research article kinetics of thermolysis of nickel(ii...

Research ArticleKinetics of Thermolysis of Nickel(II) PerchlorateComplex with n-Propylamine

Chandra Prakash Singh and Abhishek Singh

Department of Chemistry DBS College Kanpur 208006 India

Correspondence should be addressed to Chandra Prakash Singh cpsingh4usgmailcom

Received 25 November 2013 Accepted 10 January 2014 Published 19 February 2014

Academic Editors J Luo and H S Yathirajan

Copyright copy 2014 C P Singh and A Singh This is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work is properlycited

Complex of nickel perchlorate with n-propylamine has been synthesised with molecular formula [Ni(n-pa)3(ClO4)(H2O)]ClO

4

It has been characterised by elemental analysis thermogravimetry UV-VIS and IR spectroscopic data Thermal properties havebeen investigated by thermogravimetry (TG) in static air and by simultaneous thermogravimetry-derivative thermogravimetry-differential thermal analysis (TG-DTG-DTA) in flowing nitrogen atmosphere Kinetics of thermolysis has been analysed applyingmodel-fitting andmodel-free isoconversionalmethod on isothermal TGdata recorded at five different temperatures To observe theresponse of complex towards fast heating explosion delay time has been recorded at various temperatures and kinetics of explosionhas been studied using these data

1 Introduction

Metal perchlorates have strong oxidizing properties andamines are reducing in nature Amines have strong eminusdonation power due to presence of lone pair eminus on theirnitrogen atom These two oxidizing and reducing groupscan be easily incorporated in a single molecule by reactingmetal perchlorate with amine resulting in the formationof metal amine perchlorate coordination compounds Anycomposition having strong oxidizing and reducing groupssimultaneously in a molecule will exhibit the propertiesof high energetic materials Thus metal perchlorate aminecomplexes will exhibit the properties of energetic materialand undergo autotransmitted decomposition reactions [1ndash3]when subjected to a stimuli (heat friction shock wave etc)Owing to their energetic properties these types of complexeshave found applications in explosives pyrotechnics andpropellants Such type of complexes has been proved tobe a strong burning rate modifier for hydroxyl terminatedpolybutadiene-ammonium perchlorate (HTPB-AP) basedpropellants [4 5] In search of insensitive high energeticmaterials a strong interest is being given by the researcheson such type of complexes (having oxidizing and reducing

group in one molecule) and they have been synthesized andtheir properties have been extensively investigated [5ndash14] Inthe present paper we report the preparation characterisa-tion thermolysis and explosion characterisation of nickelperchlorate complex with n-propyl amine water and ClO

4

minus

as ligands Kinetics of early thermolysis was also investigatedby applying model-fitting and isoconversional method

2 Experimental

21 Materials Nickel carbonate perchloric acid n-propylamine (sdfine) ethanol (Changshu Yangyuan ChemicalChina) petroleum ether (Merk) and all of AR grades wereused as received

22 Preparation The complex was prepared via two-stepprocedure In first step hexahydrate nickel perchlorate wasobtained by reacting nickel carbonate with 60 perchloricacid followed by recrystallisation In second step ethanolicsolution of nickel perchlorate and n-propyl amine was mixedtogether stirred well at room temperature and filtered outsome obtained light green ppt From the filtrate after 2-3 days

Hindawi Publishing CorporationIndian Journal of Materials ScienceVolume 2014 Article ID 787306 5 pageshttpdxdoiorg1011552014787306

2 Indian Journal of Materials Science

Table 1 IR frequencies and elemental analysis data for the complex

IR Element observedcalculated] (cmminus1) Assignments448 MndashN C 224221627 Ionic perchlorate N 8685753 CndashH def H 6164990 CndashN str Ni 129513271089 Ionic perchlorate1112 Bidentate1145 ClO

4

minus

1395 CndashNH2

1503 NndashH bend15702705 CndashH str29943034 NH2 (Pri)3434 OndashH (H2O)

Ni

0

20

40

60

80

100

50 100 150 200 250 300 350

Mas

s (

)

Temperature (∘C)

Figure 1 TG curve of complex in static air atmosphere

light green crystals of desired complex were obtained Thecrystals were washed with alcohol and dried

