#001 Hydrogen Embrittlement

#002 Hydrogen Embrittlement - Hydrogen Overvoltage

#003 Hydrogen Embrittlement - Absorbed Hydrogen

#004 Hydrogen Embrittlement - The Source

#005 Hydrogen Embrittlement - Pickling

#006 Hydrogen Embrittlement - Inhibitor

#007 Hydrogen Embrittlement - Dehydrogenation prior to Plating

#008 Hydrogen Embrittlement - Plating Embrittlement

#009 Hydrogen Embrittlement - Baking Process - 1

#010 Hydrogen Embrittlement - Baking Process - 2

#011 Hydrogen Embrittlement - Baking Process - 3

#012 Hydrogen Embrittlement - Baking Process - 4

#013 Hydrogen Embrittlement - Test and Measurement Methods - 1

#014 Hydrogen Embrittlement - Test and Measurement Methods - 2

#015 Hydrogen Embrittlement - Test and Measurement Methods - 3

#016 Hydrogen Embrittlement - Test and Measurement Methods - 4

Hydrogen Embrittlement

It is frequently mentioned that electro-plated steel alloy objects can suffer breakage due to
hydrogen embrittlement. What then is hydrogen embrittlement?
There are several definitions mentioned in JIS. Some are: "A phenomenon where plated object
becomes brittle by absorption of hydrogen during plating and pre-treatment processes" (Electro-
plating term), "Degradation of steel alloy's ductility or toughness caused by absorbed hydrogen
into the steel alloy. This phenomena often occurs during pickling and electro-plating processes.
The object may often break when subjected to tensile stress." (Steel alloy term). In all cases, it
points to a phenomenon where materials become brittle due to hydrogen.

Occurrence of hydrogen embrittlement

Hydrogen embrittlement has been known for quite some time. It had become a problem when
electroplating high carbon spring steel, notably. It has attracted technical attention in the late
1950s when high strength steel alloys came into wide usage by aerospace industry, and frequent
failure of electro-plated aircraft parts produced from the high strength alloys occurred.

What type of surface finishing processes cause hydrogen embrittlement? General surface finishing
process methods are classified in the following [Fig.].

Since the wet process methods use aqueous solutions, dangers of hydrogen embrittlement exits if
hydrogen formation at base metal surface occurs.
On the other hand, the dry process methods which do not use aqueous solutions are not subject to
hydrogen embrittlement, but pre-processes such as de-greasing and de-rusting processes are wet
and they contain risks of hydrogen embrittlement.
As mentioned above, not just the actual plating process but all the associated processes must be
evaluated when evaluating the risk of hydrogen embrittlement.
#002 Hydrogen Embrittlement - Hydrogen Overvoltage
Category : Hydrogen embrittlement
July14, 2009
Hydrogen formation during wet processes, including pre-processes, occurs in the following
scenario.
During pickling, following chemical reaction occurs.

FeO + 2HCL → H2O + FeCL2(Dissolution of oxides only)

Fe + 2HCL → 2H+ + FeCL2(Dissolution of host steel alloy also)

As seen above, hydrogen does not form when oxides only dissolve, but hydrogen ion is generated
if the base steel alloy is dissolved also.
In zinc plating, redox of the zinc and electrolysis of water causes hydrogen ions, and hydrogen is
formed.

Zn2+ + 2e → Zn (Zinc redox = Zinc deposition)

2H2O + 2e → 2H+ + 2OH- (Electrolysis of water generates hydrogen)

Hydrogen ions generated as seen above immediately becomes atomic state hydrogen H, and the
hydrogen penetrates the steel alloy's interstitial structure.

In this scenario, hydrogen will not be formed if all the electrical energy applied is spent on zinc
metal deposition (redox). This condition is called Cathode Current Efficiency = 100%.
This cathode current efficiency varies depending on plating bath composition and cathode current
density, etc. In general, the cathode current efficiency is good with mildly acidic single salt bath
for nickel plating bath, but the efficiency tends to be low in zinc cyanide plating bath, and the
hydrogen formation increases as the current density becomes higher.

