~ Designation: F2004- 05 (Reapproved 2010)
`~u11 7
`
`INTERNATIONAL
`
`Standard Test Method for
`Transformation Temperature of Nickel-Titanium Alloys by
`Thermal Analysis 1
`
`Thi s standard is issued under the fixed designation F2004; the number immediately following the designation indicates the year of
`original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
`superscript epsilon (E) indicates an editorial change since the last revision or reapproval.
`
`1. Scope
`J. J This test method defines procedures for determining the
`transformation temperatures of nickel-titanium shape memory
`alloys.
`
`1.2 The values stated in SI units are to be regarded as
`standard. No other units of measurement are included in this
`standard.
`1.3 This standard does not purport to address all of the
`safety concems, if any, associated with its use. It is the
`responsibility of the user of this standard to establish appro(cid:173)
`priate safety and health practices and to determine the
`applicability of regulatoty limitations prior to use.
`
`2. Referenced Documents
`2.1 ASTM Standards: 2
`E473 Terminology Relating to Thermal Analysis and Rhe(cid:173)
`ology
`E967 Test Method for Temperature Calibration of Differen(cid:173)
`tial Scanning Calorimeters and Differential Thermal Ana(cid:173)
`lyzers
`E 1142 Terminology Relating to Thermophysical Properties
`F2005 Terminology for Nickel-Titanium Shape Memory
`Alloys
`
`3. Terminology
`3.1 Specific technical terms used in this test method are
`found in Terminologies E473 , E1142, and F2005.
`
`4. Summary of Test Method
`4.1 This test method involves heating and cooling a test
`specimen at a controlled rate in a controlled environment
`through the temperature interval of the phase transformation.
`
`1 T his test method is under the jurisdiction of ASTM Committee F04 on Medical
`and Surgical Materials and Devices and is the direct responsibility of Subcommiuee
`F04.15 on Material Test Methods.
`Current edition approved June I , 2010. Published September 2010. Originally
`approved in 2000. Last previous edition approved in 2005 as F2004- 05. DOl:
`I 0.1520/F2004-05R I 0.
`2 For referenced ASTM standards, visit the ASTM website, www.astrn.org, or
`contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
`Standards volume infonnation, refer Lo the standard's Document Summary page on
`the ASTM website.
`
`The difference in heat flow between the test material and a
`reference material due to energy changes is continuously
`monitored and recorded. Absorption of energy due to a phase
`transformation in the specin1en results in an endothermic peak
`on heating. Release of energy due to a phase transformation in
`the specimen results in an exothermic peak on cooling.
`
`5. Significance and Use
`5.1 Differential scanning calorimetry provides a rapid
`method for determining the transformation temperature(s) of
`nickel-titanium shape memory alloys.
`
`5.2 This test method uses small, stress-free, annealed
`samples to determine whether a sample of nickel-titanium alloy
`containing nominally 54.5 to 56.5 % nickel by weight is
`austenitic or martensitic at a particular temperature. Since
`chemical analysis of these alloys does not have sufficient
`precision to determine the transformation temperature by
`measuring the nickel to titanium ratio of the alloy, direct
`measurement of the transformation temperature of an annealed
`sample of known thermal history is recommended.
`5.3 This test method is useful for quality control, specifica(cid:173)
`tion acceptance, and research.
`5.4 Transformation temperatures derived from differential
`scanning calorimetry (DSC) may not agree with those obtained
`by other test methods due to the effects of strain and load on the
`transformation.
`
`6. Interferences
`6.1 Make sure the material to be tested is homogeneous
`since milligram sample quantities are used.
`
`6.2 Take care in preparing the sample. Cutting and grinding
`can cause cold work, which affects the transformation tempera(cid:173)
`ture. Oxidation during heat treatment can change the thermal
`conductance of the sample.
`
`6.3 Set the gas flow to provide adequate themml conductiv(cid:173)
`ity in the test celL
`
`7. Apparatus
`7.1 Use a differential scanning calorimeter capable of heat(cid:173)
`ing and cooling at rates up to 10°C/min and of automatically
`
`Copyright C ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428·2959. United States
`Copyright by ASTM Int'l (all rights reserved); Wed Aug 13 19:36:06 EDT 2014 I
`D ownloaded/printed by
`Bernard Cowger, Jr (Rothwell, Figg, Ernst Manbeck, P.C.) pursuant to License Agreement. No further reproductions authorized.
`
`GOLD STANDARD EXHIBIT 2018
`US ENDODONTICS v. GOLD STANDARD
`CASE PGR2015-00019
`
`

`
`F2004 − 05 (2010)
`
`recording the differential energy input between the specimen
`and the reference to the required sensitivity and precision.
