COMPOSITE POWDER WITH IRON BASED PARTICLES COATED WITH GRAPHENE MATERIAL
20220339697 · 2022-10-27
Assignee
Inventors
- Ulf JANSSON (Uppsala, SE)
- Simon TIDÉN (Uppsala, SE)
- Mamoun TAHER (Uppsala, SE)
- Luis DIAZ (Sollentuna, SE)
- Tommi REMONEN (Mariehamn, FI)
Cpc classification
B22F10/28
PERFORMING OPERATIONS; TRANSPORTING
B22F2998/10
PERFORMING OPERATIONS; TRANSPORTING
B33Y80/00
PERFORMING OPERATIONS; TRANSPORTING
B22F2303/20
PERFORMING OPERATIONS; TRANSPORTING
B22F2999/00
PERFORMING OPERATIONS; TRANSPORTING
B22F2304/10
PERFORMING OPERATIONS; TRANSPORTING
B33Y70/10
PERFORMING OPERATIONS; TRANSPORTING
Y02P10/25
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
B22F1/16
PERFORMING OPERATIONS; TRANSPORTING
Abstract
The present invention relates to graphene coated iron based particles and a method of producing such. Provided is a composite powder suitable for powder metallurgy and additive manufacturing processes comprising particles of an iron based material with a coating of a graphene based material wherein the concentration of the graphene based material is between 0.1 wt % and 1.0 wt %.
Claims
1. A composite powder suitable for powder metallurgy and additive manufacturing processes, the composite powder comprising particles with a core of an iron based material and a coating of a graphene based material, wherein concentration of graphene based material is between 0.1 wt % and 1.0 wt %.
2. The composite powder according to claim 1, wherein the concentration of graphene based material is between 0.1 wt % and 0.95 wt %.
3. The composite powder according to claim 1, wherein the iron based material of the particles is pure iron.
4. The composite powder according to claim 1, wherein the iron based material of the particles is a stainless steel.
5. The composite powder according to claim 1, wherein the iron based material core has a size distribution wherein a majority of the particles is in the range of 1-100 μm.
6. The composite powder according to claim 5, wherein the iron based material core has a size distribution wherein a majority of the particles is in the range of 1-50 μm.
7. The composite powder according to claim 1, wherein the graphene based material of the coating is graphene oxide (GO).
8. The composite powder according to claim 1, wherein the graphene based material of the coating is a reduced graphene oxide (rGO).
9. The composite powder according to claim 1, wherein the graphene based material of the coating is a mixture of graphene oxide (GO) and reduced graphene oxide (rGO).
10. A method of producing a composite powder suitable for powder metallurgy and additive manufacturing processes, the composite powder comprising particles of an iron based material with a coating of a graphene based material, the method comprising the steps of: providing an iron base metal powder with a known size distribution; providing a graphene based material in dispersion; diluting the graphene based material and adjusting the pH with addition of a basic substance, while recording the concentration of the graphene based material in the solution, wherein the pH is adjusted to be between 3 and 9; separating graphene agglomerates of the graphene material by sonication or agitation; dispersing the iron based metal powder in de-ionized water to create a slurry with predetermined iron based metal to water weight ratio; adding the graphene material dispersion to the iron based metal powder slurry in intervals or at a predetermined rate and mixing thoroughly for a predetermined time period; and drying the composite powder, wherein the amount of the added graphene material dispersion is adjusted so that the concentration of the graphene material in the dried composite powder is between 0.1 wt % and 1.0 wt %.
11. The method according to claim 10, wherein the amount of the added graphene material dispersion is selected so that the concentration of the graphene material is between 0.1 wt % and 0.95 wt %.
12. The method according to claim 11, wherein the amount of the added graphene material dispersion is selected so that the concentration of the graphene material is between 0.1 wt % and 0.5 wt %.
13. The method according to claim 10, wherein the iron based material of the particles comprises pure iron, and in the step of dilution and adjusting the pH, the pH is adjusted to be within 4-8.
14. The method according to claim 10, wherein the iron based material is stainless steel, and in the step of dilution and adjusting the pH, the pH is adjusted to be within 3-8.