Caution Perchlorates are explosivesThey should be handledwith care However I have not found any problem during allexperimental procedures

23 Characterisation Characterisation of complex was doneby elemental analysis (C H N Thermo Finnigan Flash EA1112 CHNS analyzer) infrared [15ndash17] (Perkin Elmer FT-IRspectrometer) UV-VIS spectroscopy and thermogravimetry(Table 1)

24 Thermal Analysis

241 TG in Air Thermogravimetry in static air with heatingrate of 10∘Cmin (Figure 1) was recorded using an indige-nously fabricated TG apparatus [18] (sample mass 20mg)

100 400300200 500 600 700

0

40

140

120

80

180

DTGTG

Ni

0

20

40

60

80

100

Mas

s (

)

DTA

minus20

Hea

t flow

(mW

)

Temperature (∘C)

Figure 2 TG-DTG-DTA curve of complex in flowing nitrogenatmosphere

242 Simultaneous TG-DTG-DTA These traces were ob-tained in flowing nitrogen atmosphere (100mLmin) samplewas sim25mg at a heating rate of 10∘Cmin (Figure 2 Table 2)

243 Isothermal TG Isothermal TG (Figure 3) was recordedin static air atmosphere using the same indigenously fab-ricated TG apparatus as mentioned earlier at five differenttemperatures (200 210 220 230 and 240∘C) Sample masstaken was 10mg and readings were recorded for 30 decom-position

244 Kinetic Analysis Kinetics of decomposition has beeninvestigated using isothermal TG data using model fitting(Table 3) [19] and isoconversional method [20 21] Variationof activation energy with extent of conversion 120572 is shown inFigure 4

245 Explosion Delay Experiments This experiment wasperformed using tube furnace technique [22] (sample mass10mg) at temperatures of 280 300 320 340 and 360∘Cwithin experimental limit of plusmn1∘C (Table 4) 119863

119864data were

fitted in Arrhenius equation

119863

119864= 119860 exp 119864

lowast

119877119879

(1)

where 119860 is the Arrhenius factor 119864lowast is the activation energyfor explosion 119879 is absolute temperature and 119877 is the gasconstant A plot of ln119863

119864versus 1119879 is presented in Figure 5

3 Results and Discussion

Table 1 containing elemental analysis and IR data showsa good agreement between observed and calculated per-centages of C H N and Ni The FT-IR spectra of thecomplex revealed bands at 448 cmminus1 assigned to ](MndashN)627 and 1089 cmminus1 assigned to ionic perchlorate and 1112and 1145 cmminus1 assigned to bidentate perchlorate ion (C

2Vsymmetry) [22] A broad peak at 3434 cmminus1 is due to ](OndashH)of coordinated water Other peaks are according to standardtext In the UV-VIS spectrum the absorption maxima at263 nm is due to n rarr 120587lowast transition and a peak at 378 nmis assigned for 3A

2g(F) rarr3T1g(P) overlapping with charge

Indian Journal of Materials Science 3

Table 2 TG-DTA data of the complex

Step TG DTATemperature range (∘C) decomposition Peak position (∘C) Nature of peaks

I 92ndash121 4 169 EndoII 121ndash288 12 mdash mdashIII 290ndash305 70 299 Exo

Table 3 Activation energy (119864) Arrhenius factor and correlation coefficients (119903) for the isothermal decomposition of the complex

Serial number Model ln119860 Slope 119864kJmoleminus1 119903 Mean deviation Standard deviation1 Power law34 11382 21282 177 09702 2728 28772 Power law23 12143 19781 164 09641 2613 27563 Power law12 06130 21487 178 09714 2486 26284 Power lawminus12 00605 22071 183 09740 2269 23845 Power lawminus1 minus00051 22246 185 09742 2254 23786 Mampel (1 minus 120572) minus11053 22751 189 09610 1755 18537 a-e34 07241 21771 181 09748 2570 27118 a-e23 minus00275 22498 187 09599 2268 23909 a-e12 minus04144 22602 188 09605 2085 220110 cs 02240 22491 187 09686 2393 252511 T-d-diff 02629 23051 191 09614 2470 260512 cc 01869 22234 185 09713 2349 247813 P-T minus16300 22375 186 09592 1454 153614 G-B 12040 22561 187 09698 2891 3049

