ARCHIVES of FOUNDRY ENGINEERING

Published quarterly as the organ of the Foundry Commission of the Polish Academy of Sciences

ISSN (1897-3310) Volume 7 Issue 1/2007 103 106

22/1

Evaluation of wettability of binders used in moulding sands

a

B. Hutera a, K. Smyksya, D. Droyski a,*

Faculty of Foundry Engineering, AGH University of Science and Technology, ul. Reymonta 23, 30-059 Krakw, Poland *e-mail: dd@agh.edu.pl Received 08.02.2007; Approved for print on: 12.03.2007

Abstract
Binders used in moulding sand have the differential properties. One of the main parameters influencing on moulding sand properties is wettability of the sand grain by binding material. In the article some problems concerned with wettability evaluation have been presented and the importance of this parameter for quantity description of process occurring in system: binder- sand grain has been mentioned. The procedure of wetting angle measurement and operation of prototype apparatus for wettability investigation of different binders used in moulding sand have been described, as well as the results of wetting angle measurement for different binders at different conditions. The addition of little amount of proper diluent to binder results in the state of equilibrium reached almost immediately. Such addition can also reduce the value of equilibrium contact angle. The uniform distribution of binder on the surface of the sand grains and reducing of the required mixing time can be obtained. It has also a positive effect on the moulding sand strength. Keywords: foundry technology, moulding sands, binders properties, binders wettability measurements.

1. Introduction
The relationship between the strength of the prepared moulding sand and a procedure used for its preparation is of great practical value. Many kind of binders are used in different foundry moulding sands [1]. Their properties are influencing on technological properties of prepared moulding sand and consequently on the quality of castings. The phenomena occurred on the border of the system: binder- sand grains have doubtless large influence on the moulding sand quality [1, 2, 3, and 4]. Their course depends among others on the morphology of grain surface, its superficial energy, the quantity and kind of the electric charge, and also properties of the liquid binder (i.e. the viscosity, the surface tension) and the ability to wetting of the grains surface by binder [2, 5]. The influence of the wettability on the formation of connections between sand grains is essential, especially for binder bridges geometry and also adhesion and cohesion strength of connections [6]. The wettability can be improved by modification of the solid body surface (i.e. of its

surface layer) or by modification of the applied binder [2]. The modification of a solid or liquid body is carried out by chemical and/or physical methods [7, 8]. In practice, it is rather preferred to modify the binders through the use of properly chosen diluents. The correct evaluation of the wettability is complex problem [8, 9, 10]. Difficulties create among other by: diverse proprieties of binders, physical and chemical transformations during bonding, the differentiation of the energy-state of the grains surface, the influence of ambient conditions [11]. Some aspects of measuring methodology of contact angle of selected binders representing wetting properties has been below described. Additional advantage of such tests will be not only an technological effect- higher sand strength but also economical and ecological aspects- less of binder added. The optimal features of moulding sand allow to create the balance between technological properties and properties which are useful for proper run of moulding sand processing in whole casting manufacturing process (in example preparing of moulding sand or reclamation process [12]).

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2. The apparatus for evaluating of binders wetting angle

The quick changes of the contact angle causes that in such measurement appears the necessity of the registration and the transformation of large number of images. On the present level of the technique the automation of the measurement is possible due to utilization of computer for images processing [13, 14, 15, 16]. In the investigation of wettabilty phenomena it is important to evaluate not only equilibrium value of contact angle but time run of this quantity [14, 15]. It is also important from practical reasons because the modern mixers and moulding devices have dynamic operations. For investigations of wettability the prototype apparatus has been elaborated- Fig.1. In first version, device has been equipped only with the heating chamber (Fig.1a). For industrial practice the measurements in temperature level below ambient temperature (usually about 293 K) are interesting (e.g. winter period) [12]. So the second version of apparatus has been equipped with dual-actions chamber for cooling or heating, basing on the Peltier module. Another basic parts of device are optical system equipped with the element CCD and illumination system, the programmable device controller with temperature gauge and portable PC. a)

controller with temperature gauge and portable PC. The image of the drop is digitalised (the element CCD) and can be observed onscreen of the small liquid crystal monitor or on the PC monitor. The configuration of the regulator and output circuits assure the stabilization of the temperature in the chamber of the device during the research. In definite time intervals the images of the drop were converted and recorded in the PC memory. Till now, in the chamber of the device were made periodically humidity measurements (hygrometer HD 8902, the Delta OHM Company).

