〔環境材料工学科 〕〔区 分 Ａ〕
松英 達也
RELAXATION OF RESIDUAL STRESSES IN THIN FILMS INVESTIGATED USING SYNCHROTRONRADIATUION
Tatsuya MATSUE*1, Takao HANABUSA*2, Kazuya KUSAKA*2, Osami SAKATA*3*1

Niihama National College of Technology, *2Institute of Technology and Science,The

University of Tokushima,*3 Japan Synchrotron Radiation Research Institute/SPring-8
Advaces in x-ray Analysis・vol.52・233・2009年.
The crystal structure and residual stresses of TiN thin films deposited by arc ion plating(AIP) on a steel substrate were investigated using a synchrotron radiation system whichemitted ultra-intense X-rays. In a previous study, the crystal structure of TiN films
deposited by AIP was found to be strongly influenced by the bias voltage during deposition.
However, for film thickness of approximately 200 nm, TiN films deposited under bias voltagesof -100 V and 0 V had a preferred orientation of {110}. In the present study, the two-tilt
method was used to evaluate the residual stresses in TiN films by measuring lattice strainsin two directions determined by the crystal orientation. The TiN films deposited under abias voltage of -100 V were found to have a compressive residual stress of -8.0 GPa. Thiswas observed to decrease with increasing annealing temperature, and reached a value of -3.5
GPa at 800ºC. On the other hand, TiN films deposited under a bias voltage of 0 V had acompressive residual stress of -6.5 GPa, which was reduced to -5.2 GPa following annealing
at 800ºC.
Keywords: TiN film, Arc ion plating, Crystal structure, Residual stress, Surface morphology,
Synchrotron radiation

松英 達也
小・中学校理科および技術教員へのものづくりを通した実技研修会
松英達也 *1、鎌田慶宣 *2、谷口佳文 *1、西井靖博 *3、占部弘治 *4 、吉川貴士 *2 、松田雄二 *2 、
松友真哉 *4、平澤英之 *1、濱田
*1

直 *5

新居浜工業高等専門学校環境材料工学科、 *2 新居浜工業高等専門学校機械工学科、 *3 新居浜工業

高等専門学校生物応用化学科、*4新居浜工業高等専門学校電子制御工学科、*5現代GPコーディネー
ター
平成21年度高専教育講演論文集･323-226・2009年

新居浜高専は平成18年度に文部科学省「現代的教育ニーズ取組支援プログラム（現代GP）」に「地域連携プロジェクト型ものづくり活動」を提案し、採択された。この活動は大きく分けて「ものづくり人材育成」と「まちづくり・地域の求心力向上」の２つのプロジェクトを柱としたものであり、それぞれに3つのプロジェクト活動を展開するよう組織化されている。
教員の実技研修会は上記の「ものづくり人材育成・ものづくり教材開発プロジェクト」に組み込まれ、先の問題を解消し、より実践的な内容とするべく活動を行った。本論文では、平成18年度から平成20年度までの3年間の活動によって得られた成果について報告する。
- 40 -

朝日 太郎Response characteristics of all-solid-state pH sensor using Li5YSi4O12 glass
Susumu Nakayama*1, Koji Onishi*2, Taro Asahi*3, Yan Lin Aung*4, Shigeki Kuwata*1*1

Department of Applied Chemistry and Biotechnology Niihama National College of Technology,*2

Department of Electrical Engineering and Information Science Niihama National College ofTechnology,*3

Department of Materials Engineering Niihama National College of Technology,*4World-Lab Co., Ltd.

Ceramics International, Vol.35, p.3057-3060, 2009.
A new type of all-solid-state pH sensor was investigated for the monitoring of pH in hightemperature. The all-solid-state pH sensor consists of two half-cells: indicator electrode using
the Li5YSi4O12 glass and an Ag/AgCl reference electrode coated with Nafion film. A stable Nafion
film was achieved by heat treating at 100 ºC for 1 hour. The electromotive force (EMF) of the
all-solid-state pH sensor decreased linearly with pH increase in water in accordance with the
Nernst’s equation. The all-solid-state pH sensor operated stably up to 80 ºC. The sensitivityof the all-solid-state pH sensor against pH was high, and the EMF was also scarcely influenced by
the presence of inorganic ions such as Li+, Na+ and Cl-. It was practically confirmed by the pH
titration test that the all-solid-state pH sensor behaved similarly to the commercial pH meter withthe conventional glass electrode.

In addition, the all-solid-state pH sensor showed sameequivalence point both at high temperature and low temperature operations.

平澤 英之
小・中学校理科および技術教員へのものづくりを通した実技研修会
松英達也*1、鎌田慶宣*1、谷口佳文*2、西井靖博*3、占部弘治*4、吉川貴士*2、松田雄二*2、松友真哉*4、
平澤英之*1、濱田 直*5*1

新居浜工業高等専門学校環境材料工学科、*2新居浜工業高等専門学校機械工学科、*3新居浜工業高等専門

学校生物応用化学科、*4新居浜工業高等専門学校電子制御工学科、*5現代GPコーディネーター
平成21年度高専教育講演論文集、PP.223･225、2009〔概要は前掲〕

平澤 英之
Heat Generation Ability in AC Magnetic Field of Nano MgFe2O4 Ferrite
Powder Prepared by Bead Milling
H. Hirazawa*1, H. Aono*2, T. Naohara*2, T. Maehara*2, M. Sato*3, and Y. Watanabe*4*1

