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Effects of hydrogen on passive film and corrosion of aisi 310 stainless steel
\ PERGAMON
Corrosion Science 30 "0888# 630Ð634
E}ects of hydrogen on passive _lm and corrosion of AISI 209 stainless steel M[Z[ Yang\ Q[ Yang\ J[L[ Luo Department of Chemical and Materials Engineering\ University of Alberta\ Edmonton\ Alberta\ Canada T5G 1G5 Received 06 November 0886^ accepted 0 October 0887
Abstract The e}ects of hydrogen in AISI 209 stainless steel on pitting were investigated in a borate bu}er solution "pH 7[4#[ The pitting susceptibility was strongly in~uenced by the hydrogen in the alloy and was correlated with the semiconductive properties of the passive _lm[ Hydrogen in specimens caused a pÐn inversion for the _lm[ Þ 0888 Elsevier Science Ltd[ All rights reserved[
0[ Introduction Corrosion\ the application of cathodic protection\ electroplating and other pro! cesses are major sources of hydrogen in metals ð0\ 1Ł[ Hydrogen entering into metals has a signi_cant in~uence on the mechanical properties and electrochemical behavior of metals ð0\ 2Ð8Ł[ The nature of passive _lms on metals and alloys is the ultimate factor which controls their corrosion behavior ð09\ 00Ł[ A knowledge of the electronic structure of the passive _lm is therefore required for better understanding the corrosion process[ For this reason\ much work has been devoted to the study of the electronic properties and chemical compositions of passive _lms on metals and alloys ð09\ 01Ð03Ł[ Nevertheless\ few studies of the electronic structure of passive _lms have been carried out on hydrogen!facilitated corrosion[ In this work\ new results about the change of electronic properties of a passive _lm induced by atomic hydrogen dissolved in AISI 209 stainless steel "209 SS# are reported[ The results are also discussed by taking into account the susceptibility of such speci! mens to pitting with or without hydrogen in the specimens[ Corresponding author[ Tel[] ¦990!392!381!2210^ Fax] ¦990!392!381!1770 E!mail address] jingli[luoÝualberta[ca "J[L[ Luo# 9909!827X:88:, ! see front matter Þ 0888 Elsevier Science Ltd[ All rights reserved[ PII] S 9 9 0 9 ! 8 2 7 X " 8 7 # 9 9 0 3 6 ! 3
631
M[Z[ Yang et al[ : Corrosion Science 30 "0888# 630Ð634
1[ Experimental method The test material was commercial AISI 209 stainless steel foil of 9[0 mm thickness[ The samples were prepared by precharging hydrogen at cathodic currents of various densities for di}erent times[ Prior to the electrochemical measurements\ the charged and uncharged samples were ground with 599 grit SiC grinding papers and then rinsed using deionized water and ethanol\ successively[ A three!electrode cell was used which included a saturated calomel electrode "SCE# as reference electrode and a platinum mesh as counter electrode[ The solution for hydrogen charging was 9[4 M H1SO3 ¦149 ppm As1O2[ The solution for the impedance measurement was 9[91 M H2BO2 ¦9[994 M N1B3O6=09H1O "pH 7[34#[ Polarization was performed in the borate bu}er solution containing 0 mM Fe"CN#52− and 0 mM Fe"CN#53− [ All solutions were pre! pared with deionized water and analytical grade reagents[ The MottÐSchottky plots were determined by measuring the capacitance of the passive _lm\ C\ as a function of potential\ E\ at a rate of 01[4 mV:step in the anodic direction[ An A[C[ voltage signal\ 0 kHz in frequency and 09 mV peak to peak in magnitude\ was applied to the system[ The scanning rate of the polarization curve was 9[22 mV:s[ Prior to detecting imp! edance or measuring the polarization curve\ the working electrode was cathodically polarized to 299 mV more negative than the corrosion potential for 4 min to reduce the air!formed passive _lms[ The passivation was performed at 699 mV for 1 h to form passive _lms on the surface of the specimens prior to the impedance and Tafel slope measurements[ Electrochemical noise was recorded with an ACM Auto ZRA "zero resistance ammeter#[ Current ~uctuations were recorded between the two nominally identical working electrodes[ Potential ~uctuations were recorded between working electrodes and the reference electrode "SCE#[ The electrochemical cell for all experiments was open to air and solutions were quiescent[ All experiments were performed at room temperature[