3. The elaboration of selected tests results

Examples of images of the sessile drop of binder on quartz plate are presented on fig. 2. Outlines of the drop image after converting of image (with special software) allow evaluating the right and the left-sided wetting angle (fixed in relation to the horizontal reference line). Problems of the image analysis for the purpose of wetting angle evaluation were described precisely in [13, 16]. Elaboration of results of experiments series has proved that in the most cases the outlines of drop images drops (above reference line) can be treated as part of circle (with good approximation). Only at the first image of the drop- after binder application on the quartz plate the difference between left and right contact angles is larger. a) b)

c)

d)

b) Fig. 2. Images of drop of epoxy binder with diluent on quartz plate; temperature in test chamber 283 K: a- start of testing, b2 min. after start , c- 4 min. after start, d- 20 min. after start. The time run of contact angle can be evaluated from modified equation:

cos R cos ( ) = a e
( )
Fig. 1. View of prototype apparatus for investigation of binding agents wettability: a - version 1(with heating chamber), bversion 2 (with heating and refrigerating chamber): 1- chamber of apparatus, 2- controller, 3- optical system with CCD element, 4- LC monitor, 5-portable computer, 6- stand, 7-dualaction chamber (heating or refrigeration), 8- lighting system. Another basic parts of device are optical system with the element CCD and illumination system, the programmable device

(1)

- current value of wetting angle,

R - equillibrum value of wetting angle: R = () , - time a, b - constants

This equation differs from the origin ([8]) due to existed exponent (0,5) at time value. The procedure of constants a and b evaluation has been precisely presented in [15]. Fig.3 (and the further

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figures) illustrates good correlation between experimental time changes of contact angle and description by equation (1). The results of changes of the contact angle concerned various binder and different research conditions have been presented on further figures 3, 4, 5 and 6.
50
Wetting angle ; degree

45

Investigation results Model- equation (1)

Correlation coefficient- kr=0,993

40

35

30 0 30 60 90 120 Time ; min Fig.3. Comparison of time dependence of wetting angle between research results and calculation results from empirical equation /1/.Temperature 293 K: binder: epoxy resin- 95 %, methyl acetate- 5 %; plate material quartz.

value of the angle r. So large variations in this angle value can be explained by prevalence of the intermolecular forces present in the resin over the interfacial forces acting in a quartz resin system. The dynamics of changes in the angle within the above mentioned time interval can be expressed by means of equation (1)- continued lines. In run = f() plotted for resin with 30 wt.% of diluent no more significant changes in the value of the angle have been observed. This means that the state of equilibrium has been achieved almost immediately by the system with the corresponding angle r. Mathematically, this is expressed by more straight line. The instantaneous state of equilibrium, i.e. an equilibrium angle, reached by the system is caused, on one hand, by a drop of intermolecular forces, and, on the other, by adsorption on the quartz surface of a polar-active compound, causing an increase of the free surface energy. An addition of diluent (in eg. ethyl acetate) to epoxy resin has a favourable effect on the mechanical properties of a silica sand-based moulding mixture. The sand bonded with resin containing diluent takes much shorter time to reach its maximum strength than it happens in the sand bonded with the sole resin.

The series represented on Fig. 5 shows the possibility of the influencing on the rate of reaching of equilibrium value of contact angle by the addition of the diluents. From this diagram it follows that both time runs of the contact angle considerably differ from each other. In run = f() obtained for the sole resin one can observe great variations in the values of the angle within the time interval of (0 20 min), after the lapse of which the value of the angle is made stable due to the state of equilibrium having been achieved by the system with the corresponding equilibrium

70 65 60 55 50 45 40 35 30 25 20 0 30

Wetting angle ; degree

no diluent 5% cyklohexsanone 30% cyklohexsanone

60 Time ; min

90

120

70
Wetting angle ; degree

60 50 40 30 20 10 0 30

Epoxy resin
Epoxy resin-95%, xylene-5%
Alkyd resin LT-72

Fig.5. Time dependence of wetting angle for epoxy resin with different addition of diluent (cyklohexanone) at 283 K; plate material quartz. The addition of diluent to resin decreases its viscosity and, by favouring the formation of envelope-free bonds between the sand grains conferring to the sand high mechanical strength [1, 2, 6] with parallel improvement of its wettability, increases the strength of the sand - binder bond. Therefore, when chosen correctly, a diluent of the binder should be characterised by chemical inactivity combined with appropriate evaporating point to make it easily removed from the sand during consolidation and hardening. The temperature is also one of the strong factors influencing on wettability phenomena (fig. 6) and another properties of binders [3, 5, 17]. The addition of diluent to resin decreases its viscosity and, by favouring the formation of envelope-free bonds between the sand grains conferring to the sand high mechanical strength [1, 2, 6] with parallel improvement of its wettability, increases the strength of the sand - binder bond. Therefore, when chosen correctly, a

60 Time ; min

90

120

Fig.4. Time dependence of wetting angle for different binders at 283 K; plate material quartz.

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diluent of the binder should be characterised by chemical inactivity combined with appropriate evaporating point to make it easily removed from the sand during consolidation and hardening.

