ES2504740B2 - Use of phase change materials in thermoplastic polymers - Google Patents

Abstract

Use of phase change materials in thermoplastic polymers. # The present invention relates to parts formed by a thermoplastic resin characterized in that its matrix and / or its surface comprises at least one inorganic material with phase change and because the temperature of The glass transition of the thermoplastic resin (calculated by DSC) is 2 to 20ºC higher than the melting temperature of the inorganic material with phase change.

Description

USE OF PHASE CANIBIUM MATERIALS IN THERMOPLASTIC POLYMERS

The present invention relates to the use of phase change materials in thermoplastic polymers. Therefore, the invention could be framed in the

field of materials science and technology more specifically in the

field of the thermoplastic polymeric materials.

STATE OF THE TECHNIQUE

Thermoplastic polymers subjected to cyclic mechanical stresses can reduce their fatigue resistance due to the appearance of cracks. Cyclic mechanical stress produces an increase in temperature that modifies

the flexibility and mechanical behavior of these materials.

the use of thermoplastic polymers in engineering parts remains

restricted when temperature values are reached that exceed the glass transition Tg, characteristic of each material. For example, in the case of dry polyamide 6.6 (PA 6.6), the Tg (calculated by DSC) of Differential English Scanning Temperature, with a heating ramp of 10 ° C / min in nitrogen atmosphere) is set at 53 oC what you want

say that when the piece reaches higher temperatures, defects may appear that worsen its mechanical properties.

In general, when polymeric parts are used, it is customary to increase

its temperature of use resort to the increase in the percentage of its fiber reinforcement, for example with glass fibers, although this circumstance

penalizes the toughness of the composite material.

Therefore, it is necessary to increase the operating temperature range of engineering polymeric parts in a manner that does not imply an increase

fragility of it.

Phase change materials (PCM) are materials with high latent heat that store or release large amounts of energy at the phase change temperature (solid ~ liquid).

During the phase change, the temperature remains constant while

that the material absorbs or releases energy. The main application of

these PCM is its use in construction for thermal energy accumulation

(Sharmaet al., Renewable and Sustainable Energy Reviews 13, (2009), 318

3. 4. 5).

DESCRIPTION OF THE INVENTION

The present invention relates to the use of phase change materials in

thermoplastic polymers.

The parts of the invention have the following advantages:

-

they have greater fatigue resistance than pieces of the same tennoplastic queen without inorganic materials with phase change; -the materials with qwa phase change can be used in the invention are

abundant;

-

The process for obtaining the parts of the invention is simple and does not require large adaptations in the production of said parts; -the small amount of the material with phase change to be incorporated, would not significantly influence the final cost of the pieces.

Therefore, a first aspect of the present invention relates to a part

formed by a thermoplastic resin characterized in that in its matrix and / or on its surface it comprises at least one inorganic material with change

phase; and the glass transition temperature of the thermoplastic resin, calculated by OSC with a heating ramp of 10 "Clmin under nitrogen atmosphere,

It is 2 to 20 · C higher than the melting temperature of the inorganic material with phase change.

Inorganic material with phase change means inorganic materials with a latent heat that at the phase change temperature store or release large amounts of energy .. They are classified between hydrates and metals.

In an embodiment of the first aspect of the present invention, the glass transition temperature of the thermoplastic resin, calculated by OSC with a heating ramp of 10 · C / min under nitrogen atmosphere, is 5 · C a

10 ° C higher than the melting temperature of the inorganic material with change

phase

In an embodiment of the first aspect of the present invention, the resin

Thermoplastic is selected from polyamide, polyoxymethylene, polyethylene, polypropylene, polystyrene, acrylonitrile-butadiene-styrene, polyacrylonitrile acrylonitrile-styrene-acrylate, polyvinylchloride, polyphenylene sulfide, polymethylmethethalate polyethaphthalate, polyethylene terephthalate methacrylate, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephosphate, thermoplastics , preferably the thermoplastic resin is selected from acrylonitrilebutadiene-styrene, polyacrylonitrile, polystyrene, polyvinylchloride, polyphenylene sulfide, polyethylene terephthalate, polymethylmethacrylate and polyamide,

more preferably the thermoplastic resin is polyamide, and even more preferably the thermoplastic resin is selected from polyamide 6.6, polyamide 11 and polyamide 6.10.

In an embodiment of the first aspect of the present invention, the thermoplastic resin is glass fiber reinforced polyamide, since it is an engineering polymer commonly used in high technical applications.

responsibility

In an embodiment of the first aspect of the present invention, the phase change inorganic material is a hydrate. Preferably the inorganic material with phase change is sealed from the hydrates of the following

list, and any of its combinations:

PCM stainless steel MgCl2.6H2O KAI (S04) 2.12H2O Mg (NÜJ) 2.6H2O Ba (OH) 2.8H2O AI (N03) 2.9H2O LiCH3COO.2H2O Na, P04.12H2O NaOH.H2O NaAI (S04) 2.10H2O Fe ( N03) 2.2H2O CH3COONa.3H2O MgCI2.4H2O MnCI2.4H2O Ni (N03) 2.6H2O FeCI3.2H2O Zn (N03) 2 · 2H2O Ca (N03) 2.3H2O Na2S20 3.5H2O MgS04.7H2O K2HP04.3H2O Na202.3H2O2. 5H2O Fe (NÜJ) 3.9H2O Ca (N03) .4H2O Mg (N03) 2.4H2O Zn (N03) 2.4H2O K2HP04.7H2O Cai2.6H2O

