Natural and Synthetic Graphite Powders for PM: Comparison of Graphite Properties and Effect on Final Parts

Authors: G. Juri, S. Zuercher, N. Probst and M. Coluccia - Timcal Graphite and Carbon, Via Industria, CH-6743 Bodio, Switzerland

Abstract
Graphite powder is a key additive in PM formulations, but depending on the grade used its properties can vary quite a lot, leading to different effects on the final PM parts. For instance for the production of hard metals high purity is a key property, whereas for structural PM parts lower purity grades can also be used, with dimensional stability, compactability and lubrication being the key issues. Timcal Graphite and Carbon offers a broad range of TIMREX powders for PM, from natural graphite (NG) grades, like E-PG10 and PG25, to primary synthetic graphite (PSG) grades, like F10 and E-F25. An extensive survey of graphite properties was made on the existing products. The above-mentioned grades have been compared in terms of purity, density, compactability, particle shape, crystallinity, etc. The same results are also presented for two commercially available NG grades widely used in the PM industry. Experimental data from a PM test program carried out at an external lab will be shown and discussed with the aim of establishing correlations between properties of graphite and PM parts.

Graphite Powders for PM: Key Properties and Morphology

Key Properties
The property summary includes data on natural graphite grades, like E-PG10 , PG25, and on primary synthetic grades, like F10 and E-F25. For comparison, data on two typical natural graphite grades used in PM are also shown. They are denominated with N96/25 and N96/10, based on their carbon content and their PSD (d90). All analysis is made on powder samples in loose or compact form, but without addition of binders or additives.
Graphite Powders for PM: Summary of Properties
Ash (810C) Xylene density Lc c/2 d10 d50 d90 BET Oil adsorp. Scott Springdensity back PD* @0.47 t/cm2 PD* @2.5 t/cm2 El. resist. XY Bend. strgth.

Grades E-PG10 N96/10 F10 PG25 N96/25 E-F25

(%wt) 3.445 3.349 0.028 3.524 4.313 0.032

(g/cm3) 2.280 2.268 2.253 2.270 2.279 2.255

(nm) 162 117 91 227 234 167

(nm) 0.3357 0.3357 0.3359 0.3356 0.3356 0.3357

(m) 2.8 2.0 2.1 4.3 3.4 4.2

(m) 6.3 5.5 5.2 9.8 9.1 11.8

(m) 12.2 11.8 10.6 19.3 21.0 26.4

(m2/g) 9.6 13.9 15.0 6.6 7.0 8.6

(%wt) 165.8 123.8 141.9 163.2 136.0 136.0

(g/cm3) 0.096 0.125 0.090 0.077 0.132 0.126

(%) 9.3 7.4 13.7 8.5 8.8 14.2

(g/cm3) (g/cm3) (m.cm) (N/mm2) 1.704 1.684 1.621 1.776 1.897 1.686 1.968 1.969 1.865 2.014 2.001 1.907 1.54 1.80 1.98 1.23 1.73 1.52 9.2 12.3 8.2 8.5 9.1 5.3

* Pressed density

Table 1 Analysis results on different graphite grades for PM

Powders properties: ash, BET, PSD and Scott

30 25
(%, m2/g, m)

0.150

Powder properties: springback, pressed density and crystallinity

Ash (810C) d90
(g/cm3)
(%, nm) (g/cm3) 100 1.700 1000 2.000
30

Powder properties: pressed density, bending strength and el. resistivity

Bend. strgth. PD @2.5 t/cm2 El. resist. XY

2.100

20 15 10 5 0 E-PG10 N96/10 F10 N96/25 E-F25 PG25

0.100

BET

0.050 Scott density 0.000

10 Springback 1 N96/25 E-F25 F10 PG25 E-PG10 N96/10 Lc PD @0.47 t/cm2

1.400

(N/mm2)

20

1.800

10 0

1.500

1.100

1.200

N96/25

E-PG10

Fig. 1 Analysis of ash, surface area (BET), particle size distribution (d90 by laser diffraction) and apparent density (Scott). Scott density is plotted on the right axis.

