PROCESS FOR PREPARING CERAMIC-LIKE MATERIALS AND THE CERAMIC-LIKE MATERIALS

Abstract: This invention relates to a process for preparing ceramic-like materials with specific properties by binding an inorganic filler in the form of a dry composition with a grain size of up to 25 mu m, containing in the volume ratio 1:0.-1.52 a waste phosphogypsum and magnetite or glass-forming oxides, with an unsaturated polyester resin in an amount of 46-220 volume parts per 100 volume parts of the filler. The use of magnetite makes it possible to prepare materials with magnetic properties, while glass-forming oxides enable preparing materials effective to absorb an X-radiation of 45-55 keV and a hard radiation of 0.6-1.25 MeV. When an expanding agent is added to the raw composition according to this invention, an expanded material is obtained, having completely closed pores, particularly useful in the building industry. The resultant ceramic-like materials are characterized by good adhesion to metals, plastics, glass, wood, concrete and can be easily joined with them both at the stage of polymerization and after its termination by using a prepolymerized resin as a binder.

Description: Process for preparing ceramic-like materials and the ceramic-like materials The present invention is concerned with a process for preparing ceramic-like materials and the ceramic-like mate¬ rials produced thereby suitable for manufacturing articles with magnetic properties as well as products absorbing hard and X-radiations and also goods with insulating pro¬ perties useful particularly in the building industry due to their very low moisture absorbability. There are known various processes of binding inorga¬ nic fillers, including phosphogypsum, with synthetic poly- mers in aqueous systems, as is shown in Polish patent spe¬ cifications 113573 and 147599, to prepare compositions to be used as flooring or raw materials for making stuccoes. The drawback of theses processes is that the resultant products are rather brittle and porous and therefore show- ing a high water imbibition. On the other hand, the poly¬ merization process, involded proceeds rather slowly, which excludes the use of extrusion or injection moulding me¬ thods. There is also knowm from Polish patent application no. _P„ 283240 a process for manufacturing a ceramic-ϋke plastics by binding a waste phosphogypsum with polyester resins in non-aqueous systems containing an accelerant, a curing agent and, in case of need, acetone. The resultant material is suitable for processing into various articles by extrusion or injection moulding and is characterized by a good mechanical strenght. as well as low water and oil absorbabilities. It has unexpectedly turned out that the use of a com¬ posite inorganic filler consisting of a waste phosphogyp¬ sum, especially apatite derived phosphogypsum, and other inorganic compounds such as metal oxides or salts, in the form of physically homogenized composition with a grain size not exceeding 25 urn, and binding this filler with unsatu¬ rated polyester resins in a non-aqueous system, make it po¬ ssible to prepare ceramic-like materials with specific pro¬ perties, which can be easily moulded, also by casting, and machine processed. It has also turned out that by adding a C0 2 producing substance to the composition of a waste phosphogypsum and an unsaturated polyester resin, one can prepare an expanded ceramic-like material. The process for preparing a ceramic-like material with magnetic properties by binding an inorganic filler with a synthetic resin in a non-aqueous system, according to the present invention consists in carrying out the process in two stages, while at the first stage a physically homogeni¬ zed dry composition with a grain size of 25 pm at most is prepared, containing magnetite and waste phosphogypsum, pre¬ ferably an apatite derived phosphogypsum, in volume ratio 0.66-1.52 : 1, respectively, the phosphogypsum being pre¬ viously heated at least for 1 hour at a temperature not lower than 127 °C. Then, at the secnd stage, the prepared