CN101781186A - Cobalt oxalate powder and its application for producing co powder with superior cold compression and sintering characters - Google Patents
Cobalt oxalate powder and its application for producing co powder with superior cold compression and sintering characters Download PDFInfo
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- CN101781186A CN101781186A CN200910126165A CN200910126165A CN101781186A CN 101781186 A CN101781186 A CN 101781186A CN 200910126165 A CN200910126165 A CN 200910126165A CN 200910126165 A CN200910126165 A CN 200910126165A CN 101781186 A CN101781186 A CN 101781186A
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- C01P2004/60—Particles characterised by their size
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- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention provides cobalt oxalate powders and their application for producing Co powder with superior cold compression and sintering characters, specifically the invention provides acicular shaped cobalt oxalate powders whose average acicular degree ratio (length/diameter) are 3-20, characterized in that the powder has a mean particle size of 1.7-5[mu]m detected by a Fisher subsieve stage powder size determinator, specific surface area of 4-12 detected by BET. The cobalt oxalate powder is obtained by the following method: precipitating from the cobalt solution and oxalate ion source, wherein the cobalt solution temperature is equal to or below the temperature of the oxalate ionic solution; subsequently using an energy of at least 0.01W/kg to mix for at least one hour. The Co powder obtained by thermal deoxidization of the cobalt oxalate has superior cold compression and sintering character for forming high performance diamond tools.
Description
Technical field
The present invention relates to have the cobalt oxalate powder of specific acicularity ratio (acicularity ratio), Fei Shi size (Fisher size) and specific surface area, its purposes, and the method that obtains this powder.Described oxalate powder proves the staple that obtains following Co powder, and described Co powder has and is used to cold pressing (cold compaction) and required form and the size of diamond tool application used, more specifically is used for to sintering.
Technical field
Co powder morphology and size are along with the variation of production method is open in EP 0770693.According to the application of powder, introduce these differences of form and size.This also is shown in the US 3574685 that is used for magnetic particle, and the US 6464750 that is used for iron powder, and this iron powder is suitable for being used for heat hot pile composition.
A kind of preferable methods of making the Co powder is by the thermal reduction cobalt oxalate.What sell at present is the cobalt dust that derives from a youngster supplier that is obtained by cobalt oxalate, but because powder morphology and dimensional change are big, so cold pressing and the sintering property noticeable change, usually causes the diamond tool adhesive material of poor quality.The purpose of this invention is to provide special Co oxalate powder, it obtains having good colding pressing and the Co powder of sintering character after thermal reduction.
Summary of the invention
The invention provides cobalt oxalate powder with needle-like form, it has 3～20 average acicularity ratio (length/diameter), it is characterized in that described powder has the mean particle size of 1.7～5 μ m of Yong Feishi subsieve level particle size determination instrument (Fisher Sub Sieve Sizer) measurement, and have the 4～12m that measures according to BET
2The specific surface area of/g.Preferably, described oxalate powder has 1.7～2.5 μ m that Yong Feishi subsieve level particle size determination instrument is measured, the more preferably mean particle size of 2.0～2.3 μ m.In addition, preferred described powder has the 7～10m that measures according to BET
2The specific surface area of/g.Even more preferably has 0.25～0.30g/cm
3The powder of apparent density.
After the thermal reduction step of application of known, cobalt oxalate powder according to the present invention provides to have and is used for the required form of diamond tool application and the cobalt dust of size.
The invention also discloses aforementioned cobalt oxalate manufacturing method of power, it comprises the following steps:
-aqueous solution of the hydrochloride, nitrate, vitriol or the acetate that contain cobalt is provided,
-make this aqueous solution and the solution reaction that contains oxalate denominationby, thus obtain to comprise the slurry of sedimentary cobalt oxalate powder, and
The cobalt oxalate powder of-precipitation separation,
It is characterized in that the temperature of the described aqueous solution is equal to or less than the temperature of the solution that contains oxalate denominationby, and be that described slurry stands the specific mechanical energy that the stirring by 0.1～5W hour/kg provides.Preferably, described slurry stands at least one hour of power of agitator of 0.1W/kg at least.In addition, preferred described slurry is without undergoing the power of agitator greater than 5W/kg.
