Saas pesca seas I 8-1 International Standard 3146 [Tran TOTOWA ZATION FOR ET DATDTATIONS MERIT AOU O° ARTONIIR RO CTA APTTUAIIISORGAIATION TERUATIONALEDEORNALSATION Plastics — Determination of melting behaviour (melting temperature or melting range) of semi-crystalline polymers Plostiques — Détermination du comportement & fa fusion (température do fusion ou plage de température de fusion) des polyméres semicrstallins Second edition — 1985-12-15 UDC 678.7 : 620.1: 536.421.1 Ref. No. 1SO 3146-1985 (E) Descriptors: plastics, polymers, tests, daerminaton, meking pols, test equipment Price based on 10 pages i $ oon fal ganization For Standadeation~BLUb-85 Foreword 180 (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International Standards is normaly carried out through ISO technical committees. Each member ‘body interested in a subject for which a technical committee has been established has the right to be represented on that committee. Intemational organizations, govern- ‘mental and non-governmental, In laizon with ISO, also tako part in tho work. Draft Intemational Standards adopted by the technical committees are circulated the member bodies for approval before their acceptance as International Standards by the ISO Council. They are approved in accordance with ISO procedures requiing at least 75 % approval by the member bodies voting. International Standard !S0 3148 was prepared by Technical Committee 1SO/TC 61, Plastics. ‘This socond edition cancels and replaces the first ection (ISO 3146-1974), of which it constitutes a minor revision, Users should nate that all International Standards undergo revision from time to time {and that any reference made herein to eny other International Standard implos its latest edition, unless otherwise stated. © International Organization for Standardization, 1965 © Prlotod in Switzarland rik by the Internal Organ For Standard Tus aur 30 020710 1998 Bovssiso3 ooueaes 9gt by graces eines oomaae of INTERNATIONAL STANDARD 180 3146-1985 (E) Plastics — Determination of melting behaviour (melting temperature or melting range) of semi-crystalline polymers 0. Introduction ‘The melting behaviour of a crystaline or partly crystaine polymor isa structure-sensktve property In polymers a sharp melting point, such as is observed for low molecular mass substances, usually does not occur; instesd melting temperature range is observed on heating, from the fist change of shape ofthe solid partcies to the teansfermation into a highly viscous or viscosiastic Kquld, with accompanying sisappearance of the crystalline phaso, I pracent. The melting range depends upon a number of parameters, such as molgcular mass, molecular mass. distribution, per cent erystalinty, andl thermodynamic properties. Ik may also depend on the provious thermal history of the ‘specimens. Tho lower oF upper limit of the melting range, or ts average value, is sometimes conventionally refered to as the “melting temperature”. 1 Scope and field of application This International Standard spocfies three methods for ‘evaluating the melting behaviour of semi-crystaline polymers. Section one spectias a capilary tubo method (method Al, ‘which is bated on the changes in shape of the polymer. This ‘method is applicable to all polymers and their compounds, even if there is no crystaline phase, Section two specifies a polarizing microscope method (method 8), which is based on changes in the optical proper- ties of the polymer. Irernaonal Organon For Stndardeatin ‘un 30 09:07:10 1298 ‘This method is applicable to polymers containing a bitefingent crystallin phase; it may not be suitable for plastics compounds | containing pigments and/or other additives which could interforo with the biretingence of tho polymaric erystaline thermal Seotion three specifies a method (method Cl, having two variants naval —_ method C1, which uses Difforential Thermal Analysis (oral; = method C2, which uses Differential Calorimetry (OSC Scenning Both are applicable to all polymers containing @ ervstaline phase and their compounds ‘The moking temporatures determined by the afferent methods usually iffer by several kelvins for tha reasons explained in the Introduction. Of the methods given above, exporimants have indicatod DSC [Differential Scanning Calorimetry) t0 bo the mothod of choice ‘3s having the best reproducblity of results. 