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s ~d JURNAL FISIKA 122, 074511 2005

Tekanan ketergantungan viskositas

Jrn W. P. Schmelzer
Institut fr Physik der Universitt Rostock, Universittsplatz, 18051 Rostock, Jerman dan Vitreous Laboratorium bahan, teknik Departemen bahan, Federal University of Sao Carlos UFSCar, 13565-905 So Carlos, Sao Paulo, Brasil

Edgar D. Zanotto

Laboratorium bahan vitreous, Departemen bahan-bahan teknik, Federal University of Sao Carlos, UFSCar, 13565-905 So Carlos, Sao Paulo, Brasil

Vladimir M. Fokin

Laboratorium bahan vitreous, Departemen bahan-bahan teknik, Federal University of Sao Carlos, UFSCar, 13565-905 So Carlos, Sao Paulo, Brasil dan S. I. Vavilov negara optik Institute, Uliza Babushkina 36-1, 193171 St. Petersburg, Rusia

sMenerima 3 Agustus 2004; diterima 1 Desember 2004; diterbitkan online 11 Februari 2005

Kami reanalyze ketergantungan viskositas cairan konstan komposisi di bawah tekanan isotermal kondisi. Berdasarkan pertimbangan-pertimbangan yang sangat umum tentang hubungan antara viskositas dan free volume, kita menunjukkan bahwa, pada nilai-nilai yang moderat tekanan, viskositas meningkat, sebagai suatu peraturan, dengan meningkatnya tekanan, asalkan cairan dalam stabil atau metastable sundercooledd keseimbangan Serikat. Namun, bahkan jika perilaku viskositas diatur oleh gratis Efek volume, penyimpangan dari ketergantungan tekanan positif mungkin, Kapan cair ekspansi termal coef Sien negatif. Kita memperoleh persamaan yang memungkinkan seseorang untuk kuantitatif menentukan ketergantungan tekanan dari viskositas, yang memerlukan, dalam kasus sederhana, hanya pengetahuan tentang ketergantungan suhu dari viskositas pada tekanan konstan, ekspansi termal coef efisien, dan compressibility isotermal cairan. Sebagai contoh, tekanan negatif ketergantungan air di kisaran suhu 04 C dan beberapa silikat cairan, seperti albite, jadeite, dacite, basalts, dll, dapat dijelaskan sedemikian rupa. Cairan lainnya membentuk kaca d awalnya s untuk moderat tekanan menunjukkan tekanan positif ketergantungan viskositas yang berubah ke satu negatif ketika mengalami tinggi s, IPK d isostatik tekanan. Analisis rinci air dan telah disebutkan silikat mencair pada tekanan IPK menunjukkan bahwa, Selain efek volume gratis, lain disebabkan tekanan struktural transformasi mungkin harus dipertanggungjawabkan dalam berbagai kasus. sd Dengan alasan ini, analisis teoritis diperpanjang saya untuk menggambarkan ketergantungan tekanan s yaitu, viskositas untuk sistem yang ada di gelas Serikat beku-di termodinamika nonequilibrium, d s d undercooled cairan di bawah temperatur transisi gelas t dan ii untuk sistem yang mengalami, di g Selain variasi dari volume gratis, tekanan disebabkan perubahan parameter struktural lainnya. Dalam kasus seperti itu mungkin terjadi penurunan viskositas dengan meningkatnya tekanan, pada prinsipnya, bahkan jika ekspansi termal coef Sien positif. Dengan cara ini, analisis hadir hibah alat umum untuk memperkirakan ketergantungan tekanan viskositas dan seharusnya mengendap kontroversi pada saat ini f g sastra. 2005 Institut Fisika Amerika. DOI: 10.1063/1.1851510
SAYA. PENGENALAN

nosilicate mencair, menjadi lebih kompleks nonmonotonichavior viskositas dalam ketergantungan pada tekanan ditemukan di 14 Sementara ketergantungan suhu dari viskositas di iso tekanan tinggi di kisaran IPK. s meningkatkan kondisi Baric adalah mapan viskositas Penurunan disebutkan viskositas dengan meningkatnya dengan penurunan suhu, saat d ini diskusi mengenai detekanan, diperoleh dalam beberapa rentang tekanan dan temperasdi isotermal mengelola pembangu viskositas pada tekanan eksternal saan, telah denoted sebagai anomali dan menjadi bertentangan d kondisi menunjukkan spektrum pernyataan kontroversial. 10,14 dengan hasil free volume teori viskositas. Misalnya, di Refs. 15 itu menyimpulkan bahwa viskositas Spesimen yang harus meningkat, sebagai suatu peraturan, seiring dengan meningkatnya tekanan dan ini terkumpul ini kation ketergantungan tekanan negatif viskositas sebagai anomali menunjukkan bahwa peningkatan viskositas harapan telah con rmed dalam berbagai percobaan 15 dengan meningkatnya tekanan dianggap sebagai aturan, tapi itu studi. Sebaliknya, sebaliknya eksperimental ditemukan untuk beberapa kaca-membentuk silikat cairan, seperti basal, dacite, penyimpangan juga tersedia. Dengan cara ini, muncul pertanyaan pada bagaimana semacam perilaku dapat dijelaskan secara teoritis Jadeite, dan albite 613 dan disebutkan sebagai possibil utamadan apakah mereka, memang, pengecualian. s d ity mengambil sebagai contoh perilaku air juga di Ref. Salah satu upaya dalam arah ini diajukan oleh 2. Dalam kasus ini, penurunan viskositas satu 15 10 Gupta. Kemudian pada, Bottinga dan ia menjabat juga sebagai berasal urutan besarnya telah dilaporkan untuk tekanan semakin meningkating oleh dua ke ve kali. Untuk berbagai silikat dan alumipersamaan untuk ketergantungan tekanan viskositas berdasarkan
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2005 Institut Fisika Amerika

