1、Designation: F 1609 03e1Standard Specification forCalcium Phosphate Coatings for Implantable Materials1This standard is issued under the fixed designation F 1609; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last rev
2、ision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.e1NOTEMercury warning was editorially added in April 2008.1. Scope1.1 This specification covers the material requirements forcalcium phos
3、phate coatings for surgical implant applications.1.2 In particulate and monolithic form, the calcium phos-phate materials system has been well-characterized regardingbiological response (1,2)2and laboratory characterization (2-4). Several publications (5-10) have documented the in vitroand in vivo p
4、roperties of selected calcium phosphate coatingsystems.1.3 This specification includes hydroxylapatite coatings,tricalcium phosphate coatings, or combinations thereof, with orwithout intentional minor additions of other ceramic or metal-lic,3and applied by methods including, but not limited to, thef
5、ollowing: (1) mechanical capture, (2) plasma spray deposition,(3) dipping/sintering, (4) electrophoretic deposition, (5) porce-lainizing, and (6) sputtering.1.4 Substrates may include smooth, porous, textured, andother implantable topographical forms.1.5 This specification excludes organic coatings
6、that maycontain calcium and phosphate ionic species.1.6 WarningMercury has been designated by EPA andmany state agencies as a hazardous material that can causecentral nervous system, kidney, and liver damage. Mercury, orits vapor, may be hazardous to health and corrosive tomaterials. Caution should
7、be taken when handling mercury andmercury-containing products. See the applicable product Ma-terial Safety Data Sheet (MSDS) for details and EPAs website(http:/www.epa.gov/mercury/faq.htm) for additional informa-tion. Users should be aware that selling mercury or mercury-containing products, or both
8、, in your state may be prohibited bystate law.2. Referenced Documents2.1 ASTM Standards:4E 376 Practice for Measuring Coating Thickness byMagnetic-Field or Eddy-Current (Electromagnetic) TestMethodsF 1044 Test Method for Shear Testing of Calcium Phos-phate Coatings and Metallic CoatingsF 1088 Specif
9、ication for Beta-Tricalcium Phosphate forSurgical ImplantationF 1147 Test Method for Tension Testing of Calcium Phos-phate Coatings and Metallic CoatingsF 1160 Test Method for Shear and Bending Fatigue Testingof Calcium Phosphate and Metallis Medical and CompositeCalcium Phosphate Metallic CoatingsF
10、 1185 Specification for Composition of Ceramic Hydroxy-lapatite for Surgical ImplantsF 1854 Shear and Bending Fatigue Testing of CalciumPhosphate and Metallis Medical and Composite CalciumPhosphate Metallic CoatingsF 1926 Test Method for Evaluation of the EnvironmentalStability of Calcium Phosphate
11、CoatingsF 2024 Practice for X-Ray Diffraction Determination ofPhase Content of Plasma-Sprayed Hydroxylapatite Coat-ings2.2 Pharmacopeia Convention Documents:5National Formulary XVI, Tribasic Calcium PhosphateUnited States Pharmacopeia:U.S. Pharmacopeia XXI, Chemical Tests CaP (191), Lead, Mercury ,
12、Arsenic , and HeavyMetals Method (1)2.3 Other Documents:U.S. Geological Survey Method, Cadmium6U.S. Code of Federal Regulations Title 21 (CFR 21), Part1This specification is under the jurisdiction of ASTM Committee F04 onMedical and Surgical Materials and Devices and is the direct responsibility ofS
13、ubcommittee F04.13 on Ceramic Materials.Current edition approved Sept. 10, 2003. Published October 2003. Originallyapproved in 1995. Last previous edition approved in 1995 as F 1609 95.2The boldface numbers in parentheses refer to the list of references at the end ofthis specification.3The Joint Com
14、mittee on Powdered Diffraction has established a PowderDiffraction File. The committee operates on an international basis and cooperatesclosely with the Data Commission of the International Union of Crystallinity andASTM. Hydroxylapatite data can be found on file card No. 9-432; beta tricalciumphosp
15、hate data can be found on file card No. 9-169.4For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.5Available from
16、 U.S. Pharmacopeia Convention, Inc., 12601 Twinbrook Park-way, Rockville, MD 20852.6Crock, J. G., Felichte, F. E., and Briggs, P. H., “Determination of Elements inNational Bureau of Standards Geological Reference Materials SRM 278 Obsidianand SRM 688 Basalt by Inductively Coupled Argon PlasmaAtomic
17、EmissionSpectrometry,” Geostandards Newsletter, Vol 7, 1983, pp. 335340.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.820Quality System Regulation7X-Ray Diffraction Analyses33. Terminology3.1 Definitions:3.1.1 amorphous calcium pho
18、sphatea non-crystalline cal-cium phosphate.3.1.2 beta tricalcium phosphatea calcium phosphate sub-stance of empirical chemical formula, Ca3(PO4)2(see Specifi-cation F 1088).3.1.3 calcium phosphateany one of a number of inorganicchemical compounds containing calcium and phosphate ions asits principal
