RU2757582C1 - Composite material - Google Patents

Abstract

FIELD: additive technology.SUBSTANCE: invention relates to the field of creating composite materials intended for use in the additive technology (3D printing). The composite material is based on polyphenylene sulphone, polycarbonate, and fibreglass and additionally includes organomodified clay, at the following ratio, pts. wt.: polyphenylene sulphone 100, polycarbonate 32 to 35, fibreglass 1 to 3, organomodified clay 0.5 to 2. The organomodified clay constitutes a product of modification of montmorillonite clay with a cation exchange capacity of 95 mg-eq/100 g of clay with urea in the amount of 7% of the mass of montmorillonite.EFFECT: production of polymer materials complying with the requirements for physical and mechanical characteristics and hygroscopicity, intended for the additive technology.1 cl, 2 tbl, 6 ex

Description

The invention relates to the field of creating composite materials intended for use in additive technologies (3D printing).

Additive technologies (3D printing) are a type of radical technological innovation. Today, additive technologies (AT) are actively used in industry. These are not future technologies, they are effective now. This is evidenced by the rapid growth of the market for additive technologies - about a quarter annually. As for the future, the technologies of layer-by-layer synthesis have far from exhausted their potential. Composite materials intended for additive technologies are known from the field of science and technology, but they retain a number of drawbacks, the elimination of which are being dealt with by world developers and researchers of polymer materials for 3D printing.

Known composite material according to the invention DE No. 1998513345 from 30.07.1998, describing a method of obtaining a thermoplastic composition containing at least one polyarylene ether, at least one filler or reinforcing material, and one modified carboxyl-containing polyarylene ether having repeating structural elements. According to the applicants, the composite material has improved melt stability and mechanical properties. However, the materials of the application do not indicate that the composite material according to the invention can be used in additive technologies.

Patent for invention US 6495615 dated December 17, 2002 relates to a thermoplastic polymer material with improved impact strength, comprising a) a thermoplastic polyethersulfone polymer and b) glass fiber treated with a polyolefin wax. The polymeric material of the present invention has high modulus of elasticity and improved toughness.

Patent for invention US No. 8703862B2 dated April 22, 2014 describes a composite material comprising at least one polyarylene ether having on average not more than 0.1 phenolic end groups per polymer chain in an amount from 20 to 92 wt%, and one polyarylene ether having an average of 1.5 phenolic end groups per polymer chain in an amount from 3 to 20 wt%, one fibrous or dispersed filler from 5 to 60 wt%, and may also include additional additives and / or technological additives in an amount from 0 to 40 wt.%. The composite materials of the invention are characterized by markedly improved melt stability together with good mechanical properties.

The main disadvantages of composite materials according to these inventions is that there is no complete information about the properties of the material, that is, there is no information about hygroscopicity, which are not a little important characteristics of the created polymer material and they cannot be used in additive technologies.

The closest in technical essence and the intended effect is the composite material according to the patent for invention RU No. 2688140 dated 05/20/2019. The invention relates to a method for producing a composite material based on polyphenylene sulfone used as a superstructure polymer material for additive 3D technologies. The method of obtaining a composite material is that a preliminary dry mixture of 75-85 wt.% Polyphenylene sulfone and 10 wt.% Filler is extruded and granulated. Next, the filled polyphenylene sulfone granulate is mixed with the polycarbonate granules used as a plasticizer. Then, the resulting mixture is extruded. Polycarbonate is taken in an amount of 5-15 wt.%. Talc is used as a filler. The invention improves the impact strength and modulus of elasticity of the composite material.

The objective of the present invention is to create polymeric materials intended for additive technologies containing an improved complex of such properties as physical and mechanical and reduced values of hygroscopicity of materials.

The problem is solved by obtaining a composite material based on polyphenylene sulfone (PPSn), polycarbonate (PC), glass fiber and organomodified clay (OG), with a quantitative ratio of components, respectively, wt.h:

Polyphenylene sulfone 100, Polycarbonate 32-35, Fiberglass 1-3, Organomodified clay 0.5-2

As polyphenylene sulfone, it is preferable to use the Radel R5100 brand, polycarbonate is a granulate of the Carbomix brand manufactured in accordance with TU 2226-002-13619882-2006, chopped strands of glass fibers with a fiber length of 3 mm are used as glass fibers.

