CN102168195A - Method for preparing gradient porous Ti-Mg-based composite material - Google Patents
Method for preparing gradient porous Ti-Mg-based composite material Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 98
- 239000000463 material Substances 0.000 claims abstract description 78
- 238000000498 ball milling Methods 0.000 claims abstract description 45
- 239000011812 mixed powder Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 19
- 238000009966 trimming Methods 0.000 claims description 31
- 238000002360 preparation method Methods 0.000 claims description 27
- 238000000748 compression moulding Methods 0.000 claims description 17
- 238000009413 insulation Methods 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 9
- 210000001519 tissue Anatomy 0.000 abstract description 8
- 239000007943 implant Substances 0.000 abstract description 7
- 210000000988 bone and bone Anatomy 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910001069 Ti alloy Inorganic materials 0.000 description 9
- 238000010586 diagram Methods 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000003475 lamination Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 229910001000 nickel titanium Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 241000282465 Canis Species 0.000 description 1
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 1
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- 239000012620 biological material Substances 0.000 description 1
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- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 230000037182 bone density Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
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Abstract
The invention discloses a method for preparing a gradient porous Ti-Mg-based composite material with a structure similar to an actual bone structure. The method comprises the following steps of: mixing Ti powder, Mg powder and Zr powder in a certain mixture ratio, and performing ball milling; mixing powder obtained after ball milling and pore-forming agents with different contents respectively to obtain all kinds of mixed powder, pouring the mixed powder into a mould for first prepressing, pouring powder used for another layer into the mould for secondary prepressing, and finally, compressing and molding under the pressure of 550MPa to obtain a gradient compact; and finally, removing the pore-forming agents, and sintering to obtain the gradient porous Ti-Mg-based composite material. Compared with a uniform-porosity porous Ti-Mg-based composite material of which the porosity is the same as that of the gradient porous Ti-Mg-based composite material, the gradient porous Ti-Mg-based composite material prepared by adopting the appropriate content and distribution of the pore-forming agents and the appropriate gradient layer number has the advantages that: the mechanical properties and the structural performance are greatly improved; meanwhile, mechanical and structural compatibilities of hard tissue implant materials in human bodies are met.
Description
Technical field
The invention belongs to sclerous tissues and replace and repair and use bio-medical porous field of compound material, be specifically related to the preparation method of the corresponding to gradient porous Ti-Mg based composites of a kind of and actual skeletal structure.
Background technology
Hard tissue material is the important branch of biomedical material.The replacement material of human body hard tissues such as artificial bone, joint prosthesis and canine implant because its wide application, demand are big, has become the focus of various countries' research and development, and the speed of goods and industrialization is very fast, is one of important content of biomaterial research.The material of hard tissue repair and replacement is first elected Metal and Alloy.Titanium or titanium alloy becomes one of the most promising medical material because of having unique medical value.
Human body is implanted with hard tissue material and is being advocated biocompatibility, structural compatibility and the mechanical compatibility that as far as possible improves on the basis that guarantees safety non-toxic between implant and the tissue.At present, that be mainly used in the human body implantation is metal Ti and Ti6Al4V, but fine and close titanium and titanium alloy (90-110GPa) can not cause " stress shielding " with matching of skeleton (0.3-30GPa) Young's modulus.A kind of effective ways that reduce the titanium alloy elastic modulus are preparation porous titanium alloys, and the circulation of vesicular structure growing into of can promoting to organize and body fluid, improve structural compatibility.The problem of the maximum that exists is when hole is introduced at present, and the mechanical property of titanium alloy also reduces rapidly, can't satisfy the requirement to the implant mechanical property.The structure of actual bone is to wrap up the formed gradient porous structure of inner spongy porotic bone by the high compact substance bone of surperficial bone density.This structure can guarantee the high-intensity high porosity that has simultaneously.Therefore, the corresponding to gradient porous titanium alloy of actual skeletal structure is a kind of human body hard tissue implant that development potentiality is arranged very much.Chinese patent ZL200810209700.6 " method for preparing gradient porous material " discloses a kind of method that adopts foaming forming technique to prepare gradient porous material, and successful prepares and the corresponding to gradient porous material of skeleton structure.But the material mechanical performance that these class methods are prepared is very low, and the gradient number of plies of preparation is limited.Chinese patent ZL201010104527.0 " a kind of preparation method of super-elastic gradient porous NiTi alloy " discloses a kind of compression molding that utilizes, prepare the method for gradient porous NiTi alloy by the powder diameter of adjusting each layer, successfully prepare and the corresponding to gradient porous NiTi alloy of organization of human body.But the porosity of the titanium alloy that these class methods are prepared is very low, and has only announced the preparation method of the gradient porous NiTi alloy of cylinder shape, does not study the preparation method of square type gradient porous material.