0

02

04

06

08

1

0 20 40 60 80 100 120Time (min)

Ni

200

120572

Figure 3 Isothermal TG of complex in static air atmosphere atdifferent temperatures

transfer band A band at 870 nm is assigned for 3A2g(F) rarr

1Eg(D) transition Thus as suggested by the overall evidencegiven above the complex can be formulated as [Ni(n-pa)3(ClO4)(H2O)]ClO

4in which Ni2+ is hexacoordinated

Out of six coordination sites three sites are satisfied withnitrogen atoms one from each n-propylamine and three siteswith O-atoms one from water molecule and two from oneof the perchlorate ions acting as a bidentate ligand (C

2Vsymmetry)

A perusal of TG curve recorded in static air with lineartemperature increase shows that the complex decomposes inthree steps The very first step (92ndash121∘C) is gradual in which

0

10

20

30

40

50

0 02 04 06 08 1

Ni

120572

E(k

J mol

minus1)

Figure 4 Variation of activation energy of thermolysis for thecomplex with extent of conversion (120572)

coordinated H2O leaves the complex (sim4 wt Loss) In the

second step (121ndash288∘C) one of the n-propylamines is released(sim12 wt Loss) In the third step (290ndash305∘C) the remainingresidue [Ni(n-pa)

2(ClO4)]ClO

4(might be tetracoordinated

complex of Ni2+) ignites with smoke and low noise givinga sharp weight loss (sim70) At lost sim15 mass is left whichcorresponds to NiO (calculated mass 1527) In flowing N

2

atmosphere (Figure 2) the decomposition pattern of complexis similar to static air A DTG peak has been obtainedcorresponding to third step sudden weight loss DTG werenot obtained for first step because this step is very gradualDTGpeak for second stepmight be incorporated in third step


Table 4 Explosion delay activation energy for thermal explosion (119864lowast) and correlation coefficient (119903) of complex

119863

119864119863

119864(s) at temperature (∘C)

119864

lowast (kJmolminus1) 119903 ln 119896280 plusmn 1 300 plusmn 1 320 plusmn 1 340 plusmn 1 360 plusmn 1

123 93 83 58 54 309 09842 minus1915

0

2

4

6

000155 000165 000175 000185

Ni

1T

ln D

E

Figure 5 Graph representing ln119863119864versus 1119879 for the complex

of DTGpeak InDTA curve an endotherm at 169∘Cand this isto be in harmony with second step (removal of one of the n-pa molecule) A strong exothermic peak at 299∘C has beenreceived which suits the ignition of partially decomposedresidue in the third step

Thus in the light of the above discussion the thermolysispattern of the complex can be given as

[Ni(n-pa)3(ClO4) (H2O)]ClO

4

minusH2O

997888997888997888997888997888997888997888997888rarr

92ndash121∘C[Ni(n-pa)

3(ClO4)]ClO

4

[Ni(n-pa)3(ClO4)]ClO

4

minusn-pa997888997888997888997888997888997888997888997888997888997888rarr


2(ClO4)]ClO

4


4

290ndash305∘C997888997888997888997888997888997888997888997888997888997888997888rarr NiO + gaseous products

(2)

In the order to calculate activation energy (119864119886) for the

removal of ligands (30 wt Loss which includes H2O and

2 n-pa molecule) a set of reaction models (Table 3) [19]was used on isothermal TG data in the temperature range200ndash240∘C (Figure 3) 119864

119886values obtained (sim18 kJmoleminus1) are

almost equal irrespective of the reaction model usedKinetic analysis of isothermal TG data applying isocon-

versional method [20 21] concerns with the calculation ofactivation energy independent of the model but correspond-ing to the extent of conversion (120572) of the complex Figure 4shows that at different values of 120572 119864

119886values in are different

Model-free isoconversional method is a better approach toobtain reliable and consistent kinetic data as compared tomodel-fitting methods

