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Brakes can be strange sometimes. There may be a "Hard Spot" on the brake shoe/pad or even on the drum/rotor. You may need to have the drum/rotor turned. Sometimes they can sand or rough up the shoe/rotor to resolve the issue. Make sure the wear sensors are not damaged or alignment.
A grinding or rumbling noise can also be symptoms of a wheel bearing or constant velocity joint in a driveshaft. A worn wheel bearing can also cause a 'whistling' sound (as can a worn CV joint).
A grinding noise with brakes is either worn pads causing metal to metal contact on the brake disk/rotor, or the brake backing plate catching on a spinning rotor ... or a loose/missing anti squeal brake shim (they stop the pads from rattling and vibrating).
However, as you say a mechanic has looked at the brakes and can't find anything wrong .. I think I would begin to suspect a wheel bearing or constant velocity joint on the driveshaft (front wheel drive cars).
I believe you have drum brakes on the back. Not sure. If so, it probably is the automatic adjuster is frozen. This comes into play when you go backwards and apply the brakes. It is used so that the emergency brake is in proper alignment, that is, it only takes a few clicks before the emergency brakes start being applied. If there were no adjuster, as the brakes go old, you would lose the emergency brakes entirely.
To your direct question - I don't know the Highlander model in detail, but as a general response, if the brakes are noisy when NOT applied, the piston in your new caliper may not be returning properly.
The return spring in disc brakes is actually the rubber fitted around the caliper piston. If this is causing the piston to be wrongly positioned, the brakes will be noisy. Check that the rotor can be turned by hand when the brakes are not applied. Also check that the piston is not retracting from the pads a very long way, which it should not do.
It is worth making very sure the spring clips are fitted correctly. Some can be easily put in the wrong way round.
If the brakes are squealing when applied, that is a different problem. You can get a disc brake anti squeal liquid, which is applied to the back of the pad on assembly to the caliper. Also double check all the anti squeal shims are correctly installed.
At this range, that's all I can think of right now.
brakes typically only last about mas 30k miles. might be the brake lining warning shims letting you know its low or that plus glazed rotors/ drums needing to be replaced and or cut.
Your rear brake pads are most likely worn to the wear indicator which can make a high pitch squealing noise. It is very common that it will squeal when backing up, but not when applying the brakes. 50,000 miles is about the average life for rear brake pads on your car.
Two things, in my experience, makes brakes squeal. If you can apply brakes but they don't squeal until you are nearly stopped, that's benign. The sleeves and backing of the brake pads need some special high temperature brake grease. But you can live with it. But if you get a scraping, screeching sound whenever brakes are applied and possibly to a lesser extent even when they are not applied, then the brake wear feelers are touching the brake disk. You need to get brake pads or shoes replaced soon or cause damage.
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