first developer - 125px125px.com/docs/chemicals/kodak/z-6_7_082604.pdfprocess control handbook •...

KODAK Q-LAB Process Monitoring ServicePROCESS CONTROL HANDBOOK • Z-6

First DeveloperThe first developer is the most criticalstep in Process E-6. The solution isessentially a black-and-white film de-veloper, because it forms only anegative silver image in each layer ofthe film; no dye images are formed.

FUNCTIONS• The first developer converts

exposed silver halide to metallic sil-ver to form a negative silver imagein each layer of the film.

• Proper formation of the negativesilver image in the first developer isrequired for correct formation ofdye images in the color developer.

COMPONENTSDeveloping Agents:

KODAK Developing Agent, DA-1KODAK DIMEZONE S Developing

AgentThese developing agents react with

exposed silver halide to form metallicsilver. They do not react with the dyecouplers in the film. As the silver image is formed, the developing agents are oxidized.Ag*X + Dev → Ag0 + X- + Devox

AG*X = exposed silver halideDev = developing agentAg0 = metallic silver

X- = halide ion

DevOX = oxidized developing agent

Replenishment is required to main-tain the concentration of the devel-oping agent.

Silver Halide Solvents:

Sodium thiocyanatePotassium sulfiteThese chemicals affect the physical

development of the film (they helpdissolve “fine” silver halide grains).Thiocyanate is not consumed oroxidized; its concentration is affectedonly by replenisher concentration andevaporation. Sulfite is oxidized andconsumed, but it is a much weakersolvent than thiocyanate; it actsprimarily as a preservative.

A change in the concentration ofthese solvents will have a greatereffect on the smaller grains in theemulsion (toe densities) than on thelarger grains.

Preservative:

Potassium sulfitePotassium sulfite acts as a preser-

vative to protect the developingagents from oxidation, and helps tomaintain their concentration. It alsoacts as a mild silver halide solvent.

Restrainers:

Sodium bromidePotassium iodideBromide and iodide ions are

released into the first-developer solu-tion as development by-products.Ag*Br + Dev → Ag0 + Br-

+ Devox

Ag*I + Dev → Ag0 + I- + Devox

Ag*Br = exposed silver bromideAg*I = exposed silver iodideDev = developing agentAg0 = metallic silverBr- = bromide ion

I- = iodide ion

DevOX = oxidized developing agent

These ions act as inhibitors to theaction of the developer. Replenish-ment is needed to dilute the con-centration of these ions and reducetheir restraining effect. If your replen-ishment rate is too low, developeractivity will decrease because theconcentration of bromide and iodideions increases, resulting in higher filmdensities. If the replenishment rate istoo high, developer activity increasesbecause the concentration of bro-mide and iodide ions decreases, re-sulting in lower densities.

The KODAK Bromide Test Kit, Pro-cess E-6, enables you to measure theconcentration of bromide in your Pro-cess E-6 first developer and detectchanges in the concentration beforethey affect the film you process.Instructions for using this kit aregiven on page 7-4.

KODAK Q-LAB Process Moni tor ing Serv iceP R O C E S S C O N T R O L H A N D B O O K • Z -6

FIRST DEVELOPER • 5/047-2

Buffers:

Potassium carbonateSodium bicarbonateCarbonate acts as a buffer. The

bicarbonate provides a convenientmeans of controlling pH.

Sequestering Agents:

KODAK Anti-Calcium, No. 4KODAK Anti-Calcium, No. 8These components prevent the

precipitation of calcium and magnesium salts to ensure solutioncleanliness.

Sensitometric Effects ofSolution Component ConcentrationThe following tables list the effects onprocessed film of high and low con-centrations of first-developer solutioncomponents.

HIGH CONCENTRATION

Solution Component Sensitometric Effect

KODAK Developing Lower densitiesAgent, DA-1

KODAK DIMEZONE SDeveloping Agent

Sodium thiocyanate Lower densitiesHigher toe contrast

Potassium sulfite Lower densitiesSlightly higher toe contrast

Sodium bromide Higher densities

Potassium iodide Higher densities

Potassium carbonate Little to none

KODAK Anti-Calcium Little to none

LOW CONCENTRATION

Solution Component Sensitometric Effect

KODAK Developing Higher densitiesAgent, DA-1KODAK DIMEZONE SDeveloping Agent

Sodium thiocyanate Higher densitiesLower toe contrast

Potassium sulfite Higher densitiesLower toe contrast

Sodium bromide Lower densities

Potassium iodide Lower densitiesDecrease in blue upper-scale contrast and D-max

Potassium carbonate Little to noneKODAK Anti-Calcium Little to none

12/99 • FIRST DEVELOPER 7-3


SPECIFICATIONS

Parameter Aim ToleranceAcceptable Plot

Range ParameterTime 6 minutes ± 5 seconds 5 to 7 minutes X

Temperature 100.4°F ± 0.3°F 98 to 103°F X(38°C) (± 0.2°C) (36.7 to 39.4°C)

Replenishment 200 mL/ft2 ± 20 mL/ft2*— XRate (2153 mL/m2) (± 215 mL/m2)*

SpecificGravitySeasoned Tank 1.060 atSolution 80°F (27°C)

± 0.003 — X1.057 at100.4°F (38°C)

Fresh Tank 1.055 atSolution† 80°F (27°C)

± 0.003 —1.052 at100.4°F (38°C)

Replenisher 1.057 at80°F (27°C)

± 0.003 —1.054 at100.4°F (38°C)

BromideConcentrationSeasoned Tank 2.5 g/L ± 0.3 — XSolutionFresh Tank 2.57 g/L ± 0.3 —Solution†

Replenisher 1.43 g/L ± 0.3 —

Agitation 2-second nitrogenburst every10 seconds — —

(5/8-inch [17 mm]solution rise)‡

*For optimum performance, maintain your replenishment rate to within ± 5% of the specifiedaim (± 10% tolerance allows for measurement “noise”).

