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The Role of Process Parameters In Platinum Casting By Dr. Ulrich E. Klotz & Tiziana

The Role of Process Parameters In Platinum Casting

By Dr. Ulrich E. Klotz & Tiziana Drago, Research Institute Precious Metals & Metals Chemistry (FEM)

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

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Klotz The Role of Process Parameters in Platinum Casting Dr. Ulrich E. Klotz Tiziana Drago Research

The Role of Process Parameters in Platinum Casting

Dr. Ulrich E. Klotz Tiziana Drago Research Institute Precious Metals & Metals Chemistry (FEM) Schwäbisch Gmünd, Germany

1. Introduction

In recent years several articles on casting properties of platinum have been published. 1, 2 Different aspects such as suitable alloys for casting, 3-6 tree design 7-10 and investment reactions 11,12 have been treated. Articles from South African authors describe the effect of centrifugal casting parameters for different alloys and investments. 12-14 95Pt5Co was identified as a very versatile casting alloy showing excellent form filling of filigree parts even for flask temperatures as low as 100°C (212°F). 95Pt5Ru, on the other hand, showed poor form filling of filigree parts for flask temperatures below 800°C (1472°F). 12 Besides casting properties, functional alloy properties such as color, hardness, ductility and magnetic properties have to be taken into account for jewelry purposes. In this regard 95Pt5Ru is more versatile compared to 95Pt5Co or 95Pt5Cu and can be used for all jewelry purposes. 95Pt5Ru also offers higher hardness and finer grain size compared to 95Pt5Cu, which results in easier polishing and higher scratch resistance. In the present project the focus has been on 95Pt5Ru and 95Pt5Co as the most common alloys for jewelry purposes.

Casting is a process with many variables that can’t be controlled at will, and therefore has a somewhat chaotic nature. 15 This requires many casting trials and a statistical analysis of the results obtained. It also appears very difficult to make simple recommendations about a specific set of working parameters.

The findings on platinum investment casting described in this paper are the result of a research project commissioned by the Platinum Guild International, USA (PGI) in cooperation with several industrial partners. In the following sections the properties of platinum alloys will be described as a basis for discussion of the observed casting behavior. Then experimental details will be described, followed by the casting results obtained with centrifugal and tilting casting. The paper will close with a summary of results and an outlook recommending topics for further research on platinum jewelry alloys.

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2. Properties of Platinum Alloys

2.1 Phase Diagrams

Phase diagrams describe the stability of the different phases (for instance, liquid and solid phase) as a function of temperature and composition. Phase diagrams of the Pt-Ru and Pt-Co systems are given in Reference 16. From the phase diagram the basic alloy properties given in Table 1 can be determined. However, the phase diagram describes the conditions in thermal equilibrium, which are most often not reached in technical processes such as investment casting. In order to describe real cooling conditions, the Scheil-Gulliver method was applied. During solidification, segregation takes place where certain elements are enriched to melt and solid phases, respectively. In the case of Pt alloys, Ru and Co are segregating to the solid phase and melt, respectively. Comparable data and the amount of segregation are described in Reference 17. Such segregation, especially of impurities such as Si, strongly affects the behavior of the melting (melting range!) and investment reactions. The melting range under practical conditions increases remarkably by a factor of 2 (Pt-Ru) or 4 (Pt-Co) as given in Table 1 (i.e., the solidus temperature under real casting conditions is considerably lower than the value given in the phase diagram).

Table 1 Basic alloy properties of 95Pt5Ru and 95Pt5Co

 

95Pt5Ru

95Pt5Co

Alloy composition [mass%]

950Pt - 50Ru

950Pt - 50Co

Liquidus temperature [°C/°F]

1815/3299

1672/3042

Solidus temperature [°C/°F]

1797/3267

1654/3009

Melting range [°C/°F]

18/64

18/64

Melting range (Scheil) [°C/°F]

39/102

78/172

During melting and casting in silica-containing crucibles and investment, contamination of the melt with Si can occur. This can heavily affect the melting range of an alloy. Silicon is known to form a deep melting eutectic with platinum at 830°C (1526°F) and 4.2 mass percent. 16 The effect of Si content on the melting range of silicon-contaminated Pt-Ru and Pt-Co alloys was assessed using thermodynamic calculations with the ThermoCalc ® software package and a database dedicated to precious metals (SNOB1). Results of Scheil-Gulliver

calculations for two different silicon contents in the melt, 0.05 mass% Si and 0.2 mass% Si, are presented in Figure 1 and Figure 2. Even traces of silicon (0.05 mass%) lower the solidus temperature by about 50°C (90°F) compared to the binary alloys. Higher amounts (0.2 mass%) result in a reduction of 150°C (270°F) and 250°C (450°F) for Pt-Co and Pt-Ru, respectively. The extension of the melting range is caused by the strong segregation of Si to the melt by a factor of about

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Figure 1 Scheil calculation with ThermoCalc ® software; influence of silicon contamination on solidus temperature

Figure 1 Scheil calculation with ThermoCalc ® software; influence of silicon contamination on solidus temperature

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Figure 2 Scheil calculation with ThermoCalc ® software; segregation of silicon to the melt

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2.2 Thermophysical Properties

The thermophysical properties of platinum and its alloys are the key for understanding the challenge in casting compared to other precious metals. Some important data, namely density, viscosity, surface tension and thermal conductivity, were compared to other precious metals. As far as available, data were taken from the Degussa Precious Metals Handbook. 18 It remains mandatory to determine further data for jewelry alloys in order to obtain better understanding of casting properties and to allow casting simulation in the future.

The normalized density for gold and platinum and some of their alloys is plotted in Figure 3. The pure metals show a very large density reduction during freezing, resulting in high sensitivity to shrinkage porosity. For gold alloys this density reduction is much lower than for the pure metal, while platinum alloys show shrinkage comparable to pure Pt. Furthermore, the slope of the density- temperature curve is a factor of two higher compared to gold (i.e., overheating required during melting further increases the proneness to shrinkage porosity of platinum alloys).

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Figure 3 Density of precious metals and their alloys in the liquid and solid state

Platinum alloys have a high viscosity compared to gold or silver (Figure 4a). Alloying with Co and Cu reduces viscosity, but alloying contents typical for jewelry alloys are too low, allowing values comparable to gold alloys (Figure 4b). Surface tension of platinum is about a factor of 1.5 higher compared to gold. 18 Thermal conductivity of Pt is about one-third of Au and a factor of six lower than Ag. These three properties–surface tension, viscosity and thermal conductivity–are important factors influencing the filling of filigree items during casting. High surface tension and viscosity make it more difficult for the melt to flow smoothly into small cavities of the flask. Low thermal conductivity results

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in inhomogeneous temperature of the melt and premature freezing of filigree parts, especially if the temperature difference of melt and flask is high as in the case of platinum. In practice, centrifugal casting is used to apply extra force and to enhance form filling. Experiments with centrifugal and static (tilting) casting machines were made during the project to highlight the role of casting conditions.