At present, adopt compression molding, the content by adjusting each layer pore-forming material and do not appear in the newspapers as yet with the preparation of corresponding to square type of the actual skeletal structure of human body and cylindric gradient porous material is domestic.
Summary of the invention
The present invention be directed to present human body and implant the deficiency of using titanium alloy, provide a kind of and the preparation method corresponding to gradient porous Ti-Mg based composites of the actual skeletal structure of human body, make human body implant the requirement that to satisfy dependency structure consistency and mechanical compatibility with the Ti-Mg based composites.
Technical scheme provided by the invention: a kind of preparation method of gradient porous Ti-Mg based composites, the preparation process of this method is as follows:
A, batching: take by weighing 6～9 parts of Ti powder and 1～2 part of Mg powder mixes according to mass parts, mixed powder carries out ball milling under the condition of vacuum, and is with powder behind the ball milling and pore-forming material mixing and stirring, standby then;
B, mixed powder is molded into stratiform or circular radial column gradient pressed compact: in the mold process of layered gradient pressed compact, the mixed powder that will be used for the orlop pressed compact is poured mould into and is shaken up, put into the upper trimming die precompressed, the layer overlay mixed powder shakes up above the mixed powder of orlop pressed compact then, put into the upper trimming die precompressed, by that analogy, shake up back compression moulding, the demoulding then at the mixed powder of putting into the superiors' pressed compact at last;
In the mold process of circular radial column gradient pressed compact, the mixed powder that will be used for the innermost layer pressed compact is poured internal layer precompressed mould into and is shaken up, and puts into the upper trimming die precompressed, deviates from preformed compact from mould one time; With the heart portion that preformed compact is put into time internal layer mould, the mixed powder that will be used for time internal layer pressed compact is poured time internal layer precompressed mould into and is shaken up, and puts into the upper trimming die precompressed, from mould, deviate from the secondary preformed compact, by that analogy, at last put into the outermost layer powder shake up the back compression moulding, the demoulding then;
Above-mentioned precompressed all is precompressed 30 seconds under 50MPa pressure; Above-mentioned compression moulding all is to suppress 2min under 550MPa;
Pore-forming material in c, the removal gradient pressed compact: at first the gradient pressed compact is put into vacuum drying oven, vacuumize, under vacuum state, be warmed up to 80 ℃ of insulation 3h, take out vacuum per half an hour one time; Then the loft drier temperature is set to 110～120 ℃ of insulation 2h;
D, sintering: sintering 2h after the gradient pressed compact that will remove pore-forming material is heated to 631～650 ℃ with the heat-up rate of 6～10 ℃/min, sintering is prepared gradient porous Ti-Mg based composites.
Also contain the Zr powder that is no more than 3 parts of mass parts in the powder after described Ti powder and the Mg powder mixes.
Described pore-forming material is NH
4HCO
3
Powder diameter behind the described ball milling is less than 50um.
The gradient pressed compact number of plies is three layers, five layers or seven layers in the layered gradient pressed compact; Described three layer by layer in the shape gradient pressed compact pore-forming material content be followed successively by 5～10 wt.% by orlop to the superiors, 11～48 wt.%, 5～10 wt.%; Described five layer by layer in the shape gradient pressed compact pore-forming material content be followed successively by 5～10 wt.% by orlop to the superiors, 11～20 wt.%, 21～38 wt.%, 11～20 wt.%, 5～10 wt.%; Described seven layer by layer in the shape gradient pressed compact pore-forming material content be followed successively by 5～10 wt.% by orlop to the superiors, 11～20 wt.%, 21～25 wt.%, 26～35 wt.%, 21～25 wt.%, 11～20 wt.%, 5～10 wt.%; Above-mentioned pore-forming material content is mass percentage content.