15. The method according to claim 10, wherein, the iron based material of the particles comprises pure iron.
16. The method according to claim 10, wherein the iron based material of the particles is a stainless steel.
17. The method according to claim 10, wherein the graphene based material comprises graphene oxide (GO).
18. The method according to claim 10, wherein the graphene based material comprises reduced graphene oxide (rGO).
19. The method according to claim 13, wherein, in the step of dilution and adjusting the pH, the pH is adjusted to be within 5-7.
20. The method according to claim 14, wherein, in the step of dilution and adjusting the pH, the pH is adjusted to be within 4-7.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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[0040]
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[0042]
[0043]
[0044]
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DETAILED DESCRIPTION
[0047] The following terms are defined and used throughout the description and claims:
[0048] at % is short for atomic percent, i.e. the number of one kind of atom relative to the total number of atoms;
[0049] wt % is short for weight percent, i.e. the weight of one compound relative to the total weight of all compounds in a mixture or composite;
[0050] Graphene is an atom thick planar sheet of carbon atoms arranged in a hexagonal lattice structure;
[0051] Graphene-based material is a layered material that comprises at least 30 at % carbon and has the properties commonly ascribed to the graphene class of materials The graphene-based material may be any type of graphene, such as single layer graphene, few layers graphene, multi-layered graphene, graphene oxide (GO), reduced graphene oxide (rGO) and graphene nanoplatelets (GNP).
[0052] Iron based powder material is a material in which iron is the major constituent such as, but not limited to pure iron and stainless steel. The stainless steel may for example be austenitic steel grade 316 or equivalent. Typical particle size of powder materials suitable for AM and PM is in the range 1-500 μm, depending of AM/PM method to be used. For AM methods utilizing Laser melting/sintering a particle size in the range of 1-100 μm is most suitable, as well as for traditional PM. A comprehensive review is “Powders for powder bed fusion: a review”, Silvia Vock et al, Progress in Additive Manufacturing https://doi.org/10.1007/s40964-019-00078-6, which is incorporated herein by reference. Iron based powder materials which is the starting material for the method according to the invention are commercially available in a wide range of compositions, size distributions and qualities. Starting materials may be produced by for example gas atomization or water atomization.
[0053] Flowability or powder flowability is defined as the ease with which a powder will flow under a specified set of conditions. Some of these conditions include: the pressure on the powder, the humidity of the air around the powder and the equipment the powder is flowing through or from. Flowability may be measured with revolution powder analysis (RPA) giving a set of parameters characterising the flow properties of the analysed powder material. The properties include: avalanche angle [.sup.0], the break energy [KJ/Kg], avalanche energy [KJ/Kg] and surface fractal.
[0054] Avalanche Energy [kJ/kg]—Energy released by an avalanche. Calculation: energy level of the powder after an avalanche minus energy level before the avalanche. The RPA reports the average avalanche energy for all powder avalanches.
[0055] Break Energy [kJ/kg]—Calculation: Maximum energy level of the sample powder before an avalanche begins minus lowest possible energy level for the powder (flat and even surface). It's based on the powder volume and mass. This value represents the amount of energy required to start each avalanche.
[0056] Avalanche Angle [°]—Powder angle at the maximum powder before the start of an avalanche. The measurement is the average value for all the avalanche angles. It's calculated from the centre point on the powder edge to its top point. This angle is the average angle required to start and maintain powder flow.
[0057] Surface fractal—The surface fractal is the fractal dimension of the surface of the powder and provides an indication of how rough the surface is. The measurement is made after each avalanche to determine how the powder reorganizes itself. If the powder forms a smooth even surface, the surface fractal will be near two. A rough and jagged surface will give a surface fractal greater than five. For applications requiring an even distribution of powders, such as AM, the closer the surface fractal is to two, the better the powder will perform.
[0058] The method of producing a metal powder suitable for AM, the metal powder comprising iron based particles, will be described with references to
[0066] The method may optionally comprise the steps, one or both, to be taken before the drying step, of: [0067] (e2) Filtering of the composite powder [0068] (e3) Additionally cleaning the filter cake (filtered off composite powder) with a solvent to remove any impurities, such as for example free graphene or salts.
[0069] The steps of filtering should be seen as a non-limiting example. As appreciated by the skilled person filtering or separation may be performed in various ways using different known filtering or sieving techniques.