IT 'C

117.0 91, 0 89.9 78.0 72.0 70.0 65.0 64.3 61, 0 60.5 58.0 58.0 58.0 57.0 56.0 55.0 51, 0 48.5 48.5 48.0 48.0 47.0 47.0 47.0 45.0 45.0 42.0

Mg12.8H, O KF.2H, O CoS04.7H20

Na, HPO •. 12H, O Mn (NO,) 2.4H, O FeCIJ.6H, OR Zn (NO,), 6H, OR. liB ".2H, O CaB ".6H, O KFe (SO ') "12H, O Na, SO •. 10H, O Na2CO, .10H, O liNO, .3H, O liNO'.2H, O CaCI '. 12H, O FeBr, .6H, O Mn (NO,), 6H, OR. K, HPO • .6H, O

'Tr: melting temperature

42.0 42.0 40.7

40.0 37.1 37.0 36.1 34.0 34.0 33.0 32.4 32.0 30.0 30.0 29.8 27.0 25.5 14.0

Table 1 shows combinations of thermoplastic resins and inorganic materials with phase change that can be used with each

thermoplastic resin to improve its mechanical properties:

Tennoplastic Acrylonitrile Butadiene Styrene Polyacrylonyl Polystyrene Polyvinylchloride

TA ("C) '110 104 100 87 Inorganic PCM KAI (SO.) ,. 12H, O Mg (NO,) '. 6H, O Mg (NÜJ),. 6H, O Ba (OH), .8H, or AI (NO') 2.9H20 liCH, COO.2H, O TfpCM ("C) 91.0 89.9 89.9 78.0 72.0 70.0 TA-Tf 19.0 14.1 10.1 9.0 15.0 17.0

SuWuro polyphenylene

85 Ba (OH) 2.8H20 78.0 7.0

AI (N03) 2.9H20

72.0 13.0

LiCH3COO.2H20

70.0 15.0

Na3P04.12H20

65.0 20.0

Polyethylene Terephthalate

69 Na3P04.12H20 65.0 4.0

NaOH.H20

64.3 4.7

NaAI (S04) 2. 1OH20

61.0 8.0

Faith (N03) 2.2H20

60.5 8.5

CH "COONa.3H20

58.0 11.0

MgC12.4H20

58.0 11.0

MnC12.4H20

58.0 11.0

Ni (N03) 2.6H20

57.0 12.0

FeCI3.2H20

56.0 13.0

Zn (N03) 2 · 2H20

55.0 14.0

Ca (N03) 2.3H20

51.0 18.0

Polymethylmethacrylate

60 CH "COONa.3H20 58.0 2.0

MgC12.4H20

58.0 2.0

MnC12.4H20

58.0 2.0

Ni (~ J03) 2. 6H20

57.0 3.0

FeCI3.2H20

56.0 4.0

Zn (N03) 2.2H20

55.0 5.0

Ca (N03) 2.3H20

51.0 9.0

Na2S203.5H20

48.5 11.5

MgS04.7H20

48.5 11.5

K2HP04.3H20

48.0 12.0

Na2Si03.5H20

48.0 12.0

Faith (N03) 3.9H20

47.0 13 O

Ca (NO,) .4H20

47.0 13.0

Mg (NO,) 2.4H20

47.0 13.0

Zn (N03) 2.4H20

45.0 15.0

K2HP04.7H20

45.0 15.0

Cal: 1.6H20

42.0 18.0

Mg12.8H20

42.0 18.0

KF.:2H20

42.0 18.0

COS04.7H20

40.7 19.3

Na2HP04.12H20

40.0 20.0

Polyamide 6.6

53 Ca (N03) 2.3H20 51.0 2.0

MgS04.7H20

48.5 4,5

Zn (N03), 6H, O 36.1 3.9

LiBr, .2H, O

34.0 6.0

GaElr, .6H, O

34.0 6.0

KF ,, (S04), 12H, O

33.0 7.0

Na! S04.10H, OR

32.4 7.6

Na, G03. 10H, O

32.0 8.0

LiN03. 3H, O

30.0 10.0

LiN03.2H, O

30.0 10.0

GaCI, .12H, O

29.8 10.2

Fe8: r3.6H, O

27.0 13.0

Mn (N03), 6H, O

25.5 14.5

'Value determined through the DSG technique, with a heating ramp of 10 G / min in atmospheres, nitrogen nitrogen.

In an embodiment of the first aspect of the present invention, the resin

Thermoplastic is acrylonitrile-butadiene-styrene and the inorganic material with phase change is KAI (S04), · 12H, O.

In another embodiment of the first aspect of the present invention, the thermoplastic resin 10 is polyacrylonitrile and the phase change inorganic material is Mg (N03), 6H, O.

