CN105641741A - HA (Hydroxyapatite) coating with high degree of crystallinity and nano-structure and preparation method of HA coating - Google Patents
HA (Hydroxyapatite) coating with high degree of crystallinity and nano-structure and preparation method of HA coating Download PDFInfo
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Abstract
The invention relates to an HA (Hydroxyapatite) coating with high degree of crystallinity and a nano-structure and a preparation method of the HA coating. The HA coating comprises 95% or above of hydroxyapatite, the degree of crystallinity is 85% or above, and the surface structure of the HA coating comprises the nano-structure. The HA coating has high purity and high degree of crystallinity, so that the problems that the phase decomposition and low degree of crystallinity of the traditional coating cause the coating degradation, and further, the coating falls off, an implant becomes loose, and the like, are solved; meanwhile, the coating has the nano-structure, and can promote the adhesion and proliferation of osteoblasts and the osteogenic differentiation, so that the osseointegration performance of the implant of the HA coating is improved.
Description
Technical field
The present invention relates to air plasma spraying to combine with water at low temperature heat treatment technics and realize the preparation of high-crystallinity, nanostructure HA coating, there is the novel hard tissue alternate material of excellent Integrated implant performance, belong to biomedical materials field.
Background technology
Due to reasons such as disease, traffic accident and agings, a large amount of sclerous tissues's impaired subjects is had to need operative treatment every year. According to statistics, bone renovating material in 2013 year market value just up to 2,000 ten thousand dollars, and continue to increase with the annual growth of 20��27%.
Titanium alloy, owing to having the advantages such as excellent mechanical property, easily processing, corrosion resistance are good, becomes clinical conventional metal implant material, especially in mechanics weight bearing area bone/dental restortion field. But, long-term clinical study finds: the bone regeneration capability of titanium alloy class implant is poor, cause implant surfaces can not direct skeletonization, and wrapped up by fibrous tissue, synostosis cannot be formed. After considering that titanium and titanium alloys implants, being had an effect by surface and surrounding environment at first, therefore implantation effect is had bigger impact (Int.J.Appl.Ceram.Technol., 2013 by its surface tissue and characteristic; 10:1 10.), by suitable surface treatment, on the basis retaining the original premium properties of titanium and titanium alloys, can effectively promote the surface property (biological activity, Integrated implant and the performance such as antibacterial) of medical titanium alloy, thus improve implantation and the Clinical practice effect of implant. Hydroxyapatite [Ca10(PO4)6(OH)2, HA] biological ceramics because of its chemical composition similar and there is excellent biocompatibility and bone guided performance with human body bone inorganic components so that it is become desirable and plant bone coated material (Biomaterials, 2010; 31:1465-85; MaterialsScienceandEngineering:R:Reports, 2010; 70:225-42.). Titanium alloy bone-grafting material surface HA coating technology and research and development of products are the investigation and application focuses in bone material field, especially at joint prosthesis and tooth implant etc. by power bone renovating material field (inorganic materials journal, 2013; 28:12-20.).
So far, HA coating technology mainly contains high-temperature plasma thermospray, laser pulse vapour deposition, laser melting coating, sol-gel, electron-beam vapor deposition, electrophoretic deposition, magnetron sputtering etc. These preparation methods respectively have its relative merits. Wherein, high-temperature plasma hot-spraying techniques has the plurality of advantages such as technique is simple, coat-thickness is easy to control, preparation efficiency height, it it is HA coat preparing technology the most frequently used in the world at present, successfully realize commercialization and it is applied to clinical (JournalofSolidStateChemistry, 2003;172:339-50.). But, plasma thermal sprayed technology carries out under ultrahigh-temperature environment, unavoidably causes HA phase transformation and decomposes the tetracalcium phosphate (Ca generating high-dissolvability in a large number4P2O9), tricalcium phosphate (Ca3(PO4)2), and generate the materials such as cytotoxicity caused calcium oxide (CaO). And in quick cooling thereafter, form a large amount of non-crystalline state HA thing phases, greatly reduce HA crystal content and degree of crystallinity (ActaMaterialia, 2004 in coating; 52:1171-81.), cause the content of HA crystalline phase general only about 40%, even lower, especially atmospheric plasma spraying technology. Low-crystallinity and low HA crystal content greatly accelerate dissolving/degradation rate (Biomaterials, 2004 of coating; 25:415-21.), serious also cause disbonding because of it and then cause the failure of Using prosthesis art (MaterialsLetters, 2004; 58:71-3.). China medical device industry standard YY0304-1998 specifies that the content of HA crystalline phase in coating should be not less than 62%. Although research confirms that secondary vacuum anneal can improve HA crystal content (Biomaterials, 2007 in plasma thermal sprayed coating; 28:2923-31; AppliedSurfaceScience, 2008; 255:3426-33.). Further, the content of HA crystalline phase with second heat treatment temperature raise and increase, 600 DEG C of isothermal holding can reach about 65%, temperature continue raise time degree of crystallinity change less, higher than 750 DEG C then degree of crystallinity again start decline. But, the thermal treatment of more than 500 DEG C causes again coating stress increase, crackle to increase, and then cause coating cracking, bonding strength to decline, even peeling phenomenon (SurfaceandCoatingsTechnology, 2007 simultaneously; 201:7187-93.). Vacuum plasma hot-spraying techniques has certain advantage in higher crystallinity HA coating preparing, but required equipment is extremely expensive and degree of crystallinity increase rate is also limited.
