GELATION IN CASTING SLIPS This discussion will deal briefly with the mechanisms of Pie ' flocculation, and how these two mechanisms function in a casting slip. TiBuré t shows a defloccualtion curve generated using a Gallenkamp V fecometer othe a tion of sodium silicate results in a reduction in viscosity. The Botte. eee Is the viscosity measured on freshly stirred slip. Curve Tg is the viscosity me Sured after the slip has been at rest for six minutes. The difference betwee these readings is called build-up or gelation. The curve labeled build-up the effect of sodium silicate on gelation. be pos- Without exploring the basic theory behind these processes, it should sible to develop a mental picture of the casting process. The double layer theory of Helmholtz and others and the existence of the Zeta Potential explains how we are able to develop the forces of repulsion between particles. ‘This 1s accomplished by selectively exchanging ions on the clay surface which result in the particles ex~ hibiting a negative surface charge. The negative charge causes the particles pel each other. i duction in This is the deflocculation step in the process. This also causes a re the thickness of the layer of water which is essentially fixed to the surface of al Particles. By reducing this layer, there is an effective increase in the water aval able for the liquid phase or lubricating phase. There are also the forces of coagulation. In the absence of any surface charges the random motion of particles within the system will cause collisions between particl The existence of Van der Waals forces would keep two contacting particles bonded to gether. We then have two counteracting systems of forces operative in the slip. One ter to keep the particles separated by developing negative charges on the particles. Th other tends to coagulate the system into a single structural mass. By manipulating these systems a high solids slurry is produced in which the coagulation occurs in a ¢ trolled manner by the removal of a relatively small amount of water by the capillary action of the mold. Casting slips are always relatively high solids suspensions in which the inter~ particles distance is critically controlled. It is a generally true statement that the average interparticle distance in a solids-liquid suspension is controlled by the pack density of the solids and the amount of water present. However, all the water prese should not be considered as a liquid. There Is a film of water associated with the st face of the solid particles which is so firmly attached that it should be considered to @ solid that increases the effective radius of the particles and in addition depletes tl amount of liquid available for lubrication, The majority of the surface area exists or the relatively small fraction of the material which is in the colloidal size range, this fraction coming from the clay substance in the body. The non plastic portion of the body serves primarily as a filler in the casting process. As such, it can significantl affect the packing density but has only a minor role in the deflocculation-flocculatior mechanism. To obtain a workable high solids casting slip it 1s necessary to develop enough negative charges on the particles and sufficient thinning of the bound layer of water that there is freedom of movement of the particles, i.e, they are not bonded togethe fil there is sufficient unbound water to fill all void ‘space and provide an adequate Thorieating phase between particles. On the other hand, in most good casting slips there are sufficient forces of attraction that in the absence of agitation a structural network of bonds between particles begins to form. These are the result of agglom- eration or flocculation of particles and can be detected by an increase in viscosity.‘The bonds so formed are very weak and the process is reversible. This is the thixotropy or gelation under discussion. i ly adjusted Figure 2 is a plot of viscosity versus shearing rate of a proper! casting slip, The Brookfield Viscometer is not designed to measure viscosity at zero shearing rate, nevertheless, the very rapid increase in apparent viscosity at very low shearing rates demonstrates the gelation taking place. This curve is reversible. i illary action of During the casting process, the removal of water by the cap: the mold causes the solid particles to approach each other until the Van cas Wom forces of attraction exceed the repelling forces of the negative charges on the Particles. Thus, each particle forms bonds with its adjacent neighbors. The distribution of the negative charges and the density of the charges are controlled by a complex surface chemistry affected by the following: Particle Size Surface Area Mineralogy Soluble Salts Deflocculants (Alkaline Polyelectrolytes) Floceulants (Anions & Cations) Surface Modifiers (Organic Colloid) This balance, in turn, controls the structure that is formed when the particles are forced close enough together to establish particle to particle bonding. In