Chemical Machining Processes For Aircraft Parts Manufacturing (May 2019)

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Chemical Kinetics
Chemical Milling for Aircraft Parts Manufacturing
(When Corrosion is a Good Guy)

Luis Gustavo Pacheo
2
Summary
1. Introduction
2. History
3. The Process
4. Undesirable Reactions
5. Quality Control
Appendices
1. Chemical Milling Chemistry
2. Hydrogen Sulfide (H2S)
3. Aluminum and its Alloys
4. Aluminum Etching as a Corrosion Process
5. The Aluminum-Air Battery
6. References

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Introduction
Why Advanced (non-conventional) machining processes are required?
 Machining processes involve material removal by mechanical means  chip

formation, abrasion, or microchipping
 Situations where mechanical methods are not satisfactory, economical or
possible:
 Very high strength and hardness

 Material is too brittle
 Workpiece is too flexible
 Workpiece is too thin
 Shape of the part is complex
 Surface finish and dimensional
tolerance requirements
 Temperature rise during processing

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Introduction

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Chemical Milling
History

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History
The earliest written evidence of deliberate use of etching
on iron appears in a fteenth-century English manuscript.
The manuscript describes an etchant consisting of salt,
charcoal and vinegar and a ‘‘maskant’’ of linseed oil paint.
The paint was brush applied in the required pattern, and

later the etchant was applied to all unprotected areas. The
use of chemical etching as a technique for engraving
weapons and body armor became more widespread in the
early fifteenth-century.

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History
As weapons and body armor were gradually being forged with materials as hard as a the craftsman’s
engraving tools, hence the old engravin technique was quickly replaced chemical etching process.
The chemical etching technique as

developed for armor etching also found
use in the early printing industry and had
profound affect on graphic printing. The
primary advantage of an etched line over
that of an engraved line is that the etched
line is produced without an upstanding
burr.

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History
The main industrial application of chemical machining was developed after the war II. In 1953,
North American Aviation Inc. (California USA) used the process to etch aluminum components for
rockets. The company named the process "chemical milling" and patented it (US Patent No:
2739047) in 1956.
Before the chemical milling process, sheet metal structures for

aerospace applications were created by forming two or more
identical parts; routing one or more parts to create lightening
holes, then joined all parts with rivets or threaded fasteners.
With chemical milling one part is formed from a thicker

substrate, then selected areas are removed by etching to create
a lighter and stronger part without the concerns of sandwich or
crevice corrosion.

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History
Chemical Milling (CHM) is developed based on the observation
that chemicals attack metals and etch them by using chemical
solutions.
CHM is the removal of metal by chemical attack by a corrosive
liquid.
The area affected by the chemical reagent is controlled by
masking or by partial immersion
The areas of the workpiece which are not to be machined are
masked.
The workpiece is either immersed in or exposed to a spray of
chemical reagent.
CHM was basically developed for aerospace industry to maintain
strength of part at reduced weight.

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Chemical Milling
The Process

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Chemical Milling Process
The Art of Chemical Milling

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The generally accepted reaction in aluminum chemical milling is:
2H2O + 2NaOH + 2Al → 2NaAlO2 + 3H2↑
It can be summarized in the following steps:
Cleaning. The first step is a cleaning operation to ensure that extraneous and undesirable
material will be removed uniformly from the surfaces to be etched.
Masking. A protective coating called a maskant is applied to certain portions of the part
surface. This maskant is made of a chemically resistant material to the etchant, applied on those
portions of the work surface that are not to be etched.
Etching. The part is immersed in an etchant that chemically attacks those unmasked portions.
The usual method of attack is to convert the work material (e.g. a metal) into a salt that
dissolves in the etchant and is thereby removed from the surface. When the desired amount of
material has been removed, the part is withdrawn from the etchant and washed to stop the
process.
Demasking. The maskant is removed from the part.

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ETCH RATE (E)

Workpiece is etched for a duration necessary to produce the required depth of etching.
E=d/t in micron/min or mm/min.
depth of etch …………. d (micron or mm),

etching time …………… t (min),
rate of etching ……….. E (per side).
Example, If thickness of material is 3.0mm, etching time is 10 min and thickness of material
after simultaneously etching from both side is 2.5mm, then
E= (3.0-2.5)/ (2x10)= 0.5/20 = 0.025mm/min

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15
The constant of proportionality Fe called etch factor for the material is defined as
Undercut in chemical machining.
The dimensions u and d are defined in the figure above. Different work materials have
different etch factors in chemical milling. Some typical values are presented in Table 26.2.

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Strong acid or alkaline solution is used to dissolve materials selectively.
An etchant resistant mask, made typically of rubber or plastic is used to protect those regions
of the component from which no material is to be removed.
Sheet aluminum stock is stretched formed and Appearance immediately after the chemical milling process
coated with maskant. Select areas of maskant have
been removed and the part is ready for the
chemical milling process

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1. SCOPE:
1.1 This recommended practice provides recommendations concerning the chemical milling
of aluminum, magnesium, and titanium alloys, and specialty alloys.
1.2 The detailed recommendations are based on practical engineering and production
experience that will enable industry to make proper use of the chemical milling process.
1.3 Safety - Hazardous Materials:
While the materials, methods, applications, and processes described or referenced in this
specification may involve the use of hazardous materials, this specification does not address
the hazards which may be involved in such use. It is the sole responsibility of the user to
ensure familiarity with the safe and proper use of any hazardous materials and to take
necessary precautionary measures to ensure the health and safety of all personnel involved.