References
[1] J.L. Lewandowski, Materials for foundry moulds, Akapit, Cracow 1997 (in Polish) [2] B. Hutera, An effect of non-activated diluent addition on strength of moulding sand with epoxy binder, Archives of Foundry, R. 6, no. 18 (2/2) (2006) 441446 (in Polish). [3] B. Hutera, K. Smyksy, Influence of increased temperature on the strength of sand with epoxy binder, Archives of Foundry, R. 6, nr 18 (2/2) (2006) 447452 (in Polish). [4] S. M. Dobosz, Water in moulding and core sands, Akapit Cracow, 2006 (in Polish). [5] B. Hutera, Temperature influence on viscosity of selected foundry binders, Archives of Foundry, R. 3, nr 9 (2003) 203208 (in Polish). [6] B. Hutera, J. L. Lewandowski, K. Smyksy, Influence of preparation conditions and thickness of synthetic resin hardened layer on tensile strength determination, Archives of Foundry, R. 1, nr 1(2/2) (2001) 483488 (in Polish). [7] J. J. Bikerman: The Science of Adhesive Joints. Acad. Press, N. York-London, 1961. [8] M. enkiewicz, Adhesion and modification of surface layer of high-molecular materials, WNT, Warsaw, 2003 (in Polish). [9] E. L. Decker, B. Frank, Y. Suo, S. Garoff, Physics of contact angle measurement, Colloids and Surfaces A: Physicochem. Eng. Aspects 156 (1999) 177-189. [10] T. D. Blake, Y. D. Shikhmurzaev, Dynamic wetting by liquids different viscosity, Journal of Colloid and Interface Science 253 (2002) 196-202. [11] J. Zych, Effecting the weather conditions on the surface layer condition of moulds made with moulding sand with the chemical bonding, Archives of Foundry, R. 6, nr 22 (2006) 576581 (in Polish). [12] J. Dako, M. Holtzer, R. Dako, The choice of effective reclamation processes and used moulding sands management in the aspect of the best available techniques. Archives of Foundry. 2006 R. 6 nr 20 s. 3138 (in Polish). [13] Z. Adamczyk, A. Karwiski, G. Para: Characteristics of physical and chemical properties of binders and ceramic mixtures used in foundry engineering. Publishing House of Foundry Institute , Krakw 1999. (in Polish). [14] M. de Ruijter, P. Klsch, M. Vou, J. De Coninck, J. P. Rabe, Effect of temperature on the dynamic contact angle, Colloids and Surfaces A: Physicochem. Eng. Aspects 144 (1998) 235-243. [15] B.Hutera, K.Smyksy: Chosen aspects of the description of temporay alteration of the wetting contact angle of the quartz by binding materials. Faculty of Foundry Engineering AGH UST, XXX Scientific Conference on the occasion The Day of Foundryman, Krakw 2006 r., pp. 447-452.(in Polish) [16] M. Kucharski, P. Fima, P. Skrzyniarz, W. PrzebindaStefanowa, Surface tension and density of {Cu-Ag}, {Cu-In} and {Ag-In} alloys, Archives of Metallurgy and Materials, 2006 vol. 51 iss. 3 s. 389397 [17] B. Hutera, J. L. Lewandowski, K. Smyksy, Influence of temperature on the properties of selected binders used in core and moulding sand, Archives of Foundry, R. 6, nr 20 (2006) 7176 (in Polish).

65 60 55 50 45 40 35 30 25 20 0 30

Wetting angle ; degree

methyl acetate 5%, temp. 383 K methyl acetate 5%, temp. 403 K xylene 5%, temp. 383 K xylene 5%, temp. 403 K

60 Time ; min

90

120

Fig.6. Time dependence of wetting angle for epoxy resin with different addition of diluent (methyl acetate) at 283 K and 403 K; plate material quartz.

4. Conclusions
The good wettability of the sand grains by the binder is a mostly desirable feature of the binder influencing on the wide range of properties of prepared moulding sands. Adding different diluents to epoxy resin in different amount results in the an equilibrium contact angle r reached almost instantaneously by the quartz binder system within the examined range of temperatures. In practice this means an easy and uniform distribution of binder on the surface of the silica sand grains with mixing time made shorter, which is of great practical importance, specially in the case of high viscosity binders. Diluents, when added to epoxy resin, makes the value of an equilibrium contact angle decrease , which is also very important for a uniform, high-quality distribution of binder on the surface of the silica sand grains and for the sand mixing time required for this even distribution to be effectively obtained. Quantitative estimation of wettability demands however usages of carefully passed experiments at the utilization of the modern apparatus. In the article the outline of the above mentioned methodology with example-performance of measurement has been presented. Most important aspects of the investigation of wetting processes with reference to industry practice of preparing of core and moulding sand has been underlined. The functionality of the prototype device has been confirmed by large number of experiments series.

Acknowledgments
The research was supported by the State Committee of Scientific Research - grant no. 3T08 A 02226

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