In another embodiment of the first aspect of the present invention, the thermoplastic resin is polystyrene and the phase change inorganic matHrial is

15 Mg (N03), 6H, O.

In another embodiment of the first aspect of the present invention, the resin

Thermoplastic is polyvinyl chloride and inorganic material with change of

phase is selected from Ba (OH), .8H, O, AI (N03), 9H, O, LiGH3GOO.2H, O and

In any of its mixtures, preferably the thermoplastic resin is vinyl chloride and the inorganic material with phase change is Ba (OH), 8H, O.

In another embodiment of the first aspect of the present invention, the thermoplastic resin is polyphenylene sulfide and the phase change inorganic material is selected from Ba (OH), 8H, O, AI (NO,) 2.9H, O, LiCH, COO.2H, ONa, PO • .12H, O and any of their mixtures, preferably the thermo plastic resin is polyvinylchloride and the inorganic material with phase change is Ba (OH) 2.8H, O.

In another embodiment of the first aspect of the present invention, the thermoplastic resin is polyethylene terephthalate and the phase change inorganic material is selected from Na, PO •. 12H, O, NaOH.H, O, NaAI (SO.) 2.10H, O, Fe (NO,) 2.2H, O, CHJCOONa.3H, O, MgCI, .4H, O, MnCI'.4H, O , Ni (NOJ) 2.6H, O, FeCh.2H, O, Zn (NO,): 1.2H, O, Ca (NO,), .3H, O, and any of their mixtures, preferably the thermoplastic resin is polyethylene Terephthalate and inorganic material with phase change are selected from NaAI (SO.) 2.10H, O, Fe (NOJ) 2.2H, O and any of their mixtures.

In another embodiment of the first aspect of the present invention, the thermoplastic resin is polymethylmethacrylate and the phase change inorganic material is selected from CHJCOON.3.3, O, MgCI, .4H, O, MnCI, .4H, O, Ni (NO ,), .6H, O, FeCh.2H, O, Zn (NOJ),.: 2H, O, Ca (NOJ) 2.3H, O, Na, S, OJo5H, O, MgSO •. 7H, O, K2HPO •. 3H, O, Na, SiO, .5H, O, Fe (NOJ) J.9H, O, Ca (NO,) .4H, O, Mg (NOJ) 2.4H, O, Zn (NOJ) 2.4H, O , K2HPO • .7H, O, Cal, .6H, O, Mgl '.8H, O, KF.2H20, CoSO • .7H20, Na2HPO •. 12H20 and any of its mixtures, preferably the thermoplastic resin, a is polymethylmethacrylate and the inorganic material with phase change is selected from Zn (NO ') 2.2H, O, Ca (NOJ) 2.3H, O and any of its mixtures.

In another embodiment of the first aspect of the present invention, the resin

Thermoplastic is polyamide 6.6 and the inorganic material with phase change is selected from Ca (NOJ) 2.3H20, MgS04.7H, O, Na, S, OJ.5H20, K2HPO •. 3H20, Na, SiOJ.5H, O, Fe (NO,), 9H20, Ca (NOJ) .4H20, Mg (NOJ) 2.4H20, Zn (NO,) 2.4H, O, K2HPO • .7H, O, Cal'.6H, O, Mgl'.8H, O, KF.2H20, CoS04.7H20, Na2HP04.12H20, Mn (N03) 2.4H20, FeCIJ.6H20, Zn (N03) 2.6H20, LiBr2.2H20, CaBr2. 6H20, KFe (S04) 2.12H20 and any of its mixtures, preferably the thermoplastic resin is polyamide 6.6 and the inorganic material with phase change is selected from K2HP04.3H2Ü,

Ca (N03) .4H20, K2HP04.7H20 and any of their mixtures, more preferably the material

Inorganic with phase change is Na2Si03.5H20.

In another embodiment of the first aspect of the present invention, the thermoplastic resin is polyamide 11 and the inorganic material with phase change is selected from Cai2.6H20, Mg12.8H20, KF.2H20, CoS04.7H20, Na2HP04.12H20, Mn ( N03) 2.4H20, FeCIJ.6H20, Zn (N03) 2.6H20, LiBr2.2H20, CaBr2.6H2Ü, Na2S04.10H20, Na2CO, .10H20, KFe (S04) 2.12H20, LiN03.3H20, LiN03.2H20, CaCI2. 12fi20, FeB ".6H20, Mn (N03) 2.6H20 and any of its mixtures, preferably the inorganic material with phase change is selected from Na2HP04.12H20, Mn (N03) 2.4H20, FeCIJ.6H20, Zn (N03) 2.6 H20 and any of its mixtures.

