CN110449584A - The method that powder metallurgic method prepares medical degradable open celled foam zinc - Google Patents

The method that powder metallurgic method prepares medical degradable open celled foam zinc Download PDF

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Publication number
CN110449584A
CN110449584A CN201910842273.3A CN201910842273A CN110449584A CN 110449584 A CN110449584 A CN 110449584A CN 201910842273 A CN201910842273 A CN 201910842273A CN 110449584 A CN110449584 A CN 110449584A
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China
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powder
zinc
pore creating
celled foam
open celled
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穆永亮
葛启琦
王书豪
王丁丁
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Northeastern University China
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Northeastern University China
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/04—Metals or alloys
    • A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/56—Porous materials, e.g. foams or sponges
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/58—Materials at least partially resorbable by the body
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/02—Inorganic materials
    • A61L31/022—Metals or alloys
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/146—Porous materials, e.g. foams or sponges
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L31/148—Materials at least partially resorbable by the body
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007—Atmosphere
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
    • B22F3/1134—Inorganic fillers

Abstract

A kind of method that powder metallurgic method prepares medical degradable open celled foam zinc, carries out according to the following steps；(1) it will be mixed after zinc powder and pore creating material drying；(2) alcohol is added；(3) it is filled into compression moulding in mold；(4) it is placed in sintering furnace, carries out vacuum-sintering or covering graphite powder sintering, furnace cooling；(5) sintered material is placed in water, and keeps pore creating material soluble in water, and surplus material takes out drying.Method of the invention can control the size and porosity in aperture；The mechanical strength and mechanical property of sample can be controlled by sintering temperature and time, prepared open celled foam zinc compression strength is higher than human body spongy bone, and elasticity modulus matches with spongy bone, can satisfy body implanting material requirement.

Description

The method that powder metallurgic method prepares medical degradable open celled foam zinc
Technical field
The invention belongs to metallurgy and materials processing technology field, in particular to a kind of powder metallurgic method to prepare medical degradable The method of open celled foam zinc.
Background technique
Porous material is that recent decades start to rise, and foam metal has good buffering effect, heat-insulating sound-insulating, shielding Electromagnetic wave excellent effect, can be used for space flight, automobile, and the fields such as building can be used for biological implants in vivo, for that can drop The foam metal of solution does not need second operation taking-up as the intracorporal implantation material of biology, patient's pain is reduced, with biocompatibility Well, there are similar bony structures, be conducive to the growth of cell.
For using magnesium and magnesium based alloys, iron and ferrous alloy now for degradable stephanoporate material in organism more, The foam metal of zinc and zinc-containing alloy is as biological implants in vivo, magnesium base alloy foam metal degradation speed in simulated body fluid Too fast, ferrous alloy foam metal was degraded slowly, and zinc-containing alloy foam metal degradation rate between two, can be used as conjunction at it Suitable biodegradable material.
Have a great impact in terms of medicine and biology for degradable foamed metal, this material and organism have very well Compatibility and degradability, primarily now be applied to bracket and Bone Defect Repari field, future have very big development prospect；However, It is more to the research of foamed aluminium and foam magnesium since the mechanical property of pure zinc is not strong, it is relatively fewer to the research of foam zinc.
It is moderate that a kind of degradation speed is developed at present, and controlled porosity has the porous material of certain mechanical properties, for medicine The development of the porous material in field is significant.
Summary of the invention
The object of the present invention is to provide a kind of methods that powder metallurgic method prepares medical degradable open celled foam zinc, pass through tune The temperature of the ratio of whole zinc powder and pore creating material, the pressure of compacting and sintering prepares elasticity modulus and peak stress etc. and biology Foam Zinc material similar in body sclerotin solves screw material, intravascular stent, the medicine such as porous marrow multi-joint for orthopaedy Aspect application problem.
