CN105749354A - Normal forming method for sodium alginate containing three-dimensional scaffold - Google Patents
Normal forming method for sodium alginate containing three-dimensional scaffold Download PDFInfo
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- CN105749354A CN105749354A CN201410805019.3A CN201410805019A CN105749354A CN 105749354 A CN105749354 A CN 105749354A CN 201410805019 A CN201410805019 A CN 201410805019A CN 105749354 A CN105749354 A CN 105749354A
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Abstract
The invention provides a normal forming method for a sodium alginate containing three-dimensional scaffold.The method includes steps: (1) preparation of the sodium alginate containing three-dimensional scaffold, to be more specific, dissolving sodium alginate into a solvent to obtain a sodium alginate solution, adding PVA (polyvinyl alcohol) into the sodium alginate solution, and well mixing at 80-95 DEG C to obtain slurry; taking the slurry as three-dimensional printing slurry to print at the normal temperature to obtain the sodium alginate containing three-dimensional scaffold; (2) forming, to be more specific, soaking the sodium alginate containing three-dimensional scaffold into a calcium salt solution at the normal temperature to react for 10-24h, and performing curing, washing and freeze drying to obtain the sodium alginate containing three-dimensional scaffold.The normal forming method for the sodium alginate containing three-dimensional scaffold is mild in condition and simple in process.
Description
Technical field
The present invention relates to technical field of bioengineering, be specifically related to the normality forming method of a kind of three-dimensional rack containing sodium alginate.
Background technology
Three-dimensional printing technology is a kind of based on mathematical model file, uses cohesible material, by optionally successively piling up material, ultimately forms the technology of the 3D solid of product.Compared with traditional bone tissue engineering scaffold construction method, three-dimensional printing technology has unrivaled advantage: can freely design the three dimensional structure of support, by adjust machined parameters obtain accurate overall dimensions, internal completely through Prevascularized network, controlled porosity and obtain changeable controlled mechanical strength.The trend of bone tissue engineer development jointly prints after requiring somatomedin even cell and material blended and builds bone repairing support.
The three-dimensional printing technology being presently used for building bone tissue engineering scaffold mainly has following several: Stereolithography technology, Selective Laser Sintering, fusion sediment technology and preparation technology in low temperature.Photocuring technology, mainly uses light-sensitive material, by the irradiation coagulation forming of laser or ultraviolet source.The technological process of Selective Laser Sintering is that dusty material is optionally sintered by laser under the control of the computer according to cross section hierarchical information, one layer complete after carry out next layer of sintering again, finally give the three-dimensional rack sintered, be a kind of thermoforming process.Fusion sediment technology is heating thermoplastic material to be melted, and successively piles up by support section configuration after extrusion, solidifies the method obtaining three-dimensional rack after through natural cooling.The technological process of Low-temperature Deposition Manufacturing is by the extruding of solution state moulding material or is ejected in low temperature environment, and cryocoagulation makes solvent volatilize with postlyophilization, leaves gradient pore structured support.Comprehensive prior art, find that these methods suffer from the drawback that the condition of molding is harsh, complicated, need such as high temperature, ultralow temperature, irradiation under ultraviolet ray and use the conditions such as organic solvent, the condition of molding of these harshnesses certainly will make somatomedin and cell inactivation, is unfavorable for three-dimensional printing technology popularization and application in bone tissue engineer.
Summary of the invention
For solving the problems referred to above, the invention provides the normality forming method of a kind of three-dimensional rack containing sodium alginate, this forming method is gentle, technique is simple, the harsh conditions avoiding conventional molding techniques make somatomedin or cell lose activity in the process building three-dimensional rack, jointly print with material for somatomedin or cell and build bone tissue engineering scaffold and provide most suitable condition of molding.
The normality forming method of a kind of three-dimensional rack containing sodium alginate, comprises the following steps:
(1) preparation three-dimensional rack containing sodium alginate
Sodium alginate is dissolved and obtains sodium alginate soln in a solvent, described sodium alginate soln adds polyvinyl alcohol (PVA), at 80-95 DEG C, is uniformly mixing to obtain slurry；Then using described slurry as the slurry of 3 D-printing, the three-dimensional rack obtained containing sodium alginate is printed at normal temperatures；
(2) molding
It is soaked in the described three-dimensional rack containing sodium alginate in calcium salt soln at normal temperatures to react 10-24h and carries out curing molding, after washing, lyophilization, obtain the three-dimensional rack containing calcium alginate.
Preferably, the viscosity of described sodium alginate is 1.05-1.15Pa s.
