ASTM F602-2009(2014) Standard Criteria for Implantable Thermoset Epoxy Plastics《可植入的热固性环氧塑料的标准规范》.pdf

1、Designation: F602 09 (Reapproved 2014)Standard Criteria forImplantable Thermoset Epoxy Plastics1This standard is issued under the fixed designation F602; the number immediately following the designation indicates the year of originaladoption or, in the case of revision, the year of last revision. A

2、number in parentheses indicates the year of last reapproval. A superscriptepsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 These criteria cover thermoset plastics based on digly-cidyl ethers of bisphenol A (DGEBPA) and appropriate curingagents or catalysts a

3、s opposed to thermoplastics based onepoxy structures.1.2 These criteria are generic and are intended to providedefinitions and a standard description of epoxy plastics used inimplantable devices. It is also intended to serve as a standardguide for the preparation of more specific documents withvalue

4、s and limits covering specific end uses.1.3 Compliance with these criteria shall not be construed asan endorsement of implantability. The biocompatibility ofepoxy plastics as a class has not been established. Epoxyplastic is a generic term relating to the class of polymersformed from epoxy resins, c

5、ertain curing agents or catalysts,and various additives. Since many compositions and formula-tions fall under this class, it is essential that the formulator orfabricator ensure biocompatibility of the specific compositionor formulation in its intended end use. Since these criteriaprovide guidance f

6、or the preparation of more specific docu-ments covering specific end uses, these documents will providebases for standardized evaluation of biocompatibility appropri-ate for a specific end use.1.4 Each of the properties listed shall be considered inselecting materials for specific end uses. A list o

7、f selectedproperties with limiting values assigned is suggested forseparate product specifications.1.5 All of the properties and test methods listed may not bepertinent in any specific situation, nor may all of the testsoutlined be required.1.6 These criteria are limited to functionally or fully cur

8、edepoxy plastics. Uncured or incompletely cured formulationsare specifically excluded.1.7 The epoxy plastics covered by this standard are those tobe evaluated for use in implantable biomedical devices. Theterm implantable is herein considered to include devices usedin vivo for time periods in excess

9、 of 30 days.1.8 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2.

10、Referenced Documents2.1 ASTM Standards:2D149 Test Method for Dielectric Breakdown Voltage andDielectric Strength of Solid Electrical Insulating Materialsat Commercial Power FrequenciesD150 Test Methods for AC Loss Characteristics and Permit-tivity (Dielectric Constant) of Solid Electrical Insulation

11、D257 Test Methods for DC Resistance or Conductance ofInsulating MaterialsD570 Test Method for Water Absorption of PlasticsD621 Test Methods for Deformation of Plastics Under Load(Withdrawn 1994)3D638 Test Method for Tensile Properties of PlasticsD785 Test Method for Rockwell Hardness of Plastics and

12、Electrical Insulating MaterialsD792 Test Methods for Density and Specific Gravity (Rela-tive Density) of Plastics by DisplacementD952 Test Method for Bond or Cohesive Strength of SheetPlastics and Electrical Insulating MaterialsD1042 Test Method for Linear Dimensional Changes ofPlastics Caused by Ex

13、posure to Heat and MoistureD1434 Test Method for Determining Gas Permeability Char-acteristics of Plastic Film and SheetingD1763 Specification for Epoxy ResinsD2393 Test Method for Viscosity of Epoxy Resins andRelated Components (Withdrawn 1992)3D2471 Practice for Gel Time and Peak Exothermic Temper

14、a-ture of Reacting Thermosetting Resins (Withdrawn 2008)3D2562 Practice for Classifying Visual Defects in Parts1These criteria are under the jurisdiction of ASTM Committee F04 on Medicaland Surgical Materials and Devicesand are the direct responsibility of Subcommit-tee F04.11 on Polymeric Materials

15、.Current edition approved Nov. 1, 2014. Published November 2014. Originallyapproved in 1978. Last previous edition approved in 2009 as F602 09 . DOI:10.1520/F0602-09R14.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annua

16、l Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3The last approved version of this historical standard is referenced onwww.astm.org.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United S

17、tates1Molded from Reinforced Thermosetting PlasticsD2734 Test Methods for Void Content of Reinforced PlasticsD3137 Test Method for Rubber PropertyHydrolytic Sta-bility (Withdrawn 0)3E96/E96M Test Methods for Water Vapor Transmission ofMaterialsF74 Practice for Determining Hydrolytic Stability of Pla

18、sticEncapsulants for Electronic Devices (Withdrawn 1994)3F619 Practice for Extraction of Medical PlasticsF748 Practice for Selecting Generic Biological Test Methodsfor Materials and Devices2.2 AAM1 Standard:EOS-D 10/75 Standard for Ethylene Oxide Sterilization42.3 ISO Standard:ISO 10993 Biological E

