Diffusion
Carbide Coating For Distortion Control
by Steve Harper and Tohru Arai
(Reprinted
with permission from Die Casting Engineer, March/April 2000 issue.)
Carbide coating by TRD (Thermo-Reactive Deposition
and Diffusion) can ensure very high adhesion strength of the carbide
layers onto substrates due to the nature of the carbide formation
mechanism. Carbide coatings made by this method have very good resistance
to erosion and corrosion against molten cast metals.
Therefore, carbide coating by TRD has large potential
to prevent failures of mold components used in die casting and other
casting methods and to provide tremendous benefits to the die casting
industry. In fact, many field test results recently obtained are
accelerating the wide application of the process in the American
die casting industry as in Japan, where the process has been successfully
used since the mid-1970s.
TRD coating is usually carried out at temperatures
similar to hardening temperatures for steels; for example 1877°F
(1025°C) for H-13. Steel substrates are quench-hardened during
cooling from the coating temperatures and followed by tempering.
Therefore, distortion may occur. Overcoming distortion was the key
point for successful application of the process. Working surfaces
of the molds must meet required dimensional specifications on completion
of the coating operation since the coated molds are put into use
without a finishing process. Carbide layers formed in the TRD process
are too thin to be polished off for dimension control.
Distortion in application of high temperature coating
processes such as TRD and CVD is often overstated by recalling the
distortion in ordinary hardening of steels. People often expect
the degree of distortion to be similar to that in ordinary hardening
of die molds based on past experience. This thinking is not correct.
Ordinary hardening is done in most cases on the premise that the
articles are to be ground to the finish size with grinding allowance
large enough to get the finish size. This premise lessens the incentive
to heat treaters to minimize distortion. Equipment and procedures
are well organized and extra care is usually taken in the coating
application to minimize distortion. Furthermore, ordinary hardening
is applied to annealed steels while TRD coating, in most cases,
is applied to already hardened steels. This brings about a good
effect on dimensional change due to a smaller difference in microstructure
change before and after TRD processing. Thus, the coating has been
successfully applied to very close tolerance tools with tolerances
of some µm in diameter. Following is an explanation of causes
and countermeasures for distortion and some examples of results
obtained on die casting molds.
Criteria of distortion
Dimension (size) change: Symmetric change
and shape of tools remains unchanged ("a change of size without
a change of shape"). This includes size difference between
the edges and in the center of the faces.
Deformation: Non-symmetric and shape is
changed ("a change of shape and size").
Most tools change shapes to barrel or spool, more
or less, depending on the shape and size of molds, and the coating
condition. This is usually symmetric and stays in the category of
dimension change.
Deformation becomes evident by curvature of long
axes of slender tools and non-symmetric-shaped tools. Another typical
one is out-of-roundness of ring-shaped tools.
Dimension of molds after TRD coating
Dimensions of molds will be changed by the following
two reasons:
- Buildup
of carbide on substrate
- Dimensional
change of substrate material before and after the coating operation.
The dimension of tools after the coating, therefore,
can be shown in relation to the initial dimension:
Da
= Db + 2 Tc + D
Da ; Dimension after coating
Db ; Dimension before coating
Tc ; Thickness of coatings
D ; Dimension
change of substrate
Carbide layer thickness, Tc, is usually selected
from 0.0002 to 0.0005 in. (5 to 12 µm) in die casting application
regardless of shape, size and kind of mold components to be coated.
Tc can usually be small enough to not be a concern. D
can be much larger than Tc in the case of large cores, large core
pins, etc., depending on various factors and should be a more serious
concern than Tc. Under-sizing or over-sizing to the targeted final
dimension can compensate for the possible dimensional changes. Therefore,
scattering of Db, Tc, and D
should be of more serious concern rather than their individual values.
Causes of the dimension change and
related factors
Tc is controlled mainly by TRD bath temperature,
immersion time in the bath, and bath control and has a very minor
effect. Scattering of chemical composition and microstructure of
substrate steels can change the thickness of carbide layers through
scatter of carbon content in the matrix phase (austenite) at the
coating temperatures. However, this problem is not serious in H-type
steels widely used in die casting since they contain relatively
small carbon and alloying elements. Therefore, scattering of Tc
can usually be out of consideration in die casting applications.
D
and its scattering can be affected by a number of factors related
to the shape and size, substrate materials, heat treating condition,
and coating condition. Volumetric change of the substrate by change
of microstructures of the substrates is the primary reason for D.
That is to say, from pearlite to martensite and retained austenite,
(in the case TRD on the un-hardened molds), change in amount of
austenite (in the case of TRD on hardened substrates), and tempering
of martensite. However, D
is not isotropic.
