CN109746445A - A kind of processing method suitable for 4D printing niti-shaped memorial alloy - Google Patents
A kind of processing method suitable for 4D printing niti-shaped memorial alloy Download PDFInfo
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- CN109746445A CN109746445A CN201910080768.7A CN201910080768A CN109746445A CN 109746445 A CN109746445 A CN 109746445A CN 201910080768 A CN201910080768 A CN 201910080768A CN 109746445 A CN109746445 A CN 109746445A
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- Y—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
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Abstract
The invention belongs to alloys to form manufacture correlative technology field, it discloses a kind of processing methods suitable for 4D printing niti-shaped memorial alloy, and the processing method is the following steps are included: (1) prints niti-shaped memorial alloy part using SLM printing-forming 4D；Wherein, the Nitinol that the material of the 4D printing niti-shaped memorial alloy part is made of nickel and titanium, based on mass fraction, the mass fraction of nickel is 55%~56%；The mass fraction of titanium is 44%~45%；(2) by 4D printing niti-shaped memorial alloy heat parts to 300 DEG C~700 DEG C, and 30min~90min is kept the temperature；(3) 4D printing niti-shaped memorial alloy part is cooled to room temperature, thus completes the processing of the 4D printing niti-shaped memorial alloy part.Process of the present invention is simple, easy to implement, and flexibility is preferable, with strong applicability.
Description
Technical field
The invention belongs to alloys to form manufacture correlative technology field, be suitable for 4D more particularly, to one kind and print NiTi
The processing method of marmem.
Background technique
With the rapid development of marmem, NiTi based alloy with its excellent shape memory effect, super-elasticity with
And good mechanical performance and obtained most extensively research and application.Due to the continuous development and progress of manufacturing technology, scholars
The research of memorial alloy is started gradually deeply, document points out that Ultimum Ti is made to possess better shape after processing
Memory effect and super-elasticity, three kinds of heat treatment process of usual memory, i.e. heat-treated under medium temperature (are protected after cold working in 400 DEG C~500 DEG C
Temperature), low-temperature treatment (full annealing post-processing molding, then at 200 DEG C~300 DEG C keep the temperature), (800 DEG C~1000 DEG C of high-temperature process
Chilling after uniform treatment is kept the temperature then at 400 DEG C or so), heat-treated under medium temperature and high-temperature process can improve the limit stress of sliding deformation,
Easily obtain good shape memory effect and superelastic properties.
It after 4D printing technique was suggested from 2013, just has received widespread attention, 4D printing technique is 3D printing technique
The variation of shape, performance and function occurs by extraneous stimulation for the product combined with intellectual material, the finished product that 4D is printed,
And be aided with mathematically modeling method and be achieved specific change, so that it be made to meet the application demand in every field.In biology
Medical aspect, 4D printing marmem can be used as the manufacture material of orthopaedics inner fixation surgical instrument, can manufacture shape memory
With the serial orthopaedics inner fixation surgical instrument such as fund " long Bone plate ", " patella claw ".Having now been found that has " memory " shape energy
For the alloy of power up to 80 kinds, what is applied is mainly nickel-titanium shape memory alloy material.
But the research that 4D prints Nitinol at present is still in infancy, technological parameter is to phase-change characteristic, mechanical property
Energy, porosity and geometrical characteristic have a significant impact, however, the hardly seen shape note about 4D printing niti-shaped memorial alloy
Recall effect and hyperelastic research.Correspondingly, this field can be improved 4D printing nickel-titanium shape memory conjunction there is one kind is developed
The technical need of the hyperelastic processing method suitable for 4D printing niti-shaped memorial alloy of gold.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, it is suitable for 4D the present invention provides one kind and prints NiTi shape
The processing method of memorial alloy studies and devises one based on the preparation characteristic of existing 4D printing niti-shaped memorial alloy
Kind can be improved the hyperelastic processing side suitable for 4D printing niti-shaped memorial alloy of 4D printing niti-shaped memorial alloy
Method.The processing method by using reasonable process conditions, improve 4D printing niti-shaped memorial alloy super-elasticity and
Shape memory effect, process is simple, easy to implement, and flexibility is preferable, with strong applicability.