Method of the invention carries out according to the following steps；
1, moisture removal is respectively dried in zinc powder and pore creating material, is then uniformly mixed and mixed-powder is made；The pore-creating Agent is sodium chloride powder or urea powder, and the volume ratio of zinc powder and pore creating material is 1:(1~4)；
2, dehydrated alcohol is added into mixed-powder, mixed slurry is made；
3, mixed slurry is filled into mold, using press machine compression moulding, 100~400MP of pressing pressure is made pre- Body processed；
4, precast body is placed in sintering furnace, carries out vacuum-sintering or covering graphite powder sintering, sintering temperature 340~410 DEG C, then 2~4h of sintering time cools to room temperature with the furnace, obtain sintered material；
5, sintered material is placed in water, keeps pore creating material soluble in water, surplus material take out drying moisture, be made it is medical can Degradation open celled foam zinc.
18~150 μm of the partial size of above-mentioned zinc powder.
Partial size≤1.7mm of above-mentioned sodium chloride powder；Partial size≤1.7mm of urea powder.
In above-mentioned step 1,70 ± 2 DEG C of drying temperature, time at least 30min.
In above-mentioned step 2, the ratio of dehydrated alcohol and mixed-powder is 0.1~0.3mL/g by liquid-solid ratio.
In above-mentioned step 3, dwell time at least 15min when compression moulding, pressure maintaining number at least 2 times, pressing speed 0.5~1KN/s.
In above-mentioned step 4, when carrying out vacuum-sintering, it is first evacuated to vacuum degree≤0.09MPa, then with 15~30 DEG C/speed of min is warming up to 340~410 DEG C and is sintered；When carrying out covering graphite powder sintering, the grain of the graphite powder of use 38~48 μm of degree, is covered on precast body surface, 10~15mm of cladding thickness, then with the speed of 15~30 DEG C/min for graphite powder 340~410 DEG C are warming up to be sintered.
In the above method, when the pore creating material used is urea powder, after precast body is made, precast body is placed in water In, keep pore creating material soluble in water, moisture removal is removed in then removal drying, then is sintered in the way of step 4, and the sintered material of acquisition is straight It connects as medical degradable open celled foam zinc.
In the above method, sintered material is placed in water, 24~48h of standing time, during this period, when sodium chloride is dense in water Degree reaches 6.0 ± 0.2mol/L or when urea concentration reaches 19.0 ± 0.45mol/L, sintered material taking-up is placed into new In water.
Above-mentioned medical degradable open celled foam zinc is open-celled structure, porosity 40~78%, 0.8~2mm of aperture.
The relative density 86~97.5% of above-mentioned medical degradable open celled foam zinc.
In the above method, pore creating material is divided into bulky grain pore creating material, middle particle pore creating material and little particle pore creating material；Work as progress When step 1, zinc powder mixes respectively with bulky grain pore creating material, middle particle pore creating material and little particle pore creating material, and bulky grain is respectively prepared Mixed-powder, middle particle mixed-powder and little particle mixed-powder；When carrying out step 2, be respectively prepared bulky grain mixed slurry, Middle particle mixed slurry and little particle mixed slurry；When carrying out step 3, by bulky grain mixed slurry, middle particle mixed slurry In order or inverted order is filled into mold with little particle mixed slurry, precast body is made；After step 5, aperture edge is made The medical degradable open celled foam zinc of axial gradient distribution；Wherein partial size≤the 1.7mm and > 0.88mm of bulky grain pore creating material, in Partial size≤the 0.88mm and > 0.5mm of particle pore creating material, partial size≤0.5mm of little particle pore creating material.
In the above method, when using sodium chloride powder as pore creating material, the medical degradable open celled foam zinc of acquisition 0.2~1GPa of elasticity modulus, 4~45MPa of peak stress；When using urea powder as pore creating material, the medical of acquisition is dropped Solve the 0.2~0.4GPa of elasticity modulus, 3~20MPa of peak stress of open celled foam zinc.