2[ Results The passive region of 209 SS in the borate bu}er solution is from −9[1 to 9[7 V and its corrosion potential is −9[18 V[ For the sample charged at 0 mA:cm1 for 13 h\ the corrosion potential shifts toward −9[67 V and the current in the passive region increases by more than one order of magnitude[ The time dependence of noise resistance\ Rn\ de_ned as the ratio of the standard deviation of the potential ~uc! tuations to the standard deviation of the current ~uctuations ð04Ł\ for uncharged and charged samples was plotted in Fig[ 0[ The Rn of the sample cathodically charged at 0 mA:cm1 for 3 h is one order of magnitude less than the uncharged sample[ According to the de_nition of Rn\ the decrease in Rn is due to the increase of current ~uctuations resulting from the breakdown and repassivation of the passive _lm[ The optical microscopic observation con_rmed that pits occurred on the surface of the charged sample\ whereas no obvious pit was found on the optical microscopic graph for the
M[Z[ Yang et al[ : Corrosion Science 30 "0888# 630Ð634
632
Fig[ 0[ Time dependence of noise resistance for 209 SS\ uncharged "0# and charged at −0 mA:cm1 for 3 h "1#\ in the borate bu}er solution containing 9[5) FeCl2[
uncharged sample immersed in the same aggressive medium[ Therefore\ hydrogen dissolved in 209 SS signi_cantly increased the susceptibility of the alloy to pitting[ The MottÐSchottky plots\ C−1 vs[ E\ were obtained for charged and uncharged samples in a borate bu}er solution after passivation at 9[6 V for 1 h "Figure 1#[ The MottÐSchottky relation describes the potential dependence of the space charge capacity\ C\ of a semiconductor electrode under depletion conditions ð05Ł] 0
0
1
1 kT 2 DU− \ eNoo9 e C 1
"0#
where the negative sign is for p!type and the positive sign for n!type conductivity\ e is the electron charge\ N the donor density for n!type or acceptor density for p!type semiconductors\ o the relative dielectric constant of the semiconductor\ o9 the vacuum permittivity\ k Boltzmann|s constant and T absolute temperature[ DU U−Ufb
for n−type semiconducters
DU Ufb −U for p−type semiconducters\
Fig[ 1[ MottÐSchottky plot of charged and uncharged 209 SS in borate bu}er solution[
"1a# "1b#
633
M[Z[ Yang et al[ : Corrosion Science 30 "0888# 630Ð634
Fig[ 2[ Polarization curves of charged and uncharged 209 SS in borate bu}er solution containing 0 mM Fe"CN#52− :Fe"CN#53− [
where U is the electrode potential and Ufb the ~at band potential\ that is\ the charac! teristic potential of the junction where the bands are ~at throughout the solid[ Straight lines are observed in Fig[ 1 for both charged and uncharged samples[ A negative slope of the straight line for the uncharged sample corresponds to p!type conductivity and a positive slope of the straight line for the charged sample corresponds to n!type conductivity[ This inversion of conducting types of passive _lm\ induced by hydrogen entering 209 SS\ was con_rmed by the polarization curves shown in Fig[ 2[ The conducting type of electrodes can be di}erentiated by a comparison of their anodic and cathodic polarization curves obtained in a redox system ð00Ł[ According to Bianchi|s criterion ð00Ł\ when the anodic transfer coe.cient\ aA\ is