CN108863341A - Titanium alloy-silicate transition zone-hydroxy-apatite halite bioceramic preparation method - Google Patents

Titanium alloy-silicate transition zone-hydroxy-apatite halite bioceramic preparation method Download PDF

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CN108863341A
CN108863341A CN201810971470.0A CN201810971470A CN108863341A CN 108863341 A CN108863341 A CN 108863341A CN 201810971470 A CN201810971470 A CN 201810971470A CN 108863341 A CN108863341 A CN 108863341A
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powder
titanium alloy
silicate
apatite
halite
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徐淑波
常诚
王彦鹏
刘凤华
景财年
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Shandong Jianzhu University
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Shandong Jianzhu University
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Abstract

The invention belongs to biomedical materials field, especially titanium alloy-silicate transition zone-hydroxy-apatite halite bioceramic porous materials.By titanium alloy substrate material powder, titanium alloy-silicate-hydroxy-apatite halite transition zone powder and hydroxyapatite salt powder composition, powder is all made of plus dehydrated alcohol method that mechanization ball milling is carried out in ball mill refines powder grain, by after configured each powder cold compaction 10‑6Degasification is gradually heated under de- vacuum condition, 3D printing model is constructed by CAD according to the characteristics of implantation material, CAD model is layered by computer, obtain each layer of model of cross section information, according to the design feature of implantation material section, dynamic regulation lays titanium alloy substrate material powder from inside to outside, titanium alloy-silicate transition zone-hydroxy-apatite halite transition zone powder and hydroxyapatite salt powder, powder is loaded according to the more gradients of the streamline of implantation material from bottom to top, then at 500-600 DEG C, 50-200Mpa argon atmosphere protects lower selective laser to melt 3D printing, it prepares using titanium alloy-hydroxy-apatite halite as the titanium alloy of matrix-silicate transition zone-hydroxy-apatite halite bioceramic porous material.Material of the present invention is significantly improved compared with traditional handicraft toughness, wearability, intensity after tested.

Description

Titanium alloy-silicate transition zone-hydroxy-apatite halite bioceramic preparation method
Technical field
The invention belongs to biomedical materials field, especially titanium alloy-silicate transition zone-hydroxy-apatite halite biologies Ceramic porous material.
Background technique
Currently, the bio-medical material of clinical application, such as skeleton implant, cardiac stent mostly use titanium alloy, titanium is closed Fitting has good biocompatibility, corrosion resistance and mechanical property, therefore titanium alloy is very widely used, cures in clinic Educational circles gets the nod.Metal bone existing for titanium alloy etc. is implanted into material, and there is the mechanical compatibility differences with biological bone Problem.5.3 times higher than natural bone of the tensile strength of titanium alloy etc materials or more, elasticity modulus is even more high 11 times or more.Titanium closes The skeleton implants such as gold generate very big " stress shielding " effect to body local bone tissue, can induce blocking property bone loss. Lead to original biological bone fragility of skeleton implantation material and surrounding, the area of new bone undergrowth around skeleton implantation material And stress concentrates initiation inflammation between skeleton implantation material and biological bone.Develop novel mechanics and biocompatibility more Ideal bio-medical material is very necessary.Meanwhile skeleton implantation material operation take out, increase medical person pain, Time and expense, therefore, the high medical material that is tough and can degrading in vivo of research and development is current medical field One of important directions of development.And hydroxyapatite is the main constituents of vertebrate skeletal and tooth, is had good Bioactivity and biocompatibility.Relative to traditional metal(Stainless steel, titanium alloy)And ceramics(Aluminium oxide, silicon nitride)Class bone Before alternative materials, not only corrosion resistance is strong for hydroxyapatite, self-bone grafting generative nature is strong, but also its degradation in vivo also eliminates The security risk of person.Hydroxyapatite coating layer refers to using titanium alloy as substrate, using physical chemistry means by hydroxyapatite coat Cover the hard tissue implanting material being prepared on its surface.After the material is implanted into human body, titanium alloy can provide enough mechanical strengths, The hydroxyapatite coating layer on surface be easy to human body synosteosis, induce the generation of new bone, general several months in human body bone surface Induce the generation of new bone.But the disadvantage that current technology is not strong enough there are still binding force, so that occurring after being implanted into vivo The phenomenon that coating shedding.
