Barokalorično hlađenje
    Nedjelja, 12 Svi 2019 09:42

    Barokalorično hlađenje

    Otkrivena je krutina koja se tlačenjem hladi! Tlačenjem jedne obične i posve bezopasne kemikalije, neopentil-glikola, može joj se sniziti temperatura do 50 stupnjeva. I evo fizikalne osnove za novu vrstu hladnjaka – bez rashladnog plina. Da se plinovi sabijanjem zagrijavaju (adijabatska kompresija), a širenjem hlade (adijabatska ekspanzija) zna svatko tko je pumpao gumu od bicikla (prvi slučaj), a za drugi slučaj, eh za drugi slučaj... Da se i ovo drugo događa zna pak onaj tko je naglo otvorio bocu protupožarnog aparata za električne instalacije (onaj s plinom, ne s prahom), pa mlaz ugljikova dioksida usmjerio prema tkanini, krpi ili kaputu. Na njoj se stvorilo inje, no to nije bilo inje od vode nego od ugljikova dioksida, koje može postojati tek na temperaturi nižoj od -78,5 oC. To inje ne može se okom razlikovati od onoga pravog, zimskog, no pri zagrijavanju od njega ne nastaje nikakva tekućina, ponajmanje voda. Zato se i zove – suhi led. Na tim se pojavama, pojavama adijabatske kompresije i ekspanzije temelji rad praktički svih uređaja za hlađenje, od hladnjaka i ledenice u našoj kuhinji do klima-uređaja u našem uredu i našem automobilu. Plin se najprije sabije, a potom se zračnim hladilom ohladi na sobnu temperaturu. Potom stlačeni plin ekspandira i pritom se ohladi – i tako uokrug. I sve bi bilo lijepo da nije plina koji se sabija i širi. Riječ je o freonu, što nije ništa drugo nego trgovačko ime za fluorklorugljike, spojeve – samo im ime kaže – fluora, klora i ugljika (npr. CF2Cl2 je freon 12, a CCl3F freon 11). Freoni uništavaju ozonski sloj u stratosferi, pa se u posljednje vrijeme nastoje zamijeniti nečim bezopasnijim, spojevima koji u molekuli imaju i vodik (fluorirani i klorirani ugljikovodici). No nisu ni oni bez mane. Iako ne razaraju ozonski sloj, podižu temperaturu Zemljine atmosfere. „U slučaju istjecanja 1 kg rashladne tekućine u atmosferu, njezin bi utjecaj na globalno zagrijevanje bio 2088 puta veći od utjecaja 1 kg CO2 u razdoblju od 100 godina“, piše u tehničkoj knjižici klimatizacijskog uređaja. Konkretno, riječ je o rashladnom sredstvu R-410A, kemijske formule CHF2CF3. Možemo li izbjeći toj tužnoj sudbini – i napraviti hladnjak bez plina? Takav bi se uređaj zaista mogao pojaviti u našim trgovinama uspiju li znanstvenici tehnološki iskoristiti pojavu o kojoj su objavili, u ožujku ove godine, članak u vrhunskom znanstvenom časopisu Nature pod bombastičnim naslovom: „Colossal barocaloric effects in plastic crystals“ (Kolosalni bakokalorični efekti u plastičnim kristalima). No nije samo naslov i efekt kolosalan, nego je i ime efekta kolosalno, jer su mu pridjenuli kraticu CBCE, dakle colossal barocaloric effect. Zbog čega? Barokalorični efekt znači da se kruta tvar tlačenjem hladi. Taj je pojava odavno poznata, zapažena je i kod obične gume, no efekt koji koji su autori članka (23 znanstvenika iz Kine, Japana, Tajvana, Sjedinjenih Država i Australije) istraživali najmanje je deset puta veći nego u drugim tvarima. Riječ je o kristalima neopentil-glikola (NPG), dvovalentnog alkohola sustavnog imena 2,2-dimetil-1,3-propandiol i formule (CH3)2C(CH2OH)2. Kada se kristali te praktički bezopasne i nimalo neobične kemikalije podvrgnu tlaku od 45 MPa, ohlade se za 50 oC. Zašto? Riječ je da su kristali NPG, kako u naslovu