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a)

to highlight the role of casting conditions. Klotz a) b) Figure 4 Viscosity of precious metal

b)

Figure 4 Viscosity of precious metal melts and alloys

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3. Experimental Setup

3.1 Casting Machine and Machine Parameters

Most of the casting experiments were made using a TopCast TCE10 casting machine with induction heating (Figure 5). For melting it was operated with full power of 10kW. Metal temperature during heating and melting was registered by a computer-controlled quotient pyrometer (Maurer, model QKTR1085) with 100Hz acquisition rate. A typical heating curve is shown in Figure 6. At the melting point the heating curve reaches a plateau until the complete amount of alloy is liquid. Alloy weight used in the casting trials was 100 – 180g. Complete melting was observed by the caster and the melt was then overheated for 5(±1) seconds before casting. During this time temperature increases linearly with time. As the temperature increases very quickly, precise control of overheating is important. From the slope of the time-temperature curve the variation of casting temperature can be estimated to be ±40°K during the one-second reaction time of the caster. Complete heating time until casting was only 30-40 seconds, depending on amount and type of alloy. Cooling time was measured by pointing the pyrometer on the metal button in the flask. In vacuum, cooling time of the melt button is by a factor of 2 longer compared with gas atmosphere (air/argon), explaining the occurrence of gas porosity in vacuum casting.

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the occurrence of gas porosity in vacuum casting. Klotz Figure 5 (a) Topcast TCE10 centrifugal casting

Figure 5 (a) Topcast TCE10 centrifugal casting machine with pyrometer and temperature data acquisition system; (b) detail of centrifugal arm, heating coil and orientation of tree in casting machine

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Klotz Figure 6 Metal temperature during heating for two casting experiments. Drop of melt temperature in

Figure 6 Metal temperature during heating for two casting experiments. Drop of melt temperature in case of vacuum casting is due to manual operation.

The TopCast TCE10 machine allows rotation speeds up to 450rpm with adjustable accelerations up to 1000rpm/second (rpm/s). Before starting actual casting experiments with platinum alloys, experiments with fine gold were made in order to determine optimum parameters to avoid material losses by crucible leftovers. A minimum speed is required to force the material to climb up the steep crucible wall and to leave the crucible through the nozzle. Results for different machine parameters are given in Figure 7. The crucible could be emptied with different centrifugal combinations. However, acceleration and speed have to meet a certain ratio; otherwise, the material might spill over the crucible wall. For the present machine two combinations, namely 300rpm–300rpm/s and 440rpm– 600rpm/s, were chosen.

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Klotz Figure 7 Effect of centrifugal speed and acceleration for TopCast TCE10 casting machine; results for

Figure 7 Effect of centrifugal speed and acceleration for TopCast TCE10 casting machine; results for fine gold (density 19.3 g/cm³)

Selected experiments were made using an Indutherm MC15 tilting casting machine. The machine contains a vacuum chamber with integrated induction- heated crucible (power 3.5kW) and flask holder. Crucible and flask are oriented to each other under 90° angle. Melting is done with the crucible in vertical position. For casting, the complete vacuum chamber is titled by 90°. Form filling is assisted by argon over pressure immediately after casting. Metal temperature is controlled by internal thermocouples.

3.2 Tree Design

The tree design was selected with the following considerations: main sprue and button should be lightweight in order to save material; heavy and lightweight filigree pieces should be included to study reactions with investment and form filling, respectively; standard samples such as ball rings were put on every ring in identical positions for comparison of different castings. Several tree designs were tested during the project. Most trees used a Diabolo-type setup. 10 Typical trees containing some standard items (ball rings and grid) together with jewelry pieces are shown in Figure 8. For special purposes other tree designs were used and are mentioned later.

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Klotz Figure 8 Example of two typical tree designs; tree #3AG (left) and tree #4AG (right)
Klotz Figure 8 Example of two typical tree designs; tree #3AG (left) and tree #4AG (right)

Figure 8 Example of two typical tree designs; tree #3AG (left) and tree #4AG (right) with Diabolo setup.

During centrifugal casting three forces act on the material. First, inertia of the melt acts during the acceleration of the flask and results in increased form filling of the parts on the trailing side of the flask. Second, centrifugal force is constant for all positions on the tree depending on distance from the center. Third, gravity assists filling of bottom parts of the flask. Therefore, tree design plays an important role for optimization of casting results. All items were characterized by their position on the tree relative to the centrifugal direction as given in Figure 8. During placement of the flask in the casting machine, the flask is tilted upside down. Therefore, position 90° is on the top of the flask during casting. Best form filling is expected for positions 0° and 90° because of the combined action of inertia and gravity.

3.3 Investment

Four different investments from different suppliers were tested during the project. Table 2 gives an overview on the properties of the investment and briefly describes the experience in working with them.

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Table 2 Investment properties

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No. 4

No. 3

No. 2

No. 1

Investment

 
 

fiber

2-part/

fiber

2-part/

3-part

3-part

Type

 
 

Rubber base

Rubber base

and liner

Paper

and liner

Paper

Base and liner

 

base

base

 

8

8

20-25

30

time [min]

Mixing

 

5-7

5-7

10-12

10-12

time [min]

Working

 

10.0

11.5

12.0

12.0

time [h]

Burnout

 

900/1652

900/1652

870/1598

871/1600

[°C/°F]

temp.

Burnout

filigree parts, especially plastic parts

Cold water required to reach upper working time limit; high viscosity, risk of bending of

time limit; high viscosity

Cold water required to reach upper working

extended working time possible

Curing does not start at room temperature;

Curing does not start at room temperature; extended working time possible

Remarks

 
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Investments No. 1 and No. 2 are three-part investments. They do not cure at room temperature and therefore have sufficient working time. However, they require a paper base and liner to absorb excessive water during burnout. The paper base requires wax sealing and careful handling of the flask. Prior to casting, ash residues have to be removed from the hot flask.

Investments No. 3 and No. 4 are two-part and quickly cure at room temperature during the investing process. No. 4 is fiber reinforced; therefore, working time can be very short and viscosity increases during working. In some cases this caused filigree parts to bend during the investing process or caused gas bubbles to stick on the surface of the wax parts. Mixing with cold water allowed slight extension of working time. These two investments can be handled with rubber bases and cure sufficiently before actual burnout.

The burnout cycles of the investments are compared in Figure 9. No. 1 and No. 2 require several steps before reaching final burnout temperature. A first step at around 100°C (212°F) is required to evaporate the water from the flask; wax melting takes place at around 200°C (392°F); and final burnout and curing of the investment during heating to and holding at around 900°C (1652°F). No. 4 and No. 3 become solid already at room temperature. Therefore, only one step at 200°C to melt the wax is required before reaching the burnout temperature of 900°C. All investments require burnout times of 10-12 hours (i.e., overnight burnout).

