Study of new rubber to steel adhesive systems based on Co(II) and Cu(II) sulphides coats

Transcription

1 Study of new ruer to steel dhesive systems sed on Co(II) nd Cu(II) sulphides cots Ivn Lj 1,*, Drin Ondrušová 1, Andrej Duec 1, Mrin Pjtášová 1, Mrcel Kohutir 1, Bet Pecušová 1 1 Alexnder Duček University of Trenčín, Fculty of Industril Technologies in Púchov, I. Krsku 941/30, Púchov, Slovk Repulic Astrct. The presented pper dels with the preprtion of new ruer to steel dhesive systems using the steel surfce tretment with deposition of dhesive cots sed on Co(II) nd Cu(II) sulphides. Efficiency of new prepred dhesive systems contining Co(II) nd Cu(II) sulphides hs een compred with the efficiency of doule lyer dhesive system commonly used in industry. The chemicl composition of prepred dhesive systems ws determined using the EDX nlysis. Scnning Electron Microscopy (SEM) ws used for study of topogrphy nd microstructure of prepred ruer to steel dhesive systems (Co(II), Cu(II) sulphide, doule lyer dhesive system). For determintion of dhesion strength etween ruer lends nd metl pieces with vrious dhesive systems deposited on these pieces, the test ccording to ASTM D429 stndrd relting to Ruer to metl dhesion, method A ws used. For ll test smples, the sme type of ruer lend nd the sme curing conditions hve een used. Keywords: Ruer lend, dhesive systems, colt sulphide, copper sulphide, doule dhesive system 1 Introduction In mny pplictions of ruer lends, the reinforcing mterils is used for chievement of the required properties. Adhesive systems hve importnt function in the interfce etween two min mterils, such s ruer lend nd steel reinforcement mteril. There re mny types of dhesive systems (e.g. dhesive systems mixed into ruer lends, spry ppliction dhesive systems nd two components dhesive systems), the effectivity of which is influenced y mny fctors. Effectivity of dhesive systems cn e defined y strength of joint, which is expressed s force (N) on the surfce of the joint (mm 2 ). The other fctors, tht ffect effectivity of dhesive systems re: composition of ruer lend, type of reinforcing mteril nd surfce tretment of reinforcing mteril. The grdul development of reinforcing mterils leds to development nd innovtion of the dhesive systems. Adhesive systems hve ppliction in mny sectors of industry, where there is requirement to ensure onding of ruer lends nd reinforcing mterils, such s steel, fiers or textile. The utomoile industry represent one of the lrgest consumers of * Corresponding uthor: ivn.lj@fpt.tnuni.sk Reviewers: Andrej Czán, Ev Tillová The Authors, pulished y EDP Sciences. This is n open ccess rticle distriuted under the terms of the Cretive Commons Attriution License 4.0 (

2 dhesive systems, ecuse these systems re used for tyres, silenlocks nd selings. The life time s well s sfety of finl product cn e ensured the hight strength of joint. 2 Experimentl 2.1 Mterils nd methods Preprtion of Co(II) nd Cu(II) sulphides cots Co(II) nd Cu(II) sulphides cots hve een prepred using the dsorption procedure involving tretment of the working electrode representing the tested metl piece in solution contining hepthydrte of colt sulphte (high purity, purchsed from Kemcore), hydroxylmine sulphte, nd mmoni (ph 12) for Co(II) sulphide cot nd penthydrte of copper sulphte, hydroxylmine nd mmoni(ph 12) for Cu(II) sulphide cot, respectively. After preprtion of cots, the reduction to sulphides in the solution of sodium sulphide ws crried out nd then the smples were wshed with distilled wter [1, 2] Preprtion of smples for dhesion test Steel test smples hve een prepred ccording to ASTM D 429 method A (ASTM D429 - Ruer to Metl Adhesion Test Equipment). For preprtion of metl prts of test smples, the common type of steel ws used. The test smples preprtion procedure is in Tle 1. Tle 1. Smple numer nd following preprtion procedure Smple numer Smple 1 Smple 2 Smple 3 Smple 4 Smple 5 Smple 6 Smple 7 Smple 8 Smple 9 Smple 10 Smple 11 Test smples preprtion procedure smple without surfce tretment, only degresing in KOH surfces of smple treted only with sndlsting surfces of smple treted only with phosphting sndlsting with following ppliction of commonly used doule dhesive system (this process is commonly used in industry) phosphting with following ppliction of commonly used doule dhesive system (this process is commonly used in industry) sndlsting with following preprtion of Co(II) sulphide cot sndlsting with following preprtion of Cu(II) sulphide cot phosphting with following preprtion of Co(II) sulphide cot phosphting with following preprtion of Cu(II) sulphide cot degresing in KOH solution, etching in HCl, with following preprtion of Co(II) sulphide cot degresing in KOH solution, etching in HCl, with following preprtion of Cu(II) sulphide cot All of the mentioned steel test smples (Fig. 1) were used for the preprtion of smples for dhesion test, where these steel smples were comined with the industrilly used ruer lend of the sme composition. Smples for dhesion test were cured in the curing press t the temperture of 160 C during 6 minutes. After the curing procedure, the 2

