Materials Characterization 49 (2003) 313 320

Characterization of powder injection molding feedstock

Z.Y. Liu, N.H. Loh*, S.B. Tor, K.A. Khor
School of Mechanical and Production Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore Received 1 February 2002; accepted 1 July 2002

Abstract Powder injection molding (PIM) is a cost-effective technique for producing small, complex, precision parts in high volumes. PIM consists of four main processing steps: mixing, injection molding, debinding and sintering. To reduce the design-to-manufacture cycle time for injection molding, simulation software could be used. To have a good understanding of the PIM process and to provide the necessary data for simulation, characterization of the material is essential. This paper presents the characterization of PIM feedstock consisting of 91 wt.% M2 high speed steel (HSS) powder and 9 wt.% PAN250 polymer binder. The mechanical properties (Youngs modulus, Poissons ratio, in-plane shear modulus), thermal properties (coefficient of thermal expansion (CTE), softening point, transition temperature, specific heat, thermal conductivity) and rheological property of the feedstock were established. The CTE of the molded feedstock in three perpendicular directions differed significantly. Except for the specific heat, the mechanical and thermal results showed that the feedstocks properties were generally closer to a polymer rather than a metal. Rheological results exhibited pseudoplastic or shear thinning flow behavior, where its viscosity decreased with increasing shear rate. The feedstock viscosity also decreased with increasing temperature and was found to be suitable for molding. D 2002 Published by Elsevier Science Inc.
Keywords: Powder injection molding; M2 high speed steel; Rheology; Simulation; Mechanical properties; Thermal properties

1. Introduction Powder injection molding (PIM) is cost effective for producing small, complex, precision parts in high volume. The PIM process developed from the traditional shape-making capability of plastic injection molding and the materials flexibility of powder metallurgy [1,2]. The process consists of four main steps: mixing, injection molding, debinding and sintering. In the mixing step, the powder is mixed with a

* Corresponding author. Tel.: +65-6790-5540; fax: +656791-1859. E-mail address: mnhloh@ntu.edu.sg (N.H. Loh).

binder, with a typical binder volume percentage of 35 50 vol.%, to form a homogeneous feedstock. The binder is a key component, which provides the powder with the flowability and formability necessary for molding [3]. After molding, the binder holds the particles in place. The binder is then removed in the debinding step. Various debinding methods have been used, for example, thermal decomposition and solvent debinding. The debound part is then sintered to give the required mechanical properties. The quality of the feedstock affects the quality of the molded and sintered parts. After the part has been molded to the required shape, there is little that can be done to remedy defects caused by inhomogeneous feedstock [4].

1044-5803/02/$ see front matter D 2002 Published by Elsevier Science Inc. doi:10.1016/S1044-5803(02)00282-6

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Although the PIM process offers many advantages, it requires extensive trial-and-error procedures to determine the proper molding condition [5]. Defects such as voids, sink marks, weld lines and density variations can result if the molding parameters and tool features are not properly specified. One efficient way to reduce the design-to-manufacture cycle time is through the use of computer-aided engineering (CAE) simulation. Such simulation could reduce the mold fabrication time, optimize mold design and molding parameters. For molding, there are many similarities between the flow and filling of polymer and metal powder. There are also unique differences such as higher thermal conductivity for PIM feedstock and apparent powder binder sliding phenomenon during mold filling. Because of the many similarities between molding polymer and metal powder, CAE simulation software used traditionally for plastic injection molding, such as CMOLD and MOLDFLOW, have also been used to simulate the PIM process. Simulation studies of PIM have been conducted by various researchers [5 8] to predict defect formation and property distribution such as weld lines, jetting, short shot, temperature distribution, cooling rates, and density. Information about the filling patterns and weld-line locations can be used as a tool to optimize the gate location and to achieve a better mold design [6]. Simulation analysis requires material property data to generate the best prediction. Obtaining reliable and accurate data is critical, as simulation results can only be as good as the input data used. In addition, the thermal and flow properties of the material have to be obtained over the processing temperature range. Until now, many relevant data do not exist or are widely scattered in the literature [9]. This paper presents the characterization of PIM

feedstock: mechanical and thermal properties, which will be useful for understanding the PIM process and for simulation purposes.