2. Definitions Polymers containing @ is 2.1 semberystalline polymers Cystine phase surrounded by amorphous mat 2.2 melting range: The temperature range over which Crystaline polymers lace thee erystaiity when heated. NOTE ~ The conventional “mating temparstures” deterined by methods A and are cetned in clauses 3 ond 81SO 3146-1985 (E) Tivoces Bp vassa0a oowee? 2 Section one : Method A — Capillary tube 3. Principle Heating ofa specimen, ata controlled rate, and observation for cchango in shape. Reporting ofthe temperature of the specimen atthe ft visible deformation as the melting temperature NOTE — This method may algo be used for non-eystaine materia ‘ccordng to tho rolvantepactcations or by agreement between the intrest parte, 4 Apparatus (see figure 1) 4.1 Melting apparatus, consisting of the folowing toms : 2) ovindrical metal block, the upper part of wich is hollow and forms a chamber; metal plug, with two or more holes, allowing a ther- ‘momater and one or more capilary tubes to be mounted into the rota block a); Mota pg — } heating system for the metal block a) provided, for ‘example, by an electrical rasistance enclose in the box 4) theostat for regulation of the power input, if electrical heating ls sed: (four windows of heat-resistant glass on the lateral walls fof the chamber, diametrically disposed at right angles to other In front of one of theso windows is mounted an ‘eyepiece for observing the capilary tube, The other three Windows reused for iluminating the inside of ‘the enclosure by means of lamps. NOTE ~ Other sutable meting apperatuses may be that thoy ive the came result providod 4.2 Capillary tube, of heat-resistant glass, closed at one nd. nove 15mm. ‘The meximum exteral ameter should preferably be 4.3. Calibrated thermometer, graduated in divisions of 1 K. ‘The thermometer proba shall be positioned in such a way that, heat dispersion In tho apparatus Is not impeded. ‘Thormometor| — copitary tube ‘Meta heating block occa rsstance Figure 1 — Apparatus for method A. Sch bye reward Ounce For Sanda weft by te rterntonal Organon For Standard i: sur 30 NOTE ~ Other witabletomporaturemesturing devices may bo ust 5 Test specimens “The specimens used shall be representative of the sample of ‘material to be tested 5.1 Characteristics Powder of particle size up to 100 jim ar eut pioces of fms of thickness 10 to 20 um should preferably be used. Comparison tots shall bo carried out on spacimons of the samo or sknar particle size, or similar thickness in the case of layers or fims. 5.2 Conditioning {not otherwise spectied or agreed to by ts intrested partes, tho sample shall be conditioned at 23 + 2.°C and relative humidity of 60 + 5 % for 3 h prior to the mescurement. 6 Procedure 6.1 Calibration Calibrate the temperature-moasuring system patiodically over ‘the temperature range used for the test, with roagent grade or certified chemicals. Chemicals recommended for callcation are Bsted in table 1 6.2 Determination 6.2.1. Insert the thormometer (4.3) and the capilry tube (4.2) containing the specimen into the heating chambor{4.ta)] and start the heating. When the temperature of the specimen Is ‘about 20 K below the expected melting temperature, regulate ‘the rate of temperature increase to 2 + 0,8 K/min, Record the ‘temperature at which the specimen begins 1o change shape. 6.2.2 Repeat the operations specified in 6.2.1 with a second ‘specimen, I the two results obtained by the same operator an ‘the same sample differ by more than 3K, repeat the procedure fn two new specimens. Insufficlont data are avaiable for establishing raproductity. 710 1998 auH 35 wasi903 ooneeee 4 I ISO 3146-1985 (E) ‘Table 1 — Calibration standards Wetting Chemioat temperatura! (°C) Menthol B-Hydroxyquinolne Naphthalene env ‘Acotoniido enzoie ood Pheracotin IV 4athoxypheny acetal Aap sod Suifortamide Hydreauinone Suocni aid 2.chiorantivequone ‘anthracene Sacchern Tin Tit chore Phanoiphesion 1) The temperatures indicated rar to theoretically pure chemin: the values of th actual meting point forthe andra mater uted ‘should ba cetiad by the supper. 