新居浜工業高等専門学校環境材料工学科、*2 愛媛大学大学院理工学研究科、*3

アドメテック(株)、*4 愛媛大学医学部第二外科

Proc. of the 6th International Symposium on Electromagnetic Processing of Materials, pp.189-192,
10/2009
The nano sized MgFe2O4-based ferrite powder having a heat generation ability in an AC magnetic
field was prepared by bead milling and studied for thermal coagulation therapy applications. The
crystal size and the particle size significantly decreased by bead milling. The heat generation
ability in the AC magnetic filed improved with the milling time, i.e., a decrease in the crystal
size. However, the heat generation ability decreased for excessive milled samples with crystal sizes- 41 -

less than 5.5 nm. The highest heat ability (ΔT=34 oC) in the AC magnetic field (370 kHz, 1.77 kA/m)
was shown for the fine MgFe2O4 powder having an ca. 6 nm crystal size (the samples milled for 6-8
h using 0.1mmφ beads). The heat generation of the samples was closely related to the hysteresis
loss for the B-H magnetic property. The reason for the high heat generation properties of the samples
milled for 6-8 h using 0.1mmφ beads was ascribed to the increase in the hysteresis loss by formationof the single domain. Moreover, the improvement in the heating ability was obtained by calcination
at low temperature of the bead-milled sample. In this case, the maximum heat generation (ΔT=41oC) ability was obtained for an ca. 11 nm crystal size sample prepared by the crystal growth during

the sample calcination.

平澤 英之
Computer simulation gf heat generation ability in AC magnetic field for bneedle-type materials
T. Naohara*1, H. Aono*1, T. Maehara*2, Y. Watanabe*3, H. Hirazawa*4, and S. Matsutomo*4*1

愛媛大学工学部、*2 愛媛大学理学部、*3 愛媛大学医学部第二外科、*4 新居浜工業高等専門学校環境材料工学科
Proc. of the 6th International Symposium on Electromagnetic Processing of Materials, pp. 193-196,
10/2009
Considering the application for the novel ablation therapy of liver cancer, the heat generation
ability of needle-type materials was studied in an AC magnetic field at 370kHz. The significant
difference in the heating properties among the ferromagnetic Fe, Fe-based alloys and Ni wasreasonably explained by the effect of the hysteresis loss. Moreover, that of the ferromagnetic Ni
and non-magnetic Ti rod specimens was investigated using a computer simulation (JMAG Studio,
ver.9.0) together with the experimental work. The Ni-rod specimen exhibited a markedly larger heatgeneration ability as compared to that of the Ti-rod specimen, resulting from the magnetic flux
concentration at the surface and its vicinity. For these conducting materials, the reason for thetemperature enhancement in the AC magnetic field was associated with the effect of eddy current
loss. The heat generation abilities calculated from the computer simulation almost agreed with theexperimentally obtained values. When the electrical resistivity is changed in the computer
simulation, the peaks of the temperature and heat generation ability appeared around 0.40μΩm for
the Ti-rod specimen. These results allowed us to conclude that the electrical resistivity plays
a key role through the effects of the eddy current loss and magnetic penetration depth.

平澤 英之
High Heat Generation Ability under AC Magnetic Field for Y3Fe5O12 Prepeared
by Reverse Coprecipitation Method
H. Aono*1, H. Hirazawa*2, T. Naohara*1, T. Maehara*1, and Y. Watanabe*3*1

愛媛大学大学院理工学研究科、*2 新居浜工業高等専門学校環境材料工学科、*3 愛媛大学医学部第二外科

Proc. of the 6th International Symposium on Electromagnetic Processing of Materials, pp. 185-188,
10/2009
Magnetic materials having a high heat generation ability in an AC magnetic field have been studied
for use in new thermal coagulation therapy for cancers. Y3Fe5O12-based powder materials, i.e., theGd-substituted Y3-XGdXFe5O12 system, were synthesized by a reverse coprecipitation method for this- 42 -

new therapy. The obtained precursors of homogeneous hydroxides using this method were calcined at1000 oC - 1200 oC for the preparation of the Y3Fe5O12-based oxide powder. A mixed cubic and orthorhombic
phase was formed for the samples calcined below 1100 oC for all the examined X values. A single
cubic phase was obtained for the samples heated at 1150 oC and higher. The maximum heat generation
ability in an AC magnetic field (370 kHz, 1.77kA/m) was for the sample calcined at 1100oC. However,
the heat ability was poor for the samples calcined at the lower and higher temperatures. The
calcination temperature at around the phase transition between the two phases influenced the highheat generation ability. In particular, the particle growth with the formation of the cubic single
phase acted to decrease the heat ability. The heat generation ability of the Y3-XGdXFe5O12 system
was almost the same for the X region from X=0 to X=2.5. However, the heat generation significantly
decreased to zero for Gd3Fe5O12 (X=3.0).

平澤 英之
Effect of crystal sizes on heat generation ability in AC magnetic field for
FeFe2O4 ferrite powder prepared by bead milling
H. Hirazawa*1, H. Aono*2, T. Naohara*2, T. Maehara*2, M. Sato*3, and Y. Watanabe*4*1