2. Experimental materials and procedure 2.1. Materials Water-atomized M2 high speed steel (HSS) powders were used in the present research [10]. The powders were largely spherical in shape. The average density of five powder samples measured using a Quantachrome Ultrapycnometer was 8.02 g/cm3. The mean particle size measured by a Fritsch Particle Sizer Analysette 22 was 10.5 mm and the particle size distribution curve is displayed in Fig. 1. The multicomponent polymer binder used was PAN250 [10] from Adeka Fine Chemicals, Japan. Some of the binder components were natural wax, fatty acid wax, stearic acid, poly-oxi-alkylen ether and olefin-hydrocarbons. The average density of the binder as measured by a Quantachrome Ultrapycnometer was 1.026 g/cm3. 2.2. Preparation of specimens A Linden sigma blade mixer was used for mixing the powder and binder. The mixing temperature was set at 95 C. The total mixing time was 100 min and the rotational speed of the blade was 30 rpm. A powder loading of 91 wt.% (or 56.4 vol.%) was used and the feedstock density was 4.975 g/cm3. In order to characterize the mechanical and thermal properties, the feedstock was molded into tensile bars and 30 mm diameter discs with a Battenfeld BA 250 CDC injection-molding machine. In order to

Fig. 1. Particle size distribution of M2 HSS powders.

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Fig. 2. Tensile curves.

obtain defect-free molded parts, a suitable set of molding parameters were established and a Fein focus X-ray microscope was used to scan for internal defects such as cracks and voids. This was to ensure that only defect-free molded parts were used for subsequent characterization. 2.3. Mechanical properties 2.3.1. Youngs modulus The Youngs modulus of the feedstock influences molding and part distortion. The modulus value depends on the binder composition and powder loading. Tensile tests were performed on an Instron tester 5566 with a 10-kN capacity. Six tests were conducted. The tensile curves are shown in Fig. 2 and the results are summarized in Table 1. The average Youngs modulus was 0.82 GPa. This is much lower than the 190 210 GPa for steel [11] but within the 0.01 10 GPa for polymer [12] as shown in Table 2. Also, a low tensile strain at break, about 1% was recorded, indicating that the tensile bars are very brittle. The tensile bars have a relatively low ultimate tensile strength (UTS), ranging from 3.61 to 4.25 MPa, giving an average of 4.00 MPa. The average yield stress as determined by 0.2% strain offset was 3.53 MPa. This is much lower than the 200 2000 MPa listed for steel [11].
Table 1 Mechanical properties of molded parts Mechanical properties Average Youngs modulus (GPa) 0.82 Ultimate tensile stress (MPa) 4.00 Yield stress (MPa) 3.53

2.3.2. Poissons ratio Poissons ratio is defined as the absolute value of the ratio of transverse strain to the corresponding axial strain, resulting from uniformly distributed axial stress below the proportional limit of the material. Five tensile tests were performed with strain gages specially mounted on the gage sections of each tensile bar prior to testing. Axial strain is the linear strain in a plane parallel to the longitudinal axis of the tensile bar while transverse strain is the linear strain in a plane perpendicular to the axis of the tensile bar. The longitudinal and transverse strains (in the elastic region) were sensed by the strain gages and recorded by a data logger. The calculated Poissons ratio ranged from 0.37 to 0.42, giving an average of 0.40. 2.3.3. In-plane shear modulus The in-plane shear modulus ( G) is defined as the ratio of the shear stress (t) to the shear strain (g). It was calculated using the following formula: G t E g 21 n 1

where E is Youngs modulus and n is Poissons ratio.

Table 2 Comparison of mechanical properties Mechanical properties Youngs modulus (GPa) Poissons ratio In plane shear modulus (GPa) PIM feedstock 0.82 0.40 0.29 Steel [11] 190 210 0.27 0.3 75 80 Polymer [12] 0.01 10 0.45 0.5 0.003 3.33

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Fig. 3. DMA curve.

For the feedstock, the average E is 0.82 GPa and the average n is 0.40. Thus, the in-plane shear modulus is 0.29 GPa. From Table 2, it can be seen that the mechanical properties of the feedstock are closer to a polymer. 2.4. Thermal properties 2.4.1. Coefficient of thermal expansion (CTE) and softening point The CTE is a measure of the amount by which a unit length of the material will expand when the temperature rises by 1 C. The softening point can be viewed as the temperature at which the feedstock softens rapidly. This provides a qualitative measure of the temperature resistance of a material. CTE is an important parameter used to decide on the mold cavitys dimension whereas the softening point serves as a guideline for establishing the molding temperature. To obtain the CTE and softening point of the feedstock, a Perkin-Elmer DMA-7 system was used. Rectangular specimens were cut from the gage section of the tensile bar. The cut surface was ground with sandpaper to achieve good flatness. The specimens were cut from three directions of the tensile bar: 1. longitudinal (along the longitudinal axis of the tensile bar) 2. transverse (along the width of the tensile bar) 3. thickness (along the thickness of the tensile bar). The tests were conducted in nitrogen gas, in the temperature range of 10 to 80 C, with a heating rate