The gradient pressed compact number of plies is two layers, three layers or four layers in the described concentric(al) circles column gradient pressed compact; Pore-forming material content is followed successively by 5～10 wt.% by outermost layer to innermost layer, 11～48 wt.% in the described two-layer concentric(al) circles column gradient pressed compact; Pore-forming material content is followed successively by 5～10 wt.%, 11～20 wt.%, 21～38 wt.% in described three layers of concentric(al) circles column gradient pressed compact to innermost layer by outermost layer; Pore-forming material content is followed successively by 5～10 wt.% by outermost layer to innermost layer, 11～20 wt.%, 21～25 wt.%, 26～35 wt.% in described four layers of concentric(al) circles column gradient pressed compact; Above-mentioned pore-forming material content is mass percentage content.
Beneficial effect:
The present invention is by changing the powder mixture ratio and the gradient number of plies behind pore-forming material and the ball milling in mold process, the gradient porous Ti-Mg based composites of preparation, on mechanical property and structure properties, all the even porosity porous Ti-Mg based composites than same porosity has had large increase.Satisfy human body simultaneously and implanted the mechanics and the structural compatibility of hard tissue material.
Description of drawings
Fig. 1, three is precompressed one deck pressed compact synoptic diagram in the pressing process of the gradient porous Ti-Mg based composites of shape layer by layer;
Fig. 2, three is precompressed two lamination base synoptic diagram in the pressing process of the gradient porous Ti-Mg based composites of shape layer by layer;
Fig. 3, three is compression moulding synoptic diagram in the pressing process of the gradient porous Ti-Mg based composites of shape layer by layer;
Precompressed innermost layer pressed compact synoptic diagram in the pressing process of Fig. 4, two layers of gradient porous Ti-Mg based composites of concentric(al) circles column;
Compression moulding synoptic diagram in the pressing process of Fig. 5, two layers of gradient porous Ti-Mg based composites of concentric(al) circles column;
Among the figure: 1, upper trimming die; 2, mould tube; 3, following punch die; 4, one deck preformed compact; 5, two-layer preformed compact; 6, three shape gradient pressed compacts layer by layer; 7, outer mould upper trimming die; 8, outer mould tube; 9, punch die under the outer mould; 10, two layers of concentric(al) circles column gradient pressed compact.
Embodiment
Below in conjunction with accompanying drawing 1-5, the invention will be further described by specific embodiment:
Embodiment 1: three is the preparation method of the gradient porous Ti-Mg based composites of shape layer by layer
To put into ball grinder after Ti powder and the weighing by a certain percentage of Mg powder, pour normal hexane into as the ball milling agent, then ball grinder is vacuumized and logical argon gas, on planetary ball mill, prepare the ball milling powder with 300r/min ball milling 10h, and the powder diameter behind the ball milling is less than 50um, this example of enumerating is selected Ti powder 90wt.%, Mg powder 10wt.%.
To require the pore-forming material and the ball milling powder of mass percent to put into beaker, use glass stick to stir 30min, guarantee that pore-forming material and ball milling powder thorough mixing are even.
Three layer by layer the gradient porous Ti-Mg based composites of shape the compacting synoptic diagram as Figure 1-3.Pour the powder that is used for the outermost layer pressed compact after the mixing of interpolation pore-forming material into mould tube 2 and shake up, put into upper trimming die 1, precompressed obtained one deck preformed compact 4 in 30 seconds under 50MPa pressure; Take out upper trimming die 1, pour the powder that is used for heart portion lamination base after the mixing of interpolation pore-forming material into mould tube 2 and shake up, put into upper trimming die 1, precompressed obtained two lamination bases 5 in 30 seconds under 50MPa pressure; Take out upper trimming die 1, shake up adding the powder that is used for the outermost layer pressed compact after pore-forming material mixes, pouring in the mould tube 2 at last, put into upper trimming die 1, compression moulding under the pressure of 550MPa, pressurize 2min, the demoulding obtains three layers of gradient pressed compact 6 of stratiform.Trilaminar each layer pore-forming material content of the example that this is enumerated is followed successively by: 10wt.%, 48 wt.%, 10 wt.%;
The gradient pressed compact of preparing is put into vacuum drying oven, adopt two step heating means to remove pore-forming material.