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Aluminum and its Alloys

To a greater or lesser extent, all metals develops a protective layer of oxide on its surface. In
conditions of significant humidity, the oxygen atoms further hydrates, forming hydroxyls (OH-, a
fairly polarized group).
Camadas superiores de moléculas de água;

Espessura= f(temperatura, umidade)
1a camada de moléculas de água
Grupos hidroxila superficiais

resultantes da interação com a umidade
da atmosfera envolvente
Camada passivadora feita de óxidos do
próprio metal base devido à interação
com O2 atmosférico
As a result, hydroxyls formed will
strongly attract other substances that
Substrato Metálico
are polarized to each other (eg Water,
Free radicals, acidic or alkaline
industrial waste, etc.).
M = Metal, O = Oxygen, O: = H2O, O.= OH-1

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Al2O3 oxide layer formation on
Aluminum and its discontinuites

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Surface
Discontinuites:
Flaws and
Imperfections
In Oxide Film.

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Surface Treatment (e.g.: Passivation, Anodizing ...)

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Amphoteric Nature of Aluminum

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Amphoteric behavior is the ability of a
compound to be soluble in both high and
low pH but not in between the two
The amphoteric nature of aluminum can be

demonstrated by varying the pH of the
solution in the presence of an indicator.
Other metal hydroxides demonstrate
amphoteric behavior including hydroxides of
zinc, copper, lead, chromium and tin.
The solid that forms in a solution around

intermediate pH and makes the solution
cloudy is termed a “precipitate”.

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E-pH diagram for pure Al at 25˚C in aqueous solution (adapted

from Pourbaix 1974). The lines (a) and (b) correspond to water
stability and its decomposed product.

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Aluminum hydroxide precipitate (Al(OH)3) formed by adding few drops of a 1M solution of

sodium hydroxide (NaOH) to 0.2 M solution aluminum sulfate (Al2(SO4)3). The reaction is:
Al2(SO4)3 + NaOH → Al(OH)3↓ + Na2SO4 OR Al+3(aq) + 3OH-1 (aq)→ Al(OH)3 (s)↓

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Bath Composition & Additives

Two etchant types based on NaOH are used for aluminum chemical milling, Type I and Type II
(Table 1). A preferred practice in some chemical milling operations is to mill 80% of the cut in
Type I Etchant, and finish the cut in Type II Etchant to improve surface finish.

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Chemistry

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Aluminum etchant may consist of only
NaOH and water, but most always
include additives for improvement
process and final quality parameters.
For example, sulfur or its compounds
are added to both Type I and II
etchants.
Sulfur additives such as sodium sulfide

are included in the etchant formula to
improve chemical milling end quality
such as chem-mill radius, undercut,
fillet smoothness, surface finish and
pocket dishing. All are attributes
directly related to the etchant formula.
Ethylenediamine-tetraacetic acid (EDTA) is also a useful chelating agent that can influence chem-mill
fiIlet quality.

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Like aluminum ions, other heavy metals Theoretical Solubility of Metal Hydroxides vs. pH
show also marked amphoteric behavior,
their hydroxides reaching minimum
solubility at a specific pH for each metal.
Hydroxide precipitation is initiated by
adding an appropriate hydroxide to waste
waters in stirred reaction tanks to form
the insoluble heavy metal hydroxide
precipitates:
M+n +nOH-  M(OH)n↓

Heavy metals dissolved in water are
precipitated from acid or neutral solutions
by adding sodium hydroxide or lime
(Ca(OH)2), but the results are far from
satisfying in many cases.

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Complete hydroxide precipitation at neutral pH does not take place except in presence of complexing
agents. For best performance, the pH-value of the solution shall be adjusted to a slightly alkaline
range. The minimal solubility of hydroxides of the majority of metals is reached at an approximate pH
of 9.5–10.0. Example: below, metal hydroxides precipitates formed by adding few drops of 1M
solution of sodium hydroxide (NaOH) to 0.2 M solutions containing various metal salts.
(1) Aluminum hydroxide: Al(OH)3 Al2(SO4)3 + NaOH → Al(OH)3↓ + Na2SO4

(2) Copper (II) hydroxide: Cu(OH)2 CuCl2 + NaOH → Cu(OH)2↓+ NaCl
(3) Cobalt hydroxide: Co(OH)2 CoCl2 + NaOH → Co(OH)2↓ + NaCl
(4) Iron (III) hydroxide: Fe(OH)3 FeCl3 + NaOH → Fe(OH)3↓ + NaCl
(5) Iron (II) hydroxide: Fe(OH)2 FeSO4 + NaOH → Fe(OH)2↓+ Na2SO4
(6) Zinc hydroxide: Zn(OH)2 ZnSO4 + NaOH → Zn(OH)2↓ + Na2SO4
1 2 3 4 5 6