Multilizer PDF Translator Free 074511-2 Schmelzer, Zanotto dan Fokin

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16 d generalisasi persamaan AdamGibbs. Gupta mem- di bawah temperatur transisi gelas, yaitu, kacamata. Dalam detik. V, pendekatan ini adalah lebih umum memberikan kemungkinan menyimpulkan bahwa, dalam kebanyakan kasus menarik, peningkatan viskositas dengan meningkatnya tekanan harus diharapkan, meskipun excep - untuk memperhitungkan efek tekanan disebabkan perubahan sdengan kehendakNya pendekatan d ketika re struktur cairan pada perubahan viskositas dengan prestions mungkin sesuai yakin. Ternyata mekanisme seperti menentukan pada dasarnya ekspansi laxational coef Sien Da the perbedaan antara ketergantungan tekanan viskositas berbagai kacaekspansi termal coef menyediakan keseimbangan cairan s pembentukan cairan, khususnya, di cf. tekanan tinggi, juga Ref. dan kaca di diberikan nilai-nilai tekanan dan temperatureis dRingkasan kesimpulan dasar dan diskusi 22. negatif. Namun, untuk menghitung ketergantungan tekanan s menyelesaikan d hasil Sec. VI karya. viskositas persamaan dihasilkan memerlukan pengetahuan perbedaan antara entropies keseimbangan cairan dan kaca, dan ekspansi relaxational coef efisien. The II. ANALISIS: APLIKASI GRATIS VOLUME KONSEP masing-masing data jarang tersedia, dan untuk suhu di atas kaca suhu transisi data tidak tersedia, Kami rst mempertimbangkan cairan konstan komposisi dalam 10 pada prinsipnya. Dengan alasan ini, adalah menarik untuk mengekspresikan sstabil atau metastable kesetimbangan d s yaitu, termodinamika menyatakan tekanan ketergantungan dari viskositas oleh lebih dapat diakses d di atas temperatur transisi gelas masing-masing. Menurut termodinamika coef cients, yang merujuk secara eksklusif untuk aturan fase Gibbs, jumlah derajat kebebasan dari cairan dalam keadaan yang sebenarnya dianggap, menghindari cara ini, di sistem sama dengan 2, dan dengan demikian seseorang dapat memilih temperaSelain itu, beberapa inkonsistensi yang melekat dalam pendekatan seperti saan dan tekanan sebagai variabel independen yang menentukan s juga Sec. VI. d mereka diikuti di Refs. 10 dan 15 lihat sifat-sifat sistem. Dalam kasus tersebut, viskositas h Alternatif pendekatan teoretis menghubungkan penurunan dapat dianggap sebagai fungsi dari tekanan dan suhu, viskositas dengan perubahan-perubahan struktural sistem masing-masing yaitu, s di bawah tekanan koordinasi perubahan, SiO bond melemahkann d s1d h = h sp, T. ing, perubahan tingkat polimerisasi, perubahan Q dispartai tribution, pembentukan vefold dan enam kali lipat terkoordinasi Si Dalam penyelidikan mereka diperpanjang dari persamaan dan berbedad spesies, dll, yang tidak dijelaskan dengan tepat oleh gratis ences cairan-uap dan cair-padat tahap transisi, Skri911, 14, 1721 4,5 konsep volume. Untuk sistem yang kompleks ini, POV dan Faizullin dianalisis ketergantungan viskositas h penurunan dari viskositas dengan tekanan diamati sebagai aturan, pada suhu T dan tekanan p untuk beberapa kelas liqs, IPK d setidaknya, untuk suf ciently tinggi tekanan. Dengan cara ini, uids. Mereka terbatas analisis mereka kasus-kasus dimana kita harus memeriksa, rst, apakah penurunan viskositas dengan ekspansi termal coef Sien cairan positif ini s meningkatnya tekanan itu, memang, bertentangan dengan gratis volproperti adalah ful lled di atmosfer tekanan untuk kebanyakan tapi tidak stanpa memihak viskositas tertentu apapun Ume teori d Analisis data literatur kedua dan mereka sendiri Semua cairan. d teori dan, kedua, bagaimana menggabungkan seperti tambahan hasil dipimpin-penulis untuk menyimpulkan bahwa real berikutefek struktural umumnya menjadi teori secara independen tions harus ful lled mekanisme tertentu perubahan struktural yang dianggap. Oleh ]h alasan-alasan yang disebutkan diatas, dan untuk sampai pada beberapa s2d , 0, solusi untuk kontroversi dimaksud pada efek dari tekanan ]T p pada viskositas, hal ini sangat menarik untuk meninjau kembali masalah ini dalam ]h untuk mengembangkan gambaran yang komprehensif mengenai phenom inis3d . 0. Enon. Pelaksanaan tugas ini adalah tujuan dari sekarang ]p T kontribusi. Karya ini disusun sebagai berikut. Dalam Sec. II, kami memperoleh Hubungan ini menyiratkan bahwa viskositas harus menurunkan dengan s d sebuah persamaan yang menentukan ketergantungan tekanan viscos- meningkatkan suhu untuk isobaric proses, dan harus dis lipatan dengan meningkatnya tekanan pada kondisi isotermal. d ity multicomponent cairan konstan komposisi dalam Serikat kesetimbangan stabil atau metastable untuk kasus gratis Selain itu, mengingat viskositas sebagai fungsi dari tekanan dan suhu, yaitu, mereka menuliskan mengikuti Kampa h= h sp, T,d volume variasi menentukan perilaku. Ini hubungan memmelenguh identitas: s nects jenis respon dari viskositas pada tekanan meningkatkan d dengan atau mengurangi viskositas dengan meningkatnya tekanan ]h ]T ]p s4d = 1. tanda ekspansi termal coef Sien cairan. Itu T p ] p ] h ]h T menggambarkan, setidaknya, dalam cara yang kualitatif benar tekanan Persamaan s4d mempertimbangkan berikut dari murni matematikaketergantungan dari viskositas paling cairan di moderat presations dan tidak melibatkan awalnya semua fisika. Sures. Satu pengecualian, ketergantungan tekanan viskositas Mempertimbangkan dependensi viskositas yang diberikan oleh air pada tekanan moderat, dianalisis secara rinci dalam Sec. III. s d 3, mereka s d menyimpulkan bahwa ketidaksetaraan EQS. 2 dan Untuk menutupi juga ini dan kasus serupa, dasar equation adalah umum untuk account untuk tambahan struktur]p s5d . 0 tural perubahan sistem terhadap tekanan varia]T h tions dan efeknya pada viskositas. Sebagai rst langkah, ini persamaan diperpanjang dalam Sec. IV untuk menggambarkan presharus ful lled. Equationappearing ini di sini rst sebagai yakin ketergantungan dari viskositas untuk sistem di frozen-in relationhas matematika murni, tentu saja, de cukup nite Serikat nonequilibrium termodinamika scairan undercooled arti fisik. Seperti disebutkan sebelumnya, viskositas liq-

