IS&T©s 50th Annual Conference IS&T©s 50th Annual Conference Copyright 1997, IS&T Study of Toning Processes for Photographic Paper S.Chernov1, R.Heron2, S.Rifkin3 and V.Zakharov4 1 - Research Center of Molecular Diagnostics, Moscow, Russia 2 - Indiana University, Bloomington, Indiana, USA 3 - ( Hank's ) Minneapolis, Minnesota, USA 4 - M.V.Lomonosov Moscow State University, Moscow, Russia Introduction 2 - “Ilford” IV RC Deluxe mgd.1M, multigrade, resin-coated base; Toning is a process giving a possibility to change black or 3 - “Samshite” (produced by “Slavich” TU 6-56-00205133- grey colour of a print as a result of a transformation of 30-92, Pereslavl, Russia) white, normal contrast, medium image silver into colored chemical compounds or a dye1,2. weight, resin-coated base. Dyeing of photographic image into sepia (different hues of brown from purple brown to yellow brown) is usually Direct Toning made by a transformation of metallic silver into silver sulfide with the use of sodium sulfide, thiourea or other The scheme of chemistry of direct toning process: sulfur-containing compounds. By converting metallic silver into colored metal salts is Ag + S Þ A g2S 3- 3+ possible to change a black and white image into many Ag + [Fe(CN)6] + Fe Þ Fe4[Fe(CN)6]3 3- 2+ different colors. Thus, toning by salts of iron gives the Ag + [Fe(CN)6] + UO 2 Þ (UO2)2[Fe(CN)6] 3- 2+ image dyed in blue, by salts of uranium - in red brown, by Ag + [Fe(CN)6] + Cu Þ Cu 2[Fe(CN)6] salts of copper - from pink orange to dark cherry, by salts of nickel - in bright red, by salts of lead - in yellow. To obtain For direct toning we used the following toning solutions: some colours and their hues several salts of different metals DT1 . are used simultaneously, e.g. to obtain green salts of iron Na2S 9H2O 0,1M and lead are used. DT2 . Experimental and Discussion Na2S2O3 5H2O 0,1M H2SO4 0,1M Two types of developers were used: DT3 "a", compensating developer Kodak D-76 giving saturated “1” - K3[Fe(CN)6] 0,05M . black tones; “2” - FeCl3 6H2O 0,05M Working solution ”1”+”2”=1+1 "b", a developer giving warmer (brown) tones, with the following composition: Na2SO3 38 g, hydroquinone 10 g, DT4 K2CO3 50 g, KBr 1 g, H2O up 1 l. “1”- K3[Fe(CN)6] 0,05M . “2” - CuSO4 5H2O 0,05M However, these tones differ only while comparing Potassium citrate 0,2M samples. We can speak only about slight hues of colours. Working solution ”1”+”2”=1+1 That's why we generally used developer D-76. The cases when the initial samples were developed by the "b" DT5 developer are specially marked. “1” - K3[Fe(CN)6] 0,05M Three types of photographic paper were chosen for K2CO3 0,05M . investigation (the sample's numbers are marked by “2” - CuSO4 5H2O 0,05M numerals) (NH4)2C2O4 0,2M Working solution “1”+ “2”=1+1 1 - “AGFA” MCC118FB, multicontrast, classic, fine grained matt; 1813 IS&T©s 50th Annual Conference IS&T©s 50th Annual Conference Copyright 1997, IS&T Table 1 For indirect toning we used followed bleach solutions: Samples Toning solution Photo- Colour B1 number paper K3[Fe(CN)6] 0,1M 1 control sample 1 Black 2 control sample 2 Black B2 K [Fe(CN) ] 0,1M 3 control sample 3 Black 3 6 o Na2CO3 0,2M 4 DT1 (t = 60 C) 3 Black-brown a - KCl 0,1M o 5 DT2 (t =45-60 C) 1 Dark-brown b - KBr 0,1M o 6 DT2 (t =45-60 C) 3 Brown c - Kl 0,1M 7 DT3 3 Blue 8 DT3 followed by 3 Olive-brown B3 DT1 K2Cr2O7 0,1M 9 DT4 1 Dark-red-brown H2SO4 0,1M 10 DT4 3 Red-brown a - KCl 0,1M 11 DT4 followed by 3 Olive-brown b - KBr 0,1M DT1 c - Kl 0,1M 12 DT5 1 Dark-violet-red 13 DT5 3 Violet-red B4 “1” - KMnO 0,03M 14 DT5 followed by 3 Dark-olive- 4 DT1 brown a - KCl 0,1M b - KBr 0,1M 15 DT5 followed by 3 Sepia . c - KI 0,1M 25% NH3 aq “2” - H2SO4 0,1M Indirect Toning “3” - K2S2O5 0,1M Working solution:”1”+”2”= 1+1. The scheme of chemistry of indirect toning process: Colourless in solution ”3”. 