The present invention uses powder metallurgic method, can change the size and hole in aperture by the size and ratio of pore creating material Rate；When the partial size of zinc powder determines, the relative density of precast body is approximate with target product, therefore by by the opposite of precast body Curve is made in consistency and pressing pressure, and the pressing pressure of sample can be determined by the relative density of precast body；By being sintered Temperature and time controls the mechanical strength and mechanical property of sample, and selective chlorination sodium or urea is pore creating material；Pore creating material is easy to Removal, harmless to the body, foam zinc porosity is easily controllable；Human body cancellous bone elasticity modulus is in 0.06~3GPa, peak stress In 0.3~1.5MPa, prepared open celled foam zinc compression strength is higher than human body spongy bone, and elasticity modulus and spongy bone phase Match, so that elasticity modulus is matched with spongy bone by changing porosity, can satisfy body implanting material requirement.
Detailed description of the invention
Fig. 1 shows for the method flow that the powder metallurgic method in the embodiment of the present invention 1 prepares medical degradable open celled foam zinc It is intended to；
Fig. 2 is about 66.7% (i.e. zinc powder and pore creating material volume under the conditions of Different Zinc powder diameter of the present invention, to select porosity Than the precast body for 1:2), pressing pressure is controlled between 100~400MPa, is tested every 50MPa, manufactured compacting pressure Power-relative density curve graph；In figure, ★ is 150 μm of zinc powder partial size, ● it is 18 μm of zinc powder partial size；
Fig. 3 is the x-ray diffraction pattern of the medical degradable open celled foam zinc in the embodiment of the present invention 4；In figure, upper figure is Vacuum-sintering, the following figure are covering graphite powder sintering；
Fig. 4 is corrosion rate curve of the medical degradable open celled foam zinc in simulated body fluid in the embodiment of the present invention 2 Figure；
Fig. 5 is the stress-strain curve diagram of the medical degradable open celled foam zinc in the embodiment of the present invention 1~4；In figure, 1- 1 is embodiment 1, and 1-2 is embodiment 2, and 1-3 is embodiment 3, and 1-4 is embodiment 4；
Fig. 6 is the embodiment of the present invention, the stress-strain curve diagram of the medical degradable open celled foam zinc in 5~8；In figure, 2-1 is embodiment 5, and 2-2 is embodiment 6, and 2-3 is embodiment 7, and 2-4 is embodiment 8；
Fig. 7 is the displaing micro photo figure of the medical degradable open celled foam zinc in the embodiment of the present invention 1~8；In figure, a is real Example 1 is applied, b is embodiment 2, and c is embodiment 3, and d is embodiment 4, and e is embodiment 5, and f is embodiment 6, and g is embodiment 7, and h is real Apply example 8；
Fig. 8 is the appearance photo figure of the medical degradable open celled foam zinc in the embodiment of the present invention；In figure, a is embodiment 5, b be embodiment 6, and c is embodiment 7, and d is embodiment 8, and e is embodiment 2, and f is embodiment 3.
Specific embodiment
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
The zinc powder purity 99.99% used in the embodiment of the present invention.
In the embodiment of the present invention, determine that the quality dosage of zinc powder and pore creating material calculates according to the theoretic porosity of target product Method is pressed:
m1=V × ρ1×(1-P) (1)
With
m2=V × ρ2×P (2)
In formula, m1For zinc powder quality, unit g；m2For pore creating material quality, unit g；V is medical degradable open celled foam zinc Volume, unit cm3；P is the theoretic porosity of medical degradable open celled foam zinc, ρ1For the density of zinc, value 7.14g/cm3；ρ2 For pore creating material density；When pore creating material is sodium chloride, ρ2Value 2.16g/cm3, when pore creating material is urea, ρ2Value 1.35g/ cm3；
According to the quality dosage of formula (1) and (2) calculated zinc powder and pore creating material, volumetric usage is calculated by known density Than.
Corrosion test is carried out to medical degradable open celled foam zinc using simulation liquid in the embodiment of the present invention, is impregnated weightless Testing the electrolyte solution used selects pH as shown in table 1 for 7.4 simulated body fluid SBF, SBF proportion；
Table 1
Sequentially Drug Additive amount Purity Relative molecular mass
1 NaCl 8.035g 99.5% 58.4430
2 NaHCO3 0.355g 99.5% 84.0068
3 KCl 0.225g 99.5% 74.5515
4 K2PHO4.3H2O 0.231g 99.0% 228.2220
5 MgCl2.6H2O 0.311g 99.0% 203.3034
6 C (HCl)=1mol/L 39mL --- ---
7 CaCl2 0.292g 95.0% 110.9848
8 NaSO4 0.072g 99.0% 142.0428
9 Tris (trishydroxymethylaminomethane) 6.118g 99.0% 121.1356
10 C (HCl)=1mol/L 0~5mL --- ---
The size of medical degradable open celled foam zinc in the embodiment of the present invention is 50 × 5mm of Φ.