And, plasma thermal sprayed technology at high temperature HA material is melt into drop high speed deposition in the titanium alloy-based end. Drop forms the crystal particle scale of micron when cooling fast. Relative to the nanostructure of people's bone, micron grain yardstick HA coating lacks the effect of induced dry-cell Osteoblast Differentiation and induced osteogenesis, new bone often can not gap between filling implant and host tissue well, make early stage skeletonization and Integrated implant performance undesirable (Biomaterials, 2005; 26:3631-38.). Recent study shows: nano surface structure can promote scleroblast and bone marrow stem cell to stick, breed and Osteoblast Differentiation (Nature, 2007; 6:997-1003.). Therefore, making Nano surface improves the biological activity of material and one of important channel improving implant Integrated implant performance, has important scientific meaning and clinical value.
In sum, if high-crystallinity and surface nano-structure design are combined, then both can solve tradition HA coating degradation property height, implant after the defect easily peeling off and come off, the making Nano surface structure being expected to play again coating is to improve the Integrated implant performance of implant.
Summary of the invention
For prior art Problems existing, it is an object of the invention to prepare the novel HA coated on titanium alloy implant of high-crystallinity, nanostructure. Based on the specific requirement of sclerous tissues's implant stability and Integrated implant performance, air plasma spraying and water at low temperature heat treatment technics is adopted to combine, combined with the design of material surface nanometer by HA coating high-crystallinity, and then develop the novel HA coated on titanium alloy implant of stability height, service life length, the early stage excellent combination property such as skeletonization and Integrated implant, thus meet clinical on demand.
At this, on the one hand, the present invention provides a kind of high-crystallinity, nanostructured hydroxyapatite coating, and described coating comprises the hydroxyapatite of more than 95%, and degree of crystallinity is more than 85%, and described coating surface structure is nanostructure.
The HA coating of the present invention has high purity and high-crystallinity, thus avoids phase decomposition and low-crystallinity because of conventional coatings to cause coating degradation and then cause the problems such as coating shedding and implant loosen; Meanwhile, and this coating has nanostructure, scleroblast can be promoted to stick, breed and Osteoblast Differentiation, and then improve the Integrated implant performance of HA coating implant.
Goodly, in described coating, hydroxyapatite grain-size is 5��100nm.
Goodly, the thickness of described coating is 50��120 ��m.
Goodly, described coating formation is in the surface of medical titanium alloy substrate.
On the other hand, the present invention also provides the preparation method of above-mentioned high-crystallinity, nanostructured hydroxyapatite coating, comprises the following steps:
A () adopts air plasma spraying technique to be sprayed on titanium alloy substrate to form hydroxyapatite coating layer by the hydroapatite particles that particle diameter is 20��100 ��m, spraying parameter is: the flow of arc plasma gases argon is 35��45slpm, the flow of arc plasma gas hydrogen is 7��15slpm, the flow of powder carrier gas Ar is 1.5��3.5slpm, spray distance is 80��120mm, powder feeding rate is 8��30rpm, and spraying current is 500��700A;
B the hydroxyapatite coating layer of gained is carried out hydrothermal treatment consists with obtained high-crystallinity, nanostructured hydroxyapatite coating by (), wherein the condition of hydrothermal treatment consists is: hydrothermal temperature is 120��250 DEG C, hydro-thermal medium is the aqueous solution of pH=7��12 or concentration is the phosphate solution of 0.05��2.0mol/L, and the hydro-thermal time is 6��72 hours.