Based on above-mentioned purpose, it is more that the present invention develops a kind of titanium alloy-silicate transition zone-hydroxy-apatite halite bioceramic Porous materials use more gradient proportion mixed-powders for raw material, use metal three-dimensional printer printing bone implant etc..Of the invention Titanium alloy-silicate transition zone-hydroxy-apatite halite bioceramic porous material main chemical compositions Si, O, P, H, Ca, Remaining is Ti.The existing titanium alloy material in China is in patent 104710188A at present, through research, analysis shows having as Zn, Mg Equal elements addition, but service performance raising is limited.Therefore, titanium alloy-is generated by more gradient 3 D-printings in the present invention Silicate transition zone-hydroxy-apatite halite bioceramic porous material purpose.
Summary of the invention
The purpose of the invention patent is:It is to overcome the above-mentioned prior art insufficient, a kind of stable processing technology, production is provided Low in cost, non-pollution discharge, titanium alloy-silicate transition zone-hydroxy-apatite halite that production can be organized under normal conditions Bioceramic porous material, the biomedical materials such as more traditional stainless steel, titanium alloy have better biocompatibility, more often The toughness for advising ceramic biomedical material is substantially improved.
Scheme material requested presses following specific preparation step:
(1)The preparation of titanium alloy substrate powder:
The preparation process of titanium alloy substrate powder is:Titanium alloy substrate dusty material chemical component is:Titanium, silver, magnesium, vanadium, nickel and Copper is constituent element, and composition can be indicated with aTi-bAg-cMg-dV-eNi-fCu, wherein a:83-90, b:1-3, c:3-5, d:5-8, e:1-2, f:1-2 and a+b+c+d+e+f=100.Add dehydrated alcohol in ball milling the titanium alloy substrate composite powder prepared in proportion It is carried out mechanization ball milling 24 hours in machine, obtaining has 50-150 μm of crystallite dimension superfines, and powder is packed into crystal vessel In, under the conditions of argon atmosphere protection and 1300 DEG C -1600 DEG C of temperature, keep the temperature 90min-180min.
The present invention is to obtain optimal comprehensive mechanical property and biological antiseptic corrosion energy, the content of strict control impurity:Ti Degree of purity be more than or equal to 99.99%;The degree of purity of Mg is more than or equal to 99.999%, and tramp element total amount is not more than 0.3%.
(2)The preparation of silicate bioceramic material powder:
The chemical component and weight percent CaO of silicate bioceramic material:42-50%, SiO2:48-52%, B2O3:0.3- 2.4%, ZnO:0.2-3.0%, MgO:0.8-4.5%.The silicate bioceramic material powder prepared in proportion is added into dehydrated alcohol It is carried out mechanization ball milling 24 hours in ball mill, obtaining has 50-150 μm of crystallite dimension superfines.
(3)The preparation of hydroxyapatite salt powder:
The chemical component of hydroxyapatite salt powder:6 (OH) 2 of Ca10 (PO4) will add dehydrated alcohol by hydroxyapatite salt powder It is carried out mechanization ball milling 24 hours in ball mill, obtaining has 50-150 μm of crystallite dimension superfines.
(4)Titanium alloy-silicate-hydroxy-apatite halite transition zone powder preparation:
Configuration forms titanium alloy-silicate-hydroxy-apatite halite transition zone of more gradients from the inside to the outside, is always divided into 5 layers, most Internal layer to outermost powder weight ratio is respectively:
First layer:Titanium alloy substrate powder:Silicate biomaterial powder=81.6:18.4
The second layer:Titanium alloy substrate powder:Silicate biomaterial powder=72.4:27.6
Third layer:Titanium alloy substrate powder:Silicate biomaterial powder=54:46
4th layer:Hydroxyapatite salt powder:Silicate biomaterial powder=72.4:27.6
Layer 5:Hydroxyapatite salt powder:Silicate biomaterial powder=81.6:18.4
It prepares titanium alloy-silicate-hydroxy-apatite halite transition zone powder respectively according to weight ratio, adds dehydrated alcohol in ball It is carried out mechanization ball milling 24 hours in grinding machine, obtaining has 50-150 μm of crystallite dimension superfines.