rada piše, plastični, ili – znanstveno ispravnije – pripadaju skupini distordiranih krutina. Kristal ne može postojati, uči se u kristalografiji, ako čestice (atomi, ioni ili molekule) nisu u njemu pravilno raspoređene. Tako je i u kristalu NPG. U jediničnoj ćeliji ima simetrično raspoređene četiri molekule, no taj „simetrični raspored“ odnosi se samo na njihove centre masa. Kada se međutim kristal stlači on prelazi u uređeniju strukturu. A kada nešto prelazi iz stanja nereda u stanje reda (entropija sustava pada) za to treba utrošiti energiju, a utrošena energija u ovom slučaju upravo je unutrašnja energija sustava (kristala). Rezultat: kristal se adijabatski hladi kada ga se tlači (ili crpi toplinu iz svoje okoline ako mu temperatura ostaje nepromijenjena). Precizna su kalorimetrijska mjerenja pokazala da maksimalni pad entropije tlačenjem iznosi 389 J kg-1 K-1 uz temperaturu prijelaza blisku sobnoj (40 oC). Još su veću promjenu entropije izmjerili kod kristala AMP (2-amino-2-metil-1,3-propandiol), od čak 629 J kg-1 K-1, no do nje dolazi pri višem tlaku i temperaturi (150 oC). Stoga je primjena tog spoja, barem što se tiče uređaja u kućanstvu, neprikladna. I što sad? Hladnjak s krutim hlađenjem ne bi imao plin, ali bi ipak trebao imati motor za pokretanje tekućina. Nešto bi, najbolje voda, trebalo prenositi toplinu u blok i iz bloka za hlađenje, a morao bi postojati i uređaj za tlačenje, možda najbolje s uljem, na principu hidraulike. Sve skupa nimalo jednostavno. Još ćemo se dakle načekati...
    Nenad Raos, rođen 1951. u Zagrebu, je kemičar, doktor prirodnih znanosti i znanstveni savjetnik, sada u mirovini. Još od studentskih dana bavi se popularizacijom znanosti pišući za časopise Prirodu (kojoj je sedam godina bio i glavni urednik), Čovjek i svemir, ABC tehnike, Smib, Modru lastu, a u posljednje vrijeme i za mrežne stranice Zg-magazin te, naravno, BUG online. Autor je i 13 znanstveno-popularnih knjiga od kojih je posljednju, „The Cookbook of Life – New Theories on the Origin of Life“ (izišlu 2018. godine), napisao na engleskom jeziku. Urednik je rubrike „Kemija u nastavi“ u časopisu Kemija u industriji, za koji piše i redovite komentare. Nagrađen je Državnom godišnjom nagradom za promidžbu i popularizaciju znanosti 2003. godine.
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    Colossal barocaloric effects near room temperature in plastic crystals of neopentylglycol
    There is currently great interest in replacing the harmful volatile hydrofluorocarbon fluids used in refrigeration and air-conditioning with solid materials that display magnetocaloric, electrocaloric or mechanocaloric effects. However, the field-driven thermal changes in all of these caloric materials fall short with respect to their fluid counterparts. Here we show that plastic crystals of neopentylglycol (CH3)2C(CH2OH)2 display extremely large pressure-driven thermal changes near room temperature due to molecular reconfiguration, that these changes outperform those observed in any type of caloric material, and that these changes are comparable with those exploited commercially in hydrofluorocarbons. Our discovery of colossal barocaloric effects in a plastic crystal should bring barocaloric materials to the forefront of research and development in order to achieve safe environmentally friendly cooling without compromising performance.

