# Patent

## Title
Lubricant for powder metallurgical compositions

## Abstract

An iron-based powder metallurgical composition is provided comprising an iron or iron-based powder and a particulate composite lubricant, the composite lubricant comprising particles having a core comprising a solid organic lubricant having fine carbon particles adhered thereon. A particulate composite lubricant and a method for producing the same also are provided.

## Background
This is a 35 U.S.C. §371 filing of International Patent Application No. PCT/SE2006/001384, filed Dec. 6, 2006. The benefit is claimed under 35 U.S. §119(a)-(d) of Swedish Application No. 0502934-3, filed Dec. 30, 2005, and under 35 U.S.C. §119(e) of U.S. Provisional Application No. 60/754,672, filed Dec. 30, 2005.


The present invention relates to a powder metallurgical composition. Specifically, the invention relates to a powder metal composition comprising a new particulate composite lubricant. The invention further relates to the new particulate composite lubricant as well as a method of preparing this lubricant.
In the Powder Metallurgy industry (PM industry) powdered metals, most often iron-based, are used for production of components. The production process involves compaction of a powder metal blend in a die to form a green compact, ejecting the compact from the die and sintering the green compact at temperatures and under such conditions that a sintered compact having sufficient strength is produced. By using the PM production route costly machining and material losses can be avoided compared to conventional machining of components from solid metals as net shape or nearly net shape components can be produced. The PM production route is most suitable for the production of small and fairly intricate parts such as gears.
In order to facilitate the production of PM parts lubricants may be added to the iron-based powder before compaction. By using lubricants the internal frictions between the individual metal particles during the compaction step are reduced. Another reason for adding lubricant is that the ejection force and the total energy needed in order to eject the green part from the die after compaction are reduced. Insufficient lubrication will result in wear and scuffing at the die during the ejection of the green compact.
The problem with insufficient lubrication can be solved mainly in two ways, either by increasing the amount of lubricant or by selecting more efficient lubricants. By increasing the amount of lubricant, an undesired side effect is however encountered in that the gain in density through better lubrication is reversed by the increased amount of the lubricants.
A better choice would then be to select more efficient lubricants. This is however a problem as compounds having good lubricity in PM context tends to agglomerate during storage or contributes to agglomerate formation in the powder metallurgical composition, a consequence of which is that the subsequently compacted and sintered component may include comparatively large pores which have a detrimental effect of the static and dynamic mechanical properties of the component. Another problem is that lubricants having good lubrication properties often have negative effects on the so-called powder properties, such as flow rate and apparent density (AD). The flow rate is important because of its impact on the die filling which in turn is important for the production rate of the PM parts. A high AD is important in order to enable shorter filling depths and even AD is important in order to avoid variations in dimensions and weight of the finished components. It is thus desirable to obtain a new lubricant for powder metal compositions that overcomes or reduces the above mentioned problems.
OBJECTS OF THE INVENTION
An object of the present invention is therefore to provide a lubricant having good lubrication properties but no or reduced tendency to agglomerate.
Another object of the present invention is to provide a lubricant having good lubrication properties and yet imparting flow or improved flow properties when it is used in an iron or iron-based powder composition.
Another object is to provide a new iron or iron-based powder composition which includes the new lubricant and which has good flow properties and a high and even apparent density.
Still another object is to provide a process for producing a lubricant.
SUMMARY OF THE INVENTION
According to the invention it has now unexpectedly been found that the above objects can be met by an iron-based powder metallurgical composition comprising an iron or iron-based powder and a new particulate composite lubricant, said composite lubricant comprising particles having a core comprising a solid organic lubricant having fine carbon particles adhered thereon.
The invention also concerns the particulate composite lubricant per se as well as the preparation thereof.