`7.2 Use sample capsules or pans composed of aluminum or
`other inert material of high thermal conductivity.
`7.3 Use helium gas purge supply. See 10.3.1.
`7.4 Use an analytical balance with a capacity of 100 mg
`capable of weighing to the nearest 0.1 mg.
`
`8. Sampling
`8.1 Use a sample size of 25 to 45 mg. Cut the sample to
`maximize surface contact with the (DSC) sample pan.
`8.2 Anneal the sample at 800 to 850°C for 15 to 60 min in
`vacuum or inert atmosphere, or in air with adequate protection
`from oxidation. Rapidly cool the sample to prevent precipita-
`tion of phases which may change transformation temperature
`of the alloy.
`8.3 Clean the sample of all foreign materials such as cutting
`fluid. If the sample is oxidized in heat treatment, grind, polish,
`or etch the sample to remove the oxide. Take care to avoid cold
`working the sample as this will change its thermal response.
`Slight oxidation is permissible but remove all heavy oxide
`scale.
`
`9. Calibration
`9.1 Calibrate the temperature axis of the instrument using
`the same heating rate, purge gas, and flow rate as those used for
`analyzing the specimen in accordance with Practice E967.
`
`10. Procedure
`10.1 Place the sample on the sample pan and place the pan
`on the test pedestal.
`10.2 Place an empty pan on the reference pedestal.
`10.3 Turn on the purge gas at a flow rate of 10 to 50
`mL/min.
`10.3.1 Use helium as the purge gas for the sample chamber.
`10.3.2 Use a dry air, helium, or nitrogen cover gas. The dry
`gas shall have a dew point below the lowest temperature of the
`cooling cycle.
`
`10.4 Run the cooling and heating program.
`10.4.1 Use the heating and cooling rates of 10 6 0.5°C/min.
`10.4.2 Heat the sample from room temperature to a tem-
`perature of at least Af + 30°C; hold at temperature for a time
`sufficient to equilibrate the sample with the furnace.
`10.4.3 Cool the sample to a temperature of below Mf –
`30°C; hold for a time sufficient to equilibrate the sample with
`the furnace. Then, heat the sample to a temperature of at least
`Af + 30°C.
`10.5 Data Acquisition—Record the resulting curve from the
`heating and cooling program from Af + 30°C to Mf – 30°C.
`
`11. Graphical Data Reduction
`11.1 Draw the baselines for the cooling and heating portions
`of the curve as shown in Fig. 1.
`11.2 Draw the tangents to the cooling and heating spikes
`through the inflection points as shown in Fig. 1. If a computer
`program is used to construct the tangents, care must be taken in
`locating the tangent points.
`11.3 Obtain Ms, Mf, As, and Af as the graphical intersection
`of the baseline with the extension of the line of maximum
`inclination of the appropriate peak of the curve as shown in
`Fig. 1. Ap is the peak minimum of the endothermic curve, and
`Mp is the peak maximum of the exothermic curve. Read Ap and
`Mp directly from the graph as shown in Fig. 1.
`
`12. Report
`12.1 Report the following information with the test results:
`12.1.1 Complete identification and description of the mate-
`rial tested including the specification and lot number.
`12.1.2 Description of the instrument used for the test.
`12.1.3 Statement of mass, dimensions, and geometry.
`12.1.4 Material for the specimen pan and temperature pro-
`gram.
`12.1.5 Description of the temperature calibration procedure.
`12.1.6 Identification of the specimen environment by gas,
`flow rate, purity and composition.
`12.1.7 Results of the transformation measurements using
`the nomenclature in accordance with Terminology F2005.
`Temperature results should be reported to the nearest 1°C.
`
`13. Precision and Bias
`13.1 An interlaboratory study was conducted in accordance
`with Practice E691 in seven laboratories with three different
`materials, with each laboratory obtaining five results for each
`material. There were two rounds of testing. In the first round,
`all the test samples were annealed in one laboratory; in the
`second round, the samples were annealed by the laboratory that
`conducted the test. The details are given in ASTM Research
`Report No. F04–1008.3
`13.2 The results of round one are summarized in Tables 1-6
`for each transformation temperature parameter (Mf, Mp, Ms,
`As, Ap, Af). The values are in degrees Celsius. The terms
`
`FIG. 1 DSC Curve for Nickel-Titanium (NiTi)
`
`3 Supporting data have been filed at ASTM International Headquarters and may
`be obtained by requesting Research Report RR:F04-1008.