Additionally, hydrogen overvoltage is another dominating factor for the formation of hydrogen
during plating. Hydrogen overvoltage is an electrical potential difference that exists between
atomic state hydrogen (H) becoming gaseous state hydrogen (H2) when the hydrogen ions
electrically discharge on the surface of the host metal, and it varies with metal surface conditions.
Generally, it is high for metals with low melting point, and small when the surfaces are rough.
Hydrogen is more easily formed when hydrogen overvoltage is small.

Therefore, more hydrogen is generated during precious metal plating such as gold and silver, but
less for zinc and tin plating. For instance, when zinc plating steel alloys, initial hydrogen generation
is small since the hydrogen overvoltage is small with the steel alloy, but once the base metal is
covered with zinc the hydrogen overvoltage increases thus the hydrogen generation is reduced.

The hydrogen generated here will penetrate the host metal as atomic state hydrogen. It is
generally said that gaseous hydrogen cannot penetrate the host metal. Therefore, it can be
assumed that hydrogen embrittlement will not occur if all the generated hydrogen is gasified and
dispersed. A plating bath with chemical additives that promote such a reaction is highly
anticipated.
#003 Hydrogen Embrittlement - Absorbed Hydrogen
Category : Hydrogen embrittlement
July15, 2009
Hydrogen atom is the smallest of all atoms, and it's size is 1.06 angstrom = 1.06 x 10-10m. On
the other hand, the lattice structure spacing of metal is 2~3 angstrom so the hydrogen atoms can
easily penetrate into metals.
For example, sulfuric acid and hydrochloric acid used for pickling will dissolve the surfaces of steel
alloys. The dissolution of the steel and hydrogen ion generation occur simultaneously, and the
hydrogen ions will electrically discharge and become hydrogen atoms at the steel's surface. Much
of the hydrogen atoms will be dissipated into air as hydrogen gas, but some will penetrate the
steel.

As for the plating process, some hydrogen will also penetrate the steel if cathode current efficiency
is low due to hydrogen generated by electrolysis of water. In some cases, hydrogen may penetrate
the coating and increase the hardness of the coating, but this hydrogen may also penetrate the
steel under certain conditions.
The hydrogen absorbed by steel exists in various places such as interstitial lattice, transitional
region, grain boundary, and inclusions. The hydrogen in the interstitial structure maybe ignored as
the cause of hydrogen embrittlement induced breakage since the existing amount is negligibly
small. It is said that the hydrogen more closely related is "defective hydrogen".
With high strength steel alloys, hydrogen embrittlement induced breakage/crack occurs at grain
boundaries. Hydrogen concentrates at grain boundaries and weakens the metal's atomic binding.
With low strength steel alloys, stress loadings cause transitions to gather around inclusions, and
hydrogen is attracted towards the same area and result in destruction.

Hydrogen embrittlement induced destruction cases are organized as below.

（1）Destruction occurs at the point of tensile stress. Does not occur at the point of compressive stress.
（2）Destruction is likely to occur where stress is concentrated around notches.
（3）The destructive hydrogen in steel is of diffusible in nature and can freely move about within the steel and concentrate
around notched features. The amount of absorbed hydrogen and hydrogen embrittlement risk do not necessarily
coincide.
（4）Steel material's susceptibility to hydrogen embrittlement mainly depends on the material's strength, and is not
dependent on the alloy's atomic composition. Most destruction incidents occur with high tensile strength steel alloys
with high hardness of HRC40 or more.
（5）The breakage type is either inter-granular or trans-granular. The absorbed hydrogen congregates at inter-crystalline
region and weakens the metal's atomic bound.
（6）Hydrogen embrittlement induced delayed failure does not typically prevail against high strain rate shocks. For
example, aircraft landing gear usually does not fracture with shocks from landing, but typically fails while the craft is
static or during taxiing.
（7）Steel alloys are more insensitive to hydrogen embrittlement as the material is more thermodynamically stable.
（8）Hydrogen embrittlement fracture is temperature sensitive. More often occurs at temperatures of −10〜120 deg. C.
（9）It takes time for hydrogen to diffuse and accumulate for the destruction to occur.
#004 Hydrogen Embrittlement - The Source
Category : Hydrogen embrittlement
July24, 2009
Plating, in general, has required processes of [Pre-treatment > Surface finish > Post treatment].
Each process is shown in Table 1 as electro-plating as examples.

