Method of making gas curable resin-coated sand cores

A method of making sand cores to obtain optimum mechanical properties and particularly to obtain accurate adjustment of the gas curing cycle for making optimum resin-coated sand cores. The method comprises blowing, into a core box cavity, mixture of core making particulated sand and gas curable liquid resin having a first level of pH, such mixture containing a uniform distribution of a pH indicating dye additive that changes color in response to a change in pH level, in contact therewith, such blowing being continued to fill the cavity to a desired density and form an uncured sand core shape with a predetermined porosity, (b) introducing a catalyst gas having a second level of pH, through the pores of the core shape to cure the resin and contact the dye additive, (c) concurrently, or subsequent to step (b), sensing the degree of color change of any part of the core shape that is or has taken place as a result of exposure to the flow front of the catalyst gas, and (d) responding to such color sensing to modify the parameters of catalyst gas introduction (i.e. exposure time, gas pressure, gas concentration or gas inlet/out location) to ensure the desired degree of catalyst reaction in the desired time period.

TECHNICAL FIELD 
This invention relates to the technology of making resin-coated sand cores 
useful in making metal castings, and more particularly to technology that 
assures complete core curing of the resin-coated sand within a core box 
within the shortest possible time. 
DISCUSSION OF THE PRIOR ART 
The cold box process of making bonded sand cores is well known and uses a 
gas or vaporized catalyst to cure the resin-coated sand while the catalyst 
is in contact with the sand at room temperature within a closed core box. 
It remains a problem how to determine whether a consistent and sufficient 
concentration of the catalyst has permeated the different parts of the 
core to react with the resin coating while held in such closed core box. 
Without precise knowledge of the catalyst flow front and concentration 
which may vary with time, an operator cannot know whether the catalyst gas 
has fully penetrated the entire core body, risking core defects, such as 
spongy core areas, or areas that are so brittle that they easily break or 
fall away during subsequent handling. Moreover, the operator cannot know 
precisely when to open the core box, thereby risking not only exposure of 
the operator to noxious catalyst gases if the resin has not been properly 
cured or thereby risking an improperly bonded sand core leading to high 
rates of scrap. 
To Applicant's knowledge, there is no known method to detect, measure and 
monitor the concentration of the catalyst flow front in the core box and 
the degree to which the catalyst gas has penetrated the core body. The 
operator either can err on the side of excess cycle time to fully ensure 
that the catalyst gas has migrated sufficiently and completed its curing 
job even at low unintended concentrations. As a result, shortened time 
cycles are not possible for the cold box process. 
An example of a poorly cured sand core is one that is cured on its outer 
surface but not cured sufficiently inside. It will not have the proper 
handleability and will break in subsequent core assembly steps. If such 
defective core is not detected before hot metal is cast against it, the 
core will deform during casting. As a consequence, the expensive metal 
casting must be scrapped or the metal casting must be subjected to 
expensive grinding to remove excess metal that represents a wrong geometry 
(areas filled with metal that are supposed to be open passageways). 
Certainly batch techniques which, over a long period of time, gather a 
detectable gas sample and which take an even longer period of time to 
analyze the sample by use of wet chemicals requiring titration, cannot 
give information that would aid in telling the extent of gas permeation or 
that would aid in shortening the cycle time of core box usage. Other prior 
techniques that monitor the total mass of gas, entering at the inlet to 
the core box, fail to enable an understanding of how the catalyst gas flow 
front is affecting the sand core in any given case, and therefore there is 
no knowledge as to what is happening within the cold box core process. 
SUMMARY OF THE INVENTION 
It is an object of this invention to provide a technique for the cold box 
process that allows the degree of advancement of the flow front of the 
catalyst gas to be accurately determined or observed for each set of 
conditions (gassing concentration, gassing pressure, gas volume, gas 
temperature, corebox sealing, and gassing inlet and outlet locations). 
Such ability to observe or determine will lead to reduced core defects, 
reduced casting scrappage and better design of the core boxes. 
The invention herein that meets such object is a method of making sand 
cores to obtain optimum mechanical properties, and particularly to obtain 
accurate adjustment of the gas curing cycle for making optimum 
resin-coated sand cores. The method comprises (a) blowing into a core box 
cavity a mixture of core making particulated sand and gas curable liquid 
resin having a first level of pH, such mixture containing a uniform 
distribution of a pH indicating dye additive that changes color in 
response to a change in pH level in contact therewith, such blowing being 
continued to fill the cavity to a desired density and form an uncured sand 
core shape with a predetermined porosity, (b) introducing a catalyst gas 
having a second level of pH, through the pores of the core shape to cure 
the resin and contact the dye additive, (c) concurrently, or subsequent to 
step (b), sensing the degree of color change of any part of the core shape 
that is or has taken place as a result of exposure to the flow front of 
the catalyst gas, and (d) responding to such color sensing to modify the 
parameters of catalyst gas introduction to ensure the desired degree of 
catalyst reaction in the desired time period.

