CN104772473B - A kind of preparation method of 3D printing fine grained sized spherical titanium powder - Google Patents
A kind of preparation method of 3D printing fine grained sized spherical titanium powder Download PDFInfo
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Abstract
The preparation method of a kind of 3D printing fine grained sized spherical titanium powder, belongs to metal dust preparing technical field.Using high pure metal titanium bulk is raw material, in an inert atmosphere arc evaporation, is filled with hydrogen simultaneously, titantium hydride nanometer powder is synthesized by gas phase；Then titantium hydride nanometer powder is carried out agglomeration granulation, obtain the micron order titanium hydride powders of higher density；Finally micron order titanium hydride powders after pelletize is carried out heat treatment, by degumming, dehydrogenation and densification consolidation, it is thus achieved that granularity, sphericity and mobility meet 3D and print the pure titanium powder granule required.This method is strong to the sphericity of titanium powder granule and the controllability of particle diameter distribution；Technique is simple, low cost；By firstly generating the new way of sludge proof titantium hydride nano-powder particles, stably there is the Titanium of greatly activity, the oxygen content in the titanium powder granule finally prepared can be controlled.
Description
Technical field
The present invention relates to the preparation method of a kind of 3D printing fine grained sized spherical titanium powder, belong to gold
Belong to powder preparing technical field.
Background technology
3D printing technique is particularly suitable for developing high added value complex structure product, personalized customization
Be applied to large-scale production before the link such as the checking that designs and research and develop.First intake with the current world
Putting down and compare, in terms of 3D prints the research and development of required moulding material, still there is a big difference in China, material
Material design and preparation technology currently mainly follow the tracks of foreign progress.Produce at 3D printing moulding material
Product aspect, domestic required fine grain spherical titanium and titanium alloy powder etc. be almost completely dependent on into
Mouthful.The shortage of high-quality 3D printing moulding material is that restriction China 3D printing technique is promoted
One of bottleneck key element with application.
For 3D printing fine-grained metals titanium powder, dusty material is had very by technical process
High requirement, such as particle size range 20-50 micron, high sphericity, low oxygen content etc..Existing
Titanium valve technology of preparing mainly has: electrochemical process, mechanical attrition method, atomization, reducing process etc..
Titanium or titanium alloy powder pattern that at present these methods are prepared are difficult to control to, particle diameter thicker and
Distribution is wider.Wherein, gas atomization is relatively low due to air velocity, the metal prepared
Or alloy powder granularity reaches the yield rate generally only about 30% of below 50 μm；Electrochemistry,
Reducing process is relatively costly, and the solvent and the reducing agent that use have a severe toxicity more, and be readily incorporated halogen,
The impurity such as sulfur；Ball-milling method is only used for fragile material, and usual oxygen content is higher and uncontrollable powder
End granule-morphology.Therefore, current pressing needs low cost, high-purity, the 3D of size tunable
Print by the preparation method of metal or alloy powder.
For above-mentioned domain background, in order to solve the limitation of prior art, the present invention provides a kind of
It is applicable to the preparation method of the fine grained sized spherical titanium powder of 3D printing technique.
Summary of the invention
The technological process of preparation method and principle that the present invention provides be: uses high pure metal titanium block
Material is raw material, in an inert atmosphere arc evaporation, is filled with hydrogen simultaneously, anti-by gas phase
Should synthesizing hydrogenated nano-ti powder end；Then titantium hydride nanometer powder is carried out agglomeration granulation, obtain
The micron order titanium hydride powders of higher density；Finally micron order titanium hydride powders after pelletize is carried out
Heat treatment, by degumming, dehydrogenation and densification consolidation, it is thus achieved that granularity, sphericity and stream
Dynamic sexual satisfaction 3D prints the pure titanium powder granule required.This method compared with other processes,
Strong to the sphericity of metallic particles and the controllability of particle diameter distribution；Technique is simple, low cost；Logical
Cross the new way firstly generating sludge proof titantium hydride nanometer powder, stably there is very big activity
Titanium, can effectively control the oxygen content in the metal powder granulates finally prepared.
