CA2091350C - Molecular alloys for storing and giving back thermal energy by phase change - Google Patents

Abstract

The compositions of the invention are formed from one or more molecular alloys capable of storing or restoring thermal energy at a temperature level (T), over a temperature interval 8, corresponding to those required for a given application such as phase change material, these alloys belonging to a phase diagram with a transition domain located in a temperature interval including that required and whose geometrical locus (EGC) is close to the horizontal. These compositions are useful as phase change materials, in particular in the agro-food and paramedical fields.

Description

WO 93101250 PCTiFR92 / 00636 ~ n ü
MOLECULAR ALLOYS FOR STORING AND RE-ESTABLISHING THERMAL EN ~ RGIE ' BY PHASE CHANGE
The subject of the invention is useful compositions as phase change materials for storage and restitution of thermal energy by latent heat.
It is recalled that there are two main types of storage of energy in thermal form, namely by sensible heat and latent heat.
Storage by sensible heat through a material proceeds from an increase in its temperature or, during the restoration, a decrease of its temperature.
Unlike sensible heat storage, the latent heat storage is isothermal if the material is pure or with some variation of temperature with mixtures: it is the change of phase of the material that is involved.
Phase change materials or MCPs are therefore compounds capable of storing and restore thermal energy through their phase transitions, most often from solid to liquid, but also from solid to solid.
When heated, the material takes calories from outside environment and reaches a temperature Ttr, transition temperature, then passing from a phase 1 at the end of phase 2 by absorption of heat. When the transition is completed, its temperature can increase to new.
If we cool it down, the reverse transition is product: at Ttr, material goes from phase 2 to phase 1 and restores on the outside environment the energy he had stored beforehand while remaining at temperature Ttr.

WO 93/01250 PC'T / FR92 / 00636 t ~ 'a ~ u 2 ... .3 J
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The energy involved is the enthalpy variation of OH phase change.
Widely used PCMs are 1a ice, saline hydrates. We also proposed some eutectic. But these materials have the disadvantage to operate at a single non-adjustable temperature.
Many of them, especially saline hydrates, are corrosive and have an incongruous fusion entrafnant frequent phenomena of segregation difficult to control, giving them poor grip thermal cycling.
It has also been proposed for the storage of the energy of defined organic compounds, such as acids fat, paraffin, or some mixtures of paraffins.
Mixtures of paraffins solid at 25 ° C, put in as MCP, are thus described in the patent FR 2368529. However, this patent focuses on improving thermal properties of such mixtures by addition of metals, their oxides or their silicates. The example given relates to the improvement of properties 82/18 mixture of n-docosane / n-tetracosane by addition of oxides of magnesia, alumina, emery, kaolin and aluminum at 25 to 55% by weight.
The interest of mixing paraffins as such and the conditions to be met to meet the requirements of a given application, at a temperature level defined, however, are not considered.
In the applications W087 / 03290 and EP 0344013 and 0344014, polyolefin composites are disclosed containing phase-change materials formed especially C 14 or higher paraffin mixtures. These WO 93/01250 PCTlFR92 / 00636 ~. ;; 1:, ~ i ~
t) .a.
composites are provided for the storage of energy solar.
Salyer's article in l5th North American Thermal Analysis Society Conference Cincinnati, OH, Sep.
21-24, 1986, relates to the analysis of hydrocarbons paraffinic crystals particularly envisaged for storage of solar energy. Mixtures of commercial paraffins are studied with regard to their properties as phase change materials for this application.
This study concerns mixtures of alkanes, according to given proportions, formed of odd chains, that is, an odd number of carbon atoms (designated Cni), (mixtures C15 / C19, C17 / C19), of chains pairs, that is, an even number of carbon atoms (hereinafter referred to as Cnp) (mixtures C14 / C16, C16 / C18, C16 / C20), even chains and odd chains (C16 / C17, C18 / C19) or of Cni or Cnp of longer chains (> C20). Ternary mixtures are also reported (C16 / C17 / C18: C17 / C18 / C19: C16 / C18 / C20; C17 / C19 / C21;
C14 / C1? / C20 and C16 / C19 / C21), all taken at concentration 0.25 / 0.50 / 0.25.
Similarly, Salyer reports the results obtained with synthesized mixtures with multicomponents corresponding to commercial products.
The conditions used for measuring However, it is not possible to appreciate with sufficient the characteristics of the studied melanges and by there to determine for what temperature level they are really appropriate and do not provide the means to obtain compositions perfectly adapted to a temperature level as required precisely in a given application.

e The work done by the inventors in this domain have shown that to have compositions effective, highly reliable, the Starting compounds must meet requirements accurate, evaluated according to rigorous methods.
This work led to the development of new compositions and new materials to phase change.
The purpose of the invention is therefore to provide new compositions elaborated with regard to parameters determined, allowing their phase change to store and return high amounts of energy through latent heat.
It also aims at the preparation of these phase change compositions.
It also aims to use compositions of this type, as materials presenting a change phase over a narrow temperature range, located in a temperature range to cover largely industrial needs.
The compositions of the invention, capable in particular to store and restore the thermal energy by latent heat, are caraotériaées in that they are formed from one or more molecular alloys - as characterized by X-rays, - able to store or restore energy at a temperature level T, over an interval of temperature 0, corresponding to those required for a application given as a phase change material, WO 93/01250 PCTlFR92 / 00636 , '; ~. : ',;'j ~
5J ~ .i R ~.:. tj V
- belonging to a phase diagram with, if the alloy is binary, a spindle, in the case of a total miscibility, or part of a spindle, in the case 5 of partial miscibility, or if the alloy is ternary or more, a transition domain, this time zone or this domain being within a temperature range including the one required for a given application and whose curve EGC (Equal G curve), or generally speaking the place geometric EGC, is slightly curved and close to horizontality to ensure a 6 not exceeding the width desired, - having a satisfactory behavior during cycling thermal, these alloys being obtained from organic compounds . latent heat required in such a way classical to be phase change materials, . having a degree of molecular homeomorphism Ek greater than 0.8 and, preferably, greater than 0.90 for binary alloys, or having this property for them various components taken in pairs if they are alloys multicomponent, whose intermolecular interactions are relatively comparable for the different buildings components.
"Molecular alloy" means a phase generated from the organic compounds to develop it, this phase behaving like a pure body from the crystallographic point of view. This phase unique, obtained by syncrystallization, can also be referred to as the terms solid solution or crystal mixed.

WO 93! 01250 PCT / FR92 / 00636 X-ray analyzes were performed by powder diffractometry, and especially in the chamber of Guinier Lenné or Guinier Simon.
EGC (Equal G Curve) means the place geometric points where solid and liquid (or solid 1 and solid 2) in equilibrium at the transition (for a binary), or in a general way the different phases in equilibrium at transition have the same energy of Gibbs. (Ref HAJ
OONK, PHASE THEORY, ELSEVIER 1981).
The expression "satisfactory behavior during cycling "as used above means that repeated cycles of storage-destocking exceeding notably 30 cycles for cases of non-repetitive applications and About 5,000 cycles for very applications repetitive effects do not result in chemical modification or segregation that can damage the material.
Temperatures and associated enthalpies are measured by differential scanning calorimetry, with pre-calibration performed in accordance with the invention strictly under the same experimental conditions as those of the analyzes, which makes it possible to perfectly characterized compositions including the point from their thermodynamic properties and that will be fully adapted to the intended application ~ 1 a level given temperature.
The degree of EK molecular homeomorphism organic compounds used to form the alloy is obtained by superimposing the two molecules involved in such that the recovery volume r is maximum, their volume of non-recovery in this position, o, is then minimum. The degree of homeomorphism is given by the formula WO 93! 01250 PCT / FIt92100636 iv u û .i ~~ ~ rv E k ._ 1 -More molecules have sizes and shapes neighbors and more Ek is close to 1. We will find the made practice of obtaining Ek in the reference Haget et al.
J. Appl. Cryst (1990), 23, 492-496.
Thus, for practically varying temperatures continuously, we have compositions whose behavior thermal fusion or solidification are comparable to that of pure compounds.
The molecular alloys of the invention, which constitute phase-change materials and are hereinafter also referred to by the abbreviation MCPAM, present a window of thermal efficiency b, defined 95% of 0H.
It is recalled in this respect that the transition, and particular fusion, an alloy is a continuum extending from Tsolidus to Tliquidus ~ The interval of Total storage is equal to ~ Tsol-Tliq ~. The temperature Tg5%
(between Tsol and Tliq) MCPAM is such that between Tg5% and Tliq is stored 95% of the energy of transition.
The interval b = 4Tg5% - Tliq ~ is therefore a efficiency window (95%) of the MCPAM.
In what follows, the MCPAMs will be characterized by Tg, T being taken equal to Tliq.
The invention is aimed more specifically at compositions defined above in which b does not exceed not +8 ° C, especially +6 ° C, and this in a field of temperature ranging from -100 ° C to + 300 ° C.

; ~~; j: ~ ~~~~ 8 Particularly preferred compositions according to the invention have a window of thermal efficiency not exceeding + 4 ° C, as measured in strict conditions mentioned above and advantageously not exceeding + 2 ° C or + 1 ° C.
In one embodiment of the invention, the organic compounds used to form alliances are not miscible in all proportions before the transition, but the level of invariance this who from fact, characterizes the phase diagram, is narrow, of the order of a few cents in concentration, in and General port to one of the starting compos. These crystalline forms involved are not necessarily isomorphic. Two cases are possible. non forms are isomorphic and in this case, there are 2 types of alliances each of which is solid, a temperature a curve of G, to the forms of the constituents of are isomorphic but their degree of isomorphism is insufficient to drive total miscibility: a only G curve is enough da ~ ire all alloys a ( temperature T gives) but it has two poles inflection and only they are stable and therefore usable alloys with concentrations outside the segment of double tangency.

In either case, the (the) partial ones of the phase diagram concerned) is (are) those) located (s) outside the invariance level.
In another embodiment of the invention, the organic compounds used to form the alloys Molecules are miscible in all proportions before the transition.
Their crystalline forms are then isomorphic and their degree of crystalline isomorphism ~ m close to 1.

i ~ ~! ~ ci v tj The degree of crystalline isomorphism Em is defined for two compounds (generalizable notion if necessary in taking the compounds two by two in the case of alloys multicomponents) by superimposing the crystalline meshes of the two compounds involved so that the volume of recovery t is maximum; their volume of no recovery in this position, Dm, is then minimum and Em = 1 _ drw ~ '~ R ~
(Ref Haget et al given above).
The solidus-liquidus spindle can take three aspects, - that of a simple spindle: the alloys that we can make from organic compounds will have a intermediate fusion domain between those constituents of the alloy, - that of a minimum point spindle; so he is possible to make an alloy that melts at temperatures lower than those of the compounds;
- that of a maximum Gibbs point spindle, some of the alloys obtained melting at a temperature greater than that of the starting compounds.
In another embodiment, the miscibility compounds used is weak; the phase diagram is characterized by a large invariance stage of type eutectic; we obtain a mixture of alloys particularly interesting by its thermal window (ë ~ 0) for eutectic concentration and operating at the temperature of the eutectic invariant. The compounds have Ek weak; they are either non-isomorphic or isomorphous with weak Ems.

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According to another provision of the invention, the compositions in question are still characterized in that that they contain one or more of the organic compounds defined above as doping agents present at less than 5% in molar proportions, the the main compounds being present) at the rate of $ 90 or more This doping advantageously allows to adjust T according to a given application.
The molecular alloys of the invention meet especially in formula (I).
Axa Zxz (I) in which - A is an acyclic organic compound or cyclic, saturated or unsaturated, where appropriate substituted, the exclusion of benzene and substituted benzenes, Z represents one or more organic compounds different from A, but chosen) from among the meanings data for A, the organic compounds represented by A and by Z
meeting the requirements defined above, and xa and xz represent respectively the molar proportions of A and Z.
By acyclic organic compound is meant the straight or branched chained compounds of 2 ~ 1 120 atoms carbon and more for polymers. These compounds are preferably alkanes, alkenes or alkynes.
Cyclic organic compounds are formed from a at several cycles of 5 to 30 carbon atoms, more particularly aromatic rings, such as . naphthalene, anthracene, benzene being excluded. In alternatively, they are formed of one or more heterocycles.
The heterocycles are advantageously chosen from among the WO 93/01250 PCI'l FR92 / 00636 11 'r,'~.; ~ Ai i. ti nitrogenous heterocycles such as imidazoles, pyridine, pyrimidine, pyridazine, oxygenated heterocycles as oxazoles, oxygenated and nitrogenous heterocycles such as oxadiazoles or sulfur heterocycles such as thiazole. According to yet another variant, the compounds cyclic organic compounds include one or more rings carbon atoms and one or more heterocycles.
Organic compounds represented by A and Z
where appropriate, one or more substituents chosen from halogens F, Cl, Br, I, the groups -OH
or -OR1, alkyl, alkylene and alkyne groups, these different groups preferably having 1 to 8 carbon atoms carbon, more especially from 1 to 4 carbon atoms, -COOH, -COOR1, -COR1, -CH2OH, -CH (R1) -OH, -C (R1) groups;
R2) OH, or their ethers, -CHO, -C = O -CONH2, -NH2, NH (R1), or -N (R 1, R 2), -S, -SH, -NO 2, R 1 and R 2, which are identical or different from one another, being an alkyl group of 1 to 8 carbon atoms, preferably from 1 to 4 carbon atoms carbon, functional groups such as amine, ketone, sulfhydryl, amide, which may constitute one or more links of the chain. Substituents of the compounds Acyclic organic compounds also include cycles and heterocycles listed above.
In organic compounds or their ethers acyclic, the above substituents occupy a any position on the carbon chain, and / or find at one end of the chain or at each of the two ends.
In cyclic organic compounds, these substituents occupy any position on the cycle.
In a family of molecular alloys the invention, A and Z belong to the same class of compounds.