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Solubility of Metal Hydroxides and Sulfides as a
But adjusting pH and adding small amounts of sodium Function of pH
sulfide (Na2S) solves this problem: The precipitation
Souce: EPA publication, EPA-600/2-82-011C, 1981

will be completed and the remaining residues of, e.g.,
cadmium, copper, lead, mercury, nickel, or silver are
reduced to an extremely low level.
Sulfides precipitates zinc, copper and other alloying
elements from solution, prevent them from plating
back onto the aluminum substrate surtace, a
phenomenon known as secondary masking.
Metals may be precipitated as sulfide by using

reagents like Na2S, NaHS, H2S or FeS (e.g., M = Metal
which oxidation state of +2, such as Zn2+, Fe2+, ... ):
M+2(aq)+ S−2(aq) MS(s)↓

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Secondary Masking Effect

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Adjusting the solubility of these ions using pH such that we can selectively precipitate Metal Sulfide
solids from a mixture and effectively separate the metal ions as we filter off the precipitates in turn.
(1) MS(s) M2+(aq) + S2-(aq)

and
(2) S2-(s) + H2O(l) HS-(aq) + OH-(aq)

S2- ion is a strong base (Kb~105) and will react immediately to form HS- and a hydroxide ion (OH-). So,
the two the concentration of S2- in solution is negligible and therefore, the actual dissolution process
can be approximated as the sum of the reactions 1 and 2 above:
(1) + (2): MS(s) + H2O(l) M2+(aq) + HS-(aq) + OH-

Thus, the true Ksp for the dissolution of a metal II sulphide is:
Ksp = [M2+][HS-][OH-]

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IRON SULFIDE PRECIPITATION COPPER SULFIDE PRECIPITATION
The addition of the Iron to sodium sulfide Copper sulphide (CuS) precipitate (dark indigo) formed by
(Na2S) solution is used to cause a adding 0.25 M solution of copper sulphate (CuSO4) drop by
precipitate (FeS) to find other metal drop to 0.25 M solution of sodium sulphide (Na2S). The
contaminants in water systems. reaction is:
Na2S + CuSO4 → CuS ↓ + Na2SO4

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Chemistry of Inhibitors
The effectiveness of the corrosion inhibitors lays in their chemical structure. Due to the high
compression on the metal and wide area occupied on metal, organic corrosion inhibitors may
screen metal atoms in the alloy with a protective barrier film.
Schematic diagram showing pitting potential as a function of chloride

ions and the range of corrosion organic inhibitors (Ormellese et al. 2009).

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Among many available methods of efficient protection of aluminum against corrosion is the application
of organic inhibitors. According to NACE International, a corrosion inhibitor is “a chemical substance
that, when added in small concentration to an environment, effectively decreases the corrosion rate”
Another definition can be found in ISO 8044: “A chemical substance that decreases the corrosion rate
when present in the corrosion system at suitable concentration, without significantly changing the
concentration of any other corrosion agent”.

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Corrosion undergoes faster when water adsorbs on the metal. Due to the process of adsorption
by physisorption, organic inhibitors replace the water on the metal surface. The ability of the
inhibitor replacing water depends on electrostatic interactions between it and metal, as well as the
orientation of inhibitor structure.
When the organic inhibitor is added to the system, the hydrophobic group from the polar
compound orients itself perpendicularly to the metal surface and blocks aggressive corrosive fluids.

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For example, presence of the nitrogen atom in compounds like in amines or alkanolamines
(aminoalcohols such as triethanolamine - TEA) influences the effectiveness of inhibition by decreasing
corrosion rates attacking cathodic sites on aluminum, where oxygen picks up electrons and is reduced
to OH- ions (they are also able to adsorb on anodic sites). Triethanolamine added to Type II etchants is
present to promote smooth fillets and to reduce/controI chem-mill undercut.
Their adsorption involves electrostatic interactions between charges of organic molecules dipoles and
the charge of the metal surface. Inhibitors absorbed via heteroatoms block the active sites with their
polar groups and subsequently decrease corrosion rates.
Scheme of functional groups:
a) Amines on the metal surface,

b) carboxylates on the metal surface.

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Chemical Milling
Undesirable Reactions

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In high-pH bath the sodium aluminate will “hydrolyze” or combine with water in the bath to
form free sodium hydroxide and aluminum hydroxide. The aluminum hydroxide is insoluble and
will “drop out” of solution. The global reaction is:
This reaction is rapid when an unbalance of caustic soda, dissolved aluminum and bath agitation
and temperature occurs.
Aluminum hydroxide forms a very hard scale

in the bottom of the tank, which is not easily
removed and will eventually shut the process
down. To help prevent this, maintain a bath
with a sufficient concentration of chelating
additives to hold the dissolved aluminum in
suspension, preventing it from precipitating.