Figure 3, the diagrams depict graphically the forces which interact between particles. Extending out from the face of the particles is the diffuse layer of con- terions. Adsorbed on the surface of the clay is the layer of negatively charged ions which causes repulsion forces shown by the curve (R, or R,). As the particles ap- proach each other this force increases. There are alsb the forces of attraction which are also a function of distance, as shown by the lower curve. If these factors are summed to determine the net force acting on the particles, the resultant curve shows that there is a net repulsion until the distance is reduced to a specific point. At dis- tances less than this, the net force is one of attraction and the particles will bond to- gether. Since the repulsion curve is a function of the strength of the negative field and since the attraction forces are a function of particle size, no two particles necessarily have the same net force curve. As a result the critical distance is different for dif- ferent particles so that in the complex environment of a casting slip, some particles will Sgglomerate while others will not. ‘The regulations of this balance is called slip control, Taking some oversimplified situations will illustrate the point. In the absence of sufficient flocculating ions and organic colloid the cast structure of » defloccula ya tera oanaa caning & ee ny and therefore a slow rate of build-up o! cast. In a , there is not sufficient water retained in the cast plasticity. The cast is brittle. . oT ae The addition of only organic colloid with its associated lyophilic nature will in- Grease the amount of water retained in the cast. Thus a degree of plasticity can be developed by utilizing the affinity of water for the organic colloid. ‘But, this will result in an even slower rate of cast than the body without the colloid addition.Moisture retention can also be increased by the addition of flocculating solu ite Suciras sulfate. However, high sulfate bodies insufficiently buffered by the protective action of organic colloid result in the necessity for using excessive amounts of deflocculants and the resultant cast may be dilatant or just soft as opposed to plastic. In order to get @ mental picture of the mechanisms of the casting PrOOE SS we can represent the distribution of the particles in water by @ series of circles. Figure 4 depicts the condition existing at the moment of pouring. the viscosity is Tepresented by the line shown which shows the viscosity to be @ single value throughout the slip mass. Within a very short period, i. e., one minute. & portion of the water is withdrawn from the slip at the mold interface and there is an #2, mediate and sharp rise in the "viscosity" of that portion of the slip. (Figure 5) The "viscosity" is so high that we can refer to that portion of the cast as Delns aries athes than'a liquid, ‘There will exist a very sharp interface between the Solid portion and liguid portion. As the slip remains in the mold for a longer period, there is a change in the casting mechanism. The slip starts to gel. triguro 6) This can be measured as a change in the viscosity. It is caused by Sn Jgglomeration of the finest colloidal particles, either with each other or with large particles. These agglomerates then act as larger particles. ‘The agglomerated particles have established a stand off distance from each other which is greater than the agglomeration which results from forcing the particles together by de-watering. As a result, the subsequent cast will have (higher moisture retention. It is interesting to note at this point that while the Tate of deposition of clay on the mold is diminishing with time, if the rate of cast is viewed as a property of slip, then the rate of cast increases as the slip sits in the mold. ‘The loss in the rate of build-up on the wall is due to a diminishing of moisture gradient thru the cast. Because of gelation taking place within the liquid portion of the slip, the density of the cast being formed from this slip is diminishing. We therefore, start to experience the development of the differential between the outside and the in- side of the cast. (Figure 7) If this gradient becomes too great, then when the ware dries, stresses develop which frequently result in cracking of the ware. In Figure 8 the successive time intervals show a continuing increase in viscosity and a decrease in the firmness of cast. If this process were to proceed indefinitely, ‘there would be no clear distinction between the cast portion and the slip portion and the piece could not be drained. i . It is necessary to control the build-up of the viscosity to the point that the shear value of the stationary slip is low enough to permit a clean drain from the interior Faves aftsr te desited wall thickness te obtained. a a After the slip is drained from the interior surface, if the cast portion remains in contact with the casting face of the mold then a further do-watering takes place and the interior of the