SD SD

SD S DS D SD

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s stabil dan metastabled uids konstan komposisi dalam ada Kemudian, untuk mengamankan keteguhan dari viskositas, salah satu harus menuntut bahwa total volume sistem dijaga jika modynamic keseimbangan Serikat dapat dianggap sebagai functekanan dan suhu yang bervariasi sedikit oleh dT dan tion dua negara variabel, tekanan dan suhu, yaitu, h DP, masing-masing. Dari = h sp, T.d Namun, jika satu menganggap viskositas sebagai konstan f yaitu,h = = const, g maka hubungan ini memberikan depen h sp, T d ]V ]V yang paling ketat antara tekanan dan suhus konstan viscoss6d d dT + DP = 0, dV s p, T = ]T p ]p T d. S o E q . s5d berarti thatin agar viskositas untuk ity tetap constantan peningkatan suhu mengarah ke efek Kami kemudian mendapatkan hasil sebagai berikut yang dapat dikompensasi oleh peningkatan tekanan. ]V sd Itu harus menekankan bahwa Eqs. 2 dan s 3d di corrobodinilai oleh berbagai hasil penelitian dan menyebabkan ]T ]T ]p T s7d = . s5. dNamun, satu dapat teoritis konsekuensi yang diberikan oleh EQ ]p h ]p V ]V dengan mudah terbalik di atas argumentasi. Memang, mempertimbangkan ac]T p menghitung konsep-konsep umum yang menghubungkan viskositas dengan gratis s dkami nally memperoleh Dengan 4 EQ, volume dalam cairan4,5,23,24 kita dapat menganalisis secara teoritis bagaimana s] p / ] turunan parsial T d seharusnya berperilaku. Mempertimbangkan h ]V d dapat tiba kemudian di derekening, Selain itu, EQ 2,ssatu ]p T ]h ]h k Tsp, Td ] h sired teoritis prediksi tentang tekanan Encryptions8d = = , ]p T ]T p ]V a Tsp, Td ] T p mengumpulkan bukti dari viskositas. 23 Memang, setelah klasik bekerja ya. I. Frenkel, ]T p inti dari konsep-konsep volume gratis dapat dinyatakan sebagai mana k T adalah compressibility isotermal dan a T isos d volume unik menentukan nilai berikut: gratis ekspansi termal Baric coef Sien, yaitu, sd viskositas h ; volume II gratis secara unik ditentukan oleh s p, T dcairan dan tidak oleh tekanan p dan Total volume V 1 ]V 1 ]V s9d , aT = . kT = suhu T secara terpisah. Frenkel disebutkan di Batchinskij V ]p T V ]T persamaan sebagai satu contoh untuk tipe ketergantungan. The Marilah kita, sekarang, menganalisis kemungkinan konsekuensi dari Eq. masing-masing ide telah dikembangkan kemudian oleh berbeda s d 8 . Untuk sistem di sstabil atau metastable d termodinamika penulis memajukan tertentu model teori-teori volume gratis keseimbangan, kondisi stabilitas termodinamika untuk ketergantungan dari viskositas pada termodinamika parameter negara. Dalam kontras untuk menyempurnakannya sebelumnya, di sini kami ] p s10d . 0 kT = mempekerjakan hanya di atas diberikan esensi dari konsep-konsep volume gratis ]V T tanpa menentukan setiap model tertentu untuk ow kental. satau sd Untuk melanjutkan, kita menyadari bahwa volume gratis harus ful lled. Mempertimbangkan 2 EQ, itu k. T 0d s cairan, sebagai suatu peraturan, berkurang dengan tekanan. Dengan cara ini, dalam rangka Berikut yang The tanda-tanda dari The derivatif p d ] T /] h s yang dihasilkan mengatakan membangun kembali nilai volume gratis dan p d ] T /] ] h / ]p dT ditentukan oleh tanda V dan s d kita harus bervariasi suhu seperti itu s nilai dari viskositas, ekspansi termal coef Sien, yang pada atmosfer pres d sebagai suatu peraturan, sebuah kuantitas positif. Dalam kasus s dini, Eq. 8 batas untuk mengimbangi perubahan volume gratis karena yakin, pengaruh tekanan. Akibatnya, dari umum sepertimemprediksi peningkatan dari viskositas dengan meningkatnya tekanan. pertimbangan Oretical, salah satu tiba langsung di ketidaksetaraan Skripov dan Faizullin 4,5 terbatas analisis mereka seperti s tapi d sekarang secara independen dari pengetahuan tentang experi- kasus. Akibatnya, kesimpulan mereka benar sejauh ini EQ 5, mental data. Mengambil secara eksklusif ketergantungan yang diberikan oleh kondisi Eq. ini ful lled. s2d dari percobaan, kami kemudian tiba, memanfaatkan s d EQ 4, atEq.Namun, beberapa zat memiliki negatif penyusunan termals3d. Dengan cara ini, mempekerjakan hanya konsep umum menghubungkan Sion coef cients tertentu Rentang suhu di atmo sd viskositas dengan gratis volume cairan dansasumsi spheric tekanan. Untuk kasus ini luar biasa, EQ 8 memprediksi tidak adanya perubahan struktural lainnya selain densipenurunan viskositas dengan meningkatnya tekanan. Terbaik kationd yang kita dapat menyimpulkan bahwa, dalam kondisi isotermal, contoh yang dikenal adalah air dalam kisaran suhu dari viskositas telah meningkat, sebagai suatu peraturan, seiring dengan meningkatnya 0 hingga 4 tekanan. C. Dengan cara ini, kita mengharapkan penurunan viskositas Namun, pengecualian dari aturan umum ini mungkin, sebagai air dengan meningkatnya tekanan dalam kisaran suhu ini. akan menjadi jelas dari analy kuantitatif berikutKesimpulan ini adalah con rmed, namun, seperti yang kita lihat dari SIS. analisis di bagian berikutnya, situasi dengan reSelain kesimpulan kualitatif yang diberikan di atas, SPECT untuk ketergantungan tekanan air jauh lebih satu dengan mudah dapat merumuskan sebuah metode untuk memperkirakan kompleks. secara kuantitatif s isotermal condiketergantungan tekanan viskositas dalam Untuk air pada suhu rentang 04 C, mentionsd disediakan ketergantungan suhu dari viskositas di s tioned di atas silikat anomali, yaitu, turunnya viskositas tekanan konstan d dan beberapa lain murni termodinamika dengan meningkatnya tekanan eksperimental ditemukan untuk berbagai Karakteristik dari cairan dikenal. Memang, menurut kaca-membentuk silikat cairan, seperti basalt, dacite, jadi atas analisis, kami dapat menghubungkan variasi viskositas dengan deite, dan albite, 613 dapat juga dijelaskan disediakan variasi gratis volume dan rasa bahwa volume gratis adalah ekspansi termal coef cients sistem ini yang nega unik terhubung dengan total volume dari sistem. tive di masing-masing rentang tekanan dan temperatur.