Preferably, the mass concentration of described sodium alginate soln is 8%-12%.
Preferably, described solvent is deionized water or distilled water.
Preferably, in described slurry, the mass ratio being also added with bioactivity glass, described bioactivity glass and described sodium alginate is x:1, wherein 0 < x≤1.Described bioactivity glass can improve biological activity and the mechanical property of three-dimensional rack.
It is highly preferred that the mass ratio of described bioactivity glass and described sodium alginate is 0.5:1.
Preferably, described bioactivity glass includes the component of following mole percent: 6%Na2O, 8%K2O, 8%MgO, 22%CaO, 54%SiO2And 2%P2O5。
Preferably, described bioactivity glass is 1393 types.
Preferably, in described slurry, the quality of described polyvinyl alcohol is described sodium alginate quality or the 1/6-1/2 of described sodium alginate and described bioactivity glass gross mass.
Preferably, described calcium salt is calcium chloride or calcium nitrate.
Preferably, the concentration of described calcium salt soln is 0.5mol/L-5mol/L.
Preferably, the described three-dimensional rack containing sodium alginate be shaped as cuboid.
Preferably, the bottom surface length of side of the described three-dimensional rack containing sodium alginate is 5-15mm, is highly 2.4-6mm, and line space is 1.15mm-1.50mm.
Polyvinyl alcohol (PVA) is as binding agent, it is possible to make sodium alginate and bioactivity glass be bonded together, it is prevented that subsiding of three-dimensional rack.
During printing, the line space of support is more big, and the porosity of the three-dimensional rack containing calcium alginate finally given is more big, and the compressive strength of support is more little；During identical line space, along with bioactivity glass content increases, the compressive strength of the three-dimensional rack containing calcium alginate first increases and reduces afterwards, and when the mass ratio of bioactivity glass and sodium alginate is 0.5:1, the compressive strength of three-dimensional rack is maximum.
nullThe present invention utilizes the sodium alginate at normal temperatures can with calcium ion generation crosslinked action thus the characteristic solidified，Calcium salt soln curing molding it is soaked at normal temperatures by printing the three-dimensional rack containing sodium alginate obtained，Condition of molding is gentle，Technique is simple，Additionally，The quality of line space and bioactivity glass by controlling support when printing，Porosity and the intensity of three-dimensional rack can be controlled，Finally give profile、Structure、Porosity and compressive strength are controlled and possess bioactive bone repairing support，Be conducive to osteocyte in timbering material surface adhesion、Growth inside，It is beneficial to bone cell proliferation，Its ossification can be promoted，It is beneficial to the maintenance of osteocyte configuration of surface simultaneously，Jointly print structure bone tissue engineering scaffold for next step somatomedin or cell and material to lay a good foundation，Further promote three-dimensional printing technology application in bone tissue engineer.Meanwhile, described normality forming method is simple to operate, and energy consumption is relatively low, and support builds speed.
Beneficial effects of the present invention includes following aspect:
The method mild condition of the three-dimensional rack curing molding containing sodium alginate provided by the invention, technique is simple.
Accompanying drawing explanation
Fig. 1 is the three-dimensional rack shape appearance figure containing calcium alginate that embodiment 2 prepares.
Detailed description of the invention
The following stated is the preferred embodiment of the present invention; it should be pointed out that, for those skilled in the art, under the premise without departing from the principles of the invention; can also making some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Embodiment 1
The normality forming method of a kind of three-dimensional rack containing sodium alginate, comprises the following steps:
(1) preparation three-dimensional rack containing sodium alginate
3g sodium alginate being dissolved and obtains the sodium alginate soln that mass concentration is 10% in deionized water, add 1gPVA, 90 DEG C stir as printing slurry；Then using this slurry as the slurry of 3 D-printing, utilize and print, under printer (the Bioscaffolder printer that Gesim company of Germany produces) room temperature, the three-dimensional rack obtained containing sodium alginate, this support design parameter is the cradle bottom surface length of side is 15mm, being highly 6mm, support line space ranges for 1.15mm；
(2) molding
Being soaked in the calcium chloride solution that concentration is 0.5mol/L at normal temperatures overnight by printing the three-dimensional rack containing sodium alginate obtained, use deionized water wash three times after immersion, lyophilization to constant weight obtains the three-dimensional rack containing calcium alginate.The detection three-dimensional rack porosity containing calcium alginate is 63.6%, and support compressive strength is 0.71MPa.