新居浜工業高等専門学校環境材料工学科、*2 愛媛大学大学院理工学研究科、*3 アドメテック(株)、*4

愛媛大学医学部第二外科

Proc. of 25th International Japan-Korea Seminar on Ceramics, pp.760-763, 11/2009
For the treatment of cancerous tissues, the thermal coagulation techniques of radio frequency
and microwave coagulation therapies have been applied as effective methods. Thermal coagulation
can also be realized by application of an AC magnetic field from external coils to the tumors using
powder type magnetic materials [1-3]. Moreover, the drug delivery system (DDS) using nano sizedmagnetic particles encapsulated in a liposome is applicable for this therapy.
Up to now, a fine magnetite (FeFe2O4) powder has been investigated as the candidate material forthis type of therapy [1]. For the FeFe2O4, the heat generation ability in an AC magnetic field is
influenced by the crystal size [2]. In our previous paper, it was reported that the FeFe2O4 preparedby coprecipitation method showed the maximum heating ability in an AC magnetic field when the crystal
size was ca. 12 nm [3]. The heat generation in an AC magnetic field is strongly influenced by thehysteresis loss of the B-H magnetic property [2,3]. We have prepared the FeFe2O4 material bycoprecipitation and reverse precipitation method [2]. However, the effect of the crystal size on
the heat generation was not clear for these materials, because the particle size and the crystal
size of the samples prepared by chemical processes might not be small enough to study theseproperties.
In this study, we investigated the heat generation ability in an AC magnetic field of fine FeFe2O4
powders physically prepared using a bead-milling method and calcinations in order to discuss theheating properties of the fine particles.

平澤 英之
Feasibility of chemohyperthermia with docetaxel-embedded
magnetoliposomes as minimally invasive local treatment for cancer
Motohira Yoshida*1, Yuji Watanabe*1, Mitsunori Sato*2, Tsunehiro Maehara*3, Hiromichi Aono*4, Takashi- 43 -Naohara*4, Hideyuki Hirazawa*5, Atsushi Horiuchi*1, Shungo Yukumi*1, Koichi Sato*1, Hiromichi
Nakagawa*1, Yuji Yamamoto*1, Hiroki Sugishita*1 and Kanji Kawachi*1*1

愛媛大学医学部医学科臓器再生外科学分野、*2アドメテック(株)、*3愛媛大学大学院理工学研究科数理物質科学専攻、*4愛媛大学大学院理工学研究科物質生命工学専攻、*5新居浜高専環境材料工学科
International Journal of Cancer, 126, pp.1955-1965, 2010
Hyperthermia is a minimally invasive approach to cancer treatment, but it is difficult to heat
only the tumor without damaging surrounding tissue. To solve this problem, we studied theeffectiveness of chemohyperthermia with docetaxel-embedded magnetoliposomes (DMLs) and an appliedalternating current (AC) magnetic field. Human MKN45 gastric cancer cells were implanted in thehind limb of Balb-c/nu/nu mice. Various concentrations of docetaxel-embedded DMLs were injected
into the tumors and exposed to an AC magnetic field (n 5 6, each). For comparison with hyperthermia
alone, magnetite-loaded liposome (ML)-injected tumors were exposed to an AC magnetic field.
Furthermore, the results of DML without AC treatment and docetaxel diluted into PBS with AC treatment
were also compared (n 5 10, each). Tumor surface temperature was maintained between 42 and 43_C.
Tumor volume was reduced in the DML group with a docetaxel concentration > 56.8lg/ml, while a
docetaxel concentration > 568.5lg/ml was required for tumor reduction without hyperthermia.
Statistically significant differences in tumor volume and survival rate were observed between the
DML group exposed to the magnetic field and the other groups. The tumor disappeared in 3 mice inthe DML group exposed to the magnetic field; 2 mice survived over 6 months after treatment, whereas
all mice of the other groups died by 15 weeks. Histologically, hyperthermia with DML damaged tumor
cells and DML diffused homogeneously. To the best of our knowledge, this is the first report toshow that hyperthermia using chemotherapeutic agent-embedded magnetoliposomes has an anticancer
effect.

〔区 分 Ｃ〕
松英 達也
The structure of Cr-N films deposited by arc ion plating investigated using synchrotron radiation
Tatsuya MATSUE *1, Takao HANABUSA*2, Kazuya KUSAKA*2, Osami SAKATA*3,*1

Niihama National College of Technology, *2 School of Eng., The Univ. of Tokushima,*3

Japan Synchrotron Radiation Research InstituteThe 10th International Symposium on Sputtering & Plasma Processes2009(ISSP2009)・ 531・
2009年．
The structures of CrN films deposited by arc ion plating on steel substrates were
investigated using a synchrotron radiation system that emits ultraintense X-rays. The CrN
films were found to be mainly composed of {110} oriented CrN crystals, but they also hada small component of randomly oriented Cr2N crystals. The CrN220 diffraction shifts to ahigh diffraction angle as the annealing temperature increases. In contrast, the peak
position of the Cr2N211 diffraction hardly changes with an increase in the annealing
temperature up to 873K. The ratio of nitrogen and oxygen to chromium at the film surface
and inside in the film was estimated by Auger electron spectroscopy. After annealing at 973K,
the surface layer was oxidized, but the composition inside the CrN film (N/Cr=0.83) remained- 44 -

unchanged.