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Chemistry
Summary of thermodynamic properties of the aluminate ion
Summary of thermodynamic properties of gibbsite, boehmite, diaspore and corundum

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Similar to what happens with AAB cells, the discharging anode reaction in alkaline media is:
The cooling of temperature and/or the progressive consumption of hydroxyl ions at the
aluminum electrode makes the electrolyte saturated with the aluminate. Eventually, the
aluminate concentration exceeds the supersaturation and a crystalline form of aluminum
hydroxide precipitates with the regeneration of hydroxyl ions:
Cristallization
In addition, aluminum is thermodynamically unstable in an alkaline electrolyte and reacts with the
electrolyte to generate hydrogen (H2):
Hydrogen Polarization
This parasitic corrosion reaction, or self-discharge, degrades the coulombic efficiency of the anode
and must be suppressed in order to minimize the capacity loss. Therefore, the global is:
Chemical Milling

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The part is submerged into the chemical milling Hydrogen gas being burned off during the
etchant. chemical milling process.

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Chemical Milling
Quality Control

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Quality Control
Etching Defects

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Quality Control

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Appendices

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Chemical Milling
Chemistry

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Summary of Chemical Equilibrium

In a chemical reaction, as reactants start to react, products start to form. Therefore, reactants
continuously decrease and products continuously increase till a point is reached where
eventually no change in concentrations can be detected.
In the so called reverse reactions, this is the point of equilibrium which is a point where the rate
of the forward reaction (product formation) equals the rate of backward reaction (reactants
formation). Equilibrium implies continuous transformation between infinitesimally small
amounts of products and reactants.

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For chemical reactions that do not proceed to completion, an equilibrium constant can be written as
the quotient of multiplication of molar concentrations of products divided by that of reactants, each
raised to a power equal to its number of moles.
aA + bB  cC + dD
Where, the small letters represent the number of moles of substances A, B, C, and D. The equilibrium
constant is written as:
Keq = (c[C]×d[D])
(a[A]×b[B])
Equilibrium constants may be written for dissociations, associations, reactions, or distributions.

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Calculation of Equilibrium Constants
We know from thermodynamics that a reaction occurs spontaneously if it has a negative DG (Gibbs free
energy) where:
DG = DH - TDS
Where, DH is the change in enthalpy of the reaction and DS is the change in entropy. At standard
conditions of temperature and pressure (standard state) we have the standard free energy DGo where:
DGo = DHo - TDSo
The standard free energy is related to equilibrium constant by the relation:
DGo = - RT ln Keq ↔ Keq = e- DGo/RT

Where R is the gas constant (8.314 deg K-1mol-1) and T is the absolute temperature (K).
It should be clear that DGo gives us good information about the spontaneity of the reaction but it
offers no clue on the rate at which the reaction may occur.

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LE CHATELIER'S PRINCIPLE
The equilibrium concentrations of reactants and products can be changed by applying an external
stress to the system, e.g. increasing or decreasing the concentration of a reactant or product,
changing temperature or pressure. The change occurs in a direction which tends to counterpart
the applied stress. Examples:
a. Increasing the temperature of an exothermic reaction will shift the reaction to left (more
reactants and less products). The opposite is observed if the reaction is exothermic or if heat is
removed from an exothermic reaction.
b. In a reaction where the number of gaseous molecules produced is more than the number of
reacting gaseous molecules, increasing the pressure of the system will shift the reaction toward
the reactants in an attempt to decrease the number of moles and vice versa. Reactions in
solutions are usually insensitive to changes in pressure.
c. Increasing the concentration of a reactant or removing a product will result in a shift of
reaction towards more products and vice versa.
d. Some reactions can be facilitated by addition of a catalyst (a substance that is not part of
reactants or products but its presence makes the reaction faster). The catalyst does not change
the position of equilibrium but makes the time required to reach this equilibrium point shorter.

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A strong electrolyte is any electrolyte (acid, base, salt) that dissociates about 100% into ions. A
weak electrolyte sets up an equilibrium in water so that some exits as the original undissociated
species and some exists as ions in solution or as undissolved solid.
“Insoluble” salts are governed by equilibrium reactions and are really sparingly soluble. There is
a dynamic equilibrium between the solvated ions and the crystalline solid.
The extent to which a substance dissolves is its solubility. Solubility, as with all equilibria, is highly
temperature dependent. Solubility may be expressed as grams of compound/100 mL of H2O, or
as molarity, M.
In general, for the reaction:
AxBy(s) x Am+(aq) + y Bn-(aq), Ksp = [Am+]X[Bn-]Y

we have Ksp = [Am+]X[Bn-]Y at equilibrium. Ksp is the solubility product constant and the right hand
side of this equation is often called the ion product.
In reactions involving ions which have the potential to form insoluble compounds, we must
consider equilibrium conditions in order to decide whether or not a precipitate (ppt) will form.