WO 93/01250 PCTlFR92 / 00636 iW
A group of this family is formed of chains hydrocarbons, more particularly alkanes, alkenes or alkynes, to the exclusion of mixtures expressly described in the documents of the prior art cited above.
Molecular alloys particularly preferred are from alkanes containing from 8 to 100 carbon atoms, with straight or branched chains, the where appropriate substituted as indicated above.
Molecular alloys made from of normal alkanes, of chemical formula CnH2n + 2. or in abbreviated Cn, will be hereinafter referred to as ALCAL.
In this family, all interactions intermolecular types are Van Der Waals, giving oGexcess very low both for solid solutions only for liquid solutions which induces curves EGC little curved.
The so-called admissible ALCALs, that is to say, respondent requirements set out above, have excellent thermal cycling behavior; they can undergo several thousands of cycles without damage (provided that the sublimation which could distort their content). This is due to the joint actions of the weak O, because they are chemically inert and that their densities are similar.
In addition, supercooling phenomena are very weak non-existent, if we stick to conditions of use close to those of the envisaged applications further.
They also have the advantage of being chemically inert, non-corrosive, impervious to water and admissible from the point of view of sanitary requirements.

WO 93/01250 PCe / FR92 / 00636 13 '''.'t''-' ~ =. 9 ~ a : ~ ~. ~,: ~ ~ ~ 3 Admissible ALCALs, covering a field of temperature corresponding to a wide range such as most commonly required in the industry, are trained chains ranging from C8 to C100, more especially from C8 to C50.
In these ALCAL, the constituent chains are Cnp or Cni or Cnp and Cni. These chains can be Cni / Cni, or Cnp / Cnp or Cni / Cnp, or CNP / Cni. Alternatively, they differ from several links, in particular of more than 4 or 5 carbon rings. We for example ALCALs containing at least one string C14 or more, other string (s) with more than 5 additional carbon links.

According to a particular provision of the invention, the ALCAL above contain at least one chain with a or more substituents as defined above.
Among these substituents, there will be mentioned groups carboxyl, esters and halogens, which may occupy advantageously one or both ends of the chain.
According to the requirements to be met 'for a given application, those skilled in the art will choose the most appropriate substitutions to get the T value desired. Similarly the proportions of each cha ~ .ne will be easily chosen by considering the label diagrams 8 as illustrated by the examples.
As mentioned above, one or more of the constituents of ALCAL may be present doping. The molar proportion of each dopant is then in the order of less than $ 5.
In another group, the alloys of the invention are made from mono or poly organic compounds ~ t3 ~. ~~~~ 7 ~ 14 cyclical, especially aromatic, with the exception that indicated above substituted or unsubstituted benzene.
Alternatively, it is heterocycles.
In another group still the alloys are formed from hydrocarbon chains having one or several rings and / or one or more heterocycles.
It is recalled that, in an advantageous form of the invention, these different alloys are doped.
In yet another group of the invention, the Organic compounds are polymer chains.
In another family of alloys of the invention, A and Z belong to different classes of compounds.
Favorite alloys of these different families are binary and correspond to formula (II).
Axa Bxb (II) with xa + xb = 1, again A1_x Bx Other alloys are ternary and present the formula (III).
Axa Bxb Cxc (III) aVAC xa + Xb + xp ~ 1 Other alloys are still quaternary and correspond to formula (IV).
Axa Bxb Cxc Dxd (IV) aven xa + xb + xc + xd ~ 1 In these formulas the various constituents A, B and where appropriate C and D and indices corresponding to WO 93/01250 PCf / FR92 / 00636 respective molar concentrations; respond to requirements defined above and B, C and D show the meanings given above for A but are different from each other.
Other alloys contain more than four organic compounds, namely 5, 6 or more. .
The invention also aims at a method of preparation of the compositions defined above.
For this purpose, the compounds are used organic substances defined above according to the proportions desired in the final alloy and subjected to classical techniques such as fusion-crystallisation, melt-quenching, dissolution-evaporation, simultaneous sublimation, the elevating zone or chemical interdiffusion. The zone technique is described in particular by Kolkert WJ, thesis 1974, Utrecht, Netherlands.
In an advantageous embodiment of the invention, to prepare the ALCAL, when all the Cn are liquid at room temperature, the solution is formed desired liquid by mixing and stirring the compounds of initially used in the proportions desired in the alloy. When all Cn starting; or some of them are solid, we proceed by dissolution of commodities according to the appropriate proportions in a common solvent such as ether, followed by evaporation of saluting (preferably under a stream of inert gas). In In the alternative, the weighed products are subject to a merger shaking to ensure the homogeneity of the product, then soaked.
Alternatively, the compositions of the invention are obtained by operating according to separative methods, which presents the interest of using the by-products of WO 93/01250 PC.'T '/ FR92 / 00636 the oil industry. Thus, we submit a mixture of organic compounds containing the desired composition an extraction step to isolate the latter.
When this mixture does not contain all the compounds desired organic and / or sought, the mixture is treated in such a way as to enrich it in one or more constituents or, as the case may be, to eliminate them, until obtaining the desired composition.
In general, the invention provides, for a same temperature level, several formulations admissible, which allows a choice according to the conditions and / or availability of commodities.
The implementation of alloys offers indeed the possibility to choose the content and therefore to search for suitable formulations for optimum performance of stored energy and / or to meet the requirements for at the temperature of use and / or at the window thermal o desired.
The work carried out allowed to show the feasibility of at least three functions of great interest, know those of energy sensor. molecular alloys allow to store and restore important amounts of heat and this practically temperature constant; at the kg scale, and even the mg for the case particular of ALCAL, supercooling is very weak nonexistent.
- temperature smoothing. a space surrounded by a molecular alloy of the invention can be maintained approximately at the temperature. T (included in the transition interval of the alloy). When the outside undergoes large thermal fluctuations, the increase in temperature is reduced by the storage heat in the form of latent heat, and all abrupt lowering of temperature will be minimized by the inverse transformation, - Thermal screen . molecular alloys can be used to slow down the effect of a wave thermal.
The tests carried out (mg, g, kg scales) on Molecular alloys of the invention have shown that these materials possess particularly excellent yields and thermal reliabilities and their resistance to cycling thermal is remarkable.

For example, a guarantee of 30 years of service can be ensured in a cycling rhythm every day for molecular alloys whose domain the melting point does not exceed 4 ° C and the density of constituents is close, which is the case of alkanes.
(All properties that are not possessed by hydrates saline, conventional MCP).
The advantageous properties of the compositions defined above are put to use by using them in as phase change materials for storage and the restitution of energy at a temperature level given as required in a particular application, The invention therefore aims at the application as a phase change materials of formed compositions of one or more molecular alloys, such as defined above, this application being characterized in what we implement a composition capable of storing and restore the thermal energy to a level of temperature. T, over a temperature range 6, strictly corresponding to those required for given application.

'i ~':>'': r ~ 'U 1 ~
! I tJs The invention aims in particular as MCPAM, the different Axa Zxz compositions defined above in packaging appropriate for an application given.
In these applications, the basic principle is on the fact that a non-equilibrium thermodynamics will be created and will necessarily be followed by a path to return to equilibrium. The MCPAM will either heat up by taking calories at outside environment to melt or cool in restoring calories to the outside environment for solidify. In both cases, the transition will manifest itself by a long, almost isothermal stage (its slope will be weaker than sS will be smaller).
Thanks to the characteristics mentioned above, MCPAM of the invention allow to respond to many unmet needs to date, in very varied. For example, the agro-food sectors paramedical, and those related to the protection or domestic uses.
Thus, in the agri-food sector, all non-breaking problems of the cold chain are concerned. The alloys of the invention can provide responses for thermal protection and / or transport of foodstuffs typically from -50 ° C to about 100 ° C.
In the gamma from -50 ° C to -10 ° C, these MCPAMs are particularly suitable for bulk transport, at the individual scale of frozen products, or for their conservation. Their use makes it possible to guard against power outages in freezers, (large surfaces and family) by equipping these are appropriate MCPAMs.

WO 93/01250 PC1 '/ FR92 / 00636 19. ,. ,.
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The use according to the invention of the MCPAMs described above is also of great interest in the field temperature from -10 ° C to + 6 ° C. So, it allows to ensure in the best conditions the transport of drinks and ice cream for example in cooler type while keeping them at the temperature desired. It is also possible to carry out plates, dishes or dish-holders ensuring freshness required.
MCPAMs that are admissible in this area of temperature can also be used to develop refrigerated stalls; which, for example, meets the needs of fishmongers.
The MCPAMs according to the invention also prove valuable in a temperature range between +6 ° C and +16 ° C
which is the one required for food not to undergo freezing but requiring conservation and / or tasting at a temperature relatively low, for example dairy products, fourth range products and chambered wines.
MCPAMs with a transition temperature of phase greater than + 16 ° C., and in particular up to + 35 ° C.
have an interest in chambering some other wines requiring a higher temperature for their tasting, and in the kitchen for butter dishes, sauciers, yogurt makers or packaging for leavened dough, or for the maintment of pastries or warm pies.
In areas of higher temperatures, + 35 ° C to + 100 ° C approximately, the MCPAMs defined above are useful for ensuring thermal stabilization of devices, for example fermenters from ~ + 35 ° C to + 37 ° C, or for keeping warm, at a stable temperature, up to temperatures up to + 100 ° C. We will mention ~, ~~. ~ 5 ~ 20 example keeping warm cooked meals (which is of great interest to caterers, in particular deliveries at home, cafeterias, corporate restaurants, supermarkets), dishes, dish holders, baby bottles, porridge plates, plates hot, warming dishes, meal trays, hot drinks.
A marker of color and / or flavor of quality food will be favorably associated with ALCAL for alert the consumer in the event of an accidental the food.
MCPAMs particularly suitable for these applications are formed of molecular alloys having a thermal window not exceeding + 2 ° C, or better + 1 ° C, or even less.
ALCAL is in this respect MCPAM
particularly effective. They also have a remarkable admissibility from a military point of view.
Various formulations of ALCAL having a transition temperature T in the aforementioned fields are data in the examples. It is understood that other appropriate formulations will be easily developed by referring to the different parameters defined above.
If the year remains in the case of consecutive Cn (from same parity or not), the temperature level has a role relatively decisive both on the possibilities of syncrystallization only on the label O and all the more that goes with the level of En. This coefficient is used to appreciate the degree of homeomorphism molecular Ek. In this is defined In = 1. -gn n minimum 21 s ~; y: ~ ~~~ ('~
Fs ~ ~ JZ J.
where is the difference nA - ng between the 2 CnA and Cng molecules to compare, and nminimum the value of, n of the shortest molecule.
At low temperatures, we will have mainly interesting possibilities of eutectic mixtures of ALCAL
(with 0 = 0 ° G), as the level of temperature T will rise, syncrystallization limits will increase and high-label beaches will become more important.
If we choose non-consecutive Cn, the roles 0T and En will play in the same direction and will be applied to the level of T explained above.
It is thus that a significant difference between the nA and nZ will be associated with oT all the stronger and En all lower than the T level will be low. On the contrary, the more T level will be high, plus we will have ALCAL to ô admissible with distant n's and so bigger will be the possibility to have different formulations for ûn Tg required because it will then be easier to increase the number of components.
Among the ALCAL, we will mention those trained in particular from C8 to C16, in particular each of these doped alkanes, binaries, ternaries, quaternary or more, consecutive or not, if applicable also doped, with molar proportions such as the Tg values strictly correspond to the requirements required.
The applications mentioned above will be performed advantageously with ALCAL containing mostly chafnes of more than 14 atoms of carbon, if necessary doped.