In another embodiment of the first aspect of the present invention, the resin

Thermoplastic is polyamide 6.10 And the inorganic material with phase change is selected from Mn (N03) 2.4H20, FeCb.6H20, Zn (N03) 2.6H20, LiBr2.2H20, CaBI "2.6H20, KFe (S04) 2.12H20, Na2S04 .10H20, Na2C03.10H20, LiN03.3H20, LiN03.2H20, CaCI2.12fi20, FeBrJ.6H20, Mn (N03) 2.6H20 and

Any of your mixtures. preferably inorganic material with change

phase is selected from LiBr2.2 ~ i20. CaBr2.6H20. KFe (SO,), 12H20. Na2S04.10H20, Na2C03.10H20, LiN03.3H20, LiN03.2H20 and any of

their mixtures

In an embodiment of the first aspect of the present invention, the part is

Select from stop, hinge, gear, thyme, fixing clip, connector and clamp, preferably the piece is a stop in a cross-rail fastening system.

In an embodiment of the first aspect of the present invention, the part selected is a stop in a rail-cross fastener system and the resin

Thermoplastic is polyamide 6, polyamide 6.6 and any of its mixtures, preferably fiberglass reinforced polyamide 6, glass fiber reinforced potamide 6.6, more pnoferibly reinforced with fiberglass.

glass in percentages of 30-35% by weight, which are the resins approved by the Spanish railway administrations.

In an embodiment of the first aspect of the present invention, the piece as and

as defined above it is characterized because in its matrix

It comprises the inorganic phase change material. That is, the material

inorganic with phase change has been included in the resin matrix itself

thermoplastic before forming the piece.

In another embodiment of the first aspect of the present invention, the part as defined above is characterized in that on its surface

It comprises the inorganic phase change material. Surprisingly, as illustrated in the examples of the invention, it has been seen that putting the

inorganic fasle change material in superficial contact with the

thermoplastic resin piece improves fatigue resistance properties

of that piece. That these mechanical improvements with a surface contact are achieved makes the use of these materials in combination with

thermoplastic resins since the manufacturing method is simple and does not require

major modifications It is believed that a superficial contact improves the

mechanical properties of the thermoplastic resin part because heat exchange occurs on the contact surface.

In an embodiment of the first aspect of the present invention,

the thermoplastic resin comprises poly amide; the inorganic material with phase change is Na, S, 0 3.5H, O; The piece comprises the inorganic material of phase change on its surface.

The inorganic material of change of the phase can be contacted

surface with the tennoplastic resin in the interstices of the piece, which can be interstices or grooves on the surface of the piece or in chambers inside

of the piece manufactured with such use. If the inorganic phase change material is contacted with the temlOplastic resin in an inner chamber of the part, the inorganic phase change material would be sealed and isolated from the

external medium by the own terrnoplastic resin. If the inorganic material is contacted with the thermoplastic resin in a groove or interstitium

surface of the piece, said groove or interstitium can be sealed later

to isolate the inorganic phase change material from the outside environment. This

Sealing can be carried out with different products depending on the application of the piece. For example with petrolatum \ '/ 0 stearic acid.

A second aspect of the present invention relates to the use of an inorganic material with phase change for the manufacture of a fatigue resistant part formed by a thermoplastic resin.

A third aspect of the present invention relates to a method of

Obtaining the part as described in SE> where

inorganic phase change material · is in its matrix comprising the

stages of:

-

mixing the thermoplastic resin with at least one inorganic material with phase change, where the material: inorganic with phase change is

dispersed in the polymer matrix; and -form of the piece.

This forming is carried out with the usual techniques in thermoplastic resins such as thermoforming, extrusion and injection.

In an embodiment of the third aspect of the present invention, the method also has a third stage of hydrating the newly formed part in the previous stage.

A fourth aspect of the present invention relates to a method of

obtaining the piece as described above where the

inorganic phase change material is on the surface that comprises

the stages of:

-

confined with the thermoplastic resin of the piece with interstices;

-filling the interstices with at least one inorganic material with change phase; -sealing of the interstices.

As described above by interstitium, interstices are understood

or grooves on the surface of the piece or in chambers inside the piece. If the inorganic phase change material is contacted with the resin

thermoplastic in an inner chamber of the piece, the inorganic phase change material would be sealed and isolated from the outside by the thermoplastic resin itself. If the inorganic material is contacted with the thermoplastic resin in a groove or surface interstitium of the piece, said groove or gap can be subsequently sealed to isolate the material

inorganic phase change of the external environment.

In an embodiment of the third and fourth aspect of the present invention. the

Thermo plastic resin is selected from polyamide. polyoxymethylene. polyethylene. polypropylene, polystyrene, acrylonitrile butadiene styrene, polyacrylonitrile acrylonitrile styrene acrylate, polyvinyl chloride, polyphenylene

sulfide, polymethylmethacrylate, polycarbonates, polyethylene terephthalate, terephthalate

of polybutylene, thermop elastomers, static and any of their mixtures,

preferably the thermoplastic resin is selected from acrylonitrile

butadiene-styrene, polyacrylonitrile, polystyrene, polyvinylchloride, polyphenylene sulfide, polyethylene terephthalate, polymethylmethacrylate and polyamide,

more preferably the tennoplastic resin is polyamide, and even more preferably the tennoplastic resin is selected from polyamide 6.6, polyamide 11 and pOliamide 6.10.

In an embodiment of the third and fourth aspect of the present invention, the

Tennoplastic resin is pOliamide reinforced with fiberglass.