The dehydrated alcohol used in the embodiment of the present invention is commercial products.
In the embodiment of the present invention, using 18 μm and 150 μm of zinc powder of partial size, using partial size≤0.88mm and the chlorine of > 0.5mm Change sodium powder end as pore creating material, carries out precast body relative density and pressing pressure test, carry out 7 groups of experiments, pressure point respectively Not Wei 100,150,200,250,300,350 and 400MPa, by the precast body preparation method of embodiment 1, the pressing pressure-of acquisition Relative density Dependence Results are as shown in Figure 2.
In the embodiment of the present invention, when sintered material is placed in water, 24~48h of standing time, during this period, when in water Sodium chloride concentration reaches 6.0 ± 0.2mol/L or when urea concentration reaches 19.0 ± 0.45mol/L, and sintered material is taken out It is placed into new water.
In the embodiment of the present invention, when precast body is placed in water, 24~48h of standing time, during this period, when being urinated in water When plain concentration reaches 19.0 ± 0.45mol/L, sintered material taking-up is placed into new water.
70 ± 2 DEG C of drying temperature in the embodiment of the present invention, time at least 30min.
The relative density 86~97.5% of medical degradable open celled foam zinc in the embodiment of the present invention.
The following are the preferred embodiment of the present invention.
Embodiment 1
Process is as shown in Figure 1；
Moisture removal is respectively dried in zinc powder and pore creating material, is then uniformly mixed and mixed-powder is made；Pore creating material is chlorination The volume ratio of sodium powder end, zinc powder and pore creating material is 1:1；18 μm of the partial size of zinc powder；Partial size≤0.88mm of sodium chloride powder and > 0.5mm；70 ± 2 DEG C of drying temperature, time at least 30min；
Dehydrated alcohol is added into mixed-powder, mixed slurry is made；The ratio of dehydrated alcohol and mixed-powder is solid by liquid Than for 0.1mL/g；
Mixed slurry is filled into mold, using press machine compression moulding, precast body is made in pressing pressure 400MP；Pressure Dwell time 15min when system reaches 400MPa, pressure maintaining number 4 times, pressing speed 1KN/s；
Precast body is placed in sintering furnace, carry out covering graphite powder sintering, 400 DEG C of sintering temperature, sintering time 2h, then It cools to room temperature with the furnace, obtains sintered material；Graphite powder is covered on precast body surface, cladding thickness 15mm, then with 20 DEG C/ The speed of min is warming up to 400 DEG C and is sintered；
Sintered material is placed in water, keeps pore creating material soluble in water, surplus material takes out drying moisture, and medical drop is made Solve open celled foam zinc；Its porosity 41.6%, 0.8~2mm of aperture, elasticity modulus 0.977GPa, peak stress 44.690MPa, Fail modulus 0.625GPa；Stress-strain diagram is as shown in figure 5, microphoto is as shown in Figure 7a.
