The criteria, with which one should be guided at the assessment of the binding properties of bentonites used for moulding sands, are proposed in the paper. Apart from the standard parameter which is the active bentonite content, the unrestrained growth indicator should be taken into account since it seems to be more adequate in the estimation of the sand compression strength. The investigations performed for three kinds of bentonites, applied in the Polish foundry plants, subjected to a high temperature influences indicate, that the pathway of changes of the unrestrained growth indicator is very similar to the pathway of changes of the sand compression strength. Instead, the character of changes of the montmorillonite content in the sand in dependence of the temperature is quite different. The sand exhibits the significant active bentonite content, and the sand compression strength decreases rapidly. The montmorillonite content in bentonite samples was determined by the modern copper complex method of triethylenetetraamine (Cu(II)-TET). Tests were performed for bentonites and for sands with those bentonites subjected to high temperatures influences in a range: 100-700ºC.
In the foundry industry, many harmful compounds can be found, which as a result of gradual but long-term exposure to employees bring negative results. One of such compounds is phenol (aromatic organic compound), which its vapours are corrosive to the eyes, the skin, and the respiratory tract. Exposition to this compound also may cause harmful effects on the central nervous system and heart, resulting in dysrhythmia, seizures, and coma. Phenol is a component of many foundry resins, especially used in shell moulds in the form of resincoated sands. In order to identify it, the pyrolysis gas chromatography-mass spectrometry method (Py-GC/MS) was used. The tests were carried out in conditions close to real (shell mould process – temperature 300°C). During the measurement, attention was focused on the appropriate selection of chromatographic analysis conditions in order to best separate the compounds, as it is difficult to separate the phenol and its derivatives. The identification of compounds was based on own standards.
No-bake process refers to the use of chemical binders to bond the moulding sand. Sand is moved to the mould fill station in preparation for filling of the mould. A mixer is used to blend the sand with the chemical binder and activator. As the sand exits the mixer, the binder begins the chemical process of hardening. This paper presents the results of decomposition of the moulding sands with modified ureafurfuryl resin (with the low content of furfuryl alcohol below 25 % and different activators: organic and inorganic) on a quartz matrix, under semi-industrial conditions. Investigations of the gases emission in the test foundry plant were executed according to the method extended in the Faculty of Foundry Engineering (AGH University of Science and Technology). Article presents the results of the emitted chosen aromatic hydrocarbons and loss on ignition compared with the different activators used to harden this resin. On the bases of the data, it is possible to determine the content of the emitted dangerous substances from the moulding sand according to the content of loss on ignition.
Organic binders applied in foundry plants based on synthetic resins, from the one side influence obtaining the required technological properties by the moulding sand and – in consequence – obtaining good quality castings, and on the other side are the source of volatile organic compounds (VOC). Together with synthetic resins their hardeners, which although added in very small amounts emit during their thermal decomposition substances negatively influencing the natural environment, are also used. Both, resins and hardeners only at the influence of high temperatures accompanying moulds pouring with liquid metal generate harmful volatile organic compounds including compounds from the BTEX group. Investigations of the temperature influence on the kind and amount of organic compounds formed during the thermal decomposition of selected binders and hardeners and their mixtures allow to determine temperature ranges the most favourable for emitting harmful substances as well as to compare their emission from the selected materials. The aim of this study was the determination the temperature influence on formation substances from the BTEX group, during thermal decomposition of the selected binder, its hardener and their mixture. The BTEX group emission constitutes one of the basic criteria in assessing the harmfulness of materials applied for moulding and core sands and it can undergo changes in dependence of the applied system resin-hardener. Investigations were carried out on the specially developed system for the thermal decomposition of organic substances in the temperature range: 5000 C – 13000 C, at the laboratory scale. The investigations subject was the furan resin, its hardener and hardened furan resin. The assessment of the emission degree of the BTEX group in dependence of the system subjected to the temperature influence was performed, within the studies. The temperature range, in which maximal amounts of benzene, toluene, ethylbenzene and xylenes were emitted from tested materials – was defined. The qualitative and quantitative analysis of the BTEX group were carried out with using the gas chromatography technique coupled with the mass spectrometry (GC/MS).
The article presents research results of physico-chemical and environmental issues for the dust generated during dedusting of the installation for the processing and preparation of moulding sand with bentonite. Particular attention was paid to the content of heavy metals and emission of gases from the BTEX group, which is one of the determinants of the moulding sands harmfulness for the environment. The analysis of heavy metals in the test samples indicate that there is an increase of the content of all metals in the dust compared to the initial mixture of bentonite. The most significant (almost double) increase observed for zinc is probably related to the adsorption of this element on the dust surface by contact with the liquid metal. The study showed, that dust contained more than 20% of the amount of montmorillonite and had a loss on ignition at a similar level. The addition of 1% of dust to the used moulding sand results in almost 30% increase in the total volume of gases generated in casting processes and nearly 30% increase of the benzene emission.