19、valuation of Medical Devices53. Terminology3.1 Definitions:3.1.1 acceleratoran additive used to increase the rate ofcure. An accelerator may also be a catalyst, or it may actuallychange composition and, therefore, not qualify as a catalyst.3.1.2 additivea chemical added to epoxy resins or hard-eners

20、 to modify the handling characteristics or curedproperties, or both, of the epoxy-hardener combination.3.1.2.1 diluenta chemical used in admixture to modify orenhance the properties of either or both the uncured or curedformulations. A primary use is to reduce the viscosity of themixed system althou

21、gh other properties such as exotherm rate,stiffness, moisture absorption, and so forth, may be modified orenhanced also.3.1.2.1.1 nonreactive diluenta diluent not containingchemically reactive functional groups.3.1.2.1.2 reactive diluenta diluent that reacts chemicallywith the epoxy resin or hardene

22、r, or both, during cure.3.1.2.2 fillera relatively inert solid particulate materialadded to an epoxy formulation to modify its strength,permanence, working properties, or other qualities, or to lowercosts.3.1.3 curing agent or hardenera compound normally usedin a predetermined concentration to react

23、 chemically (copoly-merize) by means of several different mechanisms (forexample, condensation or addition polymerization) with orwithout heat or pressure in order to change its form from aliquid or fusible, friable, soluble solid to an infusible, insolublesolid having useful and desirable applicati

24、on or end-useproperties.3.1.3.1 initiatoran additive used to cause a thermosettingresin to react with itself (polymerize). Usually, theseadditivesused in relatively very small amountsinitiatehomo-polymerization of the epoxy resin resulting in etherlinkages.NOTE 1The term “catalyst” is frequently mis

25、used to denote anymaterial added to a resin to cause a reaction to occur. This usage shouldbe discouraged. The Society of Plastics Industries defines a catalyst as “acompound which alters the speed of a reaction without changing itsoriginal composition.”3.1.4 epoxyoxirane ring structures.ORCHCH23.1.

26、4.1 epoxy plasticthermoplastic or thermosetting plas-tics containing ether or hydroxyalkyl repeating units or both,resulting from the ring-opening reactions of lower molecularweight polyfunctional oxirane resins or compounds, withcatalysts or with various polyfunctional acidic or basic core-actants.

27、3.1.4.2 epoxy resingenerally, any resin (liquid or solid)with a chemical structure at least difunctional in oxirane.Specifically for this standard, the diglycidyl ethers of bisphenolA or the equivalent. These compounds are defined as Grade 1in Specification D1763.3.1.5 Terms Relating to Cure: 3.1.5.

28、1 cure, vto change the properties of a polymericsystem into a final, more stable, usable condition by the use ofheat, radiation, or reaction with chemical additives.3.1.5.2 cure cyclethe schedule of time periods at specifiedconditions to which a reacting thermosetting material is sub-jected to reach

29、 a specified property level.3.1.5.3 cure timethe interval of time from the start ofreaction to the time at which specified properties of the reactingthermosetting composition are reached. For materials that reactunder the conditions of mixing, the start of reaction is the timeof initial exposure to

30、the conditions necessary for reaction tooccur.3.1.5.4 functionally curedthe term used to denote anepoxy plastic that has attained sufficient cure to achieve stableproperties.3.1.5.5 fully curedthe term used to denote total disappear-ance of epoxy groups as detected by infrared spectroscopy, orother

31、equally sensitive physicochemical methods.3.1.5.6 one-component systema formulation based on anepoxy resin preblended with a heat, moisture, or otherwiseactivated curing agent or catalyst. The mixture is storable butcures under the appropriate activation conditions.3.1.5.7 postcurethe additional and

32、 separate curing opera-tions to which a “hardened” thermosetting plastic compositionis subjected in order to enhance one or more properties. Alsoused to ensure stabilization of physical properties under useconditions.3.1.5.8 two-component systema formulation based on anepoxy resin to which a curing

33、agent or catalyst is added justprior to use.4. Chemical Composition4.1 Epoxy ResinsOxirane-terminated reaction products ofepichlorohydrin and bisphenol A (DGEBPA) or the equivalent.4.2 Reactive DiluentsThe following are examples of com-pounds that may be included as reactive diluents:4.2.1 Butyl gly

34、cidyl ether (BGE).4Available from the Association for the Advancement of MedicalInstrumentation, 1901 N. Ft. Myer Dr., Suite 602, Arlington, VA 22209.5Available from American National Standards Institute (ANSI), 25 W. 43rd St.,4th Floor, New York, NY 10036, http:/www.ansi.org.F602 09 (2014)24.2.2 Ph

35、enyl glycidyl ether (PGE).4.3 Nonreactive DiluentsThe following are examples ofcompounds that may be included as nonreactive diluents:4.3.1 Phthalate esters.4.3.2 Nonyl phenols.4.3.3 Miscible polymers.4.3.4 Flexibilizers.4.4 FillersThe following are examples of fillers that maybe incorporated in the

