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Analisa Termal

Teknik Analisa Termal


Sejumlah teknik pengukuran dimana sifat-sifat fisik diukur sebagai fungsi dari suhu, dimana sampel dikenakan proses pemanasan atau pendinginan tertentu. Differential Thermal Analysis (DTA)
Perbedaan suhu antara sampel dengan material standar yang inert, diukur saat keduanya diberi perlakuan panas tertentu.

T = TS - TR,

Differential Scanning Calorimetry (DSC)


Sampel dan standar dijaga pada suhu yang sama, bahkan selama terjadi perubahanperubahan termal tertentu pada sampel. Variabel yang diukur adalah besarnya energi yang diperlukan untuk menjaga perbedaan suhu sampel dan standar sama dengan nol, d q/dt.

Thermogravimetric Analysis (TGA)


Pengukuran dilakukan pada perubahan massa sampel akibat pemanasan.

Prinsip-prinsip dasar analisa termal


Instrumentasi modern yang digunakan pada analisa termal biasanya terdiri dari empat bagian: 1)Sample/sample holder 2)Sensor untuk mendeteksi/mengukur sifat-sifat tertentu sampel dan suhu. 3)Pengaturan yang memungkinkan paremeter-parameter eksperimen dapat dikontrol. 4)Komputer yang memungkinkan pengumpulan dan pemrosesan data.

DTA

power compensated DSC

heat flux DSC

Differential Thermal Analysis


sample holder
sample and reference cells (Al) alumina block
heating coil

sensors
Pt/Rh atau chromel/alumel thermocouples Satu untuk sampel dan satu untuk reference Dihubungkan dengan pengontrol suhu diferensial
sample pan reference pan

furnace
alumina block berisi sampel dan reference

inert gas vacuum

Pt/Rh or chromel/alumel thermocouples

temperature controller
Mengontrol program suhu dan atmosfer furnace

Differential Thermal Analysis


keuntungan:

Instrumen dapat digunakan pada suhu yang sangat tinggi


Instrumen sangat sensitif Volume dan bentuk crucible fleksibel Transisi atau suhu reaksi yang karakteristik dapat ditentukan dengan akurat,

kelemahan:
Ketidakpastian estimasi panas bagi reaksi, transisi dan fusi sekitar 20-50%

DTA

Differential Scanning Calorimetry


DSC differs fundamentally from DTA in that the sample and reference are both maintained at the temperature predetermined by the program. during a thermal event in the sample, the system will transfer heat to or from the sample pan to maintain the same temperature in reference and sample pans two basic types of DSC instruments: power compensation and heat-flux

power compensation DSC

heat flux DSC

Power Compensation DSC


individual heaters controller

sample pan

reference pan

sample holder

Al or Pt pans
sensors

inert gas vacuum thermocouple

inert gas vacuum

T=0

Pt resistance thermocouples separate sensors and heaters for the sample and reference furnace separate blocks for sample and reference cells

temperature controller
differential thermal power is supplied to the heaters to maintain the temperature of the sample and reference at the program value

Sample Preparation
accurately-weigh samples (~3-20 mg) small sample pans (0.1 mL) of inert or treated metals (Al, Pt, Ni, etc.) several pan configurations, e.g., open , pinhole, or hermetically-sealed pans the same material and configuration should be used for the sample and the reference material should completely cover the bottom of the pan to ensure good thermal contact avoid overfilling the pan to minimize thermal lag from the bulk of the material to the sensor * small sample masses and low heating rates increase resolution, but at the expense of sensitivity

Al

Pt

alumina

Ni

Cu

quartz

Heat Flux DSC


heating coil

sample holder sample and reference are connected by a low-resistance heat flow path Al or Pt pans placed on constantan disc sensors
constantan chromel/alumel wires
inert gas vacuum

sample pan

reference pan

thermocouples

chromel wafer

chromel-constantan area thermocouples (differential heat flow) chromel-alumel thermocouples (sample temperature) furnace one block for both sample and reference cells temperature controller the temperature difference between the sample and reference is converted to differential thermal power, d q/dt, which is supplied to the heaters to maintain the temperature of the sample and reference at the program value