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In the paramedical field, applications are also very diverse and cover in particular an area of temperature ranging from -80 ° C to + 75 ° C.
Particularly concerned sectors include conditioning, protection instruments, isothermal manipulations or controlled temperatures, clothing development isotherms, functional insufficiencies and therapies symptomatic.
For packaging applications and / or transport, with no break in the cold chain, MCPAMs that are given temperature in a range from -80 ° C to + 16 ° C
about.
Thus, MCPAMs having a phase change to a temperatures close to -80 ° C are particularly useful for the preservation and / or transport of bone grafts and / or tendons, plasma or serum.
MCPAMs admissible around -30 ° C
allow to perform in the best conditions the transport of drugs or plasma.
It is particularly interesting to use MCPAM receivable around -20 ° C for bone banks or again for post-mortem transport.
At higher temperatures, MCPAMs from -10 ° C to + 6 ° C are of great interest. Is the thus uses with advantage including lice transportation organs or amputees and for the preservation of red blood cells or organs.
MCPAMs having phase transitions in a range between + 6 ° C and + 16 ° C also present a W ~ 93/01250 PCT / FR92 / 00636 23 mt ~ ~ ~ ~~
high interest. They allow in particular to preserve various types of tissues or cells such as corneal grafts or some sperms. They also allow conservation vaccines that can be so transported and available to the patient at the time of an accident In a temperature range greater than + 16 ° C
approximately, MCPAMs are used more particularly for the transport of medicines.
Other applications in the paramedical field refer to isothermal or temperature manipulations controlled:
The MCPAMs of the invention having a temperature of transition in a range from -80 ° C to -10 ° C
are particularly suitable for cryomicrotomy, for example example of spine or joints. Those who own a transition temperature in a range from About 10 ° C. to + 6 ° C. are of great use for the defrosting plasma and cells for exploration hemodynamics, the analysis of blood gases, for sterile tissue samples, for example from muscles or of vessels, and cell cultures.
MCPAMs with transition temperatures higher, especially in a temperature range of + 20 ° C and above, are useful in increasing order of temperature, lice and crops of specimens (from +20 ° C to +50 ° C) in electrophysiology of nerve (between + 30 ° C and + 35 ° C), for the warming of transplants, for enzymatic tests (between + 35 ° C and + 37 ° C) and for warming blood before transfusion (towards + 37 ° C).
Other applications in the paramedical field concern functional deficiencies and symptomatic therapies.

~. '_ ~ ~~ ~' l1 24 dt! . e .., Thus, the MCPAMs of the invention having a phase transition - in a range of -ZO ° C to + 6 ° C, are especially suitable for pre- and post-treatment operating procedures, particularly in ophthalmology (between 0 ° C and + 6 ° C), - in a range of + 6 ° C to + 16 ° C approximately, care or cryotherapy for example for to build bandages for sprains, and - in a temperature range higher than I5 + 16 ° C, in cryotherapy, to obtain effects refreshing and especially for some care (around + 35 ° C).
- for the range above + 37 ° C, they will be useful for incubators or for ~ warming local or general patient during operation or in post-operative care (blankets, mattresses, for example mattress with built-in resistance in which the MCPAM
may be associated with other materials, such as fibrous or expanded materials for reasons of comfort).
Thermally insulating layers on the outer faces, who are not in contact with the patient, will prolong autonomy of operation.
They will also be useful in calathérapie for for example treating rheumatism, or latent heat pumps.
To facilitate use in a family environment, especially in this type of application, provision is made to add to the MCPAM a low dose of dye, of high quality in order not to disturb the admissibility sanitary materials. This provision allows a 25 _ W ~ ~~~~~
easy identification of the T-level of the application (examples blue for T = + 6 ° C, green for + 25 ° C, colorless for + 35 ° C, yellow for + 39 ° C, orange for + 45 ° C and red for + 50 ° C).
The requirements for the use of this or that range of temperature will come naturally from the medical profession.
Finally, it should be noted that having access to MCPAM with Tg label, at the desired T level, offers the practitioners the opportunity to carry out clinical tests at various temperatures in order to identify the most relevant ones.
In these applications in the paramedical field, at the different temperature levels considered, the use of MCPAMs constituted by ALCALs, the case with functional groups proves to be especially advantageous.
The MCPAMs of the invention also make it possible resolve security and / or protection issues products, installation and premises. These applications relate to a wide range of temperature typically from -80 ° C to + 200 ° C.
They constitute a solution of great interest especially for - the transport of flammable chemicals and / or dangerous, at low temperature, - the proteotian of electrical installations, electronic or computer systems, where they are possibly coupled with alarm systems (the temperature ranges lice this type of use are very varied, up to + 200 ° C and above, for example in the case of fires), a temperature range particularly interesting is between + 70 ° C and 90 ° C, ~ I> ~
- against untimely power outages, this which avoids the use of very expensive contracts concerning the non-breaking of current in installations requiring an isothermal hold, for example ripening fruit or vegetables, or vats fermentations.
The MCPAMs of the invention are also particularly useful in the field of protection as a solution to the problems of saving energy. They constitute highly effective means of protection for example for cumulus, hot baths, bringing additional comfort, the thermal tanks for heat pumps (+ 4S ° C to + 55 ° C for sources warmer, and + 3 ° C to + 10 ° C for cold sources), cold heat shields for large assemblies (range from + 4 ° C to + 8 ° C), or domestic heating (by latent heat) that can be integrated as an element of decoration (transparent objects or not, statues by example).
In addition, they can be used in cultures and in particular provide protection for roots of plants in a greenhouse, avoiding complete heating from the greenhouse, or in test tube racks.
In domestic applications or the MCPAMs of the invention will be used with advantage for self-contained artioles home or outdoors, such as curlers, irons ironing, baby bottles, camping for example.
They also make it easy to manufacture increasing or decreasing thermal gradients that can be as strong or as weak as you want and so are usable for gradient speaker control such as those required for example in crystal growth.

T3 ~ ~ ~~ .dj In the different applications mentioned above above, use is made advantageously for the development of MCPAM, ALCAL, substituted or not, if applicable doped, as well as cyclic and heterocyclic compounds as defined above. Other molecular alloys interesting include hydrocarbon chains, different from alkanes with functional groups.
Other molecular alloys still consist of polymer chains.
It goes without saying that in the various applications MCPAM the way of use can be diversified, a MCPAM that can be used alone, associated with one or more other MCPAMs and / or MCP so as to constitute multilayer (which is advantageously usable for form temperature gradients).
In many applications, MCPAM
operates in relay with a source of energy.
In general, the invention provides the means of making the most suitable materials for a given application. This manufacture is all the more facilitated that the compositions of the invention are malleable. Liquid compositions are thus perfectly adapted and are solidified on a forma appropriate.
MCPAMs are packaged in structures adapted to their use.
These packages comprising, in a manner general, a double wall made of a material with high power thermal insulation, at least with regard to the wall in contact with the outside environment when both walls are made using different materials.

WO 93! 01254 PCT / FIt92 / 00636 ~ iiJ LJ

Suitable materials include glass, metals, the material marketed under the brand name plastishieldR, based on glass and polymers, the plastics and expanded polymers with cells closed.
As an indication, mention may be made of polyolefins, like high density polyethylene (HDPE) or low density (LDPE) or polypropylene (PP), the polyesters in Especially polyethylene terephthalate or acrylates, styrenes, such as polystyrene (PES) or expanded polystyrene (SE), or acrylonitrile-butadiene styrene (ABS) polyamides (PA), polyvinyls such as polyvinyl chloride (PVC), fluorinated polymers as polytetrafluoroethylene or PTFE.
These materials make it possible to produce surfaces smooth, corrugated, or alveolate.

2 ~ They may be reinforced where appropriate by example by struts to ensure an outfit satisfactory structure.
To get them in shape, we use usual techniques of plasturgists. So for make gourds, cans, bottles, flasks, pitchers, kegs, barrels, tanks, tanks, bins, crates, on uses methods of infection, infection blowing, Injection injection by bi-orientation, extrusion blowing, blowing or rotational molding.
Packaging such as jars, cups, trays, bells, meal trays, honeycombs or not, with reinforcement or not, and, where appropriate, clipages, will be manufactured by thermoforming or injection.
When conditioning does not require double wall, for example to make containers of the WO 93/01250 PCT / Fdt92 / 00636 f. .:
d ,; : r.
type pouches, flexible doses, cartridges, sleeves, bags, sachets, briquettes, we will have recourse advantageously to extrusion or calendering techniques.
Packaging filling by MCPAM is made from the liquid or powder composition.
It will be possible, if necessary, to preform the alloy liquid placed in a matrix by solidifying it with nitrogen liquid. It can then be transferred to the solid state in final packaging.
The invention will be illustrated hereinafter by examples of preparation of molecular alloys and their applications like MCPAM.
In these examples, reference is made to Figures 1 to 9, which represent the diagrams giving the b labels of various ternary molecular alloys.
Characterization of materials 1. RX analysis (Guinier-Lenné, Guinier-Simon) for specify the number and nature of the phases involved in function of the temperature, highlight the phase changes, and prove that prior to the merger the materials are in the form of alloys (and not mixtures of initial compounds).
S0 2. Differential Scanning Calorimetry (AED, DSC). for the determination, precise temperatures and associated enthalpies, respecting the two following requirements S5 - prior calibration carried out strictly in the same experimental conditions as those of analyzes, WO 93/01250 PCT / F1t92 / 00636 i ~ l: J ~~ 'J ~ 30 - use of AED or DSC signals by the "form factor method" developed by Haget and al, Calorim. Anal. Therm. (1987), 18, 255, and Courchinoux et al., J. Chim. Phys. (1989), 86, 3, 561.
The following examples numbered 1 to 5 are report to ALCAL, examples 6 to 9 to alloys Molecules containing or formed functional chains acid and Examples 10 to 12 to, applications of Molecular alloys of the invention. (Note that values of Tg and b given in these examples are understood T and O in ° C).
Examples 1 to 7 respectively relate to EXAMPLE 1 Sputtered ALCAL Formulations - example 2 binary ALCAL formulations doped - example 3. ternary ALCAL formulations and more doped, - example 4. the study of the evolution of ALCAL
binary, . ALCAL binary of the same parity [1) consecutive;
2) not consecutive], ALCAL binary with different parity (1) consecutive: 2) nonconsecutive], - example 5: ternary ALCAL
a) study of the evolution of ALCAL [1] consecutive, 2) not directly consecutive], b) various ternary ALCAL formulations (1 to 9) WO 93/01250 PC'l '/ FR92 / 00636 . Notes on alkanes.
When 8 5 n <_ 20, the forms before fusion of odium alkanes (Cni) are of the hexagonal type and those with n pairs (Cnp) of triclinic type.
When 21 5 n 5 43, all the alkanes are of type hexagonal before fusion.
Finally when n> _ 44, all the alkanes are orthorhombics before fusion.
. General method of preparation.
When using all solid alkanes, or some of them solid, we first dissolve the starting alkanes, in the appropriate proportions, in a common solvent such as ether, and then the solvent, preferably under a stream of inert gas such as nitrogen. Alternatively, the products are subjected to fusion by stirring, to have a homogeneous mixture, then to a tempering.
lie 1; Formulations of doped alkanes Table 1 below shows doped alkane formulations. For each formulation of alloy, the transition temperature T is indicated in ° C, the thermal window δ in ° C, and the variation of enthalpy 0H in J / g.

'~~~. ~~ â~
Cn Formulations T (C) b (C) oH (J / g) ____ ______________________________________________________ C8 CBp, ggp 0100.020 -57.2 1.4 170 C9 090.995 0100.005 -53.0 1.3 117 010 C100, gg0C11p, 010 -29.0 1,2,196 011Cl10, gggCl2p, p010130,001 -25.0 1.3 141 012 0120,9930110,0040130,004 -9,4 1,2,210 013 0130.9990110.0010120.001 -4.7 0.6 162 014 C14p, 9gg0130,001 +5.9 1.5 216 015 0150.994C14p, 0010160,005 +10.0 0.6 159 016 0160,9960150,0030170,001 +17.9 1.0 227 017 0170.998C15p, 0010160,001 +22.2 0.5 168 018 0180.9940190,006 +28.4 0.9 232 019 Cl9p, ggp0200.020 +32.3 0.9 168 020 C200, g8p0190.020 +36.4 5.0 240 020 C20p, gg40190,006 +36.5 1.6241 021 0210.997C230, p03 +39.9 0.3 156 ~

022 0220.9900210.020 +43.3 0.9 152 022 C22p, gg70210.003 +43.8 0.9 152 023 0230,9960220,0020240,002 +47.5 0.2 158 023 C23p, gg00240.020 +48.2 0.8 160 024 C24p, g50C22p, 050 + 50.1 0.2 157 024 C24p, g3p0200.050C22p, 020 +50.5 1, l 158 024 0240.9500260.050 +50.9 0.2 158 025 C25p, gg2C24p, p05C26p, 003 +53.8 0.2 161 026 0260.999C24p, 002 +56.9 0.1 161 026 0260.9990250,001 +56.9 0.1 161 It will be noted from the table that the different doped formulations studied have a transition on a narrow temperature range, always lower at 2 ° C, except for formulation, and not exceeding not 1 ° C for the majority, the oH being mostly above 150 J / g and even exceeding for some 200 J / g.