[Table 1] Plating processes

Pre-treatment Electro-plating Post-treatment

Immersion degreasing Zinc plating Chromate coating

Electrolytic degreasing Copper - Nickel - Chrome plating Anti-discoloration, drying

Pickling (acid wash) Nickel - Chrome plating Baking process

Electro-polish Nickel - Gold/Silver plating Paint - baking

Plating removal Hard-chrome plating, etc.

Many of these processes may result in hydrogen formation due to dissolution of steel and
electrolysis of water. Care must be taken since the hydrogen may penetrate the steel under
certain conditions.
The hydrogen penetration levels vary depending on the plating metals and solution bath
compositions. However, the possibility of whether hydrogen embrittlement fracture may occur or
not will largely depend on the host metal's susceptibility to hydrogen embrittlement.
Carbon steel's hydrogen embrittlement rate per process is shown next.

(1)Pickling

The pickling process is performed to remove scales and rust from the surface of steel objects to be
plated. Normally, this process uses hydrochloric acid, sulfuric acid and the like, and prone to cause
hydrogen embrittlement.
If this process is performed unconscientiously, the steel will certainly absorb hydrogen and
embrittlement induced fracture will occur. For high tensile strength steel applications where safety
is strongly desired, dry processes such as shot blasting and honing are therefore often specified.

(2)Pickling by hydrochloric acid

Pickling bath most typically used for steel alloys is at 10% solution strength, and the steel
immersed in this bath in just a few minutes will reach 70% hydrogen embrittlement rate (see
[Graph]). This is a significant problem for high tensile strength steel. Higher hydrochloric acid
concentration will further raise the embrittlement rate. The immersion rate versus time will
saturate beyond a few minutes.
In order to prevent this problem, commercially available inhibitors are usually added to the
solution. The inhibitors will be mentioned later.
#005 Hydrogen Embrittlement - Pickling
Category : Hydrogen embrittlement
July31, 2009

(3) Pickling process with other acids

The following table shows various hydrogen embrittlement rates of a steel alloy ([SK5] [W1-8]
[1.1525_C80W1]) in varying acid bath solutions.

The use of hydrochloric acid has been mentioned before, and other acid bath pickling also shows
similar results. Pickling with sulfuric acid is as common as with hydrochloric acid. Sulfuric acid
shows low hydrogen embrittlement rates at lower temperatures but has low rust removing
capability, thus it is typically used at around 60 deg.C. At this temperature, sulfuric acid shows
hydrogen embrittlement rate similar to that of hydrochloric acid. Phosphoric acid is also similar.
As seen in the table above, fluorine acids such as hydrofluoric acid, fluoroboric acid, and
hydrochloric acid with commercial inhibitor shows low hydrogen embrittlement rates. And it can be
recognized that de-smut bath used after pickling is also low in embrittlement rates.
(4)Electro rust removal and electro de-greasing, etc.

Rust removal, de-greasing, de-smutting, and activating by electrolysis are performed in acidic and
alkaline solutions, after pickling processes. In these cases where products are processed by
cathode electrolysis, hydrogen embrittlement occurs due to electrolysis of water. With anode
electrolysis in alkali baths, very little embrittlement occurs. In acid bath, hydrogen embrittlement
occurs during non-energized durations due to chemical dissolution.
#006 Hydrogen Embrittlement - Inhibitor
Category : Hydrogen embrittlement
August 7, 2009
Pickling process is performed to remove rust and scales from surfaces of steel parts, and inhibitors
have been in use to prevent excess dissolution of the steel parts. In fact, the inhibitors, in addition
for prevention of excess steel dissolution, act to prevent hydrogen embrittlement as well.
Following chemical reactions occur in hydrochloric acid pickling without inhibitor addition.

Fe2O3 + 6HCL → FeCL3 + H2O(Dissolution reaction of steel rust.)