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SD S D MENGATAKAN D S SD SD S D SD SD SD SD

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074511-4

Schmelzer, Zanotto, and Fokin

J. Chem. Phys. 122, 074511 ~ 2005 !

This seems to be the case for lithium disilicate at the considered values of pressure and temperature. 25 There are indications that also other glass-forming liquidssuch as albite, jadeite, dacite, basalts, etc.show a negative thermal expans, GPad isostatic sion coefcient when subjected to high pressures. However, to the best of our knowledge, direct experimental measurements of the thermal expansion coefcients of the respective systems in the GPa-pressure range are very rare. Thus, more denite experimental analyses are required before some nal conclusions can be drawn on this issue. Summarizing, we rst conclude that free volume concepts do not, in general, forbid a decrease of viscosity with increasing pressure. They lead to such result as well, if the thermal expansion coefcient of the liquid is negative in the respective ranges of pressure and temperature. However, at low and moderate pressures, the thermal expansion coefcient is, in general, a positive quantity and, in such cases, the viscosity should increase with increasing pressure provided the behavior is determined by free-volume effects. As a second conclusion, we can state: If the viscosity of a liquid decreases with increasing pressure and the thermal expansion coefcient is positive, then the pressure dependence for these anomalously behaving systems cannot be explained, in principle, exclusively by free volume concepts. One example in this respect will be analyzed in detail in the subsequent Sec. III. The question, for which classes of liquids free volume concepts in the most general form, as employed here and s ,d resulting in Eq. 8 can give a satisfactory description of the pressure dependence of viscosity, will be addressed in a separate investigation. 26 Here we concentrate, in the subsequent analysis, on the solution of the complementary task to establish the general form of the equations describing the pressure dependence of the viscosity if free volume concepts s also Ref. 22 . In d alone are not sufcient cf., such cases, alternative, more sophisticated approaches must be utilized. A general method to incorporate such additional effects into the theory will be outlined in Sec. V.
III. A FIRST EXCEPTION: WATER

s FIG. 1. Density of water vs temperature at different pressures in MPa as d s 27 .d specied in the gure Ref. The line crossing the curves obtained for different pressures species the location of the density maximum. At the left-hand side of this line, the thermal expansion coefcient is negative. To the right-hand side of this line, the thermal expansion coefcient is positive.

range from 0 to 25 C . d In the whole range of temperature sdh /dpd and pressure considered here, the slope T of the d not depend on pressure and is curves h = h sp,T=const does exclusively a function of temperature. Latter dependence is illustrated in Fig. 3 s h .dAs it turns out, the absolute value of d the slope of the curves h = with inh sp,T=const decreases creasing temperature. Figure 4 shows the viscosity of water as a function of pressure for wider ranges of the thermodynamic state params eters pressure values in the range from 0 to 100 MPa and temperatures 0 and 25 C .d As evident from the gure, with an increase of temperature, the dependence of the viscosity s on pressure changes qualitatively and a minimum occurs illustrated in the gure for the temperature 25 C.d For values

In Figs. 1 and 2, density and thermal expansion coefcients of ordinary water are shown as functions of temperature for different values of pressure in the range 020 MPa. At 0 C, water has negative thermal expansion coefcients in the range of pressures from 0 to 20 MPa. According to s ,done expects in this range a decrease of viscosity with Eq. 8 increasing pressure. This is indeed the case as it follows, for example, from the results shown in Table I. However, it is evident from the same column of Table I that the viscosity of water at 0 C decreases with increasing pressure also in the range where the isothermal expansion coefcient becomes s8d positive. Consequently, in this range of pressures, Eq. cannot describe the experimental data even qualitatively correctly. s 3 d g s,d In Figs. 3 a the viscosity of water in s mPa sd is sin the range from shown as a function of pressure sin the 0 t o 2 0 M P ad for different values of temperature