less than the cathodic transfer coe.cient\ aC\ the _lm is n!type\ whereas greater aA values "i[e[\ aA 9[3# and aA×aC correspond to p!type _lms[ Gamry CMS 094 software was used to _t the data in Fig[ 2 into the SternÐGeary equation to estimate the cathodic and anodic transfer coe.cients[ For the uncharged sample\ the anodic transfer coe.cient is equal to 9[36\ greater than the cathodic one "9[01#[ However\ the charged sample produced a cathodic transfer coe.cient of 9[28 which is greater than the anodic transfer coe.cient of 9[07[ Because of the limitation of the Tafel linear region\ the MottÐSchottky method is more reliable than the transfer coe.cient criterion for determining the semiconductivity of a passive _lm[ Figure 2 is displayed in this paper is to con_rm the results of the MottÐSchottky plots\ that the passive _lm on the uncharged sample is a p!type _lm and the presence of hydrogen in 209 SS inverts the p!type passive _lm to n!type _lm[ The results exhibit that dissolved hydrogen in a specimen can induce an inversion of conductivity of the passive _lm from p! to n!type\ and n!type _lm on stainless steel has a greater pitting susceptibility than p!type _lm[ The correlation of the susceptibility of stainless steel to pitting with the conductivity type of passive _lm is consistent with the work of Bianchi et al[ ð00Ł\ who have obtained a relationship between pitting densities and transfer coe.cients for stainless steel specimens after di}erent thermal treatments[
M[Z[ Yang et al[ : Corrosion Science 30 "0888# 630Ð634
634
3[ Conclusions
0[ Susceptibility of 209 SS to pitting nucleation is strongly in~uenced by hydrogen caused by cathodically charging the sample[ 1[ Susceptibility to pitting nucleation can be correlated with the electronic properties of the passive _lm on 209 SS[ High susceptibility corresponds to n!type conductivity of the passive _lm[ On the contrary\ low susceptibility is connected with p!type conductivity[
Acknowledgements This work was supported by the Natural Sciences and Engineering Research Coun! cil of Canada[
References ð0Ł H[ Gray\ Corrosion 07 "0861# 36[ ð1Ł L[J[ Qiao\ W[Y[ Chu\ C[M[ Hsiao\ Scripta Metall[ 11 "0877# 516[ ð2Ł P[ G[ Marsh\ W[W[ Gerberich\ Stress corrosion cracking of high!strength steels[ in] R[H[ Jones "Ed[#\ Stress Corrosion Cracking[ ASM International\ Metal Park\ Ohio\ 0881\ p[ 52[ ð3Ł G[E[ Kerns\ M[T[ Wang\ R[W[ Staehle\ Stress corrosion cracking and hydrogen embrittlement in high strength steels[ in] R[W[ Staehle\ J[ Hochmann\ R[D[ McCright\ J[E[ Slater "Eds[#\ Stress Corrosion Cracking and Hydrogen Embrittlement of Iron Based Alloys[ NACE\ Houston\ 0866\ p[ 699[ ð4Ł M[ Hasegawa\ M[ Osawa\ Corrosion 28 "0872# 004[ ð5Ł L[J[ Qiao\ W[Y[ Chu\ C[M[ Xiao\ Metal[ Trans[ 13A "0882# 848[ ð6Ł H[P[ Kim\ R[H[ Song\ S[I[ Pyun\ Br[ Corros[ J[ 12 "0877# 143[ ð7Ł M[E[ Armacanqui\ R[A[ Oriani\ Corrosion 33 "0877# 585[ ð8Ł Q[ Yang\ L[J[ Qiao\ S[ Chiovelli\ J[L[ Luo\ E}ects of Hydrogen on the Pitting Susceptibility of 209 Stainless Steel\ Corrosion 43 "0887# 517[ ð09Ł C[ Sunseri\ S[ Piazza\ A[ Di Paola\ F[ Di Quarto\ J[ Electrochem[ Soc[ 023 "0876# 1309[ ð00Ł G[ Bianchi\ A[ Cerquetti\ F[ Mazza\ S[ Torchio\ in] R[W[ Staehle et al[ "Eds[#\ Localized Corrosion[ NACE\ Houston\ 0863\ p[ 288[ ð01Ł A[M[P[ Simoes\ M[G[S[ Frreira\ B[ Rondot\ M[ da Cunha Belo\ J[ Electrochem[ Soc[ 026 "0889# 71[ ð02Ł P[ Schmuki\ H[ Bohni\ J[ Electrochem[ Soc[ 028 "0881# 0897[ ð03Ł U[ Stimming\ Passivity of metals and semiconductors[ in] M[ Froment "Ed[#\ Proceedings of the Fifth International Symposium on Passivity[ Elsevier Science Publishers\ B[V[\ Amsterdam\ 0872\ p[ 366[ ð04Ł F[ Mansfeld\ C[ Chen\ C[C[ Lee\ H[ Xiao\ Corrosion Science 27 "0885# 386[ ð05Ł Y[V[ Pleskov\ Y[Y[ Gurevich\ Semiconductor Photoelectrochemistry\ Chapter 2[ Consultant Bureau\ New York 0875[