[0070] According to one embodiment of the invention the graphene material is a graphene oxide (GO) in the form of a high concentration (about 2.5 wt %) graphene oxide paste or solution. The iron based material is a pure iron or a stainless steel, for example a austenitic steel grade 316 or equivalent steel, with a particle size distribution within the range of 1-100 μm. According to the embodiment the method comprises the steps of: [0071] (A) Dilution and pH adjusting of the Graphene Oxide Paste. [0072] 1. Transfer a specified, by effective mass, amount GO paste to a container. [0073] 2. Add DI Water. [0074] 3. Check pH of the diluted GO solution. Note: Initial pH of the solution is often around pH 2. [0075] 4. Adjust the pH of the solution to a pH within the range of 5 to 8 by adding NaOH 1M solution (pH 14) or equivalent. Finalize the adjustment to the desire pH by adding NaOH 0.1M solution or equivalent. For the stainless steel material a pH in the range 3-8 is suitable. For a pure iron material a pH in the range 4-8 is suitable, due to the increased oxidation at lower pH. [0076] 5. Weight the mass of the solution and calculate the final concentration. [0077] (B) Separating graphene agglomerates by sonication of the GO solution for at least 1 hour. [0078] (C-D) Coating of metal particles. [0079] 1. Weight the desire quantity of metal powder. [0080] 2. Calculate based on the desire concentration the amount of GO Solution required for coating the particles. [0081] 3. Transfer the GO Solution to an appropriate container and add 1:1 ratio of deionized (DI) water. [0082] 4. Sonicate the solution for 1 hour at room temperature. [0083] 5. Transfer the metal powder to a rotary mixing apparatus such as a rotary evaporator, and add DI water until the powder is completely covered. [0084] 6. Mix the metal powder in the rotary mixing apparatus for 15 min at 90 r.p.m. [0085] 7. Add the prepared GO solution into the rotary mixing apparatus. [0086] 8. Mix the powder with the GO solution in the rotary mixing apparatus for 2 h at 90 r.p.m. [0087] 9. Start the rotary evaporator vacuum pump, chiller and hot water bath in order to dry the solvents. Alternatively transfer the mixture to separate rotary drying container. [0088] a. Temperature water bath: 88° C. [0089] b. Speed: 90 r.p.m [0090] c. Vacuum 200 mbar-100 mbar [0091] d. Chiller temperature: 3° C.-10° C. [0092] 10. Once the powder is completely dried, turn off the rotary evaporator and remove the material from the container/balloon. [0093] 11. Grind the material to a fine powder without agglomerations. [0094] 12. Dry the powder in a vacuum oven at 88° C. for 24 h to 35 h in high vacuum.
[0095] The embodiment of the method may optionally comprise on of the steps or a combination of the steps, to be taken before the drying step (step 9), of: [0096] Filter of the coated powder to remove most of the water in a buchner funnel using suction [0097] Clean the filter cake in the Buchner funnel with DI-water (or Ethanol) to remove free graphene and/or salts [0098] Place the filtered powder in an oven at 60° C. (or place the powder in a flask and continue with step 9) for drying at least 12 h then continue at step 11.
[0099] In the above example water is used as the process liquid. Also other water miscible solvents could be used, for examples an alcohol such as ethanol or mixtures of alcohols. Also mixtures of water and one or more alcohols, for example an water/ethanol mixture, are embodiments of the method.
[0100] The experimental parameters, the detailed times, pressures, solvents and temperatures given in the embodiments using GO should be seen as indications. The exact parameters will depend on the equipment used, the amount of material used and individual choices or preferences regarding for example a processing time in relation to temperature. However, from these indicative parameters the skilled person will be able to make the necessary adjustments for specific equipment and other conditions.
[0101] As described in the steps (a) of the general method and steps 3-4 in the above embodiment controlling and adjusting the pH is a way to control the coating formation. At lower pH (1-2) there are attractive electrostatic forces between the GO and the Fe particles, but there is insufficient repulsion between the GO sheets, resulting in agglomerates which are unfavorable when trying to achieve a homogeneous coating. Mostly mixing occur instead. There is also severe oxidation of the Fe particles at low pH (1-2). When the pH is increased (3-4), fewer GO agglomerates are formed and for some application's acceptable corrosion of the Fe particles occurs. At a certain point there is not much oxidation occurring (during the processing step/time) and there are few agglomerates, but there are still attractive electrostatic forces between the GO sheets and the Fe particles. This is in the pH 5-9(10) region.