The preparation of a kind of fine grained sized spherical titanium powder being applicable to 3D printing demand that the present invention provides
Method, it is characterised in that comprise the following steps:
(1) using high purity titanium bulk as anode, under noble gas argon or helium environment,
Forming high intensity electric arc by discharge process, striking current is 100～250A, and arc voltage is
10～30V, then pass to hydrogen, hydrogen is 1:(1～3 with the volume ratio of noble gas),
Titantium hydride (TiH is generated by gas phase reaction2), form solid-state titantium hydride nano-particle after condensation；
(2) hydrogenation prepared by polyvinyl alcohol, Polyethylene Glycol and deionized water and step (1)
Titanium nano-particle is configured to suspension slip, after agglomeration granulation, it is thus achieved that 20～50 μm spherical
Titanium hydride particles；
(3) spherical hydrogenation after the pelletize that step (2) is prepared by the tube furnace of employing argon shield
Titanium granule carries out heat treatment, and first stage heat treatment temperature is 230～280 DEG C, and temperature retention time is
60～120min；Second stage heat treatment temperature is 700～750 DEG C, and temperature retention time is
120～180min；Phase III heat treatment temperature is 900～950 DEG C, and temperature retention time is
60～90min, finally cool to room temperature with the furnace, obtain having high compactness, high fluidity, low
The fine grained micron-size spherical titanium powder of oxygen content.
Technical characteristic and the advantage of the present invention mainly have: the process that (1) evaporates in the titanium bulk starting the arc
In, it is filled with hydrogen, at high temperature hydrogen reacts rapidly with metal gas, and product is mutually pure
Titantium hydride, utilizes the regulation and control of striking current, voltage and hydrogen and inert gas ratio, can adjust
The productivity of whole titantium hydride and particle size, make mean diameter controlled in the range of 30～80nm；(2)
With the titanium hydride powders of good stability as original material, utilize the method pelletizes such as centrifugal spray, can
Effectively to control the introducing of the impurity such as oxygen in granulation process, obtain good sphericity and relatively simultaneously
High micron particles consistency；(3) Technology for Heating Processing after pelletize, obtains completely final
It is extremely important that foot 3D prints the metal dust required.In the present invention, use three phase heat treatment
Mode, the effect of first stage heat treatment is to make the organic binder bond added in granulation process wave
Send out；The effect of second stage heat treatment is to make titantium hydride decompose completely to obtain Titanium；3rd rank
The effect of section heat treatment is to make to form solid phase bonding between titanium powder granule, both ensures have enough
An interparticle bond strength and consistency, the most there is not granule (or internal microstructure) Fast Coarse
Change or integral sintered.The present invention is combined by the parameter regulating and controlling each processing step, can be prepared into
To have excellent sphericity, high fluidity and mean diameter and particle diameter distribution meet 3D print want
The high-quality fine grained spherical titanium metal dust asked.Especially, by firstly generating sludge proof
The new way of titantium hydride nano-powder particles, stably has the Titanium of greatly activity, can be effective
Oxygen content in the titanium powder granule of the final preparation of control, and whole piece syntheti c route technique is simple,
Easily operated, greatly reduce cost compared with the preparation method having other pure titanium micron powders.
Accompanying drawing explanation
The thing of the nanometer titanium hydride powders of Fig. 1 embodiment of the present invention 1 preparation detects collection of illustrative plates mutually.
The microstructure of nanometer titanium hydride powders of Fig. 2 embodiment of the present invention 2 preparation, crystal
Structure and particle diameter distribution；Wherein a is the high power transmission electron microscope shape appearance figure of nanometer titanium hydride powders,
B is the SEAD collection of illustrative plates of nanometer titanium hydride powders granule, and c is nanometer titanium hydride powders
The particle diameter distribution statistics result of granule.
The thing of the titanium powder that Fig. 3 embodiment of the present invention 1 prepares detects collection of illustrative plates mutually.
The microstructure of the titanium powder granule that Fig. 4 embodiment of the present invention 2 prepares and particle diameter
Distribution；Wherein a is the scanning electron microscope shape appearance figure of titanium powder, and b is the high power shape of single titanium granule
Looks figure, c is the particle diameter distribution statistics result of titanium powder granule.
The Titanium powder particle that table 1 Example 1 and Example 2 of the present invention prepares
Sphericity, mobility and Density Detection result.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but the present invention is not limited to following
Embodiment.