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Figure 9 Investment burnout cycles according to manufacturer’s recommendation

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4. Casting Trials with Centrifugal Casting Machine

4.1 Experimental Conditions

A large number of casting experiments was carried out to analyze the influence of casting parameters (melt temperature, flask temperature, casting atmosphere, casting machine type, alloy, and investment material) by using standard sample geometries such as ball rings and grids. The ball ring represents heavy section pieces. With the large ball acting as hotspot, it will provoke investment reactions and is prone to shrinkage porosity. The grid represents filigree items and will show form-filling ability under certain process parameters. The as-cast samples were evaluated in terms of surface quality and by metallographic investigation. A complete list of all casting trials is given in Table 3.

Table 3 List of centrifugal casting experiments with Topcast TCE10 machine

       

Casting

Flask

   

Acceleration

Trial

no.

Alloy

Tree

Investment

temp.

temp.

Atmosphere

Speed

[rpm]

[rpm/s]

[°C]

[°C]

GPt001

95Pt5Ru

4A

No. 1

 

850

Air

300

300

GPt002

95Pt5Ru

1A

No. 1

 

850

Air

300

300

GPt003

95Pt5Ru

2A

No. 1

 

850

Air

300

300

GPt004

95Pt5Ru

3A

No. 1

 

850

Air

300

300

GPt005

95Pt5Ru

2A

No. 1

 

850

Air

300

600

GPt006

95Pt5Ru

2A

No. 1

 

850

Air

440

600

GPt007

95Pt5Ru

1A

No. 1

 

850

Air

440

600

GPt008

95Pt5Ru

1A

No. 1

 

850

Air

300

600

GPt009

95Pt5Ru

1

No. 1

 

850

Air

300

300

GPt010

95Pt5Ru

1

No. 1

 

850

Air

440

600

GPt011

95Pt5Ru

1A

No. 1

 

950

Air

440

600

GPt012

95Pt5Ru

2

No. 1

 

950

Air

440

600

GPt013

95Pt5Ru

2A

No. 1

 

950

Air

440

600

GPt014

95Pt5Ru

5

No. 1

 

950

Air

440

600

GPt015

95Pt5Ru

6

No. 1

 

950

Air

440

600

GPt016

95Pt5Ru

5

No. 1

 

950

Air

440

600

GPt017

95Pt5Ru

6

No. 1

 

950

Air

440

600

GPt018

95Pt5Ru

7

No. 1

 

950

Air

440

600

GPt019

95Pt5Ru

7

No. 1

 

950

Air

440

600

GPt021

95Pt5Ru

4AG

No. 1

 

950

Vacum

440

600

GPt022

95Pt5Ru

3AG

No. 1

 

950

Vacum

440

600

GPt023

95Pt5Ru

3AG

No. 1

 

950

Air

440

600

GPt024

95Pt5Ru

3AG

No. 1

 

950

Vacuum

440

600

GPt025

95Pt5Ru

4AG

No. 1

 

550

Vacum

440

600

GPt026

95Pt5Ru

4AT

No. 1

 

850

Vacum

440

600

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GPt027

Pt--5Co

4AG

No. 1

 

850

Air

440

600

GPt028

95Pt5Co

4AG

No. 1

 

850

Vacum

440

600

GPt029

95Pt5Co

4AS

No. 1

 

850

Vacum

440

600

GPt030

95Pt5Co

4AS

No. 1

 

850

Air

440

600

GPt031

95Pt5Co

4ATS

No. 1

 

950

Air

440

600

GPt032

95Pt5Co

4ATS

No. 1

 

950

Vacum

440

600

GPt033

95Pt5Ru

4ATS

No. 1

 

950

Air

440

600

GPt034

95Pt5Ru

4ATS

No. 1

 

950

Vacum

440

600

GPt041

95Pt5Co

13

No. 4

1947

850

Air

440

600

GPt042

95Pt5Ru

13

No. 4

2016

850

Air

440

600

GPt043

95Pt5Co

13

No. 4

1980

950

Air

440

600

GPt044

95Pt5Ru

13

No. 4

2059

950

Air

440

600

GPt045

95Pt5Co

13

No. 2

1989

850

Air

440

600

GPt046

95Pt5Ru

13

No. 2

2019

850

Air

440

600

GPt047

95Pt5Co

13

No. 2

1983

950

Air

440

600

GPt048

95Pt5Ru

13

No. 2

2065

950

Air

440

600

GPt049

95Pt5Co

13

No. 2

2180

950

Air

440

600

GPt050

95Pt5Ru

13

No. 2

2252

950

Air

440

600

GPt051

95Pt5Co

13

No. 2

1994

1050

Air

440

600

GPt052

95Pt5Ru

13

No. 2

2045

1050

Air

440

600

4.2 Platinum-Ruthenium Alloy 4.2.1 Filigree Items

In previous studies 95Pt5Ru showed higher hardness but worse form filling than 95Pt5Co. A set of experiments proving the form-filling ability of 95Pt5Ru was made using trees containing standard grids (5 x 12 mesh) with a ligament of 0.8 x 1.0mm. In these tests (GPt014 – GPt019), investment No.1 was used at constant flask temperature of 950°C (1742°F) with casting parameters of 440rpm-600rpm/s. Three different tree setups were used (Figure 10). On Tree #5 all grids are oriented perpendicular to centrifugal direction while they are parallel to it on Tree #6. Tree #7 used a short main sprue holding all grids in radial direction. The form filling was evaluated for each grid and was found to depend strongly on the type of tree and the grid position. The Diabolo-type trees #5 and #6 showed much better form filling than Tree #7 with a main sprue where maximum values reached only about 80% fill (Figure 11). On all trees best form filling was achieved for positions 0° - 90° where for both Tree #5 and Tree #6, nearly 100% fill was achieved. At positions 135° - 315° grid fill falls to 70-80% and 80-90% for Tree #5 and Tree #6, respectively. Tree #7 shows 50-70% grid fill and is therefore not suitable for filigree items. As a result of these tests, filigree parts should be mounted on a Diabolo-type tree with the long axis of the part parallel to centrifugal direction. It is expected that positions 0°-90° result in best form filling.

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Klotz Figure 10 Different tree setups (a = Tree #5, GPt014/016; b = Tree #6, GPt015/017;
Klotz Figure 10 Different tree setups (a = Tree #5, GPt014/016; b = Tree #6, GPt015/017;
Klotz Figure 10 Different tree setups (a = Tree #5, GPt014/016; b = Tree #6, GPt015/017;

Figure 10 Different tree setups (a = Tree #5, GPt014/016; b = Tree #6, GPt015/017; and c = Tree#7, GPt018/019) using standard grids to evaluate the influence of position on tree. Centrifugal direction is to the right.