DETAILED DESCRIPTION AND BEST MODE 
As shown in FIG. 1, the method of this invention comprises the steps of (1) 
homogeneously distributing a curing indicating dye throughout a supply of 
resin-coated sand to form a treated mixture, (2) forming the treated 
mixture into a core shape with controlled porosity, (3) introducing or 
forcing a catalyst gas through the core to cure the resin, (4) observing 
the extent to which the distributed dye has changed in color, and (5) 
responding to the color change to adjust the parameters of catalyst gas 
introduction if needed. 
Material for the cold box process is prepared for purposes of this 
invention by adding a pH sensitive dye 30 (as the curing indicator) to a 
mixture 34 of particulated core making sand 31 and gas curable liquid 
resin 32. The resin can be selected from the group of phenolic urethane, 
phenolic CO.sub.2, sodium silicate CO.sub.2, furan SO.sub.2, acrylic epoxy 
SO.sub.2, having a pH in the range of 2-9. The dye is selected to exhibit 
a first color when exposed to the resin 32 (which possesses a first level 
of pH), and change to a distinctly different color when exposed to a 
catalyst gas 33 (having a different pH level) that attempts to permeate 
the mixture 34 during step (3). The dye can be selected from sulfone 
phthaleins which are sensitive to a change in pH within a range of 2-10. 
Core making sand 31 is usually silicon lake sand with an average particle 
size of 200-300 microns. Other types of sand or refractory grains can be 
used, such as zircon. The resin 32 for the sand mixture is preferably a 
liquid phenolic urethane carried in a solvent, the phenolic urethane 
having separate hydroxyl and isocyanate functionality which react in the 
present of an amine catalyst (i.e., triethylamine) to produce a solid 
binder in the form of urethane. Other binder resins may include furan 
resins, epoxy resins, and polyesters, all of which depend upon hydrocarbon 
bonds, oxygen-carbon bonds, or nitrogen-carbon bonds when cured. The 
phenolic urethane resin usually has a pH in the range of 2-6, whereas 
furan resins may have a pH level in the range of 2-5. 
The curing indicating dye (pH sensitive additive), is selected so that a 
distinct first color 35 in the presence of the resin will change to a 
distinctly different color 36 when exposed to the catalyst gas that is 
brought into contact therewith. For this to occur, the additive is 
uniformly distributed throughout the treated mixture 34 so that any one 
particle of dye exposure to the catalyst gas will occur at the same time 
as an adjacent particle of resin is exposed to such catalyst gas. The 
indicating dye, for example, may consist of aqueous dispersion of 
bromocresol green dye, wherein such dye is yellow or brown (color 35) in 
the presence of the predominantly acidic resin sand mixture (pH of 2-6) 
and turns blue (color 36) when the catalyst gas (triethylamine) contacts 
it, the catalyst gas having essentially a more basic pH of greater than 5 
but less than 11. The indicating dye dispersion 37 is prepared so that it 
is formed as a water solution with the dye being present in the dispersion 
in an amount of 0.5 to 1.5% by weight, preferably about 1.1% by weight. 
The dispersion or solution in turn is added to the resin-coated sand 
mixture in an amount of amount 0.5-1.0% by weight of the resin sand 
mixture. This is an extremely small amount and steps must be taken to 
ensure that the dye is uniformly distributed throughout the treated 
mixture. To this end, the resin-coated sand is prepared by introducing the 
sand, as well as the liquid resin, into a mixing device 38, such as a 
muller, which utilizes stainless steel rollers in a stainless steel 
container to mix the contents therein. 
Utilizing such treated mixture 34, the cold box process will then consist 
of four steps: blowing the treated mixture into a core box, gassing the 
contents therein, purging the core box contents of gas and removing the 
bonded core. As shown in FIG. 2, a core box 10, having upper and lower box 
portions 10(a) and 10(b) define an internal cavity 11 with one or more 
small inlets 12 and one or more screened outlets 13. To effect blowing of 
the treated mixture, a fluidizing chamber or sand magazine 14 is placed on 
top of the core box and has conically shaped portions 14(a) in 
communication with each inlet 12 to the core box. The resin-coated sand 
mixture 34 (containing the dye), in a predetermined volume, is introduced 
to the chamber 14 to a level 15 such as illustrated; a supply of 
fluidizing gas 16, such as pressurized air at about 80 psig from a supply 
17, is admitted into the chamber 14 to create an air/sand mixture 
suspension which then flows into the inlets 12 packing the cavity 11 with 
the sand mixture while the fluidizing gas migrates through the sand to 
exit through the screened outlets 13. 