Modulated DSC (MDSC)


introduced in 1993; heat flux design sinusoidal (or square-wave or sawtooth) modulation is superimposed on the underlying heating ramp total heat flow signal contains all of the thermal transitions of standard DSC Fourier Transformation analysis is used to separate the total heat flow into its two components: heat capacity (reversing heat flow) glass transition melting kinetic (non-reversing heat flow) crystallization decomposition evaporation enthalpic relaxation cure

Modulated DSC Heating Profile

Analysis of Heat-Flow in Heat Flux DSC


temperature difference may be deduced by considering the heat flow paths in the DSC system heating block Tfurnace TS

temperature

TR TRP

TSP TR reference TL sample TS

thermocouple is not in physical contact with sample

thermal resistances of a heat-flux system change with temperature the measured temperature difference is not equal to the difference in temperature between the sample and the reference

Texp TS TR

DSC Calibration
baseline evaluation of the thermal resistance of the sample and reference sensors measurements over the temperature range of interest 2-step process the temperature difference of two empty crucibles is measured the thermal response is then acquired for a standard material, usually sapphire, on both the sample and reference platforms amplified DSC signal is automatically varied with temperature to maintain a constant calorimetric sensitivity with temperature

DSC Calibration
temperature goal is to match the melting onset temperatures indicated by the furnace thermocouple readouts to the known melting points of standards analyzed by DSC should be calibrated as close to the desired temperature range as possible heat flow use of calibration standards of known heat capacity, such as sapphire, slow accurate heating rates (0.52.0 C/min), and similar sample and reference pan weights calibrants high purity accurately known enthalpies thermally stable light stable (h ) nonhygroscopic unreactive (pan, atmosphere) metals In 156.6 C; 28.45 J/g Sn 231.9 C Al 660.4 C inorganics KNO3 128.7 C KClO4 299.4 C organics polystyrene 105 C benzoic acid 122.3 C; 147.3 J/g anthracene 216 C; 161.9 J/g

Thermogravimetric Analysis (TGA)


thermobalance allows for monitoring sample weight as a function of temperature two most common instrument types reflection null weight calibration weights using calibrated
Sample: Calcium Oxalate Size: 7.9730 mg

TGA

File: Y:\Data\TGA\Calcium oxalate\032304.001 Operator: SLT Run Date: 23-Mar-04 14:57 Instrument: 2950 TGA HR V5.4A

120

Weight (%)

temperature calibration based on ferromagnetic transition of Curie point standards (e.g., Ni) larger sample masses, lower temperature gradients, and higher purge rates minimize undesirable buoyancy effects

100
12.15%

80

19.32%

60
29.99%

40

20 0 20 40 60 80 100 120 140 160

Time (min)

Universal V3.7A TA Instruments

TG curve of calcium oxalate

Typical Features of a DSC Trace for a Polymorphic System


endothermic events melting sublimation solid-solid transitions desolvation chemical reactions exothermic events crystallization solid-solid transitions decomposition chemical reactions baseline shifts glass transition

sulphapyridine

Thermal Methods in the Study of Polymorphs and Solvates


polymorph screening/identification

thermal stability melting crystallization solid-state transformations desolvation glass transition sublimation decomposition
heat flow heat of fusion heat of transition heat capacity

1.0

0.5

0.0

Heat Flow (W/g)

-0.5

-1.0

-1.5
Form I I Form Form II II Form Variable Form III Hydrate Dihydrate Acetic acid solvate

-2.0

-2.5 0
Exo Up

50

100

150

200

250

300

350

Temperature (C)

mixture analysis chemical purity physical purity (crystal forms, crystallinity) phase diagrams eutectic formation (interactions with other molecules)

Sample: INDIUM CRIMPED PAN CHECK Size: 7.6300 mg Method: indium Comment: P/N 56S-107 0.5

Definition of Transition Temperature


DSC
156.50C 28.87J/g

File: C:...\10C per min crimped\DSC010920A.3 Operator: Ron Vansickle Run Date: 20-Sep-01 09:13 Instrument: 2920 MDSC V2.6A

0.0

-0.5

extrapolated onset temperature

Heat Flow (W/g)

-1.0

-1.5

-2.0

peak melting temperature


157.81C

-2.5 140
Exo Up

145

150

155

160

165

170

175
Universal V3.3B TA Instruments

Temperature (C)