33 Ni.i ~. ~ J ~ iU
Exe 1n e 2: Spiked binary ALCAL formulations.
Table 2 shows the following characteristics of doped binary alloys.
Examples Cn-Cn Formulation T (C) (C) oH (J / g) C8-010 C8p, g30 0100.060Cg0.010 -57.7 2.8 170 010-011 0100,690 0110,3000120,010 -35,9 2.1 137 010-011 0100.490 C11p, 490C120, p20 -33.2 4.2 129 010-011 0100.310 C11p, 680Cl2p, p10 -30.4 4.2 125 011-012 C110, gg0 C12p, 100C13p, 020 -24.9 1.1 141 011-012 0110.490 0120.4900130.020 -21.6 2.0 134 012-013 0120,690 0130,3000110,010 -13,5 2,7 146 012-013 0120.480 C130.4g00110.040 -11.8 2.2 146 012-013 0120,200 C130,7gp0110,020 8, ~ 0 2,4,150 013-015 C130.78p 0150.2000140.020 -5.0 1.0 144 013-014 0130.690 0140.3000150.010 -3.9 1.4 152 013-014 0130.485 0140.4900150.025 -2.5 1.8 152 013-015 0130,530 0150,4500140,020 0 7.0 148 014-016 0140,790 0160,200ClSp, Olp +2,9 2,0 159 014-016 0140.990 0160.1000150.010 +3.2 1.9 164 014-015 0140.400 0150.5700130.030 +5.2 3.9 147 013-015 0130,200 0150,7900140,010 +6.0 8.0 159 014-015 0140,260 0150,7000160,040 +7.7 2.0 155 014-016 0140.410 0160.5800150.010 +8.8 4.9 148 015-016 0150,840 0160,1300140,030 + g.5 1.0 153 015-016 0150,840 0160,1500140,010 +10.5 0.8 150 015-016 0150.640 0160.3300140.030 +10.7 2.0 152 015-016 0150.690 0160.3000140.010 +11.2 1.3 156 015-017 0150.6850170.300 +11.3 1.3 146 0160.015 015-016 0150.490 0160; 5000140.010 +12.3 1.7 157 015-017 0150.480 0170.5000160.020 +14.0 3.0 150 014-016 0140,100 0160.8900150.010 +16.0 3.2 175 ~ 'ci .L e ~
r>

015-017 0150.300 0170.690 0160.010 +17.0 4.4 154 016-018 0160.690 0180.290 0170.020 +18.0 1.9 170 016-018 0160,550 0180,440 0170,010 +19.8 2.0 165 016-017 0160.300 C170.685C15p, O1OC180.005 +19.8 1.5 160 015-017 0150,100 0170.890 C16p, 010 +20.4 2.9 158 016-017 C16p, 100 C170.8850150.005C180.010 +21.3 1.1 165 017-018 0170.300 0180.690 0180.010 +25.7 1.2 159 018-022 Cl8p, g70 0220,100 0200,030 +27.8 1.8 164 018-019 0180,800 0190,170 0170,030 +27.9 1.5 156 018-020 0180,780 0200,200 0190,020 +28.3 1.8 155 018-019 0180.780 0190.200 C20p, 020 +28.4 1.5 155 018-020 C180.7gp C20p, 2pp 0220.020 +28.5 2.0 154 018-019 0180.580 0190.400 0170.020 +28.8 1.6 156 018-019 0180.580 0190.390 0200.030 +29.4 1.6 156 018-022 C18p, 700 0220.280 0200.020 +30.8 3.9 139 018-020 0180,540 0200,450 0180,010 +30.8 1.9 146 018-020 C18p, 530 0200.440 0220.030 +30.9 2.0 146 018-020 C18p, 190 0200.800 0220.010 +33.9 2.0 150 018-020 0180,200 0200,780 0190,010 +33.9 2.0 150 019-020 0190.300 C20p, 680 0210.020 +35.2 0.9 151 019-021 0190.280 C21p, 690 C20p, 020 +35.5 1.2 151 020-022 0200,770 0220,200 0180,030 +37.5 0.9 146 020-022 0200.7840220,200 C19p, 004C210,002 +37.6 0.8 146 020-022 0200,800 0220,170 0210,030 +37.8 0.8 146 020-022 0200,780 0220,200 0240,020 +38.0 0.8 145 020-024 0200.870 C24p, 110 0220.020 +38.6 1.2 145 020-022 0200,480 0220,480 0210,030 +39.7 1.5 148 020-022 0200,4710220,5240180,0030210,002 +39.8 1.3 148 020-022 C20p, 500 0220.480 0240.020 +40.0 1.5 147 020-022 C20p, 4p0 C22p, 580 0180.020 +40.1 1.5 147 020-022 C200.376C22p, 620 0180.0020210,002 +40.3 1.2 147 020-022 0200,3800220,6000240,020 +40.6 1.4 147 020-022 C200.3pOC220.690021p, 010 +41.2 1.4 147

3 5: : - ..:; . ~
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020-022 C20p, 27gC22p, 717019p, 002C21p, 002 +41.3 1.2 147 020-022 C20p, 180022p, 800018p, 020 +41.8 1.1 147 021-022 C21p, 490022p, 490023p, p20 +41.8 0.6 150 020-022 C20p, 184C22p, 812C19p, 001C21p, pp3 +42.0 0.9 147 020-022 C20p, p900220, 900021p, 010 +42.8 0.9 150 020-022 C20p, p93022p, gp3C19p, 001C21p, 003 +42.9 1.0 150 021-023 C21p, 5800230.400C22p, 020 +43.3 1.3 152 022-024 C22p, 700C24p, 280C20p, p2p +45.2 0.8 153 022-023 C22p, 4gpC23p, 500C24p, 010 +45.7 0.5 155 022-024 C22p, 700C24p, 280C23p, p20 +45.7 0.9 152 022-024 C22p, 680C24p, 300C26p, 020 +45.7 0.8 153 I5 022-024 C22p, 300C24p, 6800200.020 +48.1 0.9 155 022-024 C22p, 2800240,700C23p, 020 +48.4 0.9 156 022-024 C22p, 300C24p, 680C26p, 020 +48.6 0.9 155 023-024 C23p, 470C24p, 500C22p, p30 + 48.9 0.5 158 022-024 C22p, 050C24p, 9300230.020 +50.2 0.4 158 022-026 C22p, 500C26p, 490C24p, 010 +50.2 2.6 157 024-026 C24p, gp0C26p, 08pC20p, p20 +50.2 0.4 158 024-025 C24p, 500C25p, 49pC26p, p10 +51.7 0.4 159 024-026 C24p, 490C26p, 500C20p, 010 +52.2 0.9 158 023-025 G23p, 100C25p, 890C24p, p10 +53.0 0.9 161 024-026 C24p, 490C26p, 500C22p, 010 +53.5 0.9 162 026-032 C26p, 800C32p, 190C30p, 010 +57.3 2.0 160 028-032 C28p, 7gpC32p, 200030p, p1.0 +62.4 0.4 160 030-032 C30p, 100032p, ggpC31p, 0100330,010 +66.2 0.5 159 035-036 C35p, ggpC36p, pgpC37p, 02p +75.2 0.4 160 044-050 C44p, 765050p, 210046p, 0100480,015 +86.7 0.7 223 044-050 C44p, 490050p, 485046p, 005048p, 020 +87.4 0.5 220 044-050 0440.395050p, 585046p, 005048p, p15 +89.2 1.5 225 046-050 C46p, 100 C50p, ggp C44p, plp +91.9 0.6 215 Example 3, Ternary ALCAL Formulations, and more, doped.
Table 3 below contains the characteristics of doped ternary alloys or alloys higher.
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93/01250 3 ~ PCT / FR92 / 00636 i, ~ 'S; v I

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Ex ~ R.le 4: ALCAL binary. Study of evolution In this example and the following, the degree of molecular homeomorphism Ek is appreciated by the coefficient In defined above where is the difference nA - ng between the 2 CnA and Cng molecules to compare, and nminimum the value of n of the shortest molecule.
I BI,: binary CALs of same parity A and Z are both taken in even alkanes or both taken in odd alkanes.
1 ALCAL consecut ~ s They are of type Cnp-C (np + 2) or of type Cni-C (ni + 2).
Both types have very similar behaviors. We can basically distinguish 4 cases the case. # 12; we then have In 5 0.80, and 0T ~ 20 ° C (0T being the difference between the temperatures of fusion of the two constituent ALCALs of the binary).
Miscibility is incomplete; we have eutectic.
~ $ ~ çl ~: In ~ 0.75; 0 ~ 27.1 ° C, a eutectic is formed for the overall composition 82 ~ G8 + 18 ~ C10 T = -62 ° C, δ = 0.01 = 190J / g.

"~, ~~, ~, ~~" PCT / FR92 / 00636 , _, ..- ~.,. ~. ~ J ~
39 ~ ' ~~ 'û
MCPAM-forming compositions are obtained interesting for C81-x ClOx with x <_ 0.15, especially with, x = 0.05 (T = -57.5 ° C, δ = 2.8, and oH = 170 J / g) x = 0.11 (T = -59.3 ° C, b = 1.6, oH = 180 J / g).
C1Q-C12. In = 0, 80, oT = 20.1 ° C ~. we form a eutectic for the overall composition 80 ~ C10 ~ 20 $ C12 (T = -38 ° C, δ = O, oH = 195 J / g).
12 5 n 5 18; we then have 0, 80 <En ç
0.88 and 10 5 0T <20 The more n will increase, the more the miscibility will to extend (in the field of concentration) and more will become narrow.
~ ',, 1 ~ -C14: In ~ 0.83: oT = 15.5 ° C
the miscibility extends but the spindles are wide.
Satisfactory alloys are obtained with pure constituents, especially C12. (In what follows, the thermal windows ô concerning a field of concentration are given with a global label taken equal to an integer . 1 when ô 5 l, 2 when 1 <ô 5 2, 4 when 2 <5 4. On the other hand for particular examples O is given with its real value).
Description of alloys C12 ~, _x Cl4x receivable according to the invention, 0 5 x <0, 05: ô m 2 0, 05 sx <0.15. s ~ 4, for example, xm 0.11: T = -12.0 ° C, δ = 3.1, AH ~ 175 J / g 0.15 S x 5 Gold 22: δ = 2, for example, x = 0.19: T = -14.2 ° C, δ = 1.7, OH = 159 J / g WO 93! 01250 PCTJFR92 / 00636 N ~ ~ i. ~~~~ 40 0, 92 sx 5l: δ = 4, for example, x = 0.95: T = + 5.0 ° C, b = 3.6, oH = 205 J / g ~~ - ~: In = 0.85; oT = 15.5 ° C, we observe a miscibility in all proportions but wide spindles except on the C13 side.
Description of Acceptable C131-x ClSx Alloys 0 <_ x <0, 20: s = 1 0, 20 x <0, 30: b = 2, for example x = 0.200: T = -5.1 ° C, 6 = 0.9, 0H = 144 J / g 0, 30 5 x <0, 40: δ = 4 0, 40 5 x <0, 95: b> 6, for example, x = 0.464: T = -0.5 ° C, δ = 6.0, oH = 148 J / g x = 0.794: T = + 6.1 ° C, s = 7.8, oH = 159 J / g 0, 95 5 x 5 1: b = 4 with doping C130.78 C15p, C140.02: T = -5.0 ° C, d = 1.0, OH = 144 J / g C130.53 C150.45 C14p, O2: T = 0.0 ° C, δ = 7.0, oH = 148 J / g C14-C16: en = 0.86, oT = 12.3 ° C, total miscibility is observed when mixing chains regardless of the proportions. The width of the spindle varies with zones.
Among the alloys C141_x Cl6x, the results obtained with various values of x.
0 5 x <0, 30: δ = 2 for example, x - 0.10: T at + 3.2 ° C, δ = 1.9, oH = 164 J / g x = 0.20: T = + 2.9 ° C, δ = 2 oH = 147 J / g 0, 30 5 x <0, 47: δ = 4 for example, x = 0.35: T = + 4.7 ° C, b = 2.8, aH = 137 J / g 0, 47 5 x <0, 80: δ = 6 W ~ 93/01250 PCTJFR92 / 00636 41 t ;: ~ v ~ G ~
for example, x = 0.60: T = + 9.0 ° C, δ = 4.9, oH 148 J / g 0, 80 5 x <0, 95: b = 4 for example, x = 0.90: T = + 16.1 ° C, & = 3.2, 0H = 176 J / g 0, 95 _ <x __ <1. ô = 2 Spiked 014-016 formulations C140.7gp 0160.200Cl5p, p10: T = + 2.9C, 2.0, 0H 159 = = J / g 0140.890 0160.100Cl5p, OlO: T = + 3.2C, 1.9, 0H 164 = = J / g 0140.410 0160.580C150, O10: T = + 8.8C, 4.9, 0H 148 = = J / g 0140,100 0160,890C150,010: T = + 16.0c, 3.2, aH 175 s = = J / g x: 15-017: In = 0.57; oT = 12.0 ° C
The miscibility is total for C151_x Cl7x, but 6 is more wide in the center right.
0 5 x <0, 20 m 1 0, 20 5 x <0, 425 s 2 for example, x 0.30 = + 11.3C, b = 1 ~, 2, aH = 146 =: TJ / g 0, 425 5 x <0, 57 = 4 for example, x = 0.50 = + 14,1C, b = 2,9, oH = 156 : TJ / g 0, 57 5 x <0, 80 8 = 6 for example, x = 0.70 = + 17.0C, b = 4.4, where is 154 : TJ / g 0, 80 5 x <0, m 4 for example,. x = 0.90 = + 20.2C, b = 2.9, oH = 158 : TJ / g 0, 95 sxs 1 s = 2 C15p, 685C170.300C160.015: T = + 11.3C, ~ 1.3.0H = 146 J / g C150.480C170.500C160.020: T = +14.0C, 6 ~ 3.0, oHa 150 J / g C150.300C170.690C160.010: T = + 17.0C, = 4.4.0H = 154 J / g C150.10pC170.890C160.010: T = + 20.4C, = 2.9, oH = 158 J / g c16-c18: In = 0.88. ; oT = 10.0 ° C