[0102] Increasing the pH will also create more negatively charged groups on the basal planes of the GO sheets, which would be favorable to achieve a good coating. However, at too high pH, the net surface charge of the Fe particles also become negative which creates electrostatic repulsion between the GO sheets and the Fe particles which can clearly be seen for pH values above 10, but could affect the quality of the coating from pH values above 7. If the iron based material has good corrosion resistance by itself, for example a stainless steel grade like grade 316 a lower pH could be chosen without risking surface oxidation of the particles. The influence of pH is summarized in table
TABLE-US-00001 TABEL 1 Effects of pH on coating formation and oxidation of the pure iron particles. Oxidation during pH Coating of powder processing 1 NO (MIXING OCCURE) HIGH 2 NO (MIXING OCCURE) HIGH 3 YES ACCEPTABLE 4 YES ACCEPTABLE 5 YES NO 6 YES NO 7 YES NO 8 YES NO 9 YES NO 10 YES (LOWER DEGREE) NO 11 YES (LOW DEGREE) NO 12 NO NO 13 NO NO
[0103] According to one embodiment of the invention the pH is adjusted to be within 3-9, and preferably within 3-7.
[0104] According to one embodiment of the invention the pH is adjusted to be within 5-8.
[0105] According to one embodiment the iron based material is pure iron and the pH is be adjusted to be within 4-8, and preferably within 5-7.
[0106] According to one embodiment the iron based material is stainless steel and the pH is adjusted to be within 3-8, and preferably within 4-7.
[0107]
[0108] In one embodiment of the invention the graphene material is reduced graphene oxide (rGO), a partly reduced graphene oxide or a mixture of graphene oxide and reduced graphene oxide
[0109] It should be noted that the graphene oxide may be affected by the method. For example, if the starting material is graphene oxide (GO) certain steps, in particular the final drying step, may induce a reduction of the graphene oxide, so that the final composite powder may comprise also reduced graphene oxide (rGO). The reduction mechanisms of GO and how to control them are well known for the skilled person.
[0110] According to one embodiment the metal particles are pure iron.
[0111] The method according to the invention produces a composite powder comprising Fe-based metal particles with a graphene coating. The method makes it possible to fine-tune the degree of coating and optimize the flowability of the composite powder by varying the concentration of the graphene material in the process and thereby also the concentration in the final composite powder.
[0112]
[0113] The SEM images of
[0114] The SEM image of
[0115] Increasing the graphene material concentration to or above 1.3 wt % will cause some agglomerations of the particles in the composite powder as illustrated by the SEM image of
[0116] The SEM images of
[0117]
[0118] The flowability properties were measured with revolution powder analysis (RPA) and the parameters avalanche angle [°], the break energy [KJ/Kg], avalanche energy [KJ/Kg] and surface fractal for the stainless steel samples are given in table 2a (stainless steel) and table 2b (pure iron and illustrated in the graphs of
TABLE-US-00002 TABEL 2a avalanche angle, the break energy, avalanche energy and fractal surface for composite powders with stainless steel particles. Concentration Ref. 0.05 wt % 0.1 wt % 0.2 wt % 0.5 wt % 0.95 wt % 1.3 wt % Avalanche Angle [°] 63.10 67.03 51.23 57.70 59.83 60.20 61.10 Break Energy [KJ/Kg] 103.98 104.45 77.34 81.83 93.60 96.80 94.33 Avalanche Energy [KJ/Kg] 40.24 37.14 32.30 25.35 35.76 41.33 35.80 Fractal surface 6.64 4.74 2.81 3.11 3.46 3.33 3.56
TABLE-US-00003 TABEL 2b avalanche angle, the break energy, avalanche energy and fractal surface for composite powders with pure iron particles. Concentration Ref. 0.05 wt % 0.1 wt % 0.2 wt % 0.5 wt % 1.0 wt % Avalanche Angle [°] 55.67 53.8 56.1 56.2 57.2 60.5 Break Energy [KJ/Kg] 97.99 80.4 77.8 81.83 80.5 79.6 Avalanche Energy [KJ/Kg] 16.37 23.3 15.9 15 20 18.3 Fractal surface 4.31 3.42 3.16 3.14 3.34 3.42
[0119] As evident from the flowability measurements a significant reduction in the parameters relating to flowability and surface fractal is apparent also for particles of pure Fe.