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Klotz Figure 11 Grid filling in casting trials GPt014 – 019 with 95Pt5Ru as a function

Figure 11 Grid filling in casting trials GPt014 – 019 with 95Pt5Ru as a function of tree setup and grid position on tree; averaged values of two casting trials per tree setup

For the numerous tests, grid filling was evaluated for 95Pt5Ru as a function of casting parameters as given in Figure 12 – Figure 15. The averaged values for all grids per tree were chosen for evaluation, and results for 95Pt5Co are given for comparison. The 45° position was present on all trees, while on some trees positions 135°, 225° and 315° were also used. In general, like in previous investigations, 14 large scatter is observed for grid fill because not all casting parameters can be fully controlled. 15 However, some clear tendencies can be determined from the grid filling results:

• Flask temperature (Figure 12) has a strong effect on form filling. Higher form filling is obtained for 950°C (1742°F); in most cases grid fill of >60% is reached. For 850°C (1562°F) the maximum value is below 60%.

• Centrifugal speed (Figure 13) has a strong effect and promotes form filling.

• Casting atmosphere (Figure 14) has a moderate effect on form filling. Form filling is usually better in vacuum than in air casting. However, perfect fill can also be obtained with air casting and in most cases grid fill was above

60%.

• Casting temperature (Figure 15) has a weak effect on form filling. Higher flask temperature tends to promote form filling. Casting temperature is difficult to measure and can only be controlled by the melting time and visual control of complete melting, which depends on the appraisal of the caster.

• Perfect form filling was always achieved for 95Pt5Co independent of casting conditions. Therefore, this alloy is superior to 95Pt5Ru in terms of form filling ability.

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Figure 12 Grid filling as function of flask temperature for air casting (except value for

Figure 12 Grid filling as function of flask temperature for air casting (except value for 550°C); averaged values of all grids per tree

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Figure 13 Grid filling as function of centrifugal speed for air casting; averaged values of all grids per tree

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Figure 14 Grid filling as function of casting atmosphere for centrifugal speed of 440rpm; averaged

Figure 14 Grid filling as function of casting atmosphere for centrifugal speed of 440rpm; averaged values of all grids per tree

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Figure 15 Grid filling as function of casting temperature and atmosphere for centrifugal speed of 440rpm; averaged values of all grids per tree

4.2.2 Heavy Items (Ball Ring)

A ball ring with ring shank diameter of 3.6mm, ball diameter of 9.5mm and total diameter of 24.5mm was used as the standard object in all casting trials. The ball ring was sprued either on the ball or on the ring shank opposite to the ball in order

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to test for form filling, surface appearance and shrinkage porosity under different casting conditions.

Form filling of the heavy ball ring was no problem under most casting conditions. Even at a very low flask temperature of 550°C/1022°F (Trial #GPt025), complete filling of the ball ring was achieved. At a flask temperature of 1050°C/1922°F (Trial #GPt051 and 052 with No. 2), the investment breaks down and form filling is incomplete. Maximum flask temperature for this type of investment should therefore not exceed 950°C – 1000°C (1742°F – 1832°F).

The surface of the ball ring is characterized by areas with glossy and matte surface. Table 4 gives a relative appraisal of surface quality, with the best surface quality indicated by +++, while the worst was indicated by +.

Table 4 Relative comparison of investment performance in terms of surface quality for air casting: +++ (best), ++ (medium), + (worst). Investment No. 3 was only used for casting trials with Indutherm MC15 tilting machine.

Investment

Devesting

Surface quality of 95Pt5Co @ Tflask

Surface quality of 95Pt5Ru @ Tflask

850°C

950°C

1050°C

850°C

950°C

1050°C

No. 1

+

++

++

n.a.

+++

+++

n.a.

No. 2

+++

++

++

+

++(+)

++(+)

+

No. 4

++

+

+

n.a.

+ +

 

n.a.

         

+ +

   

No. 3

+

+++

+++

n.a.

(cracks)

(cracks)

n.a.

The investment material has strong influence on surface quality. The three-part investments No. l and No. 2 show much better performance than the two-part investments No. 3 and No. 4. Of the three-part investments No. 1 appears slightly better with lower tendency to show fins. However, the difference between No. 1 and No. 2 is very small. For No. 1 and No. 2 there is no obvious influence of flask temperature or casting atmosphere. The ball always has a matte surface, while the ring shank is partially glossy. No. 4 shows a rougher surface for a flask temperature of 950°C (1742°F) compared to 850°C (1562°F).

SEM investigations of the ball and the ring shank showed the topology of the surface. For No. 2 and No. 1 the surface is fully dendritic (Figure 16). Almost no residues of investment were found. On the matte part of the surface, the dendrites did not reach the surface of the ring cavity in the flask. This can be explained by premature freezing of the ring shank close to the sprue, preventing directional solidification and therefore complete form filling. In some cases the dendritic surface was restricted to one side of the sample, which was on the trailing sample side relative to centrifugal direction. In this case the liquid metal is forced to one side of the flask cavity by centrifugation, resulting in a glossy surface on this side and a matte, dendritic surface on the other side. In the glossy part of the surface

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dendrites are still visible (Figure 16b), but the surface appears relatively smooth (i.e., the melt was in direct contact with the flask cavity during solidification). No signs were found that the matte surface was caused by investment reactions.

that the matte surface was caused by investment reactions. a) b) Figure 16 SEM investigation of

a)

the matte surface was caused by investment reactions. a) b) Figure 16 SEM investigation of as-cast

b)

Figure 16 SEM investigation of as-cast surface of trial 95Pt5Ru/No. 2/950°C/air. a) matte surface of the ball; b) glossy surface of the ring shank

With investment No. 4 the surface of the ball rings strongly depends on flask temperature. At 850°C (1562°F) the surface is similar to investment No. 2 or investment No. 1 (Figure 17). However, micro shrinkage and residues of investment material are frequently found in the matte areas. Even in the glossy parts the surface shows micro shrinkage and is less smooth compared to the other investments. At a flask temperature of 950°C/1742°F (Figure 18), the surface appears very rough (please note that Figure 18a was taken with the same magnification as the other pictures). Larger shrinkage pores and investment residues are sticking to the surface. In the glossy parts the surface is comparable to 850°C (1562°F), especially for samples with thinner cross section. These findings indicate that at 950°C (1742°F), investment No. 4 might be beyond its working temperature for heavy parts such as the ball ring, where the ball acts as a hotspot, strongly heating up the investment and promoting investment breakdown. For filigree parts the surface is smoother at both flask temperatures and comparable to investment No. 1 and investment No. 2.

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a) b) Figure 17 SEM investigation of as-cast surface of trial 95Pt5Ru/No. 4/850°C/ air. a)

a)

a) b) Figure 17 SEM investigation of as-cast surface of trial 95Pt5Ru/No. 4/850°C/ air. a) surface

b)

Figure 17 SEM investigation of as-cast surface of trial 95Pt5Ru/No. 4/850°C/ air. a) surface of the ball; b) surface of the ring shank close to sprue

Klotz
Klotz

a)

ball; b) surface of the ring shank close to sprue Klotz a) b) Figure 18 SEM

b)

Figure 18 SEM investigation of as-cast surface of trial 95Pt5Ru/ No. 4/950°C/air. a) surface of the ball with dark inclusions of investment material; b) surface of the ring shank close to sprue

The liquid metal can erode the investment during form filling, resulting in hard investment particles embedded in the cast sample (Figure 19). EDX measurement showed that such particles consist of SiO 2 , which is the main component of the investment. The particles were found at an inner shrinkage pore surface and were in intimate contact with the melt. However, no signs of reactions like rounding off of edges were observed for 95Pt5Ru. Nevertheless, eroded investment particles, which were observed for all investments, will act as hard spots during jewelry finishing.