The size and shape of molds highly affects the difference
in temperature between the surface and core during hearing or cooling
which produces thermal stress and transformation stress. The barrel-
and spool- shaped changes are determined not only by the values
of these stresses but also the sequence in time by which the transformation
stress is added to the thermal stress. Temperature differences and
stresses will also be induced by change of thickness within a mold.
Larger size, higher temperature, and larger rate of heating and
cooling will make D
more considerable.
The banded structure in forged and rolled steels,
which is large amounts of carbide particles in a line parallel to
the rolling direction, make the expansion and construction heterogeneous.
This carbide alignment usually leads to larger size movement in
length than in diameter, thickness and width. The banded structure
is determined not by the size of steel stocks but by steel making
processing, including ingot size, forging ratio, and rolling direction
etc.
Size change of tools can occur even at room temperature
by transformation of "retained austenite" (high temperature
phase of steel) to "martensite" (the phase caused by quench-hardening
of steel). Except for tools that need very strict dimensional tolerance,
this change of size is usually negligible.
In some cases, some factors are very serious and
others are small and negligible.
Causes of deformation and related factors
Distortion is formed by the following reasons:
- Non-uniform
heating and cooling during high temperature coating and heat treatment
- Non-uniform
micro-structure in substrate material
Residual stress produced during tool making, such
as machining and grinding.
Creep by gravity during high temperature coating
and heat treatment.
Most heating and quenching equipment is not likely
to make uniform heating and cooling within tools. The complicated
shape accelerates this tendency. Not enough spacing between molds,
or molds and basket components also results in differences of the
heating and cooling rate. The heterogeneous microstructure in forged
and rolled steels gives rise to different transformation temperatures
and the time lag in transformation within a mold leading to deformation.
Improper machining conditions bring about residual stress in molds,
and relieving of the stress at high temperature can cause deformation,
if heating rate is high. Steels have very small yielding stress
at high temperature. The loading of self-gravity easily results
in deformation such as warpage of long slender cools loaded in the
baskets in such a way that the end of tools arc placed on the basket
bottom, or disk shaped tools placed on a plate with bend, for example.
How
to get TRD coated molds with minimum distortion
Following are
some countermeasures to ensure minimized distortion:
- Select good
type of substrate materials
- Select premium
quality materials
- Cut out molds
from steel stocks in consideration of rolling direction
- Machine and
grind under proper condition to minimize residual stress
- Make molds
with tight dimensional control
- Apply under-
or over-sizing on targeted size
- Harden molds
under precisely controlled conditions
- Apply TRD
coating under precisely controlled conditions
- Control movement
and deformation by selection of proper tempering conditions
- Apply deformation
correction after TRD coating
- Design mold
with consideration of finish grinding on non-working surface to
ensure extremely tight tolerance.
As mentioned
before, the H-type steels are basically good materials. It is, however,
highly recommendable to use steel stock produced by the same steel
maker since there is some scattering in quality, difference in smelting
method, forging ratio, and scattering of chemical composition etc.,
between steel makers and even between steel stock made by the same
steel maker.
D
and scattering is usually greatest in the direction parallel to
the rolling direction. Therefore, it is recommendable to machine
molds so that the critical dimensions are transverse of the rolling
direction. Large scattering will be produced if this could not be
ensured each time of repeated making of the same type of molds.
All molds requiring
close tolerance should be made with high accuracy dimensionally
since any kind of additional processing can increase the dimension
range. As shown later, TRD coating can expand the dimension range:
Max.-Min., about 0.0005 in. (13 µm).
We can obtain
actual dimensional change values through repeated application to
specified molds. Accumulating this data provides us the information
on how large a dimension change will occur on the specified molds,
as shown in the next paragraph. The targeted dimension can be obtained
by making molds under- or over-size by these values. It should be
kept in mind that these values vary more or less with change of
all other factors related to distortion.
Scattering in
the hardening condition should be minimized since D
is caused by the difference in microstructure in the substrate between
before and after TRD coating. We have found through the TRD coating
business that there is very large scattering of the hardness in
the molds sent for coating, including standard core pins in market
as exemplified in Figure 1a and Figure 1b. This large scattering
in hardness is probably caused by the use of large vacuum furnaces
where a large number of molds were set in a basket without consideration
to ensure uniform heating and quenching on each mold. It is recommended
to apply TRD coating onto finished molds without hardening, if the
hardening condition cannot be well controlled. Applying TRD coating
on un-hardened molds can decrease the probability of deformation.
Slender and long pins are also likely to bend in the preliminary
hardening operation. Substantial bending will be produced if these
pins were mechanically corrected for the bending after preliminary
hardening due to the residual stress generated by such bending correction.

Fig.
1a Hardness of pins, as received and after the
TRD coating- pins received from a die caster in a day.