Melting Processes by DSC


pure substances

linear melting curve


melting point defined by onset temperature impure substances
eutectic melt

concave melting curve melting characterized at peak maxima eutectic impurities may produce a second peak

melting with decomposition exothermic endothermic

Glass Transitions
second-order transition characterized by change in heat capacity (no heat absorbed or evolved) transition from a disordered solid to a liquid appears as a step (endothermic direction) in the DSC curve a gradual volume or enthalpy change may occur, producing an endothermic peak superimposed on the glass transition

Sample: INDIUM CRIMPED PAN CHECK Size: 7.6300 mg Method: indium Comment: P/N 56S-107 0.5

Enthalpy of Fusion
DSC
156.50C 28.87J/g

File: C:...\10C per min crimped\DSC010920A.3 Operator: Ron Vansickle Run Date: 20-Sep-01 09:13 Instrument: 2920 MDSC V2.6A

0.0

-0.5

Heat Flow (W/g)

-1.0

-1.5

-2.0

157.81C

-2.5 140
Exo Up

145

150

155

160

165

170

175
Universal V3.3B TA Instruments

Temperature (C)

Burgers Rules for Polymorphic Transitions


enantiotropy monotropy

endothermic

Heat of Transition Rule endo-/exothermic solid-solid transition Heat of Fusion Rule higher melting form; lower Hf

endothermic

exothermic solid-solid transition


higher melting form; higher Hf

Enthalpy of Fusion by DSC


single (well-defined) melting endotherm area under peak minimal decomposition/sublimation readily measured for high melting polymorph can be measured for low melting polymorph

multiple thermal events leading to stable melt solid-solid transitions (A to B) from which the transition enthalpy ( HTR) can be measured*

HfA = HfB - HTR


crystallization of stable form (B) from melt of (A)

HfA = area under all peaks from B to the stable melt


* assumes negligible heat capacity difference between polymorphs over temperatures of interest

Purity by DSC
eutectic impurities lower the melting point of a eutectic system purity determination by DSC based on Vant Hoff equation

Tm = To -

RTo2

Ho

97%

f
99%

applies to dilute solutions, i.e., nearly pure substances (purity 98%) 1-3 mg samples in hermetically-sealed pans are recommended polymorphism interferes with purity determination, especially when a transition occurs in the middle of the melting peak

benzoic acid

99.9%

melting endotherms as a function of purity.

Plato, C.; Glasgow, Jr., A.R. Anal. Chem., 1969, 41(2), 330-336.

Effect of Heating Rate


many transitions (evaporation, crystallization, decomposition, etc.) are kinetic events they will shift to higher temperature when heated at a higher rate the total heat flow increases linearly with heating rate due to the heat capacity of the sample increasing the scanning rate increases sensitivity, while decreasing the scanning rate increases resolution to obtain thermal event temperatures close to the true thermodynamic value, slow scanning rates (e.g., 15 K/min) should be used

DSC traces of a low melting polymorph collected at four different heating rates. (Burger, 1975)

Effect of Phase Impurities


lots A and B of lower melting polymorph (identical by XRD) are different by DSC

0
2046742 FILE# 022511DSC.1

Lot A - pure

-1

Heat Flow (W/g)

-2

2046742 FILE# 022458 DSC.1 Form II ?

Lot B - seeds

-3

-4

-5 80
Exo Up

130

180

230

280
Universal V3.3B TA Instruments

Temperature (C)

Lot A: pure low melting polymorph melting observed Lot B: seeds of high melting polymorph induce solid-state transition below the melting temperature of the low melting polymorph

Polymorph Characterization: Variable Melting Point


lots A and B of lower melting polymorph (identical by XRD) appear to have a variable melting point
0.1

-0.1

Lot A
-0.3

Heat Flow (W/g)

-0.5

Lot B

-0.7

-0.9
DSC010622b.1 483518 HCL (POLYMORPH 1) DSC010622d.1 483518 HCL

-1.1 110
Exo Up

120

130

140

150

160

170

180
Universal V3.3B TA Instruments

Temperature (C)

although melting usually happens at a fixed temperature, solid-solid transition temperatures can vary greatly owing to the sluggishness of solid-state processes

Polymorph Characterization: Variable Melting Point


the low temperature endotherm was predominantly non-reversing, suggestive of a solid-solid transition small reversing component discernable on close inspection of endothermic conversions occurring at the higher temperatures, i.e., near the melting point
0.00