Emission of gases under high temperature after pouring molten metal into moulds, which contain the organic binder or other additives (solvents or curing agent), may be an important factor influencing both on the quality of the produced castings, and on the state of environment. Therefore, a comprehensive study of the emitted gases would allow to determine restrictions on the use of the moulding sands in foundry technologies, eg. the probability of occurrence of casting defects, and identify the gaseous pollutants emitted to the environment. The aim of the research presented in this paper was to determine the amount of gases that are released at high temperatures from moulding sands bonded by biopolymer binder and the quantitative assessment of the emitted pollutants with particular emphasis on chemical compounds: benzene, toluene, ethylbenzene and xylenes (BTEX). The water-soluble modified potato starch as a sodium carboxymethyl starch with low (CMS-NaL) or high (CMS-NaH) degree of substitution was a binder in the tested moulding sands. A tests of gases emission level were conducted per the procedure developed at the Faculty of Foundry Engineering (AGH University of Science and Technology) involving gas chromatography method (GC). The obtained results of the determination of amount of BTEX compounds generated during the decomposition process of starch binders showed lower emission of aromatic hydrocarbons in comparison with binder based on resin Kaltharz U404 with the acidic curing agent commonly used in the foundries.
A determination of the heating degree of the moulding sand with bentonite on the grounds of simulating investigations with the application of the MAGMA program, constitutes the contents of the paper. To this end the numerical simulation of the temperature distribution in the virtual casting mould was performed. It was assumed that the mould cavity was filled with a moulding sand with bentonite of a moisture content 3,2 % and bentonite content 8 %. A computer simulation can be used for predicting the heating degree of moulding sands with bentonite. Thus, prediction of the active bentonite (montmorillonite) content in individual layers of the overheated moulding sand can be done by means of the simulation. An overheating degree of a moulding sand with bentonite, and thus the bentonite deactivation depends on a temperature of a casting alloy, casting mass, ratio of: masssand : masscasting, moulding sand amount in the mould and contact area: metal – mould (geometry of the casting shape). Generally it can be stated, that the bentonite deactivation degree depends on two main factors: temperature of moulding sand heating and time of its operation.
It was found that the addition of carbon fibers (CFs) does not affect the crosslinking process in the microwave radiation (800 W, 2.45 GHz) of the BioCo2 binder, which is a water solution of poly(acrylic acid) and dextrin (PAA/D). It has influence on BioCo2 thermal properties. The CFs addition improves the thermostability of a binder and leads to the reduction of gas products quantity generated in the temperature range of 300-1100°C (TG-DTG, Py-GC/MS). Moreover, it causes the emission of harmful decomposition products such as benzene, toluene, xylene and styrene to be registered in a higher temperatures (above 700°C). BioCo2 binder without CFs addition is characterized by the emission of these substances in the lower temperature range. This indicates the positive effect of carbon fibers presence on the amount of released harmful products. The selected technological tests (permeability, friability, bending strength, tensile strength) have shown that the moulding sand with the 0.3 parts by weight carbon fibers addition displays the worst properties. The addition of 0.1 parts by weight of CFs is sufficient to obtain a beneficial effect on the analyzed moulding sands properties. The reduction of harmful substances at the higher temperatures can also be observed.
The organo-inorganic commercial binder Albertine F/1 (Hüttenes-Albertus) constituting the starch-aluminosilicate mixture was directed to structural studies. The paper presents a detailed structural analysis of the binder before and after exposure to physical curing agents (microwaves, high temperature) based on the results of infrared spectroscopy studies (FTIR). An analysis of structural changes taking place in the binder system with the quartz matrix was also carried out. Based on the course of the obtained IR spectra, it was found that during the exposure on physical agents there are structural changes within the hydroxyl groups in the polymeric starch chains and silanol groups derived from aluminosilicate as well as in the quartz matrix (SiO2). The curing of the molding sand takes place due to the evaporation of the solvent water and the formation of intramolecular and intermolecular cross-linking hydrogen bonds. Type and amount of hydrogen bonds presence in cured molding sand have an impact on selected properties of molding sand. Results indicates that for molding sand with Albertine F/1 during conventional heating a more extensive network of hydrogen bonds is created.
The effects of silica additive (Poraver) on selected properties of BioCo3 binder in form of an aqueous poly(sodium acrylate) and dextrin (PAANa/D) binder were determined. Based on the results of the thermoanalytical studies (TG-DTG, FTIR, Py-GC/MS), it was found that the silica additive results in the increase of the thermostability of the BioCo3 binder and its contribution does not affect the increase in the level of emissions of organic destruction products. Compounds from group of aromatic hydrocarbons are only generated in the third set temperature range (420-838°C). The addition of silicate into the moulding sand with BioCo3 causes also the formation of a hydrogen bonds network with its share in the microwave radiation field and they are mainly responsible for maintaining the cross-linked structures in the mineral matrix system. As a consequence, the microwave curing process in the presence of Poraver leads to improved strength properties of the moulding sand (���� �� ). The addition of Poraver's silica to moulding sand did not alter the permeability of the moulding sand samples, and consequently reduced their friability. Microstructure investigations (SEM) of microwave-cured samples have confirmed that heterogeneous sand grains are bonded to one another through a binder film (bridges).