1-st step-bleaching: 2- B5 Ag + Cr2O7 Þ Ag2Cr2O7 - 2- (NH4)2S2O8 0,1M Ag + Hal + Cr 2O7 Þ AgHal - 2- H2SO4 0,1M Ag + Hal + S2O8 Þ AgHal - - + a - KCl 0,1M Ag + Hal + MnO4 + H Þ AgHal Ag + Hal- + Cu2+ Þ AgHal b - KBr 0,1M - 3- c - KI 0,1M Ag + Hal + [Fe(CN)6] Þ AgHal 3- Ag + [Fe(CN)6] Þ Àg4[Fe(CN)6] 3- 2+ B6 Ag + [Fe(CN)6] + Ni Þ Ni2[Fe(CN)6] 3- 2+ K3[Fe(CN)6] 0,1M Ag + [Fe(CN)6] + Cd Þ Cd2[Fe(CN)6] 3- 2+ Pb(NO3)2 0,05M Ag + [Fe(CN)6] + Pb Þ Àg2Pb[Fe(CN)6] Ag + Cu2++ SCN- Þ AgSCN.CuSCN CH3COOH 0,5M 2-nd step - toning: B7 2- “1” - CdCl2 0,2M AgHal + S Þ Ag2S 2- “2” - K3[Fe(CN)6] 0,1M AgHal + Se Þ Ag2Se 3+ “3” - Potassium citrate 1M Ag4[Fe(CN)6] + Fe Þ Fe 4[Fe(CN)6]3 2+ Working solution: ”1”+”2”+”3”= 1+1+1. Ag4[Fe(CN)6] + UO2 Þ (UO2)2[Fe(CN)6] Ag [Fe(CN) ] + Cu2+ Þ Cu [Fe(CN) ] 4 6 2 6 B8 Ni2[Fe(CN)6] + C4H6N2O2 Þ Ni(C 4H6N2O2)2 Cd [Fe(CN) ] + Na S Þ CdS “1” - Potassium citrate 1M 2 6 2 . 3+ 2- “2” - NiCl2 6H2O 0,1M Ag2Pb[Fe(CN)6]+Fe +Cr2O7 Þ Fe4[Fe(CN)6]3 + “3” - K3[Fe(CN)6] 0,1M PbCrO4 2- Working solution: ”1”+”2”+”3”= 1+1+1. Ag2Pb[Fe(CN)6] + S Þ Ag2S + PbS 2- Ag2Pb[Fe(CN)6] + Cr2O7 Þ PbCrO4 Ag Pb[Fe(CN) ] + Co2+ Þ Co [Fe(CN) ] B9 2 6 2 6 . AgSCN.CuSCN + dye Þ adsorbed dye CuSO4 5H2O 0,5M H2SO4 0,1M 1824 IS&T©s 50th Annual Conference IS&T©s 50th Annual Conference Copyright 1997, IS&T a - KCl 0,1M 30 B1 T4 1 Green b - KBr 0,1M 31 B1 T4 3 Light-green c - KI 0,1M 32 B2a T3 1 Dark-blue 33 B2a T3 1* Blue For indirect toning we used followed solutions: 34 B2a T3 2 Dark-blue T1 35 B2b T3 2 Grey 36 B2c T3 2 Light-yellow C4H6N2O2 0,1M NaOH 0,4M 37 B2a T3 3 Blue T2 38 B2b T3 3 Grey . * CuSO4 5H2O 0,2M 39 B2a T2 1 Brown HNO 3 0,1M 40 B2a T2 1 Beige 41 B2a T2 2 Beige T3 42 B2b T2 2 Grey . FeCl3 6H2O 0,1M 43 B2c T2 2 Light-yellow 44 B2a T2 3 Beige-red T4 45 B2b T2 3 Grey CoCl .6H O 1M 2 2 46 B2c T2 3 Light-yellow T5 47 B2a T7 1 Dark-brown . 48 B2a T7 2 Black-brown FeCl3 6H2O 0,1M 49 B2b T7 1 Dark-brown K2Cr2O7 0,02M 50 B2b T7 2 Black-brown T6 51 B2c T7 1 Brown K2Cr2O7 0,1M 52 B2c T7 2 Black-brown 53 B2c T7 3 Light-brown T7 54 B6 T2 3 Violet-red . Na 2S 9H2O 0,3M 55 B6 T3 3 Blue 56 B6 T3 3 Olive Table 2 followed Samples Bleach Toning Photo- Colour by dev.”b” number solution paper 57 B6 T4 3 Green 16 B1 T3 1* Dark-blue 58 B6 T4 3 Light-brown 17 B1 T3 1 Blue followed . 18 B1 T3 2 Blue by NH3 aq 19 B1 T3 3 Light-blue 59 B6 T6 3 Yellow 20 B1 T2 1* Brown 60 B6 T6 3 Yellow-brown 21 B1 T2 1 Brown followed 22 B1 T2 2 Beige by dev.”b” 23 B1 T2 3 Light-brown 61 B6 T5 3 Dark-green 24 B1 T2 1* Black-brown 62 B6 T5 3 Dark-yellow- followed followed brown . by T7 by NH3 aq 25 B1 T2 2 Black 63 B7 T7 1 Light-yellow followed 64 B8 T7 2 Dark-brown by T7 65 B8 T1 1 Purple (high 26 B1 T2 3 Dark-brown-red fog) followed 66 B8 T1 2 Light-brown- by T7 purple 27 B1 T7 1* Brown 67 B8 T1 3 Purple 28 B1 T7 2 Black 68 B8 T1 3 Violet-purple 29 B1 T7 3 Light-olive- followed brown by T4 1831 IS&T©s 50th Annual Conference IS&T©s 50th Annual Conference Copyright 1997, IS&T 69 B8 T1 3 Brown-purple If a high concentration of potassium bromide is used in followed the developer, subsequent toning will produce a warmer by T4, T7 tonality. 70 B8 T1, T4, 3 Light-violet- As a general rule if toning is achieved by the use of T7, purple sulfur compounds the density of the toned image decreases, . if use is made of metal salts, density increases in the toned NH3 aq image. The use of copper, lead or uranium compounds, produces images whose colors change gradually (according to It is possible to use B3, B4, B5, B9 bleach instead of B2 a definite sequence) as the toning proceeds. In toning bleach in the cases "a", "b", "c".