Organomodified clay is a product of the modification of montmorillonite clay, with a cation exchange capacity of 95 meq / 100 g of clay with urea, in an amount of 7 wt% based on the mass of montmorillonite. Organomodified clay is prepared as follows: urea is added to a suspension of montmorillonite clay in water, prepared by stirring on a magnetic stirrer for 30 minutes, and the mixture is stirred for another 2 hours at room temperature. The ratio of urea and montmorillonite clay, wt%: 93: 7. The resulting organoclay is washed with water by repeated decantation and dried at room temperature for 24 hours.

The following examples characterize but do not limit the invention.

Composite materials are produced according to the invention (example 1-6). Composite material formulations are shown in Table 1.

Example

The operating mixer is sequentially loaded in the quantities provided by the recipe (Table 1), PFSn, PC, fiberglass and exhaust gas. The resulting powder mixture is poured into an extruder and processed in zones Ι-V, at a temperature of 146 ° C, 149 ° C, 155 ° C and 160 ° C, respectively.

A polymer thread with a diameter of 1.75 mm is made from the obtained granulate, which is subsequently used to obtain samples for testing by 3D printing. Samples obtained using a RobozeOne +400 3D printer.

When studying the composite material, the following standards were used:

1. GOST RF 9550-81. Plastics. Methods for determining the modulus of elasticity in tension, compression and bending;

2.GOST RF 4648-2014 (ISO 178: 2010). Plastics. Static bend test method (as amended);

3. GOST RF 11262-80 (ST SEV 1199-78) Plastics. Tensile test method (with Amendment No. 1);

4. GOST RF 4650-2014 (ISO 62: 2008) Plastics. Methods for determining water absorption.

The test results are shown in Table 2.

Table 1

Composition of composite material

Composition component name Composite material 1 2 3 4 5 6 PFSn 100 100 100 100 100 100 PC 33 34 35 35 33 32 Fiberglass 3 1,2 2.5 1.0 1,2 2.4 OG 0.5 0.5 1 1.5 2 0.5

table 2

Composite material properties

Indicator name Composition Raw material 1 2 3 4 5 6 Flexural modulus, GPa 5.32 7.45 5.48 11.4 7.5 9.9 2.55 Flexural strength, MPa 117.0 99.54 147 100.1 104.5 102.3 98.2 Tensile modulus, GPa 3.9 2.10 5.1 5.3 5.02 4.5 2.10 Breaking strength, MPa 79.5 84.0 81.0 85.3 83.3 80.2 79 Water absorption,% mass, 0.1 0.09 0.07 0.05 0.05 0.08 0.6

The starting material is supposed to use polyphenylene sulfone brand Radel R5100 from Solvay.

The data presented in table 2 showed that the introduction of modifiers into the polymer material improves the values of physical and mechanical characteristics. This improvement is associated with a decrease in the degree of fiber breakdown, which is the result of the introduction of organomodified clay. In many cases, with the introduction of fibrous fillers, the water resistance of the composite material deteriorates due to the penetration and accumulation of water at the polymer - filler interface.In this case, the introduction of organomodified clay is very effective, which significantly reduces the water absorption of the composites and reduces the change in their mechanical characteristics.

The technical result is the production of composite materials that meet the requirements for physical and mechanical characteristics and hygroscopicity, intended for additive technologies.

Claims (3)

A composite material intended for additive technologies based on polyphenylene sulfone, polycarbonate and glass fiber, characterized in that it additionally includes organomodified clay, in the following ratio, parts by weight: Polyphenylene sulfone 100, Polycarbonate 32-35, Fiberglass 1-3, Organomodified clay 0.5-2, moreover, organomodified clay is a product of modification of montmorillonite clay, with a cation exchange capacity of 95 meq / 100 g of clay with urea, in an amount of 7% by weight of montmorillonite.