†See the mixing instructions at the right. Plot the specific gravity and bromide concentrationof the new mix on Form Y-34. Note “NEW FIRST-DEVELOPER TANK MIX” on Form Y-33.

‡For rack-and-tank machines.

PREPARING A FRESHTANK SOLUTIONTo prepare a fresh tank solution thatwill give results similar to those pro-duced by a seasoned tank solution,follow the appropriate mixing in-structions given below. (These in-structions are different from thoseprovided with the chemicals.)Following either procedure will helpyou obtain results closer to thoseproduced at optimum process levels.You may need to make slight adjust-ments to optimize the process; see“Optimizing Your Process,” page 6-7.Note: These instructions are for mix-ing solutions from KODAK PROFES-SIONAL First Developer Replenisher,Process E-6 and E-6AR (5-gallon flex-ible container).

From Mixed Replenisher Solution

1. For each litre of tank solution,mix 950 mL of replenisher with50 mL of water.

2. Add 5 mL of starter per litre ofsolution.

From Concentrate

1. For each litre of tank solution,mix 190 mL of concentrate with810 mL of water.

2. Add 5 mL of starter per litre ofsolution.

Note: When you prepare the solutionin either of these ways, the specificgravity and bromide concentrationwill be within the tolerances for afresh tank solution.



USING THE KODAKBROMIDE TEST KIT,PROCESS E-6Use this kit to measure the bromideconcentration in your Process E-6first developer. Read these instruc-tions before you run the test so thatyou are familiar with the procedure.To obtain accurate results, followthese instructions exactly and usegood laboratory techniques.

Use only distilled water as re-quired in the procedure. (Your re-sults will be unreliable if you useother types of water [e.g., demin-eralized, deionized, tap, etc].) The sil-ver-nitrate solution in the titrationcartridge is light-sensitive. Store thecartridge in a drawer or in the testkit case when you are not using it.

To determine the bromide concen-tration of your first-developer tanksolution, you will use the results ofthis test in conjunction with an ac-curate measurement of the tank-solution specific gravity.Note: To run this test, you will use aprocedure called a titration. A ti-tration is a quantitative chemicalanalysis of a solution.

When you perform a titration, youdetermine the concentration of acertain chemical component(e.g., bromide) of a solution sampleby adding a standardized solution—called a titrant—that causes a chem-ical reaction. Silver nitrate solution isthe titrant used for this test.

The titrant first reacts with thechemical component that you aremeasuring. When the initial reactionis complete, the titrant then reactswith an indicator or another chemicalin the solution to cause the color ofthe sample to change. The colorchange marks the end point of thereaction. It is important to stop addingtitrant as soon as the reaction reachesthe end point.

1. Fill the flask to the 30 mL line withdistilled water.

2. Add the contents of one BromideIndicator Powder Pillow to the flask.Swirl the flask until the powder iscompletely dissolved; this will takeapproximately 30 to 40 seconds.

3. Remove 1.0 mL of first-developertank solution with the TenSette Pi-pet, and add it to the flask. Swirlthe flask.

4. Add 5 drops of Polyvinyl AlcoholSolution to the solution in the flask;swirl the flask.

5. Use the digital titrator (with thecounter reset to zero) with theSilver Nitrate Titration Cartridge totitrate the solution in the flask. Addtitrant and swirl the flask until thecolor of the solution begins tochange; determine the end pointwhen the solution changes from its

original color (yellow-green) to grayor gray-green, and the solutionremains gray or gray-green afteryou swirl it continuously for 5 to10 seconds. Be careful that youdo not titrate the solution beyond the end point. If you ti-trate beyond the end point, thecolor of the solution will change toturquoise and then a distinct blue.

6. Read the number from the digitalcounter.

7. Make a specific-gravity measure-ment of your first-developer tanksolution.

8. To determine the bromide concen-tration, use the titrator reading(from step 6) and the specific-gravity measurement (from step 7)in the appropriate equation belowor with the appropriate table onpage 7-5 or 7-6.

9. Calculate and plot your variationfrom aim on Form Y-34; see “UsingForms Y-34, Y-35, and Y-36”on page 4-13 for more informationCheck the plots of bromideconcentration for outliers,shifts, trends, and cycling to deter-mine the state of control. If youdetect an out-of-control condi-tion, refer to the diagnostic chartson pages 7-14 and 7-16.

10. Discard the solution from theflask, and rinse the flask thor-oughly with distilled water.Remove the tip from the pipet anddiscard it.

Specific gravity measured at 100.4°F (38°C)

Specific gravity measured at 80°F (27°C)

Bromide concentration =

0.063

- 0.997Specific-gravity

measurement(titrator reading - 3) x 0.02902 - x 1.2692

Bromide concentration =

0.063

- 1Specific-gravity

measurement(titrator reading - 3) x 0.02902 - x 1.2692

0.060

0.060



(Continued on next page)

Find your specific-gravity measure-ment along the top of the table andyour titrator reading along the side ofthe table. The bromide concentration

is the number where the verticalcolumn and the horizontal columnintersect.