松英 達也
RESIDUAL STRESSES OF Cr-N FILMS DEPOSITED BY ARC ION PLATINGINVESTIGATED USING SYNCHROTRON RADIATION
Tatsuya MATSUE*1，Takao HANABUSA*2，Kazuya KUSAKA*2，0sami SAKATA*3，Masayuki NISHIDA*4*1

Niihama National College of Technology, *2 School of Eng., The Univ. of Tokushima,*3

Japan Synchrotron Radiation Research Institute, *4 Kobe City College of Technology

・The 5th International Conference on Mechanical Stress Evaluation by Neutrons andSynchrotron Radiation (MECASENSⅤ) Book of Abstracts・152・2009年．
The structures of Cr-N films deposited by arc ion plating on steel substrates were
investigated using a synchrotron radiation system that emits ultraintense X-rays. The Cr-N
films were found to be mainly composed of {110} oriented CrN crystals, but they also hada small component of randomly oriented Cr2N crystals. The CrN220 diffraction shifts to ahigh diffraction angle as the annealing temperature increases. In contrast, the peak
position of the Cr2N211 diffraction hardly changes with an increase in the annealing
temperature up to 873 K. The ratio of nitrogen and oxygen to chromium at the film surface
and inside in the film was estimated by Auger electron spectroscopy. After annealing at 973
K, the surface layer was oxidized, but the composition inside the Cr-N films (N/Cr = 0.83)
remained unchanged. The residual stress in a 1600-nm-thick as-deposited CrN layer was foundto be -11.0GPa. The residual stresses of Cr-N films relaxed to thermal stress levels on
annealing. However, the residual stress in the Cr2N layer could not be evaluated.

松英 達也
Stress Estimation of Titanium Casting AIIoy by x-ray Measurement Techniqueof Single Crystal
Masayuki NISHIDA*1 , Takao HANABUSA*2 , Ayumi SHIRO *3 and Tatsuya MATSUE*4*1

Kobe City College of Technology,*2 School of Eng., The Univ. of Tokushima, *3Graduate Student,

School of Eng., The Univ. of Tokushima,*4 Niihama National College of Technology
・The 5th International Conference on Mechanical Stress Evaluation by Neutrons andSynchrotron Radiation (MECASENSⅤ) Book of Abstracts・83・2009年．
Residual stresses in titanium casting alloy were estimated by X-ray stress measurement
technique. There are two problems in the condition of X-ray stress measurement. Firstly,
the titanium casting alloy has the large crystal grains. These coarse grains were generated
under solidification processes and those sizes are approximately 2 millimeter in this study.
These coarse crystal grains interfere with an accurate stress measurement due to the unstablediffraction profile. This is because the existence of a sufficient number of isotropic
crystal grains in the X-ray irradiation area are based on the X-ray diffraction theory. In
this study, the stress measurement technique of single crystal materials was adopted forthe solution of this fundamental problem. Because the coarse crystal grain was treated asa single crystal, the high intensity diffraction profiles were observed from a certain
direction with investigations of crystal orientation. The problem with the coarse crystal- 45 -

grain in titanium casting alloy were cleaned up by the employment of the single crystal
measurement technique. Secondly, the results from this study show that the position of
crystal grain within the X-ray irradiation area greatly influenced the residual stressvalues. Therefore, in the present paper the erasing method of this position effect was triedand discussed. Finally, the improvement of the accuracy of this method for the residual
stress measurement in titanium casting alloy under the several bending stresses was
confirmed. These results show that the erasing method in this study is an effective
correction method.

松英 達也
Neutron Stress Measur6ment of Coarse Crystal Griin in Aluminum Casting AIIoy
Masayuki NISHIDA*1，Takao HANABUSA*2， Tatsuya MATSUE*3 and Hiroshi SUZUKI*4*1

Kobe City College of Technology， *2School of Eng.，The Univ. of Tokushima， *3Niihama National

College of Technology，*4Japan Atomic Energy Agency
・The 5th International Conference on Mechanical Stress Evaluation by Neutrons andSynchrotron Radiation (MECASENSⅤ) Book of Abstracts・133・2009年．
Internal stresses in aluminum casting alloy were measured by the neutron stress measurement
method with the apparatus RESA in Japan Atomic Energy Agency (JAEA). In usual cases, coarse
crystal grains are included in aluminum casting alloy. These coarse crystal grains makeit extremely difficult to estimate the internal stresses by the neutron diffraction. The
two problems arise because of the existence of the coarse crystal grains. The first problem
is the production of an unstable diffraction profile in the necessary direction. The second
is the edge effect which is generated by the overhang of the coarse crystal grains from theneutron irradiation area (gage volume). In this study, two kinds of new techniques used were
proposed to resolve these problems. Firstly, the elastic theory based on the sin2ψ method
is shown. Diffraction peaks in several directions were found by use of the rocking curve
method. Following that, the lattice spaces in each principal direction were calculated fromthese diffraction peaks using the elastic theory. Secondly, the distribution of edge effectaround the gage volume was measured using a small bit of copper single crystal. From thisresult, the edge effect was canceled out by the modified measurement method which was done
symmetrically. Finally, the aluminum casting sample which included coarse crystal grains
was set to the tensile testing machine on RESA’s measurement table and the applicabilityof these new techniques were confirmed experimentally.

朝日 太郎
部分安定化ジルコニアの低温熱劣化特性
中山 享*1、塩出昌弘*2、辻 久巳*3、塩見正樹*3、朝日太郎*4、鈴木敏久*5*1

新居浜工業高等専門学校生物応用化学科、*2㈱住化分析センター、*3 新居浜工業高等専門学校技術室、*4

新居浜工業高等専門学校環境材料工学科、*5 第一稀元素化学工業㈱新居浜工業高等専門学校紀要、第 46 巻、p.29-32、2010.
1400、1500、1600℃で焼結した ZrO2－x mol% Sm2O3、ZrO2－x mol% Gd2O3、ZrO2－x mol% Dy2O3、ZrO2－x mol%
Y2O3、ZrO2－x mol% Yb2O3（x＝3、4、5）セラミックスの低温熱劣化特性について、X 線回折測定によって- 46 -

検討したところ、以下のことがわかった。より低温で焼結したサンプルで、低温熱劣化が容易に起こらなかった。安定化剤量が多いサンプルで、低温熱劣化が容易に起こらなかった。よりイオン半径の大きな希土類元素で安定化されたサンプルで、低温熱劣化が容易に起こらなかった。