Fe + 2HCL → FeCL2 + 2H(Dissolution reaction of steel alloy)

The hydrochloric acid will dissolve rust and scales on steel surface and forms chlorides but will not
generate hydrogen (see Dissolution reaction of steel rust, above). Further into the process, base
steel surface is exposed as the rust/scale layer is dissolved and the steel will begin to dissolve (see
Dissolution reaction of steel alloy, above), causing hydrogen formation. Here the steel alloy begins
to occlude the hydrogen in atomic state and hydrogen embrittlement will result.
The inhibitor prevents this dissolution of the steel alloy thus preventing the formation of hydrogen.
The inhibitor prevents the hydrogen formation by selectively adhering to the exposed steel surface
to prevent the acid solution from contacting the surface, thus preventing the hydrogen from
forming.

As seen above, the use of inhibitors in pickling are effective in hydrogen embrittlement prevention.
However, since chemical composition details are unclear for many commercially available
inhibitors, it is advisable to test them before actual use.
For sulfuric acid, hydrochloric acid, and phosphate pickling baths, diethylthiourea and dibutylurea
are well known.
The chemical compositions of commercial inhibitors are not published, but the following are know
to be effective for hydrogen embrittlement suppression, according to some published material.

（1）Organic compounds containing nitrogen, amines

（2）Organic compounds containing oxygen, carboxylic acid, etc.
（3）Organic compounds containing phosphor, thiourea, etc.
（4）Acetylene compounds, propargylalcohol, etc.

There is, however, a problem with the commercial inhibitors. Since the chemical composition
details are unknown, proper concentration management becomes difficult. At low concentration
levels, effective prevention of hydrogen embrittlement cannot be expected, and on the other hand
at high concentration levels, the agent that may be carried over may affect the next process
negatively.
#007 Hydrogen Embrittlement - Dehydrogenation prior to Plating
Category : Hydrogen embrittlement
August14, 2009
The occluded hydrogen during pickling process is thought to be retained near the steel surface,
and is recommended that the hydrogen be released prior to plating layer is deposited. The
hydrogen is slowly released by simply letting the part sit out in the air, as shown in [Fig.1] below.

Diffusion movement of hydrogen accelerates at higher temperatures, so the dissipation time of

occluded hydrogen can be shortened by heating. Normally, an alkaline wash process follows a
pickling process, and relatively high temperature of 60~70 deg.C for this wash process is
advantageous for the hydrogen dissipation. A test result is shown in [Fig.2] below.
In actual plating work practices, it is difficult to setup the alkaline wash stage for the purpose of
dehydrogenation due to variations of rust and scales on the subject metal and wash process time.

For steel parts that are subjected to long pickling processes, a separate dehydrogenation process
(baking) is required. Although it is more effective to bake for long durations at high temperatures,
this will cause oxide layers to form on the steel surface, requiring a pickling again. So the baking
takes place at i.e. 200 deg.C for 30 minutes, as shown in [Fig.1] above.

For example, baking is typically performed after zinc plating, because this is intended to release
the hydrogen occluded during the zinc plating. But, the hydrogen occluded during pickling needs to
be released before plating or else the zinc coating will prevent sufficient emission.

#008 Hydrogen Embrittlement - Plating Embrittlement

Category : Hydrogen embrittlement
August21, 2009
[Fig.1] shows a listing of hydrogen embrittlement rates of various plating processes. It is easily
imaginable that possibilities of hydrogen embrittlement exists for electro-plating processes, which
uses the work piece as a cathode electrode for the electrolysis. However, non-electrolysis process
such as electroless nickel plating could also cause hydrogen embrittlement as well. Here, the
hydrogen generation is thought to be caused by reducing agents used in place of the direct current
used for electro-plating.
Also, in chrome plating where non dissolving anodes such as lead and graphite are used, unlike
other plating processes where dissolving anodes (zinc, nickel, etc.), vigorous electrolysis of water
takes place during redox of chromate ions dissolved in the plating bath in order to obtain the
chromium metal. This vigorous electrolysis causes hydrogen generation.