Titrator Readings90 1.38 1.36 1.34 1.32 1.30 1.28 1.26 1.23 1.21 1.19 1.17 1.15 1.1391 1.41 1.39 1.37 1.35 1.33 1.31 1.28 1.26 1.24 1.22 1.20 1.18 1.1692 1.44 1.42 1.40 1.38 1.36 1.33 1.31 1.29 1.27 1.25 1.23 1.21 1.1993 1.47 1.45 1.43 1.41 1.36 1.36 1.34 1.32 1.30 1.28 1.26 1.24 1.2294 1.50 1.48 1.46 1.44 1.41 1.39 1.37 1.35 1.33 1.31 1.29 1.27 1.24

95 1.53 1.51 1.49 1.46 1.44 1.42 1.40 1.38 1.36 1.34 1.32 1.29 1.2796 1.56 1.54 1.51 1.49 1.47 1.45 1.43 1.41 1.39 1.37 1.35 1.32 1.3097 1.58 1.56 1.54 1.52 1.50 1.48 1.46 1.44 1.42 1.40 1.37 1.35 1.3398 1.59 1.59 1.57 1.55 1.53 1.51 1.49 1.47 1.45 1.42 1.40 1.38 1.3699 1.64 1.62 1.60 1.58 1.56 1.54 1.52 1.50 1.47 1.45 1.43 1.41 1.39

100 1.67 1.65 1.63 1.61 1.59 1.57 1.55 1.52 1.50 1.48 1.46 1.44 1.42101 1.70 1.68 1.66 1.64 1.62 1.60 1.57 1.55 1.53 1.51 1.49 1.47 1.45102 1.73 1.71 1.69 1.67 1.65 1.62 1.60 1.58 1.56 1.54 1.52 1.50 1.48103 1.76 1.74 1.72 1.70 1.68 1.65 1.63 1.61 1.59 1.57 1.55 1.53 1.51104 1.79 1.77 1.75 1.73 1.70 1.68 1.66 1.64 1.62 1.60 1.58 1.56 1.53

105 1.82 1.80 1.78 1.75 1.73 1.71 1.69 1.67 1.65 1.63 1.61 1.59 1.56106 1.85 1.83 1.80 1.78 1.76 1.74 1.72 1.70 1.68 1.66 1.64 1.61 1.59107 1.88 1.85 1.83 1.81 1.79 1.77 1.75 1.73 1.71 1.69 1.66 1.64 1.62108 1.90 1.88 1.86 1.84 1.82 1.80 1.78 1.76 1.74 1.71 1.69 1.67 1.65109 1.93 1.91 1.89 1.87 1.85 1.83 1.81 1.79 1.76 1.74 1.72 1.70 1.68

110 1.96 1.94 1.92 1.90 1.88 1.86 1.84 1.81 1.79 1.77 1.75 1.73 1.71111 1.99 1.97 1.95 1.93 1.91 1.89 1.86 1.84 1.82 1.80 1.78 1.76 1.74112 2.02 2.00 1.98 1.96 1.94 1.92 1.89 1.87 1.85 1.83 1.81 1.79 1.77113 2.05 2.03 2.01 1.99 1.97 1.94 1.92 1.90 1.88 1.86 1.84 1.82 1.80114 2.08 2.06 2.04 2.02 1.99 1.97 1.95 1.93 1.91 1.89 1.87 1.85 1.83

115 2.11 2.09 2.07 2.04 2.02 2.00 1.98 1.96 1.94 1.92 1.90 1.88 1.85116 2.14 2.12 2.09 2.07 2.05 2.03 2.01 1.99 1.97 1.95 1.93 1.90 1.88117 2.17 2.14 2.12 2.10 2.08 2.06 2.04 2.02 2.00 1.98 1.95 1.93 1.91118 2.20 2.17 2.15 2.13 2.11 2.09 2.07 2.05 2.03 2.00 1.98 1.96 1.94119 2.22 2.20 2.18 2.16 2.14 2.12 2.10 2.08 2.05 2.03 2.01 1.99 1.97

120 2.25 2.23 2.21 2.19 2.17 2.15 2.13 2.10 2.08 2.06 2.04 2.02 2.00121 2.28 2.26 2.24 2.22 2.20 2.18 2.16 2.13 2.11 2.09 2.07 2.05 2.03122 2.31 2.29 2.27 2.25 2.23 2.21 2.18 2.16 2.14 2.12 2.10 2.08 2.06123 2.34 2.32 2.30 2.28 2.26 2.23 2.21 2.19 2.17 2.15 2.13 2.11 2.09124 2.37 2.35 2.33 2.31 2.28 2.26 2.24 2.22 2.20 2.18 2.16 2.14 2.12

125 2.40 2.38 2.36 2.33 2.31 2.29 2.27 2.25 2.23 2.21 2.19 2.17 2.14126 2.43 2.41 2.38 2.36 2.34 2.32 2.30 2.28 2.26 2.24 2.22 2.19 2.17127 2.46 2.44 2.41 2.39 2.37 2.35 2.33 2.31 2.29 2.27 2.24 2.22 2.20128 2.49 2.46 2.44 2.42 2.40 2.38 2.36 2.34 2.32 2.30 2.27 2.25 2.23129 2.51 2.49 2.47 2.45 2.43 2.41 2.39 2.37 2.35 2.32 2.30 2.28 2.26

130 2.54 2.52 2.50 2.48 2.46 2.44 2.42 2.40 2.37 2.35 2.33 2.31 2.29131 2.57 2.55 2.53 2.51 2.49 2.47 2.45 2.42 2.40 2.38 2.36 2.34 2.32132 2.60 2.58 2.56 2.54 2.52 2.50 2.47 2.45 2.43 2.41 2.39 2.37 2.35133 2.63 2.61 2.59 2.57 2.55 2.52 2.50 2.48 2.46 2.44 2.42 2.40 2.38134 2.66 2.64 2.62 2.60 2.57 2.55 2.53 2.51 2.49 2.47 2.45 2.43 2.41