jr 1j v -y All C161-x Cl8x formulations have _ <4.
restrictions for 0.03 <x <0.10 and 0.75 <x <0.97 correspond to enlargements of the solidus-liquidus related to interferences with s sound (this phenomenon appears in several other whether the pure alkanes are same transition, ie that it is induced by the other Cn, as is the case in this binary) 0.10 5 x <0.50. 8 = 2 0.50 5 x 0.57. ô = 4 Spiked formulations C160.690C180.290C170.020 ~ T = + 18.0 ° C, δ = 1.9, 0H = 170 J / g C16p, 550C180.440C170.010 ~ T = + 19.8 ° C, δ = 2.0, 0H = 165 J / g 18 5 n 5 22; then 0.88 <in 50.90 and 7 ° C <oT <10 ° C
The miscibility is total, all the molecular alloys have ô 5 2 alone is felt to be very weak disturbance due to the eventual solid-solid transition (C20 in particular) ~ ', ~ 18-C20: In = 0.89; 0T = 8.6 ° C
The following results were obtained with C181-x C20x O 5 x <0.03 (doping). dal 0.03 5 x <0.05 with transition effect of C18 0.05 sx <0.90: 8 ~ 2 for example x = 0.20: T = + 28.2 ° C δ = 1.6 0H = 154 Jjg x = 0.45: T = + 30.6 ° C d = 1.8 oHml46 J / g x $ 0, $ 0: T m + 33.7 ° C ome2.0 oH = 150 J / g 0.90 5 x <0.97 with transition effect of C20 0, 97 sxs 1: s ~ 1 WO 93/01250 PC1 '/ FR92 / 00636 43 ~ ....,; "~ H ~
w ~; x: .t ~ i With doped binaries, the following results were obtained C180.7g C200.20C190.02 T + 28.3C = 1.8 =

C180.7g C200.20C220, p2 T + 28.5C = 2.0 =

C180.54 C20p, 45Cl9p, o1 T + 30.8c s = 1.9 =

C180.53 C200.44C220, p3 T + 30.9C = 2.0 =

Clsp, ig C200, g0C220, p1 T + 33.9C δ = 2.0 =

C180.20 C20p, 7gCl90, p1T + 33.9C = 2.0 =

It can therefore be seen that the C18-C20 binaries doped or no, answer substantially the same way. So, the doping of a given MCPAM makes it possible to adjust T without affecting b (ni oH) for a value of x.
C19-C21: In = 0.89; ~ T = 8.4 ° C
C191-x C2lx 0 5 x <0.20. ô = 1 0, 20 5 x <0, 90: δ = 2 0, 90 5 x 5 1. 8 = 1 With doping (example) C190.290 C21p, 690 C200.020 ~ T = + 35.5 ° C, 6 m 1.2 GHml51 J / g C20 C2 ?. : In = 0, 90, oT = 7, 6 ° C
It is found that the spindle is thinner compared to those of previous alloys. There is no effect of solid-solid transition of C20 only between 0.02 <x <0.05.
With, x <0.40, we obtain b ~ 1, 0, 40 5 x <0, 75: δ = 2 0, 75 5 x 5 1: ô - 1 Examples of doped formulations, classified according to T
(the 0H are practically equal to 147 J / g) Nv t_ ~ ~. ~~~~
C20p, 7g4 C22p, 2000190,004C21p, 002 T = + 37.6C = 0.8 C20p, 8p C22p, 17 C21p, p3 T = + 37.8C = 0.8 C20p, 7g C22p, 2p C24p, p2 T = + 38.0C 6 = 0.8 c20p, 4g c22p, 4g C21p, p3 T = + 39.7c s = 1.5 C19p, 003 C20p, 471Cl2p, 002C22p, 524 T = + 39.8C = 1.3 C20p, 5p C22p, 4g C24p, p2 T = + 40.0C b = 1.5 C19p, 002 C20p, 376C21p, 002C22p, 620 T = + 40.3C = 1.2 C20p, 3g C22p, 60 C24p, 02 T = + 40.6C b = 1.4 C20p, C22p, 69 C21p, 01 T = + 41.2C = 1.4 Cl9p, pO2 C20p, 279C21p, 002C22p, 717 T = + 41.3C 6 = 1.2 C19p, 001 C20p, 184C21p, 003C22p, g12 T = + 42.0C = 0.9 C20p, p9 C22p, gp C21p, p1 T = + 42.8C = 0.9 C19p, 001 C20p, 093C21p, 003C22p, gp3 T + 42.9C & = 1.0 =

021-023: In = 0.90 ~ OT = 7.1 ° C
0211-x C23x 0 sxs 0, 35. ô = 1 0, 35 <x <0, 60: ô ~ 2 0, 60 sx 5 1. ô = 1 Spiked formulation C21p, 580023p, 4ppC22p, O20: T = 43.3 ° C, 6m 1.3, oH = 152 J / g Ms case: n ~ 22 In> 0.90 0T <7 ° C
From 022-024 inclusive all binaries have total miscibility with 8 <1 whatever x knows. x1 is similarly for doped binaries. We will report later some examples of doped, complementary examples given in Table 2 022-024; In ~ 0.91 ~ 0T = 6.5 ° C
C22p, 7p C24p, 2g C20p, p2. Tm + 45.2 ° C, δ = 0.8, AH = 153 J / g C22p, 68 C24p, 3p C26p, p2 T = + 45.7 ° C, δ = 0.8, AH = 153 J / g C22p, 3p C24p, 68 C20p, p2 T = + 48.1 ° C, δ = 0.9, aH = 155 J / g s H, w SJ. ~ ~ ~ 't ~
0220.28 0240.70 C23p, 02 T = + 48.4 ° C, d = 0.9 oH = 156 J / g C., 3-025: In = = 91; 0T = 6, 1 ° C
0230,100 C250, gg0 C240, O10: T = + 53.0 ° C, δ = 0.9, oH = 161 J / g

5 024-026: In = 0.92; oT = 5.5 ° C
0240.90 C260.0g C20p, p2: T = + 50.2 ° C, δ = 0.4, OH = 158 J / g 0240.49 0260.50 0200.01: T = + 52.2 ° C, δ = 0.9, OH = 158 J / g 0240.49 0260.50 0220.01: T = + 53.5 ° C, 6 = 0.19, oH = 162 J / g If n continues to increase, we can get easily alloys where whatever x is the b is less than 0.5 even for central concentrations. We give two examples 030-032: In = 0.93; 0T = 3.9 ° C
δ 5 0.5 for any x of 0301-x C32x example: C30p, 50 C32p, 50 T ~ + 67.0 ° C, b = 0.2, oH = 160 J / g ~: 44-046_: In = 0, 95; 0T = 1, 6 ° C

6 <0.5 for any x of 0441-x C46x for example: C44p, 50 0460.50 'P s + 87.4 ° C, δ = 0.2, 0H = 220 J / g 2) ALCAL not onc '~ ifa The typical case Cnp C (np + 4) and type Cni C (ni + 4) ~ We find substantially the same evolution as for consecutive ALCAL with an increase of the extent of miscibility domains and an improvement the quality of the thermal window as and when as n increases and aT decreases, this last parameter being relatively determinant.
We must have En z 0.80 to have ~ a miscibility in any proportion. It must be; moreover, that 0T _ <10 ° C for ~~~~ LJ ~ i ~ 46 that all the alloys have been 5 2 It must be in ~ 0,90 so that all the alloys have their ô 5 1.
C18-C22: In = 0.78; AT = 16.2 ° C
C18 (1-x) C22x receivable for 0.05 <x 0.20 with δ = 2 0, 20 <x _ <0, 40 with 'ô = 4 0, 90 5 x <_ 1 with ô = 4 Cl8p, g70 C220.100 C200.030: T = +27.8 δ = 1.8, aH = 164 J / g C180.700 C220.280 C200.020: T = +30.8 δ = 3.9, 0H = 139 J / g C22-C26: In = 0.82; 0T = 12.0 ° C
C22 (1_x) C26x receivable for 0 5 x _ <0.35 with ô = 2 0, 35 <x <0, 75 with ô = 4 0, 75 5 x 5 1 with 6 = 2 C220,500 C260.490 C24p, p1p; T = + 50.2 ° C, δ = 2.6.0H = 157 J / g C28-C32; In = 0.86; 0 m at 8.3 ° C
C28 (1-x) C32x receivable for 0 5 x 5 0.30 with δ = 1 0.30 <x 5 0.90 with 0 = 2 0, 90 <x 5 1 aven δ = 1 C280.7gp c320.200 c3op, 010: T = + 62.4 ° C, s = 0.4, oH = 160 J / g C46-C50: In = 0.91; ~ T = 4.1 ° C
O <1 whatever the content C460.100C500.890C4a0, O10: T = + 91.9 ° C 8 ~ 0.6, 0H ~ 215 0 / g 2 -me ~. type Cnp C (np + k) and type Cni C (ni + k) where k is a greater peace number ~ 4.
To get quite large domains of miscibility with o good quality, we use np (or ni) relatively high so as to have simultaneously In> 0.80 and 0T <10 ° C