The complex when subjected to sudden high temperatureexplodes with noise To determine the activation energyof explosion (119864lowast) explosion delay time has been recordedat five different temperatures (Table 4) Activation energyfor explosion was found to be 309 kJmolminus1 A graph ofln119863119864versus 1119879 (Figure 5) shows that explosion delay time

exponentially depends on temperatures

4 Conclusion

The complex has been prepared and characterised by varioustechniques TG-DTA study reveals that the complex decom-pose in three steps After an initial weight loss (sim16) oxidiser(ClO4

minus) and fuel (reducing group ie n-pa) lead to ignitiongiving a sharp exothermic peak in DTA End product ofthermolysis corresponds to NiO Complex explodes whenkept suddenly under high temperatures

Conflict of Interests

The authors declare that there is no conflict of interestsregarding the publication of this paper

Acknowledgments

The authors thank the Secretary Board ofManagement Prin-cipal and Head of Department of Chemistry DBS CollegeKanpur for providing laboratory facilities and UniversityGrants Commission New Delhi for financial assistanceThanks are also due to Sophisticated Test and Instrumenta-tion Centre Cochin University of Science and Technologyfor CHN FT-IR UV-VIS and TG-DTA analyses

References

[1] G Singh C P Singh and S M Mannan ldquoKinetics of thermol-ysis of some transition metal perchlorate complexes with 14-diaminobutane ligandrdquo Thermochimica Acta vol 437 no 1-2pp 21ndash25 2005

[2] G Singh and D K Pandey ldquoStudies on energetic com-pounds part 40 Kinetics of thermal decomposition of somebis(propylenediamine)metal perchlorate complexesrdquo Journal ofThermal Analysis and Calorimetry vol 82 no 2 pp 353ndash3602005

[3] G Singh S P Felix and D K Pandey ldquoStudies on energeticcompounds part 37 kinetics of thermal decomposition ofperchlorate complexes of some transition metals with ethylene-diaminerdquoThermochimica Acta vol 411 no 1 pp 61ndash71 2004

[4] G Singh I P S Kapoor and D K Pandey ldquoHexammine metalperchlorates as energetic burning rate modifiersrdquo Journal ofEnergetic Materials vol 20 pp 223ndash244 2002


[5] G Singh and D K Pandey ldquoStudies on energetic com-pounds part 27 kinetics and mechanism of thermolysis ofbis(ethylenediamine)metal nitrate and their role in the burningrate of solid propellantsrdquo Propellants Explosives Pyrotechnicsvol 28 no 5 pp 231ndash239 2003

[6] K C Patil V R P Verneker and S R Jain ldquoRole of metal per-chlorate ammines on ammonium perchlorate decompositionrdquoCombustion and Flame vol 25 pp 387ndash388 1975

[7] K S Rejitha and S Mathew ldquoThermal behaviour of nickel(II)sulphate nitrate and halide complexes containing ammine andethylenediamine as ligands kinetics and evolved gas analysisrdquoJournal of Thermal Analysis and Calorimetry vol 106 no 1 pp267ndash275 2011

[8] FWalmsley A A Pinkerton and J AWalmsley ldquoSynthesis andx-ray crystal structures of 1 1 complexes of nickel(II) nitratewith 110-phenanthroline and with 221015840-bipyridylrdquo Polyhedronvol 8 no 5 pp 689ndash693 1989

[9] L Jianmin Z Jianbin K Yanxiong and W Xintao ldquoA novelstructure of bipyridine coordinated with copper (II) [Cu(bipy)(H2O)3] (NO

3)2rdquo Crystal Research and Technology vol 31 no

5 pp 589ndash593 1996[10] A Rujiwatra S Yimklan and T J Prior ldquoA second crystal

form of [Ni(221015840-bipyridine)(H2O)3(NO3)](NO

3) featuring a

different molecular orientationrdquo Polyhedron vol 31 no 1 pp345ndash351 2012

[11] D Kumar I P S Kapoor G Singh N Goel and U PSingh ldquoPreparation characterization and thermal behaviourof polymeric complex of cadmium hexamethylenetetraminenitraterdquo Solid State Sciences vol 14 no 4 pp 495ndash500 2012