    Introduction
    Plastic crystals (PCs), also known as orientationally disordered crystals, are materials that lie at the boundary between solids and liquids. They are normally made of nearly spherical small organic molecules whose centres of mass form a regular crystalline lattice, unlike liquid crystals that normally comprise highly anisotropic organic molecules with no long-range positional order. The globular shape of these molecules provides little steric hindrance for reorientational processes, such that plastic crystals tend to be highly orientationally disordered away from low temperature. This dynamical disordering often implies high plasticity under uniaxial stress, and hence the materials are known as plastic crystals. On cooling, plastic crystals typically transform into ordered crystals (OCs) of lower volume via first-order phase transitions, whose latent heats arise primarily due to thermally driven large changes of orientational order, and this has led to proposals for passive thermal storage. Here we exploit commercially available samples of the prototypical plastic crystal neopentylglycol (NPG), i.e., 2,2-dymethyl-1,3-propanediol. This material is an alcoholic derivative of neopentane C(CH3)4 made from cheap abundant elements, and enjoys widespread use in industry as an additive in the synthesis of paints, lubricants and cosmetics.

    We achieve colossal pressure-driven thermal changes (barocaloric effects) near room temperature that are an order of magnitude better than those observed in state-of-the-art barocaloric (BC) materials and comparable to those observed in the standard commercial hydrofluorocarbon refrigerant R134a18. Our BC effects are colossal because the first-order PC-OC transition displays an enormous latent heat that is accompanied by an enormous change in volume, such that moderate applied pressure is sufficient to yield colossal thermal changes via the reconfiguration of globular neopentylglycol molecules (whose steric hindrance is low). Moreover, reversibility is achieved at temperatures above the hysteretic transition regime. Our higher operating pressures do not represent a barrier for applications because they can be generated by a small load in a large volume of material via a pressure-transmitting medium, e.g., using a vessel with a neck containing a driving piston, whose small area is compensated by its distance of travel. Therefore, our demonstration of colossal BC effects in commercially available plastic crystals should immediately open avenues for the development of safe and environmentally friendly solid-state refrigerants.

    PC-OC phase transition in NPG at atmospheric pressure
    At room temperature and atmospheric pressure, NPG adopts an ordered monoclinic structure (P21/c) with four molecules per unit cell. On heating, the material undergoes a reversible structural phase transition to a cubic structure (Fm3¯m) with four molecules per unit cell that adopt an orientationally disordered configuration at any typical instant. The first-order structural phase transition yields sharp peaks in dQ/|dT| (Q is heat, T is temperature) recorded on heating and cooling, with a well-defined transition start temperature T0 ~ 314 K on heating. By contrast, as a consequence of the nominally isothermal character of the PC-OC transition, the temperature ramp rate influences the transition finish temperature on heating, and the transition start and finish temperatures on cooling (e.g., by up to ~5 K for 1–10 K min−1). Integration of the calorimetric peaks yields a large latent heat of |Q0| = 121 ± 2 kJ kg−1 on heating, and |Q0| = 110 ± 2 kJ kg−1 on cooling. These values of |Q0| are independent of the temperature ramp rate, and in good agreement with previous experimental values1,22,23 of |Q0| ~ 123–131 kJ kg−1.

    Integration of (dQ/|dT|)/T and Cp/T, permits the evaluation of entropy S′(T) = S(T)−S(250 K) over a wide temperature range, as explained in the Experimental Section (Cp is specific heat at atmospheric pressure). The large entropy change at the transition (|ΔS0| ~ 383 J K−1 kg−1 on heating and |ΔS0| ~ 361 J K−1 kg−1 on cooling) is in good agreement with previous experimental values of |ΔS0| ~ 390–413 J K−1 kg−1. This large value of |ΔS0| arises due to a non-isochoric order-disorder transition in molecular configurations, such that it exceeds values of |ΔS0| << 100 J K−1 kg−1 for first-order structural phase transitions associated with changes of ionic position and electronic densities of states. Consequently, the configurational degrees of freedom that are accessed via the non-isochoric order-disorder transition in our solid material yield entropy changes that compare favourably with those associated with the translational degrees of freedom accessed via solid-liquid-gas transitions in various materials, including the hydrocarbon fluids used for commercial refrigeration.

    On heating through the transition, x-ray diffraction data confirm the expected changes in crystal structure. The resulting specific volume V undergoes a large ~4.9% increase of ΔV0  = 0.046 ± 0.001 cm3 g−1 across the transition, for which (∂V/∂T)p=0 > 0, presaging large conventional BC effects that may be evaluated by using the Maxwell relation (∂V/∂T)p = −(∂S/∂p)T to calculate the isothermal entropy change ΔS(p1→p2)=−∫p2p1(∂V/∂T)pdp due to a change in pressure from p1 to p2. Near the transition, the volumetric thermal expansion coefficients for the OC and the PC phases are both ~10−4 K−1, implying the existence of additional BC effects ΔS+ that are large and conventional at temperatures lying on either side of the transition. These additional BC effects are evaluated here using the aforementioned Maxwell relation, for changes in pressure |p−patm| ~ |p| where atmospheric pressure patm ~ 0 GPa, to obtain ΔS+(p) = −[(∂V/∂T)p=0]p, where (∂V/∂T)p is assumed to be independent of pressure shows the error in (∂V/∂T)p to be ~20% for the PC phase, which implies an error in the total entropy change ΔS of ~3%).