DETAILED DESCRIPTION OF THE INVENTION
The type of solid organic lubricant of the composite lubricant according to the invention is not critical, but due to the disadvantages with metal-organic lubricants, the organic lubricant should preferably not include metal constituents. Thus the organic lubricant may be selected from a wide variety of organic substances having good lubricating properties. Examples of such substances are fatty acids, waxes, polymers, or derivates and mixtures thereof.
Preferred solid organic lubricants are fatty acids selected from the group consisting of palmitic acid stearic acid, behenic acid and; fatty acid monoamides selected from the group consisting of palmitamide, stearamide, behenamide, oleamide and erucamide, fatty acid bisamides, such as ethylene bisstearamide (EBS), ethylene bisoleamide (EBO), polyethylene, polyethylene wax; secondary fatty acid amides selected from the group consisting of erucyl stearamide, oleyl palmitamide, stearyl erucamide, stearyl oleamide, stearyl stearamide, oleyl stearamide.
Especially preferred solid organic lubricants are stearamide, erucamide, stearyl oleamide, erucyl stearamide, stearyl erucamide, EBO, EBS, and EBS in combination with oleamide, erucamide, stearyl oleamide stearyl erucamide or erucyl stearamide. Presently available results indicate that powder metal compositions comprising these composite lubricants according to the invention are distinguished by especially high apparent densities and/or flow rates. Additionally these lubricants are known for their excellent lubricating properties.
The average particle size of the organic core particles may be 0.5-100 μm, preferably 1-50 μm and most preferably 5-40 μm. Furthermore it is preferred that the particle size of the core is at least five times the particle size of the carbon particles and it is preferred that the fine carbon particles form a coating on the core surface.
In this context the term “fine carbon particles” is intended to mean crystalline, semi-crystalline or amorphous carbon particles. The fine carbon particles may originate from natural or synthetic graphite, carbon black, activated carbon, coal and anthracite etc and may also be a mixture of two or more of these. The fine carbon particles adhered onto the surface of the solid organic lubricant core may preferably be selected from the group consisting of carbon black and natural or synthetic graphite, having an average particle size of less than 10 μm and larger than 5 nm.
The primary particle size of the carbon black may be less than 200 nm, preferably less than 100 nm, and most preferably less than 50 nm and larger than 5 nm. The specific surface area may be between 20 and 1000 m2/g as measured by the BET-method. Carbon black may be obtained from a supplier such as Degussa AG, Germany. The content of carbon black in the composite lubricant may be 0.1-25% by weight, preferably 0.2-6% by weight and most preferably 0.5-4% by weight.
The average particle size of the graphite may be less than 10 μm and larger than 500 nm. The content of graphite in the composite lubricant may be 0.1-25% by weight, preferably 0.5-10% by weight and most preferably 1-7% by weight. Graphite may be obtained from a supplier such as Graphit Kropfmühl AG, Germany or a synthetic graphite with an ultra-high surface area from Asbury Carbons, USA.
The content of the composite lubricant in the powder metal composition may be 0.05-2% by weight.
The particulate composite lubricant according to the invention may be prepared by ordinary particle coating technique involving mixing an organic particulate lubricating material and fine carbon particles. The method may further comprise a heating step. The temperature for the heat-treatment may be below the melting point of the solid particulate organic lubricant.
The particulate solid organic lubricant may be thoroughly mixed with the fine carbon particles in a mixer. The mixer may be a high-speed mixer. The mixture may be heated during mixing at a temperature and during a time period sufficient to let the fine carbon particles adhere to the surface of the particulate organic lubricating material during a subsequently followed optional cooling step.
The iron-based powder may be a pre-alloyed iron-based powder or an iron-based powder having the alloying elements diffusion-bonded to the iron-particles. The iron-based powder may also be a mixture of essentially pure iron powder or pre-alloyed iron-based powder and alloying elements selected from the group consisting of Ni, Cu, Cr, Mo, Mn, P, Si, V, Nb, Ti, W and graphite. Carbon in the form of graphite is an alloying element used to a large extent in order to give sufficient mechanical properties to the finished sintered components. By adding carbon as an individual constituent to the iron-based powder composition the dissolved carbon content of the iron-based powder may be kept low enhancing improved compressibility. The iron-based powder may be an atomized powder, such as a water atomized powder, or a sponge iron powder. The particle size of the iron-based powder is selected depending on the final use of the material. The particles of the iron or iron-based powder may have a weight average particle size of up to about 500 μm, more preferably the particles may have a weight average particle size in the range of 25-150 μm, and most preferably 40-100 μm.
The powder metal composition may further comprise one or more additives selected from the group consisting of binders, processing aids, hard phases, machinability enhancing agents if there is a need of machining of the sintered component, and solid lubricants conventionally used in PM-industry such as EBS, zinc-stearate and Kenolube® available from Höganäs AB. The concentration of the powdered composite lubricant according to the invention plus optional solid lubricants may be in the range of 0.05 to 2% of a powder metal composition.
The new iron or iron-based powder composition may be compacted and optionally sintered by conventional PM techniques.
The following examples serve to illustrate the invention but the scope of the invention should not be limited thereto.
EXAMPLES
Materials
The following materials were used.