dry composition in an amount of 100 volume parts is added on continuous stirring for 0.2-5.4 hours to 50-240 vo¬ lume parts of an unsaturated polyester resin containing up to , 8 % by volume of an accelerant, such as cobalt naphthe- nate, after which up to 23 volume parts of an organic di- lutant, such as acetone or styrene, is added to maintain the composition viscosity at a level of not higher than 4230 mPa.s, and then 3-20 volume parts of a curing agent is ad¬ ded, preferably in the form of solution with a concentration of 20 - 40 % by volume of cyclohexaαone peroxide or benzoyl peroxide in dibutyl phthalate, to obtain, after the termi¬ nation of the polymerization, a ceramic-like material with magnetic properties. The ceramic-like material with magnetic properties, con- taining an inorganic filler, synthetic resin and a curing a- gent, according to the present invention, per every 50 vo¬ lume parts of phosphogypsum contains 33 - 76 volume parts of magnetite, 46-220 volume parts of an unsaturated poly¬ ester resin, up to 0.4 volume parts of cobalt naphthenate, up to 23 volume parts of acetone or styrene, and 0.6-0.8 volume parts of cyclohexanone peroxide or benzoyl peroxide, and 2.4-12 volume parts of dibutyl phthalate. The process for preparing a ceramic-like material effe¬ ctive to absorb an Σ- radiation of 45 - 55 keV and a hard radiation of 0.6-1.25 MeV, by binding an inorganic filler with a synthetic resin in a non-aqueous system, according to the present invention consists, in carrying out the pro¬ cess in two stages, while at the first stage a physically homogenized dry composition with a grain size of 20 um at most is prepared, containing a waste phosphogypsum, prefe¬ rably apatite derived, previously heated for a least 1.2 hours at a temperature of not lower than 177 °C, and glass- forming oxides in a volume ratio of 1 : 0.76-1.42, respe¬ ctively, the glass-forming oxides consists mainly of 81 weight % of lead oxide, 11o5 weight % of silicon dioxide and 2o6 weight of barium oxide. At the second stage, the dry composition in an amount of 100 volume parts is added on continuous stirring of at least 10 minutes to 50-240 volume parts of an unsaturated polyester resin containing up to 8 % by volume of an accelerant, such as cobalt na- phthenate, after which, if required, an organic dilutant such as acetone or styrene is added in an amount of 1- 15 volume parts to maintain the raw composition viscosity at a level of not higher than 4230 mPa«s, and then 2.8-21.3 volume parts of a curing agent is added, preferably in the form of a solution with a concentration of 20 - 40 vo¬ lume % of cyclohexanone peroxide or benzoyl peroxide in dibutyl phthalate, to obtain, after the termination of the polymerization, a radiation absorhing ceramic-like material. A plate made from this material with a thickness of 25 mm is characterized by ability to absorb Σ-radiation of 45 - 55 keV similarly as a lead plate with a thickness of 1.1 mm as well as a hard radiation of 0.6-1.25 MeV simi- larly as a lead plate with a thickness of 6.5 mm. The ceramic-like material absorbing Σ-radiation of 45-55 keV and hard radiation of 0.6-1.25 MeV, contain¬ ing an inorganic filler, a synthetic resin and a curing a- gent, according to the present invention per every 50 vo- lume parts of phosphogypsum contain 38 - 76 volume parts of glass-forming oxides, 46-220 volume parts of an unsa¬ turated polyester resin, up to 23 volume parts of acetone or styrene and 0.6 - o 0 volume parts of cyclohexanone per¬ oxide or benzoyl peroxide and 2.4-12 volume parts of di- butyl phthalate. The process for preparing an expanding ceramic-like material by adding an expanding agent to an inorganic filler bonded with a synthetic resin, according to the present in- vention consists in that to the raw. composition obtained by binding 100 volume parts of a waste phosphogypsum, pre¬ viously heated at a temperature of not lower than 172 ©0 for at least 1.3 hours, with 60-270 volume parts of an unsaturated polyester resin containing up to 8 % by volume of an accelerant