19、 constituents.3.1.4 coatinga layer of mechanically or chemically at-tached material covering a substrate material.3.1.5 hydroxylapatitea calcium phosphate crystallinecompound of empirical chemical formula, Ca5(PO4)3OH (seeSpecification F 1185).4. Chemical or Crystallographic Requirements, or Both4.1
20、 Chemical:4.1.1 Elemental analysis for calcium and phosphorous andintentional additions (other than trace elements) will be con-sistent with the expected stoichiometry of the specific calciumphosphate compound(s).4.1.2 Trace Element Analysis for Hydroxylapatite and BetaTricalcium PhosphateThe concen
21、tration of trace elements inthe coating shall be limited as follows:Element ppm, maxAs 3Cd 5Hg 5Pb 30total heavy metals (as lead) 50For reference purposes, the U.S. Pharmacopeia XXI and U.S.Geological Survey Method, Cadmium, shall be used.4.1.3 The analysis of other trace elements may be required,ba
22、sed on the conditions, apparatus, or environments specific tothe coating application technique used.4.1.4 The analysis of intentional additional elements orcompounds such as fluorine, manganese, magnesium, carbon-ate, and so forth must be specified for calcium phosphatecoatings.4.1.5 Calcium to Phos
23、phorus ratio (Ca/P) shall be per-formed on both the powder and coating forms using a suitablemethod.4.2 Crystallographic Characterization:4.2.1 Crystallographic characterization shall be in accor-dance with Practice F 2024.4.2.2 Testing shall include quantitative phase analysis andamorphous calcium
24、phosphate content.4.2.3 FTIR (Fourier Transform Infrared Spectroscopy) shallbe performed to identify functional groups.4.3 Environmental StabilityEnvironmental stability test-ing shall be performed in accordance with Test Method F 1926to access the relative dissolution behavior of the material.5. Ph
25、ysical Characterization5.1 Coverage of Substrate:5.1.1 Microscopic examination of the surface will be madeat 103 magnification; “bare” areas, “pinholes,” cracking,foreign debris, unmelts, chips, delamination and the appear-ance at the coating/substrate interface, and so forth will bereported.5.2 Thi
26、cknessThe thickness will be measured from crosssections in accordance with Test Method F 1854. If distinctlayers exist, they should be reported.5.2.1 Alternatively, a magnetic field or eddy current tech-nique may be used if it has been shown to be equivalent to TestMethod F 1854.5.3 PorosityThe micr
27、oporosity and macroporosity char-acterization shall be determined in accordance with TestMethod F 1854.5.4 ColorA macroscopic examination of color should beperformed to guarantee a uniform and consistent appearance,in consideration of the specific process, substrate material andgeometry, and coating
28、 thickness.5.5 Surface TopographyThe surface topography shall bemeasured using equipment designed to determine surfaceroughness. Characterization of the surface topography of theunderlying substrate may be required, if applicable, for thespecific coating method. Scanning electron microscopy shallbe
29、used to provide a visual representation of the coating surfacecharacteristics.5.6 DensityDensity of both the powder and coated formsshall be performed using a suitable method.6. Mechanical Characterization6.1 The following mechanical characterizations may beapplicable to a coating, depending on the
30、substrate material orgeometry, coating thickness or location, or coating method(s).Characterization reports shall contain sufficient informationregarding the test techniques, procedures, and standards usedand details such as specimen orientation and proportional depthof thickness in order to represe
31、nt the analysis accurately.6.1.1 The tensile bond strength of the coating to the sub-strate shall be determined using Test Method F 1147.6.1.2 The shear strength shall be determined using TestMethod F 1044.6.1.3 The fatigue strength shall be determined using TestMethod F 1160. Both the coating/subst
32、rate interface, and theeffect on the substrate should be evaluated. The effect of thecoating on the resulting fatigue strength of an actual deviceshould also be considered.7. Test Specimen Fabrication7.1 All test specimens for coating characterizations shall beprepared from coating lots and samples
33、from the same produc-tion feedstock lots and prepared on the same equipment used toapply the coating to actual devices.7.2 For device characterization, all test specimens should besubjected to the same processing and sterilization as thefinished device, if applicable.7Available from Standardization
34、Documents Order Desk, Bldg. 4 Section D, 700Robbins Ave., Philadelphia, PA 19111-5098, Attn: NPODS.F160903e128. Contact with Calcium Phosphate Coatings8.1 In general, extra precautions should be taken whenhandling calcium phosphate coatings.8.1.1 Contact with the coatings should be limited to soft,b