FIG. 2. Thermal expansion coefcient of water as a function of temperature s MPa as d specied in the gure Ref. s 27 . d at different pressures in

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074511-5

Pressure dependence of viscosity

J. Chem. Phys. 122, 074511 ~ 2005 !

TABLE I. Values of the viscosity in s mPa sd of ordinary water obtained with the aid of the recommended s MPa and d temperature in C s . Data d are taken from Ref. 28. interpolation equation as a function of pressure in Note that, at high temperatures, some of the data refer to water vapor. s d Temperature C Ps MPad 0.1 0.5 1 2.5 5 7.5 10 12.5 15 17.5 20 22.5 25 27.5 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 0 1792 1791 1789 1786 1780 1774 1768 1762 1757 1752 1747 1742 1737 1732 1728 1719 1711 1704 1697 1690 1684 1679 1673 1669 1665 1661 1658 1655 1652 25 890.1 890.0 889.9 889.5 889.0 888.5 888.0 887.6 887.1 886.8 886.4 886.1 885.8 885.5 885.3 884.9 884.7 884.5 884.5 884.6 884.7 885.0 885.4 885.9 886.4 887.1 887.9 888.7 889.7 50 546.8 546.9 547.0 547.3 547.7 548.2 548.6 549.1 549.6 550.1 550.6 551.1 551.6 552.1 552.6 553.7 554.8 556.0 557.2 558.4 559.6 560.9 562.2 563.5 564.9 566.3 567.7 569.1 570.6 75 377.7 377.8 378.0 378.4 379.0 379.7 380.3 381.0 381.6 382.3 382.9 383.6 384.3 384.9 385.6 386.9 388.3 389.7 391.0 392.4 393.8 395.2 396.6 398.0 399.4 400.8 402.3 403.7 405.1 100 12.27 281.8 282.0 282.4 283.1 283.7 284.4 285.1 285.7 286.4 287.1 287.7 288.4 289.1 289.7 291.1 292.4 293.7 295.1 296.4 297.7 299.1 300.4 301.7 303.1 304.4 305.7 307.0 308.4 150 14.18 182.5 182.6 183.0 183.6 184.2 184.9 185.5 186.1 186.7 187.3 187.9 188.6 189.2 189.8 191.0 192.2 193.4 194.6 195.7 196.9 198.1 199.2 200.4 201.5 202.6 203.8 204.9 206.0 200 16.18 16.05 15.89 134.6 135.2 135.8 136.4 137.0 137.6 138.2 138.8 139.4 140.0 140.6 141.1 142.3 143.4 144.5 145.6 146.7 147.8 148.8 149.9 150.9 151.9 153.0 154.0 155.0 155.9 250 18.22 18.14 18.05 17.76 106.4 107.1 107.8 108.4 109.1 109.8 110.4 111.0 111.6 112.2 112.9 114.0 115.2 116.3 117.4 118.5 119.6 120.6 121.6 122.7 123.6 124.6 125.6 126.5 127.5 300 20.29 20.24 20.18 20.02 19.80 19.66 86.46 87.42 88.33 89.21 90.05 90.86 91.65 92.41 93.15 94.58 95.93 97.23 98.48 99.69 100.9 102.0 103.1 104.1 105.2 106.2 107.2 108.2 109.1 350 22.37 22.34 22.31 22.23 22.13 22.09 22.15 22.37 22.94 66.99 69.31 71.17 72.76 74.18 75.46 77.74 79.75 81.56 83.23 84.78 86.24 87.62 88.93 90.17 91.37 92.52 93.63 94.70 95.74 375 23.41 23.39 23.37 23.31 23.26 23.26 23.33 23.51 23.86 24.51 25.92 47.79 58.25 61.97 64.56 68.36 71.28 73.71 75.83 77.73 79.46 81.06 82.56 83.97 85.30 86.57 87.78 88.94 90.06

of pressure above those corresponding to this minimum, the viscosity behaves in the normal way, i.e., increases with increasing pressure. With a further increase of temperature, this minimum is shifted to lower values of pressure and disappears at all. Such situation is found, for example, at a temperature 40 C sand also for the temperatures T d these temperatures, the ther 50 C shown in Table I. At mal expansion coefcient of water is positive and the viscosity of water increases with increasing pressure. In this temperature range, Eq. s8d gives a qualitatively correct description of the pressure dependence of the viscosity also for water. By this reason it is of interest to check to which s can d give a quantitatively correct description. extent Eq. 8 f A quantitative comparison of theoretical based on Eq. s8dgand experimental results is shown in Figs. 5 a s and d 5 bs d for two temperatures, 40 and 150 C. In these gures, the f s k T / a Tds results of computation of the product ] h / ] Tdp g f Eq. 8 . The s dgdata required are shown by dashed lines cf., for the computations are taken from Refs. 27 and 28. The full curves refer to the value of the quantity s] h / ] pd T determined directly from experimental data on the dependence of viscosity on pressure and temperature of water as given in Ref. 28. As it turns out, for water the theoretical expression, based

exclusively on free volume concepts, leads to quantitative deviations with experimental data up to one order of magnitude. However, as evident from the gures as well, these deviations decrease with increasing pressure and temperature. Such behavior can be interpreted as a consequence of diminishing importance of structural rearrangements of water with increasing pressure and temperature in favor of free volume effects. Summarizing the results of the analysis for the pressure dependence of the viscosity of water, we conclude that free volume effects alone are obviously not sufcient to give a correct interpretation of the dependencies observed. Consequently, one can expect the occurrence of similar effects also for other classes of liquids. By these reasons, in the subsequent sections we generalize Eq. 8 s to d account for the efs addition fects of variations of other structural parameters in d the pressure dependence of the to free volume effects on viscosity.
IV. A FIRST GENERALIZATION: VISCOSITY OF GLASS-FORMING LIQUIDS IN FROZEN-IN NONEQUILIBRIUM STATES