The effect difference of basic asphalt mixture element is as follows in the present invention:
Zn is the element having a major impact to cell development, is the necessary micronutrient element of human body, the addition of Zn can The intensity of alloy is improved, while effectively facilitating the generation of the non-basal slip of titanium alloy at room temperature, improves the plastic processing of titanium alloy Ability.
Ni is good with titanium associativity, and elevated temperature strength is good, hardness is high, density is big, resistance to corrosion is strong, thermal expansion coefficient is small, can Further increase obdurability, the corrosion resistance of alloy.
V has the title of metal " vitamin ".By refining the tissue and crystal grain of titanium, grain coarsening temperature is improved, to play Increase the intensity, toughness and wearability of titanium alloy.Vanadium is the essential trace elements of the human body, vanadium and bone and tooth normal development and calcium Change related, tooth can be enhanced, normal bone growth and development is promoted to the resistance of dental caries tooth.
Ag, Cu are antiseptic elements, the anti-microbial property after improving material implantation.
The present invention provides more gradient 3 D-printings to generate titanium alloy-silicate transition zone-hydroxy-apatite halite biology pottery Porcelain porous material, it is characterised in that:The material is from inside to outside by the titanium alloy of more gradients-hydroxyapatite salt matrix material group At crystal grain diameter 200-800nm.
The present invention is by the following technical programs:Titanium alloy-silicate transition zone-hydroxy-apatite halite bioceramic is porous Material powder is by titanium alloy substrate material powder, titanium alloy-silicate-hydroxy-apatite halite transition zone powder and hydroxy-apatite Halite powder constituent, powder is all made of the method for adding dehydrated alcohol to carry out mechanization ball milling in ball mill, and powder grain is thin Change, will gradually heat degasification in the case where 10-6 takes off vacuum condition after configured each powder cold compaction, leads to according to the characteristics of implantation material CAD building 3D printing model is crossed, CAD model is layered by computer, each layer of model of cross section information is obtained, according to implantation Dynamic regulation lays titanium alloy substrate material powder, titanium alloy-silicate transition zone-hydroxyl to the design feature of object section from inside to outside Base apatite salt transition zone powder and hydroxyapatite salt powder load powder according to the more gradients of the streamline of implantation material from bottom to top End, then at 500-600 DEG C, 50-200Mpa argon atmosphere protects lower selective laser to melt 3D printing, prepares with titanium alloy- Hydroxy-apatite halite is titanium alloy-silicate transition zone-hydroxy-apatite halite bioceramic porous material of matrix.
More gradient 3 D-printings generate titanium alloy-silicate transition zone-hydroxy-apatite halite bioceramic porous material It without equipment such as vacuum melting furnace, high temperature and pressure, can organize to produce using common metal 3D printing equipment, the present invention Small investment, quick, can quickly recoup capital outlay cost.
Compared with existing casting medical titanium alloy, hydroxy-apatite halite and bioceramic technology, more gradient 3 D-printings are raw It is had the following advantages that at titanium alloy-silicate transition zone-hydroxy-apatite halite bioceramic porous material preparation method:
(1)Toughness, wearability, intensity significantly improve, and are spaced the poor mechanical property of 2 hours samples less than 6%, this is beneficial to greatly In batches, the steady production of small size medical material.It is tiny to enhance particle size, is evenly distributed, structure stability is high, closes in titanium Auri body is well combined.Toughness, hardness and the wear-resisting property of material significantly improve, and are particularly suitable for skeleton implantation material The application of equal medical materials applies also for requiring high-intensitive and high-wearing feature components.
(2)Microstructure stability is good, will not decompose toxic gas or toxic dissolved matter, have to the health of customer Place, corrosion resistance, antibiotic property, biocompatibility are good.
(3)The present invention is because of selective melting 3 D-printing, and the technology stability of production is high, low production cost, pollution-free row It puts, can organize to produce under normal conditions, the equipment such as vacuum melting furnace, high temperature and pressure.