The first step is put into vacuum drying oven with the steel sieve that fills pressed compact, vacuumizes, and under vacuum state, is warmed up to 80 ℃ of insulation 3h, takes out vacuum per half an hour one time, guarantees that bicarbonate of ammonia decomposes fully, gets rid of most of free water.
Second step was provided with 110 ℃ of loft drier temperature, and insulation 2h gets rid of remaining free water.
The gradient pressed compact of removing pore-forming material is put into tube furnace be heated to 631 ℃ of sintering 2h furnace cooling, but sintering is prepared three gradient porous Ti-Mg based composites of shape layer by layer with the heat-up rate of 10 ℃/min.Prepared three layer by layer the flexural strength and the modulus of the gradient porous Ti-Mg based composites of shape be respectively 154.97MPa and 2.21GPa, and the same terms the flexural strength and the modulus of the even porosity sample of preparation are respectively 121.03MPa and 2.02GPa down.
Adopt identical method can prepare five layers, seven layers and more multi-layered layered gradient porous Ti-Mg based composites.
Embodiment 2: five is the preparation method of the gradient porous Ti-Mg based composites of shape layer by layer
To put into ball grinder after Ti powder, Mg powder and the weighing by a certain percentage of Zr powder, pour normal hexane into as the ball milling agent, then ball grinder is vacuumized and logical argon gas, on planetary ball mill, prepare the ball milling powder with 300r/min ball milling 10h, and the powder diameter behind the ball milling is less than 50um, this example of enumerating is selected Ti powder 60wt.%, Mg powder 10wt.%, Zr powder 30wt.%.
To require the pore-forming material and the ball milling powder of mass percent to put into beaker, use glass stick to stir 30min, guarantee that pore-forming material and ball milling powder thorough mixing are even.
Pour the powder that is used for the orlop pressed compact after the mixing of interpolation pore-forming material into mould tube 2 and shake up, put into upper trimming die 1, precompressed obtained one deck preformed compact 4 in 30 seconds under 50MPa pressure; Take out upper trimming die 1, pour the powder that is used for inferior lower floor pressed compact after the mixing of interpolation pore-forming material into mould tube 2 and shake up, put into upper trimming die 1, precompressed obtained two lamination bases 5 in 30 seconds under 50MPa pressure; Take out upper trimming die 1, the rest may be inferred, shakes up adding the powder that is used for the superiors' pressed compact after pore-forming material mixes, pouring in the mould tube 2 at last, puts into upper trimming die 1, compression moulding under the pressure of 550MPa, and pressurize 2min, demoulding acquisition five is shape gradient pressed compact layer by layer.Each layer pore-forming material content is followed successively by in five layers of the example that this is enumerated: 5wt.%, 11 wt.%, 21 wt.%, 11 wt.%, 5wt.%;
The gradient pressed compact of preparing is put into vacuum drying oven, adopt two step heating means to remove pore-forming material.
The first step is put into vacuum drying oven with the steel sieve that fills pressed compact, vacuumizes, and under vacuum state, is warmed up to 80 ℃ of insulation 3h, takes out vacuum per half an hour one time, guarantees that bicarbonate of ammonia decomposes fully, gets rid of most of free water.
Second step was provided with 120 ℃ of loft drier temperature, and insulation 2h gets rid of remaining free water.
The gradient pressed compact of removing pore-forming material is put into tube furnace be heated to 650 ℃ of sintering 2h furnace cooling, but sintering is prepared five gradient porous Ti-Mg based composites of shape layer by layer with the heat-up rate of 8 ℃/min.Prepared five layer by layer the flexural strength and the modulus of the gradient porous Ti-Mg based composites of shape be respectively 238.28MPa and 5.63GPa, and the same terms the flexural strength and the modulus of the even porosity sample of preparation are respectively 168.17MPa and 4.36GPa down.