To achieve the above object, the present invention provides a kind of processing sides suitable for 4D printing niti-shaped memorial alloy
Method, the processing method the following steps are included:
(1) niti-shaped memorial alloy part is printed using SLM printing-forming 4D；Wherein, the 4D prints NiTi shape
The Nitinol that the material of memorial alloy part is made of nickel and titanium, based on mass fraction, the mass fraction of nickel is 55%~
56%；The mass fraction of titanium is 44%~45%；
(2) by the 4D printing niti-shaped memorial alloy heat parts to 300 DEG C~700 DEG C, and keep the temperature 30min~
90min；
(3) 4D printing niti-shaped memorial alloy part is cooled to room temperature, thus completes the 4D printing NiTi
The processing of marmem part.
Parameter when further, using SLM printing shaping are as follows: laser power is 150W~250W, and scanning speed is
1000mm/s~1400mm/s, thickness are 30 μm~40 μm, and sweep span is 80~120 μm.
Further, in step (2), 4D printing niti-shaped memorial alloy part is put in high temperature box furnace；
Then, the high temperature box furnace is warming up to 300 DEG C~700 DEG C with the heating rate of 80 DEG C/h.
Further, argon gas is passed through in the high temperature box furnace using as protective gas.
Further, with the heating rate of 80 DEG C/h by the high temperature box furnace be warming up to 300 DEG C, 400 DEG C, 500 DEG C or
700 DEG C of person.
Further, the high temperature box furnace is warming up to 500 DEG C with the heating rate of 80 DEG C/h, and after heat preservation 30 minutes
It is cooled to room temperature.
Further, the high temperature box furnace is warming up to 700 DEG C with the heating rate of 80 DEG C/h, and keeps the temperature 30~90 points
It is cooled to room temperature after clock.
Further, the high temperature box furnace is warming up to 400 DEG C with the heating rate of 80 DEG C/h, and keeps the temperature 30~90 points
It is cooled to room temperature after clock.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, it is provided by the invention suitable
Processing method for 4D printing niti-shaped memorial alloy mainly has the advantages that
1. based on " when Nitinol is in low temperature (Ms or less), martensitic traoformation occurs for alloy, applies load meeting to it
It grows martensite variants along preferred orientation direction, makes alloy that macroshape occur and change, alloy is sprung back after unloading, and is protected
Stay residual deformation；When temperature reaches As, martensite reverse transformation occurs for material, and due to crystallographic order, dot matrix is revert to
Home position, alloy occur shape and restore ", the 4D is printed into niti-shaped memorial alloy heat parts to 300 DEG C~700
DEG C, and 30min~90min is kept the temperature, thus improve the shape memory effect and superlastic of 4D printing niti-shaped memorial alloy part
Property.
2. the high temperature box furnace is warming up to 500 DEG C with the heating rate of 80 DEG C/h, and it is cooled to after keeping the temperature 30 minutes
Room temperature has platy morphology so that obtained sample has very high B19' content, and wherein twin is that minor structure outstanding is special
Sign, this microstructure can more freely be changed into austenite when heated, and compared with needle-shaped " lath " form, provide
Bigger strain restores chance, and the microstructure characteristic of sample improves the strain rate of recovery close to 10%.
3. the processing method eliminates residual stress by heat treatment, crystal grain is refined, adjusts tissue, eliminates tissue defects,
Homogeneous material tissue and ingredient improve material property, and process is simple, and easy to implement, flexibility is preferable, with strong applicability.
4. parameter when using SLM printing shaping are as follows: laser power is 150~250W, scanning speed 1000-
1400mm/s, thickness are 30~40 μm, and sweep span is 80~120 μm, which thereby enhance the consistency of part.