of 5 C/min. A sample DMA graph is displayed in Fig. 3. Fig. 3 shows an increase in the probe position at the beginning of the test. This is due to the expansion of the solid specimen. The CTE can be obtained by taking the slope of the initial curve ranging from 20 to 40 C. The slope of the curve is also observed to increase as the temperature increases. This is caused by the fact that the multicomponent polymer binder exhibits typical polymer thermal property where the CTE increases with temperature. As the specimen is being heated up to 49.5 C, at the maximum probe position, the curve drops suddenly indicating that softening of the specimen has occurred. By taking the interception of the two slopes of the curve after the maximum probe position, the softening point was obtained. The average results of three specimens for each of the three test directions are summarized in Table 3. Table 3 shows that there is slight deviation in the CTE values tested in the transverse and the thickness direction. However, more than 10% deviation between the CTE value tested in the longitudinal direction and the other two directions is noted. As the

Table 3 Thermal properties of molded parts Longitudinal Average CTE (10 6/C) Overall average Average softening point (C) Overall average 76.6978 Transverse 88.7733 83.969 72.083 71.902 Thickness 86.4380

71.461

72.162

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longitudinal direction is the direction of feedstock filling during mold filling, it has more metallic powder and less polymeric binder. The CTE of the metal powder is less than that of the polymer; therefore, the powder-rich longitudinal direction has a lower CTE. The CTE of the feedstock is within the general range for a polymer. 2.4.2. Transition temperature The transition temperature for the molded feedstock can be treated as the temperature corresponding to the maximum heat absorption of the feedstock. The transition temperature is valuable for PIM in providing the general mixing and molding limiting temperatures. Mixing and molding temperatures must be higher than the transition temperature. Differential scanning calorimetry (DSC) tests on molded 30-mm diameter discs were conducted with a Perkin-Elmer Differential Scanning Calorimeter-7 for determining the transition temperature. The tested temperature range was 0 to 120 C. The heating rate was 5 C/min. The nitrogen gas flowrate was 20 ml/min. The DSC curve is illustrated in Fig. 4. The feedstock containing 9 wt.% binder showed two heat flow peaks at about 54.17 and 91.64 C during heating up, indicating the melting points of the binder components. The lowest recrystallization temperature is 32.82 C. Mixing and molding must be accomplished at a temperature higher than the major melting point of the binder, that is above 91.64 C. On the other hand, the mold temperature must be below 32.82 C to prevent the molded part from sticking to the mold cavity.

2.4.3. Specific heat capacity The specific heat Cp of the feedstock determines the amount of heat that can be stored in the feedstock during the heating up process and additional heat due to internal friction in the barrel. A NETSCH DSC 404 differential scanning calorimeter was used to obtain the Cp of the feedstock over a range of temperature. The specimens were tested under nitrogen gas flow of 150 ml/min, at a temperature range of 30 to 120 C and a heating rate of 5 C/min. A reference sapphire standard specimen was used. In the test, Cp was calculated based on the equation: Cpt Cpr mr Sbt Sb mt Sbr Sb 2

where Cpt is mean specific heat of the test specimen, Cpr is mean specific heat of the reference piece, mt is the mass of the test piece, mr is the mass of the reference piece, Sb is the output signal of the base line, Sb + r is the output signal of the base line and the reference sample, and Sb + t is the output signal of the base line and test piece. A sample plot of the Cp curve is shown in Fig. 5. Table 4 summarizes the average Cp values of four specimens at five different temperatures, from 30 to 110 C. Low specific heat will result in a faster drop in the melt temperature during molding and accelerate the solidification process. This has grave consequences for the cooling phenomena during molding. The specific heat of the feedstock is close to that of a metal but lower than that of a polymer.

Fig. 4. DSC curve.

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Fig. 5. Specific heat capacity curve.

2.4.4. Thermal conductivity () Thermal conductivity is a measure of the rate at which heat will flow through the material. The magnitude of the thermal conductivity of a given substance depends on its microscopic structure and tends to vary somewhat with temperature. The thermal conductivity is calculated using the following formula: l a Cp r 3

time (t0.5). The difffusivity was calculated using the following formula: a 1:37L2 p2 t0:5 4

where l is the thermal conductivity in W/m C, a is the thermal diffusivity in m2/s, Cp is the specific heat capacity in J/kg C, and r is the density in kg/ m3 . The apparatus used to detect the thermal diffusivity is a NETZSCH Laser Flash Analyzer 427. The test piece was cut from the 30-mm diameter disc to 12.7mm diameter. The thickness was about 3 mm. Testing was carried out at room temperature. During the test, thermal diffusivity was measured by applying a high intensity, short duration heat pulse to one face of a parallel-sided homogeneous test pieces, monitoring the rise in temperature at the opposite side as a function of time, and calculating the transient half

where a is the diffusivity in m2/s, L is the thickness of the test piece in m, t0.5 is the time from the initial of the pulse until the rear face of the piece reaches half of its maximum temperature, in s. The diffusivity of the feedstock was found to be 4.38 10 7 m2/s. Using Eq. (3), together with the calculated feedstock density and specific heat capacity, the feedstock thermal conductivity was 1.375 W/m C. Table 5 summarizes the thermal properties of the feedstock together with the general thermal properties