Corrosion Science 30 "0888# 630Ð634
E}ects of hydrogen on passive _lm and corrosion of AISI 209 stainless steel M[Z[ Yang\ Q[ Yang\ J[L[ Luo Department of Chemical and Materials Engineering\ University of Alberta\ Edmonton\ Alberta\ Canada T5G 1G5 Received 06 November 0886^ accepted 0 October 0887
Abstract The e}ects of hydrogen in AISI 209 stainless steel on pitting were investigated in a borate bu}er solution "pH 7[4#[ The pitting susceptibility was strongly in~uenced by the hydrogen in the alloy and was correlated with the semiconductive properties of the passive _lm[ Hydrogen in specimens caused a pÐn inversion for the _lm[ Þ 0888 Elsevier Science Ltd[ All rights reserved[
0[ Introduction Corrosion\ the application of cathodic protection\ electroplating and other pro! cesses are major sources of hydrogen in metals ð0\ 1Ł[ Hydrogen entering into metals has a signi_cant in~uence on the mechanical properties and electrochemical behavior of metals ð0\ 2Ð8Ł[ The nature of passive _lms on metals and alloys is the ultimate factor which controls their corrosion behavior ð09\ 00Ł[ A knowledge of the electronic structure of the passive _lm is therefore required for better understanding the corrosion process[ For this reason\ much work has been devoted to the study of the electronic properties and chemical compositions of passive _lms on metals and alloys ð09\ 01Ð03Ł[ Nevertheless\ few studies of the electronic structure of passive _lms have been carried out on hydrogen!facilitated corrosion[ In this work\ new results about the change of electronic properties of a passive _lm induced by atomic hydrogen dissolved in AISI 209 stainless steel "209 SS# are reported[ The results are also discussed by taking into account the susceptibility of such speci! mens to pitting with or without hydrogen in the specimens[ Corresponding author[ Tel[] ¦990!392!381!2210^ Fax] ¦990!392!381!1770 E!mail address] jingli[luoÝualberta[ca "J[L[ Luo# 9909!827X:88:, ! see front matter Þ 0888 Elsevier Science Ltd[ All rights reserved[ PII] S 9 9 0 9 ! 8 2 7 X " 8 7 # 9 9 0 3 6 ! 3
631
M[Z[ Yang et al[ : Corrosion Science 30 "0888# 630Ð634
1[ Experimental method The test material was commercial AISI 209 stainless steel foil of 9[0 mm thickness[ The samples were prepared by precharging hydrogen at cathodic currents of various densities for di}erent times[ Prior to the electrochemical measurements\ the charged and uncharged samples were ground with 599 grit SiC grinding papers and then rinsed using deionized water and ethanol\ successively[ A three!electrode cell was used which included a saturated calomel electrode "SCE# as reference electrode and a platinum mesh as counter electrode[ The solution for hydrogen charging was 9[4 M H1SO3 ¦149 ppm As1O2[ The solution for the impedance measurement was 9[91 M H2BO2 ¦9[994 M N1B3O6=09H1O "pH 7[34#[ Polarization was performed in the borate bu}er solution containing 0 mM Fe"CN#52− and 0 mM Fe"CN#53− [ All solutions were pre! pared with deionized water and analytical grade reagents[ The MottÐSchottky plots were determined by measuring the capacitance of the passive _lm\ C\ as a function of potential\ E\ at a rate of 01[4 mV:step in the anodic direction[ An A[C[ voltage signal\ 0 kHz in frequency and 09 mV peak to peak in magnitude\ was applied to the system[ The scanning rate of the polarization curve was 9[22 mV:s[ Prior to detecting imp! edance or measuring the polarization curve\ the working electrode was cathodically polarized to 299 mV more negative than the corrosion potential for 4 min to reduce the air!formed passive _lms[ The passivation was performed at 699 mV for 1 h to form passive _lms on the surface of the specimens prior to the impedance and Tafel slope measurements[ Electrochemical noise was recorded with an ACM Auto ZRA "zero resistance ammeter#[ Current ~uctuations were recorded between the two nominally identical working electrodes[ Potential ~uctuations were recorded between working electrodes and the reference electrode "SCE#[ The electrochemical cell for all experiments was open to air and solutions were quiescent[ All experiments were performed at room temperature[