朝日 太郎
廃ガラスを用いた発泡性多孔質材料の作製
朝日太郎*1、中山享*2、大森大輔*3*1

新居浜工業高等専門学校環境材料工学科、*2新居浜工業高等専門学校生物応用化学科、*3ダイキアクシス

開発部
新居浜工業高等専門学校紀要、第46巻、p.47-50、2010.
廃ガラスの再利用化・資源化という観点から、水質浄化材や断熱材への利用を目指して、廃ガラス粉と発泡剤の焼成による発泡性多孔質材料の作製を試み、発泡剤の添加量や種類、焼成条件の変化による多孔性の検討を行った。特に、SiCを発泡助剤として使用した場合には、100μｍ付近のほぼ均一な細孔径を有する発泡体が生成することができ、SiCの添加量が多くなるほど発泡が進行し、比重が小さくなることが判明した。

〔区 分 Ｅ〕
新田 敦己
アナターゼ型酸化チタンを含む結晶化ガラスの作製
新田敦己*1、大内忠司*2*1

新居浜工業高等専門学校環境材料工学科、*2新居浜ｺﾆ業高等専門学校技術室

日本セラミックス協会 2010年年会 2010年年会講演予稿集 2010年、P.35
Crystallization of B2O3-TiO2-CaO system was investigated by the method of XRD, SEM, and EPMA. The
glass was crystallized after heat-treating at 625℃ for 60 min in the atmosphere. The precipitatedcrystal in the glass was identified by the method of XRD. The crystal was only an anatase-type TiO2.
The crystals of both anatase and rutile type were deposited in the glass heat-treated at 700℃.
But the amount of rutile-type was less than that of anatase-type. The above result shows that it
is possible to produce a glass-ceramics with a photocatalyst function.

松英 達也｢たたら｣製鉄法による炉体の設計と鋼の生成に関する研究～材料工学における「もの作り教育」～
松英達也**

新居浜工業高等専門学校環境材料工学科

・第18回日本材料科学会四国支部講演大会(松山)・2009年6月「たたら」とは、日本古来より伝わる製鉄技術であり、現代製鉄法と比べ生成効率が悪く連続操業にも向いていないが、良質の鋼を得ることができる。研究では、「たたら」製鉄による鉧の製造法の確立を目指し、主に炉体の構造および炉体材料と生成される鋼の組成について検討を行った。一方で、古式の製鉄法を学ぶことは現代の製鉄技術を理解するためには非常に有用である
ことから、このような活動を通じた材料技術者の育成にも役立つと考えられ、新居浜高専式たたら炉は携わった学生の努力の積み重ねにより完成したものである。このような研究活動が材料工学のもの作り教育の一助となり、多くの学生にもの作りの楽しさを感じる機会を与えられることを期待している。

- 47 -

松英 達也The structure of Cr-N films deposited by arc ion plating investigated using synchrotron radiation
Tatsuya MATSUE*1， Takao HANABUSA*2， Kazuya KUSAKA*2， 0sami SAKATA*3*1

Niihama National College of Technology,*2 School of Eng., The Univ. of Tokushima,*3 Japan

Synchrotron Radiation Research Institute・The 10th International Symposium on Sputtering & Plasma Processes2009(ISSP2009)・2009
年７月
The structures of CrN films deposited by arc ion plating on steel substrates were
investigated using a synchrotron radiation system that emits ultraintense X-rays. The CrN
films were found to be mainly composed of {110} oriented CrN crystals, but they also hada small component of randomly oriented Cr2N crystals. The CrN220 diffraction shifts to ahigh diffraction angle as the annealing temperature increases. In contrast, the peak
position of the Cr2N211 diffraction hardly changes with an increase in the annealing
temperature up to 873K. The ratio of nitrogen and oxygen to chromium at the film surface
and inside in the film was estimated by Auger electron spectroscopy. After annealing at 973K,
the surface layer was oxidized, but the composition inside the CrN film (N/Cr=0.83) remained
unchanged.

松英 達也
RESIDUAL STRESSES OF Cr-N FILMS DEPOSITED BY ARC ION PLATINGINVESTIGATEDUSINGSYNCHROTRON RADIATION
Tatsuya MATSUE*1 , Takao HANABUSA*2 , Kazuya KUSAKA*2, Osami SAKATA*3 , Masayuki NISHIDA *4*1

Niihama National College of Technology, *2 School of Eng., The Univ. of Tokushima,*3

Japan Synchrotron Radiation Research Institute, *4 Kobe City College of Technology

・The 5th International Conference on Mechanical Stress Evaluation by Neutrons andSynchrotron Radiation (MECASENSⅤ) ・2009年11月．
The structures of Cr-N films deposited by arc ion plating on steel substrates were
investigated using a synchrotron radiation system that emits ultraintense X-rays. The Cr-N
films were found to be mainly composed of {110} oriented CrN crystals, but they also hada small component of randomly oriented Cr2N crystals. The CrN220 diffraction shifts to ahigh diffraction angle as the annealing temperature increases. In contrast, the peak
position of the Cr2N211 diffraction hardly changes with an increase in the annealing
temperature up to 873 K. The ratio of nitrogen and oxygen to chromium at the film surface
and inside in the film was estimated by Auger electron spectroscopy. After annealing at 973
K, the surface layer was oxidized, but the composition inside the Cr-N films (N/Cr = 0.83)
remained unchanged. The residual stress in a 1600-nm-thick as-deposited CrN layer was foundto be -11.0 GPa. The residual stresses of Cr-N films relaxed to thermal stress levels on
annealing. However, the residual stress in the Cr2N layer could not be evaluated.