36、 formulations:4.4.1 Silicas:4.4.1.1 Fumed silica.4.4.1.2 Precipitated hydrated silica.4.4.1.3 Diatomaceous earth.4.4.2 Carbons.4.4.3 Certain radiopaque materials:4.4.3.1 Certain inorganic nonmetallic particles.4.4.3.2 Certain metallic particles.4.4.4 Certain pigments.4.4.5 Glass fibers.4.4.6 Glass c

37、eramic particles.4.4.7 Glass or plastic microballoons.4.5 Other AdditivesThe following are examples of addi-tives that may be used in the formulation:4.5.1 Slip agents.4.5.2 Optical brighteners.4.5.3 Surfactants.4.6 Curing AgentsThe following are examples of curingagents for epoxy resins:4.6.1 Amine

38、s (primary, secondary, and tertiary) such astriethylenetetramine (TETA).4.6.2 Anhydrides, such as phthalic anhydride.4.6.3 Acids such as phthalic acid.4.6.4 Amine-terminated polyamides.4.6.5 Acid or amine-terminated telomers.4.6.6 Schiffs bases.4.7 Catalysts:4.7.1 Lewis bases such as tertiary amines

39、.4.7.2 Lewis acids such as BF3.4.8 Accelerators:4.8.1 Tertiary amines.4.8.2 Phenols.NOTE 2Since some curing agents and catalysts may be toxic bythemselves, it may be necessary in specific end-use standards to requiretests to limit their presence in the final product.5. Physical Requirements5.1 Uncur

40、ed PropertiesThe following test methods maybe conducted on the uncured mixed formulation or appropriatecomponents:5.1.1 Peak Exotherm TemperatureTest Method D2471.5.1.2 Gel TimeTest Method D2471.5.1.3 Mix RatioThe mix ratio shall be calculated andmaintained at the ratio recommended by the manufactur

41、er ofthe formulation.5.1.4 ViscosityTest Method D2393.5.2 Cured Properties (Required)The following test meth-ods shall be conducted on the fully cured and properlyconditioned material.5.2.1 ExtractionPractice F619.5.2.2 Foreign ParticlesUpon careful visual examination,the epoxy plastic shall be free

42、 of any extraneous debris thatmay adversely affect its safety, efficacy, or reliability.5.2.3 Hydrolytic StabilityPractice F74 or Test MethodD3137.5.2.4 Biocompatibility TestingBiocompatibility of poly-mers and implant devices made using these materials shall bedetermined in accordance with Practice

43、 F748 or the ISO 10993series, unless otherwise agreed upon between the supplier andthe consumer and regulating bodies. These standards recom-mend specific biocompatibility testing, depending on the in-tended use of the device.5.2.4.1 Biocompatibility testing should be performed onspecimens that have

44、 been processed and sterilized using themethods intended for the final device.5.2.5 Sterilant Residues and Sterilization EffectsTestingregarding applicable methods of sterilization should be docu-mented. In addition to degassing time necessary for EtOsterilization, the stability of the epoxy under s

45、team andradiation sterilization should be specified if these types ofsterilization are called for.5.2.5.1 Sterilant residues shall be tested according to appro-priate methods, such as AAMI EOS-D. The concentration ofethylene oxide, ethylene chlorohydrin, ethylene glycol, anddichlorodifluoromethane (

46、or the equivalents) at the time ofimplantation shall be shown to be within safe limits prescribedby the device manufacturer. Cell culture tests can be used toshow the absence of sterilant residues. When materials aresterilized by radiation, materials subjected to maximum radia-tion dose shall be qua

47、lified by performance tests.5.2.6 Water AbsorptionTest Method D570.5.3 Cured Properties (Optional)The following test meth-ods shall be conducted on the fully cured and properlyconditioned material as is appropriate for the end use:5.3.1 AdhesionTest Method D952.5.3.2 Bacteriostasis and FungistasisSt

48、erility Tests.65.3.3 Compression SetTest Methods D621.5.3.4 Dielectric ConstantTest Methods D150.5.3.5 Dielectric StrengthTest Method D149.5.3.6 Dissipation FactorTest Methods D150.5.3.7 ElongationTest Method D638.5.3.8 Flexural StrengthTest Method D1434.5.3.9 Gas PermeationTest Method D1434.5.3.10

49、HardnessTest Method D785.5.3.11 Moisture Vapor TransmissionTest Methods E96/E96M.5.3.12 Prothrombin TimeThe effect of the material on theProthrombin time shall be tested by appropriate methods.75.3.13 Specific GravityTest Methods D792.6United States Pharmacopeia, available from U.S. Pharmacopeia (USP), 12601Twinbrook Pkwy., Rockville, MD 20852-1790, http:/www.usp.org.7Human Blood Coagulation, Haemostasis, and Thrombosis, Rosemary Biggs,ed., Blackwell Scientific Publications, 1972.F602 09 (2014)35.3.14 Stability (dimensi