[0120] The composite powder according to the invention comprises particles with a core of iron based material with a coating of graphene based material wherein the concentration of graphene based material is in the range of 0.1 wt % and 1.0 wt %, preferably between 0.1 wt % and 0.5 wt %, and even more preferably between 0.1 wt % and 0.3 wt %. As apparent for the skilled person the optimum concentration range could be adjusted depending on parameters of the iron based particles, for example their size distribution, wherein it could be accounted for that the surface area scales differently than the mass of the particles. With the knowledge that an optimum range exists, basic geometrical relations and the data here presented, such adjustment does not constitute undue burden for the skilled person. The above described method represents a preferred method of producing the composite powder according to the invention.
[0121] By comparing the flowability data (table 1a and 1b/
[0122] According to one embodiment the graphene based material of the coating comprises graphene oxide. As a result of the production method or by further treatment the graphene oxide may have been at least partly reduced so that the coating comprises a mixture of graphene oxide (GO) and reduced graphene oxide (rGO).
[0123] According to one embodiment of the invention the iron based core of the composite powder has a particle size distribution within the range of 1-100 μm, i.e. a particle size range that is known to be suitable for laser sintering/melting and traditional PM. According to one embodiment the iron based core of the composite powder has a particle size distribution is within the range of 1-100 μm.
[0124] Both the iron based material and the graphene based material may comprise unavoidable impurities associated with respective material.
[0125] Experimental Details
[0126] Influence of pH:
[0127] To investigate the influence of pH in the coating process, an experimental series ranging from pH 1 to 13 was done. Solutions with pH 1 to 13 were prepared by addition of either NaOH for samples above pH 6, or HCl for samples below pH 6, to de-ionized water. The pH of each sample was controlled with a calibrated VWR pHenomenal 1100 H pH meter. For the pH 6 sample, only de-ionized water was used, as it is slightly acidic due to dissolution of atmospheric carbon dioxide (CO2). The salt concentration was not intentionally increased further in order to avoid changes to the surface charge of graphene oxide (GO), leading to varying salt concentrations in each sample. For each sample, 0.010 g of GO was diluted in 8 ml solution of desired pH, and ultrasonicated for 1 h. Thereafter, 1 g of Fe powder was added, followed by mixing for 1 min. Visual inspection of samples were made before addition of Fe, 1 min after mixing and 1 h after mixing. In addition to this, some of the powder was removed 1 min, 1 h and 20 h after mixing and left to dry at room temperature. Pure Fe powder was also mixed in pH 3, 5 or 8 for 4 h to analyze the effect of corrosion.
[0128] GO was diluted in de-ionized water and NaOH solution to yield three dispersions with equal GO concentrations at pH 3.0, 5.4 and 8.0. The dispersions were subsequently ultrasonicated for 60 min, which dissolved all visible precipitates. Metal powder (5 g) and 10 g of de-ionized water was added to a beaker to create a slurry. The ultrasonicated dispersion of GO was slowly added to the metal powder slurry under stirring and thereafter further mixed in a rotary evaporator (Büchi R-300) for 2.5 h at 90 rpm (300 mbar pressure). The composite powder was filtered, rinsed with de-ionized water and dried at 50° C.
[0129] Stainless Steel Composition:
[0130] The stainless steel is an austenitic stain steel with the composition C 0.03%, Cr 17.0%, Ni 12.0%, Mo 2.5%, Si 0.7%, Mn 1.5%, S 0.03%, P 0.04% and balance Fe.
[0131] Metal Particle Size Distribution:
[0132] A typical size distribution for the stainless steel particles is given in table 2.
TABLE-US-00004 TABEL 2 Typical size distribution for a grade 316 stainless steel powder Particle size (μm) D.sub.10% 4.5 D.sub.50% 10.5 D.sub.90% 22
[0133] The pure iron particles comprises Alfa Aesar 99.5% Iron and has a size distribution around 10 μm.
[0134] Practical tests have been performed with the composite powder comprising iron based material to produce objects with AM (SLM) as well as sintering. The composite powder handled well in the AM equipment and adjustments of printing parameters were considered as non-problematic for the skilled operator. The produced objects have the material properties that is to be expected as compared to objects produced from non-coated starting powder material.