WO 93/01250 PCT / FR92 / 0063fi 47 ~
. I ~~. ~ '~' ~~ 1 ~~
~ nlea d bi nai rc av ~ r - 6 ç, ~, ~ f ~ -032; In = 0, 77; 0T = 13.3 ° C
The miscibility is total but the spindle is wide on the side from 032. So that we have 026 (1_x) C32x receivable for 0 5 x 5 0.10 with b = 1 0.10 <x 5 0.25 with δ = 2 0, 25 <x 5 0, 45 with δ = 4 0.90 5 x 5 1 with ô = 4 C26p, 8pp C32p, 190 C300, p10: T = + 57.3 ° C, δ = 2.0, oH = 160J / g 044-050: In = 0.86; aT = 5.7 ° C
044 (1_x) C50x receivable for all x for 0 5 x 5 0.32 with δ = 1 0.32 <x <0.75 with ô = 2 0, 75 5 x 5 1 with ô = 1 0440,3950500,5850460,0050480,015 T = + 89.2 ° C, O = 1.5, oHm225J / g If the np or ni are weak and / or if k is large, we will have admissible solutions in the form of mixtures eutectic alloys (with a few different nar x mr ~ p, C- ~ -. ~~: In = 0.57; m.p. 23.7 ° C
Eutectic at T + 46 ° C
II AL 'AL is born re ~ a ~ l ~ nari té di g ~ 8 A and B belong to one of the even alkanes and the other to odd alkanes or vice versa.
1) A .rA ~ .once.
They are of type Cnp / Cni with i = p + 1 or Cni / Cnp with pai + 1 As in the previous cases, an effect is observed Favorable of the lengthening of the chain. Nevertheless, be considered here the effect of non isomorphism which characterizes the couples Cnp / Cni or Cni / Cnp as long as the n are less than 21. There are therefore two cases At least one of the constituents has an n <21.
In this case, the miscibility can not be total but, as soon as the En are greater than 0.90, we observe, for each binary, 2 relatively small partial spindles, cutting into an excluded zone according to the invention of the point of seen b, zone systematically shifted towards the even Cn.
s', ~ -C13: In ° 0.92; 0T = 4.1 ° C
C12 (1_x) Cl3x alloys are admissible when x 0.30 0.30 5 x <0.90 with 0 ° 4 0, 90 5 x 5 1 with ô = 2 with notably the following undoped formulations C120.70p C13p, 300: T ° -13.6 ° C, o 2.6, OH = 146 J / g C120.500 C130.500 ~ T ~ -11.4 ° C, δ = 2.2, ~ H = 146 J / g the following doped formulations C12p, 690C130.300C110.010: T ~ -13.5 ° C, δ ~ 2.7, dH ° 146J / g C12p, 4gOC.13p, 480C110.040: T ~ -11.8 ° C, b ~ 2.2, CH °
146J / g C120,200C130,7gOC110,020: T ~ -8.0 ° C, 6 ~ 2.4, 0H ~ 150J / g Ci ~ id: In .. 0, 92, 0T ° 11, 4 ° C
We have C13 (1_x) Cl4x alloys when xs 0.50 0 5 x <0, 07 with 8 ° 1 0.07 5 xs 0.50 with 6 ° 2 49, ',,,, ~, r:
; ~ ~ J ~ Wi with notably as undoped formulations 0130,700 0140,300: T = -3.8 ° C, b = 1.2, QH = 153 J / g C13p, 500 0140,500: T = -2.3 ° C, b = 1.7, oH = 152 J / g as doped formulations C130.6gOC140.300C15p, p10: T = -3.9 ° C, δ = 1.4, oH = 152 J / g C13p, 4g5Cl4p, 490C150.025: T = -2.5 ° C, δ = 1.8, oH = 152 J / g 014-015: In = 0.93, oT = 4.1 ° C
We have alloys C14 ~ 1_x) ClSx when x> 0.20 0, 20 <x <0, 70 with ô = 4 0, 70 5 x <0, 90 with b = 2 0, 90 5 x 5 1 with δ = 1 examples of doped formulations C140.400C150.570C130.030: T = + 5.2 ° C, δ = 3.9, oH = 147 J / g C140.260C150.700C160.040: T = + 7.7 ° C, b = 2.0, 4H = 155 J / g ç ~ l ~: In '0.93, oT = 8.2 ° C
We have alloys 015 (1_x) Cl6x unless 0.70 <x <0.90 0 5 x 5 0, 25 with 0 z 1 0, 25 <x 5 0, 70 with 6 m 2 0, 90 5 x 5 1 with 6 m 4 examples of doped formulations C15p, 84p 0160.130 C140.030: T = + 9.5 ° C, b = 1.0, oH = 153 J / g 0150,840 0160,150 C140, p10: T = + 10.5 ° C, b = 0.8, ~ H p 150 J / g C15p, 690 C16p, 300 C140, p10: T ~ + 11.2 ° C, 8 ~ 1.3.0H ~ 156 J / g ~ 1. ~: In ~ 0.94, oT - 3.8 ° C
We have alloys 016 (1_x) Cl7x if x> 0.10 0,10 <x 5 0,40 with 8 m 1 0, 40 <x 5 0, 90 with b = 2 0.90 <x 5 1 aven bm 1 WO 93/01250 PCf / FR92 / 00636 ~~~~ ~~ l j ~
examples of doped formulations 0160.3000170.6850150.0100180.005: T = 19.8 ° C, δ = 1.5, oH = 160J / g 0160.1000170.8850150.0050180.010: 7 = 21.3 ° C, δ = 1.1, oH = 165J / g 017-018. In = 0.94; 0T = 6.4 ° C
We have alloys 017 (1-x) Cl8x for x <0.75 0 S x 5 0, 50 with δ = 1 0.50 <x <0.75 with ô = 2 example of a doped formulation c170.3000180.6900190.010: T = + 25.7 ° C, δ = 1.2, oH = 159 J / g ç19-020: In = 0.95; 0T = 4.7 ° C
We have 019 (1-x) C20x alloys with 0 <1 whatever x except between 0.90 <x <1 example of a doped formulation C190.300C200.680C210.020 ~ T = + 35.2 ° C, δ = 0.9, oH = 151 J / g dème c, ~: all the constituents have a n> 21 The pre-fusion phases of even and odd alkanes being isomorphous, total miscibility is possible and actually intervenes as all the En are greater than or equal to 0.95.
021-022: In = 0.95: OT at 3.9 ° C
All alloys 021 (1-x) C22x are receivable with 6 <1.
example of a doped formulation C21p, 490 0220.490 C23p, 020: T = + 41.8 ° C, b ~ 0.6, oH to 150J / g 022-023: In m 0.95; o7 m 3.2 ° C
All 022 (1-x) C23x alloys are receivable with ô <1.
example of a doped formulation C22p, 4900230.500024p, 010: T = + 45.7 ° C, δ = 0.5, oH = 155 J / g WO 93/01250 PG? / FR92 / 00636 C24-C25: In = 0.96; QT = 2.8 ° C
e; ~
n: .. c example of a doped formulation C24p, 500C250.490C260, O10: T = + 51.7 ° C, α = 0.4, aH = 159 J / g c35-C36: In = 0.97 ~ 0T = 1.1 ° C
example of a doped formulation C35p, ggOC36p, 090C37p, 020: T = + 75.2 ° C, δ = 0.4, oH = 160 J / g 2) Non-consecutive ALCAL
It is appropriate, if one wants broad areas of concentrations, to choose the constituents of such that their En is greater than 0.90 otherwise can usefully generate eutectic mixtures of alloys with weak sxsmp.le C15-C22: In = 0.53: CT - 34.4 ° C
eutectic at T + 9 ° C
> ~ çem 1n e 5: ALCAL ternary a) study of evolution.
The ternaries will be presented in the way following Cnl - Cn2 - Cn3 with n1 <n2 <n3 which also corresponds to the increasing order of the temperatures fusion.
For each ternary, we will give the En for the components taken in pairs in the following order CnI - Cn2: Cn2 - Cn3 and CnI - Cn3. This third value will always be the weakest given the systematic adopted.

WO 93! 01250 PCT / F1Z92 / 00636 ~ T; ~~ ~~.
1) Ternary with consecutive Cn tyus. This is of ternaries Cn-C (n + 1) -C (n + 2) As an example we will mention Cnl Cn2 Cn3 E1,2 E2,3 E1,3 C14 - C15 C16 0.93 0.93 0.86 -C15 - C16 C17 0.93 0.94 0.87 -C20 C21 C22 0.95 0.95 0.90 - -C22 - C23 C24 0.95 0.96 0.91 -The range of acceptable concentration ranges increases as the various E1,2 ~ E2,3 and E1,3 increase. For C14 - C15 - C16 systems and C15 - C16 - C17 where the E1,3 <0,90 the quality ranges b = 1 and b = 2 are small and there are beaches where ô> 4. If all En ~ 0.90, all formulations have at least the label ô s 2 (case C20 - C21 - C22 except of a small area disturbed by the solid transition -solid of C20) and even the label ô s 1 (case C22-C23-C24).
2) Ternary with Cn no ~ 3 jr ~ c ~ lt _m -n. .ona, yf, j ~ er ca ~ ç ~ gønéral: ternary Cn-C (n + 2) -C (n + 4) These are for example the following ternaries (of which 3 cases are detailed later).
Cni - Cn2 - Cn3 E1,2 E2,3 E1,3 C18 - C20 - C22 0.89 0.90 0.78 C20 - - C22 - C24 0.90 0.91 0.80 C21 - C23 - C25 0.90 0.91 0.81 C22 - C24 - C26 0.91 0.92 0.82 We find the same phenomenon as before.
increasing the range of the best label beaches. with increase of the three In concerned, the E1, 3 being the most 53, ~,. , a ~~
: l S.
1 ~~ v V
determining since bringing into play the two Cn the most distant in chain length.
The greater the gaps will be between the various Involved and the more it will be necessary to increase in the scale of alkanes, classified according to their n, to have beaches ALCAL with a good 8. Two examples complete are provided here C20 - C22 - C26 0.90 0.82 0.70 C44 - C46 - C50 0.95 0.91 0.86 If for the first, there are wide ranges of label formulations &> 6, for the latter, however, the most formulations have a label ô _ <1 and others have a 1 <6 5 2.
If we go down in the scale of n and / or if we increase the gap between the Cn, we can generate, by elsewhere, eutectic mixtures of alloys.

;;;; ~. ~ J '~~
b). Examples 1. Study of ternary ALCAL xCl4-yCl5-zCl6 The diagram giving the labels of the different alloys is reported in Figure 1. On this diagram, distinguished 8 areas (areas numbered S1 to S8).
An area oL b <1 ~ Si . Definition of S1 area (18x - 2y + 3z 5 0 y> _ 0, 75 (x + y + z = 1 with the following examples x = 0.03 y = 0.84 z = 0.13 Tg = +9.51.0 x = 0.01 y = 0.84 z = 0.15 Tg = +10.50.8 . Definition of the zone S2 = S not including S1 where S (49x - 21y + 9z 5 0 (x + y + z = 1 with the following examples x = 0.01 y = 0.49 za 0.50 Tg = +12.31.7 x = 0.01 y = 0.69 z = 0.30 Tg = +11.21.3 x = 0.07 y = 0.56 z = 0.37 Tg +10.72.0 x - 0.26 y 0.67 z 0.07 Tg +7.72.0 Definition of zone S3 (x 0.7 (3y - 5z 5 0 (x - 4y - zz 0 (x + y + z = 1 5 5 ~ t ~
~
~ 2 e ;;
..

especially with the following examples x = 0.73 y = 0.14 z = 0.13 Tg = +3.62.0 x = 0.89 y = 0.01 z = 0.10 Tg = +3.21.9 x = 0.79 y = 0.01 z = 0.20 Tg = +2.92.0 Two zones o ~ 2 <<_: Sd . Definition of S4 (4x + 29y - z 5 0 (x + y + z = 1 with in particular the following example:

x = 0.10 y = 0.01 z = 0.89 Tg = +16.03.2 . Definition of S5 total triangle excluding: S1 S2 S3 S6 S7 and Sg with the following examples x = 0.14 y = 0.23 zm 0.63 Tg + 11.93.1 =

x = 0.21 y = 0.56 z = 0.23 Tg + 8.52.3-=

x = 0.24 y = 0.33 z = 0.43 Tg +9.53.9 =

x = 0.43 y = 0.33 z = 0.24 Tg + 6.52.6 =

x = 0.57 y = 0.17 z = 0.26 Tg + 5.32.6 ~

x = 0.64 y 0.01 z 0.35 Ta +4.72.8 Two areas oti 4 <6 <6 . Definition of S6 (xz 0, 2 (y S 0, 3 (19x + 9y - 21z S 0 (x + y + z = 1 WO 93/01250 PCT / 1: R92ionfi ~~
~, ~ j; j. ~~~~~ 56 with the following examples x = 0.33 y = 0.07 z = 0.60 Tg = +9.94.4 x = 0.41 y = 0.01 z = 0.58 Tg = +8.84.9 x = 0.32 y = 0.24 z = 0.44 Tg = +8.84.4 . Definition of S7 (x - 4y - z> _ 0 (3y - 5z> _ 0 (x + y + z = 1 An area where 8> 6: SA
. Definition of Sg (x 5 0.2 (z> _ 0.7 (4x + 29y - z> 0 (x + y + z = 1 with particular example following x = 0.17 y = 0.07 z = 0.76 Tg = +13.87.4 2. Study of ternary ALCALs xCl6-yrCl6-zCl7 The diagram giving the labels of the different alloys is shown in Figure 2.
There are 5 areas (renumbered areas of S1 at S5).
üne, ~ zone where &<_ 1 ~ Sy . Definition of S1 (3x + 9y - 17zz 0 (x + y * za 1

7 i, e ~ ~ ai ~ ~ ~ ': ~
with the following examples x = 0.83 y = 0.15 z = 0.02 Tg = + 10.6p, 9 x = 0.87 y = 0.07 z = 0.06 Tg = +10.31.0 An area oL 1 <ô <2: S ~
. Definition of S2 total triangle excluding S1 S3 S4 S5 with the following examples x = 0.77 y 0.17 z = 0.06 Tg = +10.81.3 =