Specific gravity Specific-Gravity Measurementsmeasured at

100.4°F (38°C) 1.051 1.052 1.053 1.054 1.055 1.056 1.057 1.058 1.059 1.060 1.061 1.062 1.063 80°F (27°C) 1.054 1.055 1.056 1.057 1.058 1.059 1.060 1.061 1.062 1.063 1.064 1.065 1.066



Titrator Readings135 2.69 2.67 2.65 2.62 2.60 2.58 2.56 2.54 2.52 2.50 2.48 2.46 2.43136 2.72 2.70 2.68 2.65 2.63 2.61 2.59 2.57 2.55 2.53 2.51 2.48 2.46137 2.75 2.73 2.70 2.68 2.66 2.64 2.62 2.60 2.58 2.56 2.53 2.51 2.49138 2.78 2.75 2.73 2.71 2.69 2.67 2.65 2.63 2.61 2.59 2.56 2.54 2.52139 2.80 2.78 2.76 2.74 2.72 2.70 2.68 2.66 2.64 2.61 2.59 2.57 2.55

140 2.83 2.81 2.79 2.77 2.75 2.73 2.71 2.69 2.66 2.64 2.62 2.60 2.58141 2.86 2.84 2.82 2.80 2.78 2.76 2.74 2.71 2.69 2.67 2.65 2.63 2.61142 2.89 2.87 2.85 2.83 2.81 2.79 2.76 2.74 2.72 2.70 2.68 2.66 2.64143 2.92 2.90 2.88 2.86 2.84 2.81 2.79 2.77 2.75 2.73 2.71 2.69 2.67144 2.95 2.93 2.91 2.89 2.86 2.84 2.82 2.80 2.78 2.76 2.74 2.72 2.70

145 2.98 2.96 2.94 2.92 2.89 2.87 2.85 2.83 2.81 2.79 2.77 2.75 2.72146 3.01 2.99 2.97 2.94 2.92 2.90 2.88 2.86 2.84 2.82 2.80 2.77 2.75147 3.04 3.02 2.99 2.97 2.95 2.93 2.91 2.89 2.87 2.85 2.83 2.80 2.78148 3.07 3.04 3.02 3.00 2.98 2.96 2.94 2.92 2.90 2.88 2.85 2.83 2.81149 3.09 3.07 3.05 3.03 3.01 2.99 2.97 2.95 2.93 2.90 2.88 2.86 2.84

150 3.12 3.10 3.08 3.06 3.04 3.02 3.00 2.98 2.95 2.93 2.91 2.89 2.87151 3.15 3.13 3.11 3.09 3.07 3.05 3.03 3.00 2.98 2.96 2.94 2.92 2.90152 3.18 3.16 3.14 3.12 3.10 3.08 3.05 3.03 3.01 2.99 2.97 2.95 2.93153 3.21 3.19 3.17 3.15 3.13 3.10 3.08 3.06 3.04 3.02 3.00 2.98 2.96154 3.24 3.22 3.20 3.18 3.16 3.13 3.11 3.09 3.07 3.05 3.03 3.01 2.99

155 3.27 3.25 3.23 3.21 3.18 3.16 3.14 3.12 3.10 3.08 3.06 3.04 3.01156 3.30 3.28 3.26 3.23 3.21 3.19 3.17 3.15 3.13 3.11 3.09 3.07 3.04157 3.33 3.31 3.28 3.26 3.24 3.22 3.20 3.18 3.16 3.14 3.12 3.09 3.07158 3.36 3.33 3.31 3.29 3.27 3.25 3.23 3.21 3.19 3.17 3.14 3.12 3.10159 3.38 3.36 3.34 3.32 3.30 3.28 3.26 3.24 3.22 3.19 3.17 3.15 3.13

160 3.41 3.39 3.37 3.35 3.33 3.31 3.29 3.27 3.24 3.22 3.20 3.18 3.16161 3.44 3.42 3.40 3.38 3.36 3.34 3.32 3.29 3.27 3.25 3.23 3.21 3.19162 3.47 3.45 3.43 3.41 3.39 3.37 3.34 3.32 3.30 3.28 3.26 3.24 3.22163 3.50 3.48 3.46 3.44 3.42 3.40 3.37 3.35 3.33 3.31 3.29 3.27 3.25164 3.53 3.51 3.49 3.47 3.45 3.42 3.40 3.38 3.36 3.34 3.32 3.30 3.28

165 3.56 3.54 3.52 3.50 3.47 3.45 3.43 3.41 3.39 3.37 3.35 3.33 3.31166 3.59 3.57 3.55 3.52 3.50 3.48 3.46 3.44 3.42 3.40 3.38 3.36 3.33167 3.62 3.60 3.57 3.55 3.53 3.51 3.49 3.47 3.45 3.43 3.41 3.38 3.36168 3.65 3.62 3.60 3.58 3.56 3.54 3.52 3.50 3.48 3.46 3.43 3.41 3.39169 3.68 3.65 3.63 3.61 3.59 3.57 3.55 3.53 3.51 3.48 3.46 3.44 3.42

170 3.70 3.68 3.66 3.64 3.62 3.60 3.58 3.56 3.53 3.51 3.49 3.47 3.45171 3.73 3.71 3.69 3.67 3.65 3.63 3.61 3.59 3.56 3.54 3.52 3.50 3.48172 3.76 3.74 3.72 3.70 3.68 3.66 3.64 3.61 3.59 3.57 3.55 3.53 3.51173 3.79 3.77 3.75 3.73 3.71 3.69 3.66 3.64 3.62 3.60 3.58 3.56 3.54174 3.82 3.80 3.78 3.76 3.74 3.71 3.69 3.67 3.65 3.63 3.61 3.59 3.57