such as cobalt naphthenate and addition, if required, of an organic dilutant such as acetone or styrene in an amount of up to 12 volume parts to maintain the composition viscosity at a level not higher than 4050 mEa.s, and after adding 3-25 volume parts of a curing agent, pre- ferably in the form of solution with a concentration of 20-40 % by volume of cyclohexanone peroxide, or benzoyl peroxide in dibutyl phthalate, butyl isocyanate in an a- mount od up to 30 o by volume per the raw composition and 0.05-0.25 o by volume of water are introduced. The process for preparing ceramic-like materials ac¬ cording to the present invention makes it possible to uti¬ lize postproduction phosphogypsum which most often is a no¬ xious waste for the natural enviroment, whereas the cera¬ mic-like materials themselves, owing to their easy proces- sability by injection moulding as well as by casting, and their good physico-chemical properties, can be used in ma¬ ny cases instead of metals, plastics, glass, wood, concre¬ te the ceramic-like materials can be readily bonded to these materials both before and after curing, using the pre- polymerized composition as a binding agenty Moreover, arti¬ cles made from the ceramic-like materials according to this invention, after having been worn out in most, cases can be reused as fillers after their previous disintegration, and thereby utilized again. The present invention is further described by the fol¬ lowing examples wthout limiting the invention. Example I To 0 * 5 dπr of an unsaturated polyester resin, 0.7 dπr of a dry composition with a grain size up to 16 um is ad¬ ded on continuous stirring, the said composition consisting of 60 % by volume of magnetite and 40 % by volume of a waste phosphogypsum /apatite derived/, previously heated for 2.1 hours at a temperature of 217 °C, then 0.001 dm^ of cobalt naphthenate, 0.165 dπr of styrene and 0.03 dπr of a 30 % solution of benzoyl peroxide in dibutyl phthala¬ te are added. The resultant composition is casted into pre¬ pared moulds in the shape of magnetic holders for bar soap. Example II Proceeding as in example I and using a dry composi¬ tion with a grain size of up to 10 ;um, containing phospho¬ gypsum and lead glass cullet in equal volume parts, a fluid composition is obtained which is used for coating cubes for¬ med from ion-exchangers used out in installation for the concentration of radioactive effluents. Example III 1 dm^ 0 an unsaturated polyester resin is blended on continuous stirring with 1.4 dπr of a waste phosphogypsum with a grain size of up to 12 um, previously heated at a temperature of 237 °C for 1.9 hours, 0.002 dm- 5 of cobalt naphtheante, 0.33 dm 3 of acetone, 0.07 dm 3 of a 30% so¬ lution of cyclohexanone peroxide in dibutyl phthalate and 0.4 dπr of butyl isocyanate and 0.03 dπr of water. The re- sultant expanded composition is used to form profiles desig¬ ned for the insulation of hulls of yachts and boats.

Claims: Claims 1. A process for preparing a ceramic-like material with mag¬ netic properties by binding an inorganic filler with a syn¬ thetic resin in a non-aqueous system, characterized in that the process is carried out in two stages, while at the first stage a physically homogenized dry composition with a grain size of up to 25 um is prepared, containing a waste phosphogypsum, preferably an apatite derived phosphogypsum, previously heated for at least 1 hour at a t emperature of not lower than 177 °C, and magnetite in volume ratio 1 ; : 0.66-1.52, respectively, after which at the second stage, the dry composition in an amount of 100 volume parts is blended on continuous stirring for 0.2-4.8 hours with an unsaturated polyester resin in an amount corresponding to the volume ratio 0.46-2.2 : 1 per the dry composition, and then the following components are added up to 0.4 vo¬ lume parts of an accelerant such as cobalt naphthenate, up to 23 volume parts of an organic dilutant such as acetone or styrene, if required, to maintain the raw composition viscosity at a level not higher than 4230 a-ε^ and 3-20 volume parts of a curing agent, preferably in the form of solution with a concentration of 20 - 40% by volu¬ me of cyclohexanone peroxide or benzoyl peroxide in dibuty phthalate. 