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Solubility Constants Constants of Solubility Products of Metal Hydroxides
Constants of Solubility Products of Metal Sulfides

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Hydrogen Sulfide (H2S)

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Hydrogen sulfide (H2S)

Hydrogen sulfide (H2S) is a partially soluble gas which exists in aqueous solutions (i.e., wastewater)
in equilibrium with the hydrosulfide ion (HS-) and sulfide ion (S2+). At neutral pH of 7.0, roughly 50%
of the sulfide in solution will be in the H2S form, which means it can be released to the atmosphere
to cause odor and corrosion problems. At pH 9.0 less than 1% of sulfide is in the H2S form. This
relationship is shown on the following graph:

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Aluminum Aquo-Complexes

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There is a unique nomenclature to complex ions: The metal is known as the central
metal ion. The anions or molecules attached to the metal are called ligands.
The coordination number is the number of places on the metal ion where ligands are
bound. The bond between the metal ion and the ligand, where the ligand supplies both
electrons, is known as a coordinate covalent bond. What all these have got in common
is active lone pairs of electrons in the outer energy level. These are used to form co-
ordinate bonds with the metal ion. All ligands are lone pair donors. In other words, all
ligands function as Lewis bases.
The electronic structure of a naked aluminum ion before the water molecules bond to it is:
1s22s22p63s23px1.
When it forms an Al3+ ion it loses the n=3 electrons, resulting → 1s22s22p6
That means that all the 3-level orbitals are now empty. The aluminum uses of six of these
to accept lone pairs from six water molecules. It re-organises (hybridises) the 3s, the
three 3p, and two of the 3d orbitals to produce six new (hybridised) orbitals all with the
same energy.

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When aluminum ions dissolves in water, the aluminum ion reacts with water to give a hydrated
aluminum ion, Al(H2O)63+, dissolved in bulk water. What this means is that the aluminum ion has the
strongest interactions with the six closest water molecules (the so-called first solvation shell), even
though it does interact with the other water molecules surrounding this Al(H2O)63+ cluster as well.
We frequently see the formula of this ion simply as “Al3+(aq)”, without explicitly noting the six water
molecules that are the closest ones to the aluminum ion and just describing the ion as being solvated in
water (hydrated). This is similar to the simplification of the formula of the hydronium ion, H3O+ to H+.

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Six is the maximum number of water molecules it is possible to fit around an aluminum ion (and
most other metal ions). By making the maximum number of bonds, it releases most energy and so
becomes most energetically stable. The co-ordination number of the aluminum is said to be 6.
OR
Empty hybrid orbitals around

aluminum Ion
Only one lone pair is shown on each water molecule. The other lone pair is pointing away from the
aluminum and so isn't involved in the bonding. The co-ordination number of a complex ion counts the
number of co-ordinate bonds being formed by the metal ion at its centre. Because of the movement
of electrons towards the centre of the ion, the 3+ charge is no longer located entirely on the
aluminum, but is now spread over the whole of the ion.

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Chemistry

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Chemistry

68
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Aluminum Alloys And Their Characteristics
Controlled unalloyed (pure) composition, used primarily in the electrical and chemical industries
1xxx
Alloys in which copper is the principal alloying element, although other elements, notably
2xxx magnesium, may be specified. 2xxxseries alloys are widely used in aircraft where their high
strength (yield strengths as high as 455 MPa, or 66 ksi) is valued.
Alloys in which manganese is the principal alloying element, used as general-purpose alloys for
3xxx architectural applications and various products
Alloys in which silicon is the principal alloying element, used in welding rods and brazing sheet
4xxx
Alloys in which magnesium is the principal alloying element, used in boat hulls, gangplanks, and
5xxx other products exposed to marine environments
Alloys in which magnesium and silicon are the principal alloying elements, commonly used for
6xxx architectural extrusions and automotive components
Alloys in which zinc is the principal alloying element (although other elements, such as copper,
magnesium, chromium, and zirconium, may be specified), used in aircraft structural components and
7xxx other high-strength applications. The 7xxx series are the strongest aluminum alloys, with yield
strengths ≥500 MPa (≥73 ksi) possible.
Alloys characterizing miscellaneous compositions. The 8xxx series alloys may contain appreciable
8xxx amounts of tin, lithium, and/or iron.
9xxx Reserved for future use

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THE BASIC TEMPER DESIGNATIONS
Letter Meaning
As fabricated – Applies to products of a forming process in which no special control
F
over thermal or strain hardening conditions is employed
Annealed – Applies to product which has been heated to produce the lowest
O
strength condition to improve ductility and dimensional stability
Strain Hardened – Applies to products which are strengthened through cold-
working. The strain hardening may be followed by supplementary thermal
H
treatment, which produces some reduction in strength. The “H” is always followed
by two or more digits (see table 4)
Solution Heat-Treated – An unstable temper applicable only to alloys which age
W
spontaneously at room temperature after solution heat-treatment
Thermally Treated - To produce stable tempers other than F, O, or H. Applies to
product which has been heat-treated, sometimes with supplementary strain-
T
hardening, to produce a stable temper. The “T” is always followed by one or more
digits (see table 5).