松英 達也
Stress Estimation of Titanium Casting Alloy by x-ray Measurement Technique of Single Crystal
Masayuki NISHIDA*1, Takao HANABUSA*2, Ayumi SHIRO*3 and Tatsuya MATSUE*4- 48 -

*1

Kobe City College of Technology,*2School of Eng., The Univ. of Tokushima,*3

Graduate Student, School of Eng., The Univ. of Tokushima,*4

Niihama National College of Technology

・The 5th International Conference on Mechanical Stress Evaluation by Neutrons andSynchrotron Radiation (MECASENSV) ・2009年11月．
Residual stresses in titanium casting alloy were estimated by X-ray stress measurement
technique. There are two problems in the condition of X-ray stress measurement. Firstly,
the titanium casting alloy has the large crystal grains. These coarse grains were generated
under solidification processes and those sizes are approximately 2 millimeter in this study.
These coarse crystal grains interfere with an accurate stress measurement due to the unstablediffraction profile. This is because the existence of a sufficient number of isotropic
crystal grains in the X-ray irradiation area are based on the X-ray diffraction theory. In
this study, the stress measurement technique of single crystal materials was adopted forthe solution of this fundamental problem. Because the coarse crystal grain was treated asa single crystal, the high intensity diffraction profiles were observed from a certain
direction with investigations of crystal orientation. The problem with the coarse crystal
grain in titanium casting alloy were cleaned up by the employment of the single crystal
measurement technique. Secondly, the results from this study show that the position of
crystal grain within the X-ray irradiation area greatly influenced the residual stressvalues. Therefore, in the present paper the erasing method of this position effect was triedand discussed. Finally, the improvement of the accuracy of this method for the residual
stress measurement in titanium casting alloy under the several bending stresses was
confirmed. These results show that the erasing method in this study is an effective
correction method.

松英 達也
Neutron Stress Measurement of Coarse Crystal Grain in Aluminum Casting Alloy
Masayuki NISHIDA*1， Takao HANABUSA*2， Tatsuya MATSUE*3 and Hiroshi SUZUKI*4*1

Kobe City College of Technology, *2 School of Eng., The Univ. of Tokushima,*3

Niihama National College of Technology, *4 Japan Atomic Energy Agency

・The 5th International Conference on Mechanical Stress Evaluation by Neutrons andSynchrotron Radiation (MECASENSV) ・2009年11月．
Internal stresses in aluminum casting alloy were measured by the neutron stress measurement
method with the apparatus RESA in Japan Atomic Energy Agency (JAEA). In usual cases, coarse
crystal grains are included in aluminum casting alloy. These coarse crystal grains makeit extremely difficult to estimate the internal stresses by the neutron diffraction. The
two problems arise because of the existence of the coarse crystal grains. The first problem
is the production of an unstable diffraction profile in the necessary direction. The second
is the edge effect which is generated by the overhang of the coarse crystal grains from theneutron irradiation area (gage volume). In this study, two kinds of new techniques used were
proposed to resolve these problems. Firstly, the elastic theory based on the sin2ψ method- 49 -

is shown. Diffraction peaks in several directions were found by use of the rocking curve
method. Following that, the lattice spaces in each principal direction were calculated fromthese diffraction peaks using the elastic theory. Secondly, the distribution of edge effectaround the gage volume was measured using a small bit of copper single crystal. From thisresult, the edge effect was canceled out by the modified measurement method which was done
symmetrically. Finally, the aluminum casting sample which included coarse crystal grains
was set to the tensile testing machine on RESA’s measurement table and the applicabilityof these new techniques were confirmed experimentally.

松英 達也
小・中学校理科および技術教員へのものづくりを通した実技研修会
松英達也*1、鎌田慶宣*2、谷口佳文*2、西井靖博*3、占部弘治*4、吉川貴士*2、松田雄二*2、松友真哉*4、
平澤英之*1、廣田 直*5*1

新居浜工業高等専門学校環境材料工学科、*2新居浜工業高等専門学校機械工学科、*3新居浜工業高等専門

学校生物応用化学科、*4新居浜工業高等専門学校電子制御工学科、*5現代GPコーディネーター
平成21年度独立行政法人国立高等専門学校機構主催教育教員研究集会（豊田市）・2009年8月〔概要は前掲〕

朝日 太郎
Na2O-Y2O3-SiO2 系ガラスの電気特性と耐水性
朝日太郎*1、丸岡 研*2、清野 肇*3、中山 享*4*1

新居浜工業高等専門学校環境材料工学科、*2 新居浜工業高等専門学校専攻科生物応用化学専攻、*3 北海道大学、*4 新居浜工業高等専門学校生物応用化学科
第22回日本セラミックス協会秋季シンポジウム 2009年
本全固体型 Na+イオンセンサの検知極材料などへの利用を目的として、Na2O-Y2O3-SiO2 系ガラスの組成とガラス化状態、熱的特性、23Na MAS-NMR による構造、Na+イオン導電率、水への Na 浸出率について検討を行った。Na+イオン導電率は、導電種である Na 含有量が増大するにつれて高くなり、Na 含有量が一定の場
合では[Y2O3]/[SiO2]比に関係なく Na+イオン導電性はほとんど変化しなかった。また、水への Na 浸出率は、
Na 含有量が増大するにつれて高くなり、Na 含有量が一定の場合では[Y2O3]/[SiO2]比が大きくなると低下し
た。