175 3.85 3.83 3.81 3.79 3.76 3.74 3.72 3.70 3.68 3.66 3.64 3.62 3.60176 3.88 3.86 3.84 3.81 3.79 3.77 3.75 3.73 3.71 3.69 3.67 3.65 3.62177 3.91 3.89 3.86 3.84 3.82 3.80 3.78 3.76 3.74 3.72 3.70 3.67 3.65178 3.94 3.92 3.89 3.87 3.85 3.83 3.81 3.79 3.77 3.75 3.72 3.70 3.68179 3.97 3.94 3.92 3.90 3.88 3.86 3.84 3.82 3.80 3.77 3.75 3.73 3.71

Specific gravity Specific-Gravity Measurementsmeasured at

100.4°F (38°C) 1.051 1.052 1.053 1.054 1.055 1.056 1.057 1.058 1.059 1.060 1.061 1.062 1.063 80°F (27°C) 1.054 1.055 1.056 1.057 1.058 1.059 1.060 1.061 1.062 1.063 1.064 1.065 1.066



If you push-process more than25 percent of your total film load orpush-process a large amount of filmat one time, you need to considerincreasing the replenishment rate.You can use this simple calculation todetermine a “large amount of film”:

Film area (square feet) ≥ 1.5 x first-developer tank volume (litres)

For example, if you plan to push-process 150 square feet of film andyour first-developer tank volume is100 litres, 150 square feet equals 1.5x 100, and is considered to be a“large amount of film.” If the tank vol-ume is 20 litres, 30 square feet is alarge amount.

If you are push-processing morethan 25 percent of your total filmload, or square footage that is equalto or more than 1.5 times the first-de-veloper tank volume at one time,you must consider the scene con-tent and the format of the film.

If the scenes have uniform densitywith very few high-density areas(typical in some product photographywith a limited density range), do notchange your replenishment rate. Thisapplies especially to sheet film, inwhich the percentage of unexposedfilm along the edges is relativelysmall. These conditions will have littleeffect on the chemical composition ofthe solution because little or no addi-tional silver is being developed.

If scenes have a full tonal rangewith substantial shadows, or high-density areas, you should increase thereplenishment rate to maintain theproper chemical balance. The type ofscenes that require an increase arethose typical of photojournalism, especially when they are on 35 mmfilm, which includes relatively largeunexposed areas along the edges andbetween frames.

The table below includes recom-mendations for increasing replenish-ment rates based on the number ofstops the film is being pushed.

ADJUSTINGREPLENISHMENTRATES FOR PUSHPROCESSINGYou may need to adjust replen-ishment rates when you push-processKODAK PROFESSIONAL EKTACHROME Films. Push processing consumes moreof the chemical components of the first devveloper because it develops more silver than normal processing does.Longer times in the solution willchemically fog, or develop, D-max andshadow areas that normallywouldn’t be developed. This con-sumes more of the developing agentsand generates more by-products(bromide and iodide) than normalprocessing. Because this effect re-sults mainly from development of D-max and shadow areas, scenecontent of the film is an importantfactor. Scenes that have a full tonalscale or many high-density areas willcause a greater change in the first-developer chemical balance thanscenes with many low-density areas.

Because maintaining the chemicalcomposition of the first developer iscritical in operating a quality process,you may have to adjust the replen-ishment rate for push processing.Consider these two factors when youdecide whether or not you need toincrease the replenishment rate:

• The amount of film being push-processed

• The scene content of the film beingpush-processed

*Based on the specific aim of 200 mL/sq ft.The tolerance remains at ± 20 mL/sq ft.

†Based on the specified aim of 2153 mL/sq M.The tolerance remains ± 215 mL/sq M.

Film Percent NewPushed Increase in Replenishment

by Replenish- Rate(Stops) ment Rate

0 (Normal 0 200 2153process)

1/3 8 216 23241/2 12 224 24102/3 16 232 2496

1 (Push 1) 25 250 269011/2 35 270 2905

2 (Push 2) 50 300 3228

mL/sq ft* mL/sq M †



DIAGNOSTIC CHARTSThe diagrams on pages 7-8 to 7-16provide you with a step-by-step approach to diagnosing process prob-lems; they include the most commoncauses of problems. They are orga-nized according to the appearanceof your control plots for the key

FIRST DEVELOPERTEMPERATUREOutlier High or Low, Level Shift High or Low, Trend Up or Down

parameters for first developer. Therecommendations in the charts willhelp you correct outliers (data on oroutside the tolerance lines), levelshifts, trends, and cycling. For moreinformation on evaluating control-chart plots, see Process ControlA Better Way, Section 1.

PLOTPROBLEM

Outlier high (makeanother measurementto confirm)

Faulty temperaturecontrol.

Digital-thermometerbatteries weak ordead.

Poor tankrecirculation.

Check temperature-control system.

Check batteries.

Check recirculationfor proper flow rate.Check for plugged filters.

Make necessarycorrections oradjustments.

Replace batteriesand re-checktemperature.

Make necessaryadjustments torecirculation system.

Check temperature atseveral differentlocations in tank.

Check tank tempera-ture before process-ing film.



Check recirculationsystem frequentlyfor proper operation.

Routinely inspectand perform mainte-nance on tempera-ture-control system.

Change batteriesfrequently.

Outlier low (makeanother measurementto confirm)

Level shift high

Level shift low

Trend up

Trend down

CHOOSEPROBABLE CAUSE

VERIFYCAUSE

ELIMINATECAUSE

ELIMINATESYMPTOM

PREVENTRECURRENCE



FIRST DEVELOPERSPECIFIC GRAVITYOutlier High, Level Shift High, Trend Up

PLOTPROBLEM


Replenisher tooconcentrated.

Excessiveevaporation.

Check replenisherspecific gravity.

Check pumpcalibration.

Check for leaks,pinched lines, and faulty check/poppetvalves.