From [Fig.1] above, it can be seen that acidic plating baths such as nickel plating, nickel alloy
plating, and chloride zinc plating have very low hydrogen embrittlement rates, but alkaline plating
baths such as zinc cyanide bath and copper cyanide bath are more likely to cause hydrogen
embrittlement.
It is considered, in general, that most of the electrical current applied is used for electrolysis of
water resulting in high hydrogen generation with the alkaline baths due to low cathode current
efficiency, as opposed to acidic baths where the current is mostly used for redox of metal ions due
to high cathode current efficiency.

Hydrogen embrittlement rates of zinc plating in cyanide bath (alkaline) and chloride bath (acidic)
are shown in [Fig.2] below.
#009 Hydrogen Embrittlement - Baking Process - 1
Category : Hydrogen embrittlement
August28, 2009
For plating products with hydrogen embrittlement risks, baking processes are performed as means
of dehydrogenation process. The baking process typically involves heating the products in furnaces
at 190~220 deg.C to purge the hydrogen. The heating time will depend on the plating type, pre-
plating process used, deposition thickness, alloy type, and the condition of the base metal.

（1）Pre-process and effects of baking

[Fig. 1] and [Fig. 2] below show the effects of dehydrogenation by baking on material samples
with zinc plating where one sample with no hydrogen occlusion, and the other with hydrogen
occlusion during the pre-process. Zinc plating is used as a representative more likely to cause
hydrogen embrittlement.

[Fig. 1] shows zinc plated samples pre-processed in a non hydrogen occluding acid bath pickling.
The sample does occlude some hydrogen through the zinc deposition layer but one hour of baking
will effectively dehydrogenate the sample in all types of zinc baths as seen.

[Fig.2] shows samples that occluded large amounts of hydrogen during the pre-process pickling as
well as the zinc plating process. As can be seen in the graph, little hydrogen is purged from the
alloy even after long baking time.
From the above, it can be understood that prevention of hydrogen occlusion is important during
the pickling process, or some type of dehydrogenation process will be required before the baking
process if the work had already occluded some hydrogen during pickling. Effective hydrogen
occlusion prevention includes use of proper inhibitors, and in the latter case, immersion in high
temperature alkaline degreasing bath. As can be seen in the graphs, ammonium chloride zinc bath
is effective in preventing hydrogen embrittlement.
#010 Hydrogen Embrittlement - Baking Process - 2
Category : Hydrogen embrittlement
September 4, 2009

(2) Plating coat layer and effects of baking

The effects of baking have close relationship with hydrogen permeability of the plating coat layer.
Plating coat layers, since being metallic, have a variety of crystalline structure. And this structure
is related to hydrogen permeability. Zinc and cadmium are of hexagonal close-packed crystalline
structure and of low hydrogen permeability. It is considered, therefore, that dehydrogenation is
difficult by baking. For this reason, porous cadmium plating is used for aircraft parts where
hydrogen is purged through the pores and cracks. Chrome plating has chrome-specific cracks in
the layer that the hydrogen can dissipate, and the baking process is known to be effective for that
reason.

In order for the baking process to be effective...

1.plating types with pin-holes,

2.plating types with cracks and holes,
3.plating types with rough coat layers,
4.semi-gloss and non-gloss plating

seem to be in use.

(3) Plating layer thickness and effects of baking

When purging the hydrogen from base metal and plating layers, thick plating layer will naturally be
less permeable for the hydrogen. Longer baking time will be required for these cases.

(4) Process temperature and effects of baking

The baking process temperature is typically at 190~220 deg.C, but the high temperature may not
be suitable for some material that loses hardness or strength by heating. In these cases, the
baking time is extended.

(5) Sit-out time after plating

There are platers who set prescribed time between plating and baking such as within 30 minutes,
within 2 hours, etc. for example. According to experiments with sit-out times of 1~24 hours, there
seems to be little difference for the effects of baking.
#011 Hydrogen Embrittlement - Baking Process - 3
Category : Hydrogen embrittlement
September11, 2009

(6) Hardness of steel and effects of baking

Effects of baking vary with the hardness of the steel alloy material to be treated. The baking is less
effective on harder material, where softer material returning better results. This is said to be
contributed not by the hydrogen being purged out of the steel, but by the diffusive migration of
the hydrogen from the material's surface region to the inner region, lowering the surface hydrogen
concentration to below destructive limits.
For bright zinc plating and cadmium plating, the baking is effective for low hydrogen embrittlement
susceptible steel alloy with hardness of HRC40 and below. But not so with steel material with
hardness of HRC46 and above.
For material that are carburized, the baking treatment is effective since only the surfaces are hard.
It is thought that the occluded hydrogen would heat-diverge into the inner region of the material,
and the surface hydrogen content will fall below the destructive limits. However, the hydrogen still
remains within the material and may diffusively migrate to regions where stress may be
concentrated if any tensile stress is applied.