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THE BASIC TEMPER DESIGNATIONS

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Source: Kaiser Aluminum

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Aluminum and aluminum alloys – Historic Time Line

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Thermodynamic criteria of spontaneity

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79
Aluminum Etching
As a Corrosion Process

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Aluminum Etching as a Corrosion Process

Aluminum is amphoteric (soluble in both strong acids and bases). Acid based etchants are used for
aluminum cleaning operations, but seldom used for chemical milling. They yeld slow etch rates and
leave a rough surface. The most widely used aluminum etchants are alcaline based with sodium
hydroxide as the most popular alcali.
We have already seen that the generally accepted reaction in aluminum chemical milling is:

Or taking into account just the most important participants (in ionic form):
There have been no extensive studies to define the chemical mechanisms of etching or metal
dissolution. However, the process is thought to be a electrochemical reaction similar to lhe
accepted description of general corrosion.

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The sequence below is an aluminum plate (Al) placed in an aqueous copper chloride solution
(CuCl2). Sodium chloride (NaCl) is added to help break the alumina layer (Al2O3). With a higher
oxidation tendency than copper, aluminum dissolves in solution (Al+3). Copper ions (Cu+2), which
give the blue color to the solution), disappear as copper deposits on the aluminum sheet are
formed. Although not easily visible, there is evidence of corrosion of aluminum during the
process that runs concurrently with copper deposition.
To = 0 T1 > T o T2 > T 1 T3 >>> T2

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To = 0 T > To
!!!!
ANODE: OXIDATION
M0 (metal)  Mn+ (solução) + ne- (metal)
CATHODE: REDUCTION

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Reference or Standard Hydrogen Electrode CONVENTION ( IUPAC, 1953 )
(SHE), E°SHE=0,00 V (25°C, 1 atm).
A system formed by a metal or product
immersed in solution containing its own
ions is called a half-cell. In an equilibrium
condition, there is a ddp (difference of
Eo (Volts) = ????
electric potential) between the metal and
its cation in solution. This ddp cannot be
measured by conventional means.
To overcome this obstacle, one uses the

strategy of choosing a "Primary Reference
Electrode" against which the potential of all
other electrodes will be measured. Its
electrode potential would be arbitrarily
assumed to be 0.00 V (zero volts). As an
example, we have the standard hydrogen
electrode (SHE) and the hydrogen scale.

Chemical Milling 84

In order to standardize the potentials of the other electrodes, in 1953 the IUPAC agreed to write
the half-cell reactions in the direction of the reduction reactions.
Now we have a measuring scale for comparisons, the
trends of each metal against the standard hydrogen
electrode (SHE) are compared. The electrodes that
behave prone to reduction gain a positive signal.
Those that oxidize, negative signal.
Example: A zinc electrode in Zn(NO3)2 solution tends
to oxidize relating to SHE, resulting in an electrode
potential of: - 0.76V. Your reaction in the new scale
will be:
Oppositely, copper electrode in CuSO4 solution tends

to reduce (not being corroded), resulting in a positive
potential:

Chemical Milling 85

The resulting comparisons generates the Standard Electrochemical Series in which each standard
electrode potential (E°) value shows whether the position of the equilibrium lies to the left or right
of the hydrogen equilibrium.

Chemical Milling 86

To = 0 T3 >>> To Now, the system made with zinc in aqueous copper
sulfate solution can be studied in order to analyze
the behavior of both metals in separate cells as the
sequence below. The device used here is called the
"Daniel Cell“. It consists of an assembly of two half-
cells in which each has a metal plate in a solution of
its own ions. The half cells are externally bound by
a copper wire and the solutions are bound by a salt
bridge of a neutral electrolyte with an anion
common to both solutions
To = 0 T1 = To T2 > T1 T3 >> T2 > T1
Zinc sheet (Zn) in zinc sulfate solution (ZnSO4) and copper plate in aqueous copper sulphate solution (Cu2SO4). The salt bridge and
the copper wire close the circuit.

Chemical Milling 87
ANODO CATODO

Chemical Milling 88
Higher susceptibility to elctrochemical (galvanic) Corrosion

Chemical Milling 89

Corrosion is an electrochemical process, i.e. it relies on electron transfer. Corrosion of aluminum
can be split into an anodic and cathodic part-reaction which can occur at separate places on the
metal surface provided that they are in electrical contact.

Chemical Milling 90

Proposed mechanism of dissolution of metal
oxides in acidic solutions. Two steps are
required for stoichiometric dissolution:
The bond between the metal atom and oxygen

lattice of the solid breaks, forming the metal
cation in solution;
The oxygen atoms at the surface react with H+

ions at the outer Helmholtz plane (OHP),
causing the bond between the oxygen atom
and the surface to break.
This results in either the formation of OH− ions

or of H2O if either one H+ ion or two H+ ions
form the activated complex (that is, t is either
one or two).