The present invention adopts air plasma spraying and water at low temperature heat treatment technics to combine, and develops the novel HA coated on titanium alloy implant of stability height, service life length, the early stage excellent combination property such as skeletonization and Integrated implant. The present invention have simple for process and be convenient to promote feature.
Goodly, the hydroapatite particles of described 20��100 ��m is obtained by sintering crushing method.
Goodly, the particle diameter of described hydroapatite particles is 40��80 ��m.
Goodly, spraying parameter is: the flow of arc plasma gas Ar is 40slpm, arc plasma gas H2Flow be 8slpm, the flow of powder carrier gas Ar is 2.0slpm, and spray distance is 100mm, and powder feeding rate is 22rpm, and spraying current is 550A.
Goodly, described phosphate solution is (NH4)3PO4Solution, (NH4)2HPO4Solution, Na3PO4Solution, NaH2PO4Solution.
Goodly, the condition of hydrothermal treatment consists is: hydrothermal temperature is 150��200 DEG C, and hydro-thermal medium is the Na of 0.1��1.0mol/L3PO4Solution, the hydro-thermal time is 12��36 hours.
Accompanying drawing explanation
Fig. 1 is that HA coating is at different hydrothermal condition (A: the original HA coating sample that tradition atmospheric heat spraying technology prepares; B: coating sample after 180 DEG C of hydro-thermal 24h under the aqueous solution of pH=7; C: coating sample after 180 DEG C of hydro-thermal 24h under the aqueous solution of pH=9; D: coating sample after 180 DEG C of hydro-thermal 24h under the aqueous solution of pH=11) under the XRD figure of HA coating after hydro-thermal;
Fig. 2 is that HA coating is at different hydrothermal condition (A: the original HA coating sample that tradition air plasma spraying prepares;B: coating sample after 180 DEG C of hydro-thermal 24h under the aqueous solution of pH=7; C: coating sample after 180 DEG C of hydro-thermal 24h under the aqueous solution of pH=9; D: coating sample after 180 DEG C of hydro-thermal 24h under the aqueous solution of pH=11) under degree of crystallinity calculation result after hydro-thermal;
Fig. 3 is that HA coating is at different hydrothermal condition (A: the original HA coating sample that tradition air plasma spraying prepares; B: coating sample after 180 DEG C of hydro-thermal 24h under the aqueous solution of pH=7; C: coating sample after 180 DEG C of hydro-thermal 24h under the aqueous solution of pH=9; D: coating sample after 180 DEG C of hydro-thermal 24h under the aqueous solution of pH=11; E: coating is at 0.2mol/LNa3PO4Sample after the lower 180 DEG C of hydro-thermal 24h of solution) under SEM result after hydro-thermal;
For different HA coating, (HA is coated with layer original sample to Fig. 4: the original HA coating sample that tradition air plasma spraying prepares; High-crystallinity HA coating: coating sample after 180 DEG C of hydro-thermal 24h under the aqueous solution of pH=7; High-crystallinity nano HA coating: coating is at 0.2mol/LNa3PO4Sample after the lower 180 DEG C of hydro-thermal 24h of solution) in the Tris-HCl buffered soln of pH=7.25, soak different time after survey its mass loss (A) and calcium ion (Ca thereof2+) release (B) situation;
Fig. 5 is that in different HA coating, (HA is coated with layer original sample: the original HA coating sample that tradition air plasma spraying prepares in mesenchymal stem cells MSCs cultivation; High-crystallinity nano HA coating: coating is at 0.2mol/LNa3PO4Sample after the lower 180 DEG C of hydro-thermal 24h of solution) surperficial vitro culture after Cell proliferation results;
Fig. 6 is that in different HA coating, (HA is coated with layer original sample: the original HA coating sample that tradition air plasma spraying prepares in mesenchymal stem cells MSCs cultivation; High-crystallinity HA coating: coating sample after 180 DEG C of hydro-thermal 24h under the aqueous solution of pH=7; High-crystallinity nano HA coating: coating is at 0.2mol/LNa3PO4Sample after the lower 180 DEG C of hydro-thermal 24h of solution) surperficial vitro culture after skeletonization correlation factor alkaline phosphatase (ALP) express experimental result;
Fig. 7 is that in different HA coating, (HA is coated with layer original sample: the original HA coating sample that tradition air plasma spraying prepares in mesenchymal stem cells MSCs cultivation; High-crystallinity HA coating: coating sample after 180 DEG C of hydro-thermal 24h under the aqueous solution of pH=7; High-crystallinity nano HA coating: coating is at 0.2mol/LNa3PO4Sample after the lower 180 DEG C of hydro-thermal 24h of solution) surperficial vitro culture after other Osteoblast Differentiation results of factor analysis (real-time quantitative polymerase chain reaction, qRT-PCR).