Fig. 2 - Analysis results of springback, pressed density at 0.47 t/cm2 and crystallinity by XRD. Pressed density is plotted on the right axis.

Fig. 3 - Results of pressed density, electrical resistivity and bending strength. Pressed density and el. resistivity are plotted on the right axis.

Typical ash content of synthetic graphite grades is very low in comparison to natural graphite grades. BET increases with finer PSD, but is also related to the surface structure of grains (see F-grades vs PG-grades). Scott density increases with d90: differences at same PSD indicate different shape and/or surface structure of particles, mainly due to processing or source (see N96/10). Grain shape-surface texture: the oil adsorption data of Table 1 contribute to highlight such features in combination with BET, Scott density, PSD and SEM imaging (see next Section).

Crystallinity: Lc values are reduced by fine milling, as can be seen from data on 10 and 25 micron grades. Lc of TIMREX F-grades is lower, but still comparable to NG grades, confirming high graphitization degree. Lower crystallinity of F-grades implies higher reactivity, i.e. higher carbon diffusion at lower temperature. At same PSD, springback increases for decreasing Lc, i.e. synthetics have slightly higher springback. F-grades show low and very stable values of springback, allowing quick ejection of green parts and good dimensional control.

Pressed density of compacts is higher for NGs than for PSGs due to lower springback. For NGs pressed density increases slightly with d90. El. resistivity of powder compacts is correlated to crystallinity, particle size and shape, but also to final density of samples (100% graphite). The same is valid for the bending strength. For these reasons, NG samples show lower resistivity and higher strength.

Morphology
SEM pictures of TIMREX E-F25, PG25 and N96/25, from left to right SEM pictures of TIMREX E-PG10 and F10, from left to right

Fig. 4

N96/10

E-F25

F10

PG25

Fig. 5

Fig. 4 and 5 show typical examples of SEM pictures of graphite grades. It is very well known that a powder grade includes a wide distribution of particle size and shapes, so only some generic comments can be made. Fig. 4 shows SEM pictures of three 25 m grades. The flaky shape, typical of high-crystallinity natural graphite grades, is clearly visible, both for TIMREX PG25 and for the competitor grade N96/25. E-F25 shows a slightly less flaky grain shape, so some irregular, thicker platelets are also present in the powder. In Fig. 5 the two TIMREX F10 and E-PG10 are shown. At such fine PSD the effect of milling (energy) is very big and the difference due to the raw materials become smaller. Therefore, also the synthetic grade shows to a good extent the typical fingerprintof NG, i.e. flaky grains with sharp edges and corners.

(g/cm3, m.cm)

Powder Metallurgy Data

Test Parameters
Test were carried out according to MPIF procedures with different graphite grades. Powder Mixes: F-0008: 98.40% Ancorsteel 1000B, 0.80% Graphite and 0.80% Acrawax C FC-0208: 96.40% Ancorsteel 1000B, 2.00% 165 Copper, 0.80% Graphite and 0.80% Acrawax C FN-0208: 96.40% Ancorsteel 1000B, 2.00% 123 Nickel, 0.80% Graphite and 0.80% Acrawax C Evaluation of samples-results: Six standard TRS bars molded at nominal 6.6, 6.9, and 7.08 g/cm3 density. The pressing done in a 120K Universal Testing Machine. Sintering in a production continuous belt four-zone furnace. The temperature settings was 1200F, 1400F, 2050F, and 2050F with 97% N2 - 3% H2. Sintering time approx. 20-25 minutes.

Green properties
Springback of green from die for F-0008 mix
0.25

Comments
Carney apparent density and flow rate: no significant difference between the grades. Green density: all values within narrow range. Springback from die: low values favour ejection of green parts during production. Fig. 6 shows data for the F-0008 mix at 3 target density levels. Key points: - natural graphite shows the lowest values compared to synthetic, confirming the basic correlation existing with springback of graphite powders (see Table 1 and Fig. 2) - TIMREX PG25 and E-PG10 show the lowest values at all density levels. Green strength: green strength increases with target density for all mixes, but no correlation could be found between green strength and sintered properties for specific graphite grades.

