Change the hands
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This is easy. 21C hands are designed to be interchangeable and they just pop in and out. (Male hands will only fit on male figures and female hands will only fit on female figures, however.) To remove a hand from a figure, hold the arm firmly just above the wrist. With your other hand, grab just below the wrist and pull with a twisting motion. To reattach a hand, just push in a twisting motion until it pops in. Be careful with the female hands, however, as the pin that inserts into the arm is thin and breaks easily. Gloved hands are also fairly fragile. For the male Caucasian figures, 21C has released an "Action Accessories" carded set, which contains the following hands: extended left trigger finger, extended right trigger finger, pointing finger, "V for victory", "thumbs up", clenched fist, salute.
Take off the boots
It's important to take care when removing boots from a figure, as too much misapplied force can break the foot. For stubborn boots, it's helpful to heat the boot with a hair dryer or soak it in hot water. This will make the boot softer and easier to slide off. Another trick is to lubricate the inside of the boot. Any lubricant will do the trick (water, hand soap, skin lotion, K-Y Jelly), although you should avoid petroleum-based products like Vaseline as they can stain and corrode the plastic. Put the lubricant on a Q-tip and stick it down the back of the boot down to the heel area.
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Both SS and SAM figures are hinged at the ankle so that the foot can be positioned parallel to the leg, making it easier for the boots to be removed. Be sure the foot is in this position before atempting to take off the boot.
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With your thumb on the heel of the boot and your middle and index finger on the toe, pinch the sole of the boot so that it folds in half. Pull slowly but firmly until the boot slips off the foot. Dusting the inside of the boot with talcom powder will make this task easier next time.
Swap the head
All 21C male Super Soldier and SAM heads are interchangeable. However, the new Interchangeable heads on the series 2 carded figures are not compatible with the older style SS or SAM heads. Hasbro Classic Collection and Hall of Fame GiJoe figures, the newer super-articulated Soldiers of the World figures, and Ultra Force heads are compatible with 21C figures. Dragon heads are not a good match for 21C bodies as they have a smaller neck post and require some minor surgery before they will fit somewhat awkwardly.
Swapping heads is fairly easy, provided that you have heated the head first to make it more pliable. I recommend either heating the head with a hairdryer for a few minutes or soaking the head in a cup of very hot water. I've never heard of either of these methods doing damage to factory painted headsculpts, but you may want to be careful with custom paint jobs. (BTW: watch your fingers as these heads can get very hot.) To remove the head, secure the neck with two fingers of one hand and then, with the thumb of the other hand, grab your figure's head under the chin and pull it off. To avoid breaking the neck joint, keep a firm grip on the neck and don't allow it to move around while you pull the head off. With the new super soldier body, be careful that the neck assembly doesn't pop out of the body. It's very difficult to get it back inside, short of splitting the section in half and regluing it over the neck post. The head should come off fairly easily. If it doesn't, it probably isn't hot enough. Try heating it for a longer period of time with the hairdryer or use hotter water.
To attach a head, repeat the same procedure outline above. Heat the head with a hair dyer or very hot water until it become very pliable. Push and twist the head back onto the neck post. Sometimes, in the effort to attach the head, air gets forced out of the head, giving it a squished appearance. Not to worry-- the head doesn't form a very tight seal around the neck post so it will return to normal shape in a few moments.