Adopt identical method can prepare three layers, seven layers and more multi-layered layered gradient porous Ti-Mg based composites.
Embodiment 3: seven is the preparation method of the gradient porous Ti-Mg based composites of shape layer by layer
To put into ball grinder after Ti powder, Mg powder and the weighing by a certain percentage of Zr powder, pour normal hexane into as the ball milling agent, then ball grinder is vacuumized and logical argon gas, on planetary ball mill, prepare the ball milling powder with 300r/min ball milling 10h, and the powder diameter behind the ball milling is less than 50um, this example of enumerating is selected Ti powder 80wt.%, Mg powder 10wt.%, Zr powder 10wt.%.
To require the pore-forming material and the ball milling powder of mass percent to put into beaker, use glass stick to stir 30min, guarantee that pore-forming material and ball milling powder thorough mixing are even.
Pour the powder that is used for the outermost layer pressed compact after the mixing of interpolation pore-forming material into mould tube 2 and shake up, put into upper trimming die 1, precompressed obtained one deck preformed compact in 30 seconds under 50MPa pressure; Take out upper trimming die 1, pour the powder that is used for heart portion lamination base after the mixing of interpolation pore-forming material into mould tube 2 and shake up, put into upper trimming die 1, precompressed obtained two lamination bases 5 in 30 seconds under 50MPa pressure; Take out upper trimming die 1, the rest may be inferred, shakes up adding the powder that is used for the outermost layer pressed compact after pore-forming material mixes, pouring in the mould tube 2 at last, puts into upper trimming die 1, compression moulding under the pressure of 550MPa, and pressurize 2min, demoulding acquisition seven is shape gradient pressed compact layer by layer.Each layer pore-forming material content of seven layers of the example that this is enumerated is followed successively by: 10wt.%, 20wt.%, 25 wt.%, 35wt.%, 25wt.%, 20wt.%, 10 wt.%;
The gradient pressed compact of preparing is put into vacuum drying oven, adopt two step heating means to remove pore-forming material.
The first step is put into vacuum drying oven with the steel sieve that fills pressed compact, vacuumizes, and under vacuum state, is warmed up to 80 ℃ of insulation 3h, takes out vacuum per half an hour one time, guarantees that bicarbonate of ammonia decomposes fully, gets rid of most of free water.
Second step was provided with 115 ℃ of loft drier temperature, and insulation 2h gets rid of remaining free water.
The gradient pressed compact of removing pore-forming material is put into tube furnace be heated to 640 ℃ of sintering 2h furnace cooling, but sintering is prepared seven gradient porous Ti-Mg based composites of shape layer by layer with the heat-up rate of 7 ℃/min.Prepared seven layer by layer the flexural strength and the modulus of the gradient porous Ti-Mg based composites of shape be respectively 161.24MPa and 2.18GPa, and the same terms the flexural strength and the modulus of the even porosity sample of preparation are respectively 123.22MPa and 2.09GPa down.
Adopt identical method can prepare three layers, five layers and more multi-layered layered gradient porous Ti-Mg based composites.
The preparation method of 4: two layers of concentric(al) circles column of embodiment radial gradient porous Ti-Mg based composites
To put into ball grinder after Ti powder, Mg powder and the weighing by a certain percentage of Zr powder, pour normal hexane into as the ball milling agent, then ball grinder is vacuumized and logical argon gas, on planetary ball mill, prepare the ball milling powder with 300r/min ball milling 10h, and the powder diameter behind the ball milling is less than 50um, this example of enumerating is selected Ti powder 70wt.%, Mg powder 10wt.%, Zr powder 20wt.%.
To require the pore-forming material and the ball milling powder of mass percent to put into beaker, use glass stick to stir 30min, guarantee that pore-forming material and ball milling powder thorough mixing are even.