Embodiment
Below in conjunction with accompanying drawing and the bright the present invention furtherly of following enforcement mode, it should be understood that accompanying drawing and following enforcement mode are only for illustration of the present invention, and unrestricted the present invention.
The present inventor finds after deliberation, if high-crystallinity and surface nano-structure design are combined, then both can solve tradition HA coating degradation property height, implant after the defect easily peeling off and come off, the making Nano surface structure being expected to play again coating is to improve the Integrated implant performance of implant, thus completes the present invention.
One aspect of the present invention provides a kind of high-crystallinity, nanostructured hydroxyapatite (HA) coating, and described coating is the HA coating of high purity (more than 95%); Degree of crystallinity reaches more than 85%; And HA coating surface structure comprises nanostructure. In the present invention, nanostructure can be unordered or orderly nanostructure, it is preferable to orderly nanostructure. In nanostructure, the size of nanocrystal can be 5��100nm.The HA coating of the present invention can be formed at the surface of the titanium alloy-based end (such as Ti-6Al-4V), and coat-thickness can be 50��120 ��m.
The HA coating of the present invention has high purity and high-crystallinity, thus avoid phase decomposition and low-crystallinity because of conventional coatings to cause coating degradation and then cause the problems such as coating shedding and implant loosen, simultaneously, this coating has nanostructure, scleroblast can be promoted to stick, breed and Osteoblast Differentiation, and then improve osteogenic activity and the Integrated implant performance of HA coating implant.
Curve B in Fig. 1, C, D illustrate the XRD figure of the HA coating of the present invention's three examples, and as seen from the figure, the HA coating of the present invention is almost HA pure phase (purity is more than 95%). B, C, D in Fig. 2 illustrates the result of the degree of crystallinity that the HA coating of the present invention's three examples calculates according to international standard (ISO13779-3) and People's Republic of China's national standard (GB23101.3) thereof, as seen from the figure, the degree of crystallinity of the HA coating of the present invention reaches more than 85%, and degree of crystallinity is not less than the requirement of 62% far above medical device industry standard.
B, C, D, E in Fig. 3 illustrates the SEM figure of the HA coating of the present invention's four examples, shows that the surface tissue of the HA coating of the present invention is unordered or relatively orderly nanostructure, and in the example of E, in coating, HA grain-size is 10��20nm.
Fig. 4 illustrates that (HA is coated with layer original sample: the tradition original HA coating sample for preparing of air plasma spraying for the HA coating of existing HA coating and the present invention; High-crystallinity HA coating: coating sample after 180 DEG C of hydro-thermal 24h under the aqueous solution of pH=7; High-crystallinity nano HA coating: coating is at 0.2mol/LNa3PO4Sample after the lower 180 DEG C of hydro-thermal 24h of solution) in the Tris-HCl buffered soln of pH=7.25, soak different time after survey its mass loss (A) and calcium ion (Ca thereof2+) release (B) situation, as shown in Figure 4, the high-crystallinity nano HA coating of the present invention is compared to the tradition HA coating for preparing of air plasma spraying, it is to increase chemical stability, thus overcome the risk of traditional coating high-dissolvability, it is expected to extend the work-ing life of implant.
Fig. 5 illustrates that (HA is coated with layer original sample: the original HA coating sample that tradition air plasma spraying prepares in the HA coating of existing HA coating and the present invention in mesenchymal stem cells MSCs cultivation; High-crystallinity nano HA coating: coating is at 0.2mol/LNa3PO4Sample after the lower 180 DEG C of hydro-thermal 24h of solution) surperficial vitro culture after Cell proliferation results. Experimental result shows: 1 day and 3 days cell cultures result difference little, when the 5th day, degree of crystallinity nanostructure can significantly promote cell proliferation, it was demonstrated that high-crystallinity nanostructure plays the effect promoting osteoblastic proliferation.
Fig. 6 illustrates that (HA is coated with layer original sample: the original HA coating sample that tradition air plasma spraying prepares in the HA coating of existing HA coating and the present invention in mesenchymal stem cells MSCs cultivation; High-crystallinity HA coating: coating sample after 180 DEG C of hydro-thermal 24h under the aqueous solution of pH=7; High-crystallinity nano HA coating: coating is at 0.2mol/LNa3PO4Sample after the lower 180 DEG C of hydro-thermal 24h of solution) surperficial vitro culture after skeletonization correlation factor alkaline phosphatase (ALP) express experimental result, show that the raising of degree of crystallinity can promote that ALP expresses, and high-crystallinity nanostructure can promote that ALP expresses further, and then confirm that nanostructure can effectively promote osteoblast differentiation.