Example 1, using raw material high purity titanium bulk (purity 99.99wt%) as anode, at indifferent gas
Under body ar gas environment, forming high intensity electric arc by discharge process, striking current is 100A,
Arc voltage is 10V, then passes to hydrogen, and hydrogen is 1:1 with the ratio of noble gas, logical
Cross gas phase reaction and generate titantium hydride (TiH2), form solid-state titantium hydride nano-particle after condensation,
Such as Fig. 1；Polyvinyl alcohol, Polyethylene Glycol and deionized water are configured to titantium hydride nano-particle
Suspension slip, utilizes centrifugal atomizing drying means to carry out agglomeration granulation, it is thus achieved that the ball of 20 μm
Shape titanium hydride particles；The tube furnace using argon shield carries out heat to the titanium hydride powders after pelletize
Processing, first stage heat treatment temperature is 230 DEG C, temperature retention time 120min；Second stage heat
Treatment temperature is 700 DEG C, and temperature retention time is 180min；Phase III heat treatment temperature is
900 DEG C, temperature retention time is 90min, finally cools to room temperature with the furnace, obtains having high densification
Property, the fine grained micron-size spherical titanium powder of high fluidity, low oxygen content.The titanium prepared
Powder thing detects collection of illustrative plates such as Fig. 3, its sphericity, apparent density, mobility and measurement of oxygen content mutually
The results are shown in Table 1.
Example 2, using raw material high purity titanium bulk (purity 99.99wt%) as anode, at indifferent gas
Under body helium environment, forming high intensity electric arc by discharge process, striking current is 250A,
Arc voltage is 30V, then passes to hydrogen, and hydrogen is 1:3 with the ratio of noble gas, logical
Cross gas phase reaction and generate titantium hydride (TiH2), form solid-state titantium hydride nano-particle after condensation,
Its microstructure and particle diameter are distributed such as Fig. 2；By polyvinyl alcohol, Polyethylene Glycol and deionized water with
Titantium hydride nano-particle is configured to suspension slip, utilizes centrifugal atomizing drying means to reunite
Pelletize, it is thus achieved that the spherical titanium hydride particles of 50 μm；Use the tube furnace of argon shield to pelletize
After titanium hydride powders carry out heat treatment, first stage heat treatment temperature is 280 DEG C, during insulation
Between 90min；Second stage heat treatment temperature is 750 DEG C, and temperature retention time is 120min；3rd
Phase heat treatment temperature is 950 DEG C, and temperature retention time is 60min, finally cools to room temperature with the furnace,
Obtain the fine grained micron-size spherical titanium powder with high compactness, high fluidity, low oxygen content.
The titanium valve microstructure prepared and particle diameter distribution such as Fig. 4, its sphericity, apparent density,
Mobility and measurement of oxygen content the results are shown in Table 1.
The physical parameter of the titanium powder that table 1 Example 1 and Example 2 of the present invention prepares
Claims (1)
1. being applicable to the preparation method that 3D prints the fine grained sized spherical titanium powder of demand, it is special
Levy and be, comprise the following steps:
(1) using high purity titanium bulk as anode, under noble gas argon or helium environment,
Forming high intensity electric arc by discharge process, striking current is 100～250A, and arc voltage is
10～30V, then pass to hydrogen, hydrogen is 1:(1～3 with the volume ratio of noble gas),
Titantium hydride (TiH is generated by gas phase reaction2), form solid-state titantium hydride nano-particle after condensation；
(2) hydrogenation prepared by polyvinyl alcohol, Polyethylene Glycol and deionized water and step (1)
Titanium nano-particle is configured to suspension slip, carries out agglomeration granulation, it is thus achieved that the ball of 20～50 μm
Shape titanium hydride particles；
(3) spherical hydrogenation after the pelletize that step (2) is prepared by the tube furnace of employing argon shield
Titanium granule carries out heat treatment, and first stage heat treatment temperature is 230～280 DEG C, and temperature retention time is
60～120min；Second stage heat treatment temperature is 700～750 DEG C, and temperature retention time is
120～180min；Phase III heat treatment temperature is 900～950 DEG C, and temperature retention time is
60～90min, finally cool to room temperature with the furnace, obtain having high compactness, high fluidity, low
The fine grained micron-size spherical titanium powder of oxygen content；
Utilize the regulation and control of step (1) striking current, voltage and hydrogen and inert gas ratio, adjust
The productivity of whole nanometer titanium hydride powders granule and particle size, make mean diameter at 30～80nm models
In enclosing.
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| US11590568B2 (en) | 2019-12-19 | 2023-02-28 | 6K Inc. | Process for producing spheroidized powder from feedstock materials |
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