CHAN Chin Han 1*, Max ONG Chong Hup 2, TAN Winie 1, Mohamad Kamal HARUN 1, LEE Jia Yin 3

Transcription

1 Technical aticle 1 Compae functions of FTIR softwae fo stuctual analysis of epoxy paints on steel stuctues fo coating fingepinting cetificate CHAN Chin Han 1*, Max ONG Chong Hup 2, TAN Winie 1, Mohamad Kamal HARUN 1, LEE Jia Yin 3 1 Univesiti Teknologi MARA, Faculty of Applied Sciences, Shah Alam, Selango, Malaysia cchan_25@yahoo.com.sg ( * coesponding autho) tan_winie@yahoo.com, mkhaun@gmail.com 2 Noimax Sdn Bhd, 2, Jalan TPP 5/17, Taman Peindustian Puchong, Seksyen 5, Puchong, Selango, Malaysia maxong54@gmail.com 3 Reseach Instuments (M) Sdn. Bhd., D7-1-G, Block D7, Pusat Pedagangan Dana 1, Jalan PJU 1A/46, Petaling Jaya, Selango, Malaysia michelle.lee@i.com.my Abstact This pogessive aticle on Fouie-tansfom infaed (FTIR) stuctual analysis showcases the pacticality and simplicity of the povision of Coating Fingepint Cetificate fo 2-component epoxy coatings fo the supply of polymeic coatings fom local paint manufactues as quality assuance equiement of the coatings supplied. Fingepinting egions of FTIR fo epoxy esin and hadene ae poposed and the confidence level of acceptance fo quality assuance and quality contol (QA & QC) is suggested at 90.0%. We conclude that, the stuctual analysis by FTIR fo complete Coating Fingepint Cetificate fo epoxy esin and hadene is epoducible when High Sensitivity Compae featue of the FTIR softwae is to be stictly followed. This algoithm depends on x- (wavenumbe) and y- (absobance) vectos. This function is able to disciminate minute diffeence of diffeent components as well as the compositional change of the components among samples. Besides, ejection o acceptance of the samples can be easily done by setting the theshold value at 0.90 using High Sensitivity Compae featue of the FTIR softwae. Finally, we attempt to compae inoganic filles fo polyme coatings (e.g. Rutile o Anatase of TiO 2 ) using FTIR, which seems to be pactical as well. Intoduction Cuently, only 2-component epoxy coating (intemediate mateials) was used in the evaluation of the pacticality of the stuctual analysis by Fouie-tansfom infaed (FTIR) fo complete Coating Fingepint Cetificate [1] intoduced by Institute of Mateials, Malaysia (IMM) Task Foce on Coatings Fingepinting. Deliveies of 1 st phase of the task foce ( ) ae: 1. Tentative Coating Fingepint Cetificate fo 2- component intemediate mateials of epoxy coatings was pesented. 2. FTIR is a simple and eliable tool fo the study of epoducibility (i.e. to fingepint) of the epoxies and hadenes as well as to diffeentiate diffeenttypes of epoxies and hadenes without any intusion of paint fomulations. 3. Fingepinting egions of FTIR fo epoxy esin and hadene ae poposed and the confidence level of acceptance fo quality assuance and quality contol (QA& QC) is poposed at 90.0%. July Septembe 2014 Issue 8 We would like to ecapitulate hee, the complete Coating Fingepint Cetificate [1] fo polymeic coatings consist of two pats, i.e. (1) physical analyses (e.g. viscosity, density, colo code, non-volatile matte (by mass), weight solid of Zn metal/total Zn etc; and (2) stuctual analysis by FTIR (which shall be caied out immediately afte each batch of the poduction in the paint factoy). Fo this aticle, we ae looking into the Compae functions of FTIR softwae fo stuctual analysis of 2-component intemediate mateials of epoxy coatings, which seve as an impotant tool fo QA & QC fo the batch-to-batch epoducibility of the epoxies and hadenes as well as fo diffeent epoxies and hadenes by estimation of coelation (). We shall emphasize hee once moe, this FTIR analysis coupled with the consideations needed using the Compae functions of FTIR softwae shall not be limited to 2-component epoxy coating, but has to be extended to inoganic zinc coating, epoxy-zinc coating, polyuethane coating, acylic coating, polyeste coating etc. Expeimental FTIR sample collection Sample collection was published in ef. [2] and is biefly sketched hee. Polymeic coatings, i.e. epoxy