cast will become more firm, thereby partially reducing the dif- ferential created during the casting period as indicated by the dash lines in Figure 9, SUMMARY In summary, to produce a satisfactory casting slip, it is not suffici Bite yet 1xe patevinls. wd enough wster and enough defiocculant to ah a system fluid. Just having enough fluidity t se eas aren: hari 8 enoug) y to get a clean drain does not insure an ac~It is necessary to balance the entire system so that the flocculation that occurs from the de-watering will result in a cast which has the structural quality demanded by the plant processes. This means controlling the packing density, the amount of water retained, hot w it is held in the structure and how much differential exists across the thickness of the cast.APR 2 4 1961 y GELATION RAT INDEX AND CAST QUALITY BY1_W._. BRODIE e The goal of those industries using casting slips 1s to develop a cast of ade~ quate thickness in a reasonable length of time. It 4s desirable to have as much Plasticity as possible with an equivalent firmness. The term plastic-firmess 15 fenerally used in the industry when referring to this property. Exceeding the Plastic range is a soft gumy alip. Exceeding the firmness range is a hard brittle Slip. Establishing the range of maximum plasticity with a good firmness 1s diffs: cult to accomplish and maintain, This is the reason slip conferences are so popu- lar, and new ideas or methods get so much attention, The procedures and methods # company uses to structure its casting slip system to its particular forming method has a major impact on reducing clay and glost losses. Unfortunately casting slip industries cannot anneal the formed product 1ike the glass industry. The annealing of cast products has to take place during the casting of the product by the proper plastic-firmnese structure of the cast. With the optimum plostic-firmess the ware can be cast with less strains, handled with Jess strains developing, and dried with less differential shrinkage. I asked Burt Carter, formerly general Ceramic Engineer for American Standard, and one of the greats in our industry, his definition of a clay crack, or clay check. lle used just two words, differential shrinkage. ‘The real goal in any plastic-firmness cas! ing system is to reduce all strains resulting in a truly annealed cast product. 1 refer to this as a plastic-firmess casting system because it should be looked at fas a vhole system, Often we only look at single changes - anew material, or in~ creasing or decreasing materials like {ine clay, coarse clay, sodium silicate, sul- fates, calcium, soda ash, etc. The quality of the plastic-firmess casting systen can be improved not only by the selection of rav materials, but by the use of certain additives, processing methods, adjusting procedures, and evaluation of pro- @ verse ‘This paper will deal with the evaluation of those plastic-firmess properties that give the best climate for improved clay and glost results. There are many good methods to evaluate your casting system. The method that Bill Kelly has des— eribed has a nev approach where thixotropic properties are measured in conjunction Sith the firet contact of the slip with the plaster mold. The test gives an inmedi~ te reading on what kind of plastic-firmess system is being developed. In my Opinion this initial formulation of the plastic-firmness gives a clue to the future quality of the ware, not only to reduce clay cracks or checks, but to reduce one fire and refire dunting. When Cyprus Minerals developed the vibrating sphere viscometer in this manner just described by Bill Kelly, they used the term gelation rate index for the two inate reading. I will on occasion refer to this as the protective gel, because T feel that gelation rate index in the proper range is actually a protective gel that protects the quality ‘of the cast from the onslaught of the mo! My primary interest ds the practical application of the information the instrument provides to improve the plastic-firmess casting system for less clay and glost loss. et Minerals loaned Mansfield the instrument last March so that large quanti- ties of production casting slip could be evaluated. As we started using the in— it became apparent that what was being measured was a protective gel being ictually keep the casting slip from being Literally torn apart and separat~ uction of the plaster mold. As the cast tarts, there has to be a Structure as the mold attacks the slip. It may sound dramatic, but that water, and 4t will separate particles, change moisture ‘up the whole structure of your cast to get it.I would Like to emphasize at this point that in my opinion there are no bad casting slips. You could not stay in business with a bad casting slip. What ve e have are casting slips not quite in phase with the plastic-firmess requirements of various processes and conditions. No casting slip will ever reach 100% in phase, but the closer the slip will adjust to the variables in manufacturing the better the climate for improved result: If there is no protective gel as the slip casts, there could be a tendency for the following: (it must be emphasized that for various reasons the following may never occur even with no protective gel, but.the cast is more prone to develop the following cast problems) 1. Pull the finer particles to the initial casting surface causing a poor release. 