Fig.
1b Hardness of pins, as received and after the
TRD cooling- pins received from a die caster on 28 different days.
The TRD coating
operation should be done under well controlled conditions. To make
0.00023 - 0.00046 in. (6-12 µm) thick carbide coatings on
H type steels, TRD coating is carried out by immersion into a molten
borax salt bath at around 1877°F (1025°C) for 4-10 hours.
The temperature of molds, as is the nature of molten salt, is very
close to the temperature of salt, which can be easily controlled.
The molds are taken out of the bath after a specified time ( D
is not sensitive to immersion time) and quenched into a salt bath
at 1000°F (540°C) followed by air cooling, after being kept
in the bath long enough to equalize the temperature between the
center and surface of the molds. This quenching is the best way
to be industrially applied to minimize both dimensional change and
deformation. Bad effects of other molds on uniform heating and cooling
of molds should be minimized by well considered setting in a basket.
The distortion problem is more remarkably affected not by the temperature
and time but by uniformity in heating and cooling, which can be
considerably influenced by the worker's procedures such as direction
of molds in a basket, the space between basket components and other
articles to be coated in the same basket, etc. Proper loading configuration
is a significant factor in assuming the uniformity of heating and
cooling of molds.
After the coating
and simultaneous hardening of the substrate, tempering is carried
out under the following condition: 1100-1125°F (590-620°C),
2 hours, 2-3 times.
The tempering
operation makes dimensional changes by the tempering effect on the
martensite phase produced during quenching , and decomposition of
retained austenite to martensite/bainite. The dimensional change
produced by tempering can be altered with tempering temperature,
time and repetition of tempering, while keeping substrate hardness
within acceptable values to die casting applications. Thus, precise
control of dimension can be done by changing tempering conditions.
Slender and
long pins are susceptible to bending. The residual stress formed
during heat treating, correction of bend, grinding, etc. should
be minimized. Stress relief annealing before TRD coating is recommended.
Mechanical loading and local heating can be applied to correct the
bend after TRD processing.
Add a grinding
allowance on the non-working mating face requiring close tolerance
and grind to the targeted dimension after TRD processing. This is
widely applied since it is an easy way to ensure tight tolerance.
However, it takes more time and adds cost in mold making and should
be the second choice.
Use of good
material, use of under- or over-sizing, cutting out molds in consideration
of rolling direction, well controlled machining condition, and well
controlled heat treating and TRD coating are key factors for eliminating
distortion.
However, TRD
coaters or mold makers can only do some of these things. The mold
designer, mold makers, steel makers, heat treaters, and TRD treaters
should be equally responsible for the problems of distortion. Whenever
dimensional tolerances are critical, close liaison between each
is highly required. It can be said that minimizing distortion is
a matter of will.
Examples
of distortion
Example
1:
The first example
shows results of an experiment which was carried out by using H13
steel un-hardened rod specimens 0.513 in. (13 mm) dia. and 3.82
in. (77mm) long. Thirty specimens were cut out from long steel stock
and TRD coated in three different loads, ten specimens each per
load in a production bath. The specimens were located in the bath
so that they were distributed uniformly over the whole effective
space in the bath.
Two major causes
for dimensional change namely, the scattering in steel quality and
in preliminary hardening were eliminated in this test. Hence, dimension
change and its standard deviation were negligibly small; average
0.00066 in. (8 µm) and 10.00009 in. (02.5 µm) for OD
and 0.0001 in. (2.5 µm) and 0.00079 in. (20 µm) for
length, respectively (Figure 2 a & b). The results suggest that
TRD coating can be applied to un-hardened pins and, in fact, has
been applied in Japan.

Fig.
2 Changes of (a) OD and (b) length obtained on
un-hardened small rod specimens of H-13 in an experimental test.
Example
2:
A similar
test was done on relatively large round specimens simulating an
actual production core insert. There was no preliminary hardening
but three specimens were cut out from three different steel stocks
of premium H13 for a total of nine specimens. One specimen was
picked out from each of the three steel stocks, and were TRD coated
in a load to distinguish the effect of scattering in steel stock
and TRD coating operation.
The effects
of steel stock and the loads were not observed and standard deviation
values were very small, especially in diameters 0.0001 to 0.0004
in. (2.5 to 10 µm) for ID, 0.0003 to 0.0004 in. (8-10 µm)
for OD, and 0.0008 in (20 µm) for height. The specimens
were TRD coated again, without annealing, under the same condition.
The size change and scattering in this test seem to be almost
the same as those in the application of TRD coating on the specimens
preliminarily hardened under the condition very close to that
of TRD. The standard deviations obtained were also small. The
dimension changes are different between the coating onto un-hardened
specimens and Re-TRD coating.