    Two contributions to |ΔS0| may be identified as follows. One is the configurational entropy given by M−1Rln Ω, where M = 104.148 g mol−1 is molar mass, R is the universal gas constant, and Ω is the ratio between the number of configurations in the PC and the OC phases. The other is the volumetric entropy (α¯/κ¯) ΔV0, where the coefficient of isobaric thermal expansion α¯ , and the isothermal compressibility κ¯, have both been averaged across the PC-OC transition. Molecules of (CH3)2C(CH2OH)2 display achiral tetrahedral symmetry (point group Td, subgroup C3v), yielding one configuration in the OC phase and configurations in the PC phase (10 molecular orientations that each possesses six possible hydroxymethyl conformations). Therefore the configurational entropy is M−1Rln 60 ~ 330 J K−1 kg−1, and the volumetric entropy is ~60 J K−1 kg−1. The resulting prediction of |ΔS0| ~ 390 J K−1 kg−1 agrees well with the experimental values reported above, and the previously measured experimental values.

    PC-OC phase transition in NPG under applied pressure
    Measurements of dQ/|dT| under applied pressure reveal that the observed transition temperatures vary strongly with pressure, with dT/dp = 113 ± 5 K GPa−1 for the start temperature on heating, and dT/dp = 93 ± 18 K GPa−1 for the start temperature on cooling, for pressures p < 0.1 GPa. These values of dT/dp are amongst the largest observed for BC materials, and indicate that the first-order PC-OC transition of width ~10 K could be fully driven in either direction using |Δp| ~ |p| ~ 0.1 GPa. At higher pressures, values of dT/dp fall slightly, but remain large).

    Integration of (dQ/|dT|)/T at finite pressure reveals that the entropy change |ΔS0| decreases slightly with increasing pressure. This decrease arises because the additional entropy change ΔS+(p) increases in magnitude on increasing temperature in the PC phase [(∂V/∂T)p=0 at 370 K is ~240% larger than (∂V/∂T)p=0 at 320 K, whereas it is nominally independent of temperature in the OC phase near the transition. The fall seen in both dT/dp and |ΔS0| implies via the Clausius–Clapeyron equation dT/dp = ΔV0/ΔS0 that there is a reduction in |ΔV0| at finite pressure, as confirmed using pressure-dependent dilatometry and pressure-dependent x-ray diffraction.

    In order to plot ΔS(T,p), we obtained finite-pressure plots of S′(T,p) = S(T,p)−S(250 K,0) by integrating the data and displacing each corresponding plot by ΔS+(p) at 250 K, as explained in the Experimental Section. (Note that ΔS+(p) was evaluated below T0(p = 0) to avoid the forbidden possibility of T0(p) rising to the temperature at which ΔS+(p) was evaluated at high pressure.) we see that the entropy change associated with the transition ΔS0(p) combines with the smaller same-sign additional entropy change ΔS+(p) away from the transition, yielding total entropy change ΔS(p).

    BC performance
    By following isothermal trajectories in our plots of S′(T,p) obtained on cooling, we were able to evaluate ΔS(T,p) on applying pressure, as cooling and high pressure both tend to favour the low-temperature low-volume OC phase. Similarly, by following isothermal trajectories in our plots of S′(T,p) obtained on heating, we were able to evaluate ΔS(T,p) on decreasing pressure, as heating and low pressure both tend to favour the high-temperature high-volume PC phase.

    Discrepancies in the magnitude of ΔS(T,p) on applying and removing pressure are absent in the range ~314-342 K, evidencing reversibility. Our largest reversible isothermal entropy change |ΔS| ~ 510 J K−1 kg−1 arises at ~330 K for |p| ~ 0.57 GPa, and substantially exceeds the BC effects of |ΔS| ≤ 70 J K−1 kg−1 that were achieved using similar values of |p| in a range of materials near room temperature, namely magnetic alloys ferroelectric and ferrielectric materials, fluorides and oxifluorides hybrid perovskites, and superionic conductors. Moreover, our largest value of |ΔS| substantially exceeds the values recorded for magnetocaloric, electrocaloric, and elastocaloric materials, and is comparable to the values observed in the standard commercial hydrofluorocarbon refrigerant fluid R134a, for which |ΔS| = 520 J K−1 kg−1 at ~310 K for much smaller operating pressures of ~0.001 GPa. We can also confirm that NPG compares favourably with other BC solids when normalizing the peak entropy change by volume to yield |ΔS| ~ 0.54 J K−1 cm−3 (the NPG density is 1064 kg m−3 at ~320 K). 