In an embodiment of the third and fourth aspect of the present invention, the thermoplastic resin is acrylonitrile-butadiene-styrene and the inorganic material

with phase change is KAI (SO ') 2 · 12H; .Q.

In another embodiment of the third and fourth aspect of the present invention, the tennoplastic resin is pOliacrylonitrile and the phase change inorganic material is Mg (N03) 2 · 6H20.

In another embodiment of the third and fourth aspect of the present invention, the tennoplastic resin is polystyrene and the phase change inorganic material is Mg (N03) 2 · 6H20.

In another embodiment of the third and fourth aspect of the present invention, the thermoplastic resin is polyvinylchloride and the inorganic material with

phase change is selected ele Ba (OH) 2.8H20, AI (N03) 2.9H20,

liCH3COO.2H20 and any of its mixtures, preferably the resin

Tennoplastic is polyvinylchloride and the inorganic material with phase change is Ba (OH), 8H, O.

In another embodiment of the third and fourth aspect of the present invention, the thermoplastic resin is polyphenylene sulfide and the inorganic material with change

phase is selected from Ba (OH) 2.8H20, AI (N03) 2.9H20, LiCH3COO.2H20Na3PO •. 12H20 and any of its mixtures, preferably the tennoplastic resin is polyvinylchloride and the inorganic material with phase change is Ba (OH), 8H20.

In another embodiment of the third and fourth aspect of the present invention, the

Thermoplastic resin is polyethylene terephthalate and the inorganic material with phase change is selected from Na3P04.12H20, NaOH.H20, NaAI (S04) 2.10H20, Fe (N03) 2.2H2Ü, CH3COONa.3H20, MgC12.4H20, MnC12.4H20 , Ni (N03) 2.6H20, FeCIJ.2H20, Zn (N03) 2.2H20, Ca (N03) 2.3H20 and any of their mixtures, preferably the thermoplastic resin is polyethylene terephthalate and the inorganic material with phase change is selected from NaAI (S04) 2,10H20, Fe (N03) 2.2H20 and any of its mixtures.

In another embodiment of the third and fourth aspect of the present invention, the thermoplastic resin is polymethylmethacrylate and the inorganic material with phase change is selected from CH3COONa.3H20, MgC12.4H20, MnC12.4H20, Ni (N03) 2.6H20, FeCIJ. 2H20, Zn (N03) 2.2H20, Ca (N03) 2.3H20, Na2S20 3.5'20H20, MgS04.7H20, K2HP04.3H20, Na2Si03.5H20, Fe (N03) J.9H20, Ca (N03) .4H20, Mg ( N03) 2.4H20, Zn (N03) 2.4H20, K2HP04.7H20, CaI2.6H2Ü, Mg12.8H20, KF.2H20, CoS04.7H20, Na2HP04.12H20 and any of their mixtures, preferably the thermoplastic resin is polymethylmethacrylate and the material Inorganic with fa change, Zn (N03) 2.2H2Ü, Ca (N03) 2.3H20 and any of its mixtures are selected.

In another embodiment of the third and fourth aspect of the present invention, the

Thermoplastic resin is polyamide 6.6 II the inorganic material with phase change is selected from Ca (N03) 2., IH20, MgS04.7H20, Na2S20 3.5H20, K2HP04.3H20, Na2Si03.5H20, Fe (N03) J.9H20, Ca (NO,) 4H20, Mg (N03) 2.4H20, Zn (N03) 2.4H20, K2HP04.7H20, Ca12.6H20, Mg12.8H20, KF.2H20, CoS04.7H20, Na2HP04.1: 2H20, Mn (N03 ) 2.4H20, FeCIJ.6H20, Zn (N03) 2.6H20, LiBr2.2H20, CaBI "2.6H20, KFe (S04) 2.12H20 and any of their mixtures, preferably the thermoplastic resin is polyamide 6.6 and the inorganic material with change of f: ase is selected from K2HP04.3H20, Na2Si03.5H20, Fe (N03) J.9H20, Ca (N03) .4H20, Zn (N03) 2.4H20, K2HPO • .7H20 and any of their mixtures, more preferably the material Inorganic with phase change is Na2SiOJ.5H20.

In another embodiment of the third and fourth aspect of the present invention, the thermoplastic resin is polyamide 11 and the inorganic material with phase change is selected from Ca12.6H20, M! II.8H20, KF.2H20, Na2HPO •. 12H20, Mn (NOJ) 2.4H20, FeCIJ.6H20, Zn (NCJ,) 2.6H20, LiS ".2H20, CaS" .6H20, Na2S04.10H20, Na2COJ.10H20, KFe (SO ') 2.12H20, CoSO •. 7H20, LiNClJ.3H20, LiNClJ.2H20, CaCI2.12 ~ "O, FeSrJ.6H20, Mn (NOJ) 2.6H20 and any of their mixtures, preferably the inorganic material with phase change is selected from Na2HPO •. 12H20, Mn (NOJ) 2.4H20, FeCb.6H20, Zn (NOJ) 2.6H20 and any of its mixtures.