Detailed description of the invention
Here is that specific embodiments of the present invention are described in detail in conjunction with the accompanying drawings and embodiments.
Fig. 1 is titanium alloy-silicate-hydroxy-apatite halite buffer layer material schematic diagram;
It can be seen that titanium alloy-silicon from titanium alloy-silicate shown in FIG. 1-hydroxy-apatite halite buffer layer material schematic diagram The configuration of hydrochlorate-hydroxy-apatite halite transition zone, forms titanium alloy-silicate-hydroxyapatite of more gradients from the inside to the outside Salt transition zone is always divided into 5 layers.
Specific embodiment
Highly preferred embodiment of the present invention is given below:Titanium, silver, magnesium, vanadium, nickel and copper are constituent element, and composition can use aTi- BAg-cMg-dV-eNi-fCu indicates, wherein a:83-90, b:1-3, c:3-5, d:5-8, e:1-2, f:1-2 and a+b+c+d+e+f =100.Dehydrated alcohol is added to carry out mechanization ball milling 24 in ball mill the titanium alloy substrate composite powder prepared in proportion small When, obtaining has 50-150 μm of crystallite dimension superfines, powder is fitted into crystal vessel, in argon atmosphere protection and 1300 Under the conditions of DEG C -1600 DEG C of temperature, 90min-180min is kept the temperature.By silicate transition zone bioceramic material according to weight percent Than for CaO:42-50%, SiO2:48-52%, B2O3:0.3-2.4%, ZnO:0.2-3.0%, MgO:0.8-4.5%.It will match in proportion The silicate bioceramic material powder of system adds dehydrated alcohol to carry out in ball mill mechanization ball milling 24 hours, is had 50-150 μm of crystallite dimension superfines.By hydroxyapatite salt powder Ca10 (PO4) 6 (OH) 2 plus dehydrated alcohol in ball mill Middle progress mechanization ball milling 24 hours, obtaining has 50-150 μm of crystallite dimension superfines.According to powder weight proportional arrangement By titanium alloy-silicate-hydroxy-apatite halite transition zone powder of internal layer to outer more gradients, 5 layers are always divided into, innermost layer is extremely Outermost powder weight ratio is respectively:
First layer:Titanium alloy substrate powder:Silicate biomaterial powder=81.6:18.4
The second layer:Titanium alloy substrate powder:Silicate biomaterial powder=72.4:27.6
Third layer:Titanium alloy substrate powder:Silicate biomaterial powder=54:46
4th layer:Hydroxyapatite salt powder:Silicate biomaterial powder=72.4:27.6
Layer 5:Hydroxyapatite salt powder:Silicate biomaterial powder=81.6:18.4
It prepares titanium alloy-silicate-hydroxy-apatite halite transition zone powder respectively according to weight ratio, adds dehydrated alcohol in ball It is carried out mechanization ball milling 24 hours in grinding machine, obtaining has 50-150 μm of crystallite dimension superfines.By configured each powder Degasification is gradually heated in the case where 10-6 takes off vacuum condition after cold compaction, 3D printing model is constructed by CAD according to the characteristics of implantation material, CAD model is layered by computer, each layer of model of cross section information is obtained, according to the design feature of implantation material section by interior And outer dynamic regulation lays titanium alloy substrate material powder, titanium alloy-silicate transition zone-hydroxy-apatite halite transition zone powder With hydroxyapatite salt powder, powder are loaded according to the more gradients of the streamline of implantation material from bottom to top, then at 500-600 DEG C, 50- 200Mpa argon atmosphere protects lower selective laser to melt 3D printing, prepares using titanium alloy-hydroxy-apatite halite as the titanium of matrix Alloy-silicate transition zone-hydroxy-apatite halite bioceramic porous material.Then T6 processing is carried out, and is tested for the property. Can get high-intensitive medium plasticity titanium alloy-hydroxy-apatite halite bioceramic porous material under the technique, (tensile strength is 411MPa, yield strength 370MPa, elongation percentage 6.3%).Corrosion rate under simulated body fluid environment is 0.27mm/ year.The requirement of orthopaedics inner implantation material bone plate, bone nail etc. can be met.