Example
3:
Figures 3a
and 3b exhibit the relation between OD dimension or length and
change of OD or length which was obtained with large numbers of
pins from a number of customers. Average change of shank OD is
not sensitive to change of OD and is only 0.0002 - 0.0008 in.
(5-20 µm) in the most popular size of pins; 0.2 - 0.6 in.
(5 - 15 mm) OD. Very similar values were obtained to point OD.
Length changed more remarkably, but was about 0.004 in. (100 µm)
in pins with less than 6 in. (150 mm) length. The trend lines
for average change of OD and length can be used to determine the
recommendable over- or under-sizing values, if it is necessary.
However,
scattering of dimension change should be considered here. It is
presumed in this case that the all factors related to distortion
problems were not necessarily well controlled in pin making procedures.
Heat treating was done by a number of different companies under
different conditions, resulting in a wide range of hardnesses,
as shown before. Another big problem is the uncertainty of steel
type. Notice of steel type from die casters is not necessarily
correct and there may be a large probability of mixing different
types of steels in the results. Some pins were possibly nitrided
or carburied. These problems cannot be completely eliminated in
practical applications in the die casting industry. Therefore,
the results in Fig.3 should be considered to be normal in applications
to the die casting industry.

Fig.
3 Change of (a) OD and (b) length of pins mode
of H-13 in relation to OD and length.
Bending
Bending of pins
was measured on two long pins. A pin 7 in. (180mm) long with 0.4
in. (10 mm) shank diameter and long tapered portion bent about 0.003
in. (0.08 mm). Another pin 7 in. (180 mm) long with 0.6 in. (15mm)
shank diameter and short taped working area bent 0.0016 to 0.0024
in. (0.04 to 0.06 mm). These bendings were successfully corrected
by pressing.
Out-of-Roundness
Deterioration
of out-of-roundness was evaluated in several examples. Out-of-roundness
of the un-hardened round core specimens increased only 0.00015 -
0.00047 in. (4 - 12 µm) in both ID and OD. Those of hardened
round core specimens showed only small increases: 0.00004 - 0.0004
in. (1-10), and 0.00008 - 0.00075 in. (2 - 19 µm).
Range
of Diameter and Length
The relation
between the range (maximum — minimum) of diameter and length were
investigated, in the core pins before coating and those after the
coating. The size range can increase by max. 0.00067 in. (17 µm)
in diameter and max, 0.0018 in (40 µm) in length. Making the
molds with minimized scattering of dimension should be the first
step to satisfy the tight dimensional tolerance.
Application
to die casting molds
As for TRD application,
benefits similar to those obtained in Japan were reported in the
USA two years ago. The application in American die casting is now
being accelerated and a large number of pins and cores have been
put into production reporting satisfactory results. Application
on various types of pins including squeeze pins ranging in size
from very small pins such as 0.157 in. (4 mm) in shank diameter
to large pins as 1.57 in. (40 mm) in shank diameter and 19.7 in.
(500 mm) long. Some types of core inserts with very complicated
shapes, and sprue cores with 6 in. (150 mm) in diameter have been
successfully used. Substrate steels are usually H-13 and other H
type steels. Modified high speed steels are rarely used.
Conclusive
Summary
It seems to
be commonly believed that high temperature coating processes cannot
be applied to dimensionally tight products. This is not necessarily
true. Punch makers in Japan have been making standard type punches
for metal stamping with 0.00008 to 0.00012 in. (2 to 3 µm)
tolerance in diameter and less than 0.0002 in. (5 µm) in bend
for more than twenty years. The results of Example 1 and others
suggest that die casting pins with similar tolerances can be made
without difficulty by well-considered procedures. It cannot be expected
to industrially realize similar tight tolerances for some large
cores, especially with complicated shapes. However, the examples
of actual applications shown in the previous paragraphs suggest
that even relatively large cores can be successfully TRD coated,
satisfying the required tolerance.
Unfortunately,
a number of factors relate to distortion problems, most of which
are out of the die caster's specialty. It should be emphasized that
to easily control all these factors, the die caster should keep
in close contact with steel makers, heat treaters, tool makers and
especially with the coaters if he wants to apply the high temperature
coating process to tight toleranced molds. The extra effort will
be worthwhile and shown through cost savings.
This
article, Diffusion Carbide Coating for Distortion Control
was originally published and copyrighted in 2000 by the North
American Die Casting Association (NADCA) in Die Casting
Engineer, in March 2000. It is published here with the
permission of NADCA and may only be republished with the permission
of NADCA by contacting dce@diecasting.org. NADCA is the worldwide
leader in stimulating growth and improvement in the die casting
industry.
by
Steve Harper and Tohru Arai
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