Improper ratio ofconcentrate to waterfrom in-line dilutionpumps.

Calibrate pumps toprovide 1 part con-centrate to 4 partswater.

Add water to replen-isher; see Table 1 on page 7-18.

Ensure agitation/turbulence is notexcessive.

Minimize air flow andexhaust.

Maintain constanthumidity.

Use floating lidswhenever possible.

Check tank specificgravity several timesper shift/day.

Add water to tanksolution; see Table 2on page 7-18.



Ensure correctmixing procedures.

Routinely calibratepumps and plotdata.

Monitor level ofhumidity.

Make repairs asnecessary.

Measure and plotspecific gravity forevery replenishermix.

Perform regularmaintenance onreplenishmentsystem.

Compensate forremaining evapora-tion, if necessary.(See Appendix 4A.)

Level shift high

Trend up


VERIFYCAUSE

ELIMINATECAUSE

ELIMINATESYMPTOM

PREVENTRECURRENCE



FIRST DEVELOPER SPECIFIC GRAVITYOutlier Low, Level Shift Low, Trend Down

PLOTPROBLEM


Replenisher toodilute.

Overcompensationfor evaporation.

Check replenisherspecific gravity.




Calibrate pumps toprovide 1 part con-centrate to 4 partswater.

Add concentrate to replenisher; see Table 3 on page 7-18.

Reduce amount ofwater added to tankor replenisher.

Check tank specificgravity several timesper shift/day.

Add concentrate totank solution; see Table 4 on page 7-18.

Add concentrate to tank solution; see Table 4 on page 7-18.

Add concentrate to tank solution; see Table 4 on page 7-18. If necessary,add concentrate toreplenisher (pre-mixed solutions) oradjust amount ofwater added by pump(in-line dilution/blender systems).


Routinely calibratepumps and plotdata.



Measure and plotspecific gravity forevery replenishermix.


Determine propercompensation forevaporation; seeAppendix 4A.

Level shift low

Trend down


VERIFYCAUSE

ELIMINATECAUSE

ELIMINATESYMPTOM

PREVENTRECURRENCE



FIRST DEVELOPERTIMEOutlier High or Low, Level Shift High or Low

FIRST DEVELOPERTIMETrend Up or Down

PLOTPROBLEM

Outlier high (makeanother measure-ment to confirm) orLevel shift high

Outlier low (makeanother measure-ment to confirm) orLevel shift low

Machine adjusted forpush processing.

Machine drive ortransport not func-tioning properly.

Machine adjusted forpull processing.

Check time setting.

Check film transportfor mechanicalproblems. Check fordirty racks and rollers. Check forfluctuations involtage to processor.

Check time setting.

Readjust machine fornormal processing.

Make repairs orclean as necessary.

Readjust machine fornormal processing.

Check adjustment of machine beforeprocessing.

Check adjustment of machine before processing.

Inspect drive systemregularly.

Check voltageregularly.


VERIFYCAUSE

ELIMINATECAUSE

ELIMINATESYMPTOM

PREVENTRECURRENCE

PLOTPROBLEM

Trend up or downMachine drive ortransport not func-tioning properly.

Check film transportfor mechanicalproblems. Check fordirty racks and rollers. Check forfluctuations involtage to processor.

Make repairs orclean as necessary.

Inspect drive systemregularly.

Check voltageregularly.


VERIFYCAUSE

ELIMINATECAUSE

ELIMINATESYMPTOM

PREVENTRECURRENCE

FIRST DEVELOPERREPLENISHMENT RATEOutlier High or Low, Level Shift High or Low



PLOTPROBLEM



In-line dilutionpumps not in propercalibration.

Film sensor notfunctioning properly.

Pump leaks or faultycheck valves.

Replenishment notcalculated properly.


Check sensor.

Check pumps andvalves.

Check calculation;see procedure inSection 4.

Recalculatereplenishment rate.

Routinely calibratepumps and plot data.

Check sensorsregularly.


Ensure all replenish-ment-rate calcula-tions are donecorrectly.


VERIFYCAUSE

ELIMINATECAUSE

ELIMINATESYMPTOM

PREVENTRECURRENCE

Add replenisher orstarter to tank solu-tion. Base adjustmenton bromide con-centration; seeTable 5 or Table 7on page 7-19.



Adjust pumps toprovide 200 mL/sq ft(1 part concentrateto 4 parts water).

Adjust sensor toreplenish tank atproper interval.

Make necessaryrepairs.

PROBLEM






Replenishment notcalculated properly.


Check sensor.


Check calculation;see procedure inSection 4.

Recalculatereplenishment rate.




FIRST DEVELOPERREPLENISHMENT RATETrend Up or Down



PLOTPROBLEM


Trend up or down




Check sensor.






VERIFYCAUSE

ELIMINATECAUSE

ELIMINATESYMPTOM

PREVENTRECURRENCE





Adjust sensor toreplenish tank atproper interval.

Make necessaryrepairs.

FIRST DEVELOPERBROMIDE CONCENTRATIONOutlier High, Level Shift High, Trend Up



(Continued on next page)

PLOTPROBLEM


Replenisher tooconcentrated.

Too much first-developer starteradded.

Underreplenishment.

Excessiveevaporation.

Check specific gravityand bromide concen-tration of replenisher.

Check mixing records/procedures.

Check volume ofreplenisher used vsamount of filmprocessed.




Adjust pumps toprovide 200 mL/sq ft(1 part concentrate to 4 parts water).

Adjust concentrationof replenisher untilspecific gravity andbromide concentra-tion are correct; see Table 1 on page 7-18.

Follow mixinginstructions closely.

Adjust replenishmentrate.

Ensure agitation/turbulence is notexcessive.

Minimize air flowand exhaust.