7 Test report ‘The test roport tal include the following information 2). raference to this Intemational Standard; Db) reference of the method used {mathod Al; €} complete identification and description of the material, tested; 4) shape and size (or mess) of the specimens; 6) provious thtral history ofthe spacimons; {1 conditioning: } heating rate; hi temperatures, in degrees Celsius or in kelvns, of two suconssive individual measuremonts, and thelr arithmetic 1) any operational details not specified in this International Standard or regarded as optional, as well 98 any incidents Table to have affected the results.i: sur 30 180 3146-1985 (E) iue-8s Wp waseoa ooneaes ff Section two : Method B — Polarizing microscope 8 Principle Heating of a specimen, positioned between the polarizer and analysor of & microscope, at a controled rate Measurement of tho tomporature at which the crystaline polymer loses its optical anisotropy, as detected by tho disap pearance of birefringence, as the melting temporature. 9 Apparatus Orcinary laboratory apparatus and 9.1. Microscope, with a disk polarizer and a cap analyser, or a polerizing microscope with builtin analyser, with magnifica ton from X 50 to X 100. 9.2 Micro hot-stago, consisting ofan Insulated motal block ‘that can be mounted slighty above the microscope stags. This block shall be provided with a hole for light passage: bi) electricaly heated, with adequate controls for adjust iment of heating and cooling rates; ©) constructed to provide a chamber witha heat bette and f glass cover, for carrying out measurements in an inert at- ‘mosphere: provided with a hole for insertion of @ temperature: ‘measuring devico naar the light hole 9.3. Tharmometers, calibrated, or equivalent temperature: measuring devices, forthe test temaerature ranges. 10 Test specimens 10.1 Powdered materials Place a2 to 3 mg portion of the powder (particle size not more than 100 um) on @ clean side and cover with a cover glass Heat the specimen, the slide and the cover on a hotplate slightly above the melting temperature of the polymer. By slight prescure on the cover glass, form a thin flm of thickness 0,01 100,08 mn and allow it to cool slowly by switching off the hotplate, 10.2 Moulded or pelleted materials Cut from the sample, with a microtome, a fim of thcknoss ap- proximately 0,02 mm, place it on a clean slide and cover with a ‘over glass, Heat and malt It as spectied in 10.1 FED) We Memon Organon Po Sana 710 1998 10.3. Film or shoot materials Cut #2103 mg portion of the fm or sheet, place it on a clean lide, cover witha cover glass and proceed as specified In 10.1, [NOTE — The protminry melting ofthe specknans borwoen side and ‘over presenta the advantage of destroying ony bichingance doa to ‘rontation oF internal strases, and algo of reducing the danger of fexidtion during the teat. The noed for an Tnart gas stroam — 36 Seserbed in 112" is thus limitad to very special casos. Tho reproducblity of the measurements Ie also inceaeod. Honever, bY ‘agreement between the intrested pales, the determination ray bo Carred out deci onthe powder or cut fim place without peeerinary ‘ating, Tht deviation should be sited Inthe fst report 14.1. Calibration See 6.1 11.2. Determination Place the glass microscope slide with the specimen on the ‘micro hot stago (8.2). Adjust the light source to maximum light intensity and focus the microscope (9.1), rns that are degradable by sr aust the gas inlet to the stage eo thata aight stroam of inert gos Diankets the stage, keeping it undor sight positive prossuro to prevent ingress of ‘irs Rotate the analyser ta aban a dark fld; the crytaine al wil appear bight ona dark eld, Adjust the controler {orheat th stage gradually (et arate not higher than 10 K/min} {0 a temperature thet f ower than the meling temperature, Se 88 determined epproximately by previous test, by tho ‘Glowing amounts: 10K for By < 180 °C 1B K for 160°C < By < 200°C 20 K for Ong > 200 °C, “Then adjust the controller so thatthe temperature rises at a rato of 1102 K/min, Observe the temperature at which birefingonce disappears, leaving a totally dark field. Record this temperature 3s the melting temperature of the sample. ‘Turn off the heating and remove the glass cover, heat batt. and specimen slide. Repeat the procedure with another specimen. Ifthe two results ‘obtained by the samo operator on the seme sample differ by more than 1 K, repeat the procedure on two new specimens.wi we ‘According to the results of round robins, the repeatabilty was 2K. Insufficient data are available for establishing ropro- duchy. 