So far, we have considered liquids in stable or metastable equilibrium states. However, in treating the behavior

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074511-6

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J. Chem. Phys. 122, 074511 ~ 2005 !

d s from 0 to 25 C as FIG. 3. Viscosity of water ins mPa sd vs pressure ins the range from 0 to 20 MPa for different values of temperature in the range s dg s and d slope sdh/dp d d a function of temperature h . s d indicated in the gures a h sp,T=const as T of the curves h =

of glass-forming melts near and, in particular, below the glass transition temperature, the concept of nonequilibrium sisostructurald viscosity gains importance. 11,24,2931 Such cons cepts apply if we deal with a glass a frozen-in nonequilibrium state d which did not reach the respective metastable state yet. Also for such systems, it is obviously of interest to study the pressure dependence of viscosity. In order to treat theoretically the dependence of the nond be modied. equilibrium viscosity on pressure, Eq. 1smust In the simplest approach, we can assume that the viscosity depends, in addition to pressure and temperature, on one additional order parameter j , which is a measure of the deviation of the state of the glass from the state of the respecs e.g., Ref. 24 . In d such cases, we tive metastable liquid see, s d have instead of Eq. 1 ,

h = h sp,T, j d.

s11d

Here we will restrict the analysis to such states where the characteristic times of relaxation processes to the respective stable or metastable equilibrium state are large as compared with the characteristic times of variation of pressure or temsd perature. In such cases, we can generalize Eq. 4 considering changes of the state parameters T, p, and h of the system, the value of the order parameter j being xed. We then get

S DS DS D
]h ]T
p, j

]T ]p

h, j

]p ]h

=1.

s12d

T, j

s d8s, d Instead of Eqs. 6 we then obtain

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074511-7

Pressure dependence of viscosity

J. Chem. Phys. 122, 074511 ~ 2005 !

FIG. 4. Viscosity of water as a function of pressure 0 to 100 MPa d at 0 and 25 C.

sin the range from

dV s p ,T, j d=

SD SD SD
]V ]T
dT +
p, j

]V ]p

dp +

T, j

]V ]j

p,T

dj =0, s13d

SD S D SD SD SD SD SD SD
]T ]p
>
h, j

]T ]p

V, j

]V ]p = ]V ]T ]V ]p ]V ]T

T, j

s14d

p, j

]h ]p

T, j

]h ]T

T, j

p, j

k T,j sp,T, j d ] h a T,j sp,T, j d ] T

SD
p, j

. s15d

p, j

The derivations can be performed similarly with identical results if j is replaced by a set of order parameters h j i j scf., Sec. V d . s is d widely identical to Eq. 8 with s d the only Equation 15 d depend on difference that all quantities entering Eq. s 15 now one or a set of additional order parameters. Assuming that s remains d Eq. 2 valid in a modied form as

SD
]h ]T
p, j

f on Eq. 8 s dgand exFIG. 5. Quantitative comparison of theoretical based perimental results for the pressure dependence of the viscosity of water at d results of computation of the product f 40 C as d and 150 C b s . The s dgare shown by dashed lines. The full curve sk T / a Tds ] h / ] Tdp s cf., Eq. 8 refers to the value of the quantity s] h / ] pd T determined directly based on experimental data on the dependence of viscosity of water on pressure and temperature as given in Ref. 28. The values of a T, k T, and the density of water, required for the computations were taken from Ref. 27.

, 0,

s16d

the sign of the pressure dependence of the viscosity is determined, again, by the signs of thermal expansion coefcient and compressibility. As it turns out, the thermal expansion coefcient is, as a rule, a positive quantity, again s cf., Fig. 6 d , at least, for atmospheric pressures. One should note, however, that for the considered case of frozen-in nonequilibrium states the stability condition, Eq. s10d s system is not in a state , is not necessarily fullled the d way, deviaof a stable thermodynamic equilibrium . This

tions from a positive pressure dependence of the viscosity s positive may also occur when the system is characterized at d values of the isothermal expansion coefcient by positive s] V/ ] pd values of the partial derivative T, j . Whether such cases are indeed realized in nature is a topic for a separate analysis.
V. STRUCTURAL CHANGES OF LIQUIDS AND THEIR EFFECT ON THE PRESSURE DEPENDENCE OF THE VISCOSITY

se.g., Refs. 14 and As outlined in a variety of papers d 1721 , liquids, in general, and silicate melts, in particular,

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074511-8

Schmelzer, Zanotto, and Fokin

J. Chem. Phys. 122, 074511 ~ 2005 !

FIG. 6. Frequency distribution histogram of the thermal expansion coefcient a T for 14 794 silicate glasses below T g sdata are taken from Ref. 32 .d

can exhibit a variety of additional mechanisms of structural s adjustments change in the degree of polymerization, coordination numbers, frequency of distribution of different structural units, formation of vefold and sixfold coordinated Si, etc.d , when subjected to high isostatic pressures, as compared exclusively with variations of free volume. Such changes occur most easily at sufciently high temperatures when the liquid is in stable or metastable equilibrium states. For such cases, we have to introduce, at least, one additional state variable describing the change of the mentioned structural properties with pressure. In such cases, the viscosity can be s ,d expressed via Eq. 11 again, but now the parameter j has to be considered as a unique function of pressure and temperature. s d 15 s retain d Equations 12 their validity, but the change of viscosity with pressure has now to be written in the form

FIG. 7. Frequency distributions of silicate and germanium melts revealing sfor pressures p 1 GPa d d negative 2 pressure s d dependenpositive 1 s and cies of the viscosity. The independent variable is the viscosity of the respective systems at atmospheric pressure and temperatures above the respective melting temperatures. As it turns out systems with high viscosity show a trend to a negative pressure dependence, i.e., a decrease of viscosity with increasing pressure.