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The Role of Process Parameters in Platinum Casting

Klotz a) b) Figure 19 a) Hard investment particles (SiO 2 ) embedded in 95Pt5Ru
Klotz a)
Klotz
a)

b)

Figure 19 a) Hard investment particles (SiO 2 ) embedded in 95Pt5Ru casting (Investment No. 1/850°C/vacuum); b) EDX spectrum at position 4 showing Si and O signal

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A second type of very small, non-metallic inclusions with spherical shape was found more frequently independent from casting conditions or investment. The rounded edges indicate reaction with the alloy. The inclusions contained Si, O, Al, and Mg from the investment or crucible material. Because of their small size and low quantity, such particles are probably not critical in jewelry applications.

The porosity was assessed by metallographic sections of as-cast rings. The section was cut through the complete ring from sprue to ball. An overview of typical examples of these sections is shown in Figure 20 for 850°C (1562ºF) and 950°C (1742ºF), respectively. Porosity was evaluated qualitatively in terms of ‘low’ (acceptable, with either no porosity visible in the shanks or small pores in the heavy parts) or ‘high’ (with large pores or accumulated fine pores in the heaviest part of the casting) or ‘very high’ (unacceptable, with large pores near the surface of the casting in its heaviest section) (Table 5). In the case of 95Pt5Ru, a strongly dendritic solidification with large, intersecting dendrites was observed. The chaotic formation of a three-dimensional dendritic network by the growing crystals prevents the flow of the liquid metal. Typically, this results in numerous small pores distributed in the ball or ring shank. As shown later, 95Pt5Co showed a different freezing behavior, resulting in few but larger pores.

Klotz
Klotz

a)

behavior, resulting in few but larger pores. Klotz a) c) b) d) Figure 20 Metallography of

c)

behavior, resulting in few but larger pores. Klotz a) c) b) d) Figure 20 Metallography of

b)

behavior, resulting in few but larger pores. Klotz a) c) b) d) Figure 20 Metallography of

d)

Figure 20 Metallography of 95Pt5Ru ball rings. a) No. 1/950°C(1742°F)/air; b) No. 4/950°C (1742°F)/air; c) No. 2/950°C (3749°F)/air/melt temperature 2065°C (1742°F); d) No. 2/950°C (1742°F)/air/melt temperature 2252°C (4086°F)

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Table 5 Relative comparison of porosity in metallographic sections of 95Pt5Ru casting trials depending on investment: +++ (low = best) ++ (high = medium) + (very high = worst)

95Pt5Ru

No. 1

No. 4

No. 2

850°C/air

n.a.

+++

++

950°C/air

++

+++

++

850°C/vacuum

+

n.a.

n.a.

950°C/vacuum

++

n.a.

n.a.

The most common defect was shrinkage porosity in the ball and/or in the ring shank. Generally, porosity was low in the shank sections, while it was worse in the heaviest part of the casting (ball and sprue sections). This is caused by premature freezing of the ring shank. Under the casting parameters investigated it was not possible to achieve complete directional solidification, not even if the ring was sprued on the ball. The centrifugation forces the liquid metal to flow to one side of the ring. As a consequence, the shrinkage porosity is concentrated on the opposite side. This is illustrated in Figure 21, where the large shrinkage pore in the ball is asymmetric to the ball center. On the lower side the ball surface is rough and dendritic, while the opposite side is smooth because the liquid metal is forced to the upper side by centrifugation, and the frozen ring shank prevented directional solidification. This was the typical behavior observed for investments No. 1 and No. 2. The same principle is valid for No. 4, but this investment showed the best casting results for the ball ring in terms of porosity. Shrinkage pores did not accumulate to one big shrinkage hole but instead were scattered throughout the complete ring.

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Klotz a) c) b) d) Figure 21 Effect of melt temperature on porosity, 95Pt5Ru/No. 2/950°C/air; a),

a)

Klotz a) c) b) d) Figure 21 Effect of melt temperature on porosity, 95Pt5Ru/No. 2/950°C/air; a),

c)

Klotz a) c) b) d) Figure 21 Effect of melt temperature on porosity, 95Pt5Ru/No. 2/950°C/air; a),

b)

Klotz a) c) b) d) Figure 21 Effect of melt temperature on porosity, 95Pt5Ru/No. 2/950°C/air; a),

d)

Figure 21 Effect of melt temperature on porosity, 95Pt5Ru/No. 2/950°C/air; a), b) Melt temperature 2252°C; c), d) Melt temperature 2065°C

Casting conditions have a small influence on shrinkage porosity. No influence was observed for centrifugal speed and acceleration in their investigated range (330-400 and 440-600rpm/s). Casting atmosphere also had no clear influence on porosity. The process is controlled by the geometry of the sample and the thermal conditions. Therefore, higher flask temperature should result in directional solidification and reduced porosity as shown in previous work on silver casting. 19 However, it was not possible to increase flask temperature above 950°C – 1000°C (1742ºF – 1832ºF) without the risk of investment breakdown. Besides sprue geometry optimization, only an increase of melt temperature might change solidification behavior and reduce shrinkage porosity. In casting trial # GPt050, melt temperature was increased by 200°C (360ºF) compared to trial # GPt048 (2065°C/3749ºF). Figure 22 shows the comparison of the casting results. In both cases comparable shrinkage porosity was found in the ball, whereas porosity in the ring shank was lower at higher casting temperature. However, such extreme melt temperatures will result in high crucible erosion under practical casting conditions.

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Klotz

Klotz a) b) Figure 22 Casting trial GPt012: 95Pt5Ru/No. 1/950°C/air. a) Position 90, ball sprue; b)

a)

Klotz a) b) Figure 22 Casting trial GPt012: 95Pt5Ru/No. 1/950°C/air. a) Position 90, ball sprue; b)

b)

Figure 22 Casting trial GPt012: 95Pt5Ru/No. 1/950°C/air. a) Position 90, ball sprue; b) Position 180, ring sprue

Gas porosity was merely observed under the chosen casting conditions and for the investment materials used. Figure 20 shows a comparison of the three investments for a flask temperature of 950°C (1742ºF) at air casting. Melt temperature was about 2060°C (3740ºF) except for Figure 20d, where the melt was overheated by 200°C (360ºF). Scattered gas pores were found in all castings with a tendency for increased gas porosity with increasing flask temperature and for vacuum casting compared to air casting. Even in the case of an overheated melt, no significant gas porosity was found for the No. 2 investment. No. 4 investment showed numerous pores after casting. However, high magnification reveals that these pores are, according to their shape, scattered shrinkage pores rather than gas pores. Therefore, gas porosity was no major issue for 95Pt5Ru even under extreme casting conditions.