`
`2
`
`
`
`Copyright by ASTM Int'l (all rights reserved); Wed Aug 13 19:36:06 EDT 2014
`Downloaded/printed by
`Bernard Cowger, Jr (Rothwell, Figg, Ernst Manbeck, P.C.) pursuant to License Agreement. No further reproductions authorized.
`
`

`
`F2004 − 05 (2010)
`
`Material Mf,
`grand
`mean
`-50.0
`-26.3
`48.5
`
`A
`B
`C
`
`TABLE 1 Precision of Mf
`Repeatability
`Reproducibility
`Repeatability
`Limit
`Standard
`Standard
`Deviation
`Deviation
`0.57
`3.97
`0.95
`2.62
`1.02
`1.54
`
`1.6
`2.7
`3.0
`
`Reproducibility
`Limit
`
`11.1
`7.3
`4.3
`
`Material Mp,
`grand
`mean
`-43.8
`-20.5
`58.1
`
`A
`B
`C
`
`TABLE 2 Precision of Mp
`Repeatability
`Reproducibility
`Repeatability
`Limit
`Standard
`Standard
`Deviation
`Deviation
`0.42
`2.65
`1.10
`2.21
`0.88
`1.05
`
`1.2
`3.1
`2.5
`
`Reproducibility
`Limit
`
`7.4
`6.2
`2.9
`
`Material Ms,
`grand
`mean
`-41.6
`-16.9
`64.8
`
`A
`B
`C
`
`TABLE 3 Precision of Ms
`Repeatability
`Reproducibility
`Repeatability
`Limit
`Standard
`Standard
`Deviation
`Deviation
`0.40
`2.35
`0.95
`1.24
`0.74
`1.15
`
`1.1
`2.7
`2.1
`
`Reproducibility
`Limit
`
`6.6
`3.5
`3.2
`
`Material
`
`A
`B
`C
`
`Material
`
`A
`B
`C
`
`Material
`
`A
`B
`C
`
`As,
`grand
`mean
`-25.3
`-4.8
`72.9
`
`Ap,
`grand
`mean
`-19.4
`5.7
`94.7
`
`Af,
`grand
`mean
`-23.4
`2.5
`91.6
`
`TABLE 4 Precision of As
`Repeatability
`Reproducibility
`Repeatability
`Standard
`Standard
`Limit
`Deviation
`Deviation
`0.30
`1.85
`0.32
`1.58
`0.65
`2.68
`
`0.8
`0.9
`1.8
`
`Reproducibility
`Limit
`
`5.2
`4.4
`7.5
`
`TABLE 5 Precision of Ap
`Repeatability
`Reproducibility
`Repeatability
`Standard
`Standard
`Limit
`Deviation
`Deviation
`0.16
`1.94
`0.57
`1.50
`0.85
`3.18
`
`0.5
`1.6
`2.4
`
`Reproducibility
`Limit
`
`5.4
`4.2
`8.9
`
`TABLE 6 Precision of Af
`Repeatability
`Reproducibility
`Repeatability
`Standard
`Standard
`Limit
`Deviation
`Deviation
`0.23
`2.01
`0.67
`1.39
`0.80
`2.25
`
`0.6
`1.9
`2.2
`
`Reproducibility
`Limit
`
`5.6
`3.9
`6.3
`
`repeatability limit and reproducibility limit are used as speci-
`fied in Practice E177.
