This paper focuses on the thermal behavior of the starch-based binder (Albertine F/1 by Hüttenes-Albertus) used in foundry technology of molding sand. The analysis of the course of decomposition of the starch material under controlled heating in the temperature range of 25-1100°C was conducted. Thermal analysis methods (TG-DTG-DSC), pyrolysis gas chromatography coupled with mass spectrometry (Py-GC/MS) and diffuse reflectance spectroscopy (DRIFT) were used. The application of various methods of thermal analysis and spectroscopic methods allows to verify the binder decomposition process in relation to conditions in the form in both inert and oxidizing atmosphere. It was confirmed that the binder decomposition is a complex multistage process. The identification of CO2 formation at set temperature range indicated the progressive process of decomposition. A qualitative evaluation of pyrolysis products was carried out and the course of structural changes occurring in the presence of oxygen was determined based on thermo-analytical investigations the temperature of the beginning of binder degradation in set condition was determined. It was noticed that, significant intensification of Albertine F/1 sample decomposition with formation of more degradation products took place at temperatures above 550ºC. Aromatic hydrocarbons were identified at 1100ºC.
The intercalation into interlayer spaces of montmorillonite (MMT), obtained from natural calcium bentonite, was investigated. Modification of MMT was performed by the poly(acrylic acid-co-maleic acid) sodium salt (co-MA/AA). Efficiency of modification of MMT by sodium salt co-MA/AA was assessed by the infrared spectroscopic methods (FTIR), X-ray diffraction method (XRD) and spectrophotometry UV-Vis. It was found, that MMT can be relatively simply modified with omitting the preliminary organofilisation – by introducing hydrogel chains of maleic acid-acrylic acid copolymer in a form of sodium salt into interlayer galleries. A successful intercalation by sodium salt of the above mentioned copolymer was confirmed by the powder X-ray diffraction (shifting the reflex(001) originated from the montmorillonite phase indicating an increase of interlayer distances) as well as by the infrared spectroscopy (occurring of vibrations characteristic for the introduced organic macromolecules). The performed modification causes an increase of the ion exchange ability which allows to assume that the developed hybrid composite: MMT-/maleic acid-acrylic acid copolymer (MMT-co- MA/AA) can find the application as a binding material in the moulding sands technology. In addition, modified montmorillonites indicate an increased ability for ion exchanges at higher temperatures (TG-DTG, UV-Vis). MMT modified by sodium salt of maleic acid-acrylic acid copolymer indicates a significant shifting of the loss of the ion exchange ability in the direction of the higher temperature range (500–700°C).
In this paper the results of studies of polymeric binders on the example of the new BioCo2 binder, including the problem of its renewability, are presented. The results of structural studies (FT-IR) for the BioCo2 binder before and after crosslinking, and bending strength tests Rg u fresh and renewed cured molding sands with BioCo2 binder are discussed. The cross-linking binder and curring of moulding sand was carried out by physical agents (microwave radiation, temperature). On the basis of obtained results was shown that it is possible to restore the initial properties of the adhesive of BioCo2 binder. The initial properties of moulding sand can be achieved, after the cross-linking binders and after curing in the moulding sands with bioCo2 binder , by supplementing the moulding sand composition by the appropriate amount of water.
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.
This publication describes research on the course of the process of cross-linking new BioCo polymer binders - in the form of water-based polymer compositions of poly(acrylic acid) or poly(sodium acrylate)/modified polysaccharide - using selected physical and chemical factors. It has been shown that the type of cross-linking factor used influences the strength parameters of the moulding sand. The crosslinking factors selected during basic research make it possible to obtain sand strengths similar to those of samples of sands bonded with commercial binders. Microwave radiation turned out to be the most effective cross-linking factor in a binder-matrix system. It was proven that adsorption in the microwave radiation field leads to the formation of polymer lattices with hydrogen bonds which play a major role in maintaining the formed cross-linked structures in the binder-matrix system. As a result, the process improves the strength parameters of the sand, whereas the hardening process in a microwave field significantly shortens the setting time.
The paper presents the results of an investigation of the thermal deformation of moulding sands with an inorganic (geopolymer) binder with a relaxation additive, whose main task is to reduce the final (residual) strength and improves knocking-out properties of moulding sand. The moulding sand without a relaxation additive was the reference point. The research was carried out using the hot-distortion method (DMA apparatus from Multiserw-Morek). The results were combined with linear deformation studies with determination of the linear expansion factor (Netzsch DIL 402C dilatometer). The study showed that the introduction of relaxation additive has a positive effect on the thermal stability of moulding sand by limiting the measured deformation value, in relation to the moulding sand without additive. In addition, a relaxation additive slightly changes the course of the dilatometric curve. Change in the linear dimension of the moulding sand sample with the relaxation additive differs by only 0.05%, in comparison to the moulding sand without additive.
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 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.
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.
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.
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.
The spectroscopic FT-IR and FT-Raman methods allowed to identify the cross-linking process of the aqueous composition of poly(acrylic acid)/sodium salt of carboxymethyl starch (PAA/CMS-Na) applied as a binder for moulding sands (as a novel group binders BioCo). The cross-linking was performed by physical agent, applying the UV-radiation. The results of structural studies (IR, Raman) confirm the overlapping of the process of cross-linking polymer composition PAA/CMS-Na in UV radiation. Taking into account the ingredients and structure of the polymeric composition can also refer to a curing process in a binder - mineral matrix mixture. In the system of bindermineral matrix under the influence of ultraviolet radiation is also observed effect of binding. However, the bonding process does not occur in the entire volume of the investigated system, but only on the surface, which gives some possibilities for application in the use of UV curing surface of cores, and also to cure sand moulds in 3D printing technology