Fig. 7 illustrates that (HA is coated with layer original sample: the original HA coating sample that tradition air plasma spraying prepares in the HA coating of existing HA coating and the present invention in mesenchymal stem cells MSCs cultivation;High-crystallinity HA coating: coating sample after 180 DEG C of hydro-thermal 24h under the aqueous solution of pH=7; High-crystallinity nano HA coating: coating is at 0.2mol/LNa3PO4Sample after the lower 180 DEG C of hydro-thermal 24h of solution) surperficial vitro culture after other Osteoblast Differentiation results of factor analysis (real-time quantitative polymerase chain reactions, qRT-PCR), result shows, at specified time, the raising of degree of crystallinity and the structure of nanostructure can effectively promote relevant osteogenic factor, such as the high expression level of BSP, BMP-2, COL1, OCN, RUNX2, OPN etc., show that high-crystallinity nanostructure can promote Osteoblast Differentiation, and then promote Integrated implant performance.
The HA coating of the present invention can adopt air plasma spraying and water at low temperature heat treatment technics to combine to prepare. Specifically, exemplarily, it is possible to comprise the following steps:
A () utilizes sintering crushing method, preparation is applicable to the HA particle of plasma spraying, and particle diameter is 20-100 ��m;
B () adopts air plasma spraying technique, when following processing parameter by the HA particle deposition prepared by (a) in cleaning on the titanium alloy substrate with sandblasting. Described spraying parameter is the flow of arc plasma gases argon (Ar) is 35-45slpm (slpm refers to standard liter/min), arc plasma gas hydrogen (H2) flow be 7-15slpm, the flow of powder carrier gas Ar is 1.5-3.5slpm, and spray distance is 80-120mm, and powder feeding rate is 8-30rpm, and spraying current is 500-700A;
C () utilizes water at low temperature heat treatment technics, obtain the HA coating of high purity, high-crystallinity, nanostructure. Described low-temperature hydrothermal treatment condition are that temperature is 120-250 DEG C, and hydro-thermal medium is the aqueous solution of pH=7-12 or concentration is the phosphate solution of 0.05-2.0mol/L, and the hydro-thermal time is 6-72h.
In step (a), the particle diameter of HA particle is preferably 40-80 ��m. Again, specifically, sintering crushing method can comprise the following steps: HA powder body is pressed into the slice, thin piece that diameter is 40mm, 1050 DEG C of calcinings, after broken, crosses 200-400 mesh sieve, and choosing particle diameter is that the particle of 40-80 ��m is as plasma spraying particle. In addition, in the present invention, the method for the HA particle that preparation is applicable to plasma spraying is not limited to sintering crushing method, as long as the HA particle that particle diameter is 20-100 ��m can be obtained.
In step (b), it is preferable that spraying parameter be the flow of arc plasma gas Ar be 40slpm, arc plasma gas H2Flow be 8slpm, the flow of powder carrier gas Ar is 2.0slpm, and spray distance is 100mm, and powder feeding rate is 22rpm, and spraying current is 550A.
In step (c), the aqueous solution of pH=7-12 is by with NaOH solution, HNO3Solution regulates pH to prepare. Described phosphate solution includes but not limited to (NH4)3PO4Solution, (NH4)2HPO4Solution, Na3PO4Solution, NaH2PO4Solution. In a preferred example, the condition of hydrothermal treatment consists is: hydrothermal temperature is 150��200 DEG C, and hydro-thermal medium is the Na of 0.1��1.0mol/L3PO4Solution, the hydro-thermal time is 12��36 hours.