In one embodiment, in preceding method, the described aqueous solution is that concentration is the cobalt chloride solution of 2～4mol Co/l, and described oxalate denominationby solution comprises the dihydrate title complex of oxalic acid, and its concentration is 0.2～1.5mol H
2C
2O
42H
2O/1.In another embodiment, the described aqueous solution and the described solution that contains oxalate denominationby all have 10～30 ℃ temperature.Usually in temperature, precipitate under promptly about 20 ℃ near envrionment temperature.
According to the present invention, the staple that acquisition has the cobalt dust of required form and size is form and a size of adjusting the cobalt oxalate precursor.Adjusting the form of cobalt oxalate powder and the method for size is made up of the following step: the aqueous solution that hydrochloride, nitrate, vitriol or acetate cobalt salt are provided; Make the reaction of described solution and oxalate denominationby, the temperature of wherein said cobalt liquor is equal to or less than the temperature of described oxalate denominationby solution, thus precipitation cobalt oxalate powder.After himself precipitated, cobalt oxalate stood sequence of operations in addition: stirring, separation, washing, dry and possible screening.
After the precipitation, the preferred churning time that had at least 1 hour that exists, power of agitator is 0.1W/kg at least.Required agitation energy guarantees that the oxalate particle fragmentation with sheet or connection is tiny acicular particles.Therefore cobalt oxalate becomes more even dimensionally.Preferred power of agitator should be limited to 5W/kg, because when spicule is too tiny, it is too difficult that the separation of oxalate precipitation thing becomes.
The throw out that obtains is passed through any known liquid-solid lock out operation, as separate (or segregation) by filtration.Usually described throw out is for example used deionized water wash then; For example carry out drying by spraying drying; And stand to select the screening of desired size to operate.
The present invention also requires aforementioned cobalt oxalate powder in the right of making the purposes in the following cobalt dust by thermolysis and the described cobalt oxalate powder of reduction, described cobalt dust has 0.80～1.80 μ m that Yong Feishi subsieve level particle size determination instrument is measured, the mean particle size of preferred 1.40～1.55 μ m.Preferred described cobalt dust is under the situation of 150MPa at the pressure of colding pressing, and has the green strength less than 1% wear(ing)value (Rattler value) in wear test.
What should be mentioned in that is the importance that US 6464750 has stated oxalate shape with regard to acicularity ratio and length.Yet the document does not comprise the specification about Fei Shi size and specific surface area, and also instruction does not obtain to be used for the required oxalate character of cobalt dust that diamond tool is used, because its concern is the preparation iron powder.The temperature of the also not mentioned solution that mixes of disclosed method and the dry importance of the amount of agitation energy before.
Oxalate powder according to the present invention can access the cobalt dust of elongated condition after reduction, this cobalt dust has and is used for the required character of diamond tool application.Having more seemingly, the oxalate precursor of lamellar morphology provides the cobalt dust that is not suitable for these sintering application.Do not know fully as yet by having cobalt dust better reason of performance in diamond tool is used that the above cobalt oxalate that provides specification makes.It is believed that described cobalt particle specific grain growing performance during hot pressing has caused the better combination of diamond maintenance and free cutting property, known feature for diamond tool performance necessity.
With known thermal reduction step,, finish the transformation of cobalt oxalate to cobalt dust by under 450 ℃～650 ℃ temperature, handling with gaseous hydrogen.Required cobalt dust granularity is depended in the selection of the temperature and time of handling for this reduction.The variation of parameter can not influence the further feature of the Co powder that is obtained in the reduction step process, and therefore described further feature directly depends on the powder characteristics of cobalt oxalate.
Embodiment
By the following example explanation the present invention.