x = 0.77 and 0.07 z = 0.16 Tg = +10.91.4 =

x = 0.67 y 0.30 z = 0.03 Tg = +11.41.4 =

x = 0.50 y 0.48 z = 0.02 Tg = +12.41.7 =

x = 0.36 y 0.47 z = 0.17 Tg = +13.52.0 =

x = 0.27 and 0.66 z = 0.07 Tg = + 14.92.0 =

x = 0.70 and 0.03 z = 0.27 Tg to +11.41.4 =

x = 0.06 and 0.67 z = 0.27 Tg = +16.51.9 =

x = 0.03 y 0.27 za 0.70 Tg = +19.51.6 =

An area where 2 <ô <_ 4: S
. Definition of S3: S not including S5 (133x - 17y - 7z Z 0 (6x - 4y + llz ~ 0 S (2x - 3z 5 0 (x ~ 0.3 x + y + z ~ 1 with the following examples x = 0.44 y = 0.23z m 0.33 Tg d + 14.12.6 x = 0.27 y = 0.47z = 0.26 Tg = + 14.82.3 x = 0.27 y = 0.07z = 0.66 Tg = +17.13.9 x = 0.06 y = 0.07z = 0.87 Tg = +20.42.5 ~, ~ ~ ~ L ~ S ~ ~
j? ~~~ noS OL fi> Q: ~, S ", ~ - ~, 55 . Definition of S4 (0.25 xs 0.45 (0 5 y 5 0, 05 (0, 5 5 z 5 0, 8 (x + y + z = 1 with particular example following x = 0.40 y = 0.02 z = 0.58 Tg = ~ + 15.84.3 . Definition of S5 (7x - 3y + 17z 5 0 (x + y + z = 1 with particular example following x = 0.10 ym 0.88 z - 0.02 Tg m + 17.04.2 3: Study of ternary ALCALs xC20-yC21-zC22 Figure 3 shows the diagram giving the labels of different alloys. There are 3 zones (surfaces numbered from S1 to S3) zone ~ LÖ s 1 ~ Si . Definition of S1 area total triangle excluding S2 and S3 with the following examples xm 0.09 y - 0.01 z 0.90 Tg + 42.8p, g x 0.50 y = 0.47 z ~ 0.03 Tg - + 38.20.6 xm 0.80 to 0.03 z 0.17 Tg - +37.50.8 x ~ 0.03 y ~ 0.47 z = 0.50 Tg = + 41.6p, 6 59 ~, L ~ i. ~ J
1ne_. ~ _9îL ~ <ô <2: S ~
. Definition of zone S2 (3x - y - z? 0 (2x - 3y + 2z> _ 0 (6x + y - 9z 5 0 (x + y + z = 1 x = 0.30 y = 0.01 z = 0.69 Ts = +41.21.4 x = 0.48 y = 0.03 z = 0.49 Tg = +39.71.5 x = 0.33 y = 0.34 z = 0.33 Tg = +39.51.3 A ~ ~ b> 4: S
. Definition of zone S3 (x> _ 0, 95 (x + y + z = 1 4: Study of ternary ALCALs xC22-yC23-zC24 The diagram of the labels of the different alloys ~
is shown in Figure 4 is characterized by the existence of a single area called S where δ 5 1 . Definition of the S zone all the ternary, ie x + y + z = 1 with the following examples x '0.05 y ~~ 0.02 Z ~ 0.93 Tg - +50.20.4 x ~ 0.28 y ~ 0.02 zr 0.70 Tg ~ +48.40.8 x = 0.33 ym 0.34 z ~~ 0.33 Tg ~ +47.10.7 x = 0.70 y = 0.02 z = 0.28 Tg m 45.70.8 xn 0.48 y = 0.50 z = 0.02 Tg m 45.80.6 x = 0.03 y ~ 0.47 z = 0.50 Tg = 48.9p, 5 WO 93/01250 PCf / FR92 / 00636 'a ~ i, w ~, ~. ~ 4 ~~ 60 : Study of ternary ALCAL xCl8-yC20-zC22 The diagram of the labels of the different alloys 5 is given in FIG. 5. There are 7 zones (surfaces numbered from Sl to S7).
An area where &<1 ~ Si . Definition of S1: S not including S7 (18x - 2y + 3z <_ 0 S
(x + y + z = 1 with the following examples x = 0.06 y = 0.88 z = 0.06 Tg = +36.11.0 x = 0.03 y = 0.77 z = 0.20 Tg = +37.50.8 . Definition of zone S2 total triangle excluding S1, S3, S4, S5, S6 and S7 with the following examples x 0.78 y = 0.20 z = 0.02 Tg = +28.52.0 x = 0.53 y 0.44 z = 0.03 Tg + 30.92, 0 x 0.19 and 0.80 z 0.01 Tg + 33.92, p x 0.63 y 0.24 z 0.13 Tg a +30.01.8 x - 0.06 y 0.56 z 0.38 Tg +37.81, 3 x = 0.40 y = 0.58 z = 0.02 Tg m + 40.11.5 x 0.18 y = 0.80 zm 0.02 Tg +41.81, 1 x 0.87 y 0.10 z = 0.03 Tg + 27.81, 8 The zone ~ 7 . Definition of the S3 zone. S excluding 54 and S5 (4x -y ~ 0 S (z ~ 0.2 (x + y + z = 1 with the following examples x = 0.23 y = 0.54 z = 0.23 Tg +35.32.7 =

x = 0.33 y = 0.34 z = 0.33 Tg +35.73.7 =

x = 0.13 y = 0.33 z = 0.54 Tg +38.62.6 =

x = 0.70 y = 0.28 z = 0.02 Tg +30.83.9 =

An area o 4 S4 <

8 :

. Definition of S4 the zoned (2x + 7y - 3z> _ (y 5 0.3 (z ~ 0.4 (9x - 6y - z ~ 0 (x + y + z 1 with notably the following example x = 0.43 and 0.14 z 0.43 Tg +35.85.1 Tmi c ion c ot5 b> 6 ~ ~, . Definition of S5 (2x + 7y - 3z <0 (9x - 6y - z Z 0 (x + y + z ~ 1 with the following examples x ~ 0.48 y = 0.02 zm 0.50 Tg to +36.36.5 x ~ 0.27 y = 0.06 z ~ 0.67 To a +39.27.4 .J ~~~: ~. ~~
. Definition of S6 (x> _ 0, 95 (x + y + z = 1 . Definition of S7 (9x - y + 19z s 0 (x + y + z = 1 6: Study of ternary ALCAL xC20-yC22-zC24 On the diagram giving the labels of the different alloys, shown in Figure 6, there are 5 zones (surfaces numbered from S1 to S5) Two areas where b <_ 1. S1 and S2 . Definition of S1 (5x - y 5 0 (x + y + z = 1 with the following examples x = 0.02 y = 0.30 z = 0.68 Tg = + 48.1p, 9 x = 0.02 y = 0.70 zm 0.28 Tg = +45.20.8 x = 0.07 y = 0.76 z = 0.17 Tg = +44.70.9 . Definition of S2 (- 2x + 3y + 18z s 0 (x + y + z = 1 with the following examples x ~ 0.78 y = 0.20 zm 0.02 Tg +38.00.8 p IIIIeJ ~ '~ rie_ where L ~ .6 <2: ~ 3 . Definition of S3 total triangle excluding S1, S2, S4 and S5 63 ..; ,, ~ J ~ v ~~ â
with the following examples especially x = 0.05 y = 0.02 z = 0.93 Tg = +50.51.1 x = 0.17 y = 0.66 z = 0.17 Tg = +43.31.2 = 0.37 y = 0.46 z = 0.17 Tg = +42.01.9 x x = 0.38 y = 0.60 z = 0.02 Tg = +40.61.4 x = 0.50 y = 0.48 z = 0.02 Tg = +40.01.5 x = 0.66 y = 0.17 z = 0.17 Tg = +39.01.6 x = 0.87 y = 0.02 z = 0.11 Tg = +38.61.2 An area where 2 <ô <_ 4: S4 . Definition of S4 (- 36x + 9y + 4z> _ 0 (y <_ 0.4 (z ~ 0.2 (x + y + z = 1 with particular examples the x '0.23 and 0.03 z - 0.74 Tg +4.0, 03.0 x 0.17 y - 0.37 z - 0.46 ~ Tg = +45.62.2 -x = 0.47 y = 0.06 z = 0.47 Tg = +43.43.7 xm 0.34 y 0.33 z = 0.33 Tg +43.42, 8 x = 0.40 y = 0.20 z = 0.40 Tg m + 43.33.3 x = 0.66 y = 0.07 z - 0.27 Tg to +39.92.3 ijnQ ~ "zon _ o 'ô> 4: SS
. Definition of S5 (x - 19y - 9z zo (x + y + z ~ 1 7: Study of ALCAL ternary xC22-yC24-zC26 The diagram giving the labels of the different alloys is shown in Figure 7. There are three areas (areas numbered S1 to S3) rr ~ 64 Û ~ 3: 1 ~ ~
An area_, o, ~ ô ~ S1 . Definition of S1 (17x - 3y 5 0 (y - 2z ~ 0 (2x - 3y + 2z 5 0 (56x - 34y + 6z 5 0 (x + y + z = 1 IO
especially with the following examples x = 0.01 y 0.49 z = 0.50 Tg + 53.5p, 9 = =

x = 0.03 y 0.95 z = 0.02 Tg +50.50.5 = =

x = 0.17 and 0.66 z = 0.17 Tg + 50.3p, 8 = =

x = 0.30 and 0.68 z = 0.02 Tg +48.60.9 = =

x = 0.46 y 0.37 z = 0.17 Tg +47.71.1 = =

x 0.68 y 0.30 z = 0.02 Tg + 45.70.8 = =

U ~ zsaa ~~ to I ~~ s 2: S ~
. Definition of zone S2 total triangle excluding SI and S3 with the following examples x = 0.10 y = 0.18 z = 0.72 Tg = +54.01.9 x = 0.66 y = 0.07 z = 0.27 Tg = +47.21.6 x = 0.34 y = 0.33 z = 0.33 Tg = +44.31.4 A shingles where 2 <ô 5 4: S3 . Definition of S3 (12x + y - 4z z 0 (7x - 18y + 2z ~ 0 (x + 2y - 2z 5 0 (x + y + z = 1 WO 93/01250 fCT / FR92 / 00636 65 ~ L ~ ~ J ': ~

with examples following x = 0.27 y = 0.07z = 0.66 Tg +52.22.4 =

x = 0.50 y = 0.01z = 0.49 Tg +50.22.6 =

x = 0.40 y = 0.20z = 0.40 Tg +49.72.1 =

x = 0.47 y = 0.06z = 0.47 Tg +49.82.4 =

8: Study of ternary ALCALs xC20-yC22-zC26 The diagram giving the labels of the different alloys is shown in Figure 8. There are seven areas (areas numbered from S1 to S7).
D ~ x .onea o 1 g <1 S1 and S ~
. Definition of S1 area (7x - 3y + 27z 5 0 (x + y + za 1 with the following examples x = 0.20 y = 0.78 z = 0.02 Tg = + 42.2p, g x 0.07 y = 0.90 z = 0.03 Tg = +43.31.0 . Definition of zone S2 (- 6x + 3y + 17z 5 0 (- 3x + 57y + 17z> 0 (X + y + z = 1 with the following examples x ~ 0.78 y ~ 0.20 z ~ 0.02 Tg ~ + 37.8p, g xm 0.67 is 0.30 z ~ 0.03 Tg 0 + 38.60, g DeLx zonP ", ~ 05 t Lg s 2 . Definition of S3 (119x + 13y - 7z S 0 (x + y + z ~ 1 ~ f ~~ ~. ~~~~ 66 . Definition of S4: S excluding S1, S2 and S7 (6x + y - 24z ~ 0 S (14x - 21y + 39z 5 0 (x + y + z = 1 with the following examples x = 0.63 y = 0.23 z = 0.14 Tg = +39.51.8 x = 0.58 y = 0.40 z = 0.02 Tg = +39.11.1 x = 0.47 y = 0.50 z = 0.03 Tg = +40.41.5 x = 0.30 y = 0.67 z = 0.03 Tg = +41.81.4 x = 0.13 y = 0.74 z = 0.13 Tg = +43.81.5 ti none oû ~, <b <4: S5 = S n '; n .lly, ~ B ~, . Definition of S5: S excluding S6 (6x + y - 24z> 0 S (14x - 21y + 39z> 0 (119x + 13y - 7z <0 (x + y + zm 1 with the following examples:
xa 0.03 y = 0.47 z = 0.50 Tg = +50.03.5 x = 0.37 y = 0.46 z = 0.17 Tg = +42.62.6 x = 0.77 y = 0.03 z = 0.20 Tg = +38.82.1 x = 0.10 y = 0.02 z = 0.88 Tg = +54.53.7 Dety zona where 6> 6: S ( . Definition of S6 (x ~ 0.15 (y 5 0.45 (z ~ 0, 25 (x + y * z ~ 1 with particular example following x = 0.33 y = 0.34 z = 0.33 Tg ~ +46.66.0 . Definition of S7 (-3x + 57y + 17z 5 0 (x + y + z = 1

9: Study of ternary ALCAL x044-yC46-zC50 On the diagram giving the labels of the different alloys, shown in Figure 9, there are two areas (areas numbered S1 to S2) An area where ~ <_ i Si . Definition of S1 Total triangle not including S2 with the following examples x = 0.78 y = 0.02 z = 0.20 Tg = +86.70.7 x = 0.40 y = 0.40 z = 0.20 T0 = +87.20.5 A zor ~, ~ oL 1 <~ S <~
. Definition of S2 (x ~ 0, 25 (y 5 0.15 (z ~ 0, 35 (x + y + z ~ 1 with particular example following x = 0.40 y = 0.02 z = 0.58 Tg = +89.21.5 Fx Mile 6: ALCAL quaternaries and more The same considerations on the various constituents taken two by two allow the elaboration of ALCAL multicomponents admissible as to their label 8.
Fxem. ea of .formol ati cma;
C14p, 3300150.390C160.140C180.140: Ta + 7.5 ° C 6 ~ 3.4, oH ~ 127J / g 0140,2900150,350C160,1300170,230: T ~ + 8.6 ° C 8 ~ 4.0H ~ 146J / g C44p, 3500460.3500480.1000500,200: T '+ 86.9 ° C8 ~ 0.6, oH m 220J / g C14p, 3000150.360016p, 140C170.0600180,140: Tm + 7.6 ° C, δ = 3.5, oHs 128 J / g WO 93! 01250 PCT / FR92 / 00636 Example 7 Molecular alloys formed of chains monoacid-monoacid. The results obtained are reported with the wording [CH 3 (CH 2) 18 COOH] p, 52 LCH 3 (CH 2) COOH] 0.4 g: T = + 69.7 ° C, b = 0, 9, oH = 204 J / g Molecular alloys formed of alkane-dibasic with the following wording [C22 H4670.80 [COOH (CH2) COOH] 0.2p, ~ we obtain T = + 44.3 ° C, δ = 1.7, oH = 188 J / g Example 9. Molecular alloys formed of chains monobasic-dibasic A eutectic mixture of interesting alloys corresponds to the following overall composition 0.94 of [CH 3 (CH 2) COOH] with 0.06 of [COOH (CH2) 20 COOH]
T m + 77.2 ° C, 8 - 0, and oH = 160 J / g Example 10 Application to the manufacture of plates for fishmongers in the markets.
A plate stall containing ALCAL is covered 4. With respect to the ice commonly used, these plates have the advantage of being able to regenerated by cooling them. The case where appropriate, they may be used thickness of ice which will be better if 1a Traditional presentation is desired.
Exem lige 11. Application to cold storage of a food transport Either a food (solid or liquid) that we want ability to store in a refrigerator classic to transport it as is to a place 69 ° i: ~~ ~ ~ '''C ~
id J L7 a L f given place (eg place of work or picnic), for consume it a few hours later without any other means of protection and without its temperature exceeding 13 ° C (by example). We will advantageously choose one of the ALCAL
in the list of formulations below. The choice is widely open; it will be done according to parameters to prioritize, including constraints and the availability of commodities T (C) (C) oHJ.g-1 0140.2140150.5610160.225 +8.5 2.3 152 C14p, 290015p, 3500160,1300170,2200180,010 +8.6 4.1 146 C14p, 3200150.2400160.440 +8.8 4.4 151 0140.4000160.600 +9.0 4.9 148 0140,1070150,5920160,2200170,059018p, 022 +9.4 2.3 145 C140.030C150.840C160.130 +9.5 1.0 153 C14p, 240015p, 3300160.43p +9.5 3.9 151 .