(7) Summary of Baking Process

Effects of baking processes on plated products are as follows.

1.Removal efficiency of the hydrogen occluded during the pre-plating processes is low.
2.Baking process is highly effective against the occluded hydrogen during plating processes.
3.Effects of baking depends on the hydrogen permeability of the coating. The effects are more pronounced on coatings
with coarse-crystalline structure, with pours and cracks.
4.Baking is less effective on thick coating layers.
5.Baking effectiveness is lower at lower baking temperatures.
6.Baking effectiveness is high with steel material with low hydrogen embrittlement susceptibility.
7.Post plating sit-out time duration requirement would depend on the thickness of the material. Thin plates are not
affected.
8.Baking will cause diffusive migration of the hydrogen into the inner region of the material.
9.Chromating is to be applied after the baking process. If the baking is applied after the chromate coating process, the
chromate coat cracks due to dehydration and the anti-corrosive properties will be degraded.
#012 Hydrogen Embrittlement - Baking Process - 4
Category : Hydrogen embrittlement
September18, 2009

(8) Standards regarding the baking process

(1) ISO standards

In ISO standards, hydrogen embrittlement relief of electro-galvanized steel is provisioned as

follows.

Following heat treatment processes must be applied to certain steel alloys in order to reduce part breakage
risks due to hydrogen embrittlement, if requested by customers. Additionally, conventional zinc electro-
plating should not be applied to steel alloys with tensile strength higher than 1500N/mm2 (or hardness
shown in note 1). For steel alloys with tensile strength higher than 1000N/mm2, it should be noted that
proper heat treatment processes are required in order to reduce the hydrogen embrittlement breakage risks.
(Note 1: Hardness HRC45, HV440, HB415)

a. Stress relief before plating

Stress relieving heat treatments are necessary for parts made with steel alloys with tensile
strength higher than 1000N/mm2 (or hardness shown in note 2) that have been: extensively cold
worked, annealed, ground, or subjected to severe machining. (Note 2: Hardness HRC30, HV295,
HB280)

b. Heat treatment processes after plating

Post-plating heat treating is necessary for parts that are expected to receive stress and/or static
loadings, and for parts that are produced by severe cold working processes. (Table 1) below shows
the guideline for heat treating conditions. For parts produced from case-hardened alloys that may
be negatively affected by the heat treating guideline, processes with lower temperature at longer
durations are required.

(Table 1) Guideline for heat treating steel alloy parts after plating

Tensile strength Cross section thickness Process time at 190-210 deg.C

（N/mm2） （mm） （ｈ）

12 or less 2 or more

1000〜1150 12〜25 4 or more

25 or more 8 or more

12 or less 4 or more

12〜25 12 or more
1150〜1400
25〜40 24 or more, apply the process within 16 hours of plating.

40 or more To be derived by experimentations.

(2) JIS standards

The JIS standards also defines post-plating heat treatment references as shown in Table 2 below.
(Table 2) Heat treating guideline for stress relieving

Process time (h)

Tensile strength of steel alloy （Mpa） Temp. (deg.C)
Before plating After plating

Up to 1000 - - -

1051〜1450 190-220 1 8 or more

1451〜1800 190-220 18 18 or more

Over 1800 190-220 24 24 or more

#013 Hydrogen Embrittlement - Test and Measurement Methods - 1
Category : Hydrogen embrittlement
September25, 2009
When metals are subjected to pickling processes, the metals are dissolved by the acids and
hydrogen is generated. The hydrogen is also generated during electrolytic de-greasing, electrolytic
pickling, and electro-plating. This hydrogen is occluded (absorbed) by the base metal, especially
steel alloys and makes the steel brittle. This phenomenon is the Hydrogen Embrittlement. Parts
with hydrogen embrittlement can break after being subjected to loadings. Here, we'll look into
some testing methods to see how much hydrogen embrittlement there is on plated steel.