Detailed description of the invention
Fig. 1 is the flow diagram of the processing method provided by the invention suitable for 4D printing niti-shaped memorial alloy.
Fig. 2 is the Nitinol geneva that the processing method for being suitable for 4D printing niti-shaped memorial alloy in Fig. 1 is related to
Martensite Volume Fraction variation with temperature curve and the signal of corresponding changes in crystal structure during body phase transformation and its reverse transformation
Figure.
Fig. 3 is the Nitinol shape that the processing method for being suitable for 4D printing niti-shaped memorial alloy in Fig. 1 is related to
Memory effect schematic diagram.
Fig. 4 be the heat treatment temperature that is related to of processing method for being suitable for 4D printing niti-shaped memorial alloy in Fig. 1 with
The change curve of time.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
Please refer to Fig. 1, Fig. 2, Fig. 3 and Fig. 4, the processing provided by the invention suitable for 4D printing niti-shaped memorial alloy
Method, the processing method mainly comprise the steps that
Step 1 prints niti-shaped memorial alloy part using SLM printing-forming 4D；Wherein, the 4D prints NiTi
The Nitinol that the material of marmem part is made of nickel and titanium, based on mass fraction, the mass fraction of nickel is
55%~56%；The mass fraction of titanium is 44%~45%.
Specifically, the NiTi atomic ratio of the Nitinol is close to 1:1, and nickel mass fraction is 55%~56%, remaining is
Titanium.The part of high-compactness in order to obtain, parameter when SLM printing shaping are as follows: laser power is 150~250W, scanning speed
For 1000-1400mm/s, thickness is 30~40 μm, and sweep span is 80~120 μm.
Step 2 by 4D printing niti-shaped memorial alloy heat parts to 300 DEG C~700 DEG C, and keeps the temperature 30min
~90min.
Specifically, the part is put into high temperature box furnace, and is passed through argon gas in the high temperature box furnace；Then will
The high temperature box furnace is warming up to 300 DEG C~700 DEG C and keeps the temperature 30min~90min, wherein the heating rate used for 80 DEG C/
h.Preferably, the high temperature box furnace is warming up to 500 DEG C, then keeps the temperature 30min.In present embodiment, pretreatment temperature is also
It can be 300 DEG C, 400 DEG C or 700 DEG C.
Fig. 2 is referred to, niti-shaped memorial alloy is martensitic phase at low temperature, is denoted as M phase, has B19 ' (orderly single
Tiltedly) structure is parent phase at high temperature, i.e. austenite phase, is denoted as A phase, has B2 (orderly body-centered cubic) structure.Referring to Fig. 3,
When Nitinol is in low temperature (Ms or less), martensitic traoformation occurs for alloy, and martensite variants edge can be made by applying load to it
The growth of preferred orientation direction makes alloy that macroshape occur and changes, and alloy is sprung back after unloading, and retains residual deformation；When
When temperature reaches As, martensite reverse transformation occurs for material, and due to crystallographic order, dot matrix revert to home position, alloy
Shape occurs to restore.By heat treatment, residual stress is eliminated, refines crystal grain, adjusts tissue, eliminates tissue defects, homogeneous material
Tissue and ingredient improve material property, reduce austenite content in Alloy At Room Temperature, B19' phase can be used to B2 phase in microstructure
It is also higher to convert volume, the shape memory effect of Nitinol is improved with this.
Wherein, high cooldown rate can inhibit B2 phase to arrive the transformation of B19' phase, and the B2 phase in sample is caused to retain, in room temperature
B2 phase too high levels will affect alloy shape memory effect, and faster solidification rate also implies that it will be comprising more lockings
Dislocation, defect and thermotropic stress.