esin (o base) and hadene (o cuing agent) fom local Paint Manufactue A wee analyzed. A total of 3 samples/batch o 3 samples/ mixing tank with minimal of 50 g of sample mass fo epoxy esin as well as hadene wee supplied. Sampling of samples at the end stage of poduction (befoe packing) was done fom Top, Middle and Bottom of the mixing tanks. Samples wee sent fo FTIR analysis within 4 days afte sample collection. A total of 2 batches of samples wee used fo this study on the epoducibility of the esults. These samples wee analyzed as eceived. Epoxy_BxT(o M o B)y-z denotes epoxy esin of x th Batch fo y th sample at the location of Top (o Middle o Bottom) and with the z th FTIR scanning. Analogue sample coding was adopted fo Hadene_ BxT(o M o B)y-z. FTIR analysis To fingepint polymeic coatings, ASTM D [3] standad is followed. As mentioned befoe [4], thee is lack of guide in ASTM D fo the intepetation of FTIR 25

2 specta, i.e. the pactical appoaches on estimation of the degee of similaity (o coelation) () between two FTIR specta fo the same o diffeent polymeic coatings. Spectoscopic studies wee pefomed on the intemediate mateials of polymeic coatings, i.e. epoxy esin and hadene independently. FTIR analysis was caied out using the Attenuated Total Reflection accessoy (ATR) on Nicolet is5 (Madison, UK). FTIR specta wee ecoded in the tansmittance mode ove the ange of by aveaging 32 scans at a maximum esolution of 4. Tiplicate analysis fo each sample was caied out, whee a fesh sample was used fo each analysis. The mateial of ATR cystal is Diamond coated with ZnSe gemanium. The specta of FTIR wee analyzed by OMNIC Softwae Suite (Madison, UK). Quality contol of the intemediate mateials Absobance specta wee baseline coected. The aveage FTIR spectum of sample fom Top, Middle and Bottom of the mixing tank was adopted as the efeence spectum (c.f. ef. [2].) The degee of similaity, which is temed as coelation (), of a spectum was geneated by compaing the specta of the samples to that of the efeence using the Nomal Compae OR High Sensitivity Compae featues of the FTIR softwae. Degee of similaity is diectly popotional to quantities of, i.e. = 1 epesents complete matching of the sample spectum to that of the efeence spectum. The standad compae algoithms commonly used in infaed (IR) spectoscopy ae well suited to identify unknown mateials o to disciminate between mateials that ae significantly diffeent, i.e. coelation compae algoithm of the FTIR softwae depends on x-vecto (wavenumbe / ) only. Howeve, these standad algoithms often lack the sensitivity equied when the mateials being compaed only exhibit vey minute diffeences, e.g. fo outine quality assuance and quality contol of batch-to-batch poduction of the intemediate mateials of the epoxy paints. The Compae QCheck featue of the OMNIC Softwae (belongs to Nomal Compae featue of the FTIR softwae), is a single scale x-coelation. This compae function depends mainly on the stuctual analysis of the component(s) of the intemediate mateials of epoxy o hadene. This means, this compae function is not sensitive to compositional change of the simila stuctue(s) (o slight diffeent stuctues) of epoxy o hadene. Vey often, 1 is obseved even if thee is significant vaiation of composition change of epoxy o hadene. This function is only useful fo qualitative check to disciminate between obviously diffeent mateials. On othe hand, the high sensitivity function in OMNIC QCheck (belongs to High Sensitivity Compae featue of the FTIR softwae) effectively povides bette sensitivity when the degee of similaity between samples is high. This algoithm depends on x- (wavenumbe) and y- (absobance) vectos. This function is able to disciminate minute diffeence of diffeent components as well as the compositional change of the components among samples. Fo this study, quantities (fom 0 to 1) wee estimated fistly fo spectum with wavenumbes fom (i) , and subsequently fom (ii) 1300 & (iii) fo epoxy esin; and (iv) 1400 fo hadene. July Septembe 2014 Issue 8 Results and