Prepared HA coating not only has high HA content and high-crystallinity, and surface tissue is nanostructure. XRD figure (Fig. 1) display after hydro-thermal under different hydrothermal condition of described coating, hydrothermal treatment consists rear impurity peak disappears substantially, what obtain is almost HA pure phase, especially under the pH=7 aqueous solution, sample after 180 DEG C of hydro-thermal 24h is HA pure phase, there is no impurity peaks, the thing Dynamical property that tricalcium phosphate that when illustrating that hydrothermal treatment consists can make air plasma spraying, under hot environment, phase transformation produces, tetracalcium phosphate, calcium oxide etc. decompose becomes HA, it is achieved the preparation of high purity HA coating.Simultaneously, the degree of crystallinity of HA coating is calculated according to international standard (ISO13779-3) and People's Republic of China's national standard (GB23101.3) thereof, corresponding degree of crystallinity calculation result (Fig. 2) shows: after hydrothermal treatment consists, degree of crystallinity brings up to more than 85% by 53%, and degree of crystallinity is not less than the requirement of 62% far above medical device industry standard. In addition, SEM figure (Fig. 3) display after hydro-thermal under different hydrothermal condition of described coating, under the different pH aqueous solution regulates and controls, surface has grown micrometer structure, and has a small amount of nanostructure, but orderly not; And at 0.2mol/LNa3PO4Surface tissue after the lower 180 DEG C of hydro-thermal 24h of solution is relatively orderly nanostructure, and in coating, HA grain-size is 5-100nm, it is preferable to 10-20nm.
The experiment display of external anti-degradation property, surveys its mass loss and Ca thereof after described coating is soaked different time in the Tris-HCl buffered soln of pH=7.252+Release conditions (Fig. 4 (A, B)), showing that hydrothermal treatment consists can improve its chemical stability, making Nano surface can improve its chemical stability further, thus overcome the risk of traditional coating high-dissolvability, it is expected to extend the work-ing life of implant. In addition, external osteoblastic proliferation experiment (Fig. 5), ALP express experiment (Fig. 6) and osteogenic factor Analytical Chemical Experiment (Fig. 7) result shows, the raising of degree of crystallinity and nanostructure can significantly promote that cell proliferation, differentiation and osteogenic factor thereof are expressed, and then confirm that nanostructure can promote Osteoblast Differentiation, and then promote Integrated implant performance.
In sum, high-crystallinity and surface nano-structure design the HA coating combined, both can solve tradition HA coating degradation property height, implant after the defect easily peeling off and come off, the making Nano surface structure being expected to play again coating, to improve the Integrated implant performance of implant, has unique advantage in hard tissue substituting repair materials field.
Enumerate embodiment below further so that the present invention to be described in detail. Should understand equally; following examples are only used to further illustrate the present invention; can not being interpreted as limiting the scope of the invention, improvement and the adjustment of some non-intrinsically safes that the technician of this area makes according to the foregoing of the present invention all belong to protection scope of the present invention. The processing parameter etc. that following example is concrete is also only in OK range a example, and namely those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want to be defined in the concrete numerical value of Examples below.
Embodiment 1:
A, prepare plasma spraying particle by sintering-crush method
Getting 200gHA powder body is, after 10%PVA mixes, adopt dry-pressing formed method with 16g concentration, pressurization 25MPa, obtained diameter is the sheet of 40mm, and at 1050 DEG C sintering soak 5h, after furnace cooling HA ceramic plate. By the fragmentation in mortar of gained ceramic plate, and cross 200 orders and 400 mesh sieve, obtain particle diameter at 40-80 ��m of particle as plasma spraying raw material;
B, employing air plasma spraying prepare HA coating
First, by titanium alloy sheet (10mm �� 10mm �� 2mm) surface after sandblasting, ultrasonic 10min in ethanol solution, and with deionized water rinsing 2-3 time, at 100 DEG C, oven dry, for subsequent use; Then, adopt air plasma spraying technique, the HA particle spray coating by the particle diameter described in A being 40-80 ��m is to, plasma spray coating process parameter is at pretreated the titanium alloy-based end: the flow of arc plasma gas Ar is 40slpm, arc plasma gas H2Flow be 8slpm, the flow of powder carrier gas Ar is 2.0slpm, and spray distance is 100mm, and powder feeding rate is 22rpm, and spraying current is 550A.Described slpm refers to standard liter/min;
C, water at low temperature heat treatment technics is utilized to prepare high purity, high-crystallinity, nanostructure HA coating
First, getting HA coated on titanium alloy sheet prepared by two panels B, being placed in volume is bottom the water heating kettle liner of 25ml, and containing coat side upward; Then, in above-mentioned water heating kettle liner, add the aqueous solution of 20mlpH=7, build interior lid, tighten water heating kettle; Finally, above-mentioned water heating kettle is placed in 180 DEG C of baking oven hydro-thermal 24h.