Maximum recoverable strain is calculated as after sample initially pressurizes and unloads, and is heating the sample to 120 DEG C (all
In the case of be far below Af) when the deformation that restores completely.The sample annealed at 500 DEG C shows higher strain recovery rate,
In the range of 8.5~10%, and the strain restored in the sample annealed at 1000 DEG C is reduced, this is because stress elimination effect,
The relative concentration comprehensive function of B2 and B19' phase in microstructure characteristic and NiTi alloy sample through Overheating Treatment and cause
's.
Defect and stress are only partially buried in oblivion when due to annealing at a lower temperature, when annealing at 500 DEG C, reversely
Martensitic traoformation is suppressed.Therefore in 500 DEG C of annealing, B2 score is lower than the B2 score in 1000 DEG C of annealing, heat treatment temperature
Preferably 300 DEG C~700 DEG C of degree.
When sample to be heated on Af, the shape memory effect of generation is the result of B19' to B2 conversion.Sample tool
There are slightly lower B2 content or higher B19' content, then the available conversion volume of B19' to B2 is also higher in microstructure, can be with
Show higher recoverable strain.In addition, the concentration of B19' is even higher for the sample annealed at 500 DEG C, therefore these
Sample is shown handled than accordingly after the higher strain of sample restore.In particular, the sample annealed at 500 DEG C is with very high
B19' content, have platy morphology, wherein twin is sub-structural features outstanding, and this microstructure when heated can be more
Freely it is changed into austenite, and compared with needle-shaped " lath " form, provides bigger strain and restore chance.This is because
The latter is based on slip dislocation, the invertibity of crystal structure, the microcosmic knot of sample caused by reducing due to plastic strain accumulation
Structure feature promotes the Large strain rate of recovery close to 10%.
4D printing niti-shaped memorial alloy part is cooled to room temperature by step 3, thus completes the 4D printing
The processing of niti-shaped memorial alloy part.Specifically, the part is placed in high temperature box furnace and is cooled to room temperature.
With several specific embodiments, the present invention is further described in detail below:
Embodiment 1
What first embodiment of the invention provided, which is suitable for the processing method that 4D prints niti-shaped memorial alloy, mainly includes
Following steps: 4D printing niti-shaped memorial alloy part is put into high temperature box furnace, and is passed through argon gas in furnace；It again will be high
Warm batch-type furnace is warming up to 300 DEG C, and heating rate is 80 DEG C/h, is cooled to room temperature in furnace after keeping the temperature 30min.
Embodiment 2
What second embodiment of the invention provided, which is suitable for the processing method that 4D prints niti-shaped memorial alloy, mainly includes
Following steps: 4D printing niti-shaped memorial alloy part is put into high temperature box furnace, and is passed through argon gas in furnace；It again will be high
Warm batch-type furnace is warming up to 300 DEG C, and heating rate is 80 DEG C/h, is cooled to room temperature in furnace after keeping the temperature 60min.
Embodiment 3
What third embodiment of the invention provided, which is suitable for the processing method that 4D prints niti-shaped memorial alloy, mainly includes
Following steps: 4D printing niti-shaped memorial alloy part is put into high temperature box furnace, and is passed through argon gas in furnace；It again will be high
Warm batch-type furnace is warming up to 300 DEG C, and heating rate is 80 DEG C/h, is cooled to room temperature in furnace after keeping the temperature 90min.
Embodiment 4
What fourth embodiment of the invention provided, which is suitable for the processing method that 4D prints niti-shaped memorial alloy, mainly includes
Following steps: 4D printing niti-shaped memorial alloy part is put into high temperature box furnace, and is passed through argon gas in furnace；It again will be high
Warm batch-type furnace is warming up to 400 DEG C, and heating rate is 80 DEG C/h, is cooled to room temperature in furnace after keeping the temperature 30min.
Embodiment 5
What fifth embodiment of the invention provided, which is suitable for the processing method that 4D prints niti-shaped memorial alloy, mainly includes
Following steps: 4D printing niti-shaped memorial alloy is put into high temperature box furnace, and is passed through argon gas in furnace；Again by high-temperature cabinet
Formula furnace is warming up to 400 DEG C, and heating rate is 80 DEG C/h, is cooled to room temperature in furnace after keeping the temperature 60min.