3 smples were conditioned for 16 hours. After the condition, ll smples were tested with HOUNSFIELD H20K-W tensile testing mchine. Fig. 1. Steel test smple fter preprtion procedure : ) Smple 1, ) Smple 2, c) Smple 3, d) Smple 4 nd smple 5 the sme imge of surfce fter preprtion procedure, e) Smple 6, f) Smple 7, g) Smple 8, h) Smple 9, i) Smple 10, j) Smple Testing nd nlysis EDX nlysis The chemicl composition of prepred Co(II) nd Cu(II) sulphides cots nd chemicl composition of sic steel mteril ws evluted using Shimdzu EDX-7000 Energy Dispersive X-ry Fluorescence Spectrometer. Microstructurl SEM nlysis Microstructure nd thickness of Co(II) nd Cu(II) cots were studied using TESCAN VEGA 3 scnning electron microscope. The micronlysis ws focused on the evlution of topogrphy nd microrelief of the sulphide lyers using detector operting in the secondry electrons mode in high vcuum. Adhesion test Adhesion test of prepred test smples ws performed using the HOUNSFIELD H20K-W tensile testing mchine. Adhesive strength ws clculted using the eqution [3]: R A = dhesion strength (N.mm -2 ) F A = mximum force (N) A A = surfce of smple (mm 2 ) (1) 3

4 3 Results nd discussion In results nd discussion, there re summrized the results of : EDX nlysis, tensile test of smples with dhesive strength, study of topogrphy nd microrelief of prepred sulphides cots nd doule dhesive system. 3.1 Energy Dispersive X-Ry Anlysis (EDX) Prepred Co(II) nd Cu(II) sulphides cots nd sic mteril were sujected to the EDX nlysis for demonstrtion of chemicl composition. In Tle 2., there re the chemicl composition of sic mteril (steel) nd the chemicl compositions of the prepred sulphides cots. The common type of steel ws used for preprtion of metl prts of test smples (sic mteril). Smple Tle 2. Chemicl composition of Co(II) nd Cu(II) sulphide cot nd sic mteril Elements Fe Mn Cr Cu Co S Bsic mteril Bsic mteril + Cu(II) sulphide cot Bsic mteril + Co(II) sulphide cot In oth cses, sulphide cots were too thin, nd therefore EDX nlysis mchine mesured lso the sic mteril together with cots. Thickness of sulphides cots ws mesured with scnning electron microscope. 3.2 Microstructurl SEM nlysis In the Figs there re SEM imges of topogrphy nd microrelief of doule dhesive system, Co(II) nd Cu(II) sulphides cots. Fig. 2. SEM imges of doule dhesive system ) SE detection, ) BSE detection 4