35、iocompatible polymers.8.1.2 The only liquids to come in contact with the coatingshall be distilled water, acetone, and isopropyl alcohol.8.1.2.1 pH is critical, and should measure 7.0 or higher inany liquid that comes in contact with the coating.8.1.3 Powder-free latex gloves shall be the only glove
36、material for handling coatings.9. Quality Program Requirements9.1 The manufacture of calcium phosphate coatings willconform to the applicable FDA and ISO quality standards.10. Keywords10.1 bone implant; calcium phosphate; coating; dental im-plant materials; hydroxylapatite; mechanical tests; orthope
37、dicmedical devices; physical characterizations; tricalciumphosphateAPPENDIX(Nonmandatory Information)X1. RATIONALEX1.1 Ceramic hydroxylapatite and beta-tricalcium phos-phate are commercially available in many forms as syntheticbone grafting materials. Specifications F 1088 and F 1185 havebeen establ
38、ished for these substances as particulates. For mostimplant materials, the biological performance is criticallydependent on the materials properties, including chemical andmechanical properties and physical form. These propertiesmust be well-characterized and consistent in order to achievereproducib
39、le clinical results and reliable biocompatibility. Thisspecification shall cover biocompatible grades of calciumphosphate coatings only.X1.2 Powder X-ray diffraction analysis provides differen-tiation between crystalline forms of these various calciumphosphate crystalline species, one or more of whi
40、ch will be amajor phase in coatings covered by this specification, whileothers may occur as second or minor phases. It is anticipatedthat a separate performance standard may be necessary for eachseparate coating as designated by the major crystalline phase.The physical and mechanical property assess
41、ments are notspecific to any one type of coating for this reason, but ratherthey are listed generically as guidelines for analysis. Minor orsignificant modifications to these procedures may have to bemade to result in useful characterization data for the mainte-nance of individual coating consistenc
42、y. The sources of generaltest methods for these coatings are listed in Section 2.REFERENCES(1) Jarcho, M., Kay, J. F., Gumaer, K. I., Doremus, R. H., and Drobeck,H. P., “Tissue, Cellular and Subcellular Events at a Bone-CeramicHydroxylapatite Interface,” Journal of Bioengineering, Vol 1, 1977,pp. 79
43、92.(2) Jarcho, M., “Calcium Phosphate Ceramics as Hard Tissue Prosthet-ics,” Clin Orthop, Vol 157, 1981, pp. 259.(3) de Groot, K., “Ceramics of Calcium Phosphates: Preparation andProperties,” Bioceramics of Calcium Phosphate, K. de Groot, ed.,CRC Press, Inc., Boca Raton, FL, 1982.(4) Jarcho, M., Bol
44、en, C. H., Thomas, M. B., Bobick, J., Kay, J. F., andDoremus, R. H., “Hydroxylapatite Synthesis and Characterization inDense Polycrystalline Form,” Journal of Materials Science, Vol 11,1976, pp. 20272035.(5) “Bioceramics: Material Characteristics Versus In-Vivo Behavior,” P.Ducheyne and J. Lemons, e
45、ds., N.Y. Academy of Science, Vol 523,1988.(6) Cook, S. D., Kay, J. F., Thomas, K. A., and Jarcho, M., “InterfaceMechanics and Histology of Titanium and Hydroxylapatite-CoatedTitanium for Dental Implant Applications,” International Journal ofOral Maxillofac Implants, Vol 2, 1987, pp. 1522.(7) Cook,
46、S. D., Kay, J. F., Thomas, K. A., and Jarcho, M.,“Hydroxylapatite-Coated Porous Titanium for Use as an OrthopaedicBiological Attachment System,” Clin Orthop, Vol 230, 1988, pp.303312.(8) Kay, J. F., Golec, T. S., and Riley, R. L., “Hydroxylapatite-CoatedSubperiosteal Dental Implants: Design Rational
47、e and Clinical Experi-ence,” Journal of Prosthet Dent, Vol 58, 1987, pp. 339343.(9) Block, M. S., Kent, J. N., and Kay, J. F., “The Evaluation ofHydroxylapatite-Coated Dental Implants in Dogs,” Journal of OralMaxillofac Surg, Vol 45, 1987, pp. 601607.(10) Thomas, K. A., Kay, J. F., and Cook, S. D.,
48、“The Effect of SurfaceMacrostructure and Hydroxylapatite Coating on the MechanicalStrengths and Histologic Profiles of Titanium Implant Materials,”Journal of Biomed Mater Res, Vol 21, 1987, pp. 13951414.(11) Cullity, B. D., Elements of X-Ray Diffraction, Addison Wesley,Reading, MA, 1967.(12) Handboo
49、k of Bioactive Ceramics, II: Calcium Phosphate andHydroxylapatite Ceramics, Yamamuro, Hench, Wilson, eds., CRCPress, Boca Raton, FL, 1990.(13) Balmain, N., Legros, R., and Bonel, G., “X-Ray Diffraction ofCalcified Bone Tissue: A Reliable Method for the Determination ofBone Ca/P Molar Ratio,” Calc Tiss Res, Vol 34, 1982, pp. 9398.(14) Toth, J., Hirthe, W., Hubbard, W., Brantley, W., and Lynch, K.,“Determination of the Ratio of HA/TCP Mixtures by X-Ray Diffrac-tion,” Journal of Applied Biomaterials, Vol 2, 1991, pp. 3740.(15) Sendax, V., “Hydroxylapatite Coa