0.2

-0.05

reversing heat flow


Reversing (heat flow component)

non-reversing heat flow


Non-reversing (heat flow component)

-0.10

0.0

-0.15

-0.20

Nonrev Heat Flow (W/g)

Lot A

Lot A
-0.2

Rev Heat Flow (W/g)

-0.25

-0.30

Lot B

-0.4

Lot B

-0.35

-0.40

-0.6
DSC010622b.1 483518 HCL (POLYMORPH 1) DSC010622d.1 483518 HCL

-0.45

DSC010622b.1 483518 HCL (POLYMORPH 1) DSC010622d.1 483518 HCL

-0.50 110
Exo Up

120

130

140

150

160

170

180

-0.8 110

120

130

140

150

160

170

180
Universal V3.3B TA Instruments

Temperature (C)

Universal V3.3B TA Instruments Exo Up

Temperature (C)

the variable melting point was related to the large stability difference between the two polymorphs; the system was driven to undergo both melting and solid-state conversion to the higher melting form

Polymorph Stability from Melting and Eutectic Melting Data


polymorph stability predicted from pure melting data near the melting temperatures (G1-G2)(Tm1) = Hm2(Tm2-Tm1)/Tm2 (G1-G2)(Tm2) = Hm1(Tm2-Tm1)/Tm1 eutectic melting method developed to establish thermodynamic stability of polymorph pairs over larger temperature range
(b)
TmA A P1 P2 TmRC RC Te2 Te1 1 0 xe2 xe1 x 1 Tm1 Tm2
sdf

0.4 0.2 0 -0.2 -0.4

GON-GY, kJ/mole

Y Tt ON melting

eutectic melting

DSC Signal

ON

ON

Y ON Y Y ON Y

ON

+benzil +thymol +azobenzene +acetanilide


40 60

pure forms
120

T, o C

80

100

(G1-G2)(Te1) = Hme2(Te2-Te1)/(xe2Te2) (G1-G2)(Te2) = Hme1(Te2-Te1)/(xe1Te1) Yu, L. J. Pharm. Sci., 1995, 84(8), 966-974. Yu, L. J. Am. Chem. Soc, 2000, 122, 585-591.

Hyphenated Techniques
thermal techniques alone are insufficient to prove the existence of polymorphs and solvates other techniques should be used, e.g., microscopy, diffraction, and spectroscopy development of hyphenated techniques for simultaneous analysis TG-DTA TG-DSC TG-FTIR TG-MS
evolved gas analysis (EGA)
Weight (%)
Sample: SODIUM TARTRATE (ALDRICH) Size: 6.1176 mg Method: 25C TO 300 Comment: LOT# 22411A0 120
15.55% (0.9513mg) 24.80C 100.0%

TGA-DTA

File: C:\TA\Data\Sdtcal\2004\TGA040105A.5 Operator: Ron Vansickle Run Date: 6-Jan-04 12:09 Instrument: 2960 SDT V3.0F

4.2

3.2
179.95C 84.45%

2.2

40

1.2

0.2 0 -0.8

-40 20
Exo Up

-1.8 70 120 170 220 270


Universal V3.3B TA Instruments

Temperature (C)

TG-DTA trace of sodium tartrate

Temperature Difference (V/mg)

80

Best Practices of Thermal Analysis


small sample size good thermal contact between the sample and the temperature-sensing device

proper sample encapsulation


starting temperature well below expected transition temperature slow scanning speeds proper instrument calibration use purge gas (N2 or He) to remove corrosive off-gases

avoid decomposition in the DSC

Reversing and Non-Reversing Contributions to Total DSC Heat Flow

total heat flow resulting from average heating rate

dQ/dt = Cp . dT/dt + f(t,T)


reversing signal heat flow resulting from sinusoidal temperature modulation (heat capacity component) non-reversing signal (kinetic component)

* whereas solid-solid transitions are generally too sluggish to be reversing at the time scale of the measurement, melting has a moderately strong reversing component

Recognizing Artifacts
sample pan distortion

sample topples over in pan

shifting of Al pan

mechanical shock of measuring cell

cool air entry into cell

sensor contamination

electrical effects, power spikes, etc.

RT changes

intermittant closing of hole in pan lid

burst of pan lid