5 In figure 2, it cn e seen the structure of doule dhesive system. In the figure 2, it cn e seen the interfce etween doule dhesive system nd sic mteril. It is interesting tht in the figure 2 (BSE detection of doule dhesive system, which is compound of two lyers), the interfce etween two lyers in doule dhesive system is not visile. From this finding it possile to ssume tht the lyers in doule dhesive systems hve similr composition. Lighter re in the figure 2 (SE detection) represents only the surfce of smple, ecuse the smple ws not plced perpendiculrly in the holder. Fig. 3. SEM imges of doule dhesive system ) thickness mesurement, ) detil of structure of doule dhesive system From the figure 3, it is visile tht thickness of doule dhesive system ws uniform in the intervl from 78 to 102 μm. Even the detiled view of doule dhesive system did not revel the interfce etween two individul lyers of doule dhesive system. Fig. 4. SEM imges of Co(II) sulphide cot ) SE detection, ) BSE detection In figure 4, the structure of Co(II) sulphide cot cn e seen. In figure 4, the interfce etween Co(II) sulphide cot nd sic mteril cn e seen. In figure 4, the pores, which re in cot of Co(II) sulphide, re visile. 5

6 Fig. 5. SEM imges of Co(II) sulphide cot ) thickness mesurement, ) detil of structure of Co(II) sulphide cot Prepred Co(II) sulphide cot is uniform nd thickness of cot ws in intervl from 85 to 110 μm. In figure 5, crystls in the cot cn e seen. Detiled view (Fig. 5) ws compred with the imges of colt sulphides from scientific pper [4]. From comprison of imges, it is possile to consider tht crystls in figure 5 re Co(II) sulphide crystls. In detiled view of Co(II) sulphide cot (Fig. 5), there re the pores visile in cot (drk res), nd these pores cn e considered s eneficil feture for dhesion strength of this cot. Fig. 6. SEM imges of Cu(II) sulphide cot ) SE detection, ) BSE detection In figure 6, the structure of prepred Cu(II) sulphide cot cn e seen. In figure 6, there re the visile crcks in the cot, which cn led to rittleness of prepred cot. In figure 6, there is lso the visile crck in interfce re etween Cu(II) sulphide cot nd sic mteril. 6

7 Fig. 7. SEM inges of Cu(II) sulphide cot ) thickness mesurement, ) detil of structure of Cu(II) sulphide cot Prepred Cu(II) sulphide cot hd greter thickness in comprison with doule dhesive system nd Co(II) sulphide cot. The figure 7 represents mesurement of Cu(II) sulphide cot. Thickness of prepred cot ws in intervl from 195 to 207 μm. The detiled view (Fig. 7) reveled the more visile pores in Cu(II) sulphide cot in comprison with Co(II) sulphide cot. This phenomenon cn e eneficil feture for dhesion strength of this cot. 3.3 Adhesion test In Tle 3, there re records of the results (mximum force, dhesion strength) of dhesion test of prepred smples. These results re lso grphiclly depicted in Fig. 8 nd Fig. 9. During the test of dhesive strength, two cses of rekge my occur. There cn e either rekge in interfce etween ruer lend nd sic metl prt or rekge in ruer lend (it ws seen in the cse of smple 4 nd 5) nd it mens tht dhesive strength is higher tht strength of ruer lend. Tle 3. Vlues of mximum force nd dhesive strength of smples Smple numer Mximum force [N] Adhesion strength [N.mm 2 ] Smple Smple Smple Smple Smple Smple Smple Smple Smple Smple Smple According to the otined results of dhesion test, it cn e concluded tht mximum force nd thus mximum dhesive strength were seen for the smple 4, the preprtion of which ws sed on sndlsting with following ppliction of commonly used doule dhesive system. The second highest vlue of mximum force nd dhesive strength ws represented y the smple 5, which ws prepred y phosphting with following ppliction of commonly 7