S D SD S D S D
dh dp =
T

]h ]p

T, j

]h ]j

dj dp

s17d

s we d arrive at With Eq. 15

SD
dh dp
T

k T,j sp,T, j d ] h a T,j sp,T, j d ] T

SD SD S D
+
p, j

]h ]j

dj dp

s18d

d The rst term on the right-hand side of Eq. 18 s describes variations of the viscosity with increasing pressure provided additional structural rearrangements of the melt can be neglected. Latter effect is expressed primarily by the second term and determines, for example, the pressure dependence of viscosity for water at sufciently low temperatures as discussed in detail in Sec. III. s ,d Let us apply Eq. 18 as an additional example, to silis d cate melts and assume for this purpose that j in Eq. 18 describes the degree of polymerization. In general, one can expect that the viscosity increases then with increasing j. However, the degree of polymerization of silicate melts decreases with increasing pressure 10 sat sufciently high tems gives d peraturesd . By this reason, the second term in Eq. 18 s a negative contribution which may and this is very impor-

tantd overcompensate the rst term. Similarly, in Ref. 33 an increase of viscosity of sulfur with pressure in the GPa range was reported and interpreted as the result of gradual strucs tural changes changing content of S rings and variations of 8 the degree of polymerization 34d . Note, however, thatsince the second term in Eq. s18d d is effective only, if, in addition is proportional to s d j/dp it s as to free volume variations, structural changes occur i.e., far as j changes with variations of pressure d . By this reason, the second term will become active in the course of increase of pressure only as far as pressure induced structural adjustments start to take place. In addition, we can expect from Eq. s18d that after some pressure intervalwhere the structural reorganization process proceedsis overcome, the behavior is, again, determined by free volume effects with a normal increase of viscosity with a further pressure increase. Such switching from anormal to normal behavior ass well as the opposite switch from normal to anormal reaction with red found, indeed, in a variety of spect to pressure changes is silicate and aluminosilicate melts 14 and, again, in the particular case of water analyzed in Sec. III. Data on the pressure dependence of viscosity of silicate melts, given in Ref. 14, show another interesting feature demonstrated in Fig. 7. This gure shows the frequency distributions of melts having positive or negative pressure dependencies at atmospheric pressures and temperatures above the respective melting temperatures T m . As the ordinate, the viscosity at atmospheric pressure is chosen. Despite the poor statistics, this distribution indicates the existence of a correlation between the value of the viscosity and the response to pressure variations: the higher the melt viscosity, the higher the probability of a negative pressure dependence. This trend may be caused by negative thermal expansion coefcients or

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074511-9

Pressure dependence of viscosity

by the breakdown of free volume concepts. Indeed, high viscosities may be connected with low values of free volume. As a result, further increases of pressure cannot affect this parameter any more and other types of structural rearrangements gain importance. In this way, one can suggest the hys other pothesis that, for a variety of complex liquids where types of structural adjustments in addition to free volume may occur d with an increase of pressureas a rulea s change from positive governed by free volume tod a negas d tive governed by other types of structural adjustments pressure dependence of the viscosity may be expected. Such kind of behavior is, indeed, observed for silicate melts 14 where the respective structural rearrangements result in a decrease of viscosity. Following ideas similar to the principle of le ChatelierBrown in thermodynamics, one may expect that this kind of behaviordecrease of viscosity resulting from structural reorganizationis dominating, but exceptions from this rulei.e., structural reorganization leading to a further increase of viscositycannot be excluded. One should note as well that the occurrence of additional structural rearrangements has an effect also on the rst term d quantities entering on the right-hand side of Eq. 18s . The this term refer to the respective thermodynamic coefcients and kinetic parameters at constant values of the structure parameter j . However, in the course of the measurements such structural variations will also take place, as a rule, and will affect the values of these quantities. Taking into account these considerations, according to Eq. 9s, d we now have

kT =

aT =

1 dV V dT

SD S D SD H S D SD J SD S D
= k T, j 1 V 1 ]V V ]j +
T

1 dV V dp

SD
T

1 V

D SD J HS
]V ]p
+
T, j

J. Chem. Phys. 122, 074511 ~ 2005 !

]V ]j

dj T dp

dj dp

s19d

]V ]T

p, j

]V ]j

dj p dT .
p

= a T, j

1 ]V + V ]j

dj dT

s20d

While in the considered case the compressibility k T, measured experimentally and determining the response of the system to changes of pressure at constant temperature, is s positive thermodynamic stability condition , d the coefcient k T,j does not necessarily fulll such condition. The above given equations can be generalized to the case when several independent structural rearrangements of the liquid occur as a result of a pressure increase. In such case, we have to introduce a set of additional order params takes d the form eters h j j =j 1 j , 2 ,... and Eq. 18 k T,hj j sp,T, hj jd ] h dh dj i ]h = + . s h jd dp T ] T p,hj j i ] j i T dp T a T, hj j p,T, j

SD

SD o SD S D
s21d

s and d a similar relation for the derivative Employing Eq. 17 sdh /dTdp and utilizing, in addition, Eq. 15 s ,d we can rewrite s d Eq. 18 as

SD

dh k T,j sT,p, j d = dp T a T,j sT,p, j d

H H
1+ 1+

]h ]j ]h ]j

S D J FD S DG S Y SD S D FD S S DG J Y
p,T p,T

]h ]T ]h ]p

p, j

T, j

dj dT dj dp

dh dT

s22d

s ,d This equation can be generalized similarly to Eq. 21 when several order parameters have to be incorporated into the description. It shows that, in the general case, the pressure dependence of viscosity is not exclusively expressed by s compressibility and thermal expansion coefcient reecting d free volume concepts , but also by the reaction of the system to other types of structural adjustments to pressure variation. In case that such additional processes do not occur, we obtain s ,d d from Eq. 22 as a special case, Eq. 8 , s again.