12. Test report ‘The test report shal include the following information fa} reference to this Intemational Standard; bb) reference of the method used (method Bl; ch complete identification and description of the material rst; «d}_ shape and sla (or mass) of the specimens; Irernaonal Organon For Stndardeatin “Gisecas Bp sesieoa onneeza 2 ISO 3146-1985 (E) ©) provious thermal history of the specimens; conditioning: 12) description of preliminary heating on the slide, if ap plicable; Fh) presence and type of inert gas, if applicabio; 1) heating cate: i} temperatures, in degroes Celsius or kelvin, of two suc ‘cessive individual measurements and ther arithmetic mean; Ie) any operationel details not specitid in this International ‘Standard or regarded as optional, as well 28 any incidents liable to have affected the resis,Twn 0 ISO 3146-1985 (E) suuecés Bp vesnoo3 oowaa 4 I Section three : Method C — Thermal analysis (DTA or DSC) 18 Additional definitions 18.1. Differential Thermal Analysis; DTA :") A technique ln which the temperature difference betwen ¢ substance and a reference material is measured as a function of temperature ‘while the substance and reference material are subjected to a Controlled tomporature programme. NOTE — The record Is she diferent! tharmal or DTA cure; the temperature difernes, AT, should bo plotted onthe ordinate wth on- thot reactions downwards and temperature, 7; or tne, fon the ‘sbscln, hereon fom at to right. 18.2 Differential Seanning Calorimetry: DSC :1) A technique in which the difference in aneray inputs into a substance and a reference material i measured as a function of temperature while the substance and reference material are ‘subjected to 8 controlled temperature programms. NOTE — Two modes, powarcompansation dforenal scanning Calorimetry ang het ix diferent anning calorimetry, can be datingushod, deponding onthe method of measurement used 18.3 baseline :2! The portion or portions of tho DTA or DSC. ceuve for which AT or the hest flux is approximately constant (approximately zero in DTA For example, see AB and DE in figura 2, 13.4 peak :2) That portion of a DTA or DSC curve which departs from, and subsequently returns to, the basdine. For example, see BCD in figure 2. NOTE — A poak is attributable to tho occurrence of some slg pro- teas Ile normaly characterized by 2 dodation frm the exabihed baswine, 2 maxim defection, anda reestablshmant ofa baseline, not necessary idrtcal to tha betore the pk 135 endothermic poak: endothorm :2 (1) In DTA, a peak whora the temperature of the sample falis below that of the reference material; that Is AT Is negative. (The meting phenomenon is an endothermic change.) (2). In DSC, a poak whore the enorgy Input to the sample is larger than thet to the roference materia 13.6 peak height 2) The distance, vertical to the ternperature axis, betweon the Interpolated baseline and the peak tip. For example, see CF in figure 2 Definition taken from : Nomenclature Committea of the Internetions! Conte Pant Meu Thermal Anal. 13 1578 387.332 2}. Defriton token from: Nomencature Committee ofthe Intemational Conf Par Totnes 19 1972 1079-1081 ave Dy We smn Orgone Po San 710 1998 NOTE — Thore are coveral ways of inerpoleting the baseino; that ‘showin In figue 2s only an example. Locations of pints B and D de ‘end on th method of intrpcation of the baseline. Other examples of Imterzolstion ofthe bassline ao shown in fgur 3 18.7 _poak area :2! The area enclosed between the peak and tho intorpolatad basolino(e) (See the note to 13.6.) For example, see BCDB in figure 2 13.8 extrapolated onset temperature :2 The temperature determined by the point ofIntarsaction of the tangent drawn at tho point of greatest slope on the leading edge of the peak (for example, tangent ¢ in figure 2) with the extrapolated baseline {for example BG in figure 2. For example, sae G in figure 2, and figure 3 [NOTE — For polymars having 9 wide meting range, the extrapoled ‘onsottemersture ndlestes the inal point of tho rapid ce of tho ‘roling curve, but not necsseoriy the intl making. 