朝日 太郎
Li5YSi4O12 ガラスを用いた全固体型 pH センサの応答特性
尾西康次*1、朝日太郎*2、桑田茂樹*3、中山 享*3*1

新居浜工業高等専門学校電気情報工学科、*2 新居浜工業高等専門学校環境材料工学科、*3 新居浜工業高等専門学校生物応用化学科
第 22 回日本セラミックス協会秋季シンポジウム 2009 年
全固体型 pH センサの 25～80 ℃の温度域における水溶液の pH モニタリングについて検討した。本全固体型 pH センサは、Li5YSi4O12 ガラスを用いた pH 検知極と Nafion 膜をコーティングした金属銀/塩化銀（Ag/AgCl）参照極の 2 つの電極からできている。その起電力は、水溶液中の pH 増加に伴い Nernst 式に従って直線的に減少した。また、その起電力は、ナトリウムイオン（Na＋）や塩化物イオン（Cl-）のような無機イオンの存在にほとんど影響を受けなかった。本全固体型 pH センサが、ガラス電極を用いた市販の- 50 -

pH メータとよく似た挙動を示すことが pH 滴定によって確かめられた。加えて、この全固体型 pH センサは80℃でも安定作動した。

朝日 太郎
リン酸ジルコニウムによる Cs 固定化
近藤正太*1、高橋麻衣子*2、朝日太郎*3、中山 享*2*1

新居浜工業高等専門学校専攻科生物応用化学専攻、*2 新居浜工業高等専門学校生物応用化学科、*3 新居浜

工業高等専門学校環境材料工学科
第 16 回 ヤングセラミスト・ミーティング in 中四国 2009 年
二次元層状構造を持つプロトン型リン酸ジルコニウム（α-Zr(HPO4)2･H2O）を用いた Cs イオン固定化及びその Cs 耐浸出特性について、先に報告している三次元網目構造を持つプロトン型リン酸ジルコニウム（HZr2(PO4)3）を用いた場合と比較し検討した。

朝日 太郎
ナトリウム－ケイ酸ガラスの耐水性への添加元素の影響
丸岡 研*1、朝日太郎*2、清野 肇*3、中山 享*4*1

新居浜工業高等専門学校専攻科生物応用化学専攻、*2 新居浜工業高等専門学校材料工学科、*3 北海道大学、*4

新居浜工業高等専門学校生物応用化学科

第 16 回 ヤングセラミスト・ミーティング in 中四国 2009 年
Na2O-SiO2 ガラスの耐水性向上を目的として、添加元素の影響を調べた。さらに、ガラス転移温度、Na+
イオン導電性及び 23Na MAS -NMR による Na 周囲の構造についても検討を行った。

朝日 太郎
希土類ケイ酸塩を用いた全固体型イオン電極の応答に及ぼす電解処理効果
森野智仁*1、中山 享*2、桑田茂樹*2、朝日太郎*3*1

新居浜工業高等専門学校専攻科生物応用化学専攻、*2 新居浜工業高等専門学校生物応用化学科、*3 新居浜

工業高等専門学校環境材料工学科
全固体型 Na+イオン電極（Pt ワイヤー｜Ag ペースト｜Na5YSi4O12 ガラス板）の起電力安定性及び起電力再現性の改善を目指して、Na5YSi4O12 を負極とし Pt を正極として NaCl 水溶液中での電解処理効果について検討した。その電解処理により、電極の応答特性向上が認められた。その原因は、電極界面付近で起こるイ
オン交換による Na5YSi4O12 内のイオン活量が溶液中のイオン濃度の変化によってほとんど変化せず一定値を保つようになったためと考えられる。

平澤 英之
TiAl 合金の高温酸化高橋 知司*1、南埜 宜俊*2、平澤 英之*1、大内 忠司*1
*1

新居浜工業高等専門学校環境材料工学科、*2 大阪大学大学院工学研究科

日本材料科学会四国支部 第 18 回講演大会 2009 年 6 月
TiAl 合金は高温における強度・耐クリープ性について優れた軽量耐熱材料であり、タービンブレードや自動車用ターボチャージャーローターなどに用いられている。しかし、近年の航空機、自動車等の高速化により、それらの耐熱材料においては益々過酷な高温環境となり、さらに高温での耐酸化性の良好な超耐熱材料の開発が望まれている。
TiAl を酸化させた場合、生成する酸化物は TiO,Ti2O3,TiO2, Al2O3, Al2O,AlO, Al2TiO5 などが考えられて- 51 -

いるが、実際の TiAl 相の酸化において酸化物の形態とそれらの形成過程を明らかにし、さらに酸化反応全体を支配しているものは何かという観点から、酸化反応における構成元素の拡散に関する知見も必要である。
本研究は、TiAl 基超耐熱合金開発のための基礎研究であり、その第一段階として TiAl 合金の耐酸化特性に関するデータを得るため、大気中で 1123K～1273K の高温で酸化させた場合の酸化被膜の成長などを化
学天秤による重量変化、SEM および EPMA 観察などで調べ、本合金の酸化挙動とその特徴を明らかにするも
のである。

平澤 英之
物理的手法によるマグネタイトの粒子径制御と交流磁場中での発熱特性
平澤英之*1、佐々木裕臣*2、青野宏通*2、猶原 隆*2、前原常弘*3、渡部祐司*4、佐藤充則*5*1

新居浜工業高等専門学校環境材料工学科、*2 愛媛大学工学部、*3 愛媛大学理学部、*4 愛媛大学医学部、*5

アドメテック(株)日本セラミックス協会 第 22 回秋季シンポジウム H21 年９月
The nano-sized FeFe2O4 ferrite powder having a heat generation ability in an AC magnetic field
was prepared by beads milling. The highest heat generation ability (ΔT=26 oC) was obtained ca.
4.7nm in crystal size. Moreover, the improvement in the heating ability was obtained by calcinationin Ar atmosphere at low temperature of the bead-milled sample.