Chemical Milling 91

The rate of electron transfer between the anodic and cathodic reactions is a measure of the
corrosion rate (often called corrosion current). Half-Cell reactions in the Chemical Milling of
Aluminum and its alloys are as follows:
The anodic reaction (-) is an The cathode reaction (+) is a

oxidation process and releases reduction process and accepts
electrons: electrons:

Chemical Milling 92

C (+):
Schematic of the electrochemical
corrosion mechanism of Aluminium
dissolution in alkaline solutions. A (+):

Chemical Milling 93

Rough listing of Al alloys regarding their
corrosion resistance

Chemical Milling 94
The Aluminum-Air
Battery (AAB)

Chemical Milling 95
The Aluminum-Air Battery (AAB)

AABs are power cells in which the active cathode
material (oxygen, O2) is not stored in the battery.
Instead, oxygen can be absorbed from the
environment and then reduced by catalytic
surfaces in the air electrode. The proposed
aluminum-air fuel cell generates electrical power
in the process of the chemical reaction of
aluminum with oxygen supplied from the
surrounding (ambient) air. Aluminum anodes
lead to a high theoretical energy density of 8.1
W.h/g in AAB. In addition, the large natural
abundance and its low production make it
extremely appealing for use in battery systems.

Chemical Milling 96
Metal‐Air Battery

Chemical Milling 97

Thermodynamic Data of Pure Species Involved in the Operation of an Aluminum-Air Power Source
Thermodynamic Data of Soluble Species Involved in the Operation of an Aluminum-Air Power Source

Chemical Milling 98

Thermodynamically, an aluminum anode should
exhibit a potential of -1.66 V (SHE) in saline or neutral
solution and -2.31 V (SHE) in alkali electrolyte.
However, practical aluminum electrodes operate at a
significantly lower potential because aluminum is
normally covered by an oxide film that causes a delay
in reaching a steady-state voltage due to internal
resistance and aluminum undergoes a parasitic
corrosion reaction, resulting in less than 100%
utilization of the metal and the evolution of hydrogen.

Chemical Milling 99

In AAB cells, the discharging anode reaction in alkaline media is:
In addition to the electrochemical consumption of the anode, aluminum is thermodynamically

unstable in alkaline electrolytes and reacts with the electrolyte to generate hydrogen:
This parasitic corrosion reaction, or self-discharge, degrades the coulombic efficiency of the anode
and must be suppressed in order to minimize the capacity loss. The discharge reaction in high
pH(above 12) becomes:
The progressive consumption of hydroxyl ions at the aluminum electrode makes the electrolyte
saturated with the aluminate. Eventually, the aluminate concentration exceeds and gets
supersaturated engendering crystalline form of aluminum hydroxide precipitates with the
regeneration of hydroxyl ions (lower pH):
Therefore, the overall anodic reaction (desirable)of the aluminum-air battery is the corrosion of
aluminum into a soluble form stable in a caustic environment (AlO2 −) that can subsequently
precipitate as Al2O3·H2O, depending on the concentration of ions in solution, pH and temperature.

100
Chemical Milling
References

Chemical Milling 101
References
ASM Handbook, v.5. Surface Engineering. ASM International, 1996. USA.
Çakir, O Chemical Etching of Aluminium. Journal of Materials Processing Technology 199 ( 2008 ), 337–340.
DAVIS, J.R. Corrosion of Aluminum and Aluminum Alloys. ASM International, 1999. USA.
DAVIS, J.R. Alloying: Understanding the Basics. ASM International, 2001. USA. p351-416.
EPA publication, EPA-600/2-82-011C, 1981. USA.
Harris, W.T. Chemical Milling, The Technology of Cutting Materials by Etching. Clarendon Press. 1976. Great
Britain.
Kalpakjian, S. Schmid, S.R. Kok, Chih-Wah Manufacturing Engineering & Technology, 6th Edition. Pearson
Education. 2009. USA.
ROBERGE, P.R. Handbook of Corrosion Engineering. McGrawHill, 2000. USA.
TALBOT, D.; TALBOT, J. Corrosion Science and Technology. CRC Press, 1998. USA.

References
Petrucci et al General Chemistry: Principles and Modern Applications, chapter 18 - class notes. Available in the
domain: http://faculty.chem.queensu.ca/people/faculty/mombourquette/FirstYrChem/solubility/index.htm on
may 1st 2019.
DAVIS, J.R. Alloying: Understanding the Basics. ASM International, 2001. USA. p351-416. Available in the
domain:
https://materialsdata.nist.gov/bitstream/handle/11115/173/Aluminum%20and%20Aluminum%20Alloys%20Dav
is.pdf?sequence=3&isAllowed=y on april 1st 2019.
Tomlinson, D. & Wichmann, J. Chemical Milling Environmental Improvements, Aerospace is Green and
Growing. NASF SURFACE TECHNOLOGY WHITE PAPERS 78 (9), 1 - 7 (June 2014). Available in the domain:
https://www.pfonline.com/articles/chemical-milling-environmental-improvements-aerospace-is-green-and-
growing on april 4th 2019.
Turner, R.C. The Equilibrium Constant for the Formation of AI2(OH)24+ in Aqueous Solution. Canadian Journal
of Chemistry, 1975, 53(19): 2811-2817. Available in the domain:
https://www.nrcresearchpress.com/doi/10.1139/v75-399#.XNDZfRRKj3i on april 4th 2019.
Apps, John A. and Neil, John M. Correlation of the Solubilities of Aluminum Hydroxides and Oxyhydroxides in
Alkaline Solutions with the Thermodynamic Properties of Al(OH)4-. ACS Symposium Series, Vol. 416. Chapter
32, pp 414–428. Available in the domain: https://escholarship.org/uc/item/1ft3027d on april 4th 2019.