(1) Delta Gage

This is a method developed by Delta Research Co. headed by Mr. Takada of Takada Labs. The
method uses steel plates made of alloys susceptible to hydrogen embrittlement, press bent in a
constant speed vise, and the vise travel distance to the point of breakage is measured. The
distance traveled indicates the degradation of flexibility of the test specimen, in turn indicates the
extent of the hydrogen embrittlement. It is also called "Slow press-bent destruction method". Fig.
1 below shows the measurement principle of the Delta Gage method.

In Fig.1., consider that...

L0: Vise travel distance to breaking point for test specimen not pickled (no hydrogen embrittlement) in
mm.

L: Vise travel distance to braking point for pickled test specimen with hydrogen embrittlement.

then...

Hydrogen embrittlement rate (%) = (L0-L)100/L0

For the test specimen: material; SK5 (C0.85%), shape; 9mm x 100mm x 0.8mm thick, hardened
at 850 deg.C, tempered at 450 deg.C is used.
The test is performed by placing the flat test specimen between the jaws of the vise, and slowly
closing the jaws at a constant speed to bend the test specimen. If any hydrogen occlusion is
present in the test specimen, the hydrogen will migrate diffusively towards the area of tensile
stress concentration, and the specimen becomes brittle and likely to break in comparison to a
specimen with no hydrogen occlusion.

As seen, the Delta Gage method can numerically establish the hydrogen embrittlement rates with
easy operations, excellent for factory floors where the plating processes take place.
#014 Hydrogen Embrittlement - Test and Measurement Methods - 2
Category : Hydrogen embrittlement
October 2, 2009
There are other methods to measure hydrogen embrittlement.

(2) Notched tensile test

This method is also called Stress Rupture Test or Sustained Load Test, used by US Air Force, Navy,
Boeing, and Lockheed Martin, and is considered to be the most accurate means of testing. This is a
delayed fracture test with a tensile testing machine where a notched test specimen made of high
tensile strength steel is subjected to a static tensile load that is 75% of ultimate tensile strength. If
the specimen does not fail within 200 hours of this static loading condition, it is considered to pass
the test.
The test specimen is made of high tensile steel alloy (AISI 4340), annealed and machined, heat
hardened, and ground finished. Lastly, a V-shaped notch with a v-valley radius of 0.01 inch is
added to this test piece. The US military testing standards additionally calls for this test specimen
to be cadmium plated after dry-blasting with 100~180 mesh aluminum oxide media. After an
appropriate baking process, this test piece is subjected to a static tensile load 75% of the ultimate
tensile strength and left alone. If there is hydrogen embrittlement present in the test piece, it will
break at the notch in several ~ 100 hours.

(3) Douglas stress ring test

Also called "Stress ring test". this is a testing method provisioned in Douglas Aircraft company's
overhaul manuals. This is a delayed fracture test where a prop-bar is inserted in a ring made of
high tensile steel to obtain a static load 90% of the ultimate tensile strength. The test specimen is
considered as passed the test if it does not break after 200 hours of this static loading condition.
A heat treated ring 60mm dia., 2.5mm thickness, 25mm width made of high tensile steel 4340 is
used. Cadmium plating is applied and baked on this ring. The ring is then deformed into an oval
shape in a vise for a prop-bar called Stress Bar to be inserted. The bar statically maintains the oval
shape to create a stress equal to 90% of the material's ultimate tensile strength.

Reliability of this testing method is widely argued, and no other

aero-space manufacturers or the US Air Force do not recognize
this method, but since the method does not require any
specialized test equipment, it is considered convenient.'
C Ring is shown in Fig.1.
#015 Hydrogen Embrittlement - Test and Measurement Methods - 3
Category : Hydrogen embrittlement
October 9, 2009
There are more hydrogen embrittlement testing methods as follows.