Claims (1)

1. titanium alloy-silicate transition zone-hydroxy-apatite halite bioceramic preparation method it is characterized in that:The material by interior and It is made of outside the titanium alloy of more gradients-hydroxyapatite salt matrix material, crystal grain diameter 200-800nm, by titanium alloy substrate Material powder, titanium alloy-silicate-hydroxy-apatite halite transition zone powder and hydroxyapatite salt powder composition, powder are equal Powder grain is refined using the method for adding dehydrated alcohol to carry out mechanization ball milling in ball mill, configured each powder is cold 10 after compacting-6Degasification is gradually heated under de- vacuum condition, 3D printing model is constructed by CAD according to the characteristics of implantation material, is led to Cross computer to be layered CAD model, obtain each layer of model of cross section information, according to the design feature of implantation material section by interior and Outer dynamic regulation lay titanium alloy substrate material powder, titanium alloy-silicate transition zone-hydroxy-apatite halite transition zone powder and Hydroxyapatite salt powder loads powder according to the more gradients of the streamline of implantation material from bottom to top, then at 500-600 DEG C, 50- 200Mpa argon atmosphere protects lower selective laser to melt 3D printing, prepares using titanium alloy-hydroxy-apatite halite as the titanium of matrix Alloy-silicate transition zone-hydroxy-apatite halite bioceramic porous material, specific preparation process are as follows:
(a)The preparation process of titanium alloy substrate powder is:Titanium alloy substrate dusty material chemical component is:Titanium, silver, magnesium, vanadium, nickel It is constituent element with copper, composition can be indicated with aTi-bAg-cMg-dV-eNi-fCu, wherein a:83-90, b:1-3, c:3-5, d:5- 8, e:1-2, f:1-2 and a+b+c+d+e+f=100;Add dehydrated alcohol in ball the titanium alloy substrate composite powder prepared in proportion It is carried out mechanization ball milling 24 hours in grinding machine, obtaining has 50-150 μm of crystallite dimension superfines, and powder is packed into graphite and is held In device, under the conditions of argon atmosphere protection and 1300 DEG C -1600 DEG C of temperature, 90min-180min is kept the temperature;
(b)The preparation of silicate bioceramic material powder:The chemical component and weight percent of silicate bioceramic material CaO:42-50%, SiO2:48-52%, B2O3:0.3-2.4%, ZnO:0.2-3.0%, MgO:0.8-4.5%;By what is prepared in proportion Silicate bioceramic material powder adds dehydrated alcohol to carry out in ball mill mechanization ball milling 24 hours, and obtaining has 50-150 μm crystallite dimension superfines;
(c)The preparation of hydroxyapatite salt powder:The chemical component of hydroxyapatite salt powder:6 (OH) 2 of Ca10 (PO4), will be by hydroxyl Base apatite salt powder adds dehydrated alcohol to carry out in ball mill mechanization ball milling 24 hours, and obtaining has 50-150 μm of crystal grain ruler Very little superfines;
(d)Titanium alloy-silicate-hydroxy-apatite halite transition zone powder preparation:Configuration forms the titanium of more gradients from the inside to the outside Alloy-silicate-hydroxy-apatite halite transition zone is always divided into 5 layers, and innermost layer to outermost powder weight ratio is distinguished For:
First layer:Titanium alloy substrate powder:Silicate biomaterial powder=81.6:18.4;
The second layer:Titanium alloy substrate powder:Silicate biomaterial powder=72.4:27.6;
Third layer:Titanium alloy substrate powder:Silicate biomaterial powder=54:46;
4th layer:Hydroxyapatite salt powder:Silicate biomaterial powder=72.4:27.6;
Layer 5:Hydroxyapatite salt powder:Silicate biomaterial powder=81.6:18.4;
It prepares titanium alloy-silicate-hydroxy-apatite halite transition zone powder respectively according to weight ratio, adds dehydrated alcohol in ball It is carried out mechanization ball milling 24 hours in grinding machine, obtaining has 50-150 μm of crystallite dimension superfines.
CN201810971470.0A 2018-08-24 2018-08-24 Titanium alloy-silicate transition zone-hydroxy-apatite halite bioceramic preparation method Pending CN108863341A (en)

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