The gassing step is effected by stopping the flow of fluidizing air 16, 
removing the fluidizing chambers or sand magazine 14 from the top of the 
core box (which box cavity has now been packed with sand) and placing a 
catalyst-purging apparatus 18 in communication with the inlets 12, the 
inlets having a throat area of at least 0.25 inches and a spacing between 
the inlets of no greater than 7 inches. Pressurized amine catalyst gas 19 
is released from a supply 20 by operation of shut-off valve 21 and 
regulation of the pressure of the amine gas is carried out by way of 
pressure regulator 22 promoting a pressure of at least 2 psig, preferably 
about 5 psig. The curing gas migrates 30 through the interstices 
(porosity) of the defined sand core to eventually exit from outlets 13 as 
an effluent 23. The preferred time period for curing is in the range of 
1-30 seconds for completion. Although the mass of gas needed to cure the 
resin can be readily determined using stoichiometric data, an operator is 
never completely certain that such determined mass is sufficiently high 
enough in concentration and at the right pressure and gassing time and 
temperature for the given geometry of the core shape and outlet sizing, as 
well as the inlet/outlet placement, to permit the curing gas to fully do 
its job. The outlet sizing permits part of the curing gas to escape during 
curing and must be compensated. The amount of curing gas lost during 
curing is also dependent upon the integrity of the sealing of the core box 
parts; often undergassing or overgassing occurs. It is typical to inject 
about 2-10% by weight of triethylamine gas into the carrier gas, such as 
nitrogen, which nitrogen is flowing at a rate of about 2-20 liters per 
minute. The catalyst gas can be selected from the group of amine 
(SO.sub.2), sulfur dioxide and carbon dioxide (CO.sub.2). 
Either during the step of introducing the catalyst gas through the core box 
or subsequent thereto, observation is made as to the extent of color 
change of the core shape due to the flow front of the permeating catalyst 
gas. The operator can be certain that the catalyst has traveled through 
the entire core by observing the completeness of color change from yellow 
to blue in all areas. Areas that remain yellow or that are not a strong 
blue color are inadequately cured. 
Considerable handling, assembly and interlocking is necessary for the sand 
cores to be used in the making of a metal casting. The complexity and size 
of some of such cores (cores 24-27) are illustrated in FIGS. 3a, 3b and 3c 
for use in the casting of an automotive engine block. If such cores are to 
serve their purpose, the cured core must have a glass transition 
temperature (Tg) of about 70.degree. C. when phenolic urethane resin is 
used. The glass transition temperature is the temperature where there is 
increased molecular mobility of the polymer resin. This mobility results 
in significant changes in the mechanical properties of the cured resin 
system. Without a Tg, the core is brittle and will not have the 
compressive strength to be handled in the metal casting process; the core 
will not be able to adequately withstand the metal pouring operation and 
may result in the scrapping of very expensive metal castings. 
One of the cores, a head deck slab core, prepared and cured with the use of 
the indicating dye of this invention, is shown in FIG. 4. This example 
illustrates subtle imperfections that can be observed by the operator. 
Areas where the catalyst did not permeate are still in tan color 35 or a 
blend of tan and green (see those marked with arrows). These areas have 
not been cured properly and will have weak mechanical properties. An 
example of an inadequately cured core with more pronounced defects is 
shown in FIG. 5. It is a part of the head deck slab core shown in FIG. 4, 
such part having been broken off when ejected from the core box machine. 
It possessed spongy areas shown at 39 and broken off sections at 40. 
As the last step of the method herein, the operator responds to incomplete 
color changes by adjusting one or more of the catalyst gas parameters, 
such as: (i) changing the concentration of catalyst gas that is forced 
through the core box, preferably by increasing such concentration by 
increments of 0.1%, (ii) changing the pressure of the catalyst gas from 2 
to 20 psig, (iii) relocating the inlets 12 and/or outlets 13 for the 
conveyance of the catalyst gas 19 to be more readily distributed 
throughout the more difficult sections of the porous core, and (iv) 
changing the size of the catalyst gas inlets or outlets to promote 
increased or decreased gas flow therethrough. Other parameters that may 
also be changed include gas temperature or time of gassing. 
While particular embodiments of the invention have been illustrated and 
described, it will be obvious to those skilled in the art that various 
changes and modifications may be made without departing from the 
invention, and it is intended to cover in the appended claims all such 
modifications and equivalents as fall within the true spirit and scope of 
this invention.