2, Pull the finer particles to the initial casting surface causing a clay slur or staining of the mold surface. 3. Pull the finer parcicles toward the casting surface causing an uneven distribution with higher amounts of fine particles nearer the mold sur- face, and higher amounts of coarse particles nearer the drain or solid cast interface surface. a) A concentration of coarse particles at the solid cast interface surface is especially dangerous. There is poor interface ad- herence causing clay separation, moisture bloating, and dunting. b) In a casting body the majority of the fine particles are plastic e@ or clay particles, and the majority of the coarse particles are non-plastic or feldspar-flint particles. A separation of parti- cles causes an uneven fired matrix more prone to preheat, firiny fand cooling heat shock problem c) There ie a differential shrinkage problem as the cast dries due to particle size distribution. 4) There are various rates of set-up in the cast itself. ic 4, As the particles of the cast tend to separate the moisture distribution "also tends to be uneven. ‘This can cause the problem of hard brittle j ‘easting surface, and a soft sloppy drain surface. we habe or ‘opy control ranges at the various stages of aging. Mans— are good indicators of the status of the pla: c Two tests performed frequently ieee able. We have a long history of our c Base, Cal ashen) MIS ur egero Cae late) year, and close control is maintained. 3 sphere viscometerConclusion ‘As mentioned before, our main purpose was to evaluate the practical production information from the instrument. The following was important information to improve our slip control program: 1, It was a surprise how quickly the gelation rate index or protective gel, could change when the plastic-firmess structure was disturbed by a late ? correction in the system. When production slip readings were within all three ranges, even a slight altering would cause a loss of one or two of the desirable plastic-firmess properties. The conclusion was that it we better to age the slip into the target cast and protective gel, than to correct the system late for cast, and disturb the protective gel. If we assume that gelation rate index or protective gel is important to the quality of the cast, then the amount and consistency becomes important to the plastic-firnness structure of the cast. Many of us make casting rate or viscosity corrections late in the aging process. The question is what effect do these corrections have on protective gel. The following Table No, 1 illustrates what happens with even slight corrections in our system. TABLE NO. I Production slip new bowl line - adjusted to the firmness side, or to the plastic side of the casting range. Average Avg. 10 Min. Avg. 45 Min. Avg. 45 Min. Avg. Gelation Flow Time Cast Time Cast Time Cast Rate Index fe (in) (Gms) a) ay) (2 Min.) Increased Firmness 2.50 67 iW WG 159 Production Slip 3.04 nm 13 2+ 504 Increase Plasticity 446 7 15 9/164 964 Based on this information we started a program to get our slip aging corrections as far back into the aging system as possible. Through the skill and creativity of _ our excellent slip technicians they developed the following procedures: Concentrate specifically on correcting as early as possible to reduce the corrections. Graph No. 1 illustrates this.b) Testing D cistern, our first adjusting cistern more times in 24 hours. c) Testing all cisterns every 8 hours around the clock. 4. We found that during the period ve are using more slip across the system, the slip plasticity increases with a loss of firmess. We first picked this up when the gelation rate index increased during this period. The Gallenkamp also picked it up when we ran it at this time. It was im~ portant for us to know so we didn't go out of range during periods of heavy slip usage. 5. The gelation rate index changes due to seasonal humidity and temperature changes that cause adjustments in the plastic-firmess system. Table No. 2 shows this. TABLE NO. 2 Changes in gelation rate index due to seasional humidity and temperature changes. Winter May-June Summer Condit ion: t Period Conditions, 45 Min. Gallenkamp Overswing 35 to 45 53 to 58 62 to 68 Gelation Rate Index 500 to 800 400 to 600 250 to 350 e@ ‘The danger here is that most summer slips are adjusted to the firm side, so the gelation rate index, or protective gel could be lost without knowing it. Of te you eg hear the statement “what happened to our results, we didn't change anything". This lance is sensitive enough that it can get out of balance without William T. Brodie ‘MANSFIFLD SANITARY 4 ee Division of Int corp. Perrysvi