[12] G Singh I P S Kapoor D Kumar U P Singh and N GoelldquoPreparation X-ray crystallography and thermal decomposi-tion of transition metal perchlorate complexes with perchlorateand 221015840-bipyridyl ligandsrdquo Inorganica Chimica Acta vol 362no 11 pp 4091ndash4098 2009

[13] K Dinesh I P S Kapoor G Singh and R Frohlich ldquoPrepa-ration characterization and kinetics of thermolysis of nickeland copper nitrate complexes with 221015840-bipyridine ligandsrdquoThermochimica Acta vol 545 pp 67ndash74 2012

[14] D Kumar I P S Kapoor G Singh N Goel and U PSingh ldquoPreparation X-ray crystallography and thermolysis oftransition metal nitrates of 221015840-bipyridine (Part 63)rdquo Journal ofThermal Analysis and Calorimetry vol 107 no 1 pp 325ndash3342012

[15] K Nakamoto Infrared and Raman Spectra of Inorganic and Co-Ordination Compounds Wiley New York NY USA 1978

[16] C W RobertHandbook of Physics and Chemistry vol 66 CRCPress Boca Raton Fla USA 1996

[17] F A Miller and C H Wilkins ldquoInfrared spectra and charac-teristic frequencies of inorganic ions their use in qualitativeanalysisrdquo Analytical Chemistry vol 24 no 8 pp 1253ndash12941952

[18] G Singh and R R Singh ldquoIndigenously fabricated apparatusfor thermogravimetric analysisrdquo Research Industry vol 23 pp92ndash103 1978

[19] M E Brown D Dollimore and A K Galway Reactions in theSolid State Comprehensive Chemical Kinetics vol 22 ElsevierAmsterdam The Netherlands 1997

[20] S Vyazovkin and C A Wight ldquoIsothermal and nonisothermalreaction kinetics in solids in search of ways toward consensusrdquo

Journal of Physical Chemistry A vol 101 no 44 pp 8279ndash82841997

[21] S Vyazovkin and C A Wight ldquoModel-free and model-fittingapproaches to kinetic analysis of isothermal and nonisothermaldatardquoThermochimica Acta vol 340-341 pp 53ndash68 1999

[22] G Singh I P S Kapoor and S K Vasudeva ldquoThermolysis ofAP-PS additive mixturesrdquo Indian Journal of Technology vol 29pp 589ndash594 2004

Submit your manuscripts athttpwwwhindawicom

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NanotechnologyHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

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CoatingsJournal of

Advances in

Materials Science and EngineeringHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Smart Materials Research



MetallurgyJournal of


BioMed Research International

MaterialsJournal of


Nano

materials


Journal ofNanomaterials


Table 1 IR frequencies and elemental analysis data for the complex

IR Element observedcalculated] (cmminus1) Assignments448 MndashN C 224221627 Ionic perchlorate N 8685753 CndashH def H 6164990 CndashN str Ni 129513271089 Ionic perchlorate1112 Bidentate1145 ClO

4

minus

1395 CndashNH2

1503 NndashH bend15702705 CndashH str29943034 NH2 (Pri)3434 OndashH (H2O)

Ni

0

20

40

60

80

100

50 100 150 200 250 300 350

Mas

s (

)

Temperature (∘C)

Figure 1 TG curve of complex in static air atmosphere

light green crystals of desired complex were obtained Thecrystals were washed with alcohol and dried

Caution Perchlorates are explosivesThey should be handledwith care However I have not found any problem during allexperimental procedures

23 Characterisation Characterisation of complex was doneby elemental analysis (C H N Thermo Finnigan Flash EA1112 CHNS analyzer) infrared [15ndash17] (Perkin Elmer FT-IRspectrometer) UV-VIS spectroscopy and thermogravimetry(Table 1)

24 Thermal Analysis

241 TG in Air Thermogravimetry in static air with heatingrate of 10∘Cmin (Figure 1) was recorded using an indige-nously fabricated TG apparatus [18] (sample mass 20mg)

100 400300200 500 600 700

0

40

140

120

80

180

DTGTG

Ni

0

20

40

60

80

100

Mas

s (

)

DTA

minus20

Hea

t flow

(mW

)

Temperature (∘C)