    The large variation of transition temperature with pressure permits large entropy changes of |ΔS| ~ 445 J K−1 kg−1 to be driven with relatively moderate pressure changes of |p| ~ 0.25 GPa, yielding giant BC strengths30 of |ΔS|/|p| ~ 1780 J K−1 kg−1 GPa−1. Larger pressures extend the reversible BC effects to higher temperatures, causing the large refrigerant capacity RC to increase despite the slight reduction in |ΔS0(p)|. The BC effects in NPG are so large that unpractical changes of pressure would be required to achieve comparable RC values in other BC materials.

    By following adiabatic trajectories in S′(T, p), we established both the adiabatic temperature change ΔT(Ts,p) on applying pressure p at starting temperature Ts, and the adiabatic temperature change ΔT(Tf,p) on removing pressure p to reach finishing temperature Tf. On applying our largest pressure (p ~ 0.57 GPa), an adiabatic temperature increase of ΔT ~ 30 K with respect to Ts ~ 318 K is necessarily reversible above the thermally hysteretic regime, such that an equivalent temperature change of opposite sign is achieved on pressure removal. These BC effects substantially exceed both the BC effects of |ΔT| ≤ 10 K that were achieved in inorganic materials by exploiting room-temperature phase transitions with similar values of |p|; and substantially exceeds the BC effects of |ΔT| ~ 9 K that were achieved away from a phase transition with a smaller value of |p| = 0.18 GPa in organic poly(methyl methacrylate) at Ts ~ 368 K.

    Discussion
    To exploit our material in BC cooling devices, the non-monolithic working body and its intermixed pressure-transmitting medium may exchange heat with sinks and loads via fluid in a secondary circuit, heat pipes or fins. The requisite high pressures could be generated in large volumes using small loads and small-area pistons, just as small voltages can generate large electric fields in the many thin films of an electrocaloric multilayer capacitor. To improve the BC working body, it would be attractive to decrease the observed hysteresis using both chemical and physical approaches, enhance the limited thermal conductivity e.g., by two orders of magnitude via the introduction of graphite matrices, and combine different plastic crystals that operate at quite different temperatures. More generally, our observation of colossal and reversible BC effects in NPG should inspire the study of BC effects in other mesophase systems that lie between liquids and solids, most immediately other organic plastic crystals whose PC-OC transitions display large latent heats and large volume changes. After acceptance of our paper by Li et al. was published in Nature. In the published version they reported a barocaloric entropy change of 389 J K−1 kg−1 for NPG. This value is lower than our value because these authors used lower pressure, and only considered the contribution from the PC-OC transition, while as shown in our manuscript the contributions beyond the transition are relevant for NPG and can be as large as ~80 J K−1 kg−1 for our ~0.25 GPa driving pressure.

    Methods
    Samples
    NPG of purity of 99% was purchased as a powder from Sigma-Aldrich. The typical grain size was ~100 µm, as determined using optical microscopy.
    Techniques
    Measurements of dQ/|dT| = dQ/dt|dT/dt| were performed at atmospheric pressure in a commercial TA Q100 differential scanning calorimeter (DSC), at ±1–10 K min−1, using ~10–20 mg samples of NPG (t is time).

    Measurements of specific heat Cp were performed at atmospheric pressure in a commercial TA Q2000 DSC, at ±5 K min−1, using ~20 mg samples of NPG. Values of Cp were obtained by recording heat flow out of/into the sample as a function of temperature, and comparing it with the heat flow out of/into a reference sapphire sample under the same conditions. Latent heat |Q0|=∣∣∫T2T1dQdTdT∣∣ across the PC-OC transition was obtained after subtracting baseline backgrounds, with start temperature T1 freely chosen below (above) the transition on heating (cooling), and finish temperature T2 freely chosen above (below) the transition on heating (cooling).