S D
] ln h ]p
T

CV s T ,p d DasT,p d 2 TsDSs T ,p dd

=ln

SD H
h h0

Vs T ,p d DasT,p d , u s S D T ,p du

s23d

VI. DISCUSSION

The equation for the pressure dependence of viscosity, derived by Gupta, 15 has the form

where DS is the entropy difference between the equilibrium melt and the glass, Da the relaxational expansion coefcient sthe difference between the thermal expansion coefcients between the equilibrium melt and the glass ,d and C a coefcient in the expression for the dependence of viscosity on the state parameters in the AdamsGibbs model. 15,16 According to this expression, the sign of the temperature dependence of the viscosity is determined by the sign of the relaxational expansion coefcient. Gupta noted that this relation could be conrmed directly only for water in the range of temperatures from 1 to 4 C, for which Da is known and fullls the condition Da, 0 and the viscosity indeed de-

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074511-10

Schmelzer, Zanotto, and Fokin

J. Chem. Phys. 122, 074511 ~ 2005 !

creases with increasing pressure. As discussed here earlier in detail, this resulta decrease of the viscosity of water with s8d.In increasing pressurealso follows directly from Eq. this case, this result is a consequence of negative thermal expansion coefcients of water in the range of temperatures 04 C, where this condition is fullled. So both approaches allow one to predict a decrease of viscosity with increasing pressure and in both approaches such kind of behavior is connected with specic properties of the thermal expansion coefcient. However, we already mentioned that water exhibits a decrease of viscosity for wider ranges of pressure and temperature, where the thermal expansion coefcient is positive. It would be interesting to check Gupta's equation also for these broader ranges of thermodynamic state parameters. However, such task will meet, at part, principal difculties discussed below. s8d A comparison of both approaches shows that Eq. seems to be more satisfactory from a theoretical point of s .d d view than Eq. 23 Equation 8 s connects the properties of a given system exclusively with other thermodynamic and kinetic properties of the system in the same state. In contrast, s involves d Eq. 23 differences between the properties of the equilibrium liquid and the glassy states. Such result is in contradiction with basic assumptions of thermodynamics, where, commonly, relationships are developed between different properties at the same state of the system without any reference to alternative possible states. Moreover, as mentioned in Ref. 10 in application to silicate glasses, there is no way to measure the coefcient of thermal expansion of the respective glass at temperatures above the glass transition. We have shown in this paper that free volume concepts allow both an increase and decrease of viscosity with increasing pressure. The type of dependence is hereby determined by the sign of the thermal expansion coefcient. Since, in most cases of interest at s atmospheric pressures , d the thermal expansion coefcient is positive, commonly the normal behavior, i.e., an increase of viscosity with increasing pressure is observed. However, the situation can become quite different for complex liquids and, in particular, at pressures in the GPa range and sufciently high temperatures. Here reliable experimental data on the value of the thermal expansion coefcients are, to our knowledge, so far not available. As also demonstrated here, similar dependencies govern the behavior of the pressure dependence of liquids not only for liquids in stable and metastable equilibrium, but, with the limitations above discussed, they are also valid for s glasses liquids in frozen-in nonequilibrium states . d As a generalization, equations have been developed allowing one to incorporate the effect of additional structural variations of the liquids under consideration, which are not reected by free volume concepts, on the form of the pressure dependence of the viscosity. These relations may result in a negative pressure dependence of the viscosity even in cases if the thermal expansion coefcient a T, j is positive. They contain additional terms, which are effective, however, only in ranges of pressures and temperatures, where such additional structural changes indeed occur. By this reason, the respective equations allow one to predict an increase, a decrease and a nonmonotonic behavior of viscosity with

pressure, and cover all types of dependencies found in experimental analyses. Vice versa, latter behavior can be considered therefore as a strong indication of the existence of structural transformations in the liquid in the considered range of thermodynamic state parameters. Summarizing the results of the analysis, we have shown from general assumptions concerning the dependence of free volume of liquids and viscosity thatat isothermal conditions and moderate pressuresthe viscosity of simple liquids typically increases with pressure. In contrast, complex liquids, such as molten silicates, either show a negative pressure dependence starting from small pressures or change from a positive to a negative dependence at some sufciently high threshold pressure. An equation is derived that allows one to determine the dependence of viscosity on pressure, s the simplest case that d the temperature depenprovided in dence of viscosity, the isothermal compressibility, and the isobaric thermal expansion coefcient of the liquid are known. This equation can be generalized to situations, when, in addition to free volume effects, other mechanisms of structural reorganization of the liquid with respect to pressure variations exist. In such situation, increases, decreases, and nonmonotonic behavior of viscosity with respect to pressure variations exist.
ACKNOWLEDGMENTS

The authors would like to express their gratitude to the s ,d Deutsche Forschungsgemeinschaft DFG and to the State s of So Paulo Research Foundation, FAPESP Grant Nos. 99/ 00871-2, 03/12617-0, and 03/03575-2 ,d CNPq, and Pronex for nancial support. The discussions with Tihana Fuss sUMR, Rolla, USA d and the valuable help of M. L. F. Nascis d data mining are deeply mento LaMaV, UFSCar, Brazil in appreciated. The authors would like to express their thanks also to R. Feistel sInstitut fr Ostseeforschung, RostockWarnemnde, Germany d for supplying them with comprehensive sets of kinetic and thermodynamic data for water.
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1

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074511-11
19

Pressure dependence of viscosity

27

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