After X-ray diffraction (XRD) collection of illustrative plates confirmation hydrothermal treatment consists, coating is pure ha thing phase (as shown in the B in Fig. 1); Degree of crystallinity (as shown in the B in Fig. 2) result calculated shows, after hydrothermal treatment consists, degree of crystallinity brings up to 87% by 53%, and degree of crystallinity is not less than the requirement of 62% far above medical device industry standard; Scanning electron microscope display coating morphology is unordered nanostructure (as shown in the B in Fig. 3); Degradation property experimental result (as Suo Shi " the high-crystallinity HA coating " in Fig. 4) shows, and in the aqueous solution of pH=7, hydrothermal treatment consists can improve its chemical stability; ALP after the coatingsurface of mesenchymal stem cells MSCs vitro culture after the aqueous solution hydrothermal treatment consists of pH=7 expresses (as Suo Shi " the high-crystallinity HA coating " in Fig. 6), osteogenic factor breaks up (as Suo Shi " the high-crystallinity HA coating " in Fig. 7) result and shows: the aqueous solution hydrothermal treatment consists at pH=7 can promote that cell proliferation is (during cell cultures 5 days, promote that cultivation effect is obvious), the expression of alkaline phosphatase expression of enzymes and osteogenic factor thereof: cultivate after 4 days: the expression of OPN improves 2 times, and the expression of BSP, COL1 improves 1 times; And after 7 and 10 days, significantly promote the high expression level of BMP-2. Visible, to the aqueous solution hydrothermal treatment consists of original coating at pH=7, can obviously promote Osteoblast Differentiation, and then promote Integrated implant performance.
Embodiment 2:
The HA coating prepared by air plasma spraying in embodiment 1 180 DEG C of hydro-thermal 24h in the pH=9 aqueous solution, concrete hydrothermal treatment process is with embodiment 1. After X-ray diffracting spectrum confirmation hydrothermal treatment consists, coating is hydroxyapatite thing phase, and amorphous phase reduces (as shown in the C in Fig. 1); Degree of crystallinity (as shown in the C in Fig. 2) result calculated shows, after hydrothermal treatment consists, degree of crystallinity brings up to more than 85% by 53%, and degree of crystallinity is not less than the requirement of 62% far above medical device industry standard; Scanning electron microscope display coating morphology is unordered nanostructure (as shown in the C in Fig. 3); Degradation property experimental result shows, and hydrothermal treatment consists can improve its chemical stability. The experimental result of cell also shows: the coated material that the more traditional atmospheric heat spraying technology of the high-crystallinity nano-structured coating material prepared under this condition obtains has better short cell proliferation and Osteoblast Differentiation characteristic.
Embodiment 3:
The HA coating prepared by air plasma spraying in embodiment 1 180 DEG C of hydro-thermal 24h in the pH=11 aqueous solution, concrete hydrothermal treatment process is with embodiment 1. After X-ray diffracting spectrum confirmation hydrothermal treatment consists, coating is hydroxyapatite thing phase, and amorphous phase reduces (as shown in the D in Fig. 1); Degree of crystallinity (as shown in the D in Fig. 2) result calculated shows, after hydrothermal treatment consists, degree of crystallinity brings up to more than 86% by 53%, and degree of crystallinity is not less than the requirement of 62% far above medical device industry standard; Scanning electron microscope display coating morphology is unordered nanostructure (as shown in the D in Fig. 3);Degradation property experimental result shows, and hydrothermal treatment consists can improve its chemical stability. The experimental result of cell also shows: the coated material that the more traditional atmospheric heat spraying technology of the high-crystallinity nano-structured coating material prepared under this condition obtains has better short cell proliferation and Osteoblast Differentiation characteristic.
Embodiment 4:
The HA coating prepared by air plasma spraying in embodiment 1 is in 0.2mol/L (NH4)3PO4180 DEG C of hydro-thermal 24h in solution, concrete hydrothermal treatment process is with embodiment 1. Scanning electron microscope display coating morphology is nanostructure, and nano-scale is 30-50nm; Degradation property experimental result shows, at 0.2mol/L (NH4)3PO4Under solution, coating after hydro-thermal can significantly improve its chemical stability, thus overcomes the risk of traditional coating high-dissolvability, is expected to extend the work-ing life of implant; External mesenchymal stem cells MSCs proliferation experiment, ALP express and the display of PCR experiment result, the structure of nanostructure can promote the high expression level of cell proliferation, ALP expression and relevant osteogenic factor thereof, thus the structure confirming nanostructure is expected to promote Integrated implant performance.