Embodiment 2
With embodiment 1, difference is method；
(1) volume ratio of zinc powder and pore creating material is 1:2；50 μm of the partial size of zinc powder；Partial size≤0.88mm of sodium chloride powder And > 0.5mm；
(2) ratio of dehydrated alcohol and mixed-powder is 0.2mL/g by liquid-solid ratio；
(3) pressing pressure 300MP, dwell time 20min, pressure maintaining number 3 times, pressing speed 0.8KN/s；
(4) 340 DEG C of sintering temperature, sintering time 4h；Graphite powder cladding thickness 10mm, is warming up to the speed of 15 DEG C/min 340℃；
(5) medical degradable open celled foam zinc porosity 57.8%, elasticity modulus 0.451GPa, peak stress 11.787MPa fail modulus 0.240GPa；Stress-strain diagram is as shown in figure 5, microphoto is as shown in Figure 7b, appearance photo As figure 8 e shows；
Corrosion test is carried out to medical degradable open celled foam zinc, medical degradable open celled foam zinc is placed in simulated body fluid It is impregnated in SBF, impregnating number of days is respectively 1d, 2d, 4d, 8d, 14d, 22d and 32d, and corrosion rate curve is as shown in figure 4, can by figure See, impregnating initial phase, corrosion rate is larger, and rate changes also greatly, and after soaking time is more than four days, corrosion rate becomes Slowly, corrosion rate substantially remains in 0.15mm/year or so, i.e. 2.8g/m2/d；Bone Defect Repari instrument, which usually requires that, can maintain 3~6 Month service phase, external degradation rate is less than 0.5mm/year, it follows that medical degradable open celled foam zinc reaches Bone Defect Repari device Tool degradation standard.
Embodiment 3
With embodiment 1, difference is method；
(1) volume ratio of zinc powder and pore creating material is 1:3；85 μm of the partial size of zinc powder；Partial size≤0.88mm of sodium chloride powder And > 0.5mm；
(2) ratio of dehydrated alcohol and mixed-powder is 0.3mL/g by liquid-solid ratio；
(3) pressing pressure 200MP, dwell time 25min, pressure maintaining number 2 times, pressing speed 0.6KN/s；
(4) 410 DEG C of sintering temperature, sintering time 2.5h；Graphite powder cladding thickness 11mm is heated up with the speed of 30 DEG C/min It is sintered to 410 DEG C；
(5) medical degradable open celled foam zinc porosity 69.3%, elasticity modulus 0.404GPa, peak stress 4.981MPa, fail modulus 0.583GPa；Stress-strain diagram is as shown in figure 5, microphoto is as shown in Figure 7 c, and appearance photo is such as Shown in Fig. 8 f.
Embodiment 4
With embodiment 1, difference is method；
(1) volume ratio of zinc powder and pore creating material is 1:4；150 μm of the partial size of zinc powder；Partial size≤1.7mm of sodium chloride powder And > 0.88mm；
(2) ratio of dehydrated alcohol and mixed-powder is 0.15mL/g by liquid-solid ratio；
(3) pressing pressure 100MP, dwell time 30min, pressure maintaining number 2 times, pressing speed 0.5KN/s；
(4) parallel test is used, two groups of identical precast bodies carry out vacuum-sintering and covering graphite powder sintering, sintering respectively It 350 DEG C of temperature, sintering time 3h, then cools to room temperature with the furnace, obtains two groups of sintered materials；When carrying out vacuum-sintering, first It is evacuated to vacuum degree≤0.09MPa, then 350 DEG C is warming up to the speed of 25 DEG C/min and is sintered；When carrying out covering stone When ink powder is sintered, graphite powder cladding thickness 12mm is warming up to 350 DEG C with the speed of 25 DEG C/min and is sintered；
(5) two groups of medical degradable open celled foam zinc, respectively vacuum-sintering foam zinc and covering graphite powder sintering are obtained Foam zinc, porosity are respectively 77.1% and 77.5%, and elasticity modulus is respectively 0.270GPa and 0.264GPa, peak stress point Not Wei 4.699MPa and 4.682MPa, failure modulus be respectively 0.310GPa and 0.302GPa；The stress of vacuum-sintering foam zinc Strain curve as shown in figure 5, microphoto as shown in figure 7d；XRD diagram such as Fig. 3 institute of two groups of medical degradable open celled foam zinc Show；As seen from the figure, vacuum-sintering still covers graphite powder sintering and has all been inevitably generated zinc oxide, but vacuum-sintering aoxidizes Zinc can be less.