    
    
        (1) As iron-based water atomized powder (ASC100.29, available from Höganäs AB, Sweden) was used.
        (2) As lubricating core materials the following substances were used; ethylene bis-stearamide (EBS) available as LicowaxTM from Clariant (Germany), stearamide, erucamide, oleyl palmitamide, stearyl oleylamide, erucyl stearamide, stearyl erucamide, ethylene bis-oleamide (EBO) and polyethylene waxes. The average particle sizes of the lubricants can be seen in Table 2.
        (3) Graphite UF-4 (from Graphit Kropfmühl AG, Germany) was used as added graphite in the iron-based powder composition.
        (4) Coating particles were Graphite UF-1 (UF1) (from Graphit Kropfmühl AG, Germany) and Graphite 4827 (4827) (from Asbury Carbons, USA) having an average particle size of 2 μm and 1.7 μm respectively, and Carbon black (CB) (from Degussa AG, Germany) having a primary particle size of 30 nm.
    
    


The iron-based powder compositions consisted of ASC100.29 mixed with 0.5% by weight of graphite and 0.8% by weight of composite lubricant.
Different composite lubricants were prepared by mixing core material according to Table 1 and 2 with fine carbon particles at different concentrations in a high-speed mixer from Hosokawa. Carbon black was added at the concentrations of 0.75, 1.5, 3 and 4% by weight, respectively. Graphite was added at the concentrations of 1.5, 3, 5 and 6% by weight, respectively to the composite lubricants. The process parameters for the mixing process, such as temperature of the powder in the mixer and the mixing times for each composite can be seen in Table 2. The rotor speed in the mixer was 1000 rpm and the amount of lubricant core material was 500 g.







TABLE 1







Lubricating substances used as core materials.










Mark
Common name







ES
Erucyl stearamide



OP
Oleyl palmitamide



S
Stearamide



O
Oleamide



E
Erucamide



EBS
Ethylene bis-stearamide



PW655
Polyethylene wax



PW1000
Polyethylene wax



SE
Stearyl erucamide



EBO
Ethylene bis-oleamide



SO
Stearyl oleamide

















TABLE 2







Process parameters











Average particle
Temp. of powder in



Mark
size X50 (μm)
the mixer (° C.)
Mixing time (min)













S-1
5.2
50° C.
25


S-2
5.8
50° C.
25


S-3
15.4
50° C.
25


S-4
16.5
50° C.
45


S-5
17.8
50° C.
25


S-6
21.5
50° C.
25


S-7
4.0
83° C.
60


ES-1
24.0
25° C.
25


ES-2
29.5
25° C.
25


E
20.3
25° C.
45


OP
16.0
25° C.
45


EBS
8.5
75° C.
55


EBS/O
25.6
40° C.
20


PW655
10.0
25° C.
45


PW1000
10.0
40° C.
45


SE
27.4
25° C.
45


SO
35.4
25° C.
45


EBS/SE
29.0
25° C.
45


EBS/SO
29.2
25° C.
45


EBS/ES
20.4
25° C.
45


EBS/E
26.0
25° C.
15


S/E
24.3
25° C.
45


EBO
16.0
50° C.
10









Different iron-based powder compositions (mix no 1-63) of 25 kg each were prepared by mixing the obtained composite lubricant or a conventional particulate lubricant (used as reference) with graphite and ASC100.29 in a 50 kg Nauta mixer The solid organic lubricant particles in mixes no 36-38 and 50-61 were melted, subsequently solidified and micronised before used as a core material for preparing the composite lubricants or before added to the reference mixes. Apparent density (AD) and Hall flow (flow), were measured, according to ISO 4490 and ISO3923-1, respectively, on the obtained iron-based powder compositions 24 hours after the mixing. Table 3 shows the results of the measurements.
As can be seen from table 3, the flow rate of the iron-based powder compositions is improved and higher apparent densities may be obtained when using the different composite lubricants according to the invention as lubricants compared with the use of a conventional lubricant. In fact, when a PM composition containing a conventional lubricant has no flow the PM composition containing the inventive composite lubricant provides flow. Especially high apparent densities and/or flow rates were obtained for powder metal compositions containing composite lubricants according to the invention containing stearamide, erucamide, erucyl stearamide, stearyl erucamide, EBO, EBS and EBS in combination with oleamide or stearyl erucamide.
In order to measure the tendency of the composite lubricants and the conventional lubricants to form agglomerates the lubricants were sieved on a standard 315 μm sieve after storage of at least one week. The amount of the retained material was measured.
Table 4 shows that the tendency of forming agglomerates decreases when the organic lubricating core material is covered by fine carbon particles resulting in a composite lubricant according to the invention.
The same type of measurements as shown in table 4 was repeated with certain iron-based powder compositions in order to evaluate the tendency of forming agglomerates in an iron-based powder composition containing conventional lubricants and composite lubricants according to the invention, respectively.
Table 5 shows that the tendency of forming agglomerates is less pronounced in iron-based powder compositions containing the composite lubricant according to the invention compared with compositions comprising a conventional lubricant.