`13.3 The results of round two are summarized in Tables
`7-12 for each transformation temperature parameter (Mf, Mp,
`
`TABLE 7 Precision of Mf, When Samples are Annealed by Testing
`Laboratory
`Reproducibility
`Standard
`Deviation
`8.49
`5.93
`1.84
`
`Repeatability
`Limit
`
`Reproducibility
`Limit
`
`5.7
`5.2
`3.4
`
`23.8
`16.6
`5.1
`
`Material Mf,
`grand
`mean
`-49.1
`-27.3
`48.5
`
`A
`B
`C
`
`Repeatability
`Standard
`Deviation
`2.03
`1.85
`1.23
`
`TABLE 8 Precision of Mp, When Samples are Annealed by
`Testing Laboratory
`Repeatability
`Reproducibility
`Repeatability
`Limit
`Standard
`Standard
`Deviation
`Deviation
`1.31
`8.69
`1.67
`7.31
`1.31
`1.47
`
`Reproducibility
`Limit
`
`3.7
`4.7
`3.7
`
`24.3
`20.5
`4.1
`
`Material Mp,
`grand
`mean
`-43.0
`-21.5
`58.1
`
`A
`B
`C
`
`TABLE 9 Precision of Ms, When Samples are Annealed by
`Testing Laboratory
`Repeatability
`Reproducibility
`Repeatability
`Limit
`Standard
`Standard
`Deviation
`Deviation
`2.84
`8.29
`2.38
`6.60
`1.39
`2.29
`
`Reproducibility
`Limit
`
`7.9
`6.7
`3.9
`
`23.2
`18.5
`6.4
`
`Material Ms,
`grand
`mean
`-40.7
`-18.9
`64.8
`
`A
`B
`C
`
`TABLE 10 Precision of As, When Samples are Annealed by
`Testing Laboratory
`Repeatability
`Reproducibility
`Repeatability
`Standard
`Standard
`Limit
`Deviation
`Deviation
`0.94
`5.26
`0.52
`1.93
`0.70
`2.80
`
`Reproducibility
`Limit
`
`2.6
`1.4
`2.0
`
`14.7
`5.4
`7.8
`
`Material
`
`A
`B
`C
`
`As,
`grand
`mean
`-23.2
`-4.1
`72.9
`
`TABLE 11 Precision of Ap, When Samples are Annealed by
`Testing Laboratory
`Repeatability
`Reproducibility
`Repeatability
`Standard
`Standard
`Limit
`Deviation
`Deviation
`0.56
`5.30
`0.65
`2.71
`1.01
`3.37
`
`Reproducibility
`Limit
`
`1.6
`1.8
`2.8
`
`14.8
`7.6
`9.4
`
`Material
`
`A
`B
`C
`
`Ap,
`grand
`mean
`-19.1
`2.2
`89.5
`
`TABLE 12 Precision of Af, When Samples are Annealed by
`Testing Laboratory
`Repeatability
`Reproducibility
`Repeatability
`Standard
`Standard
`Limit
`Deviation
`Deviation
`0.87
`4.95
`0.69
`4.07
`0.91
`2.61
`
`Reproducibility
`Limit
`
`2.4
`1.9
`2.5
`
`13.9
`11.4
`7.3
`
`Material
`
`A
`B
`C
`
`Af,
`grand
`mean
`-16.6
`6.6
`94.7
`
`Ms, As, Ap, Af). The values are in degrees Celsius. The terms
`repeatability limit and reproducibility limit are used as speci-
`fied in Practice E177.
`
`3
`
`
`
`Copyright by ASTM Int'l (all rights reserved); Wed Aug 13 19:36:06 EDT 2014
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`
`

`
`F2004 − 05 (2010)
`
`14. Keywords
`14.1 differential scanning calorimeter; DSC; nickel-titanium
`alloy; NiTi; Nitinol; shape memory alloy; TiNi; transformation
`temperature
`
`APPENDIX
`
`(Nonmandatory Information)
`
`X1. RATIONALE
`
`X1.1 This test method uses small, stress-free, annealed
`samples to determine whether a sample of nickel-titanium alloy
`containing nominally 54.5 to 56.5 % nickel by weight is
`austenitic or martensitic at a particular temperature. Since
`chemical analysis of these alloys does not have sufficient
`precision to determine the transformation temperature by
`measuring the nickel to titanium ratio of the alloy, direct
`measurement of the transformation temperature of an annealed
`sample of known thermal history is recommended.
`
`transformation temperature, possibly due to stress effects
`which retain residual martensite. One method of achieving the
`desired cooling rate is to heat treat the test specimens on a foil
`tray and then allow the samples and the foil tray to cool
`together, out of the furnace, in room temperature air.
`
`X1.3 Transformation temperatures derived from differential
`scanning calorimetry (DSC) may not agree with those obtained
`by other test methods due to the effects of strain and load on the
`transformation.
`
`X1.2 It is well known that slow cooling after annealing of
`nickel-rich alloys allows precipitates of the Ni4Ti3 type to
`form, thereby increasing the Ti content of the matrix and the
`transformation temperatures. The practice is to avoid slow
`cooling preserve the “as annealed” transformation.
`It
`is
`possible, however, to cool the samples too quickly, raising the
`
`X1.4 Differences in sample preparation techniques between
`laboratories influenced the reproducibility limit. Differences in
`calibration techniques may have also influenced reproducibil-
`ity. To minimize interlaboratory variations in results, common
`sample preparation and calibration practices must be estab-
`lished.
`
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`4
`
`
`
`Copyright by ASTM Int'l (all rights reserved); Wed Aug 13 19:36:06 EDT 2014
`Downloaded/printed by
`Bernard Cowger, Jr (Rothwell, Figg, Ernst Manbeck, P.C.) pursuant to License Agreement. No further reproductions authorized.