Embodiment 6
What sixth embodiment of the invention provided, which is suitable for the processing method that 4D prints niti-shaped memorial alloy, mainly includes
Following steps: 4D printing niti-shaped memorial alloy is put into high temperature box furnace, and is passed through argon gas in furnace；Again by high-temperature cabinet
Formula furnace is warming up to 400 DEG C, and heating rate is 80 DEG C/h, is cooled to room temperature in furnace after soaking time 90min.
Embodiment 7
What seventh embodiment of the invention provided, which is suitable for the processing method that 4D prints niti-shaped memorial alloy, mainly includes
Following steps: 4D printing niti-shaped memorial alloy part is put into high temperature box furnace, and is passed through argon gas in furnace；It again will be high
Warm batch-type furnace is warming up to 500 DEG C, and heating rate is 80 DEG C/h.It is cooled to room temperature in furnace after heat preservation 30min.
Embodiment 8
What eighth embodiment of the invention provided, which is suitable for the processing method that 4D prints niti-shaped memorial alloy, mainly includes
Following steps: 4D printing niti-shaped memorial alloy part is put into high temperature box furnace, and is passed through argon gas in furnace；It again will be high
Warm batch-type furnace is warming up to 500 DEG C, and heating rate is 80 DEG C/h；It is cooled to room temperature in furnace after soaking time 60min.
Embodiment 9
What ninth embodiment of the invention provided, which is suitable for the processing method that 4D prints niti-shaped memorial alloy, mainly includes
Following steps: 4D printing niti-shaped memorial alloy part is put into high temperature box furnace, and is passed through argon gas in furnace；It again will be high
Warm batch-type furnace is warming up to 500 DEG C, and heating rate is 80 DEG C/h, is cooled to room temperature in furnace after keeping the temperature 90min.
Embodiment 10
What tenth embodiment of the invention provided, which is suitable for the processing method that 4D prints niti-shaped memorial alloy, mainly includes
Following steps: 4D printing niti-shaped memorial alloy part is put into high temperature box furnace, and is passed through argon gas in furnace；It again will be high
Warm batch-type furnace is warming up to 600 DEG C, and heating rate is 80 DEG C/h, is cooled to room temperature in furnace after keeping the temperature 30min.
Embodiment 11
The processing method suitable for 4D printing niti-shaped memorial alloy that eleventh embodiment of the invention provides mainly is wrapped
It includes following steps: 4D printing niti-shaped memorial alloy part being put into high temperature box furnace, and is passed through argon gas in furnace, then will
High temperature box furnace is warming up to 600 DEG C, and heating rate is 80 DEG C/h.It is cooled to room temperature in furnace after heat preservation 60min.
Embodiment 12
The processing method suitable for 4D printing niti-shaped memorial alloy that twelveth embodiment of the invention provides mainly is wrapped
It includes following steps: 4D printing niti-shaped memorial alloy part being put into high temperature box furnace, and is passed through argon gas in furnace；Again will
High temperature box furnace is warming up to 600 DEG C, and heating rate is 80 DEG C/h.It is cooled to room temperature in furnace after heat preservation 90min.
Embodiment 13
The processing method suitable for 4D printing niti-shaped memorial alloy that thriteenth embodiment of the invention provides mainly is wrapped
It includes following steps: 4D printing niti-shaped memorial alloy part being put into high temperature box furnace, and is passed through argon gas in furnace；Again will
High temperature box furnace is warming up to 700 DEG C, and heating rate is 80 DEG C/h.It is cooled to room temperature in furnace after heat preservation 30min.