TABLE 3







Flow rate and apparent density (AD) of compositions 1-63














Conven-

Type of Carbon
Percentage of carbon





tional
Core of
particles
particles in relation





lubricant
lubri-
adhered onto
to total amount of
Flow



Mix
used as
cating
lubricating
lubricating composite
(seconds/
AD


no
reference
composite
core material
(%)
50 g)
(g/cm3)
















1
S-1



No flow
2.97


2

S-1
UF1
3.0
No flow
2.99


3

S-1
CB
1.5
34.5
2.85


4

S-1
CB
3.0
30.4
2.92


5
S-2



No flow
2.98


6

S-2
UF1
3.0
No flow
2.99


7

S-2
CB
3.0
32.9
2.91


8
S-3



No flow
3.05


9

S-3
UF1
3.0
29.5
3.17


10
S-4



No flow
3.12


11

S-4
UF1
3.0
28.3
3.18


12

S-4
CB
0.75
27.1
3.21


13

S-4
CB
1.5
27.2
3.17


14
S-5



30.6
3.05


15

S-5
CB
0.75
28.5
3.13


16

S-5
CB
1.5
27.3
3.13


17

S-5
4827
5.0
29.3
3.17


18
S-6



31.5
3.06


19

S-6
UF1
3.0
27.7
3.20


20

S-6
CB
0.75
26.9
3.21


21
S-7



28.2
3.17


22

S-7
UF1
3.0
26.1
3.19


23

S-7
CB
3.0
26.0
3.11


24
ES-1



No flow
3.10


25

ES-1
CB
1.5
33.1
3.19


26
ES-2



No flow
3.13


27

ES-2
CB
1.5
31.3
3.15


28

ES-2
4827
1.5
29.7
3.18


29
E



No flow
3.03


30

E
CB
1.5
30.3
2.97


31

E
CB
3.0
28.8
3.01


32
OP



No flow
2.92


33

OP
CB
1.5
34.3
2.94


34
EBS



33.5
3.01


35

EBS
CB
1.5
30.8
3.00


36
EBS/O



31.0
3.03


37

EBS/O
UF1
3.0
30.4
3.10


38

EBS/O
CB
3.0
28.4
3.09


39
PW655



No flow
2.76


40

PW655
CB
1.5
32.1
2.82


41
PW1000



No flow
2.78


42

PW1000
CB
1.5
32.5
2.85


43
Zn-stearat



35.4
3.18


44
SE



No flow
2.96


45

SE
CB
3.0
29.9
3.11


46

SE
UF1
6.0
31.2
3.08


47

SE
4827
5.0
30.4
3.10


48
SO



No flow
2.95


49

SO
CB
1.5
30.9
2.98


50
EBS/SE



No flow
2.98


51

EBS/SE
CB
1.5
29.6
3.17


52
EBS/SO



No flow
2.95


53

EBS/SO
CB
1.5
30.9
3.03


54
EBS/ES



No flow
3.00


55

EBS/ES
CB
1.5
33.4
2.99


56
EBS/E



No flow
2.96


57

EBS/E
CB
1.5
30.0
3.03


58
S/E



No flow
3.00


59

S/E
CB
4.0
29.1
3.16


60

S/E
UF1
6.0
28.4
3.17


61

S/E
4827
5.0
28.2
3.18


62
EBO



No flow
2.95


63

EBO
CB
3.0
34.0
3.04
















TABLE 4







Tendency of forming agglomerates for conventional lubricants


and lubricating composites according to the invention













Type of Carbon






particles
Percentage of carbon



Conven-
Core material
adhered onto
particles in relation
Tendency of


tional
of lubricating
lubricating
to total amount of
forming


lubricant
composite
core material
lubric composite (%)
agglomerates














S-1



Aggl



S-1
CB
1.5
Less aggl



S-1
CB
3.0
Less aggl


S-2



Aggl



S-2
CB
3.0
Less aggl


S-4



Aggl



S-4
UF1
3.0
No aggl



S-4
CB
0.75
No aggl



S-4
CB
1.5
No aggl


S-5



Aggl



S-5
CB
0.75
No aggl



S-5
CB
1.5
No aggl



S-5
4827
5.0
No aggl


S-7



Aggl



S-7
UF1
3.0
No aggl



S-7
CB
0.75
No aggl


ES-2



Aggl



ES-2
CB
1.5
No aggl



ES-2
4827
1.5
No aggl


E



Aggl



E
CB
1.5
Less aggl


OP



Aggl



OP
CB
1.5
No aggl


EBS



No aggl



EBS
CB
1.5
No aggl


EBS/O



No aggl



EBS/O
UF1
3.0
No aggl


SE



Aggl



SE
CB
1.5
No aggl



SE
UF1
6.0
No aggl



SE
4827
5.0
No aggl


SO



Aggl



SO
CB
1.5
No aggl


EBS/SE



Aggl



EBS/SE
CB
1.5
No aggl


EBS/SO



Aggl



EBS/SO
CB
1.5
No aggl


EBS/ES



Aggl