平澤 英之
ガーネット系 Y3-XGdXFe5O12 型フェライトの交流磁場中での発熱特性
森谷健史*1、青野宏通*1、猶原 隆*1、前原常弘*2、渡部祐司*3、平澤英之*4*1

愛媛大学工学部、*2 愛媛大学理学部、*3 愛媛大学医学部、*4 新居浜工業高等専門学校環境材料工学科

日本セラミックス協会 第 22 回秋季シンポジウム H21 年 9 月
We prepared the Y3-XGdXFe5O12 ferrite system using a reverse coprecipitation method. The maximum
heat generation ability (ΔT) was obtained for the samples calcined at around 1100℃. However, theGd3Fe5O12 (X=3.0) has no heat generation ability in AC magnetic field. The calcined temperature of
the maximum ΔT value would depend on the crystal growth with the phase change between cubic andorthorhombic phases.

平澤 英之
様々な化学的作製法により作製した Mg1-XCaXFe2O4 系フェライトの交流磁場中での発熱特性
米田渓一*1、青野宏通*1、猶原 隆*1、前原常弘*2、渡部祐司*3、平澤英之*4*1

愛媛大学工学部、*2 愛媛大学理学部、*3 愛媛大学医学部、*4 新居浜工業高等専門学校環境材料工学科

日本セラミックス協会 第 22 回秋季シンポジウム H21 年 9 月
We prepared the Mg1-XCaXFe2O4 ferrite system using two methods of ethylene glycol method and reverse
coprecipitation method. The maximum heat generation ability (ΔT) was obtained for the samples
calcinedat around 700oC and 800oC for the two methods, respectively. The calcined temperature of
the maximum ΔT value would depend on the crystal distribution with the phase change between cubic
and orthorhombic phases.

平澤 英之
癌の交流磁場焼灼療法への応用を目的としたフェライト材料の設計- 52 -

青野宏通*1、猶原 隆*1、前原常弘*2、渡部祐司*3、平澤英之*4*1

愛媛大学工学部、*2 愛媛大学理学部、*3 愛媛大学医学部、*4 新居浜工業高等専門学校環境材料工学科

日本化学会西日本大会 H21 年 11 月
交流磁場中で著しく発熱する材料は、癌の新しい焼灼療法（図１）への応用を目的として、発熱特性の優れたものが切望されている。これは、磁性材料を腫瘍部に留置し、交流磁場により焼灼するものである。
そして、磁性材料を患部に留置する方法として３種が考えられており、(1) 針状磁性材料を患部に穿刺し、焼灼後に抜き取る方法(2) 球状磁性材料(20～30μm)をカテーテルにより患部の血管に塞栓させる方法(3) 微粒子磁性材料(50nm 以下)を抗体付きリポソームに包埋しカテーテルを用いて選択的に患部に堆積させる究極の方法である。この交流磁場焼灼法は、効果的に患部にダメージを与え、さらにヒートショックプロテイン（HSP）の発現により正常細胞の免疫機能を活性化させる。本発表の研究は(2)(3)で用いるフェライト材料の研究であり、多くの研究グループが FeFe2O4 を用いて研究を行ってきているが、我々は FeFe2O4 も含めた発熱能力の優れた材料の検索及び研究を行ってきている。そして、これまでに様々な材料を候補として報告してきている、この作製方法としては共沈法や高分子化法などによる化学的作製法による微粒子化が主であり、一方ビーズミルによるナノ微粒子への物理的粉砕も有効である。ここではそれらの材料の設計指針について述べる。

平澤 英之
癌治療への応用を目的としたガーネット系Y3Fe5012フェライトのピーズミル粉砕による微粒子化と交流磁場申での発熱特性
江原弘規*1、青野宏通*1、猶原 隆*1、前原常弘*2、渡部祐司*3、平澤英之*4*1

愛媛大学工学部、*2 愛媛大学理学部、*3 愛媛大学医学部、*4 新居浜工業高等専門学校環境材料工学科

日本セラミックス協会2010年年会 H22年3月
Fine Y3Fe5O12 ferrite powder was prepared using bead-milling. Although the commercial Y3Fe5O12 dose
not show heat generation ability (ΔT=0oC) at al., the heat generation ability was strongly improvedby the bead-milling. The maximum heat temperature (ΔT=60 oC) in an AC magnetic field was obtained
for the sample having 16 nm in crystal size.

平澤 英之
ガーネット系 Y3Fe5O12 を基本とするフェライトの交流磁場中での発熱特性
森谷健史*1、青野宏通*1、猶原 隆*1、前原常弘*2、渡部祐司*3、平澤英之*4*1

愛媛大学工学部、*2 愛媛大学理学部、*3 愛媛大学医学部、*4 新居浜工業高等専門学校環境材料工学科

日本セラミックス協会2010年年会 H22年3月
We prepared the Y3Fe5O12-based ferrite, i.e., Y3-XGdXFe5O12 system using a reverse coprecipitation
method. The maximum heat generation ability (ΔT) was obtained for the samples calcined at 1100
oC. The calcined temperature of the maximum ΔT value would depend on the crystal growth with thephase change between cubic and orthorhombic phases. However, the Gd3Fe5O12 (X=3.0) has no heatgeneration ability in AC magnetic field.

- 53 -