In another embodiment of the third and fourth aspect of the present invention, the thermoplastic resin is polyamide 6.10 and the inorganic material with phase change is selected from Mn (NOJ) 2.4H20, FeCb.6H20, Zn (NOJ) 2.6H20, LiS " .2H20, CaS ".6H20, KFe (S04) 2.1 '! H20, Na2S0 •. 10H20, Na2COJ.10H20, LiNOJ.3H20, LiNOJ.2H20, CaCI2.12 ~ "O, FeSrJ.6H20, Mn (NOJ) 2.6H20 and any of their mixtures, preferably the inorganic material with phase change is selected from LiS" .2H20, CaS ".6H20, KFe (SO ') 2.12H20, Na2S0 •. 10H20, Na2COJ.10H20, LiNOJ.3H20, LiNOJ.2H20 and any of

their mixtures

Throughout the description and the claims the word "comprises" and

its variants are not intended to exclude other technical characteristics. additives,

components or steps. For those skilled in the art, other objects, advantages and features of the invention will be partly derived from the description and

in part of the practice of the invention. The following examples and figures are provided by way of illustration, and are not intended to be limiting of the present invention.

DESCRIPTION OF THE FIGURES

Fig. 1. Perspective view of the part of Example 1. which is a stop of the rail-cross fastening system of the high-speed train tracks. 1: thermoplastic resin piece, 2: inorganic material with phase change in the interstices; L: length of the piece.

Fig. 2. Evolution of the temperature until the moment of breakage; i: part of the invention; ii: thermoplastic resin piece without material with phase change.

EXAMPLES

The invention will now be illustrated by tests carried out by the inventors, which shows the improved mechanical properties of the parts of the invention.

Example 1. Procedure for obtaining a part of the invention

At the top of the rail-crossbar fastening system (L = 110 mm) (Fig. 1) of fiberglass reinforced polyamide 6.6 type E (electric) Na, S, 0 3.5H, O was incorporated on the surface, in the interstices (2) of the workpiece geometry, reaching a proportion of PCM in the pimeric sample of 8% by weight.

The grooves were then sealed to ensure proper sealing with a putty composed of calcium salts, petrolatum and stearic acid.

Example 2. Mechanical behavior of the part of Example 1

In a high-speed rail track fastening mounting simulator device, which has a rail skate emulator and sleeper support,

approved by the Railway Infrastructure Administrator (ADIF) to perform this type of tests, according to Technical Specification, E.T. 03.360.578.3 "Lightweight layered clamping plates". The May 1998 edition, the piece of Example 1 is fastened, so that the piece is subjected to the same conditions under which its work is carried out.

Variable compression load waves are applied on the part between 5 and 55kN of sinusoidal nature, at the frequency of 5 hertz, with the help of

A universal testing machine. Once the test is started, the

evolution of the deformation due to shortening of the part by means of an inductive comparator lVDT (in English, Linear Variable Differential Transfonner) and the evolution of the temperature of the part is recorded simultaneously.

Figure 2 compares the thermal behavior of a standard part.

Free of material with change of fasE! and another one with material with change

phase, subjected to the same test of fatigue. It can be seen that the standard part (ii) breaks after 35,000 cycles (1, 9 hours) have elapsed, while the part equipped with PCM (i) extends its useful life to 190000 cycles (10.5 hours), having increased its fatigue life more than 400%. It is appreciated that once the additive phase change temperature has been reached (which in the case of Na2S203.5H20 is 48.5 · Cj, it absorbs the heat of its surroundings

to perform its change of state and there is a cooling effect on

the polyamide that tends to stabilize the temperature of the component,

prolongs its useful life.

Claims (33)