The 95Pt5Ru casting results for heavy items can be summarized as follows:

• The casting defects observed were caused by non-directional solidification and premature freezing of the ring shank or sprue.

• Shrinkage pores accumulated by centrifugation were located in the ball (in the case of shank sprue) or at the transition from ball to sprue (ball sprue).

• Defect-free casting of ball rings could not be obtained with the chosen casting parameters. Lowest shrinkage porosity was observed for investment No. 4 at 850°C (1562ºF) flask temperature.

• High flask and melt temperature tend to reduce shrinkage porosity, but chosen values are already close to investment breakdown temperature.

• Gas porosity was merely observed for all investment materials even under extreme casting conditions.

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4.3 Platinum-Cobalt Alloy

4.3.1 Filigree Items

95Pt5Co was recommended in earlier studies for filigree items because of its much better form filling. 12, 14 As shown in Figures 12-15, grid fill was always 95-100% independent of casting conditions. Therefore, just considering form filling ability, 95Pt5Co is the alloy of choice for filigree items.

4.3.2 Heavy Items (Ball Ring)

As expected from the results with 95Pt5Ru, form filling of heavy items such as the ball ring was no problem with 95Pt5Co as well. 95Pt5Co always showed some reaction with investment materials. This is obvious from the dark blue color of the investment in contact with the alloy (Figure 23). The investment material in contact with the alloy shows a deep blue color, while the fresh fracture surface of the investment appears white. The reaction is clearly visible around the 95Pt5Co particle embedded in the investment. Local composition measurement in the scanning electron microscope (SEM) found a composition close to the mineral Co 2 SiO 4 , which is known for its blue color. The surface reaction is promoted by the segregation of Co during solidification 17 and depends on casting parameters. The metallographic cross section of the reaction products shows SiO 2 particles from the investment sticking to the alloy surface (Figure 23c, position 10). The EDX measurement of these particles shows only Si and O (i.e., the quartz particles from the investment). The EDX spectrum at position 11 also contains P and traces of Al and Mg together with Co, indicating the formation of Co silicate with the binder phase of the investment. The blue color is much more pronounced for air casting and on heavy parts. With increasing melt and flask temperature, the reaction increases (i.e., oxidation of Co during melting and casting promotes the reaction with the investment material).

promotes the reaction with the investment material). 312 Figure 23a The Role of Process Parameters in
312
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Figure 23a

The Role of Process Parameters in Platinum Casting

Figure 23b Klotz May 2010 Figure 23c 313

Figure 23b

Klotz
Klotz

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Figure 23c

313
313

Klotz

Klotz Figure 23d Figure 23 a) Reaction between 95Pt5Co alloy and investment material indicated by the

Figure 23d

Figure 23 a) Reaction between 95Pt5Co alloy and investment material indicated by the dark blue color of investment in contact with the alloy; b) EDX measurement showing Co from the alloy and Si, O, Mg, Ca, and P from the investment; c) metallographic cross section through reaction products; d) EDX spectrum at position 11

The surface of 95Pt5Co ball rings usually appears rougher compared to 95Pt5Ru. No glossy parts can be found on the ring shank or sprue but the surface appears matte all over the ring. Table 4 gives a relative comparison of surface quality of as-cast parts, showing that results with 95Pt5Co were slightly worse than with 95Pt5Ru. Investment No. 2 showed the smoothed surface similar to No. 1, while parts cast in No. 4 had the roughest surface. On filigree parts, such as the grid, it was very difficult to remove the investment completely, while it fell off heavy parts.

SEM investigations of ball and ring shank showed a dendritic structure in most parts of the surface. Results for investment No. 2 are given in Figure 24 showing the transition from ring shank with dendritic structure to the sprue connection where the surface is smooth. The dendritic surface is attributed to non-directional solidification. A smooth surface only appeared directly at the sprue. The surface is partially covered with black-appearing reaction products of the alloy and No. 2 investment. For the No. 4 investment these black residues were found to a much larger extent between the dendrites (Figure 25). Practically the complete interdendritic space shows a film-like layer of reaction product. EDX measurements (Position 3) showed high concentration of Co from the alloy and O, Si, P and Mg from the investment. The EDX spectrum is similar to the measurement on the blue layer of the investment material (Figure 23). A thin layer of a second reaction product of the 95Pt5Co alloy was found on the dendrite tips (Position 2 in Figure 25). EDX measurements showed high concentrations of Co and O, while the Pt signal is coming from the alloy matrix. Co forms several black oxides, among which cobalt(II) oxide (CoO) forms a low melting eutectic with cobalt at 1451°C (2644ºF). The formation of CoO is promoted by the segregation of

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The Role of Process Parameters in Platinum Casting

Klotz

Co to the interdendritic areas. A thin layer of CoO probably forms on the surface during casting, and this reacts with the investment to form the blue Co silicate layer. For investment No. 4 this reaction is much more pronounced compared to No. 2 or No. 1. Additives of the investment may play an important role in these reactions. Casting in vacuum or protective atmosphere prevents Co oxidation and investment reaction.

atmosphere prevents Co oxidation and investment reaction. a) b) Figure 24 SEM investigation of as-cast surface

a)

atmosphere prevents Co oxidation and investment reaction. a) b) Figure 24 SEM investigation of as-cast surface

b)

Figure 24 SEM investigation of as-cast surface of trial GPt049 (905°C/air/95Pt5Co). a) Transition from sprue to ring shank. b) Backscattered image at higher magnification.

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a) b) Klotz c) d) Figure 25 SEM investigation of as-cast surface of trial GPt041

a)

a) b) Klotz c) d) Figure 25 SEM investigation of as-cast surface of trial GPt041 (No.

b)

Klotz
Klotz

c)

a) b) Klotz c) d) Figure 25 SEM investigation of as-cast surface of trial GPt041 (No.

d)

Figure 25 SEM investigation of as-cast surface of trial GPt041 (No. 4/850°C/air/ 95Pt5Co); a) Surface of the ball with interdendritic residues of investment; b) Backscattered electron image; c), d) EDX point measurements at Positions 2 and 3, respectively.

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The Role of Process Parameters in Platinum Casting

Figure 26 provides an overview of the metallographic cross sections of 95Pt5Co castings depending on casting parameters and investment. Table 6 shows the evaluation of porosity depending on investment. Usually there is one big shrinkage hole formed close to the trailing side of the ball relative to centrifugal direction. No major porosity was found on the ring shank or sprue, which is different from 95Pt5Ru, where scattered shrinkage pores were usually found in the whole ring. The different morphology of the shrinkage pores is controlled by the thermophysical properties of the alloy.

is controlled by the thermophysical properties of the alloy. a) c) b) Klotz d) Figure 26

a)

controlled by the thermophysical properties of the alloy. a) c) b) Klotz d) Figure 26 Metallographic

c)

by the thermophysical properties of the alloy. a) c) b) Klotz d) Figure 26 Metallographic investigation

b)

Klotz
Klotz

d)

Figure 26 Metallographic investigation for gas porosity in 95Pt5Co alloys; a) No. 1/850°C/air; b) No. 1/950°C/air; c) No. 1/950°C/vacuum; d) No. 4/950°C/air

Table 6 Relative comparison of porosity in metallographic sections of 95Pt5Co casting trials depending on investment:

+++ (low = best) ++ (high = medium) + (very high = worst).