discussion Geneation of efeence FTIR spectum fom Top, Middle and Bottom of the mixing tank wee sketched in ef. [2]. Afte automatic baseline coection, the specta in tansmittance mode shall be conveted to absobance mode. The thee specta fom Top, Middle and Bottom wee aveaged using the commecial FTIR softwae fo the geneation of efeence spectum fo Epoxy1 and Hadene1 (efe Figue 1). Figue 1 Refeence specta fo Epoxy1 and Hadene1 Homogeneity of epoxies and hadenes at Top, Middle and Bottom of the mixing tanks and epoducibility of the epoxies (o hadenes) of Batch 2 as compaed to Batch 1 by estimation of The degee of similaity () (in tem of paint fomulation), of (o Hadene1_B1) collected fom Top, Middle and Bottom of the mixing tank was geneated by compaing the specta of the sample to that of the efeence spectum ( o Hadene1_B1) using the Nomal and High Sensitivity featues of the FTIR softwae. Quantities fo Epoxy1 and Hadne1 and ae tabulated in Tables 1 and 2. Table 1A Estimation of fo Refeence to T(o M o B) fo 1 st FTIR scanning with High Sensitivity Compae featue (epint with pemission fom ef. [2]) Refeence Spectum B Refeence fo Epoxy1 _B1M Epoxy1 _B1 Epoxy1 _B1T Epoxy1 _B2B Epoxy1_B2M Epoxy1_B2T

3 Table 1B Estimation of fo Refeence to T(o M o B) fo 1 st FTIR scanning with Nomal Compae featue Refeence Spectum B Refeence Epoxy1 _B1M fo Epoxy1 _B1T Epoxy1 _B2B Epoxy1_B2M Epoxy1_B2T The quantities in this study ae coelated to the paint fomulation. It is elatively common to set 0.90 as the acceptable toleance in ode to suggest the similaity of diffeent samples o diffeent batches of simila samples. All epoxies and hadene ae homogenous in the mixing fo Epoxies o Hadenne 1, 2 and 3 fo Batches 1 and 2 at diffeent locations of Top, Middle and Bottom of the mixing tanks. Besides, quantities 0.90 ae ecoded fo Epoxies (o Hadenes) 1, 2 and 3 when Batch 1 was compaed to Batch 2 at diffeent locations of Top, Middle and Bottom of the mixing tanks. In all cases, High_Sensivity < Nomal_Sensitivity ae noted. In some cases, Nomal_Sensitivity = ae ecoded, which ae athe unealistic, i.e. 100% matching between the Refeence spectum and the sample. Hence, we popose hee, High_Sensivity is moe suitable to be used fo checking the homogeneity of epoxies and hadenes at Top, Middle and Bottom of the mixing tanks and the batch-to-batch epoducibility of the epoxies and hadenes Table 2A Estimation of fo Refeence Hadene1_B1 to Hadene1_B1T(o M o B) fo 1 st FTIR scanning with High Sensitivity Compae featue (epint with pemission fom ef. [2]) Refeence Spectum Hadene1_B1B Refeence fo Hadene1_B1 Hadene1_B1M Table 2B Estimation of fo Refeence Hadene1_B1 to Hadene1_B1T(o M o B) fo 1 st FTIR scanning with Nomal Compae featue Refeence Spectum Hadene1_B1B Refeence fo Hadene1_B1M Hadene1_B1 Hadene1_B1T Hadene1_B2B Hadene1_B2M Hadene1_B2T To estimate the fo Epoxy1 as compaed to Epoxy2, Epoxy3 and PU; and Hadene1 as compaed to Hadene2, Hadene3 and NCO Epoxy1, Epoxy2, Epoxy3 and poly(uethane) (PU) ae with diffeent paint fomulations. Analogues to epoxy, Hadene1, Hadene2, Hadene3 and isocyanate (NCO) ae with diffeent paint fomulations. Tables 3 and 4 clealy demonstate that FTIR analysis is a simple tool to diffeentiate diffeent types of epoxies, between epoxy & PU, diffeent types of hadenes; and between hadene & NCO with < 0.90 when High Sensitivity Compae featue is used. Again, In all cases, High_Sensivity < Nomal_Sensitivity ae noted. When Epoxy1 is compaed to Epoxy2 and Epoxy3, Nomal_Sensitivity 0.90 ae ecoded, which ae unacceptable because Epoxy1, Epoxy2 and Epoxy3 ae having stuctual and compositional diffeences. Hence, we emphasize hee, High_Sensivity is moe suitable to be used fo the compaison of diffeent types of epoxies and hadenes. Table 3A Estimation of fo Refeence to Epoxy2, Epoxy 3 and PU with High Sensitivity Compae featue (epint with pemission fom ef. [2]) Sample Code Epoxy2 _B Epoxy3_ B1 PU_B Refeence Spectum Refeence fo Table 3B Estimation of fo Refeence to Epoxy2, Epoxy 3 and PU with Nomal Compae featue Hadene1_B1T Hadene1_B2B Hadene1_B2M Hadene1_B2T Epoxy2 _B Epoxy3_B PU_B Refeence Spectum Refeence fo July Septembe 2014 Issue 8 27