1.-Piece formed by a thermoplastic resin characterized in that: in its matrix and / or its surface it comprises at least one inorganic material with phase change; and the glass transition temperature of the thermoplastic resin, calculated by DSC with a heating ramp of 10'C / min under a nitrogen atmosphere, is 2 to 20'C higher than the melting temperature of the inorganic material with phase change .  2.-Piece according to the preceding claim, wherein the transition temperature Thermoplastic resin vitreous, calculated by DSC with a heating ramp of 10'C / min under nitrogen atmosphere, is 5'C to 10'C higher than the melting temperature of the inorganic material with phase change. 3. The one according to any of the preceding claims, wherein the thermoplastic resin is selected from polyamide, polyoxymethylene, polyethylene, polypropylene, polystyrene, acrylonitrile-butadiene-styrene, polyacrylonitrile acrylonitrile-styrene-acrylate, polyvinylchloride, polyphenylene sulfide, polymethylmethacrylate, polycarbonates, polyethylene terephthalate, polybutylene terephthalate, thermoplastic elastomers and any of their mixtures. 4. The piece according to any of the preceding claims, wherein the inorganic material with 1asB change is a hydrate. 5. The part according to any of the preceding claims, wherein the thermoplastic resin is acrylonitrile-buladiene-styrene and the inorganic material with phase change is KAI (SO ') 2 · 12H "O. 6. The part according to any of claims 1 to 4, wherein the thermoplastic resin is polyacrylonitrile and the inorganic material with phase change is Mg (N03) 2 · 6H, O. 7. The part according to any of claims 1 to 4, wherein the thermoplastic resin is polystyrene and the inorganic material with phase change is Mg (N03), · 6H, O. 8. The part according to any of claims 1 to 4, wherein the thermoplastic resin is polyvinylchloride and the inorganic phase change material is selected from Ba (OH), 8H, O, AI (N03), 9H. , O, liCH3COO.2H, O and Any of your mixtures. 9. The part according to any of claims 1 to 4, wherein the lemoplastic resin is polyphenylene suffuro and the inorganic material with phase change is selected from Ela (OH),. 8H, O, AI (N03),. 9H, O, liCH3COO.2H, ONa3P04.12H, O and any of their mixtures. 10. The piece according to any of claims 1 to 4, wherein the resin Thermoplastic is polyethylene lerephthalalo and the inorganic material with phase change is selected from Na3P04.12H, O, NaOH.H, O, NaAI (S04) 2.10H, O, Fe (N03) 2.2H, O, CH3COONa.3H, O, MgCI, .4H, O, MnCI, .4H20, Ni (N03) 2.6H20, FeCI3.2H20, Zn (N03) 2 .. 2H20, Ca (N03) 2.3H20 and any of their mixtures 11. The part according to any of claims 1 to 4, wherein the thermoplastic resin is polymethyl methacrylate and the inorganic material With phase change is selected from CH3COONa.3H20, MgCI2.4H20, MnCI2.4H20, Ni (N03) 2.6H20, FeCIJ.2H, O, Zn (N03) 2.:1H20, Ca (N03) 2.3H20, Na2S20 3.5H20, MgS04.7H20, I <2HP04.3H20, Na2Si03.5H, O, Fe (N03) 3.9H20, Ca (N03) .4H20, Mg (N03) 2.4H, O, Zn (N03) 2.4H20, I <2HP04.7H, O, Cal'.6H, O, Mgl, .8H, O, KF.2H20, CoS04. 7H20, Na2HP04.12H20 and any of its mixtures. 12. The part according to any of claims 1 to 4, wherein the thermoplastic resin is polyamide 6.6 and the inorganic material with phase change is selected from Ca (N03), 3H, O, MgSO ".7H, O, Na , S, 03.5H, O, K, HPO • .3H, O, 5 Na, Si03.5H, O, Fe (N03) 3.9H, O, Ca (N03) .4H, O, Mg (N03) 2.4H, O, Zn (N03),. 4H, O, K2HPO • .7H , O, Cal'.6H, O, Mg12.8H, O, KF.2H, O, CoSO • .7H, O, Na, HPO •. 12H, O, Mn (N03), 4H, O, FeCh.6H, O, Zn (N03) '. 6H, O, LiB ".2H, O, CaB" .6H, O, KFe (SO.) 2.1 '! H, O and any of its mixtures. 13. The part according to any of claims 1 to 4, wherein the thermoplastic resin is polyamide 11 and the inorganic material with phase change is selected from Cal, .6H, (), KF.2H, O, CoSO •. 7H, O, Na, HPO •. 12H, O, Mn (N03), 4H, O, FeCh.6H, O, Zn (N03), .6H, O, LiB ".2H, O, CaB" .6H, O, Na, SO •. 10H, O, Na, C03.10H, O, 15 KFe (SO.), 12H, O, LiN03.3H, O, LiN (),. 2H, O, CaCI, .12H, O, FeBrJ.6H, O, Mn (N03),. 6H, O and Any of your mixtures. 14. The part according to any of claims 1 to 4, wherein the thermoplastic resin is polyamide 6.10 and the inorganic material with phase change 20 is selected from Mn (N03), 4H, O, FeCh.6H, O, Zn (N03), 6H, O, LiB ".2H, O, CaB" .6H, O, KFe (SO.p. 12H, O, Na, SO •. 10H, O, Na, C03.10H, O, LiN03.3H, O, LiN03.2H, O, CaCI, .12 ~ hO, FeBrJ.6H, O, Mn (N03) , .6H, O and any of their mixtures. 15. The part according to any of the preceding claims. where the piece is selected from stop, hinge, gear, thyme, fixing clip, connector and clamp. 16. The piece according to the preceding claim, wherein the piece is a stop in a rail-cross fastener system. 17. The piece according to any of the preceding claims, characterized in that its matrix comprises the inorganic phase change material. 18. The piece according to any of claims 1 to 16, characterized in that on its surface it comprises the inorganic material of phase change. 19.-Use of an inorganic material with phase change for the manufacture of a piece resistant to fatigue snorted by a thermoplastic resin. 20.-Procedure for obtaining the piece according to claims 1 to 17 which comprises the stages of:

-

mixing the tennoplastic resin with at least one inorganic material with

phase change, where the inorganic material was phase change is dispersed in the polymer matrix; Y  -formed part .. 21.-Procedure for obtaining the part according to claims 1 to 16 and 18 that breaks the stages of: -ronformed the thermoplastic resin of the piece with interstices; -fill of the interstices rum at least one inorganic material rum change phase; -sealing of the interstices.  22.-Procedure according to any day: claims 20 or 21 wherein the Thermoplastic resin is selected from polyamide, polyoxymethylene, polyethylene, polypropylene, polystyrene, acrylonitrile-butadiene-styrene, polyacrylonitrile acrylonitrile-styrene-acrylate, polyvinylchloride, polyphenylene sulfide, polymethylmethacrylate, polycarbonates, polyethylene terephthalate, polybutylene terephthalate, thermoplast elastomers and any of their mixtures. 23. Method according to any d, in claims 20 to 22, wherein the glass transition temperature of the thermoplastic resin (calculated by OSC) is 2 to 20 · C greater than 1: 0 melting temperature of the inorganic material with change phase 24. Method according to the preceding claim, wherein the glass transition temperature of the thermoplastic resin (calculated by OSC) is 5 · C to 10 · C higher than the melting temperature of the inorganic material with phase change. 25. Process according to any d, in claims 20 to 24 wherein the inorganic material with change of fasH is a hydrate. 26. Method according to any one of claims 20 to 25, wherein the thermoplastic resin is acrylonitrile-but: odiene-styrene and the inorganic material with phase change is KAI (SO ') 2 · 12H20. 27. Method according to any of claims 20 to 25, wherein the Thermoplastic resin is polyacrylonitrile and inorganic material with change of phase is Mg (N03) 2 · 6H20. 28. Procedure according to any of claims 20 to 25, wherein the terrnoplastic resin is polystyrene and the inorganic material with change of phase is Mg (N03) 2 · 6H20. 29. Method according to any of claims 20 to 25, wherein the thermoplastic resin is polychloride d, and vinyl and the inorganic material with phase change is selected from Ba (OH) 2.8H20 AI (N03) 2.9H20, LiCH3COO. 2H20 and any of its mixtures. 30. Method according to any of claims 20 to 25, wherein the thermoplastic resin is polyphenylene suH'uro and the inorganic material with change

phase is selected from Ba (OH) 2. 8H20,

LiCH3COO.2H20Na3PO, .12H20 and any of its mixtures.

31. Procedure according to any one of claims 20 to 25, wherein the

S

Tennoplastic resin is polyethylene terephthalate and inorganic material with

Phase change is selected from Na3PO, .12H20, NaOH.H20,

NaAI (SO,) 2.10H20, Fe (N03) 2.2H20, CH3COONa.3H20, MgCI2.4H20,

MnCI2.4H20, FeCIJ.2H20, Zn (N03) 2.:2H,O, Ca (N03) 2.3H, O and any of

their mixtures

10

32. Method according to any of claims 20 to 25, wherein the

thermoplastic resin is polymethylmethacrylate and inorganic material with

Phase change is selected from CH3COONa .3H20, MgCI2.4H20,

MnCI2.4H20, FeCIJ.2H20, Zn (N03) 2.2H20, Ca (N03) 2. 3H20, Na2S20 3'SH20,

fifteen

MgSO, .7H20, K2HPO'.3H20, Na2Si03.5H20, Fe (N03) 3.9H20, Ca (N03) .4H20,

Mg (N03) 2.4H20, Zn (N03) 2.4H20, K2HPO, .7H, O, CaI2.6H20, MgI2.8H20,

KF.2H20, Na2HPO, .12H20 and any of their mixtures.

33. Method according to any one of claims 20 to 25, wherein the

twenty

Tennoplastic resin is polyamide 6.6 and inorganic material with change of

phase is selected from Ca (N03),.: IH, O, MgSO, .7H20, Na2S20 3. 5H, O,

K2HPO, .3H, O, Na2Si03. 5H20, Fe (N03) 3. 9H20, Ca (N03) .4H, O,

Mg (N03) 2.4H20, Zn (N03) 2.4H20, K2HPO, .7H20, CaI2. 6H20, MgI2.8H20,

KF.2H, O, Na2HPO, .12H20, Mn (N03) 2.4H20, FeCIJ.6H20, Zn (N03) 2.6H20,

25

LiB ".2H, O, CaB" .6H20, KFe (SO,) 2.12H20 and any of its mixtures.

34. Method according to any of claims 20 to 25, wherein the

thermoplastic resin is polyamide 11) f the inorganic material with change of

phase is selected from CaI2.6H, O, Mgl, .8H20, KF.2H20, Na2HPO, .12H, O,

30

Mn (N03) 2.4H, O, FeCIJ.6H20, Zn (N03), 6H20, LiB ".2H20, CaB" .6H, O,

Na2S0, .10H20, Na2C03. 10H20, KFe (SO,), 12H, O, LiN03.3H20,

LiN03.2H20, CaCI2.12H20, FeSr3.6H20, Mn (N03) 2.6H20 and any of its mixtures 35. Method according to any of claims 20 to 25, wherein the 5 thermoplastic resin is polyamide 6.10 And the inorganic material with phase change is selected from Mn (N03) z.4H20, FeCIa.6H20, Zn (N03) 2.6H20, LiSrz.2H20, CaSr2.6H20. KFe (S04) 2.1: 2H20, Na2S04.1 OH20, Na2C03.10H20. LiN03.3H20, LiN03.2H20, CaCI2.12H20, FeSra.6H20, Mn (N03) z.6H20 and Any of your mixtures.