(4) Lawrence Hydrogen Detection Gage

This testing method was developed by a Boeing engineer Mr. Lawrence in cooperation with Mr.
Takada for the purposes of plating bath management, and determining the effects and safety of
aircraft landing gear cleaning solution and paint remover in relation to hydrogen embrittlement.

This method uses a metal cased vacuum tube as a probe to detect the hydrogen atom intrusion
penetrating through the vacuum tube's metal case wall. The metal tube case (probe) is used as
the cathode in the plating process. Hydrogen atoms generated during the plating process
penetrates the coating layer and the steel case wall, and ionize when intrude into the vacuum
tube. Here, an ionization gage is used to monitor and record the presence of hydrogen atoms.

Next, the plated probe is dried and placed into a 200 deg.C oven associated with the test
equipment, and a baking process is performed. By the baking process, the hydrogen atoms
occluded by the coating layer and the steel case wall diffusively migrates rapidly into the vacuum
tube.

A barium getter is placed inside the vacuum tube to absorb and remove the migrated hydrogen at
a constant rate. The vacuum level inside the probe can be interpreted as the change in hydrogen
release rate. As the result, plating layer's hydrogen release characteristics can be determined.

As seen above, this testing method can measure the amount of hydrogen intrusion during the
plating process, and hydrogen release characteristics by baking process.

[Fig.1] is a conceptual diagram of the testing probe. It explains how occluded hydrogen by the
plating layer is measured.

1）Electrons (e) generated from the heated cathode are

attracted to hydrogen molecules inside the vacuum tube.
2）The electrons accelerate when passing through the
positively charged grid, and collide with the hydrogen
molecules. H2+e→2H+Hydrogen molecules become
ionized.
3）Ionized hydrogen H+ is attracted to #2 cathode and
transforms into an electrical current, then read by a
meter.

#016 Hydrogen Embrittlement - Test and Measurement Methods - 4

Category : Hydrogen embrittlement
October16, 2009
There are more hydrogen embrittlement testing methods as follows.

(5) Delayed failure test using the actual part

In order to obtain the final confirmation on whether the plated part is likely to break due to the
hydrogen occluded during the plating processes, or the baking process' effectiveness of hydrogen
embrittlement removal, a delayed failure test using the actual part must be performed.
This is also necessary for failure analysis when they occur, as well as when there are changes in
part designs and intended applications for the part.
Although the problems regarding failures are complex and the delayed failure tests may not
always reveal all problems, confirmation tests are still needed for problem analysis.
A good measure in devising the delayed failure tests using the actual part is to consider the
individual application specifics and design an appropriate scheme. Failures due to hydrogen
embrittlement occur suddenly by the presence of occluded hydrogen, and at a location of notched
feature where tensile stresses concentrate. It is best to replicate this condition.
An ideal method is the one adopted by the aircraft industry. If the part has a notched feature, a
static load equal to 70% (90% if not notched) of the part's ultimate tensile strength is applied. If
the part does not fail this delayed failure test within 200 hours, the part is deemed as passed.

An evaluation method using Delta Gage is introduced below. A plated test specimen is placed in a
vise of a hydrogen embrittlement test system, and the vise is closed and the test specimen is
flexed to 90~95% of the distance where the test specimen actually failed. The condition is held
static and the time it took for the test specimen to fail was measured. There is a clear correlation
between the hydrogen embrittlement rate measured by the Delta Gage and failures as results are
shown in [Table 1]

[Table 1] Delayed failure test results

Process condition Hydrogen

No. HRC Time to failure
(*)：2A/dm2×10 minutes embrittlement rate

Zincate bath zinc plating

1 52 41.7％ 34 minutes
(2A/dm2×10minutes*)

10%HCL 10 minutes, bright cyanide zinc

2 52 69.9％ 7〜29 minutes
plating(same as above)

10％HCL+inhibitor (10 min.), chloride zinc

3 52 3.4％
plating(*)

4 Same as above 49 1.0％ No failure for more

than 200 hours
5 Same as above 45 2.7％

No3 pre-process + dull cyanide zinc plating

6 52 0.2％
(*) + baking (200 deg.C x 2hrs.)