Embodiment 1: powder is synthetic
1a) the cobalt oxalate powder is synthetic
With 1 liter of CoCl that contains 180g/l Co or 3mol/l Co
2Solution joins 6 liters of H that contain 65g/l or 0.5mol/l
2C
2O
42H
2O at deionization H
2In the oxalic acid solution among the O.Two kinds of solution all are 20 ℃, and at room temperature precipitate.In 9.4 liters of containers, utilize the helical ribbon mixer that changes rotation with per minute 1000, throw out was stirred 90 minutes, given power of agitator is 0.29 watt/kg.Than agitation energy is 0.45W hour/kg.After the filtration, that throw out is also dry with deionized water wash.The physical properties of thus obtained oxalate (A represents with sample) is shown in Table 1.
Table 1: the physical properties of the cobalt oxalate that is obtained
| Sample A | |
| The apparent density tap density | ??0.27g/cm 3??0.50g/cm 3 |
| Fei Shi SSS | ??2.1μm |
| Specific surface area, BET | ??8.2m 2/g |
| D10, laser diffraction | ??0.7μm |
| D50, laser diffraction | ??2.2μm |
| D90, laser diffraction | ??7.5μm |
| D99, laser diffraction | ??20.0μm |
1b) cobalt dust is synthetic
With cobalt oxalate (deriving from 1a) under 500 ℃ in H
210/N
2The experience reduction is 10 hours in 90 atmosphere.The physical properties of resulting cobalt dust is shown in Table 2.
Table 2: the physical properties that derives from the cobalt dust of sample A
| The apparent density tap density | ??1.16g/cm 3?2.18g/cm 3 |
| Fei Shi SSS | ??1.44μm |
| Specific surface area, BET | ??0.99m 2/g |
| D10, laser diffraction d50, laser diffraction d90, laser diffraction d99, laser diffraction | ??1.2μm??3.3μm??8.2μm??16.8μm |
The performance of colding pressing of the Co powder that 1c) is obtained
In wear test, will put into by 1mm at the height 10mm of different compaction pressure lower compression and the green part of diameter 10mm
2The rotating cylinder made of filamentary webs in.After 1200 rotations in 12 minutes, measure the relative weight loss, perhaps " wear(ing)value ".Two kinds of differences the results are shown in the table 3 of pressure of colding pressing.Lower wear(ing)value is represented higher green strength.Represent good compaction capacity less than 20% wear(ing)value, represent extraordinary compaction capacity and be lower than 10% wear(ing)value.Because the wear(ing)value that is obtained is lower than 1%, so obtain fabulous cold-pressing property.
Table 3: the wear(ing)value of the Co powder that is obtained
| The pressure of colding pressing | Wear(ing)value |
| ??150MPa | ??0.5％ |
| ??350MPa | ??0.3％ |
The sintering character of the Co powder that 1d) is obtained
In graphite jig, under 35MPa pressure, in 650,700,800,850 or 950 ℃ of following sintering Co powder 3 minutes.Measure the density and the Vickers' hardness of all sintered sheets.The result provides in following table 4, and shows obtained favorable mechanical character after sintering.
Table 4: the mechanical properties of the Co powder behind the sintering
| Temperature ℃ | Relative density g/cm 3 | Vickers' hardness |
| ??650??700??750??800??850??900??950 | ??86.1??95.7??97.3??97.8??97.8??97.8??97.8 | ??184??240??289??288??280??259??213 |
Embodiment 2: the starting soln Temperature Influence
Handle cobalt oxalate according to embodiment 1, but the temperature of change as shown in table 5 solution to be mixed.Judge granularity and form by the volume that the sedimentary oxalate of 20g in settling process is occupied.This is noting down after 10 minutes He after 25 minutes.If sedimentation very fast (oxalate occupies smaller volume) thinks that then powder is more coarse.This is confirmed by microscopic analysis.Find to work as CoCl
2When the temperature of solution is equal to or less than the temperature of oxalic acid solution, form the most tiny oxalate spicule.