The compacting synoptic diagram of two layers of gradient porous Ti-Mg based composites of concentric(al) circles column is shown in Fig. 5-6.Pour the powder that is used for the innermost layer pressed compact after the mixing of interpolation pore-forming material into internal layer precompressed mould tube 2 and shake up, put into upper trimming die 1, precompressed obtained a preformed compact 4 in 30 seconds under 50MPa pressure, deviate from preformed compact 4 from mould one time; The heart portion that preformed compact 4 is put into outer mould tube 6, pour between outer compacting tool set tube 6 and the preformed compact 4 and shake up adding the powder that is used for outer pressed compact after pore-forming material mixes, put into upper trimming die 5, compression moulding under the pressure of 550MPa, pressurize 2min, two layers of concentric(al) circles column gradient pressed compact 8 are prepared in the demoulding.Each layer pore-forming material content of two layers of the example that this is enumerated has outer being distributed as to internal layer: 5wt.%, 11 wt.%;
The gradient pressed compact of preparing is put into vacuum drying oven, adopt two step heating means to remove pore-forming material.
The first step is put into vacuum drying oven with the steel sieve that fills pressed compact, vacuumizes, and under vacuum state, is warmed up to 80 ℃ of insulation 3h, takes out vacuum per half an hour one time, guarantees that bicarbonate of ammonia decomposes fully, gets rid of most of free water.
Second step was provided with 110 ℃ of loft drier temperature, and insulation 2h gets rid of remaining free water.
The gradient pressed compact of removing pore-forming material is put into tube furnace be heated to 635 ℃ of sintering 2h furnace cooling, but sintering is prepared two layers of gradient porous Ti-Mg based composites of concentric(al) circles column with the heat-up rate of 10 ℃/min.The compressive strength and the modulus of two layers of prepared gradient porous Ti-Mg based composites of concentric(al) circles column are respectively 171.31MPa and 5.82GPa, and the compressive strength and the modulus of the even porosity sample that the same terms prepares down are respectively 127.03MPa and 4.52GPa.
Adopt identical method can prepare three layers, four layers and the more multi-layered gradient porous Ti-Mg based composites of concentric(al) circles column.
The preparation method of 5: three layers of concentric(al) circles column of embodiment radial gradient porous Ti-Mg based composites
To put into ball grinder after Ti powder, Mg powder and the weighing by a certain percentage of Zr powder, pour normal hexane into as the ball milling agent, then ball grinder is vacuumized and logical argon gas, on planetary ball mill, prepare the ball milling powder with 300r/min ball milling 10h, and the powder diameter behind the ball milling is less than 50um, this example of enumerating is selected Ti powder 80wt.%, Mg powder 10wt.%, Zr powder 10wt.%.
To require the pore-forming material and the ball milling powder of mass percent to put into beaker, use glass stick to stir 30min, guarantee that pore-forming material and ball milling powder thorough mixing are even.
Pour the powder that is used for the innermost layer pressed compact after the mixing of interpolation pore-forming material into internal layer precompressed mould tube 2 and shake up, put into upper trimming die 1, precompressed obtained a preformed compact 4 in 30 seconds under 50MPa pressure, deviate from preformed compact 4 from mould one time; Preformed compact 4 is put into the heart portion of time internal layer mould tube 6, pour between time internal layer compacting tool set tube 6 and the preformed compact 4 and shake up adding the powder that is used for time internal layer pressed compact after pore-forming material mixes, put into upper trimming die 5, precompressed obtained the secondary preformed compact in 30 seconds under 50MPa pressure, and the like last with three layers of preformed compact compression moulding under the pressure of 550MPa, pressurize 2min, three layers of concentric(al) circles column gradient pressed compact 8 are prepared in the demoulding.Trilaminar each layer pore-forming material content of the example that this is enumerated being distributed as from the outer to the inner: 10wt.%, 20wt.%, 35wt.%;
The gradient pressed compact of preparing is put into vacuum drying oven, adopt two step heating means to remove pore-forming material.
The first step is put into vacuum drying oven with the steel sieve that fills pressed compact, vacuumizes, and under vacuum state, is warmed up to 80 ℃ of insulation 3h, takes out vacuum per half an hour one time, guarantees that bicarbonate of ammonia decomposes fully, gets rid of most of free water.
Second step was provided with 110 ℃ of loft drier temperature, and insulation 2h gets rid of remaining free water.