Embodiment 5
With embodiment 1, difference is method；
(1) pore creating material is urea powder, and the volume ratio of zinc powder and pore creating material is 1:1；30 μm of the partial size of zinc powder；Urea powder Partial size≤0.88mm and > 0.5mm；
(2) ratio of dehydrated alcohol and mixed-powder is 0.25mL/g by liquid-solid ratio；
(3) pressing pressure 350MP, dwell time 15min, pressure maintaining number 5 times, pressing speed 1KN/s；
(4) progress vacuum-sintering, 360 DEG C of sintering temperature, sintering time 3.5h；When carrying out vacuum-sintering, first it is evacuated to Then vacuum degree≤0.09MPa is warming up to 360 DEG C with the speed of 15 DEG C/min and is sintered；
(5) medical degradable open celled foam zinc porosity 44.7%, elasticity modulus 0.344GPa, peak stress 18.358MPa fail modulus 0.945GPa；Stress-strain diagram as shown in fig. 6, microphoto as shown in figure 7e, appearance photo As shown in Figure 8 a.
Embodiment 6
With embodiment 1, difference is method；
(1) pore creating material is urea powder, and the volume ratio of zinc powder and pore creating material is 1:2；100 μm of the partial size of zinc powder；Urea powder Partial size≤the 0.88mm and > 0.5mm at end；
(2) ratio of dehydrated alcohol and mixed-powder is 0.2mL/g by liquid-solid ratio；
(3) pressing pressure 300MP, dwell time 20min, pressure maintaining number 3 times, pressing speed 0.8KN/s；
(4) progress vacuum-sintering, 370 DEG C of sintering temperature, sintering time 2h；When carrying out vacuum-sintering, first it is evacuated to true Then reciprocal of duty cycle≤0.09MPa is warming up to 370 DEG C with the speed of 30 DEG C/min and is sintered；
(5) medical degradable open celled foam zinc porosity 66.5%, elasticity modulus 0.288GPa, peak stress 11.054MPa fail modulus 1.882GPa；Stress-strain diagram as shown in fig. 6, microphoto as depicted in fig. 7f, appearance photo As shown in Figure 8 b.
Embodiment 7
With embodiment 1, difference is method；
(1) pore creating material is urea powder, and the volume ratio of zinc powder and pore creating material is 1:3；150 μm of the partial size of zinc powder；Urea powder Partial size≤the 1.7mm and > 0.88mm at end；
(2) ratio of dehydrated alcohol and mixed-powder is 0.3mL/g by liquid-solid ratio；
(3) pressing pressure 200MP, dwell time 25min, pressure maintaining number 3 times, pressing speed 0.6KN/s；
(4) progress vacuum-sintering, 380 DEG C of sintering temperature, sintering time 2.5h；When carrying out vacuum-sintering, first it is evacuated to Then vacuum degree≤0.09MPa is warming up to 380 DEG C with the speed of 25 DEG C/min and is sintered；
(5) medical degradable open celled foam zinc porosity 71.8%, elasticity modulus 0.282GPa, peak stress 4.733MPa, fail modulus 0.489GPa；Stress-strain diagram as shown in fig. 6, microphoto as shown in figure 7g, appearance photo is such as Shown in Fig. 8 c.
Embodiment 8
With embodiment 1, difference is method；
(1) pore creating material is urea powder, and the volume ratio of zinc powder and pore creating material is 1:4；40 μm of the partial size of zinc powder；4 urea powder Partial size≤the 0.88mm and > 0.5mm at end；
(2) ratio of dehydrated alcohol and mixed-powder is 0.25mL/g by liquid-solid ratio；
(3) pressing pressure 100MP, dwell time 30min, pressure maintaining number 2 times, pressing speed 0.5KN/s；Precast body is set Yu Shuizhong keeps pore creating material soluble in water, and moisture removal is removed in then removal drying；70 ± 2 DEG C of drying temperature, time at least 30min；
(4) precast body of the removal urea after drying is subjected to covering graphite powder sintering, 390 DEG C of sintering temperature, when sintering Between 3h；Graphite powder cladding thickness 13mm is warming up to 390 DEG C with the speed of 15 DEG C/min；
(5) sintered material is directly as medical degradable open celled foam zinc, porosity 77.1%, elasticity modulus 0.213GPa, peak stress 3.994MPa, fail modulus 0.263GPa；Stress-strain diagram is as shown in fig. 6, microphoto such as figure Shown in 7h, appearance photo is as shown in figure 8d.