13.9 peak temperature :2! The tomporature at the time at which the differential temperature or heat fx during thet peak has the maximum value. For example, sae C In figure 2, 13.10 samplo :2! The actual meteral to be tested, whether fluted with an inert material or undiluted. 13.11 specimens :2! Portions of the sample tobe tested and the reference material, 18.12 reference material 2 A substance known to be thermally inectivo over the temperature range of interest, for example a aluminium oxide (-Al,0,) 18.13 sample holder 2 The container or support for the ‘test portion of the sample 18.14. roferonce hold reference material The container or support for the 13.15 specimen holder :2'Tha compete assembly in which ‘the specimene are housed. When tha heating or cooling source is incorporated in one unit with the containars or supports for the sample and reference material, this is regarded as part of the specimen holder assembly. 13.16 block :2) A type of specimen-holder ossembly in which @ relatively large mass of materials is in intimate contact With the specimens oF specimen holders. lon for Therma Analysis. Nowenctaturo ly thermal analyse sion for harms Analy. Nomanlatre In therel analft by the Internal Organon For Standard i: sur 30 13,17 differential thermocouple: AT" thermocoupl ‘The thetmacouple system used to measure temperature ot heat fax atferences. 14 Principle Heating of @ sample and an appropriate referenco material at ¢ controled rate in ® sultable DTA (method C1) or DSC method C2) apparatus. Recording of a DTA or DSC curve from which one or several characteristic points, related to the malting behaviour, are determined. 15 Apparatus 18.1 Differential thermal analyser or differential scan- ning calorimetor ‘Most commeccally avalable and custom-built instruments may bbe used, “The principal design characteristics of such Instruments are fs heated block with two holders forthe spacimonsiden- tically positioned and quarentosing the same heat transfer ‘conditions for both; ‘b)_a temperature recording system: (©) an electrical heater inthe block ora furnace with ado ‘quate controle for adjustment of heating rate to near conc ‘dons within + 0,8 K/min Synchronous recordings ofthe DTA curve and the temperature ifference AT shall permit temperature recording with a sen- sitivity not less then 2 K por milimatra on the racorder seal. ‘The DSC apparatus 1s constructed similarly to the DTA ap- pratus but with separate compensating daviees for the two pacimen holders and with electronic equipment maintaining the temporatures ofthe specimens ofthe sample and reference material atthe same level by varation of the aquired power input. “The pook area shall bo not loss than 2 cm; the peak height shall be at lost 10 times the height of the nolo lovel. 16.2. Thermocouples, Halalyfhked in the specimen compart ments, possessing identical characteristics within the gradue tion precision limits, 16.3. Equipment for filling the specimen containers with inert gas, oF for passage of @ constant messured flow of inert gas through the containers. “Svcs asia 0a eae b ISO 3146-1985 (E) 16 Test specimens 16.1 Characteristics Recommended specimens ara given in table 2. ‘Since miligram quantities of matorial are used, itis essential to fensure that the specimens are homogeneous and represen: tative, Table 2 ~ Characteristics of test spocimens Sample form | Part ico oa Powder | dane pio OB mm shes 0.05 00.550 Cut fil ‘area : 0,25 to 4,00 mm? ‘up to 50 ng i" iii up 1 080 en Flr length : up t0 2.00 mm NOTE — Since te resute ae affected by the mass of tho specimen {and by the poricle 826 snd shape, the epacimons 19 be compared should have approximately the same paces sze and shape and tho 17 Procedure 17.4 Calibration Calibrate the temperature measuring system periodically over tho tomporature range used forthe test. Contfied