estimated minimum: 150€/kg. For comparison,
consider cost of casting granules: 75€/kg.

460 The Santa Fe Symposium on Jewelry Manufacturing Technology May 20

 4. Advantages and Disadvantages of MIM
t that Advantages
t and • Pieces with small tolerances produceable
ake a • Complex shapes can be produced, for example, sharp fins and high risers,
deep and tiny holes, true curvature and edges
• Limited subsequent work
• Homogenous, non-visible fine porosity
feed-
• Fine grain size in comparison to castings
• Less scrap, less production circulation material
Disadvantages
• High investment in machinery
• High tooling cost
• Only economical for mass production
• Today not possible with all jewelry alloys
• Today no feedstock supplier in the precious metal market

5. Summary
In conlusion, we believe that utilizing the MIM process with 18ct yellow gold is,
in general, possible, though there are still many questions. Answers obtained
through trial and error will help to optimize the process. We urge caution
because the process is very complex and it requires great technical knowledge to
employ MIM technology successfully. The financial investment in equipment is
extremely high, and such investment makes sense only for large mass production,
00 €. long production runs of findings, for example. The production costs calculated
for feedstock are not precise and require more data. Because of the limited interest
in MIM technology at this time the C. Hafner Company would be very reluctant
to invest in MIM, though it might prove worthwhile at some future time.
More questions about MIM? Contact klaus.wiesner@c-hafner.de

Acknowledgements
Many thanks and appreciation to Georg Veltl, Fraunhofer Institut, Bremen,
Germany, and to Joseph Strauss, HJE Company, Glens Falls, New York, for infor-
mation and discussions, which are the basis for this presentation. I thank
Eddie Bell, the Santa Fe Symposium for allowing me to give this presentation
and C. Hafner for permission to present this paper.

rison,

nology May 2003 461

References
1 Petzold, F., Eifert, H., Hartwig, T. and Veltl, G., “Binder Design and Process
Control for High Performance MIM-Materials” Advances in Powder
Metallurgy + Particulate Materials 1995
2 German, Randall M., Powder Injection Molding, Metal Powder Industries
Federation MPIF, New Jersey 1990, p. 68

462 The Santa Fe Symposium on Jewelry Manufacturing Technology