Maintain constanthumidity.

Use floating lidswhenever possible.

Monitor specificgravity of tanksolution closely.

Add water to tanksolution until specificgravity and bromideconcentration arecorrect; see Table 2on page 7-18.



Add replenisher totank solution untilbromide concentra-tion is correct; seeTable 5 on page 7-19.

Add replenisher totank solution untilbromide concentra-tion is correct; seeTable 5 on page 7-19.







Measure and plotspecific gravity andbromide concentra-tion for each replen-isher mix.

Perform regularmaintenance onreplenishment system.

Compensate forremaining evapo-ration, if necessary.(See Appendix 4A.)

Level shift high

Trend up


VERIFYCAUSE

ELIMINATECAUSE

ELIMINATESYMPTOM

PREVENTRECURRENCE



PLOTPROBLEM


Average density ofprocessed film lowerthan normal.

Check for highpercentage of low-density scenes.

Add replenisher totank solution toadjust bromide concentration to aim; see Table 5 on page 7-19.

Increase replenish-ment rate to compen-sate for change inaverage density of processed film; seeTable 6 on page 7-19.

Closely monitor tankbromide concentra-tion and averagedensity of processedfilm.

Level shift high

Trend up


VERIFYCAUSE

ELIMINATECAUSE

ELIMINATESYMPTOM

PREVENTRECURRENCE

FIRST DEVELOPERBROMIDE CONCENTRATIONOutlier Low, Level Shift Low, Trend Down



PLOTPROBLEM


Replenisher toodilute.

Overreplenishment.

Average density ofprocessed filmhigher than normal.

Check specific gravity and bromide concentration of replenisher.

Check volume ofreplenisher used vsamount of filmprocessed.




Adjust pumps toprovide 200 mL/sq ft(1 part concentrate to 4 parts water).

Adjust concentrationof replenisher untilspecific gravity andbromide concentra-tion are correct; see Table 3 on page 7-18.


Check for highpercentage of high-density scenes.

Add concentrate to tank solution until specific gravity and bromide concentra-tion are correct; see Table 4 on page 7-18.

Add concentrate to tank solution until specific gravity and bromide concentra-tion are correct; see Table 4 on page 7-18.

Adjust replenishmentrate to compensatefor change inaverage density ofprocessed film;see Table 6 onpage 7-19.

Add starter to tanksolution to adjust bromide concentra-tion to aim; seeTable 7 on page 7-19.

Add starter to tanksolution to adjust bromide concentra-tion to aim; seeTable 7 on page 7-19.





Measure and plotspecific gravity andbromide concentra-tion for each replen-isher mix.

Perform regularmaintenance onreplenishment system.

Closely monitor tankbromide concentra-tion and averagedensity of porcessedfilm.

Level shift low

Trend down


VERIFYCAUSE

ELIMINATECAUSE

ELIMINATESYMPTOM

PREVENTRECURRENCE

FIRST DEVELOPERCycling



TEMPERATURELook for a relationship betweencycling and events that occurregularly:

• Start-up on Monday mornings

• Power-supply fluctuations in the labduring the day/week

• Large replenisher additions beforethe temperature is measuredMake corrections or adjustments to

eliminate the cause of cycling.

SPECIFIC GRAVITYLook for a relationship betweencycling and events that occurregularly:• Start-up on Monday mornings

• Shift/operator changes

• Use of new replenisher mixes(check mixing procedures)

• Intermittent use of air conditioningCheck that you are compensating

for evaporation correctly (see theprocedure given in Appendix 4A,“Compensating for Evaporation”).Make specific-gravity measurementsevery 2 to 4 hours for 2 or 3 days todetermine the cause of cycling.

Make corrections or adjustments toeliminate the cause of cycling.

TIMELook for a relationship between cycling and events that occur regularly:

• Measurements made by differentoperators

• Power-supply fluctuations in the labduring the day/weekMake corrections or adjustments to


REPLENISHMENT RATELook for a relationship betweencycling and events that occurregularly:• Shift/operator changes

• Power-supply fluctuations in the labduring the day/week

• Fluctuations in machine utilizationMake corrections or adjustments to


BROMIDE CONCENTRA-TIONCycling in bromide concentration isfrequently caused by a combinationof a probable cause that raises theconcentration followed by a probablecause that lowers the concentration.Cycling can also be linked to fluctu-ations in the average density ofprocessed film (lower or higher thannormal). The amount of bromidereleased into the first developerdepends on film exposure, so largeruns of one scene type will causemore or less bromide to be released.

Look for a relationship between cycling and events that occur regularly:

• Start-up on Monday mornings

• Shift/operator changes

• Use of new replenisher mixes(check mixing procedures)Check that you are compensating

for evaporation correctly (see theprocedure given in Appendix 4A,“Compensating for Evaporation”).Make bromide measurements every2 to 4 hours for 2 or 3 days to deter-mine the cause of cycling.

Make corrections or adjustments toeliminate the cause of cycling.