4 Table 4A Estimation of fo Refeence Hadne1_B1 to Hadene2, Hadene3 and NCO with High Sensitivity Compae featue (epint with pemission fom ef. [2]) Sample Code Refeence Spectum Hadene2_B1 Hadene3_B Refeence fo Hadene1_B1 NCO_B Table 4B Estimation of fo Refeence Hadne1_B1 to Hadene2, Hadene3 and NCO with Nomal Compae featue Refeence Spectum Hadene2_B Refeence Hadene3_B fo Hadene1_B1 NCO_B Compaing the inoganic filles fo polyme coatings Titanium dioxide (TiO 2 ), the inoganic pigment, is commonly added into potective polymeic coatings. TiO 2 is commecially available in two cystal foms - Anatase and Rutile. The Rutile pigments ae pefeed ove Anatase pigments fo potective coatings, because they scatte light moe efficiently, ae moe stable, and ae less likely to catalyze photodegadation. Rutile is moe expensive than Anatese. Hence, it may happen that the Rutile may be subsituted by Anatase if efomulation of paints is attempted. Identification of Anatase o Rutile o the mixtues of both is often made by X-ay analysis (Test Method: ASTM D 3720 [5]), whee the testing cost is athe high. By using commecial FTIR softwae, we ae able to compae Rutile and Anatase TiO 2 specta as depicted in Figue 4. The quantity High_Sensivity = 0.3 (o Nomal_Sensitivity = 0.6) when Rutile is compaed to Anatase. Setting the theshold to eject o to accept one sample using High Sensitivity Compae featue Fo outine QA & QC check of FTIR, which shall be caied out immediately afte each batch of the poduction in the paint factoy, can be done easily with the assistance fom the commecial FTIR softwae. As in this case, when the High Sensitivity Compae featue is opted and the theshold can be set at 0.90 (equivalent to 0.90) (c.f. Figue 2), we can immediately REJECT Epoxy2, Epoxy3 and PU when these samples ae compaed to Epoxy1 (c.f. Figue 3) by simply efeing to the PASS o FAIL esults displayed. Figue 4 FTIR specta extacted fom the Polyme Libay of OMNIC softwae fo Rutile and Anatase TiO 2 Conclusion We conclude hee: 1. The stuctual analysis by FTIR fo complete Coating Fingepint Cetificate fo epoxy esin and hadene is simple and epoducible when High Sensitivity Compae featue of the FTIR softwae is to be stictly followed. 2. Rejection o acceptance of the samples can be easily done by setting the theshold value at 0.90 using High Sensitivity Compae featue of the FTIR softwae. 3. Compaing the inoganic filles fo polyme coatings (e.g. Rutile o Anatase of TiO 2 ) is also pactical by using FTIR. Figue 2 Setting the theshold to eject o to accept one sample using High Sensitivity Compae featue Figue 3 PASS o FAIL esults displayed using High Sensitivity Compae featue by setting the theshold at 0.90 July Septembe 2014 Issue 8 We note hee again, this FTIR analysis shall not be limited to 2-component epoxy coating, but has to be extended to inoganic zinc coating, epoxy-zinc coating, polyuethane coating, acylic coating, polyeste coating etc. FTIR can be used to fingepint all these types of coatings. Pogessive epots of the FTIR fingepinting studies on these types of coatings will be published in the fothcoming issues of Mateials Mind. Acknowledgement The authos gatefully acknowledge the eseach funding by Knowledge Tansfe Pogamme Gants [100-CAN(ICAN/ AIC.37/2/14) povided by Ministy of Education fo pats of the expeimental woks. Special thanks go to D. Chew Kong Chin fom Becke Industial Coatings (M) Sdn. Bhd., who povided useful tips and consideation in selection of 28