C14p, 3300150.070016p, 6pp +9.9 4.4 151 C15p, 8? 00160.070017p, 060 +10.3 1.0 158 C140, O1pC150.84pC160.150 +10.5 0.8 150 C140.0300150.640016p, 330 +10.7 2.0 152 C140.066015p, 5050160.369 +10.7 2.1 158 C150.77pC160, 1700170.060 +10.8 1.3 157 0150,? 7pC16p, 0700170,160 +10.9 1.4 154 C150.700016p, 300 +11.2 1.3 156 0150.660C16p, 250C170.0700180.030 +11.2 1.9 152 C15p, 700017p, 300 +11.3 1.3 146 C15p, 685C170.300C160.015 +11.3 1.3 146 C15p, 6700160.30001? P, 030 +11.4 1.4 155 C140,140015p, 230016p, 630 +11.9 3.1 147 For example, if we opt for the first alloy of this list, we will have a MCPAM storing at 95% efficiency between + 6.2 ° C and + 8.5 ° C. It is obvious that other suitable formulations can be easily developed by those skilled in the art.

~~ .e. ~~~ 7i ~ ~ o It is sufficient to constitute a double packaging wall (wrapping the food completely) between which will be placed the ALCAL; the layer of ALCAL to use will depend on the desired protection time.
The whole being placed in the refrigerator, the ALCAL will be solidify (since the temperature is lower than its Tsol). everything will take the temperature of the place of the refrigerator where it is placed. During transport and conservation at room temperature of all, the ALCAL
will be a barrier to the arrival of calories on the food well said. Indeed, the calories coming from outside will, in the first place, be absorbed by ALCAL to raise its temperature up to Tsol ~ Next all calories will be taken by ALCAL for its fusion and it is the energy oH.m which will thus be blocked by the MCPAM (if m is its mass). Only when all the ALCAL will be melted that the whole will be able to see its temperature rise above Tliq ~
Example 12. Application to wraps refreshing and heated blankets.
A layer of ALCAL is incorporated in the wrap or in the blanket. In the first case, this ALCAL is chosen such that its temperature of effectiveness either of the order of + 35 ° C. A stay in a cool room suffice to give its properties on the system, that is to say make ALCAL solid. The patient will remain so contact a surface at + 35 ° C, as long as the calories that it emerges have not been enough lice melt the entire MCPAM.
In the second case, we can consider the use a heating resistor to perform storage of energy, that is, to make an ALCAL
operating at + 38 ° C for example with δ 5 2; use is then done without the usual risks of the covers ~~~ v ~
heating since taken unplugged. The maintenance between + 38 ° C and + (38 - 8) ° C will persist as long as MCPAM does not not completed his transition.
Example L ~. Heating mattress for operating tables and care tables.
Some operations, of long duration, require help to the patient in the form of a thermal effort to compensate for their hypothermia. The Principe of fonctionment heating blanket (ALCAL at T - + 38 ° G and ô s 2, with built-in resistance) can be included in it associating a low voltage auxiliary system (battery example) associated with a cyclic contactor to maintain ALCAL at solid-liquid equilibrium during an operation of tongue duration or when transporting a patient. In this Examples of MCPAMs may be associated with other materials such as fibrous or foamed materials for reasons for confoxt. Thermal insulation layers on the external faces (not in contact with the patient) extend the operating autonomy.
Example 1414: Fondue apparatus.
A built-in resistance system is realized and operated with unplugged socket with MCPAM (at T
greater than + 100 ° C and with one ô s 4) placed in a double wall. The realized device thus ensures a high security during its operation. MCPAMs can be chosen advantageously in the family of diacids to chein long.
Eg ~~ nlp ~ 15: Gourde cyclist.
A double-walled gourd is produced, containing a ALCAL at 6 ° C operating at a temperature of the order + 15 ° C (or lower depending on requirements); the cyclist will thus have a cool drink during ~ v ~ y ~ w ~~ 72 _ several hours, which is a great advantage for compared to classic gourds.
Example 16: Vaccine Case We prepare a double-walled case in which we introduces an MCPAM with a temperature T lower than + 15 ° C
approximately with 8 5 4. The MCPAM is solidified by placing it in the refrigerator. This case can be used to carry a vaccine.
We will measure the interest of this use by example for the hiker who will be provided with a vaccine by example of a viper and will be able to hike with a better security.
The invention thus provides the means for elaborating MCPs responding to a wide range of temperatures required for industrial applications.
Depending on the temperature level at which make the change of phase, the person skilled in the art has the means to choose the content of the compounds organic compounds used to make the alloy conforming to the requirements defined above.

Claims (35)

1/ Compositions capable of storing and restore thermal energy by latent heat, characterized in that they are formed from a single phase of acyclic organic compounds of one or more alloys molecules corresponding to the formula (I) Axa Zxz (I) in which - A is a saturated acyclic organic compound or unsaturated, optionally substituted, organic compounds acyclics having from 2 to 120 carbon atoms, and being chosen from an alkane, an alkene and an alkyne, - Z represents one or more compounds different from A, but selected) from meanings given for A, - xa and xz represent the molar proportions of A and Z respectively, these proportions being adjusted to obtain molecular alloys, characterized as as such by X-rays, capable of storing or restoring thermal energy at a temperature level T, on a temperature interval b not exceeding +6°C, corresponding to those required for a given application such as phase change material, - belonging to a phase diagram with, if the alloy is binary, a spindle, in the case of a total miscibility, or part of a spindle, in the case of partial miscibility, or if the alloy is ternary or more, a transition domain, this spindle or this domain being located in a temperature interval including that required for a given application and whose location geometric EGC (Equal G curve) is slightly curved and close to horizontality to ensure an 8 not exceeding the width desired, - having a satisfactory hold or cycling thermal, - having a degree of molecular homeomorphism .epsilon.k greater than 0.8 for binary alloys, or having this property for the various constituents taken two by two if are multi-component alloys. 2 / Compositions according to claim 1, characterized in that the degree of molecular homeomorphism .epsilon.k is greater than 0.90. 3 / Compositions according to claim 1, characterized in that 8 does not exceed +4°C. 4 / Compositions according to claim 1, characterized in that 8 does not exceed +2°C. 5 / Compositions according to claim 1, characterized in that 8 does not exceed +1°C. 6/ Compositions according to any one of claims 1 to 5, characterized in that the compounds materials used to form the alloys are not miscible in all proportions before the transition. 7/ Compositions according to any one of claims 1 to 5, characterized in that the compounds organic materials used to form the alloys are miscible in all proportions before the transition. 8/ Compositions according to any one of claims 1 to 5, characterized in that the compounds materials used to form the alloys have a low miscibility. 9/ Compositions according to any one of claims 1 to 5, characterized in that the compounds materials used to form the alloys form a eutectic. 10/ Compositions according to one. any of claims 1 to 9, characterized in that they contain further as doping agents, one or more of said organic compounds, in an amount of less than 5% by mole, the or the main compounds being present at a rate of 90% and more. 11 / Compositions according to claim 1 or 10, characterized in that A and/or Z comprise one or more substituents chosen from halogens F, Cl, Br, I, -OH,-OR1 groups, alkyl, saturated alkylene or unsaturated, and alkynes having 1 to 8 carbon atoms, the -COOH, -COOR1, -COR1, -CH2OH, -CH(R1)-OH, -C(R1,R2)OH groups, -CHO, -C=O, -CONH2, -NH2, -NH(R1) , and -N(R1, R2) , -SH, =S, and -NO2, R1 and R2, identical or different from each other, being an alkyl group of 1 to 8 carbon atoms, these occupying substituents in acyclic organic compounds any position on the carbon chain and/or located at one end of the chain or at both ends. 12 / Compositions according to claim 11, characterized in that the saturated alkyl, alkylene groups or unsaturated and alkynes have 1 to 4 carbon atoms. 13 / Compositions according to claim 11, characterized in that R1 and R2 are an alkyl group of 1 to 4 carbon atoms. 14/ Compositions according to any one of claims 1 to 13, characterized in that A and Z are even carbon number alkane chains and/or chains of alkanes with an odd carbon number and containing from 8 to 100 carbon atoms, straight or branched, as appropriate possibly substituted, consecutive or differing by several let's link. 15 / Compositions according to claim 14, characterized in that the substituted alkane chains contain 8 to 50 carbon atoms. 16 / Compositions according to claim 14, characterized in that the chains of alkanes differ from more than 4 or 5 carbon links. 17 / Compositions according to claim 14, characterized in that they comprise at least one chain of alkane with one or more substituent as defined in claim 11, said substituent(s) occupying one or both ends of the chain. 18 / Compositions according to claim 17, characterized in that the substituent is chosen from the group comprising a carboxyl group, an ester group and an atom of halogen. 19/ Compositions according to any one of claims 1, and 11 to 17, characterized in that they meet one of the following formulas Axa Bxb (II), Axa Bxb Cxc (III), and Axa Bxb Cxc Dxd (IV), in which A, B, C and D, meet the definitions given for A for the formula I where B, C and D meet the same definition as that given for A but are different from each other, and xa to xd respectively correspond to the proportions molars of the different constituents, with xa + xb = 1 in formula (II), xa + xb + xc = 1 in formula (III), and xa + xb + xc + xd = 1 in formula (IV). 20/ Process for preparing the compositions defined in claim 1, characterized in that one puts use the organic compounds A and Z, according to the desired proportions in the final alloy and which is carried out a fusion-crystallization or fusion-quenching, or dissolution-evaporation, or sublimation simultaneous, or zone leveling or interdiffusion chemical, and only to prepare molecular alloys formed of alkanes, when all the number chains odd carbon are liquid at room temperature, we form the liquid solution sought by mixing and stirring starting compounds used in the desired proportions in the alloy and, when all the starting compounds, or some of them are solid, we proceed by dissolution of the basic products according to the proportions in a common solvent, followed by evaporation of the solvent, or that, alternatively, the basic products weighed are subjected to fusion by stirring to ensure the homogeneity of the product, then are soaked, or only according to a another variant, one operates according to a separative method, in subjecting a mixture of organic compounds containing the desired composition at an extraction step to isolate the latter, and when this mixture does not contain all of the desired organic compounds and/or according to the desired proportions, the mixture is treated so as to enrich it with one or more constituents, or as the case may be so as to eliminate them until obtaining the desired composition. 21 / A method according to claim 20, characterized in that the solvent is ether. 22 / A method according to claim 20, characterized in that the evaporation of the solvent is carried out under current of inert gas. 23/ Phase change materials, characterized in that they comprise a composition according to one any of claims 1 to 19 in the form conditioned. 24/ Application of the materials defined in the claim 23 in the agro-food field, for the thermal protection and/or food transport food. 25 / Application according to claim 24, in the food industry for transport or storage of products from -50°C to +100°C. 26 / Application according to claim 24, in the food industry for transport or storage frozen products from -50°C to -10°C. 27 / Application according to claim 24, in the food industry from -10°C to +6°C. 28 / Application according to claim 24, in the food industry between +6°C and +16°C. 29 / Application according to claim 24, in the food industry at temperatures from +16 to +35°C. 30 / Application according to claim 24, in the food industry at temperatures from +35 to +100°C. 31/ Application according to any of the claims 24 to 30, characterized in that the materials phase change used are alloys molecules formed of alkanes. 32/ Application of the materials defined in the claim 23, in the paramedical field. 33 / Application according to claim 32, characterized in that the paramedical field is for the packaging, isothermal manipulations or controlled temperatures, functional deficiencies and symptomatic therapies. 34 / Application according to claim 33, characterized in that the manipulations are carried out at temperatures between -80°C and +75°C. 35/ Application of the materials defined in the claim 23, for security protection or energy savings in a temperature range of -80°C to +200°C and to ensure autonomy of use of the articles household.