2[ Results The passive region of 209 SS in the borate bu}er solution is from −9[1 to 9[7 V and its corrosion potential is −9[18 V[ For the sample charged at 0 mA:cm1 for 13 h\ the corrosion potential shifts toward −9[67 V and the current in the passive region increases by more than one order of magnitude[ The time dependence of noise resistance\ Rn\ de_ned as the ratio of the standard deviation of the potential ~uc! tuations to the standard deviation of the current ~uctuations ð04Ł\ for uncharged and charged samples was plotted in Fig[ 0[ The Rn of the sample cathodically charged at 0 mA:cm1 for 3 h is one order of magnitude less than the uncharged sample[ According to the de_nition of Rn\ the decrease in Rn is due to the increase of current ~uctuations resulting from the breakdown and repassivation of the passive _lm[ The optical microscopic observation con_rmed that pits occurred on the surface of the charged sample\ whereas no obvious pit was found on the optical microscopic graph for the
M[Z[ Yang et al[ : Corrosion Science 30 "0888# 630Ð634
632
Fig[ 0[ Time dependence of noise resistance for 209 SS\ uncharged "0# and charged at −0 mA:cm1 for 3 h "1#\ in the borate bu}er solution containing 9[5) FeCl2[
uncharged sample immersed in the same aggressive medium[ Therefore\ hydrogen dissolved in 209 SS signi_cantly increased the susceptibility of the alloy to pitting[ The MottÐSchottky plots\ C−1 vs[ E\ were obtained for charged and uncharged samples in a borate bu}er solution after passivation at 9[6 V for 1 h "Figure 1#[ The MottÐSchottky relation describes the potential dependence of the space charge capacity\ C\ of a semiconductor electrode under depletion conditions ð05Ł] 0
0
1
1 kT 2 DU− \ eNoo9 e C 1
"0#
where the negative sign is for p!type and the positive sign for n!type conductivity\ e is the electron charge\ N the donor density for n!type or acceptor density for p!type semiconductors\ o the relative dielectric constant of the semiconductor\ o9 the vacuum permittivity\ k Boltzmann|s constant and T absolute temperature[ DU U−Ufb
for n−type semiconducters
DU Ufb −U for p−type semiconducters\
Fig[ 1[ MottÐSchottky plot of charged and uncharged 209 SS in borate bu}er solution[
"1a# "1b#
633
M[Z[ Yang et al[ : Corrosion Science 30 "0888# 630Ð634
Fig[ 2[ Polarization curves of charged and uncharged 209 SS in borate bu}er solution containing 0 mM Fe"CN#52− :Fe"CN#53− [
where U is the electrode potential and Ufb the ~at band potential\ that is\ the charac! teristic potential of the junction where the bands are ~at throughout the solid[ Straight lines are observed in Fig[ 1 for both charged and uncharged samples[ A negative slope of the straight line for the uncharged sample corresponds to p!type conductivity and a positive slope of the straight line for the charged sample corresponds to n!type conductivity[ This inversion of conducting types of passive _lm\ induced by hydrogen entering 209 SS\ was con_rmed by the polarization curves shown in Fig[ 2[ The conducting type of electrodes can be di}erentiated by a comparison of their anodic and cathodic polarization curves obtained in a redox system ð00Ł[ According to Bianchi|s criterion ð00Ł\ when the anodic transfer coe.cient\ aA\ is less than the cathodic transfer coe.cient\ aC\ the _lm is n!type\ whereas greater aA values "i[e[\ aA 9[3# and aA×aC correspond to p!type _lms[ Gamry CMS 094 software was used to _t the data in Fig[ 2 into the SternÐGeary equation to estimate the cathodic and anodic transfer coe.cients[ For the uncharged sample\ the anodic transfer coe.cient is equal to 9[36\ greater than the cathodic one "9[01#[ However\ the charged sample produced a cathodic transfer coe.cient of 9[28 which is greater than the anodic transfer coe.cient of 9[07[ Because of the limitation of the Tafel linear region\ the MottÐSchottky method is more reliable than the transfer coe.cient criterion for determining the semiconductivity of a passive _lm[ Figure 2 is displayed in this paper is to con_rm the results of the MottÐSchottky plots\ that the passive _lm on the uncharged sample is a p!type _lm and the presence of hydrogen in 209 SS inverts the p!type passive _lm to n!type _lm[ The results exhibit that dissolved hydrogen in a specimen can induce an inversion of conductivity of the passive _lm from p! to n!type\ and n!type _lm on stainless steel has a greater pitting susceptibility than p!type _lm[ The correlation of the susceptibility of stainless steel to pitting with the conductivity type of passive _lm is consistent with the work of Bianchi et al[ ð00Ł\ who have obtained a relationship between pitting densities and transfer coe.cients for stainless steel specimens after di}erent thermal treatments[
M[Z[ Yang et al[ : Corrosion Science 30 "0888# 630Ð634
634
3[ Conclusions
0[ Susceptibility of 209 SS to pitting nucleation is strongly in~uenced by hydrogen caused by cathodically charging the sample[ 1[ Susceptibility to pitting nucleation can be correlated with the electronic properties of the passive _lm on 209 SS[ High susceptibility corresponds to n!type conductivity of the passive _lm[ On the contrary\ low susceptibility is connected with p!type conductivity[
Acknowledgements This work was supported by the Natural Sciences and Engineering Research Coun! cil of Canada[
References ð0Ł H[ Gray\ Corrosion 07 "0861# 36[ ð1Ł L[J[ Qiao\ W[Y[ Chu\ C[M[ Hsiao\ Scripta Metall[ 11 "0877# 516[ ð2Ł P[ G[ Marsh\ W[W[ Gerberich\ Stress corrosion cracking of high!strength steels[ in] R[H[ Jones "Ed[#\ Stress Corrosion Cracking[ ASM International\ Metal Park\ Ohio\ 0881\ p[ 52[ ð3Ł G[E[ Kerns\ M[T[ Wang\ R[W[ Staehle\ Stress corrosion cracking and hydrogen embrittlement in high strength steels[ in] R[W[ Staehle\ J[ Hochmann\ R[D[ McCright\ J[E[ Slater "Eds[#\ Stress Corrosion Cracking and Hydrogen Embrittlement of Iron Based Alloys[ NACE\ Houston\ 0866\ p[ 699[ ð4Ł M[ Hasegawa\ M[ Osawa\ Corrosion 28 "0872# 004[ ð5Ł L[J[ Qiao\ W[Y[ Chu\ C[M[ Xiao\ Metal[ Trans[ 13A "0882# 848[ ð6Ł H[P[ Kim\ R[H[ Song\ S[I[ Pyun\ Br[ Corros[ J[ 12 "0877# 143[ ð7Ł M[E[ Armacanqui\ R[A[ Oriani\ Corrosion 33 "0877# 585[ ð8Ł Q[ Yang\ L[J[ Qiao\ S[ Chiovelli\ J[L[ Luo\ E}ects of Hydrogen on the Pitting Susceptibility of 209 Stainless Steel\ Corrosion 43 "0887# 517[ ð09Ł C[ Sunseri\ S[ Piazza\ A[ Di Paola\ F[ Di Quarto\ J[ Electrochem[ Soc[ 023 "0876# 1309[ ð00Ł G[ Bianchi\ A[ Cerquetti\ F[ Mazza\ S[ Torchio\ in] R[W[ Staehle et al[ "Eds[#\ Localized Corrosion[ NACE\ Houston\ 0863\ p[ 288[ ð01Ł A[M[P[ Simoes\ M[G[S[ Frreira\ B[ Rondot\ M[ da Cunha Belo\ J[ Electrochem[ Soc[ 026 "0889# 71[ ð02Ł P[ Schmuki\ H[ Bohni\ J[ Electrochem[ Soc[ 028 "0881# 0897[ ð03Ł U[ Stimming\ Passivity of metals and semiconductors[ in] M[ Froment "Ed[#\ Proceedings of the Fifth International Symposium on Passivity[ Elsevier Science Publishers\ B[V[\ Amsterdam\ 0872\ p[ 366[ ð04Ł F[ Mansfeld\ C[ Chen\ C[C[ Lee\ H[ Xiao\ Corrosion Science 27 "0885# 386[ ð05Ł Y[V[ Pleskov\ Y[Y[ Gurevich\ Semiconductor Photoelectrochemistry\ Chapter 2[ Consultant Bureau\ New York 0875[