% of Die Size

0.20

0.15

0.10 N25 F10 0.05 6.6 6.9 7.08 PG25 E-PG10 E-F25 N96/10

Fig. 6 Springback of green from die for F-0008 mix (at 3 density levels) with different graphite powders.

Sintered properties
Sintered Density - Mix FC-0208
PG25 N96/25 E-PG10 N96/10 F10 E-F25

Conclusions
Sintered DC from Die - Mix FC-0208
PG25 0.60 0.50 0.40 % 0.30 N96/25 E-PG10 N96/10 F10 E-F25

7.10 7.00 6.90

(g/cm3)

6.80 6.70 6.60 6.50 6.40 6.6 6.9 7.08

0.20 0.10 0.00 6.6 6.9 7.08

Commercial grade N96/10 shows the lowest values of most sintered properties, whereas N99/10 from the same supplier showed results in the top range. TIMREX E-PG10 gives results in the upper range, indicating that, beside ash content, some other factor is relevant for the performance of N96/10. The analysis results on the graphite powder (BET, Scott, etc) indicate a difference in shape and/or surface texture compared to E-PG10, most probably due to a different processing technique. The data presented here confirm again that PG25 is equivalent to N96/25 in view of all relevant properties for typical PM parts. The results on the high-purity grades F10 and E-F25 show again, that they are especially suitable for high-density applications, where they allow to reach high strength and hardness. It is known from previous test, that the high carbon content and the high reactivity of Fgrades lead to PM parts, characterized by small values of DC with a very high reproducibility, not achievable with NG grades.

Fig. 7 Sintered density of test samples made by FC-0208 mix with different graphite grades.

Fig. 8 Dimensional change from die (DC) of sintered parts made by FC-0208 mix with different graphite grades.

Key points:
TIMREX E-PG10 gives the highest value of density. For the coarser grade PG25 the value is slightly lower. Effect of PSD: also for the synthetic grades F10 and E-F25 the finer grade gives slightly higher density. Commercial grades N96/25 and N96/10 give the lowest density. Carbon diffusion: it is known that synthetic grades allow faster C-diffusion at lower temperature. In FC-type powder mixes, this would limit to some extent the negative effects of Cu-melting.

Key points:
TIMREX PG25 is essentially equivalent the commercial grade N96/25, together with TIMREX E-PG10. Synthetic grades F10 and E-F25 show values similar to the NG grades, although the springback of the synthetic graphite powders is clearly higher (see Table 1 and Fig. 2). The commercial grade N96/10 shows the highest values of dimensional change. A 2nd grade with higher %C (N99/10) from the same supplier, gives results equivalent to F10 or E-PG10 (data not shown).

Sintered TRS - Mix FC-0208

PG25 F10 N96/25 E-F25 E-PG10 N99/10 N96/10

Sintered Hardness HRBw - Mix FC-0208

PG25 F10 N96/25 E-F25 E-PG10 N99/10 N96/10

180 160 140

(ksi)
(HRBw)

90

80

70

120
60

100 80 6.6 6.9 7.08

50 6.6 6.9 7.08

Fig. 9 Transverse Rupture Strength (TRS) of sintered parts made by FC-0208 mix with different graphite grades.

Fig. 10 - Hardness HRBw of sintered parts made by FC-0208 mix with different graphite grades.

Contact address: TIMCAL SA Dr. Giovanni Juri CH-6743 Bodio TI Switzerland

Tel.: +41 91 873 2010 Fax: +41 91 873 2009 e-mail: g.juri@timcal.com

Key points:
Finer grades yield better strength, esp. at high density. TIMREX E-PG10 has the highest strength at low and medium density. N99/10 shows similar values. TIMREX PG25 is at the same level as N96/25, whereas N96/10 gives the lowest values. Synthetic TIMREX F10 and E-F25 give high strength, especially at high density.

Key points:
Finer graphite grades produce harder materials. TIMREX F10 shows the biggest hardness at high density. Synthetic TIMREX E-F25 yield high values of hardness, at all density levels. TIMREX PG25 is at the same level as N96/25, whereas N96/10 gives the lowest values.

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