2. A ceramic-like material with magnetic properties, con- taining an inorganic filler, a synthetic resin and a cur¬ ing agent, characterized in that per every 100 volume parts of phosphogypsum contains 66-152 volume parts of magnetite, 92-440 volume parts of an unsaturated polyes¬ ter resin, 0.4—0.8 volume parts of cobalt naphthenate, 1.2-16 volume parts of benzoyl or cyclohexanone peroxide, 4.8-24 volume parts of dibutyl phthalate and up to 46 vo¬ lume parts of acetone or styrene. 3. A process for preparing a ceramic-like material effective to absorb an X-radiation of 45-55 keV and a hard radia¬ tion of 0o6-1.25 MeV, by binding an inorganic filler with a synthetic resin, characterized in that the process is carried out in two stages, while at the first stage a phy¬ sically homogenized dry composition with a grain size ofup to 25 um is prepared, containing per every 100 volume parts of a waste, phosphogypsum, preferably an apatite de- rived phosphogypsum, previously heated for at least 1.2 hours at a temperature of not lower than 177 °C, 76-142 volume parts of glass-forming oxides consisting mainly of lead oxide in an amount of 81 % by weight, silicon dioxi¬ de in an amount of 11.5% by weight and barium oxide in an amount of 2.6% by weight, whereas at the second stage the dry composition in an amount of 100 volume parts is blended with an unsaturated- polyester resin in an amount corresponding to the volume ratio 0.46-2.2 : 1 per the dry composition, and then there are added up to 0.4 volume parts of an accelerant such as cobalt naphthenate, up to 23 volume parts of an- organic dilutant such as acetone ox styrene, if required, to maintain the raw composition vis¬ cosity at a level not higher than 4230 mPa.s, and a curing agent in an amount of 3-20 volume parts, preferably in the orm of solution with a concentration of 20 - 40% by volume of benzoyl or cyclohexanone peroxide in dibutyl phthalate. 4. A ceramic-like material effective to absorb an 2-radia- tion of 45-55 keV and hard radiation of 0.6-1.25 MeV, containing an inorganic filler, synthetic resin, a curing agent, characterized in that per every 100 volume parts cf phosphogypsum contains 76-142 volume parts of glass-for¬ ming oxides, 92-440 volume parts of an unsaturated poly- ester resin, 0.4-0.8 volume parts of cobalt naphthenate, 1.2-16 volume parts of cyclohexanone or benzoyl peroxide, 4.8-24 volume parts of dibutyl phthalate and up to 4 vo¬ lume parts of acetone or styrene. 5. A process for preparing an expanded ceramic-like material with completely closed pores by adding to an inorganic fil¬ ler being bonded with a synthetic resin an expanding agent, characterized in that, to the raw composition, obtained by binding 100 volume parts of a waste phosphogypsum, prefe¬ rably an apatite derived phosphogypsum, previously heated at a temperature of not lower than 172 °G for at least 1.3 hours, with 60-270 volume parts of an unsaturated po¬ lyester resin containing up to 8% by volume of an accele¬ rant such as cobalt naphthenate with an addition, if requi¬ red, of an organic dilutant such as acetone or styrene in an amount of up to 12 volume parts to maintain the composi¬ tion viscosity at a level not higher than 4050 mPa»s, and after addition of. 3- 25 volume parts a curing agent, pre¬ ferably in the form of solution with a concentratin of 20 - 40 by volume of cyclohexanone or benzoyl peroxide in dibutyl phthalate., butyl isocyanate in an amount of 30 % by volume and 0.05-0.15% by volume of water per the raw coiαposition are added.

Inventors: CYRKIEWICZ MARCELI, HERLING ERWIN, KLESZCZEWSKI JACEK, CYRKIEWICZ, MARCELI, HERLING, ERWIN, KLESZCZEWSKI, JACEK
Applicants: CYRKIEWICZ MARCELI, HERLING ERWIN, KLESZCZEWSKI JACEK, CYRKIEWICZ, MARCELI, HERLING, ERWIN, KLESZCZEWSKI, JACEK
Application year: 1993
Main classification: C08K3
IPC codes: C04B18, C04B26, C08K3, C08K5, C08L67, H01F1