8 used doule dhesive system. These two smples present the commonly used process in industry. In contrst, the miniml vlues of mesured chrcteristics were seen for Smple 1, which ws only degresed in KOH. Adhesive strength of Smple 1 hd only mechnicl chrcter. Mechnicl chrcter of dhesive strength is sed on mechnicl interlocking. From results of dhesion test, it cn e concluded, tht surfce tretment cn influence the vlue of dhesive strength nd it ws confirmed y the results of dhesive strength for smple 2 nd 3. Smple 2 nd 3 hd higher vlues of dhesive strength thn Smple 1. Incresing of dhesive strength my e cused y greter mount of pores nd cvities fter surfce tretment, ecuse there is the increse in mount of mechnicl interlocking. Influence of surfce tretment (sndlsting, phosphting) ws reflected in Smples with new dhesive systems sed on Co(II) nd Cu(II) sulphides. In comprison with the other smples with Cu(II) sulphide cot, the highest vlue of dhesive strength ws reched y smple 7. The smple 6 hd the highest vlue of dhesive strength in comprison with the other smples with Co(II) sulphide cot. Before preprtion of new dhesive system, surfces of smples 6 nd 7 were treted with sndlsting. The mutul comprison of the smples with new dhesive systems reveled the lowest vlues of dhesive strength in reltion to smple 9 (phosphting with following preprtion of Cu(II) sulphide cot)s well s smple 10, which is sed on Co(II) sulphide cot (degresing in KOH solution, etching in HCl, with following preprtion of Co(II) sulphide cot). Mximum force (N) Mximum force (N) Smple numer Fig. 8. Grphicl representtion of vlues of mximum force [N] 8

9 Adhesive strength (N.mm 2 ) Adhesive strength (N.mm 2 ) 8,0 7,0 6,0 5,0 4,0 3,0 2,0 1,0 0,0 Smple numer Fig. 9. Grphicl representtion of dhesion strength (N.mm 2 ) Conclusion Results of EXD nlysis hve confirmed the presence of Co, Cu nd S elements contined in Co(II) sulphide cot nd Cu(II) sulphide cot. SEM microstructurl nlysis ws used for mesurement of thickness of ll dhesive systems nd structure of dhesive systems. According to the otined results of dhesion test, it cn e concluded tht mximum force nd thus mximum dhesive strength were reveled in the cse of the Smple 4, which ws prepred y sndlsting with following ppliction of commonly used doule dhesive system. The second highest vlue of mximum force nd dhesive strength ws seen for smple 5, which ws prepred y phosphting with following ppliction of commonly used doule dhesive system. From the Smples with new dhesive systems, Smple 7 with dhesive system sed on Cu(II) sulphide cot exhiited the highest vlue of dhesive strength. New dhesive systems sed on Co(II) nd Cu(II) sulphide cots reched lower vlues thn doule dhesive system, which is commonly used in industry. Bsed on the otined results nd following nlysis, it cn e summrised tht the surfce tretment hd influence on dhesive strength. Surfce tretment hd lso influence on dhesive strength of ll dhesive systems. VEGA No. 1/0589/17, VEGA No. 1/0649/17, KEGA 007TnUAD-4/2017, project Center forqulitytesting nd dignostics of mterils, ITMS code , Opertionl Progrm Reserch nd Development, EF of Reg. Development References 1. G. Vliuliene, A. Ţeliene, V. Jsulitiene, I. Movzginskiene, Composition of the Colt Sulfide Coting fter Its Electrochemicl Reduction. Russin Journl of Applied Chemistry 76 (1), (2003) 2. N. Petršuskienė, R. Stokienė, S. Ţlenkienė, V. Jnickis, Formtion of colt sulfide lyers on polymide 6 y sorption diffusion method using solutions of dodecthionic cid, H 2 S 12 O 6. Chemij 26 (2), (2015) 9

10 3. J. Škývr, Hodnocení kvlity spoje kov-pryž. (Univerzit Tomáše Bti ve Zlíně, Fkult technologická, 106, 2016) 4. H. Emdi, M. Slvti-Nisri, F. Dvr, Synthesis nd chrcteriztion of colt sulfide nnocrystls in the presence of thioglycolic cid vi simple hydrotherml method. Polyhedron 31, (2012) 5. ASTM D429 - Ruer to Metl Adhesion Test Equipment. Test Resources. [online] 6. I. Lj, D. Ondrušová, A. Duec, M. Pjtášová, M. Kohutir, Preprtion nd study of new ruer to steel dhesive systems. Priemyselná toxikológi 2017, 37. Medzinárodné vedecké sympózium, Brtislv, Slovenská technická univerzit, (2017) 10