Table 5: the oxalate precipitation that solution temperature changes
| Test | Temperature CoCl 2 | Temperature H 2C 2O 2·2H 2O | 10 minutes occupied volumes of postprecipitation thing | 25 minutes occupied volumes of postprecipitation thing |
| ??1 | ??10℃ | ??10℃ | ??98cm 3 | ??97cm 3 |
| ??2 | ??10℃ | ??30℃ | ??77cm 3 | ??56cm 3 |
| Test | Temperature CoCl 2 | Temperature H 2C 2O 2·2H 2O | 10 minutes occupied volumes of postprecipitation thing | 25 minutes occupied volumes of postprecipitation thing |
| ??3 | ??20℃ | ??20℃ | ??80cm 3 | ??60cm 3 |
| ??4 | ??30℃ | ??10℃ | ??50cm 3 | ??46cm 3 |
The test 1～3 exemplary illustration the present invention.Test 4 is counter-examples.The form that obtains the cobalt oxalate that makes among the embodiment 1 (test 3) of sample A is different from the cobalt oxalate that forms in the test of representing with sample B 4 significantly, distinguishes as depicted in figs. 1 and 2.The physical properties of the sample B that measures is shown in Table 6.
Table 6: the physical properties of Co oxalate relatively
| Sample B | |
| The apparent density tap density | ??0.38g/cm 3??0.80g/cm 3 |
| Fei Shi SSS | ??5.4μm |
| Specific surface area, BET | ??2.8m 2/g |
| D10, laser diffraction | ??0.7μm |
| D50, laser diffraction | ??3.3μm |
| D90, laser diffraction | ??13.8μm |
| D99, laser diffraction | ??24.1μm |
Embodiment 3: comparative example
Handle cobalt oxalate according to embodiment 1, but the power of agitator after the precipitation is limited to 0.29W/kg, carries out 10 minutes, corresponding ratio agitation energy only is 0.05W hour/kg.The cobalt oxalate that makes among the embodiment 3, the form of sample C is shown among Fig. 3.The oxalate spicule still connects securely, looks more photo shape accidentally, and it does not provide required cobalt dust shape after reduction.The median size of measuring by Fei Shi is 6.4～6.9 μ m.
Description of drawings
Fig. 1: the scanning electron microscope image of sample A, it has shown the cobalt oxalate powder that has according to form of the present invention and size.
Fig. 2: the scanning electron microscope image of sample B, it has shown the form that has outside the claim of the present invention and the cobalt oxalate powder of size.
Fig. 3: the scanning electron microscope image of sample C, it has shown the form that has outside the claim of the present invention and the cobalt oxalate powder of size.
Claims (11)
1. cobalt oxalate powder with needle-like form, it has 3～20 average acicularity ratio, it is characterized in that described powder has the mean particle size of 1.7～5 μ m of Yong Feishi subsieve level particle size determination instrument measurement, and have the 4～12m that measures according to BET
2The specific surface area of/g.
2. cobalt oxalate powder according to claim 1 is characterized in that described powder has 1.7～2.5 μ m that Yong Feishi subsieve level particle size determination instrument is measured, the mean particle size of preferred 2.0～2.3 μ m.
3. cobalt oxalate powder according to claim 1 and 2 is characterized in that described powder has the 7～10m that measures according to BET
2The specific surface area of/g.
4. according to each described cobalt oxalate powder in the claim 1 to 3, it is characterized in that described powder has 0.25～0.30g/cm
3Apparent density.
5. make the method according to each described cobalt oxalate powder in the claim 1 to 4, it comprises the following steps:
-aqueous solution of the hydrochloride, nitrate, vitriol or the acetate that contain cobalt is provided,
-make the described aqueous solution and the solution reaction that contains oxalate denominationby, thus obtain to comprise the slurry of sedimentary cobalt oxalate powder, and
The described sedimentary cobalt oxalate powder of-separation,
The temperature that it is characterized in that the described aqueous solution is equal to or less than the described temperature that contains the solution of oxalate denominationby, and is that described slurry stands the ratio agitation energy of 0.1～5W hour/kg.
6. method according to claim 5, wherein said slurry stand the power of agitator of 0.1W/kg at least.