    Measurements of dQ/dT were performed at constant applied pressure using two bespoke differential thermal analysers (DTAs). For applied pressures of < 0.3 GPa, we used a Cu-Be Bridgman pressure cell with chromel-alumel thermocouples. For applied pressures of < 0.6 GPa, we used a model MV1-30 high-pressure cell (Institute of High Pressure Physics, Polish Academy of Science) with Peltier elements as thermal sensors. The temperature of both pressure cells was controlled using a circulating thermal bath (Lauda Proline RP 1290) that permitted the measurement temperature to be varied at ~±2 K min−1 in 183–473 K. NPG samples of mass ~100 mg were mixed with an inert perfluorinated liquid (Galden, Bioblock Scientist) to remove any residual air, and hermetically encapsulated inside Sn containers. The pressure-transmitting medium was DW-Therm (Huber Kältemaschinenbau GmbH). Entropy change |ΔS0(p)|=∣∣∫T2T1(dQ/dT)/TdT∣∣ across the PC-OC transition was obtained after subtracting baseline backgrounds, and the choice of T1 and T2 is explained above.

    Variable-temperature high-resolution x-ray diffraction was performed at atmospheric pressure in transmission, using Cu Kα1 = 1.5406 Å radiation in a horizontally mounted INEL diffractometer with a quartz monochromator, a cylindrical position-sensitive detector (CPS-120) and the Debye-Scherrer geometry. NPG samples were introduced into a 0.5-mm-diameter Lindemann capillary to minimize absorption, and the temperature was varied using a 600 series Oxford Cryostream Cooler. Using the Materials Studio software, lattice parameters were determined by pattern matching using the Pawley method for the cubic phase, and by Rietveld refinement for the monoclinic phase.

    Dilatometry was performed using a bespoke apparatus that operated up to 0.3 GPa over a temperature range of ~193–433 K. Molten NPG samples of mass ~1 g were encapsulated inside stainless-steel containers to remove any residual air. Each container was then perforated by a stainless-steel piston, whose relative displacement with respect to a surrounding coil could be detected via measurement of electromotive force.

    Variable-pressure x-ray diffraction measurements were performed at beamline MSPD BL04 in the ALBA-CELLS synchrotron, using an x-ray wavelength of 0.534 Å obtained at the Rh K-edge. The beamline is equipped with Kirkpatrick-Baez mirrors to focus the x-ray beam to 20 μm × 20 μm, and uses a Rayonix CCD detector. The NPG sample was placed with two small ruby chips at the centre of a 300 μm-diameter hole in a stainless steel gasket, preindented to a thickness of 55 μm. For room-temperature measurements, we used symmetric diamond-anvil cells (DACs) with diamonds of 700 μm. For high-temperature measurements, we used a gas-membrane driven DAC equipped with diamonds possessing 400 μm culets, and varied the temperature using a resistive heater. Temperature was measured using a K-type thermocouple attached to one diamond anvil, close to the gasket. The thermocouple was accurate to 0.4% in our measurement-set temperature range. For all the measurements, NaCl powder was used as the pressure marker61. The accuracy of pressure readings was ~±0.05 GPa. Indexing and refinement of the powder patterns were performed using the Materials Studio software, by pattern matching using the Pawley method.

    Construction of entropy curves
    Using specific heat data at atmospheric pressure, specific volume data at atmospheric pressure, and dQ/|dT| data at constant pressure, we calculated S′(T,p) = S(T,p) − S(250 K,0) where T1 is the transition start temperature, T2 is the transition finish temperature, COC is the specific heat of the OC phase, CPC is the specific heat of the PC phase, and COC-PC  = (1−x)COC + xCPC represents the specific heat inside the transition region, where the transformed fraction x on crossing the PC-OC transition was calculated using
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    Hrastović Inženjering d.o.o. od 2004. se razvija u specijaliziranu tvrtku za projektiranje i primjenu obnovljivih izvora energije. Osnova projektnog managementa održivog razvitka društva je povećanje energijske djelotvornosti klasičnih instalacija i zgrada te projektiranje novih hibridnih energijskih sustava sunčane arhitekture. Cijeli živi svijet pokreće i održava u postojanju stalni dotok Sunčeve energije, a primjenom transformacijskih tehnologija Sunce bi moglo zadovoljiti ukupne energetske potrebe društva.

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