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The first step in making a duotone from a
color image is to convert the color image to black and white.
There are several ways to do this. I prefer RGB channel conversion
as it allows you to adjust each channel's contribution to the final
image. Once you have your black and white image, flatten the
layers if needed and take the following steps:
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On the Image menu
choose MODE --> GRAYSCALE
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Again on the Image
menu choose MODE --> DUOTONE
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You should see a
pop-up dialog box that resembles this...

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On the TYPE: dropdown,
switch from Monotone to Duotone

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Notice that Ink 2: was
added with a value of white (that's duotone speak for monotone)
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Click on the white box
(directly under the black box in this case) and the color picker
will appear

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For this image, I
picked values of 253, 139, and 35 for R, G, and B, respectively.
You can pick whatever color you like, or use one of Photoshop's
presets by clicking on the "Color Libraries" button. The only
rule of thumb, if you like it, it's good!
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Last step, click on
the box with a diagonal line in it. This will pull up the
Duotone Curve dialog box.

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Here I created a
gentle S in the curve by adding the values as shown above.
(Note, you can also manipulate the curve line directly if you like.)
Changing the curve effects the blending of black and the color you
have chosen. The best way to get a feel for how this works is
to put some extreme values in and watch what happens.
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Click OK twice to
close the curve dialog and the duotone dialog.
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Save, save, save!
Notes:
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For the RGB
conversion, I choose to keep the greens at zero and emphasize
red:blue 2:1. You don't have to do this - my goal here was to
pop the girl out away from the green background somewhat.
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Don't assume that my
choice of colors and values is best. It can vary from image to
image and certainly by personal taste!
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