5 fingepint egions fo epoxy and hadene. Refeences Note: all the documents elated to the backgound of Coating Fingepint Cetificate can be viewed at Mohamed, N.A., Tentative Coating Fingepint Cetificate fo 2-component intemediate mateials of epoxy coatings, in Mateials Mind. 2014, Institute of Mateials, Malaysia: Selango, Malaysia. p Chan, C.H., Ong, C.H., Winie, T., Haun, M.K., and Lee, J.Y., FTIR stuctual analysis of epoxy paints on steel stuctue fo coating fingepinting cetificate as benchmak fo paint industy, in Mateials Mind. 2014, Institute of Mateials, Malaysia: Selango, Malaysia. p ASTM D , Standad guide fo FT-IR fingepinting of a non-aqueous liquid paint as supplied in the manufactue's containe. 2011, ASTM Intenational: United States. 4. Chan, C.H. and Teo, Y.Y., Fouie-tansfom infaed analysis of polymeic coatings as benchmak fo paint industy, in Mateials Mind. 2013, Institute of Mateials, Malaysia: Selango, Malaysia. p ASTM D , Standad test method fo atio of Anatase to Rutile in titanium dioxide pigments by X-Ray diffaction. 2011, ASTM Intenational: United States. Biodata CHAN Chin Han is an associate pofesso at Univesiti Teknologi MARA, Malaysia. He eseach inteest is devoted to physical popeties of macomolecules. She was appointed as Visiting Scientist at China Univesity of Petoleum, Beijing, China ( ), as Chai Pofesso on Advances in Hybid Mateials at Mahatma Gandhi Univesity, Kottayam, India (2014), National Repesentative (Malaysia) of Intenational Union of Pue and Applied Chemisty (IUPAC) fo Polyme Division ( ) etc. She has been one of the editos of Malaysian Jounal of Chemisty, Mateials Mind of Institute of Mateials, Malaysia and books published by Royal Society of Chemisty (2013) and Apple Academic Pess (2014) (distibuted by CRC Pess). I. Max ONG Chong Hup gaduated fom Queen May Univesity of London in 1977 with B.Sc.(Hons) in Mateials Engineeing. He has ove 30 yeas expeience in Coosion Contol coveing Potective Coatings, Decoative Paints, Cathodic Potection, Coosion Monitoing & Inspection, Fie Poofing Coatings, Themal Spay Coatings, and Mateials Selection - as a manufactue, sevice contacto, and technical consultant. He was involved in paint manufactuing in Dimet/Ameon Potective Coatings ( ) and Leighs Paints ( ). He is cuently the Chaiman of the Education Committee of the Institute of Mateials, Malaysia. TAN Winie is a senio lectue at School of Physics and Mateial Science, Univesiti Teknologi MARA, Malaysia. Solid State Ionics ae he main eseach aeas. She is an Associate Fellow of the Malaysian Scientific Association (2012 pesent), Council Membe of Institute of Mateials, Malaysia ( ) and membe of Malaysian Solid State Science and Technology Society (2009-pesent). She is appointed as one of the editos in Intenational Jounal of Institute of Mateials, Malaysia (IJIMM), Science Lettes, Mateials Reseach Innovation (2009) and Ameican Institute of Physics (2009). He contibution is also in the fom of witten chapte in books and ove 40 Intenational jounal publications. He eseach outcomes won he seveal medals and awads in intenational and national events. Pof. D. Mohamad Kamal HARUN is cuently the Deputy Vice Chancello (Reseach, Innovation and Entepeneuship) and head the Global Entepeneuship Reseach and Innovation Cente at Univesity Malaysia Kelantan. He was the Deputy Vice Chancello (Industial and Community Netwoking at Univesity Teknologi MARA fom He is also the Pesident and Fellow of the Institute of Mateials Malaysia, Fellow of the Intenational Institute of Plantation Management, Chaiman of the Malaysian Accedited Cetification Body fo the Asian Welding Fedeation, Membe of the Industial Consultative Council, Malaysian Petoleum Resouce Coopeation unde Pemandu and cuently is also the Cluste Head fo Industy and Innovation, National Council of Pofessos. His aeas of eseach ae in coosion potection by paints and inhibitos including the study of polymeic baie coating degadation unde atmospheic conditions. LEE Jia Yin has woked in commecial testing lab as a Technical Chemist. She is expeienced in handling vaious analytical instuments such as HPLC, LCMS, FTIR and UV spectomete. Cuently, she woks as an Application Chemist in Reseach Instuments, and specializes in Themo Fishe Scientific FTIR. She is esponsible fo installation, application taining and toubleshooting. IMM Annual Golf Shield 2014 Satuday 11 th Octobe 2014 Sungai Long Golf & County Club Repot will be published in Mateials Mind Issue no. 9 July Septembe 2014 Issue 8 29