Table 5 Comparison of thermal properties of molded parts Thermal properties Coefficient of linear thermal expansion (10 6/C) Softening point (C) Transition temperature (C) Specific heat capacity (J/g C) Thermal conductivity (W/m C) PIM feedstock 83.97 Steel [11] 10 18 Polymer [11] 50 600

71.90 53.92

1680 1800

40 150 0 150

Table 4 Average specific heat capacity of molded parts at various temperatures Temperature 30 C 50 C 70 C 90 C 110 C

0.4054

0.49 0.53

1.05 2.5

Average specific 0.4054 0.5653 0.5870 0.4853 0.4046 heat capacity (J/g C)

1.375

12 30

0.1 0.35

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Fig. 6. Rheological property of feedstock.

of steel and polymer [11]. It can be seen that, except for specific heat, all the thermal properties of the feedstock are closer to the polymer. 2.5. Rheological characterization In PIM, the rheological properties are important for the injection molding step as it concerns the flow of the feedstock during injection molding. Rheological analysis can be used to quantify the stability of the feedstock during the molding process [13,14]. The viscosity of the powder binder mixture is very sensitive to temperature and powder loading (amount of powder). At low temperatures, the mixture viscosity may be too high for molding. At high temperatures, the binder may be too thin, resulting in powder binder separation during molding. Besides, the binder may undergo degradation with substantial thermal stresses in the molded parts resulting in cracking. Hence, there is a range of conditions over which PIM processing is most viable. In this range, the mixture exhibits pseudoplastic flow where the viscosity decreases with increasing shear rate and this can help to reduce the required temperature and pressure for successful molding [1,15]. Pseudoplastic flow behavior eases mold filling, minimize jetting and help to retain the shape of the molded part. Generally, high packing density is desired. It is well established that viscosity varies with the relative powder loading. In the PIM process, the shear rate during molding usually ranges between 100 and 10 000 s 1. In this shear rate range, empirical studies have shown that the maximum viscosity for molding is 1000 Pas at the molding temperature [1]. The capillary rheometer test has been utilized widely in order to characterize the rheological behavior of PIM feedstock [14,16,17]. The equipment used in this study was a Shimadzu CFT-500C

Capillary Rheometer. During the capillary rheometer tests, the feedstock was forcibly extruded through a small cylindrical orifice with a 1.0-mm diameter and 10-mm length (L/D = 10). The tests were conducted at 80, 90 and 100 C. The rheological results of the feedstock are displayed in Fig. 6. The feedstocks viscosity decreases with increasing shear rate and this behavior is generally called non-Newtonian. In more precise terms, they can be termed as pseudoplastic or shear thinning. Their viscosity is also observed to be temperature sensitive. As temperature increases, there is noticeable decrease in the feedstocks viscosity. This phenomenon is mainly due to (a) a decrease in the powder volume caused by the larger expansion of the binder when heat is introduced; and, (b) disentanglement of the molecular chain when more heat is distributed to fluctuate the random molecular structure [1]. With a shear rate varying from 100 to 10 000 s 1, the viscosity of the feedstock falls below 1000 Pa s. Thus, the feedstock is suitable for injection molding.

3. Conclusions A summary of the feedstock and molded part characterization is shown in Table 6. The CTE of the molded feedstock in three perpendicular directions differed significantly. Except for the specific heat, the mechanical and thermal test results showed that the molded parts and feedstock properties are much closer to polymer than metal. The feedstock exhibits pseudoplastic or shear thinning flow behavior. The viscosity decreases with increasing shear rate and increasing temperature. As the viscosities are below 1000 Pa s at temperatures of 80, 90 and 100 C, the feedstock is suitable for molding.

Table 6 Summary of characterization Value Mechanical properties 1. Youngs modulus (GPa) 2. Poissons ratio 3. In plane shear modulus (GPa) Thermal properties 1. Coefficient of linear thermal expansion (10 6/C) 2. Softening point (C) 3. Transition temperature (C) 4. Specific heat capacity (J/g C) 5. Thermal conductivity (W/m C) 0.82 0.40 0.29

83.97 71.90 53.92 0.4054 0.5870 1.375

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Acknowledgments The authors would like to thank the Nanyang Technological University for awarding a research grant to conduct this research and ADEKA Fine Chemicals (Japan) for supplying the binder. The authors would also like to thank Mr. Lew Wei Keat for technical assistance.
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