Embodiment 9
With embodiment 1, difference is method；
(1) pore creating material is sodium chloride powder；Sodium chloride powder is divided into bulky grain pore creating material identical in quality, middle particle pore-creating Agent and little particle pore creating material；The volume ratio of zinc powder and three kinds of pore creating materials is 1:2；Wherein the partial size of bulky grain pore creating material≤ 1.7mm and > 0.88mm, the partial size≤0.88mm and > 0.5mm of middle particle pore creating material, partial size≤0.5mm of little particle pore creating material； Zinc powder mixes respectively with bulky grain pore creating material, middle particle pore creating material and little particle pore creating material, and identical in quality big is respectively prepared Grain mixed-powder, middle particle mixed-powder and little particle mixed-powder；
(2) bulky grain mixed slurry identical in quality, middle particle mixed slurry and little particle mixed slurry is respectively prepared；Nothing The ratio of water-ethanol and mixed-powder is 0.15mL/g by liquid-solid ratio；
(3) bulky grain mixed slurry, middle particle mixed slurry and little particle mixed slurry are filled into mold in order, Precast body is made；Pressing pressure 250MP, dwell time 25min, pressure maintaining number 3 times, pressing speed 0.5KN/s；
(4) 380 DEG C of sintering temperature, sintering time 3.5h；When carrying out covering graphite powder sintering, graphite powder cladding thickness 14mm is warming up to 380 DEG C with the speed of 30 DEG C/min；
(5) the medical degradable open celled foam zinc that aperture is distributed along axial gradient, porosity 59.8%, springform is made 0.428GPa, peak stress 6.392MPa are measured, failure modulus is 0.313GPa；.
Embodiment 10
With embodiment 1, difference is method；
(1) pore creating material be urea powder, urea powder be divided into bulky grain pore creating material identical in quality, middle particle pore creating material and Little particle pore creating material；The volume ratio of zinc powder and three kinds of pore creating materials is 1:2；Wherein partial size≤1.7mm of bulky grain pore creating material and > 0.88mm, the partial size≤0.88mm and > 0.5mm of middle particle pore creating material, partial size≤0.5mm of little particle pore creating material；Zinc powder and big Particle pore creating material, middle particle pore creating material and little particle pore creating material mix respectively, and bulky grain mixed powder identical in quality is respectively prepared Last, middle particle mixed-powder and little particle mixed-powder；
(2) bulky grain mixed slurry identical in quality, middle particle mixed slurry and little particle mixed slurry is respectively prepared；Nothing The ratio of water-ethanol and mixed-powder is 0.25mL/g by liquid-solid ratio；
(3) bulky grain mixed slurry, middle particle mixed slurry and little particle mixed slurry are filled into mold in order, Precast body is made；Pressing pressure 250MP, dwell time 25min, pressure maintaining number 3 times, pressing speed 0.5KN/s；
(4) 380 DEG C of sintering temperature, sintering time 3.5h；Graphite powder cladding thickness 12mm is heated up with the speed of 25 DEG C/min It is sintered to 380 DEG C；
(5) the medical degradable open celled foam zinc that aperture is distributed along axial gradient, porosity 66.6%, springform is made 0.698GPa, peak stress 7.171GPa are measured, fail modulus 0.455GPa.

Claims (10)

1. a kind of method that powder metallurgic method prepares medical degradable open celled foam zinc, it is characterised in that carry out according to the following steps；
(1) moisture removal is respectively dried in zinc powder and pore creating material, is then uniformly mixed and mixed-powder is made；The pore creating material is The volume ratio of sodium chloride powder or urea powder, zinc powder and pore creating material is 1:(1~4)；
(2) dehydrated alcohol is added into mixed-powder, mixed slurry is made；
(3) mixed slurry is filled into mold, using press machine compression moulding, 100~400MP of pressing pressure is made prefabricated Body；
(4) precast body is placed in sintering furnace, carries out vacuum-sintering or covers graphite powder sintering, 340~410 DEG C of sintering temperature, Then 2~4h of sintering time cools to room temperature with the furnace, obtain sintered material；
(5) sintered material is placed in water, keeps pore creating material soluble in water, surplus material takes out drying moisture, and medical drop is made Solve open celled foam zinc.
