How to Caulk a Chair Rail
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Cut the tip of the caulking nozzle to create an opening about the width of the gap you want to fill. Poke through the nozzle to open the foil seal with a long nail or screw. Push the thumb button on the caulking gun to release, and pull the plunger back. Slide the caulk into the gun, and push the plunger up. Pull the trigger until the caulking rises up in the nozzle.
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Apply caulk to the chair rail by inserting the nozzle into the seam at one end of the chair rail. Squeeze the trigger evenly to apply an even bead, allowing the caulk to build up slightly. Try to fill the seam in one movement if possible. Use a wet finger to smooth the caulk into the seam. With a damp rag, wipe any excess caulk from the wall and chair rail.
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Repeat the procedure for all remaining seams and joints.