95Pt5Co

No. 1

No. 4

No. 2

850°C/air

+

+

+

950°C/air

+

+

+

850°C/vacuum

+

n.a.

n.a.

950°C/ vacuum

+

n.a.

n.a.

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Klotz

As observed above, 95Pt5Co shows some reaction with investment, manifested by Co silicate formation. It was investigated whether such reaction causes gas porosity close to the ring surface. Metallographic results are given in Figure 26. The ball ring is an object susceptible to gas porosity because of its high mass and the strong heating of the investment. The most critical position where the investment heats up most during solidification is the transition from ball to sprue on the inner side of the ring. All three investments were found to show practically no gas porosity at 850°C (1562ºF)/air. At the higher flask temperature of 950°C (1742ºF)/air, there was very slight increase, while the situation was worst for 950°C/vacuum. However, gas porosity was a secondary issue for the heavy section ball ring in these casting trials. Compared to 95Pt5Ru, gas porosity was less for 95Pt5Co, probably because of the lower alloy temperature.

The 95Pt5Co casting results for heavy items can be summarized as follows:

• 95Pt5Co shows investment reactions manifested by a blue layer of Co silicate. Such reactions increase with increasing flask temperature and are stronger in air casting.

• Shrinkage porosity is caused by non-directional solidification and premature freezing of the ring shank or sprue. Flask and melt temperature had no remarkable influence on shrinkage porosity.

• Defect-free casting of ball rings could not be obtained with the chosen casting parameters. The investment material showed little influence on shrinkage porosity.

• Gas porosity was merely observed for the chosen casting parameters and investment materials.

5. Casting Trials with Tilt Casting Machine

The Indutherm MC15 casting is an induction-heated machine with a maximum power of 3.5kW. It consists of a vacuum chamber where crucible and flask are mounted in a 90° orientation. For casting the vacuum chamber is tilted and the liquid metal is poured into the flask. Immediately after casting argon pressure is applied to improve form filling. Experiments with this machine were made for comparison of static casting vs. centrifugal casting. The investment used in these tests was No. 3, which is a two-part investment similar to No. 4. All casting tests were made under vacuum in order to have improved form filling at flask temperatures of 850°C (1562ºF) and 950°C (1742ºF). Alloys used were 95Pt5Co and 95Pt5Ru with details given in Table 7. For reasons of flask size and machine power, the tree was much smaller compared to the centrifugal casting trial, containing only two ball rings and some industrial samples.

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Table 7 List of tilting casting experiments with Indutherm MC15 machine

Trial no.

Alloy

Tree

Investment

Casting

Flask

Atmosphere

temp. [Cº]

temp. [Cº]

GPt035

95Pt5Ru

MC15

No. 3

1850

950

Vacuum

GPt036

95Pt5Ru

MC15

No. 3

1962

850

Vacuum

GPt037

95Pt5Ru

MC15

No. 3

1935

950

Vacuum

GPt038

95Pt5Co

MC15

No. 3

1928

950

Vacuum

GPt039

95Pt5Co

MC15

No. 3

1886

950

Vacuum

GPt040

95Pt5Co

MC15

No. 3

1954

850

Vacuum

5.1 Surface of cast parts

Figure 27 shows the surface of as-cast parts for both alloys and flask temperatures. The surfaces are smooth for both alloys and usually smoother than the centrifugal cast parts. With 95Pt5Ru a non-metallic, glassy surface layer formed around the ball, which shows large dendrites on the surface. The glassy layer seems to stem from melting of the investment materials around the ball. The 95Pt5Co ball ring has a smooth, clean surface without dendritic structure. SEM investigation of the surface showed smooth, slightly dendritic surface for both alloys (Figure 28). In the case of 95Pt5Ru, surface cracks along the grain boundaries are present, which formed during spontaneous cracking of the ring at room temperature. The 95Pt5Co ring shows no cracks but some residues of investment.

ring shows no cracks but some residues of investment. a) b) Figure 27 Tilting casting machine

a)

ring shows no cracks but some residues of investment. a) b) Figure 27 Tilting casting machine

b)

Figure 27 Tilting casting machine results; a) surface detail of 95Pt5Ru/950°C/vacuum; b) 95Pt5Co/950°C/vacuum

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a) b) Figure 28 SEM investigation of as-cast surface (tilting casting machine); a) 95Pt5Ru/950°C/vacuum; b)

a)

a) b) Figure 28 SEM investigation of as-cast surface (tilting casting machine); a) 95Pt5Ru/950°C/vacuum; b)

b)

Figure 28 SEM investigation of as-cast surface (tilting casting machine); a) 95Pt5Ru/950°C/vacuum; b) 95Pt5Co/950°C/vacuum

5.2 Metallographic Investigation

Metallographic cross sections along the ring’s plane are shown in Figure 29 for both alloys and flask temperatures. 95Pt5Ru shows similar form filling compared to centrifugal casting experiments, with scattered shrinkage holes in the ball and the sprue. No remarkable difference in porosity between 850°C (1562ºF) and 950°C (1742ºF) flask temperature was observed.

95Pt5Ru 850°C/ Vacuum Klotz
95Pt5Ru
850°C/
Vacuum
Klotz

950°C/

Vacuum

a)

observed. 95Pt5Ru 850°C/ Vacuum Klotz 950°C/ Vacuum a) c) 95Pt5Co b) d) Figure 29 Metallography of

c)

95Pt5Co

95Pt5Ru 850°C/ Vacuum Klotz 950°C/ Vacuum a) c) 95Pt5Co b) d) Figure 29 Metallography of as-cast

b)

850°C/ Vacuum Klotz 950°C/ Vacuum a) c) 95Pt5Co b) d) Figure 29 Metallography of as-cast part

d)

Figure 29 Metallography of as-cast part from tilting casting machine

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Klotz

At 950°C (1742ºF) the 95Pt5Ru shows several grain boundary cracks perpendicular to the ring shank (Figure 30), which are partially filled with Si-rich inclusions. This is a typical situation of hot tearing due to dissolution of Si from the investment and formation of a low melting eutectic 16 at the grain boundary. Cracking was induced by thermal stresses, occurring during devesting of the sample when the sample was already at room temperature. The fracture surface shows fully interdendritic, brittle fracture.

surface shows fully interdendritic, brittle fracture. a) b) Figure 30 Metallographic section through cracked

a)

surface shows fully interdendritic, brittle fracture. a) b) Figure 30 Metallographic section through cracked 95Pt5Ru

b)

Figure 30 Metallographic section through cracked 95Pt5Ru ball ring (950°C/vacuum); a) grain boundary crack; b) silicon-rich inclusion at grain boundary

With 95Pt5Co a large shrinkage hole was present close to the center of the ball at 850°C (1562ºF) flask temperature. Compared to centrifugal casting the pore is spherical and closer to the center because no centrifugal force was acting. Very good casting results were obtained with a flask temperature of 950°C (1742ºF). The ball ring is filled completely without any shrinkage pores. Cracks were not observed in any of the 95Pt5Co castings.