Embodiment 14
The processing method suitable for 4D printing niti-shaped memorial alloy that fourteenth embodiment of the invention provides mainly is wrapped
It includes following steps: 4D printing niti-shaped memorial alloy part being put into high temperature box furnace, and is passed through argon gas in furnace；Again will
High temperature box furnace is warming up to 700 DEG C, and heating rate is 80 DEG C/h.It is cooled to room temperature in furnace after heat preservation 60min.
Embodiment 15
The processing method suitable for 4D printing niti-shaped memorial alloy that fifteenth embodiment of the invention provides mainly is wrapped
It includes following steps: 4D printing niti-shaped memorial alloy part being put into high temperature box furnace, and is passed through argon gas in furnace；Again will
High temperature box furnace is warming up to 700 DEG C, and heating rate is 80 DEG C/h.It is cooled to room temperature in furnace after heat preservation 90min.
Processing method provided by the invention suitable for 4D printing-forming niti-shaped memorial alloy, the processing method are logical
Overheating Treatment eliminates residual stress, refines crystal grain, adjusts tissue, eliminates tissue defects, homogeneous material tissue and ingredient, improves
Material property, reduce Alloy At Room Temperature in austenite content so that in microstructure B19' phase to B2 phase available conversion volume
It is higher, the shape memory effect of Nitinol is improved with this.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (8)
1. it is a kind of suitable for 4D printing niti-shaped memorial alloy processing method, which is characterized in that the processing method include with
Lower step:
(1) niti-shaped memorial alloy part is printed using SLM printing-forming 4D；Wherein, the 4D prints nickel-titanium shape memory
The Nitinol that the material of alloy part is made of nickel and titanium, based on mass fraction, the mass fraction of nickel are 55%~56%；
The mass fraction of titanium is 44%~45%；
(2) by 4D printing niti-shaped memorial alloy heat parts to 300 DEG C~700 DEG C, and 30min~90min is kept the temperature；
(3) 4D printing niti-shaped memorial alloy part is cooled to room temperature, thus completes the 4D printing NiTi shape
The processing of memorial alloy part.
2. the processing method suitable for 4D printing niti-shaped memorial alloy as described in claim 1, it is characterised in that: use
Parameter when SLM printing shaping are as follows: laser power is 150W~250W, and scanning speed is 1000mm/s~1400mm/s, thickness
It is 30 μm~40 μm, sweep span is 80~120 μm.
3. the processing method suitable for 4D printing niti-shaped memorial alloy as described in claim 1, it is characterised in that: step
(2) in, 4D printing niti-shaped memorial alloy part is put in high temperature box furnace；Then, with the heating speed of 80 DEG C/h
The high temperature box furnace is warming up to 300 DEG C~700 DEG C by rate.
4. the processing method suitable for 4D printing niti-shaped memorial alloy as claimed in claim 3, it is characterised in that: described
Argon gas is passed through in high temperature box furnace using as protective gas.
5. the processing method suitable for 4D printing niti-shaped memorial alloy as claimed in claim 3, it is characterised in that: with 80
DEG C/high temperature box furnace is warming up to 300 DEG C, 400 DEG C, 500 DEG C or 700 DEG C by the heating rate of h.
6. the processing method suitable for 4D printing niti-shaped memorial alloy as claimed in claim 3, it is characterised in that: with 80
DEG C/high temperature box furnace is warming up to 500 DEG C, and is cooled to room temperature after keeping the temperature 30 minutes by the heating rate of h.
7. the processing method suitable for 4D printing niti-shaped memorial alloy as claimed in claim 3, it is characterised in that: with 80
DEG C/high temperature box furnace is warming up to 700 DEG C, and is cooled to room temperature after keeping the temperature 30~90 minutes by the heating rate of h.
8. the processing method suitable for 4D printing niti-shaped memorial alloy as claimed in claim 3, it is characterised in that: with 80
DEG C/high temperature box furnace is warming up to 400 DEG C, and is cooled to room temperature after keeping the temperature 30~90 minutes by the heating rate of h.
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