Embodiment 2
The normality forming method of a kind of three-dimensional rack containing sodium alginate, comprises the following steps:
(1) preparation three-dimensional rack containing sodium alginate
4g sodium alginate is dissolved and obtains the sodium alginate soln that mass concentration is 10% in deionized water, then be separately added into 1g bioactivity glass and 1.67gPVA, at 90 DEG C, be uniformly mixing to obtain slurry；Then, using this slurry as the slurry of 3 D-printing, utilize and print, under printer (the Bioscaffolder printer that Gesim company of Germany produces) room temperature, the three-dimensional rack obtained containing sodium alginate, this three-dimensional rack design parameter containing sodium alginate is the cradle bottom surface length of side is 15mm, being highly 6mm, support line space ranges for 1.15mm；
(2) molding
Being soaked in the calcium chloride solution that concentration is 5mol/L at normal temperatures overnight by printing the three-dimensional rack containing sodium alginate obtained, use deionized water wash three times after immersion, lyophilization to constant weight obtains the three-dimensional rack containing calcium alginate.Detecting this three-dimensional rack porosity containing calcium alginate is 64.4%, and support compressive strength is 0.83MPa.
Fig. 1 is the three-dimensional rack shape appearance figure containing calcium alginate that embodiment 2 prepares, it will be seen from figure 1 that the three-dimensional rack good forming effect containing calcium alginate that the present embodiment is prepared by the normality forming method of the present invention.
Embodiment 3
The normality forming method of a kind of three-dimensional rack containing sodium alginate, comprises the following steps:
(1) preparation three-dimensional rack containing sodium alginate
2g sodium alginate being dissolved and obtains the sodium alginate soln that mass concentration is 10% in deionized water, then be separately added into 1g bioactivity glass and 1gPVA, 90 DEG C are uniformly mixing to obtain slurry；Then, using this slurry as the slurry of 3 D-printing, utilizing and print the three-dimensional rack obtained containing sodium alginate under printer room temperature, this three-dimensional rack design parameter containing sodium alginate is the cradle bottom surface length of side is 15mm, being highly 6mm, support line space ranges for 1.15mm；
(2) molding
Being soaked in the calcium chloride solution that concentration is 0.5mol/L at normal temperatures overnight by printing the three-dimensional rack containing sodium alginate obtained, use deionized water wash three times after immersion, lyophilization to constant weight obtains the three-dimensional rack containing calcium alginate.The detection three-dimensional rack porosity containing calcium alginate is 63.8%, and support compressive strength is 1.06MPa.
Embodiment 4
The normality forming method of a kind of three-dimensional rack containing sodium alginate, comprises the following steps:
(1) preparation three-dimensional rack containing sodium alginate
2g sodium alginate being dissolved and obtains the sodium alginate soln that mass concentration is 10% in deionized water, then be separately added into 1g bioactivity glass and 1gPVA, 90 DEG C are uniformly mixing to obtain slurry；Then, using this slurry as the slurry of 3 D-printing, utilizing and print the three-dimensional rack obtained containing sodium alginate under printer room temperature, this three-dimensional rack design parameter containing sodium alginate is the cradle bottom surface length of side is 15mm, being highly 6mm, support line space ranges for 1.36mm；
(2) molding
Being soaked in the calcium chloride solution that concentration is 0.5mol/L at normal temperatures overnight by printing the three-dimensional rack containing sodium alginate obtained, use deionized water wash three times after immersion, lyophilization to constant weight obtains the three-dimensional rack containing calcium alginate.The detection three-dimensional rack porosity containing calcium alginate is 72.3%, and support compressive strength is 0.87MPa.
Embodiment 5
The normality forming method of a kind of three-dimensional rack containing sodium alginate, comprises the following steps:
(1) preparation three-dimensional rack containing sodium alginate
2g sodium alginate being dissolved and obtains the sodium alginate soln that mass concentration is 10% in deionized water, then be separately added into 1g bioactivity glass and 1gPVA, 90 DEG C are uniformly mixing to obtain slurry；Then, using this slurry as the slurry of 3 D-printing, utilizing and print the three-dimensional rack obtained containing sodium alginate under printer room temperature, this three-dimensional rack design parameter containing sodium alginate is the cradle bottom surface length of side is 15mm, being highly 6mm, support line space ranges for 1.50mm；
(2) molding
Being soaked in the calcium chloride solution that concentration is 0.5mol/L at normal temperatures overnight by printing the three-dimensional rack containing sodium alginate obtained, use deionized water wash three times after immersion, lyophilization to constant weight obtains the three-dimensional rack containing calcium alginate.The detection porosity containing calcium alginate is 78.4%, and support compressive strength is 0.68MPa.