The furan resin offers advantages such as high intensity, low viscosity, good humidity resistance and is suitable for cast different casting alloys: steel, cast iron and non-ferrous metal casting. For hardening furan resins are used different hardeners (acid catalysts). The acid catalysts have significant effects on the properties of the cured binder (e,g. binding strength and thermal stability) [1 - 3]. Investigations of the gases emission in the test foundry plant were performed according to the original method developed in the Faculty of Foundry Engineering, AGH UST. The analysis is carried out by the gas chromatography method with the application of the flame-ionising detector (FID) (TRACE GC Ultra THERMO SCIENTIFIC).
Suitability of the given binding agent for the moulding sands preparation depends on the one hand on the estimation of technological properties of the sand and the mould made of it and the obtained casting quality and on the other hand on the assessment of this sand influence on the natural and working environment. Out of moulding sands used in the foundry industry, sands with organic binders deserve a special attention. These binders are based on synthetic resins, which ensure obtaining the proper technological properties and sound castings, however, they negatively influence the environment. If in the initial state these resins are not very dangerous for people and for the environment, thus under an influence of high temperatures they generate very harmful products, being the result of their thermal decomposition. Depending on the kind of the applied resin (phenol-formaldehyde, urea, furfuryl, urea–furfuryl, alkyd) under an influence of a temperature such compounds as: furfuryl alcohol, formaldehyde, phenol, BTEX group (benzene, toluene, ethylbenzene, xylene), and also polycyclic aromatic hydrocarbons (PAH) can be formed and released. The aim of the study was the development of the method, selection of analytical methods and the determination of optimal conditions of formation compounds from the BTEX group. An emission of these components constitutes one of the basic criteria of the harmfulness assessment of binders applied for moulding and core sands. Investigations were carried out in the specially designed set up for the thermal decomposition of organic substances in a temperature range: 5000 C – 13000 C at the laboratory scale. The object for testing was alkyd resin applied as a binding material for moulding sands. Within investigations the minimal amount of adsorbent necessary for the adsorption of compounds released during the decomposition of the resin sample of a mass app. 15 mg was selected. Also the minimal amount of solvent needed for the desorption of compounds adsorbed in the column with adsorbent was found. The temperature range, in which the maximal amounts of benzene, toluene, ethylobenzene and xylenes are released from the resin, was defined. The qualitative and quantitative analyses of compounds from the BTEX group were performed by means of the gas chromatography combined with the mass spectrometry (GC/MS).
The paper presents the results of thermoanalytical studies by TG/DTG/DTA, FTIR and GC/MS for the oil sand used in art and precision foundry. On the basis of course of DTG and DTA curves the characteristic temperature points for thermal effects accompanying the thermal decomposition reactions were determined. This results were linked with structural changes occurred in sample. It has been shown that the highest weight loss of the sample at temperatures of about 320°C is associated with destruction of C-H bonds (FTIR). In addition, a large volume of gases and high amounts of compounds from the BTEX group are generated when liquid metal interacts with oil sand. The results show, that compared to other molding sands used in foundry, this material is characterized by the highest gaseous emissions and the highest harmfulness, because benzene emissions per kilogram of oil sand are more than 7 times higher than molding sand with furan and phenolic binders and green sand with bentonite and lustrous carbon carrier.
In many foundries, the requirements placed on castings production have risen mainly over the few years. Further trends in recent years have been the ever increasing level of automation and introduction of new alloys, especially composites. On the other hand, the foundry environment has become increasingly difficult because is used many organic binders. Environmental regulations will be further tightened up. These processes are pursued at national, European and global level. Conformity with emission limits is becoming increasingly difficult. The problem is emission of aromatic hydrocarbons, phenol, odours and other harmful compounds to environment. The main purpose of many companies is reduction of this toxins. The new cold-box systems (based on phenolic resins) try to reduce the emission by introducing into the resin structure silicate modifiers. Research presented of this article evaluate the effectiveness of these methods. The results show comparison of two resins ("without" and "with" silicate modifier) for assessment of emission of harmful aromatic hydrocarbons and phenol.
Due to the presence of harmful substances in resins those mould sands may be hazardous to the natural environment and workers. The general assessment of harmfulness of sands used for molds and cores encompasses 2 basic points: emission of hazardous substances during processes of preparing sands, pouring mold with liquid metals (high temperatures), cooling and shaking-out; possibility of washing out hazardous substances from used sands to the environment, during storage or economic use outside foundries. We present the results of research on the emission of BTEX compounds from mould sands with phenolic resins during pouring liquid metal of different temperature (cast iron and Al alloy). The research was conducted according to the original method prepared by the authors, which has been used for years in cooperation with various foundries (Poland, abroad).