5.3 Summary

Casting results with a tilt casting machine were strongly dependent on alloy. 95Pt5Ru showed similar form filling compared to centrifugal casting but hot tearing due to long and intensive investment reactions because of longer process times and high metal temperature. 95Pt5Co showed perfect form filling and smooth surfaces for a flask temperature of 950°C. Form filling was better than with centrifugal casting. Whether the good form filling can be attributed to the different tree design or the applied overpressure remains open for discussion.

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6. Summary and Conclusions

Platinum alloys are a challenge for defect-free investment casting because of their inherent thermophysical properties, which are high melting point, high viscosity of the melt, high shrinkage during solidification, and low thermal conductivity compared to other precious metals alloys. In this experimental casting project numerous casting trials were conducted with a variation of:

• Casting parameters (melt and flask temperature, atmosphere, investment)

• Tree setup (position on tree, light- and heavyweight pattern)

• Casting machine (centrifugal and tilting machine)

• Platinum alloy (95Pt5Ru and 95Pt5Co)

The performance of alloys and investments was assessed qualitatively as shown in Tables 4, 5 and 6. The main results of the project are summarized as follows:

• Shrinkage porosity was the main issue for bulk, heavy patterns as well as for filigree, lightweight patterns, if directional solidification is not possible. The effect of casting parameters and the position on tree are relatively low. 95Pt5Co shows few but large pores while 95Pt5Ru often shows scattered pores built by intersecting dendrites. Investment material influences shrinkage porosity. For instance, lowest levels of shrinkage porosity were achieved for No. 4. This is probably an effect of thermal conductivity of the investment, which is assumed to be lower for two-part investments than for three-part investments.

• Form filling is a critical issue for filigree items. 95Pt5Co has superior form-filling ability over 95Pt5Ru. Form filling increases considerably with increasing centrifugal speed and flask temperature, which should be 950°C (1742ºF) for filigree items. Investment No. 4 showed best form filling for comparable casting parameters, probably because of the higher gas permeability of the investment. Vacuum casting and, in the case of 95Pt5Ru, overheating of the melt allowed complete filling of filigree items with three- part investments, while at the same time promoting investment reactions.

• The investments used require different working conditions. The two-part investments can be handled with a rubber base and cure quickly at room temperature, resulting in very short working time. In the case of centrifugal casting, No. 4 resulted in rougher surface of the as-cast parts. The three-part investments have sufficient working time but require furnace curing and therefore paper base and liner. Complete form filling was difficult with these investments unless working under vacuum or with overheated melt. The surface quality was usually superior over No. 4.

• Investment reactions were observed for 95Pt5Co independent of casting atmosphere and resulted in a blue layer of Co silicate. 95Pt5Ru did not show any investment reactions despite its considerably higher casting temperature.

• Alloy properties differ in dendrite morphology, segregation, and melting temperature, which is about 150°C (270ºF) higher for 95Pt5Ru. The phase diagrams give the same melting range of 18°C (32.4ºF) for both alloys, but due to segregation the melting range of 95Pt5Co is about twice that of 95Pt5Ru, which is probably the reason for the better form filling ability of

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95Pt5Co. Co segregates to the melt, promoting oxidation of Co and investment reactions, even for vacuum casting.

• A comparison of two types of casting machines, a centrifugal and a tilting machine, showed that form filling of filigree items was superior with centrifugal casting. Both machines provided comparable results for heavy items cast in 95Pt5Co alloy. Defect-free castings of the ball ring were obtained at 950°C (1742ºF)/vacuum, which was not possible by centrifugal casting under comparable conditions. 95Pt5Ru was difficult to cast in the tilting casting machine because of the low heating rate in the specific model used, which resulted in hot tearing of the parts. Machines with higher power and sufficiently short melting time may enable the successful casting of 95Pt5Ru also.

6.1 Recommendations for further work

In order to solve the main problem of shrinkage porosity, sprue design and tree setup are most important. Directional solidification has to be assured. Typical measures such as increase of flask temperature are limited by the thermal stability of the investment materials. However, optimization of casting behavior solely by experimental means remains challenging.

In recent years casting simulation proved to be a valuable tool for gold and silver casting. 19-23 Sophisticated software packages are available on the market to determine form filling and shrinkage porosity depending on alloy, tree setup, and melt and flask temperature, allowing optimization by computer simulation. In case of platinum this would pay off even more, because of high material price and extreme casting and flask temperatures.

Detailed knowledge of the thermophysical properties of alloys and investment is required and, as such data are scarce, they have to be determined in suitable experiments. Benchmark experiments with sophisticated thermal recording during the centrifugal casting process have to be performed to calibrate the casting simulation results. Investment materials were found to play an important role in form filling and shrinkage porosity. It is assumed that properties such as gas permeability and thermal conductivity are responsible for that behavior. Therefore, the influence of water:powder ratio, burnout cycle, flask temperature and casting atmosphere requires further investigation to understand how the physical properties of the investments can be tailored.

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ACKNOWLEDGMENTS

The authors are grateful for financial support by Platinum Guild International, with special thanks to Jurgen Maerz. C. Hafner GmbH, Germany enabled the project by providing platinum alloys, which is kindly acknowledged. The companies Ransom&Randolph, Lane Industries and Specialist Refractory Services (SRS) are acknowledged for allocation of investment materials and Indutherm GmbH, Germany for casting experiments with their MC15 casting machine. Special thanks to Dieter Ott for fruitful discussions of the project results and to the staff members of the metallurgy department at FEM, especially to Franz Held and Ulrike Schindler for casting trials and metallography.

REFERENCES

1. N. Swan, “Improvements in Platinum Casting,” Jewellery in Britain 19 (December 2004): 5-16.

2. N. Swan, “Casting Platinum Jewellery – A Challenging Process,” Platinum Metals Review 51, no. 2 (2007): 102.

3. G. Ainsley, A.A. Bourne and R.W.E. Rushforth, “Platinum Investment Casting Alloys,” Platinum Metals Review 22, no. 3 (1978): 78-87.

4. J. Huckle, “The Development of Platinum Alloys to Overcome Production Problems,” The Santa Fe Symposium on Jewelry Manufacturing Technology 1996, ed. Dave Schneller (Lafayette, CO: Met-Chem Research, 1996): 301-326.

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