7. method according to claim 6, wherein said slurry stands the power of agitator less than 5W/kg.
8. according to each described method in the claim 5 to 7, the wherein said aqueous solution is that concentration is the cobalt chloride solution of 2～4mol Co/l and the dihydrate title complex that described oxalate denominationby solution comprises oxalic acid, and its concentration is 0.2～1.5mol H
2C
2O
42H
2O/l.
9. according to each described method in the claim 5 to 8, it is characterized in that the described aqueous solution and the described solution that contains oxalate denominationby all have 10～30 ℃ temperature.
10. according to the purposes of each described cobalt oxalate powder in the claim 1 to 4 in making following cobalt dust, described cobalt dust has 0.80～1.80 μ m that Yong Feishi subsieve level particle size determination instrument is measured, the mean particle size of preferred 1.40～1.55 μ m, described cobalt dust is made by thermolysis and the described cobalt oxalate powder of reduction.
11. purposes according to claim 10, wherein said cobalt dust is under the situation of 150MPa at the pressure of colding pressing, and has the green strength less than 1% wear(ing)value in wear test.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP09000761 | 2009-01-21 | ||
| EP09000761.8 | 2009-01-21 |
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| CN101781186A true CN101781186A (en) | 2010-07-21 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387488A (en) * | 2012-05-10 | 2013-11-13 | 无锡市顺业科技有限公司 | Preparation method of square cobalt oxalate powder |
| CN110511133A (en) * | 2019-09-06 | 2019-11-29 | 辽宁星空钠电电池有限公司 | A kind of method that rapid precipitation prepares one-dimensional cobalt oxalate |
| US11607734B2 (en) | 2018-05-30 | 2023-03-21 | Hela Novel Metals Llc | Methods for the production of fine metal powders from metal compounds |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3803191A (en) * | 1971-03-24 | 1974-04-09 | Graham Magnetics Inc | Acicular salts and their preparation |
| US3892673A (en) * | 1971-03-24 | 1975-07-01 | Graham Magnetics Inc | Composition of metal salt crystals having a polymeric coating |
| JPS5467700A (en) * | 1977-11-10 | 1979-05-31 | Sony Corp | Magnetic recording medium |
| US6464750B1 (en) * | 1999-06-10 | 2002-10-15 | Asb Aerospatiale Batteries | Method of preparing metal powders, metal powders prepared in this way and compacts that include these powders |
-
2009
- 2009-03-05 CN CN200910126165A patent/CN101781186A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3803191A (en) * | 1971-03-24 | 1974-04-09 | Graham Magnetics Inc | Acicular salts and their preparation |
| US3892673A (en) * | 1971-03-24 | 1975-07-01 | Graham Magnetics Inc | Composition of metal salt crystals having a polymeric coating |
| JPS5467700A (en) * | 1977-11-10 | 1979-05-31 | Sony Corp | Magnetic recording medium |
| US6464750B1 (en) * | 1999-06-10 | 2002-10-15 | Asb Aerospatiale Batteries | Method of preparing metal powders, metal powders prepared in this way and compacts that include these powders |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103387488A (en) * | 2012-05-10 | 2013-11-13 | 无锡市顺业科技有限公司 | Preparation method of square cobalt oxalate powder |
| CN103387488B (en) * | 2012-05-10 | 2015-04-15 | 无锡市顺业科技有限公司 | Preparation method of square cobalt oxalate powder |
| US11607734B2 (en) | 2018-05-30 | 2023-03-21 | Hela Novel Metals Llc | Methods for the production of fine metal powders from metal compounds |
| CN110511133A (en) * | 2019-09-06 | 2019-11-29 | 辽宁星空钠电电池有限公司 | A kind of method that rapid precipitation prepares one-dimensional cobalt oxalate |
| CN110511133B (en) * | 2019-09-06 | 2022-04-12 | 辽宁星空钠电电池有限公司 | Method for preparing one-dimensional cobalt oxalate through rapid precipitation |
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Application publication date: 20100721 |