Figure 2 TG-DTG-DTA curve of complex in flowing nitrogenatmosphere

242 Simultaneous TG-DTG-DTA These traces were ob-tained in flowing nitrogen atmosphere (100mLmin) samplewas sim25mg at a heating rate of 10∘Cmin (Figure 2 Table 2)

243 Isothermal TG Isothermal TG (Figure 3) was recordedin static air atmosphere using the same indigenously fab-ricated TG apparatus as mentioned earlier at five differenttemperatures (200 210 220 230 and 240∘C) Sample masstaken was 10mg and readings were recorded for 30 decom-position

244 Kinetic Analysis Kinetics of decomposition has beeninvestigated using isothermal TG data using model fitting(Table 3) [19] and isoconversional method [20 21] Variationof activation energy with extent of conversion 120572 is shown inFigure 4

245 Explosion Delay Experiments This experiment wasperformed using tube furnace technique [22] (sample mass10mg) at temperatures of 280 300 320 340 and 360∘Cwithin experimental limit of plusmn1∘C (Table 4) 119863

119864data were

fitted in Arrhenius equation

119863

119864= 119860 exp 119864

lowast

119877119879

(1)

where 119860 is the Arrhenius factor 119864lowast is the activation energyfor explosion 119879 is absolute temperature and 119877 is the gasconstant A plot of ln119863

119864versus 1119879 is presented in Figure 5

3 Results and Discussion

Table 1 containing elemental analysis and IR data showsa good agreement between observed and calculated per-centages of C H N and Ni The FT-IR spectra of thecomplex revealed bands at 448 cmminus1 assigned to ](MndashN)627 and 1089 cmminus1 assigned to ionic perchlorate and 1112and 1145 cmminus1 assigned to bidentate perchlorate ion (C

2Vsymmetry) [22] A broad peak at 3434 cmminus1 is due to ](OndashH)of coordinated water Other peaks are according to standardtext In the UV-VIS spectrum the absorption maxima at263 nm is due to n rarr 120587lowast transition and a peak at 378 nmis assigned for 3A

2g(F) rarr3T1g(P) overlapping with charge







0

02

04

06

08

1

0 20 40 60 80 100 120Time (min)

Ni

200

120572






2Vsymmetry)


0

10

20

30

40

50

0 02 04 06 08 1

Ni

120572

E(k

J mol

minus1)




2(ClO4)]ClO



2




119863

119864119863


119864


123 93 83 58 54 309 09842 minus1915

0

2

4

6

000155 000165 000175 000185

Ni

1T

ln D

E





4

minusH2O

997888997888997888997888997888997888997888997888rarr


3(ClO4)]ClO

4


4

minusn-pa997888997888997888997888997888997888997888997888997888997888rarr


2(ClO4)]ClO

4


4


(2)











4 Conclusion





Acknowledgments


References














3) featuring a






















CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials









0

02

04

06

08

1

0 20 40 60 80 100 120Time (min)

Ni

200

120572






2Vsymmetry)


0

10

20

30

40

50

0 02 04 06 08 1

Ni

120572

E(k

J mol

minus1)




2(ClO4)]ClO



2




119863

119864119863


119864


123 93 83 58 54 309 09842 minus1915

0

2

4

6

000155 000165 000175 000185

Ni

1T

ln D

E





4

minusH2O

997888997888997888997888997888997888997888997888rarr


3(ClO4)]ClO

4


4

minusn-pa997888997888997888997888997888997888997888997888997888997888rarr


2(ClO4)]ClO

4


4


(2)











4 Conclusion





Acknowledgments


References














3) featuring a






















CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials





119863

119864119863


119864


123 93 83 58 54 309 09842 minus1915

0

2

4

6

000155 000165 000175 000185

Ni

1T

ln D

E





4

minusH2O

997888997888997888997888997888997888997888997888rarr


3(ClO4)]ClO

4


4

minusn-pa997888997888997888997888997888997888997888997888997888997888rarr


2(ClO4)]ClO

4


4


(2)











4 Conclusion





Acknowledgments


References














3) featuring a






















CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials












3) featuring a






















CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials










CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials



research article kinetics of thermolysis of nickel(ii...

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