In some cases the presence of flux is undesirable; flux traces interfere with e.g. precision optics or MEMS assemblies. Flux residues also tend to outgas in vacuum and space applications, and traces of water, ions and organic compounds may adversely affect long-term reliability of non-hermetic packages. Trapped flux residues are also the cause of most voids in the joints. Flux-less techniques are therefore desirable there.
For successful soldering and brazing, the oxide layer has to be removed from both the surfaces of the materials and the surface of the filler metal preform; the exposed surfaces also have to be protected against oxidation during heating. Flux-coated preforms can also be used to eliminate flux residue entirely from the soldering process.
Protection of the surfaces against further oxidation is relatively simple, by using vacuum or inert atmosphere. Removal of the native oxide layer is more troublesome; physical or chemical cleaning methods have to be employed and the surfaces can be protected by e.g. gold plating. The gold layer has to be sufficiently thick and non-porous to provide protection for reasonable storage time. Thick gold metallization also limits choice of soldering alloys, as tin-based solders dissolve gold and form brittle intermetallics, embrittling the joint. Thicker gold coatings are usually limited to use with indium-based solders and solders with high gold content.
Removal of the oxides from the solder preform is also troublesome. Fortunately some alloys are able to dissolve the surface oxides in their bulk when superheated by several degrees above their melting point; the Sn-Cu and Sn-Ag require superheating by 18–19 °C, the Sn-Sb requires as little as 10 °C, but the Sn-Pb alloy requires 77 °C above its melting point to dissolve its surface oxide. The self-dissolved oxide degrades the solder's properties and increases its viscosity in molten state, however, so this approach is not optimal.
Solder preforms are preferred to be with high volume-to-surface ratio, as that limits the amount of oxide being formed. Pastes have to contain smooth spherical particles, preforms are ideally made of round wire. Problems with preforms can be also sidestepped by depositing the solder alloy directly on the surfaces of the parts or substrates, by  chemical or electrochemical means for example.
A protective atmosphere with chemically reducing properties can be beneficial in some cases. Molecular hydrogen can be used to reduce surface oxides of tin and indium at temperatures above 430 and 470 °C; for zinc the temperature is above 500 °C, where zinc is already becoming volatilized. (At lower temperatures the reaction speed is too slow for practical applications.) Very low partial pressures of oxygen and water vapor have to be achieved for the reaction to proceed.
Other reactive atmospheres are also in use. Vapors of formic acid and acetic acid are the most commonly used. Carbon monoxide and halogen gases (for example carbon tetrafluoride, sulfur hexafluoride, or dichlorodifluoromethane) require fairly high temperatures for several minutes to be effective.
Atomic hydrogen is much more reactive than molecular hydrogen. In contact with surface oxides it forms hydroxides, water, or hydrogenated complexes, which are volatile at soldering temperatures. A practical dissociation method is an electrical discharge. Argon-hydrogen gas compositions with hydrogen concentration below the low flammable limit can be used, eliminating the safety issues. The operation has to be performed at low pressure, as the stability of atomic hydrogen at atmospheric pressure is insufficient. Such hydrogen plasma can be used for fluxless reflow soldering.
Active atmospheres are relatively common in furnace brazing; due to the high process temperatures the reactions are reasonably fast. The active ingredients are usually carbon monoxide (possibly in the form of combusted fuel gas) and hydrogen. Thermal dissociation of ammonia yields an inexpensive mixture of hydrogen and nitrogen.
Bombardment with atomic particle beams can remove surface layers at a rate of tens of nanometers per minute. The addition of hydrogen to the plasma augments the removal efficiency by chemical mechanisms.
Mechanical agitation is another possibility for disrupting the oxide layer. Ultrasound can be used for assisting tinning and soldering; an ultrasonic transducer can be mounted on the soldering iron, in a solder bath, or in the wave for wave soldering. The oxide disruption and removal involves cavitation effects between the molten solder and the base metal surface. A common application of ultrasound fluxing is in tinning of passive parts (active parts do not cope well with the mechanical stresses involved); even aluminium can be tinned this way. The parts can then be soldered or brazed conventionally.
Mechanical rubbing of a heated surface with molten solder can be used for coating the surface. Both surfaces to be joined can be prepared this way, then placed together and reheated. This technique was formerly used to repair small damages on aluminium aircraft skins.
A very thin layer of zinc can be used for joining aluminium parts. The parts have to be perfectly machined, or pressed together, due to the small volume of filler metal. At high temperature applied for long time, the zinc diffuses away from the joint. The resulting joint does not present a mechanical weakness and is corrosion-resistant. The technique is known as diffusion soldering.
Fluxless brazing of copper alloys can be done with self-fluxing filler metals. Such metals contain an element capable of reaction with oxygen, usually phosphorus. A good example is the family of copper-phosphorus alloys.