The gradient pressed compact of removing pore-forming material is put into tube furnace be heated to 645 ℃ of sintering 2h furnace cooling, but sintering is prepared three layers of gradient porous Ti-Mg based composites of concentric(al) circles column with the heat-up rate of 6 ℃/min.The compressive strength and the modulus of three layers of prepared gradient porous Ti-Mg based composites of concentric(al) circles column are respectively 105.14MPa and 2.13GPa, and the compressive strength and the modulus of the even porosity sample that the same terms prepares down are respectively 75.41MPa and 1.86GPa.
Adopt identical method can prepare two layers, four layers and the more multi-layered gradient porous Ti-Mg based composites of concentric(al) circles column.
The preparation method of 6: four layers of concentric(al) circles column of embodiment radial gradient porous Ti-Mg based composites
To put into ball grinder after Ti powder, Mg powder and the weighing by a certain percentage of Zr powder, pour normal hexane into as the ball milling agent, then ball grinder is vacuumized and logical argon gas, on planetary ball mill, prepare the ball milling powder with 300r/min ball milling 10h, and the powder diameter behind the ball milling is less than 50um, this example of enumerating is selected Ti powder 60wt.%, Mg powder 20wt.%, Zr powder 20wt.%.
To require the pore-forming material and the ball milling powder of mass percent to put into beaker, use glass stick to stir 30min, guarantee that pore-forming material and ball milling powder thorough mixing are even.
Pour the powder that is used for the innermost layer pressed compact after the mixing of interpolation pore-forming material into internal layer precompressed mould tube 2 and shake up, put into upper trimming die 1, precompressed obtained a preformed compact 4 in 30 seconds under 50MPa pressure, deviate from preformed compact 4 from mould one time; Preformed compact 4 is put into the heart portion of time internal layer mould tube 6, pour between time internal layer compacting tool set tube 6 and the preformed compact 4 and shake up adding the powder that is used for time internal layer pressed compact after pore-forming material mixes, put into upper trimming die 5, precompressed obtained the secondary preformed compact in 30 seconds under 50MPa pressure, and the like last with four layers of preformed compact compression moulding under the pressure of 550MPa, pressurize 2min, four layers of concentric(al) circles column gradient pressed compact are prepared in the demoulding.Each layer pore-forming material content of four layers of the example that this is enumerated being distributed as from the outer to the inner: 5wt.%, 11wt.%, 21wt.%, 26wt.%;
The gradient pressed compact of preparing is put into vacuum drying oven, adopt two step heating means to remove pore-forming material.
The first step is put into vacuum drying oven with the steel sieve that fills pressed compact, vacuumizes, and under vacuum state, is warmed up to 80 ℃ of insulation 3h, takes out vacuum per half an hour one time, guarantees that bicarbonate of ammonia decomposes fully, gets rid of most of free water.
Second step was provided with 120 ℃ of loft drier temperature, and insulation 2h gets rid of remaining free water.
The gradient pressed compact of removing pore-forming material is put into tube furnace be heated to 650 ℃ of sintering 2h furnace cooling, but sintering is prepared four layers of gradient porous Ti-Mg based composites of concentric(al) circles column with the heat-up rate of 6 ℃/min.The compressive strength and the modulus of four layers of prepared gradient porous Ti-Mg based composites of concentric(al) circles column are respectively 186.34MPa and 6.588GPa, and the compressive strength and the modulus of the even porosity sample that the same terms prepares down are respectively 141.12MPa and 4.97GPa.
Adopt identical method can prepare two layers, three layers and the more multi-layered gradient porous Ti-Mg based composites of concentric(al) circles column.
Above-mentioned embodiment is six descriptions that case is carried out that the present invention is selected at random; be not subjected to the restriction of above-mentioned embodiment during specific implementation of the present invention; especially aspect proportioning raw materials, every layer of pore-forming material content, precompression and compression moulding pressure and the gradient number of plies; the various technological improvements that all employing the present invention carry out are all within protection of the present invention.