TABLE 2Addition of Water

to Correct for Overconcentration ofSeasoned Tank Solution

Specific mL of Specific mL ofGravity Water per Gravity Water per

Measured Litre of Measured Litre ofat 80°F Tank at 100.4°F Tank(27°C) Solution (38°C) Solution

TABLE 1

Addition of Waterto Correct for Overconcentration of

First Developer Replenisher Solution

Specific mL of Specific mL ofGravity Water per Gravity Water per

Measured Litre of Measured Litre ofat 80°F Replenisher at 100.4°F Replenisher(27°C) Solution (38°C) Solution

TABLE 3

Addition of First-Developer Concentrateto Correct for Underconcentration of

Replenisher Solution

Specific mL of Specific mL ofGravity Concentrate Gravity Concentrate

Measured per Litre of Measured per Litre ofat 80°F Replenisher at 100.4°F Replenisher(27°C) Solution (38°C) Solution

TABLE 4Addition of First-Developer Concentrate

to Correct for Underconcentration ofSeasoned Tank Solution

Specific mL of Specific mL ofGravity Concentrate Gravity Concentrate

Measured per Litre of Measured per Litre ofat 80°F Tank at 100.4°F Tank(27°C) Solution (38°C) Solution

For each 40 mL ofKODAK First Developer Replenisher, Process E-6AR,

add 1 mL of KODAK First Developer Starter, Process E-6

1.060 0 1.057 01.061 16 1.058 161.062 31 1.059 311.063 45 1.060 451.064 60 1.061 601.065 74 1.062 741.066 87 1.063 871.067 100 1.064 1001.068 113 1.065 1131.069 125 1.066 1251.070 137 1.067 1371.071 149 1.068 1491.072 160 1.069 1601.073 171 1.070 1711.074 182 1.071 1821.075 192 1.072 1921.076 203 1.073 2031.077 212 1.074 212

1.057 0 1.054 01.058 16 1.055 161.059 32 1.056 321.060 48 1.057 481.061 63 1.058 631.062 77 1.059 771.063 91 1.060 911.064 104 1.061 1041.065 118 1.062 1181.066 130 1.063 1301.067 143 1.064 143

1.057 0 1.054 01.056 5 1.053 51.055 9 1.052 91.054 14 1.051 141.053 18 1.050 181.052 23 1.049 231.051 27 1.048 271.050 32 1.047 321.049 36 1.046 361.048 40 1.045 401.047 45 1.044 45

1.060 0 1.057 01.059 5 1.056 51.058 9 1.055 91.057 14 1.054 141.056 19 1.053 191.055 23 1.052 231.054 28 1.051 281.053 32 1.050 321.052 36 1.049 361.051 41 1.048 411.050 45 1.047 451.049 49 1.046 491.048 54 1.045 541.047 58 1.044 581.046 62 1.043 621.045 66 1.042 661.044 70 1.041 701.043 74 1.040 741.042 78 1.039 781.041 82 1.038 82



TABLE 5

Addition of Replenisher to Correct forHigh Bromide Concentration

BromidemL of Replenisher

Concentration (g/L)*per Litre of

Tank Solution3.6 4943.4 4423.2 3793.0 3002.8 1982.6 61

*If the bromide concentration is higher than 3.6 g/L, discard the solution and prepare a new first developer according to the mixing instructions on page 7-3.

TABLE 7

Addition of Starter to Correct forLow Bromide Concentration

BromidemL of Starter

Concentration (g/L)per Litre of

Tank Solution1.4 51.6 41.8 32.0 22.2 12.4 0.5

Replenishment RateBromideConcentration

(g/L)mL/sq ft mL/sq M

286 3077268 2881249 2685231 2489200 2153200 2153200 2153159 1707140 1511122 1315104 1119

3.02.92.82.72.62.52.42.32.22.12.0

TABLE 6

Adjusted Replenishment Ratesto Compensate for

High or Low Bromide ConcentrationDue to Changes in Average Density of

Processed Film



You can compensate for low utiliza-tion by following the proceduredescribed below; the procedure isbased on the theory that you mustcomplete one first-developer tankturnover every three weeks forefficient process operation.

This procedure establishes a mini-mum daily square footage requirementfor the amount of film processed. Youcan follow the procedure for anyprocessor type that uses replenish-ment.

1. To determine the minimum dailysquare footage requirement,multiply the first-developer tankvolume (in litres) by 5; thendivide by the number of days theprocessor is operated during athree-week period.

For example, a processor with afirst-developer tank volume of 70litres operated for 15 days over athree week period would have aminimum daily square footagerequirement of 23 ([70 x 5] ÷ 15= 23).

2. Throughout the day, record theamount of film you process.

3. At the end of each day, recordthe amount of film you pro-cessed (in square feet) to theminimum daily square footagerequirement.

• If the amount of film processedmeets or exceeds the minimumdaily square footage require-ment, no additional replenish-ment if required.

• If the amount of film processed isless than the minimum require-ment, replenish all of your tanksolutions for the difference in

COMPENSATING FORLOW UTILIZATION

square footage. You will alsoneed to add 1mL of first devel-oper starter to your first-devel-oper tank solution for everysquare foot of film processedbelow the minimum dailyrequirement. Do not add colordeveloper starter to the color-developer tank; additionalstarter will lower color-devel-oper activity.

The first time you use thisprocedure, you may have to re-optimize your process byfollowing the procedure for“Optimizing Your Process” insection 6.

Example—Your minimum dailysquare footage requirement is 23 ft2,but you processed only 18 ft2 of film.The difference between the mini-mum requirement and the amountof film processed is 5 ft2. Based on areplenishment rate of 200mL/ft2, youneed to add an additional 1,000mL(5 x 200mL) of first developerreplenisher to your first-developertank solution and 1,000 mL of colordeveloper replenisher to your color-developer tank solution. For proces-sors that have a 1 ft2 replenishmentcycle, you need an additional 5replenishment cycles. You also needto add 1mL/ft2 (1mL/cycle) or 5mL offirst developer starter to the first-developer tank solution. Replenish allother solutions for the differencebetween the minimum requirementand the amount of film processed.

Note: If your processor has very lowutilization, you may want to divideyour minimum daily square footagerequirement in half, and comparethe amount of film processed withthe minimum requirement twiceduring the day (i.e., at midday and atshutdown), and make any adjust-ments required.

first developer - 125px125px.com/docs/chemicals/kodak/z-6_7_082604.pdfprocess control handbook •...

Documents