2. the method that a kind of powder metallurgic method according to claim 1 prepares medical degradable open celled foam zinc, feature It is 18~150 μm of partial size of the zinc powder.
3. the method that a kind of powder metallurgic method according to claim 1 prepares medical degradable open celled foam zinc, feature It is partial size≤1.7mm of the sodium chloride powder；Partial size≤1.7mm of urea powder.
4. the method that a kind of powder metallurgic method according to claim 1 prepares medical degradable open celled foam zinc, feature It is in step (2), the ratio of dehydrated alcohol and mixed-powder is 0.1~0.3mL/g by liquid-solid ratio.
5. the method that a kind of powder metallurgic method according to claim 1 prepares medical degradable open celled foam zinc, feature It is in step (4), when carrying out vacuum-sintering, vacuum degree≤0.09MPa is first evacuated to, then with 15~30 DEG C/min's Speed is warming up to 340~410 DEG C and is sintered；When carrying out covering graphite powder sintering, 38~48 μ of granularity of the graphite powder of use Graphite powder is covered on precast body surface by m, then 10~15mm of cladding thickness is warming up to 340 with the speed of 15~30 DEG C/min ~410 DEG C are sintered.
6. the method that a kind of powder metallurgic method according to claim 1 prepares medical degradable open celled foam zinc, feature When being the pore creating material used in step (1) for urea powder, after precast body is made, precast body is placed in water, makes to make Hole agent is soluble in water, and moisture removal is removed in then removal drying, then is sintered in the way of step (4), and the sintered material of acquisition is directly made For medical degradable open celled foam zinc.
7. the method that a kind of powder metallurgic method according to claim 1 prepares medical degradable open celled foam zinc, feature It is in step (5), sintered material is placed in water, 24~48h of standing time, during this period, when sodium chloride concentration reaches in water When reaching 19.0 ± 0.45mol/L to 6.0 ± 0.2mol/L or urea concentration, sintered material taking-up is placed into new water.
8. the method that a kind of powder metallurgic method according to claim 1 prepares medical degradable open celled foam zinc, feature It is that the medical degradable open celled foam zinc is open-celled structure, porosity 40~78%, 0.8~2mm of aperture.
9. the method that a kind of powder metallurgic method according to claim 1 prepares medical degradable open celled foam zinc, feature It is when using sodium chloride powder as pore creating material, the elasticity modulus 0.2 of manufactured medical degradable open celled foam zinc~ 1GPa, 4~45MPa of peak stress；When using urea powder as pore creating material, manufactured medical degradable open celled foam zinc 0.2~0.4GPa of elasticity modulus, 3~20MPa of peak stress.
10. the method that a kind of powder metallurgic method according to claim 1 prepares medical degradable open celled foam zinc, feature It is in step (1), pore creating material is divided into bulky grain pore creating material, middle particle pore creating material and little particle pore creating material；When progress step (1) when, zinc powder mixes respectively with bulky grain pore creating material, middle particle pore creating material and little particle pore creating material, and it is mixed that bulky grain is respectively prepared Close powder, middle particle mixed-powder and little particle mixed-powder；When carrying out step (2), be respectively prepared bulky grain mixed slurry, Middle particle mixed slurry and little particle mixed slurry；When carrying out step (3), by bulky grain mixed slurry, middle particle mixing slurry Material and little particle mixed slurry are in order or inverted order is filled into mold, and precast body is made；After step (5), hole is made The medical degradable open celled foam zinc that diameter is distributed along axial gradient；Wherein partial size≤1.7mm of bulky grain pore creating material and > 0.88mm, the partial size≤0.88mm and > 0.5mm of middle particle pore creating material, partial size≤0.5mm of little particle pore creating material.
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