reference materials are available and are listed in tabio 3. Table 3 — DTA reference materials for transition temperatures in the range 125 to 435 °C. BTA risen values, PC) Reference materia” | Exxapolted Posk onset tempore, Ty] tomperature, Tp Potassium nivale we 7 Indium motel 18 19 Tn meta 20 a Silver suite a4 3 1) ICTANBS Cortiied Reference Materils for Oferenta! Thermal Anaiyas, avetabie frm the US National Bureau of Standards ‘Washington, DC 20288, USA. The Indested values rofer only to & space cried bate NOTE — The charetaistio points, and Ty) ar not tobe confused ‘nth the tuo salting temperatures 98 raportea int Heat. 5 Definiion taken from : Nomenclature Committe ofthe Intemational Confederation for Thermal Anais. Nomenclature in thermal nays: Pare, Tans 19 1872: 1079-108. 710 1998Ta i: sur 30 180 3146-1985 (E) 17.2 Determination (methods C1 and C2) 47.2.1. Weigh the speciman into the sample holder of the in ‘strument (18.1) immodiatoly after removal of the sample from the conditioning area. If applicable, start the passage of @ stream of an inert gas (freed from oxygen and dried, for ‘example by bubbling through an alkaling pyrogaliol solution) through the sample holder. Operate the instrument according to the manufacturers instructions. The maximum temperature recorded shall be atleast 60 K above the peak temperature. The recommended heating rate is 10 K/min. From the DTA or DSC curve recorded during this frst thermal cycle, determine the meting bevaviour of the material “as Feceived”, which may include thermal memories from the ‘manufacturing process. 17.22 Ifitis desired to erase the effects of the previous ther- mal history of the specimen in order to obtain an unambiguous ‘material identification, a second thermal cyce shall be perform- ed, 28 follows: = at the end of the frst cycle, hold the specimen under Inert gas atmosnhere, about 30 K above the melting peak (7) for 10 min, then cool it ata rate of 10 K/min to 60 K bbelow the peak crystallization temperature; — Immediately rapaat the heating cycle at a rate of 10 K/min and record the hating curve. 48 Expression of results ‘The folowing values, in degreos Celsius or in Kelvin, are read from the endothermic DTA or DSC curves recorded by the in strumont a) Tes extrapolated onset melting temperature; bb) T,: peak melting temperature ‘According to the results of @ raund robin cariod out in 1988, the repoatablity was within 2K and the reproducibility within 4K 7 We remnant Orgone or Sanda 710 1998 BI4L-a5 Pi vasia03 conees3 3 ff 19. Test report ‘The test report shall include tho following information a) reference to this international Standard; b) reference of the method used (method C1 or C2i; ©} complete identification and description of the material tested: 4) shapo and sie (or mass) ofthe specimens; «} previous thermal history of the specimens; 1) conditioning 6) ind of instrument used type of the sample holder (including its shape, materia etc; 1) type of temperature-measuring system (including type of thermocouple; 1) location ofthe temperature-mescuring system (inside or outside the sample holder I kind, siza and form ofthe reference material: 1) necessary, composition and physicel_ parameters Ipressure, flow rate, moisture content, ato.) of the inert 988; rm) heating rat: n} onset temperature 7, and peak temperature Ty in degrees Celsius or in kelvins, of the endothermic clive representing. the inl and final melting temperatures, respectively, af the sample, both corrected by the caliora- tion data; the resuits of both thermal cycles shall be reported; If not otherwise specified, the reference results {are those of the second eycle ‘} any operational details not specified inthis International Standard of rogatded as optional, as well as any incidents Table to have affected the routs.—Pss903 oon.034 7 IP ISO 3148-1985 (E) AT (or AH) Endothemic —wa—$toe other Figure 2 — Formalized DTA (or DSC) curve pal Organon For Stndardetion“BR4E-B5 J vssis03 coueaas 1 1SO 3146-1985 (E) AT (or AH) A Endothernic te Exothermic AT (or an Ta: Extroposted onset temperate Tp Peak temperature Figure 3 — Examples of valuation of T, and 7, on DTA (or DSC) curves ral goneaton For Sadao