Embodiment 5:
The HA coating prepared by air plasma spraying in embodiment 1 is in 0.2mol/LNa3PO4180 DEG C of hydro-thermal 24h in solution, concrete hydrothermal treatment process is with embodiment 1. Scanning electron microscope display coating morphology is relative ordered nano-structure, and nano-scale is 10-20nm (as shown in the E in Fig. 3); Degradation property experimental result (as Suo Shi " the high-crystallinity nano HA coating " in Fig. 4) shows, and coating is at 0.2mol/LNa3PO4Under solution, hydrothermal treatment consists can improve its chemical stability further, thus overcomes the risk of traditional coating high-dissolvability, is expected to extend the work-ing life of implant; External mesenchymal stem cells MSCs proliferation experiment (as Suo Shi " the high-crystallinity nano HA coating " in Fig. 5), ALP express experiment (as Suo Shi " the high-crystallinity nano HA coating " in Fig. 6) and PCR experiment (as Suo Shi " the high-crystallinity nano HA coating " in Fig. 7) result shows: the raising of degree of crystallinity and the structure of nanostructure can promote that cell proliferation, alkaline phosphatase differentiation and osteogenic factor thereof are expressed further, thus confirm that nanostructure can promote Osteoblast Differentiation, and then promote Integrated implant performance.
Comparative example 1:
Only carry out the steps A in embodiment 1 and B, and do not carry out step C, obtain original HA coating sample. Its XRD figure is see the A in Fig. 1, degree of crystallinity calculation result is see the A in Fig. 2, SEM figure is see the A in Fig. 3, degradation property experimental result is see " HA is coated with layer original sample " in Fig. 4, external mesenchymal stem cells MSCs proliferation experiment result is see " HA is coated with layer original sample " in Fig. 5, ALP expresses experimental result see " HA is coated with layer original sample " in Fig. 6, and PCR experiment result is see " HA is coated with layer original sample " in Fig. 7.
Claims (10)
1. a high-crystallinity, nanostructured hydroxyapatite coating, it is characterised in that, described coating comprises the hydroxyapatite of more than 95%, and degree of crystallinity is more than 85%, and described coating surface structure comprises nanostructure.
2. high-crystallinity according to claim 1, nanostructured hydroxyapatite coating, it is characterised in that, in described coating, hydroxyapatite grain-size is 5��100nm.
3. high-crystallinity according to claim 1, nanostructured hydroxyapatite coating, it is characterised in that, the thickness of described coating is 50��120 ��m.
4. high-crystallinity according to claim 1, nanostructured hydroxyapatite coating, it is characterised in that, described coating formation is in the surface of medical titanium alloy substrate.
5. the preparation method of high-crystallinity according to any one of a Claims 1-4, nanostructured hydroxyapatite coating, it is characterised in that, comprise the following steps:
A () adopts air plasma spraying technique to be sprayed on titanium alloy substrate to form hydroxyapatite coating layer by the hydroapatite particles that particle diameter is 20��100 ��m, spraying parameter is: the flow of arc plasma gases argon is 35��45slpm, the flow of arc plasma gas hydrogen is 7��15slpm, the flow of powder carrier gas Ar is 1.5��3.5slpm, spray distance is 80��120mm, powder feeding rate is 8��30rpm, and spraying current is 500��700A;
B the hydroxyapatite coating layer of gained is carried out hydrothermal treatment consists with obtained high-crystallinity, nanostructured hydroxyapatite coating by (), wherein the condition of hydrothermal treatment consists is: hydrothermal temperature is 120��250 DEG C, hydro-thermal medium is the aqueous solution of pH=7��12 or concentration is the phosphate solution of 0.05��2.0mol/L, and the hydro-thermal time is 6��72 hours.
6. preparation method according to claim 5, it is characterised in that, the hydroapatite particles of described 20��100 ��m is obtained by sintering crushing method.
7. preparation method according to claim 5 or 6, it is characterised in that, the particle diameter of described hydroapatite particles is 40��80 ��m.
8. preparation method according to any one of claim 5 to 7, it is characterised in that, spraying parameter is: the flow of arc plasma gas Ar is 40slpm, arc plasma gas H2Flow be 8slpm, the flow of powder carrier gas Ar is 2.0slpm, and spray distance is 100mm, and powder feeding rate is 22rpm, and spraying current is 550A.
9. preparation method according to any one of claim 5 to 8, it is characterised in that, described phosphate solution is (NH4)3PO4Solution, (NH4)2HPO4Solution, Na3PO4Solution, NaH2PO4Solution.
10. preparation method according to any one of claim 5 to 9, it is characterised in that, the condition of hydrothermal treatment consists is: hydrothermal temperature is 150��200 DEG C, and hydro-thermal medium is the Na of 0.1��1.0mol/L3PO4Solution, the hydro-thermal time is 12��36 hours.
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