Claims (6)
1. the preparation method of a gradient porous Ti-Mg based composites is characterized in that this method steps is as follows:
A, batching: take by weighing 6～9 parts of Ti powder and 1～2 part of Mg powder mixes according to mass parts, mixed powder is carried out ball milling under the condition of vacuum, then powder behind the ball milling and pore-forming material mixing and stirring are formed mixed powder, standby;
B, mixed powder is molded into stratiform or circular radial column gradient pressed compact: in the mold process of layered gradient pressed compact, the mixed powder that will be used for the orlop pressed compact is poured mould into and is shaken up, put into the upper trimming die precompressed, the layer overlay mixed powder shakes up above the mixed powder of orlop pressed compact then, put into the upper trimming die precompressed, by that analogy, shake up back compression moulding, the demoulding then at the mixed powder of putting into the superiors' pressed compact at last;
In the mold process of circular radial column gradient pressed compact, the mixed powder that will be used for the innermost layer pressed compact is poured internal layer precompressed mould into and is shaken up, and puts into the upper trimming die precompressed, deviates from preformed compact from mould one time; Preformed compact is put into the centre of time internal layer mould, the mixed powder that will be used for time internal layer pressed compact is poured time internal layer precompressed mould into and is shaken up, put into the upper trimming die precompressed, from mould, deviate from the secondary preformed compact, by that analogy, at last put into the outermost layer powder shake up the back compression moulding, the demoulding then;
Above-mentioned precompressed all is precompressed 30 seconds under 50MPa pressure; Above-mentioned compression moulding all is to suppress 2min under 550MPa;
Pore-forming material in c, the removal gradient pressed compact: at first the gradient pressed compact after the demoulding is put into vacuum drying oven, vacuumize, under vacuum state, allow loft drier be warmed up to 80 ℃ of insulation 3h automatically, take out vacuum per half an hour one time; Afterwards the loft drier temperature is set to 110～120 ℃ of insulation 2h;
D, sintering: sintering 2h after the gradient pressed compact that will remove pore-forming material is heated to 631～650 ℃ with the heat-up rate of 6～10 ℃/min, sintering is prepared gradient porous Ti-Mg based composites.
2. the preparation method of a kind of gradient porous Ti-Mg based composites according to claim 1 is characterized in that also containing the Zr powder that is no more than 3 parts of mass parts in the powder after described Ti powder and the Mg powder mixes.
3. the preparation method of a kind of gradient porous Ti-Mg based composites according to claim 1 and 2 is characterized in that described pore-forming material is NH
4HCO
3
4. the preparation method of a kind of gradient porous Ti-Mg based composites according to claim 1 and 2 is characterized in that powder diameter behind the described ball milling is less than 50 μ m.
5. the preparation method of a kind of gradient porous Ti-Mg based composites according to claim 1 and 2 is characterized in that the gradient pressed compact number of plies is three layers, five layers or seven layers in the layered gradient pressed compact; Described three layer by layer in the shape gradient pressed compact pore-forming material content be followed successively by 5～10 wt.% by orlop to the superiors, 11～48 wt.%, 5～10 wt.%; Described five layer by layer in the shape gradient pressed compact pore-forming material content be followed successively by 5～10 wt.% by orlop to the superiors, 11～20 wt.%, 21～38 wt.%, 11～20 wt.%, 5～10 wt.%; Described seven layer by layer in the shape gradient pressed compact pore-forming material content be followed successively by 5～10 wt.% by orlop to the superiors, 11～20 wt.%, 21～25 wt.%, 26～35 wt.%, 21～25 wt.%, 11～20 wt.%, 5～10 wt.%.
6. the preparation method of a kind of gradient porous Ti-Mg based composites according to claim 1 and 2 is characterized in that the gradient pressed compact number of plies is two layers, three layers or four layers in the described concentric(al) circles column gradient pressed compact; Pore-forming material content is followed successively by 5～10 wt.% by outermost layer to innermost layer, 11～48 wt.% in the described two-layer concentric(al) circles column gradient pressed compact; Pore-forming material content is followed successively by 5～10 wt.%, 11～20 wt.%, 21～38 wt.% in described three layers of concentric(al) circles column gradient pressed compact to innermost layer by outermost layer; Pore-forming material content is followed successively by 5～10 wt.% by outermost layer to innermost layer, 11～20 wt.%, 21～25 wt.%, 26～35 wt.% in described four layers of concentric(al) circles column gradient pressed compact.
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