Embodiment 6
The normality forming method of a kind of three-dimensional rack containing sodium alginate, comprises the following steps:
(1) preparation three-dimensional rack containing sodium alginate
1g sodium alginate being dissolved and obtains the sodium alginate soln that mass concentration is 10% in deionized water, then be separately added into 1g bioactivity glass and 1gPVA, 90 DEG C are uniformly mixing to obtain slurry；Then, using this slurry as the slurry of 3 D-printing, utilizing and print the three-dimensional rack obtained containing sodium alginate under printer room temperature, this three-dimensional rack design parameter containing sodium alginate is the cradle bottom surface length of side is 15mm, being highly 6mm, support line space ranges for 1.50mm；
(2) molding
Being soaked in the calcium chloride solution that concentration is 0.5mol/L at normal temperatures overnight by printing the support obtained, use deionized water wash three times after immersion, lyophilization to constant weight obtains the three-dimensional rack containing calcium alginate.The detection three-dimensional rack porosity containing calcium alginate is 80.3%, and support compressive strength is 0.53MPa.
Table 1 be the support line space of embodiment 1-6 and the porosity of the bioactivity glass mass ratio three-dimensional rack containing calcium alginate on finally giving and compressive strength affect result.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Three-dimensional rack line space containing sodium alginate | 1.15 | 1.15 | 1.15 | 1.36 | 1.50 | 1.50 |
| Bioactivity glass and sodium alginate mass ratio | 0:1 | 0.25:1 | 0.5:1 | 0.5:1 | 0.5:1 | 1:1 |
| Three-dimensional rack porosity containing calcium alginate | 63.6% | 64.4% | 63.8% | 72.3% | 78.4% | 80.3% |
| Three-dimensional rack compressive strength containing calcium alginate | 0.71 | 0.83 | 1.06 | 0.87 | 0.68 | 0.53 |
As it can be seen from table 1 the line space of three-dimensional rack is more big, the porosity of support is more big, and the compressive strength of the three-dimensional rack containing calcium alginate is more little；During identical line space, along with bio-vitric content increases, the compressive strength of support first increases and reduces afterwards, and when the mass ratio of bioactivity glass and sodium alginate is 0.5:1, the compressive strength of the three-dimensional rack containing calcium alginate is maximum.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that, for the person of ordinary skill of the art, without departing from the inventive concept of the premise, it is also possible to making some deformation and improvement, these broadly fall into protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. the normality forming method of the three-dimensional rack containing sodium alginate, it is characterised in that comprise the following steps:
(1) preparation three-dimensional rack containing sodium alginate
Sodium alginate is dissolved and obtains sodium alginate soln in a solvent, described sodium alginate soln adds polyvinyl alcohol, at 80-95 DEG C, is uniformly mixing to obtain slurry；Then using described slurry as the slurry of 3 D-printing, the three-dimensional rack obtained containing sodium alginate is printed at normal temperatures；
(2) molding
It is soaked in the described three-dimensional rack containing sodium alginate in calcium salt soln at normal temperatures to react 10-24h and carries out curing molding, after washing, lyophilization, obtain the three-dimensional rack containing calcium alginate.
2. normality forming method as claimed in claim 1, it is characterised in that the mass concentration of described sodium alginate soln is 8%-12%.
3. normality forming method as claimed in claim 1, it is characterised in that described solvent is deionized water or distilled water.
4. normality forming method as claimed in claim 1, it is characterised in that in described slurry, the mass ratio being also added with bioactivity glass, described bioactivity glass and described sodium alginate is x:1, wherein 0 < x≤1.
5. normality forming method as claimed in claim 4, it is characterised in that in described slurry, the mass ratio of described bioactivity glass and described sodium alginate is 0.5:1.
6. normality forming method as claimed in claim 1, it is characterised in that described bioactivity glass includes the component of following mole percent: 6%Na2O, 8%K2O, 8%MgO, 22%CaO, 54%SiO2And 2%P2O5。
7. the normality forming method as described in claim 1 or 4, it is characterised in that in described slurry, the quality of described polyvinyl alcohol is described sodium alginate quality or the 1/6-1/2 of described sodium alginate and described bioactivity glass gross mass.
8. normality forming method as claimed in claim 1, it is characterised in that the concentration of described calcium salt soln is 0.5mol/L-5mol/L.
9. normality forming method as claimed in claim 1, it is characterised in that described calcium salt is calcium chloride or calcium nitrate.
10. normality forming method as claimed in claim 1, it is characterised in that the bottom surface length of side of the described three-dimensional rack containing sodium alginate is 5-15mm, is highly 2.4-6mm, and line space is 1.15mm-1.50mm.
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