EBS/ES
CB
1.5
No aggl


EBS/E



Aggl



EBS/E
CB
1.5
No aggl


S/E



Aggl



S/E
CB
4.0
No aggl



S/E
UF1
6.0
No aggl



S/E
4827
5.0
No aggl


EBO



Aggl



EBO
CB
3.0
No aggl
















TABLE 5







Tendency of forming agglomerates in iron-based powder compositions containing


conventional lubricants and the composite lubricant according to the invention














Core
Type of carbon
Percentage of carbon





material
particles
particles in relation




Conven-
of
adhered onto
to total amount of
Tendency of


Mix
tional
composite
lubricating
lubricating composite
forming


no
lubricant
lubricant
core material
(%)
agglomerates















1
S-1



Aggl


3

S-1
CB
1.5
No aggl


4

S-1
CB
3.0
No aggl


5
S-2



Aggl


7

S-2
CB
3.0
No aggl


24
ES-1



Aggl


25

ES-1
CB
1.5
No aggl


29
E



Aggl


30

E
CB
1.5
Less aggl


31

E
CB
3
No aggl


32
OP



Aggl


33

OP
CB
1.5
No aggl


34
EBS



No aggl


35

EBS
CB
1.5
No aggl


39
PW655



Aggl


40

PW655
CB
1.5
No aggl


41
PW1000



Aggl


42

PW1000
CB
1.5
No aggl


43
Zn-stearate



No aggl


44
SE



Aggl


45

SE
CB
1.5
No aggl


46

SE
UF1
6.0
No aggl


47

SE
4827
5.0
No aggl


48
SO



Aggl


49

SO
CB
1.5
No aggl


50
EBS/SE



Aggl


51

EBS/SE
CB
1.5
No aggl


52
EBS/SO



Aggl


53

EBS/SO
CB
1.5
No aggl


54
EBS/ES



Aggl


55

EBS/ES
CB
1.5
No aggl


56
EBS/E



Aggl


57

EBS/E
CB
1.5
No aggl


58
S/E



Aggl


59

S/E
CB
4.0
No aggl


60

S/E
UF1
6.0
No aggl


61

S/E
4827
5.0
No aggl


62
EBO



Aggl


63

EBO
CB
3.0
No Aggl

## Claims

1. Iron-based powder metallurgical composition comprising an iron or iron-based powder and a particulate composite lubricant, said composite lubricant comprising particles having a core comprising a solid organic lubricant having fine carbon particles adhered thereon.

2. Composition according to claim 1, wherein the carbon particles are selected from natural or synthetic graphite, carbon black, activated carbon, coal and anthracite.

3. Composition according to claim 1, wherein the carbon particles are selected from natural or synthetic graphite and carbon black.

4. Composition according to claim 1, wherein the carbon particles form a coating on the core.

5. Composition according to claim 1, wherein the organic core particles are selected from the group consisting of fatty acids, waxes, polymers, or derivates and mixtures thereof.

6. Composition according to claim 1, wherein the average particle size of the organic core particles is 0.5-100 μm.

7. Composition according to claim 1, wherein the content of the composite lubricant in the powder metal composition is 0.05-2% by weight.

8. Composition according to claim 1, wherein the particle size of the core is at least five times the particle size of the carbon particles.

9. Composition according to claim 2, wherein the particle size of the carbon black is less than 200 nm.

10. Composition according to claim 2, wherein the content of carbon black in the composite lubricant is 0.1-25% by weight.

11. Composition according to claim 2, wherein the average particle size of the graphite is less than 10 μm.

12. Composition according to claim 2, wherein the content of graphite in the composite lubricant is 0.1-25% by weight.