References
Hem, J. D. and Roberson, C. E. Form and Stability of Aluminum Hydroxide Complexes in Dilute Solution.
Water Supply Paper Series number: 1827-A, 1967. USA. Available in the domain:
https://pubs.usgs.gov/wsp/1827a/report.pdf on april 18th 2019.
Parks, George A. FREE ENERGIES OF FORMATION AND AQUEOUS SOLUBILITIES OF ALUMINUM HYDROXIDES
AND OXIDE HYDROXIDES AT 25oC. American Mineralogist Vol. 57, pp. 1163-1789 (1972). Available in the
domain: http://www.minsocam.org/ammin/am57/am57_1163.pdf on april 18th 2019.
MIADOKOVÁ, M. and MOLNÁROVÁ-PLCHOVÁ, M. Kinetics and mechanism of the reaction of aluminum in

aqueous solution of sodium hydroxide. Сhem. Papers 39 (2) 229—235 (1985) . Available in the domain:
https://www.chempap.org/file_access.php?file=392a229.pdf on april 18th 2019.
Complex Ions. Available in the domain: https://www.chem.fsu.edu/chemlab/chm1046course/complexions.html

on April 4th, 2019.
Hydrolysis of Salt Solutions. Rice University. Available in the domain:

https://opentextbc.ca/chemistry/chapter/14-4-hydrolysis-of-salt-solutions/ on april 4th, 2019.
https://chem.libretexts.org/Courses/Mount_Royal_University/Chem_1202/Unit_2%3A_Acids_and_Bases/15.07
%3A_Ions_as_Acids_and_Bases
https://www.chemguide.co.uk/inorganic/complexions/aquaoh.html

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105
Chemical Milling

Chemical Machining Processes For Aircraft Parts Manufacturing (May 2019)

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Chemical Milling for Aircraft Parts Manufacturing

Chemical Milling for Aircraft Parts Manufacturing

 Machining processes involve material removal by mechanical means  chip

 Very high strength and hardness

Chemical Milling for Aircraft Parts Manufacturing

Chemical Milling for Aircraft Parts Manufacturing

Chemical Milling for Aircraft Parts Manufacturing

The paint was brush applied in the required pattern, and

Chemical Milling for Aircraft Parts Manufacturing

The chemical etching technique as

Chemical Milling for Aircraft Parts Manufacturing

Before the chemical milling process, sheet metal structures for

With chemical milling one part is formed from a thicker

Chemical Milling for Aircraft Parts Manufacturing

Chemical Milling for Aircraft Parts Manufacturing

Chemical Milling for Aircraft Parts Manufacturing

The Art of Chemical Milling

Chemical Milling for Aircraft Parts Manufacturing

2H2O + 2NaOH + 2Al → 2NaAlO2 + 3H2↑

It can be summarized in the following steps:

Chemical Milling for Aircraft Parts Manufacturing

Chemical Milling Process

ETCH RATE (E)

E=d/t in micron/min or mm/min.

depth of etch …………. d (micron or mm),

E= (3.0-2.5)/ (2x10)= 0.5/20 = 0.025mm/min

Chemical Milling for Aircraft Parts Manufacturing

Chemical Milling Process

Chemical Milling for Aircraft Parts Manufacturing

Undercut in chemical machining.

Chemical Milling for Aircraft Parts Manufacturing

Chemical Milling for Aircraft Parts Manufacturing

Chemical Milling for Aircraft Parts Manufacturing

Aluminum and its Alloys

Camadas superiores de moléculas de água;

1a camada de moléculas de água

Grupos hidroxila superficiais

Chemical Milling for Aircraft Parts Manufacturing

Aluminum and its Alloys

Chemical Milling for Aircraft Parts Manufacturing

Aluminum and its Alloys

Chemical Milling for Aircraft Parts Manufacturing

Aluminum and its Alloys

Surface Treatment (e.g.: Passivation, Anodizing ...)

Chemical Milling for Aircraft Parts Manufacturing

Amphoteric Nature of Aluminum

Chemical Milling for Aircraft Parts Manufacturing

Amphoteric Nature of Aluminum

The amphoteric nature of aluminum can be

The solid that forms in a solution around

Chemical Milling for Aircraft Parts Manufacturing

Amphoteric Nature of Aluminum

E-pH diagram for pure Al at 25˚C in aqueous solution (adapted

Chemical Milling for Aircraft Parts Manufacturing

Amphoteric Nature of Aluminum

Aluminum hydroxide precipitate (Al(OH)3) formed by adding few drops of a 1M solution of

Chemical Milling for Aircraft Parts Manufacturing

Bath Composition & Additives

Chemical Milling for Aircraft Parts Manufacturing

Bath Composition & Additives

Chemical Milling for Aircraft Parts Manufacturing

Chemical Milling for Aircraft Parts Manufacturing